CN117186438A - Emulsifier composition, protective colloid, application, phenolic resin emulsion, preparation method and application thereof - Google Patents
Emulsifier composition, protective colloid, application, phenolic resin emulsion, preparation method and application thereof Download PDFInfo
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- CN117186438A CN117186438A CN202310308573.XA CN202310308573A CN117186438A CN 117186438 A CN117186438 A CN 117186438A CN 202310308573 A CN202310308573 A CN 202310308573A CN 117186438 A CN117186438 A CN 117186438A
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 139
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 139
- 239000000839 emulsion Substances 0.000 title claims abstract description 133
- 230000001681 protective effect Effects 0.000 title claims abstract description 60
- 239000000084 colloidal system Substances 0.000 title claims abstract description 59
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 application Substances 0.000 title description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 150000002989 phenols Chemical class 0.000 claims abstract description 11
- 239000011490 mineral wool Substances 0.000 claims abstract description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 47
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 47
- 102000011632 Caseins Human genes 0.000 claims description 42
- 108010076119 Caseins Proteins 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 239000005018 casein Substances 0.000 claims description 24
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 24
- 235000021240 caseins Nutrition 0.000 claims description 24
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 21
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- 229940080237 sodium caseinate Drugs 0.000 claims description 18
- 229920002907 Guar gum Polymers 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000665 guar gum Substances 0.000 claims description 16
- 235000010417 guar gum Nutrition 0.000 claims description 16
- 229960002154 guar gum Drugs 0.000 claims description 16
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 16
- 239000004359 castor oil Substances 0.000 claims description 15
- 235000019438 castor oil Nutrition 0.000 claims description 15
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 239000012874 anionic emulsifier Substances 0.000 claims description 11
- 239000012875 nonionic emulsifier Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 7
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 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 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 3
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 3
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 30
- 239000011347 resin Substances 0.000 abstract description 30
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000010426 asphalt Substances 0.000 abstract description 7
- 239000004925 Acrylic resin Substances 0.000 abstract description 4
- 229920000178 Acrylic resin Polymers 0.000 abstract description 4
- 239000003822 epoxy resin Substances 0.000 abstract description 4
- 229920000647 polyepoxide Polymers 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000123 paper Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000004945 emulsification Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000010008 shearing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000021120 animal protein Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides an emulsifier composition, a protective colloid and a phenolic resin emulsion, wherein the phenolic resin emulsion comprises the emulsifier composition, the protective colloid, a pH regulator, raw material phenols, raw material aldehydes, a catalyst and water. The preparation method takes water as a solvent, the molecular weight of the generated phenolic resin is large, the phenolic resin can be infinitely diluted by water, the emulsion stability is good, the phenolic resin has good compatibility with other resins such as epoxy resin, acrylic resin and the like, and the phenolic resin is convenient to modify among different resins. Can be widely used for products such as coated abrasive tools, wet curtain paper, rock wool resin and the like, and can be used as road products by being mixed with emulsified asphalt and the like.
Description
Technical Field
The application relates to the technical field of phenolic resin, in particular to an emulsifier composition, a protective colloid, application, a phenolic resin emulsion, a preparation method and application thereof.
Background
Phenolic resins are one of the earlier synthetic resins, and have been widely used because of their strong adhesion, excellent heat resistance, and high carbon residue. Phenolic resin is mainly prepared by polymerizing phenol and formaldehyde under the condition of an acidic or alkaline catalyst, and as the reaction proceeds, the molecular weight gradually increases, the water solubility decreases, and phase separation is performed to a certain extent, and precipitation is performed. The traditional phenolic resin synthesis process is to add organic solvents such as methanol, ethanol and the like to form a uniform solution of the phenolic resin. This method increases the cost of the resin, and the organic solvent volatilizes during use, which causes environmental pollution and causes various physical damage to the user.
In order to solve the problems, the waterborne of the phenolic resin is taken as one of the research directions at home and abroad, and a preparation process of the emulsifiable water-based phenolic resin is disclosed in a patent document CN112661978A, which comprises the following steps: firstly, preparing bisphenol A, urea, melamine or alkylphenol modified phenolic resin prepolymer; adding emulsifying agent such as gelatin, bone gelatin, vegetable protein or animal protein; the reaction was continued again. As described in patent document CN110371994a, the phenolic resin modified by urea or melamine is prepared first, then polyvinyl alcohol, styrene-butadiene latex, styrene-acrylic emulsion, pure acrylic emulsion and the like are used as toughening agents, sodium alkylphenol ether sulfosuccinate is mainly used as an emulsifier, and a small amount of polyoxyethylene alkylphenol ether is added as a wetting agent and mixed with a pH regulator.
The method adopted in the above patent document is mainly a two-step method, respectively synthesizing phenolic resin, then mixing under the condition of a homogenizer or a high-speed shearing machine to form phenolic resin emulsion, and mainly preparing urea, melamine or bisphenol A modified phenolic resin into emulsion. The high-speed shearing equipment such as a homogenizer and the like has high energy consumption, and the stability of the final emulsion is obviously affected by the phenolic resin. The emulsion prepared in the patent document CN103570900A has smaller molecular weight formed in the earlier stage, so that free aldehyde and free phenol are higher, the environment is polluted, and the final heat resistance and other curing performances of the phenolic resin are affected by larger addition amount of the stabilizer.
Disclosure of Invention
The application aims to solve the technical problems in the background art and provides an emulsifier composition, a protective colloid, application, phenolic resin emulsion, a preparation method and application thereof.
The technical scheme of the application is as follows:
1. an emulsifier composition for preparing a phenolic resin emulsion, wherein,
including casein, anionic emulsifiers, and nonionic emulsifiers;
preferably, the method comprises the steps of,
the casein is (2-5) parts by weight and the anionic emulsifier is (1-3) parts by weight relative to 1 part by weight of the nonionic emulsifier.
2. The emulsifier composition according to item 1, wherein,
the anionic emulsifier is sodium dodecyl benzene sulfonate and/or sodium dodecyl sulfate, preferably sodium dodecyl benzene sulfonate.
3. The emulsifier composition according to item 1, wherein,
the nonionic emulsifier is one or more of polyethylene glycol, castor oil polyoxyethylene ether, octyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and allyl polyethylene glycol, and is preferably castor oil polyoxyethylene ether.
4. The emulsifier composition according to any one of the claim 1 to 3, wherein,
the emulsifier composition consists of casein, an anionic emulsifier and a nonionic emulsifier.
5. A protective colloid for preparing phenolic resin emulsion, wherein,
including polyvinyl alcohol, sodium caseinate and guar gum;
preferably, the method comprises the steps of,
the guar gum is (2-5) parts by weight and the sodium caseinate is (1-9) parts by weight relative to 1 part by weight of polyvinyl alcohol.
6. The protective colloid according to item 5, wherein,
the polyvinyl alcohol is one or more selected from polyvinyl alcohol 0588, polyvinyl alcohol 0599, polyvinyl alcohol 1788, polyvinyl alcohol 1799 and sodium polyacrylate, preferably polyvinyl alcohol 0588 and/or polyvinyl alcohol 0599.
7. The protective colloid according to item 5 or 6, wherein,
the protective colloid consists of polyvinyl alcohol, sodium caseinate and guar gum.
8. The use of the emulsifier composition according to any one of items 1 to 4 and the protective colloid according to any one of items 5 to 7 for preparing a phenolic resin emulsion.
9. A phenolic resin emulsion, wherein,
the phenolic resin emulsion is an all-aqueous emulsion, the solid content of the phenolic resin emulsion is 25-75%, preferably 35-60%, the viscosity of the phenolic resin emulsion at 25 ℃ is 100-5000, preferably 500-2000, and the weight average molecular weight of the phenolic resin in the phenolic resin emulsion is 1000-7000, preferably 3000-7000.
10. A phenolic resin emulsion prepared from the emulsifier composition of any one of items 1 to 4, the protective colloid of any one of items 5 to 7, a pH adjuster, raw phenols, raw aldehydes, a catalyst and water;
preferably, the method comprises the steps of,
the emulsifier comprises 0.5-10 parts by weight of an emulsifier composition, 0.1-10 parts by weight of a protective colloid, 0.01-5 parts by weight of a pH regulator, 50-400 parts by weight of raw material phenols, 100-800 parts by weight of raw material aldehydes, 0.5-10 parts by weight of a catalyst and 50-600 parts by weight of water.
11. The phenolic resin emulsion of item 10, wherein,
the pH regulator is one or more of ammonia water, triethylamine, triethanolamine, AMP-95 or sodium hydroxide solution.
12. The phenolic resin emulsion of item 10, wherein,
the raw material phenol is one or more than two of phenol, bisphenol A, cardanol, m-cresol and resorcinol;
the raw material aldehyde is one or more than two of formaldehyde, acetaldehyde, paraformaldehyde, glyoxal, glutaraldehyde, furfural and salicylaldehyde.
13. The phenolic resin emulsion of item 10, wherein,
the catalyst is one or more of sodium hydroxide, barium hydroxide, ammonia water, triethylamine, triethanolamine, calcium oxide, oxalic acid, hydrochloric acid, sulfuric acid and p-toluenesulfonic acid, and preferably sodium hydroxide.
14. The phenolic resin emulsion according to any one of items 10 to 13, wherein,
the weight average molecular weight of the phenolic resin in the phenolic resin emulsion is 1000-7000.
15. The method for producing a phenolic resin emulsion according to any one of items 10 to 14, comprising the steps of:
preparing an emulsion: adding water, an emulsifying agent and a pH regulator into a kettle, and uniformly mixing to obtain an emulsion;
preparation of protective colloid solution: adding the protective colloid into water for dissolution to obtain a protective colloid solution;
first reaction: adding raw material phenols, raw material aldehydes, a catalyst and part of emulsion into water, heating to 60-100 ℃ to start reaction, and reacting for 30-90min to obtain a solution containing matrix phenolic resin;
second reaction: and adding a protective colloid solution and the rest emulsion into the solution containing the matrix phenolic resin, continuing to react until the reaction viscosity is 300-1000 cp, and cooling to obtain the phenolic resin emulsion.
16. The method according to item 15, wherein,
in the second reaction, the reaction temperature is 60 to 100℃and preferably 75 to 90 ℃.
17. The method according to item 15, wherein,
in the first reaction, the reaction time is 40 to 80min, preferably 60min.
18. The phenolic resin emulsion of the 9 item, the phenolic resin emulsion of any one of the 10 to 14 item, and the phenolic resin emulsion prepared by the method of any one of the 15 to 17 item, and the application of the phenolic resin emulsion in sand paper, filter paper, rock wool and road products.
Compared with the prior art, the application has the beneficial effects that:
the phenolic resin has large molecular weight, does not need to use an organic solvent in the preparation process, does not need to use special equipment or methods such as high-speed shearing and the like, and overcomes the defect that the phenolic resin with large molecular weight needs to use the organic solvent and the special equipment in the prior art. The synthesis process of the application does not need special equipment and has low energy consumption.
The preparation method takes water as a solvent, the molecular weight of the generated phenolic resin is large, the phenolic resin can be infinitely diluted by water, the emulsion stability is good, the phenolic resin has good compatibility with other resins such as epoxy resin, acrylic resin and the like, and the phenolic resin is convenient to modify among different resins. Can be widely used for products such as coated abrasive tools, wet curtain paper, rock wool resin and the like, and can be used as road products by being mixed with emulsified asphalt and the like.
The phenolic resin emulsion prepared by the application has excellent stability and water dilutability (the larger the water dilution multiple is, the better), the phenolic resin emulsion can be diluted by more than 20 times of water, and no demulsification phenomenon and no dregs are generated after dilution.
The phenolic resin emulsion prepared by the application has good room temperature stability, does not contain an organic solvent, does not need to be diluted by the organic solvent when in use, can be diluted by water, and is environment-friendly. Can be used as adhesive for sand paper, filter paper, rock wool and other products, and can be mixed with emulsified asphalt and the like to be used as road products and the like.
The phenolic resin emulsion provided by the application only uses water as a reaction solvent, and organic reagents such as methanol, ethanol and the like are not required to be added as auxiliary solvents in the whole production process, so that the production is safer, and the use is more environment-friendly.
The phenolic resin emulsion of the application adopts the simultaneous polymerization and emulsification of phenolic resin, and the process is more convenient.
The phenolic resin emulsion of the application does not need special equipment such as a homogenizer, a high-speed shearing machine and the like during production.
The phenolic resin emulsion of the application can form stable emulsion under the conditions of acid, alkali, salt and mixed catalyst without limitation of the catalyst.
The phenolic resin emulsion can adjust the polymerization degree of the phenolic resin according to the use requirement, and can react to obtain higher polymerization degree and higher molecular weight.
The phenolic resin emulsion is not limited in use of raw material phenol and raw material aldehyde, and is suitable for common phenolic resin synthesized by phenol and formaldehyde, and is also suitable for modified phenolic resin synthesized by substances such as bisphenol A, resorcinol, melamine, urea and the like and aldehydes.
The phenolic resin emulsion has small particle size and high stability, and can be stored for a long time at room temperature.
The phenolic resin emulsion has high compatibility with other resins such as pure acrylic emulsion, styrene-acrylic emulsion, epoxy emulsion and the like.
The phenolic resin emulsion of the application does not need cosolvent such as sodium hydroxide solution and the like to enhance the water dilutability. The pH range is wide.
Detailed Description
The application will be further illustrated with reference to the following examples, which are to be understood as merely further illustrating and explaining the application and are not to be construed as limiting the application.
Unless defined otherwise, technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, the materials and methods are described herein below. In case of conflict, the present specification, including definitions therein, will control and materials, methods, and examples, will control and be in no way limiting. The application is further illustrated below in connection with specific examples, which are not intended to limit the scope of the application.
The application provides an emulsifier composition for preparing phenolic resin emulsion, which comprises casein, an anionic emulsifier and a nonionic emulsifier.
In some embodiments of the application, the casein is (2-5) parts by weight and the anionic emulsifier is (1-3) parts by weight relative to 1 part by weight of the nonionic emulsifier; wherein the casein may be 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, 3.0 parts by weight, 3.1 parts by weight, 3.2 parts by weight, 3.3 parts by weight, 3.4 parts by weight, 3.5 parts by weight, 3.6 parts by weight, 3.7 parts by weight, 3.8 parts by weight, 3.9 parts by weight, 4.0 parts by weight, 4.1 parts by weight, 4.2 parts by weight, 4.3 parts by weight, 4.4 parts by weight, 4.5 parts by weight, 4.6 parts by weight, 4.7 parts by weight, 4.8 parts by weight, 4.9 parts by weight, 5.0 parts by weight or any range therebetween, and the anionic emulsifier may be 1 part by weight, 1.2.8 parts by weight, 1.3.6 parts by weight, 1.2 parts by weight, 1.3.6 parts by weight, 2.1 part by weight, 2.6 parts by weight, 2.1 part by weight, 2.8 parts by weight, 3.9 parts by weight, 3.0 parts by weight, 4.1 part by weight, 2.1 part by weight, 2.6 parts by weight, or any range therebetween.
In some embodiments of the application, the anionic emulsifier is sodium dodecyl benzene sulfonate and/or sodium dodecyl sulfate, preferably sodium dodecyl benzene sulfonate.
In some embodiments of the present application, the nonionic emulsifier is one or more of polyethylene glycol, castor oil polyoxyethylene ether, octylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, and allyl polyethylene glycol, preferably castor oil polyoxyethylene ether.
In some embodiments of the application, the emulsifier composition consists of casein, an anionic emulsifier, and a nonionic emulsifier.
In some embodiments of the application, the emulsifier composition comprises casein, sodium dodecylbenzenesulfonate, and castor oil polyoxyethylene ether.
In the present application, casein alone can be used to emulsify a phenolic resin, but the emulsification effect is poor at a level of 5% or less by mass of phenol, and the resulting resin emulsion product is stable in a short period of time, but is easily demulsified under conditions of large sample temperature fluctuation and mechanical stirring. And casein is used in a large amount, and in the application of resin, the use performance is obviously affected by a large amount of residual emulsifying agent, and the cost is high. However, when casein is compounded with sodium dodecyl benzene sulfonate and castor oil polyoxyethylene ether, a protective layer is firstly established by the sodium dodecyl benzene sulfonate and the castor oil polyoxyethylene ether through the casein, the sodium dodecyl benzene sulfonate and the castor oil polyoxyethylene ether form a protective layer with anions through tight combination with the casein, and each phenolic resin microsphere forms a repulsive effect through negative charges of an outer layer. Enhances the emulsification effect and reduces the dosage of casein.
In some embodiments of the application, the emulsifier composition consists of casein, sodium dodecylbenzenesulfonate, and castor oil polyoxyethylene ether.
In the preparation of the phenolic resin emulsion, the emulsifier composition uniformly coats the resin particles, so that the resin particles are uniformly dispersed in water, and the emulsifying effect is improved. In addition, by compounding casein, sodium dodecyl benzene sulfonate and castor oil polyoxyethylene ether, the dosage of casein is reduced, the emulsifying capacity is improved, the water resistance of a finished product is improved when the resin is used, the service life of a finished product material is prolonged, and the raw material cost can be reduced.
The application also provides a protective colloid for preparing the phenolic resin emulsion, which comprises polyvinyl alcohol, sodium caseinate and guar gum.
In some embodiments of the present application, the guar gum is (2-5) parts by weight and the sodium caseinate is (1-9) parts by weight relative to 1 part by weight of the polyvinyl alcohol, wherein the guar gum may be 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, 3.0 parts by weight, 3.1 parts by weight, 3.2 parts by weight, 3.3 parts by weight, 3.4 parts by weight, 3.5 parts by weight, 3.6 parts by weight, 3.7 parts by weight, 3.8 parts by weight, 3.9 parts by weight, 4.0 parts by weight, 4.1 parts by weight, 4.2 parts by weight, 4.3 parts by weight, 4.4 parts by weight, 4.5 parts by weight, 4.6 parts by weight, 4.7 parts by weight, 4.8 parts by weight, 4.9 parts by weight, 5.0 parts by weight, or any range therebetween relative to 1 part by weight of the polyvinyl alcohol, the sodium caseinate may be 1 part by weight, 1.1 part by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2.0 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, 3.0 parts by weight, 3.1 parts by weight, 3.2 parts by weight 3.3 parts by weight, 3.4 parts by weight, 3.5 parts by weight, 3.6 parts by weight, 3.7 parts by weight, 3.8 parts by weight, 3.9 parts by weight, 4.0 parts by weight, 4.1 parts by weight, 4.2 parts by weight, 4.3 parts by weight, 4.4 parts by weight, 4.5 parts by weight, 4.6 parts by weight, 4.7 parts by weight, 4.8 parts by weight, 4.9 parts by weight, 5.0 parts by weight, 5.1 parts by weight, 5.2 parts by weight, 5.3 parts by weight, 5.4 parts by weight, 5.5 parts by weight, 5.6 parts by weight, 5.7 parts by weight, 5.8 parts by weight, 5.9 parts by weight, 6.0 parts by weight, 6.1 parts by weight, 6.2 parts by weight, 6.3 parts by weight, 6.4 parts by weight, 6.5 parts by weight, 6.6 parts by weight, 6.7 parts by weight, 6.8 parts by weight, 6.9 parts by weight, 7.0 parts by weight, 7.1 parts by weight, 7.2 parts by weight, 7.3 parts by weight, 7.4 parts by weight, 7.5 parts by weight, 7.6 parts by weight, 7.7 parts by weight, 7.8 parts by weight, 7.9 parts by weight, 8.0 parts by weight, 8.1 parts by weight, 8.2 parts by weight, 8.3 parts by weight, 8.4 parts by weight, 8.5 parts by weight, 8.6 parts by weight, 8.7 parts by weight, 8.8 parts by weight, 8.9 parts by weight, 9.0 parts by weight, or any range therebetween.
In some embodiments of the application, the polyvinyl alcohol is selected from one or more of polyvinyl alcohol 0588, polyvinyl alcohol 0599, polyvinyl alcohol 1788, polyvinyl alcohol 1799, sodium polyacrylate, preferably polyvinyl alcohol 0588 and/or polyvinyl alcohol 0599.
In the application, the stability of emulsion and the raw material selection of protective colloid are closely related to the viscosity, pH value and other factors, and the polyvinyl alcohol can improve the emulsification and enhance the emulsion stability to a certain extent. However, the effect is single by using only polyvinyl alcohol, and the isolation and protection effects on emulsion ions are weak due to small viscosity when the amount of the polyvinyl alcohol with smaller polymerization degree is small. If the usage amount is increased, excessive polyvinyl alcohol remains in the usage process, and the heat resistance of the finished product material is affected. The polyvinyl alcohol with higher concentration can be bonded with the phenolic resin emulsified particles, demulsification and degradation of stability are caused by inverse emulsion. If polyvinyl alcohol with high polymerization degree is used, the solubility is poor, the adhesion is serious, and other performances such as impregnation of phenolic emulsion are affected due to the high polymerization degree.
The protective colloid is used for preparing phenolic resin emulsion, and the polyvinyl alcohol, sodium caseinate and guar gum are compounded, so that the emulsion stability can be obviously improved. The polyvinyl alcohol and the sodium caseinate have certain emulsification, the sodium caseinate can be dissolved in water to play a role in assisting emulsification, guar gum has the effects of low concentration and high viscosity, and can form a stable protective film with the polyvinyl alcohol between emulsion particles, so that collision and demulsification between the emulsion particles are avoided. The protective colloid formed by compounding the polyvinyl alcohol, the sodium caseinate and the guar gum can avoid collision aggregation among resin particles. Can be stable at a larger temperature change (5-85 ℃), and can be infinitely diluted. Can be stably stored under the condition of stirring at high rotation speed. And the dosage of polyvinyl alcohol is reduced after compounding, and adverse effects on the use process and the finished product material caused by overlarge protective colloid are avoided.
In some embodiments of the application, the protective colloid consists of polyvinyl alcohol, sodium caseinate, and guar gum.
The application provides the emulsifier composition and application of the protective colloid in preparing phenolic resin emulsion.
The application also provides a phenolic resin emulsion which is an all-aqueous emulsion, has a solid content of 25-75%, preferably 35-60%, a viscosity of 100-5000, preferably 500-200, at 25 ℃, and a weight average molecular weight of the phenolic resin in the phenolic resin emulsion of 1000-7000, preferably 3000-7000.
The method for measuring the solid content comprises the following steps: 2g of phenolic resin emulsion is taken, dried in an oven at 150 ℃ for 2 hours and weighed. And obtaining the solid content by using the mass after drying/the mass of the resin liquid.
The viscosity was measured as follows: the viscosity was measured at 25℃using a type NDJ-79 viscometer.
The method for measuring the weight average molecular weight is as follows: the weight average molecular weight was measured by Gel Permeation Chromatography (GPC).
In some embodiments of the application, the weight average molecular weight of the phenolic resin in the phenolic resin emulsion may be 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 6100, 6200, 6300, 6400, 6500, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7700, 7800, 7900, 8000, 8100, 8200, 8300, 8400, 8800, 8600, 8900, or any range therebetween.
In some embodiments of the application, the solids content of the phenolic resin emulsion may be 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75% or any range therebetween.
In some embodiments of the application, the viscosity of the phenolic resin emulsion at 25 ℃ may be 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 0, 6200, 6300, 6400, 6500, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7700, 7800, 7900, 8000, 8400, 8600, 8800, or any range therebetween.
The application also provides a phenolic resin emulsion which is prepared from the emulsifier composition, the protective colloid, a pH regulator, raw material phenols, raw material aldehydes, a catalyst and water.
In some embodiments of the application, in the phenolic resin emulsion, the emulsifier composition is 0.5 to 10 parts by weight, the protective colloid is 0.1 to 10 parts by weight, the pH regulator is 0.01 to 5 parts by weight, the raw material phenols are 50 to 400 parts by weight, the raw material aldehydes are 100 to 800 parts by weight, the catalyst is 0.5 to 10 parts by weight, and the water is 50 to 600 parts by weight;
wherein the emulsifier composition may be 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or any range therebetween;
the protective colloid is 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight or any range therebetween;
The pH adjuster may be 0.01 part by weight, 0.05 part by weight, 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, or any range therebetween;
the raw material phenols may be 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, 200 parts by weight, 210 parts by weight, 220 parts by weight, 230 parts by weight, 240 parts by weight, 250 parts by weight, 260 parts by weight, 270 parts by weight, 280 parts by weight, 290 parts by weight, 300 parts by weight, 310 parts by weight, 320 parts by weight, 330 parts by weight, 340 parts by weight, 350 parts by weight, 360 parts by weight, 370 parts by weight, 380 parts by weight, 390 parts by weight, 400 parts by weight, or any range therebetween.
The raw aldehyde may be 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800 or any range therebetween;
The catalyst may be 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or any range therebetween;
the water may be 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 550, 560, 570, 580, 590, 600, or any range therebetween.
In some embodiments of the application, the pH adjuster is one or more of ammonia, triethylamine, triethanolamine, AMP-95, or sodium hydroxide solution.
In some embodiments of the application, the raw phenol is one or more of phenol, bisphenol a, cardanol, m-cresol, resorcinol.
In some embodiments of the application, the raw aldehyde is one or more of formaldehyde, acetaldehyde, paraformaldehyde, glyoxal, glutaraldehyde, furfural, salicylaldehyde.
In some embodiments of the application, the catalyst is one or more of sodium hydroxide, barium hydroxide, ammonia, triethylamine, triethanolamine, calcium oxide, oxalic acid, hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid, preferably sodium hydroxide.
In some embodiments of the application, the weight average molecular weight of the phenolic resin in the phenolic resin emulsion is 1000-7000.
The application provides a preparation method of the phenolic resin emulsion, which comprises the following steps:
preparing an emulsion: adding water, an emulsifying agent and a pH regulator into a kettle, and uniformly mixing to obtain an emulsion;
preparation of protective colloid solution: adding the protective colloid into water for dissolution to obtain a protective colloid solution;
First reaction: adding raw material phenols, raw material aldehydes, a catalyst and part of emulsion into water, heating to 60-100 ℃ to start reaction, and reacting for 30-90min to obtain a solution containing matrix phenolic resin;
second reaction: and adding a protective colloid solution and the rest emulsion into the solution containing the matrix phenolic resin, continuing to react until the reaction viscosity is 300-1000 cp, and cooling to obtain the phenolic resin emulsion.
In some embodiments of the application, the reaction temperature in the second reaction is 60-100 ℃, preferably 75-90 ℃, wherein the reaction temperature in the second reaction may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or any range therebetween. In the present application, too low a reaction temperature may result in a long reaction time and a slow reaction. The reaction temperature is too high, the reaction is fast, and the reaction is not easy to control.
In some embodiments of the application, in the first reaction, the reaction time is 40-80min, preferably 60min. The reaction is insufficient in a short time, and the emulsification effect is affected by the excessively long reaction time; for example, the reaction time of the first reaction may be 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, or any range therebetween.
The application provides application of the phenolic resin emulsion in sand paper, filter paper, rock wool and road products.
The phenolic resin emulsion can be used as a paper reinforcing agent to strengthen paper. Used in the fields of automobile air conditioner filter paper and the like. Can be mixed with emulsified asphalt in road products to strengthen the strength of asphalt materials.
The phenolic resin has large molecular weight, does not need to use an organic solvent in the preparation process, does not need to use special equipment or methods such as high-speed shearing and the like, and overcomes the defect that the phenolic resin with large molecular weight needs to use the organic solvent and the special equipment in the prior art. The synthesis process of the application does not need special equipment and has low energy consumption.
The preparation method takes water as a solvent, the molecular weight of the generated phenolic resin is large, the phenolic resin can be infinitely diluted by water, the emulsion stability is good, the phenolic resin has good compatibility with other resins such as epoxy resin, acrylic resin and the like, and the phenolic resin is convenient to modify among different resins. Can be widely used for products such as coated abrasive tools, wet curtain paper, rock wool resin and the like, and can be used as road products by being mixed with emulsified asphalt and the like.
The phenolic resin emulsion prepared by the application has excellent stability and water dilutability, can be diluted by more than 20 times of water, has no demulsification phenomenon after dilution, and has no dregs.
Example 1
Emulsifier composition
The preparation method of R1 is as follows: 20g of deionized water was weighed, 4g of casein, 2g of sodium dodecylbenzenesulfonate, 2g of castor oil polyoxyethylene ether were added thereto, and dissolved under stirring to obtain a solution of the emulsifier composition, which was designated as R1.
The preparation method of R2 comprises the following steps: 20g of deionized water was weighed, 4g of casein, 2g of sodium dodecylbenzenesulfonate, and 2g of polyethylene glycol were added thereto, and dissolved under stirring to obtain a solution of the emulsifier composition, which was designated as R2.
The preparation method of R3 comprises the following steps: 20g of deionized water was weighed, 2g of sodium dodecyl benzene sulfonate, 2g of castor oil polyoxyethylene ether was added, and the mixture was dissolved under stirring to obtain a solution of the emulsifier composition, which was designated as R3.
The preparation method of R4 comprises the following steps: 20g of deionized water was weighed, 4g of casein, 2g of castor oil polyoxyethylene ether was added thereto, and the mixture was dissolved under stirring to obtain a solution of the emulsifier composition, which was designated as R4.
The preparation method of R5 is as follows: 20g of deionized water was weighed, 4g of casein, 2g of sodium dodecylbenzenesulfonate were added, and dissolved under stirring to obtain a solution of the emulsifier composition, designated as R5.
TABLE 1
Example 2
The preparation method of J1 is as follows: 40g of deionized water is taken, 2g of polyvinyl alcohol, 4g of guar gum and 2g of sodium caseinate are added, and a solution of protective colloid is obtained after uniform stirring and is marked as J1.
The preparation method of J2 comprises the following steps: 40g of deionized water is taken, 2g of polyvinyl alcohol, 4g of hydroxyethyl cellulose and 2g of sodium caseinate are added, and a solution of protective colloid is obtained after uniform stirring and is marked as J2.
The preparation method of J3 comprises the following steps: 40g of deionized water is taken, 4g of guar gum and 2g of sodium caseinate are added, and a solution of protective colloid is obtained after uniform stirring and is marked as J3.
The preparation method of J4 comprises the following steps: 40g of deionized water is taken, 2g of polyvinyl alcohol and 2g of sodium caseinate are added, and the mixture is stirred uniformly to obtain a solution of protective colloid, which is marked as J4.
The preparation method of J5 is as follows: 40g of deionized water is taken, 2g of polyvinyl alcohol and 4g of guar gum are added, and a solution of the protective colloid is obtained after uniform stirring and is marked as J5.
TABLE 2 protective colloids
Example 3
(1) Preparation of emulsion: 8 parts by weight of the emulsifier composition shown in R1 is taken and dissolved in 20 parts by weight of deionized water, and then 0.5 part by weight of pH regulator is added and uniformly mixed to obtain emulsion, wherein the pH regulator is ammonia water;
(2) Preparation of protective colloid solution: taking 8 parts by weight of protective colloid shown in J1, and dissolving the protective colloid in 40 parts by weight of deionized water to obtain a protective colloid solution;
(3) And (3) synthesizing phenolic resin emulsion:
200 parts by weight of phenol, 259 parts by weight of formaldehyde solution, 70 parts by weight of deionized water and 1 part by weight of sodium hydroxide solution are added, 14.05 parts by weight of emulsion is added, the temperature is raised to 85 ℃ for carrying out a first reaction, the first reaction time is 60 minutes, then 14 parts by weight of residual emulsion and 48 parts by weight of protective colloid solution are added, a second reaction is carried out at 85 ℃, the second reaction time is 2.5 hours, and the temperature is reduced and the materials are discharged. The phenolic resin emulsion with 50% of solid content is obtained.
Example 4
Example 4 differs from example 3 only in that the emulsifier composition is as shown in R2, the remaining conditions being the same.
Example 5
Example 5 differs from example 3 only in that the emulsifier composition is as shown in R3, the remaining conditions being the same.
Example 6
Example 6 differs from example 3 only in that the emulsifier composition is as shown in R4, the remaining conditions being the same.
Example 7
Example 7 differs from example 3 only in that the emulsifier composition is as shown in R5, the remaining conditions being the same.
Example 8
Example 8 differs from example 3 only in that the protective colloid is shown as J2, the remaining conditions being the same.
Example 9
Example 9 differs from example 3 only in that the protective colloid is shown as J3, the remaining conditions being the same.
Example 10
Example 10 differs from example 3 only in that the protective colloid is shown as J4, the remaining conditions being the same.
Example 11
Example 11 differs from example 3 only in that the protective colloid is shown as J5, the remaining conditions being the same.
Example 12
Example 12 differs from example 3 only in that the first reaction time is 30min, the remaining conditions being the same.
Example 13
Example 13 differs from example 3 only in that the first reaction time is 90min, the remaining conditions being the same.
Example 14
Example 14 differs from example 3 only in that the first reaction time is 40min, the remaining conditions being the same.
Example 15
Example 15 differs from example 3 only in that the first reaction time is 80min, the remaining conditions being the same.
Comparative example 1
Comparative example 1 differs from example 3 only in that no emulsifier composition was present, the remaining conditions being the same.
Comparative example 2
Comparative example 2 differs from example 3 only in that no protective colloid was present, the remaining conditions being the same.
TABLE 3 Table 3
Experimental example 1
Determination of the solid content
2g of the resin solution obtained in the above example was taken, dried in an oven at 150℃for 2 hours, and weighed. The solid content was obtained by the mass after drying/the mass of the resin liquid, and the results are shown in Table 4
Experimental example 2
Determination of stability
Taking the resin liquid obtained in the embodiment, and centrifuging for 30min at 2000r/min, wherein if no layering exists, the stability is good. The results are shown in Table 4.
Experimental example 3
Determination of Water dilutability
At 25 ℃, 10g of the resin solution obtained in the above example was taken, and the deionized water was slowly added to a weight of more than 200g, and the presence or absence of dregs and the presence or absence of demulsification was observed, and the results are shown in Table 4.
TABLE 4 Table 4
In the prior art, phenolic resin is prepared according to a required process when in use, but is not used as a single component, and solvents, fillers, pigments and the like are added. The solvent includes water, and organic reagents such as methanol and ethanol. The size of the phenolic resin water solubility can have an impact on the downstream solvent selection. Poor water solubility, resin precipitation phenomenon can be generated after excessive water is added, solution is uneven, impregnation uniformity is affected, and product quality is greatly affected. Downstream, only organic solvents such as methanol and ethanol which are harmful to the environment can be selected or the dosage of alkaline substances can be increased. These organic materials produce significant amounts of VOCs during volatilization, have adverse environmental effects, and are far more costly than water. Too much alkaline material can have a very corrosive effect on the equipment and affect the final properties of the product.
The preparation method takes water as a solvent, the molecular weight of the generated phenolic resin is large, the phenolic resin can be infinitely diluted by water, the emulsion stability is good, the phenolic resin has good compatibility with other resins such as epoxy resin, acrylic resin and the like, and the phenolic resin is convenient to modify among different resins. Can be widely used for products such as coated abrasive tools, wet curtain paper, rock wool resin and the like, and can be used as road products by being mixed with emulsified asphalt and the like. According to the water dilution multiple of >20, the water can be infinitely diluted, otherwise, only a proper amount of water can be added. The phenolic resin emulsion synthesized by the application has the advantages of environmental protection and low cost by reducing the use amount of the organic solvent in production and application.
Examples 3, 4 and 7 all achieved excellent emulsification. Wherein in example 3, the water dilution ratio is more than 20, and in example 3, the phenolic resin emulsion has no demulsification phenomenon and no dregs after being diluted by more than 20 times of water; and can maintain long-term stability.
Wherein, compared with example 3, the stability and the water dilutability of example 4 and example 7 are reduced, and the water dilution factor of < 20 indicates that the phenolic resin emulsion is diluted with more than 20 times of water or has demulsification phenomenon or dregs; and cannot be maintained stable for a long period of time.
It can be seen that the emulsifier composition plays an important role in the performance of the final phenolic resin emulsion, in particular the emulsification, and ensures the stability of the phenolic resin emulsion. The protective colloid plays a role in protecting and assisting in emulsifying the performance of the final phenolic resin emulsion, and when the emulsifying agents are the same, different protective colloids can bring great influence to stability and water dilutability. It can also be seen that R1 and J1 work best when used in a phenolic emulsion at the same time.
The weight average molecular weight is one of the important indexes of phenolic resin, and the required weight average molecular weight is different in different application fields. Low weight average molecular weight, good impregnation performance, strong permeability and good fluidity. The weight average molecular weight is large, the polymer strength is high, and the binding force is strong. The phenolic resin emulsion prepared by the application has a wide molecular weight range and can meet the requirements of different downstream customers.
The solid content is one of the measures of the effective matters in the liquid, the solvent volatilizes in the later use process, the residue plays a main binding role, the solid content is low, namely the residual content is low, a large amount of volatile reagent is needed in the later use process, the energy consumption is high, the efficiency is low, and the transportation, packaging and other costs are high. Too high a solids content can result in a higher viscosity and inconvenient later use. Emulsion particles adhere to each other to break emulsion, and the stability of the resin emulsion is destroyed. The solid content of the phenolic resin emulsion is between 40 and 60, so that the industrial requirement can be well met.
It can be seen from examples 12 and 13 that in the first reaction, the reaction time has an important effect on the final properties, and the shorter reaction time is insufficient, and the long reaction time affects the emulsification effect. Example 12 has a short reaction time, which results in insufficient reaction, and when the reaction time is too long, the reaction degree is too high, and dilution with water is impossible, which is disadvantageous for its use. The overall performance is best when the reaction time is within 40-80 min.
When there is no emulsifier composition or protective colloid, i.e., comparative example 1 or comparative example 2, the stability is poor and dilution with water is impossible.
Application example 1
50g of the resin obtained in example 3 was diluted with 200g of water and stirred well. And (5) dipping the blank paper. The sizing amount is 10%, and the curing is 10min at 150 ℃. The toughness of the paper after impregnation is obviously improved, and the strength is obviously increased.
Application example 2
50g of the resin obtained in the embodiment 3 is taken, 100g of water is added for dilution, 20g of styrene-acrylic emulsion is added for uniform stirring, kraft paper is immersed in the mixture, the mixture is dried for 15min at 150 ℃, the strength of the paper is obviously enhanced, and the compatibility of the resin diluent in the embodiment 3 and the styrene-acrylic emulsion is good, and no abnormality such as demulsification and the like exists.
Although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but rather is capable of modification and variation without departing from the spirit and scope of the present invention as defined in the following claims.
Claims (10)
1. An emulsifier composition for preparing a phenolic resin emulsion, wherein,
including casein, anionic emulsifiers, and nonionic emulsifiers;
preferably, the method comprises the steps of,
the casein is (2-5) parts by weight and the anionic emulsifier is (1-3) parts by weight relative to 1 part by weight of the nonionic emulsifier;
preferably, the anionic emulsifier is sodium dodecyl benzene sulfonate and/or sodium dodecyl sulfate, preferably sodium dodecyl benzene sulfonate;
further preferably, the nonionic emulsifier is one or more than two of polyethylene glycol, castor oil polyoxyethylene ether, octyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and allyl polyethylene glycol, and is preferably castor oil polyoxyethylene ether;
more preferably, the emulsifier composition consists of casein, an anionic emulsifier and a nonionic emulsifier.
2. A protective colloid for preparing phenolic resin emulsion, wherein,
including polyvinyl alcohol, sodium caseinate and guar gum;
preferably, the method comprises the steps of,
the guar gum is (2-5) parts by weight and the sodium caseinate is (1-9) parts by weight relative to 1 part by weight of polyvinyl alcohol;
it is further preferred that the composition comprises,
the polyvinyl alcohol is one or more selected from polyvinyl alcohol 0588, polyvinyl alcohol 0599, polyvinyl alcohol 1788, polyvinyl alcohol 1799 and sodium polyacrylate, preferably polyvinyl alcohol 0588 and/or polyvinyl alcohol 0599;
More preferably, the process is carried out,
the protective colloid consists of polyvinyl alcohol, sodium caseinate and guar gum.
3. Use of the emulsifier composition of claim 1, the protective colloid of claim 2 for the preparation of a phenolic resin emulsion.
4. A phenolic resin emulsion, wherein,
the phenolic resin emulsion is an all-aqueous emulsion, the solid content of the phenolic resin emulsion is 25-75%, preferably 35-60%, the viscosity of the phenolic resin emulsion at 25 ℃ is 100-5000, preferably 500-2000, and the weight average molecular weight of the phenolic resin in the phenolic resin emulsion is 1000-7000, preferably 3000-7000.
5. A phenolic resin emulsion prepared from the emulsifier composition of claim 1, the protective colloid of claim 2, a pH adjuster, raw phenols, raw aldehydes, a catalyst and water;
preferably, the method comprises the steps of,
the emulsifier comprises 0.5-10 parts by weight of an emulsifier composition, 0.1-10 parts by weight of a protective colloid, 0.01-5 parts by weight of a pH regulator, 50-400 parts by weight of raw material phenols, 100-800 parts by weight of raw material aldehydes, 0.5-10 parts by weight of a catalyst and 50-600 parts by weight of water.
6. The phenolic resin emulsion of claim 5 wherein,
The pH regulator is one or more than two of ammonia water, triethylamine, triethanolamine, AMP-95 or sodium hydroxide solution;
the raw material phenol is one or more than two of phenol, bisphenol A, cardanol, m-cresol and resorcinol;
the raw material aldehyde is one or more than two of formaldehyde, acetaldehyde, paraformaldehyde, glyoxal, glutaraldehyde, furfural and salicylaldehyde.
7. The phenolic resin emulsion of claim 5 wherein,
the catalyst is one or more of sodium hydroxide, barium hydroxide, ammonia water, triethylamine, triethanolamine, calcium oxide, oxalic acid, hydrochloric acid, sulfuric acid and p-toluenesulfonic acid, and preferably sodium hydroxide.
8. The phenolic resin emulsion according to claim 5 to 7,
the weight average molecular weight of the phenolic resin in the phenolic resin emulsion is 1000-7000.
9. A process for preparing a phenolic resin emulsion as claimed in any one of claims 5 to 8 comprising the steps of:
preparing an emulsion: adding water, an emulsifying agent and a pH regulator into a kettle, and uniformly mixing to obtain an emulsion;
preparation of protective colloid solution: adding the protective colloid into water for dissolution to obtain a protective colloid solution;
First reaction: adding raw material phenols, raw material aldehydes, a catalyst and part of emulsion into water, heating to 60-100 ℃ to start reaction, and reacting for 30-90min to obtain a solution containing matrix phenolic resin;
second reaction: adding a protective colloid solution and the rest emulsion into the solution containing the matrix phenolic resin, continuing to react until the reaction viscosity is 300-1000 cp, and cooling to obtain phenolic resin emulsion;
preferably, the method comprises the steps of,
in the second reaction, the reaction temperature is 60-100 ℃, preferably 75-90 ℃;
it is further preferred that the composition comprises,
in the first reaction, the reaction time is 40 to 80min, preferably 60min.
10. Use of the phenolic resin emulsion of claim 4, the phenolic resin emulsion of any one of claims 5 to 8, the phenolic resin emulsion prepared by the method of claim 9 in sandpaper, filter paper, rock wool, road products.
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