CN117126421A - Production method of hydroxyl coumarone resin emulsion - Google Patents
Production method of hydroxyl coumarone resin emulsion Download PDFInfo
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- CN117126421A CN117126421A CN202210549105.7A CN202210549105A CN117126421A CN 117126421 A CN117126421 A CN 117126421A CN 202210549105 A CN202210549105 A CN 202210549105A CN 117126421 A CN117126421 A CN 117126421A
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- Prior art keywords
- coumarone resin
- hydroxyl
- oil
- resin emulsion
- hydroxyl coumarone
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- IANQTJSKSUMEQM-UHFFFAOYSA-N benzofuran Natural products C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000011347 resin Substances 0.000 title claims abstract description 166
- 229920005989 resin Polymers 0.000 title claims abstract description 166
- -1 hydroxyl coumarone Chemical compound 0.000 title claims abstract description 141
- 239000000839 emulsion Substances 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000008367 deionised water Substances 0.000 claims abstract description 45
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 45
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000003921 oil Substances 0.000 claims description 87
- 238000006116 polymerization reaction Methods 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 25
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 22
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000007764 o/w emulsion Substances 0.000 claims description 18
- 239000003381 stabilizer Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 claims description 14
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 11
- 235000011152 sodium sulphate Nutrition 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229910015900 BF3 Inorganic materials 0.000 claims description 10
- 150000002191 fatty alcohols Chemical class 0.000 claims description 10
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 10
- 150000002989 phenols Chemical class 0.000 claims description 10
- 239000007762 w/o emulsion Substances 0.000 claims description 10
- 230000007423 decrease Effects 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012874 anionic emulsifier Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000011282 acid tar Substances 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 150000003739 xylenols Chemical class 0.000 claims description 3
- 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 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 6
- 238000000614 phase inversion technique Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 14
- 238000005554 pickling Methods 0.000 description 14
- 239000003973 paint Substances 0.000 description 10
- 238000007865 diluting Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 150000003384 small molecules Chemical class 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
- C08J2345/02—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers of coumarone-indene polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a production method of hydroxyl coumarone resin emulsion, which comprises the steps of adding an emulsifier into hydroxyl coumarone resin, heating to a certain temperature, uniformly stirring, and heating deionized water to the same temperature as the hydroxyl coumarone resin; and then slowly adding deionized water into the hydroxyl coumarone resin, and preparing the oil-in-water hydroxyl coumarone resin emulsion by a phase inversion method, so that the hydroxyl coumarone resin is uniformly distributed in water, and the product has good stability, small particle size and high solid content, is simple and convenient to operate in the preparation process, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of resin emulsion preparation, relates to a preparation method of aromatic hydrocarbon resin emulsion, and in particular relates to a production method of hydroxyl coumarone resin emulsion.
Background
The coumarone-indene resin (coumarone resin for short) has excellent performances of acid resistance, alkali resistance, adhesiveness, plasticization, reinforcement and the like, is dissolved in solvents such as chlorinated hydrocarbon, esters, ketones, ethers and the like, has good compatibility with various resins such as natural rubber, epoxy resin and the like, is widely used as a modifier of various resins for a long time, and is mainly applied to the fields of paint, electronic materials, adhesives, sealants, rubber, printing ink and the like.
The anti-corrosion paint is used as a paint product, and has the development directions of energy conservation, environmental protection, high performance and functionalization, so that the anti-corrosion paint is particularly required to develop into the directions of water-based property, high solid property, multi-functionalization and the like. With the increasingly urgent and strict requirements of the public on environmental protection, the development of low-energy-consumption, low-pollution and high-performance water-based anticorrosive paint has become a hot spot of current research. At present, solid coumarone resin is used as solvent type paint, and organic solvents are added to dissolve the paint in the using process, but the organic solvents can bring about the problem of environmental VOCs.
Therefore, based on the requirements of the aqueous anticorrosive paint, the development of the aqueous coumarone resin emulsion is required to meet the requirements of markets and policy regulations on the aqueous coumarone resin emulsion. The application number CN02111259.2 discloses a preparation method of petroleum resin emulsion, which comprises the steps of mixing petroleum resin with oleic acid after melting, adding 5-15% of ethanolamine solution for emulsification, cooling and filtering to obtain petroleum resin emulsion, wherein the particle size of the product is below 0.5 microns, and the product is used in adhesives and water-based paint, but the emulsification temperature of the technology is as high as 85-100 ℃, and the emulsification period is long. The application number CN93108150.5 discloses a preparation method of water-soluble carbon pill petroleum resin, which comprises copolymerizing a byproduct carbon nine fraction produced by ethylene with derivatives such as acrylic acid, ester and amine, and the like, and saponifying the copolymer to obtain the product which is used as an oilfield water quality stabilizer, wherein the copolymerized product is an aqueous resinAffecting the water resistance and other properties of the subsequent paint. The application number CN200610063547.1 discloses a petroleum resin emulsion for slurry seal and its preparation process, including petroleum resin, cationic emulsifier, water and anhydrous CaCl 2 The petroleum resin prepared by concentrated hydrochloric acid is used for a slurry seal layer for road engineering, but the emulsification temperature of the process is higher by 120-160 ℃, and the emulsion particle size is large.
According to the production method of the hydroxyl coumarone resin emulsion, the emulsifier is added into the hydroxyl coumarone resin, and the oil-in-water emulsion is prepared by using the phase inversion method, so that the hydroxyl coumarone resin is uniformly distributed in water, the emulsion product has the advantages of good stability, small particle size, high solid content and high added value, the water resistance, chemical resistance, flexibility and the like can be improved in epoxy, polyurethane and acrylic coating systems, the product meets the environmental protection requirement, the application field is wide, and the method is suitable for industrial production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a production method of hydroxyl coumarone resin emulsion, wherein an emulsifier is added into hydroxyl coumarone resin, the mixture is heated to a certain temperature and stirred uniformly, and deionized water is heated to the same temperature as the hydroxyl coumarone resin; and then slowly adding deionized water into the hydroxyl coumarone resin, and preparing the oil-in-water hydroxyl coumarone resin emulsion by a phase inversion method, so that the hydroxyl coumarone resin is uniformly distributed in water, and the product has good stability, small particle size and high solid content, is simple and convenient to operate in the preparation process, and is suitable for industrial production.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a production method of hydroxyl coumarone resin emulsion, which comprises the following steps:
s1, preparing hydroxyl coumarone resin by taking coumarone-indene fraction as a raw material;
s2, adding an emulsifying agent into the hydroxyl coumarone resin, and uniformly stirring at a preset temperature to form a mixed solution;
s3, heating deionized water to the same preset temperature as the mixed solution, slowly adding the deionized water into the mixed solution, and keeping high-speed stirring, wherein the mixed solution gradually forms water-in-oil emulsion, the viscosity gradually increases to a phase inversion point, when the viscosity of the emulsion suddenly decreases, stopping adding the deionized water, and continuously adding the deionized water for dilution after full stirring to obtain the oil-in-water emulsion;
s4, adding the defoamer and the stabilizer into the oil-in-water emulsion, uniformly stirring, and then reducing the temperature to room temperature to obtain the hydroxyl coumarone resin emulsion.
Preferably, in the step S1, the hydroxy coumarone resin is prepared by:
preparing raw materials, namely preparing coumarone-indene fraction and a solvent into raw oil with indene content of 1-55%;
the crude coumarone fraction is depyridine dephenolized, the raw oil is subjected to conventional acid washing and alkali washing to remove pyridine dephenolization, and the dephenolized and depyridine coumarone fraction is further obtained through neutralization;
decolorizing and distilling, namely passing the dephenolized and depyridine coumarone fraction through a decolorizing tower, separating heavy fraction from the bottom of the tower, and distilling decolorizing raw oil from the top of the tower;
polymerizing, namely mixing the decolorized raw oil with a phenolic compound, alpha-methylstyrene and a catalyst, and obtaining polymerized oil through a polymerization reaction;
and (3) distilling, namely washing the polymerized oil with water, and removing impurities without polymerization through distillation to obtain the hydroxyl coumarone resin.
Preferably, in the preparation process of the hydroxyl coumarone resin:
in the raw material preparation, the solvent is one or more of toluene, xylene, para-toluene and flash oil; and/or
In the decoloring and distilling process, the heavy fraction comprises naphthalene, acid tar and asphalt; and/or
In the polymerization process, the mass ratio of the phenolic compound to the alpha-methylstyrene to the decolored raw oil is 1:1 to 8:1 to 6; and/or
In the polymerization process, the phenolic compound is selected from one of phenol, o-cresol, m-cresol, p-cresol and xylenol; and/or
In the polymerization process, the catalyst is selected from one or more of aluminum trichloride, boron trifluoride, cation exchange resin, activated clay and titanium tetrachloride; and/or
In the polymerization process, the mass of the catalyst is 0.3-10wt% of the mass of the decolorized oil raw oil;
in the polymerization process, the polymerization reaction temperature is 5-60 ℃ and the polymerization reaction time is 1-5 h.
Preferably, in the polymerization process:
the mass of the catalyst is 2-5 wt% of the mass of the decolorized oil raw oil; and/or
The polymerization reaction temperature is 20-40 ℃, and the polymerization reaction time is 2-3 h.
Preferably, in the step S2:
the emulsifier adopts an anionic emulsifier; and/or
The mass ratio of the emulsifying agent to the hydroxyl coumarone resin is 0.01-0.1: 1, a step of; and/or
The preset temperature is 30-80 ℃; and/or
The stirring speed is 500-2500 rpm.
Preferably, in the step S1:
the mass ratio of the hydroxyl coumarone resin to the emulsifier is 0.04-0.07: 1, a step of; and/or
The anionic emulsifier is selected from one of carboxylate type emulsifier, sulfate type emulsifier, sulfonate type emulsifier and phosphate type emulsifier; and/or
The preset temperature is 40-70 ℃.
Preferably, the anionic emulsifier is selected from one of fatty alcohol polyoxyethylene ether sodium sulfate, sodium alkylbenzenesulfonate and sodium alkylpolyoxyethylene ether sodium sulfate.
Preferably, in the step S3:
the total addition of the deionized water accounts for 50-100 wt% of the mass of the hydroxyl coumarone resin; and/or
The solid content of the oil-in-water emulsion is more than or equal to 50wt%.
Preferably, in the step S4:
the defoaming agent adopts mineral oil defoaming agent; and/or
The stabilizer adopts a high molecular weight polyethylene glycol stabilizer.
Preferably, the solid content of the hydroxyl coumarone resin emulsion is more than or equal to 50wt percent, and the average particle size is 0.30-0.70 mu m.
Preferably, the solid content of the hydroxyl coumarone resin emulsion is 50-70 wt%.
The production method of the hydroxyl coumarone resin emulsion provided by the invention has the following beneficial effects:
1. adding an emulsifier into the hydroxyl coumarone resin, heating to a certain temperature, uniformly stirring, and heating deionized water to the same temperature as the hydroxyl coumarone resin; then slowly adding deionized water into the hydroxyl coumarone resin, and preparing an oil-in-water hydroxyl coumarone resin emulsion by a phase inversion method, so that the hydroxyl coumarone resin is uniformly distributed in water, and the emulsion product has good stability, small particle size, high solid content and high added value, is simple and convenient to operate in the preparation process, and is suitable for industrial production;
2. according to the production method of the hydroxyl coumarone resin emulsion, the hydroxyl coumarone resin emulsion product meeting the market demand is obtained by selecting proper parameters such as the emulsifier, the temperature, the emulsifier proportion, the stirring speed and the like, the hydroxyl coumarone resin emulsion with the functional group meets the requirements of the market on the polar resin emulsion while meeting the environmental protection requirements, the water resistance, the chemical resistance, the flexibility and the like can be improved in an epoxy, polyurethane and acrylic coating system, and the application field of the product is wide.
Detailed Description
In order to better understand the above technical solution of the present invention, the technical solution of the present invention is further described below with reference to examples.
The production method of the hydroxyl coumarone resin emulsion provided by the invention is simple and convenient to operate and suitable for industrial production by selecting proper parameters such as the emulsifier, the temperature, the emulsifier proportion, the stirring speed and the like to obtain the hydroxyl coumarone resin emulsion product meeting the market demand. The key process of the invention is to select proper emulsifier and then to change different emulsification process conditions to obtain hydroxyl coumarone resin emulsion with different solid contents.
The production method of the hydroxyl coumarone resin emulsion provided by the invention is divided into two aspects, namely, the preparation of the hydroxyl coumarone resin; secondly, preparing hydroxyl coumarone resin emulsion;
1. the preparation process of the hydroxyl coumarone resin comprises the following steps:
(1) Preparing raw materials, namely preparing coumarone-indene fraction and a solvent into raw oil with indene content of 1-55%; wherein the coumarone-indene fraction comprises the following components: indene: 65-95 wt% of coumarone: 0.5 to 2 weight percent of styrene: 0.18 to 1.5 weight percent of solvent selected from one or more of toluene, dimethylbenzene, para-toluene and flash oil; flash oil refers to the light fraction of crude oil or coal tar oil from the initial distillation point to 200 deg.c, and is colorless to brown transparent liquid.
(2) The crude coumarone fraction is depyridine dephenolized: the raw oil is subjected to conventional acid washing and alkali washing to remove pyridine and dephenolization, and further neutralization is carried out to obtain dephenolized and depyridine coumarone fraction (C2 SN); wherein sulfuric acid with the concentration of 30-60% is adopted for acid washing, and sodium hydroxide with the concentration of 1-10% is adopted for alkali washing.
(3) Decolorizing and distilling, namely passing the dephenolized and depyridine coumarone fraction through a decolorizing tower, separating heavy fractions such as naphthalene, acid tar, asphalt and the like from the bottom of the tower, and distilling decolorizing raw oil (CSN) from the top of the tower;
(4) Polymerizing, namely mixing decolored raw oil with a phenolic compound, alpha-methylstyrene and a catalyst, and obtaining polymerized oil through polymerization reaction; wherein the phenolic compound and the alpha-methyl styrene are used as a modifier to modify the decolorized raw oil, and the mass ratio of the phenolic compound to the alpha-methyl styrene to the decolorized raw oil is 1:1 to 8:1 to 6; the phenolic compound is selected from one of phenol, o-cresol, m-cresol, p-cresol and xylenol; the catalyst is selected from one or more of aluminum trichloride, boron trifluoride, cation exchange resin, activated clay and titanium tetrachloride, and accounts for 0.3-10wt% of the decolorized raw oil, and in a further preferred scheme, the catalyst accounts for 2-5wt% of the decolorized raw oil. The polymerization temperature is 5-60 ℃, the polymerization time is 1-5 h, in a further preferred scheme, the polymerization temperature is 20-40 ℃, and the polymerization time is 2-3 h.
(5) Distilling, namely washing the polymerized oil with water, and removing impurities without polymerization through distillation to obtain hydroxyl coumarone resin; wherein the impurities without polymerization are mainly solvents and unreacted monomers.
2. The preparation process of the hydroxyl coumarone resin emulsion comprises the following steps:
s1, adding an emulsifier into the prepared hydroxyl coumarone resin, and heating and uniformly stirring at a preset temperature to form a mixed solution; wherein the emulsifier adopts anionic emulsifier such as carboxylate type emulsifier, sulfate type emulsifier, sulfonate type emulsifier, phosphate type emulsifier, etc., specifically alkylphenol ethoxylates, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, alkanolamide, etc.; the mass ratio of the emulsifier to the hydroxyl coumarone resin is 0.01-0.10: 1, in a further preferred embodiment, the mass ratio of the emulsifier hydroxy coumarone resin is 0.04 to 0.07:1, a step of; the preset temperature is 30 to 80 ℃, preferably 40 to 70 ℃. The stirring speed is 500-2500 rpm.
S2, heating deionized water to the same preset temperature as the mixed solution, slowly adding the deionized water into the mixed solution, keeping high-speed stirring, gradually forming water-in-oil emulsion by the mixed solution, stopping adding the deionized water after the viscosity is gradually increased to the opposite point, and continuously adding the deionized water for dilution after full stirring to obtain the oil-in-water emulsion; wherein the total addition of deionized water accounts for 50-100 wt% of the mass of the hydroxyl coumarone resin, and the specific addition of deionized water is added according to the solid content requirement of the oil-in-water emulsion; the solid content of the oil-in-water emulsion is more than or equal to 50 weight percent.
S3, adding a defoaming agent and a stabilizing agent into the oil-in-water emulsion, uniformly stirring, and then reducing the temperature to room temperature to obtain a hydroxyl coumarone resin emulsion; wherein the defoaming agent adopts mineral oil defoaming agent; the stabilizer adopts high molecular weight polyethylene glycol stabilizer.
The solid content of the prepared hydroxyl coumarone resin emulsion is more than or equal to 50wt% (in a further preferred scheme, the solid content of the hydroxyl coumarone resin emulsion is 50-70 wt%) and the average particle size is 0.30-0.70 mu m.
The production method of the hydroxyl coumarone resin emulsion of the present invention is further described below with reference to specific examples.
Example 1
The production method of the hydroxyl coumarone resin emulsion in the embodiment is as follows:
the preparation process of the hydroxyl coumarone resin comprises the following steps: the crude coumarone-indene fraction is prepared with toluene to obtain raw oil, wherein the indene content is 20%. The raw oil enters a pickling tank, is neutralized by alkali after pickling, and is washed by water to obtain neutral material C2SN. And (3) feeding the washed material C2SN into a decoloring tower, and obtaining decoloring raw oil CSN at the top of the decoloring tower. Adding o-cresol and alpha-methylstyrene into the decolored raw oil CSN, wherein the o-cresol is as follows: alpha-methylstyrene: the mass ratio of CSN is 1:6:1, a catalyst BF3 (the catalyst accounts for 2% of the weight of the raw oil) is added, and polymerization is carried out for 2 hours at 40 ℃ to obtain polymerized oil. The polymerized oil enters a distillation system to remove solvent and small molecules, and the molecular weight of the obtained resin is 280Mw, the viscosity is 800 mPas, and the hydroxyl value is 79mgKOH/g.
The preparation process of the hydroxyl coumarone resin emulsion comprises the following steps: adding 0.8 g of emulsifier fatty alcohol polyoxyethylene ether sodium sulfate into 20 g of the hydroxyl coumarone resin, heating to 60 ℃, uniformly stirring at 1500rpm, and heating deionized water to the same temperature as the hydroxyl coumarone resin; the hydroxy coumarone resin is stirred at high speed, deionized water is slowly added, the mixed solution gradually forms water-in-oil emulsion, the viscosity gradually increases to the phase inversion point, the viscosity of the emulsion suddenly decreases, and the addition of the deionized water is stopped at the moment. Continuously and slowly adding water to 20 g after fully stirring, and diluting to obtain oil-in-water emulsion; then adding a defoaming agent and a stabilizing agent, uniformly stirring, and then reducing the temperature to room temperature to obtain a hydroxyl coumarone resin emulsion with the solid content of 50%; the solid content of the hydroxyl coumarone resin emulsion product is 50%, the stability is good, the average particle size is 0.583 μm, and the results are shown in Table 1.
Example 2
The production method of the hydroxyl coumarone resin emulsion in the embodiment is as follows:
the preparation process of the hydroxyl coumarone resin comprises the following steps: the crude coumarone-indene fraction is prepared with toluene to obtain raw oil, wherein the indene content is 20%. The raw oil enters a pickling tank, is neutralized by alkali after pickling, and is washed by water to obtain neutral material C2SN. And (3) feeding the washed material C2SN into a decoloring tower, and obtaining decoloring raw oil CSN at the top of the decoloring tower. Adding o-cresol and alpha-methylstyrene into the decolored raw oil CSN, wherein the o-cresol is as follows: alpha-methylstyrene: the mass ratio of CSN is 1:6:1, a catalyst BF3 (the catalyst accounts for 2% of the weight of the raw oil) is added, and polymerization is carried out for 2 hours at 40 ℃ to obtain polymerized oil. The polymerized oil enters a distillation system to remove solvent and small molecules, and the molecular weight of the obtained resin is 280Mw, the viscosity is 800 mPas, and the hydroxyl value is 79mgKOH/g.
The preparation process of the hydroxyl coumarone resin emulsion comprises the following steps: adding 0.8 g of emulsifier fatty alcohol polyoxyethylene ether sodium sulfate into 20 g of the hydroxyl coumarone resin, heating to 80 ℃, uniformly stirring at 1500rpm, and heating deionized water to the same temperature as the hydroxyl coumarone resin; the hydroxy coumarone resin is stirred at high speed, deionized water is slowly added, the mixed solution gradually forms water-in-oil emulsion, the viscosity gradually increases to the phase inversion point, the viscosity of the emulsion suddenly decreases, and the addition of the deionized water is stopped at the moment. Continuously and slowly adding water to 20 g after fully stirring, and diluting to obtain oil-in-water emulsion; then adding a defoaming agent and a stabilizing agent, uniformly stirring, and then reducing the temperature to room temperature to obtain a hydroxyl coumarone resin emulsion with the solid content of 50%; the solid content of the hydroxyl coumarone resin emulsion product is 50%, the stability is good, the average particle size is 0.629 mu m, and the results are shown in Table 1.
Example 3
The production method of the hydroxyl coumarone resin emulsion in the embodiment is as follows:
the preparation process of the hydroxyl coumarone resin comprises the following steps: the crude coumarone-indene fraction is prepared with toluene to obtain raw oil, wherein the indene content is 20%. The raw oil enters a pickling tank, is neutralized by alkali after pickling, and is washed by water to obtain neutral material C2SN. And (3) feeding the washed material C2SN into a decoloring tower, and obtaining decoloring raw oil CSN at the top of the decoloring tower. Adding o-cresol and alpha-methylstyrene into the decolored raw oil CSN, wherein the o-cresol is as follows: alpha-methylstyrene: the mass ratio of CSN is 1:6:1, a catalyst BF3 (the catalyst accounts for 2% of the weight of the raw oil) is added, and polymerization is carried out for 2 hours at 40 ℃ to obtain polymerized oil. The polymerized oil enters a distillation system to remove solvent and small molecules, and the molecular weight of the obtained resin is 280Mw, the viscosity is 800 mPas, and the hydroxyl value is 79mgKOH/g.
The preparation process of the hydroxyl coumarone resin emulsion comprises the following steps: adding 1.0 gram of emulsifier fatty alcohol polyoxyethylene ether sodium sulfate into 20 grams of the hydroxyl coumarone resin, heating to 60 ℃, uniformly stirring at 1500rpm, and heating deionized water to the same temperature as the hydroxyl coumarone resin; the hydroxy coumarone resin is stirred at high speed, deionized water is slowly added, the mixed solution gradually forms water-in-oil emulsion, the viscosity gradually increases to the phase inversion point, the viscosity of the emulsion suddenly decreases, and the addition of the deionized water is stopped at the moment. Continuously and slowly adding water to 16.4 g after fully stirring, and diluting to obtain oil-in-water emulsion; then adding a defoaming agent and a stabilizing agent, uniformly stirring, and then reducing the temperature to room temperature to obtain a hydroxyl coumarone resin emulsion with the solid content of 55%; the solid content of the hydroxyl coumarone resin emulsion product is 55%, the stability is good, the average particle size is 0.437 mu m, and the results are shown in Table 1.
Example 4
The production method of the hydroxyl coumarone resin emulsion in the embodiment is as follows:
the preparation process of the hydroxyl coumarone resin comprises the following steps: the crude coumarone-indene fraction is prepared with toluene to obtain raw oil, wherein the indene content is 20%. The raw oil enters a pickling tank, is neutralized by alkali after pickling, and is washed by water to obtain neutral material C2SN. And (3) feeding the washed material C2SN into a decoloring tower, and obtaining decoloring raw oil CSN at the top of the decoloring tower. Adding o-cresol and alpha-methylstyrene into the decolored raw oil CSN, wherein the o-cresol is as follows: alpha-methylstyrene: the mass ratio of CSN is 1:6:1, a catalyst BF3 (the catalyst accounts for 2% of the weight of the raw oil) is added, and polymerization is carried out for 2 hours at 40 ℃ to obtain polymerized oil. The polymerized oil enters a distillation system to remove solvent and small molecules, and the molecular weight of the obtained resin is 280Mw, the viscosity is 800 mPas, and the hydroxyl value is 79mgKOH/g.
The preparation process of the hydroxyl coumarone resin emulsion comprises the following steps: adding 1.2 g of emulsifier fatty alcohol polyoxyethylene ether sodium sulfate into 20 g of the hydroxyl coumarone resin, heating to 80 ℃, uniformly stirring at 2500rpm, and heating deionized water to the same temperature as the hydroxyl coumarone resin; the hydroxy coumarone resin is stirred at high speed, deionized water is slowly added, the mixed solution gradually forms water-in-oil emulsion, the viscosity gradually increases to the phase inversion point, the viscosity of the emulsion suddenly decreases, and the addition of the deionized water is stopped at the moment. Continuously and slowly adding water to 16.4 g after fully stirring, and diluting to obtain oil-in-water emulsion; then adding a defoaming agent and a stabilizing agent, uniformly stirring, and then reducing the temperature to room temperature to obtain a hydroxyl coumarone resin emulsion with the solid content of 55%; the solid content of the hydroxyl coumarone resin emulsion product is 55%, the stability is good, the average particle size is 0.386 mu m, and the results are shown in Table 1.
Example 5
The production method of the hydroxyl coumarone resin emulsion in the embodiment is as follows:
the preparation process of the hydroxyl coumarone resin comprises the following steps: the crude coumarone-indene fraction is prepared with toluene to obtain raw oil, wherein the indene content is 20%. The raw oil enters a pickling tank, is neutralized by alkali after pickling, and is washed by water to obtain neutral material C2SN. And (3) feeding the washed material C2SN into a decoloring tower, and obtaining decoloring raw oil CSN at the top of the decoloring tower. Adding o-cresol and alpha-methylstyrene into the decolored raw oil CSN, wherein the o-cresol is as follows: alpha-methylstyrene: the mass ratio of CSN is 1:6:1, a catalyst BF3 (the catalyst accounts for 2% of the weight of the raw oil) is added, and polymerization is carried out for 2 hours at 40 ℃ to obtain polymerized oil. The polymerized oil enters a distillation system to remove solvent and small molecules, and the molecular weight of the obtained resin is 280Mw, the viscosity is 800 mPas, and the hydroxyl value is 79mgKOH/g.
The preparation process of the hydroxyl coumarone resin emulsion comprises the following steps: adding 1.4 g of emulsifier fatty alcohol polyoxyethylene ether sodium sulfate into 20 g of the hydroxyl coumarone resin, heating to 80 ℃, uniformly stirring at 2500rpm, and heating deionized water to the same temperature as the hydroxyl coumarone resin; the hydroxy coumarone resin is stirred at high speed, deionized water is slowly added, the mixed solution gradually forms water-in-oil emulsion, the viscosity gradually increases to the phase inversion point, the viscosity of the emulsion suddenly decreases, and the addition of the deionized water is stopped at the moment. Continuously and slowly adding water to 10.7 g after fully stirring, and diluting to obtain oil-in-water emulsion; then adding a defoaming agent and a stabilizing agent, uniformly stirring, and then reducing the temperature to room temperature to obtain a hydroxyl coumarone resin emulsion with the solid content of 65%; the solid content of the hydroxyl coumarone resin emulsion product is 65%, the stability is good, the average particle size is 0.318 mu m, and the results are shown in Table 1.
Example 6
The production method of the hydroxyl coumarone resin emulsion in the embodiment is as follows:
the preparation process of the hydroxyl coumarone resin comprises the following steps: the crude coumarone-indene fraction is prepared with xylene to obtain raw oil, wherein the indene content is 50%. The raw oil enters a pickling tank, is neutralized by alkali after pickling, and is washed by water to obtain neutral material C2SN. And (3) feeding the washed material C2SN into a decoloring tower, and obtaining decoloring raw oil CSN at the top of the decoloring tower. Adding p-cresol and alpha-methylstyrene into the decolored raw material oil CSN, wherein the p-cresol is as follows: alpha-methylstyrene: the mass ratio of CSN is 1:8:4, a catalyst BF3 (the catalyst accounts for 5% of the weight of the raw oil) is added, and polymerization is carried out for 3 hours at 40 ℃ to obtain polymerized oil. The polymerized oil enters a distillation system to remove solvent and small molecules, and the molecular weight of the obtained resin is 387Mw, the viscosity is 1200 mPas, and the hydroxyl value is 47.6mgKOH/g.
The preparation process of the hydroxyl coumarone resin emulsion comprises the following steps: adding 1.0 gram of emulsifier fatty alcohol polyoxyethylene ether sodium sulfate into 20 grams of the hydroxyl coumarone resin, heating to 70 ℃, uniformly stirring at 1000rpm, and heating deionized water to the same temperature as the hydroxyl coumarone resin; the hydroxy coumarone resin is stirred at high speed, deionized water is slowly added, the mixed solution gradually forms water-in-oil emulsion, the viscosity gradually increases to the phase inversion point, the viscosity of the emulsion suddenly decreases, and the addition of the deionized water is stopped at the moment. Continuously and slowly adding water to 10 g after fully stirring, and diluting to obtain oil-in-water emulsion; then adding a defoaming agent and a stabilizing agent, uniformly stirring, and then reducing the temperature to room temperature to obtain a hydroxyl coumarone resin emulsion with the solid content of 63%; the solid content of the hydroxyl coumarone resin emulsion product is 63%, the stability is good, and the average particle size is 0.611 mu m, and the results are shown in Table 1.
Example 7
The production method of the hydroxyl coumarone resin emulsion in the embodiment is as follows:
the preparation process of the hydroxyl coumarone resin comprises the following steps: the crude coumarone-indene fraction and flash oil are prepared to obtain the raw oil, wherein the indene content is 35%. The raw oil enters a pickling tank, is neutralized by alkali after pickling, and is washed by water to obtain neutral material C2SN. And (3) feeding the washed material C2SN into a decoloring tower, and obtaining decoloring raw oil CSN at the top of the decoloring tower. Adding phenol and alpha-methylstyrene, phenol, into the decolored raw oil CSN: alpha-methylstyrene: the mass ratio of CSN is 1:4:2, a catalyst BF3 (the catalyst accounts for 4% of the weight of the raw oil) is added, and polymerization is carried out for 2 hours at 30 ℃ to obtain polymerized oil. The polymerized oil enters a distillation system to remove the solvent and small molecules, and the molecular weight of the obtained resin is 350Mw, the viscosity is 625 mPas, and the hydroxyl value is 90mgKOH/g.
The preparation process of the hydroxyl coumarone resin emulsion comprises the following steps: adding 0.8 g of emulsifier fatty alcohol polyoxyethylene ether sodium sulfate into 20 g of the hydroxyl coumarone resin, heating to 80 ℃, uniformly stirring at 500rpm, and heating deionized water to the same temperature as the hydroxyl coumarone resin; the hydroxy coumarone resin is stirred at high speed, deionized water is slowly added, the mixed solution gradually forms water-in-oil emulsion, the viscosity gradually increases to the phase inversion point, the viscosity of the emulsion suddenly decreases, and the addition of the deionized water is stopped at the moment. Continuously and slowly adding water to 10 g after fully stirring, and diluting to obtain oil-in-water emulsion; then adding a defoaming agent and a stabilizing agent, uniformly stirring, and then reducing the temperature to room temperature to obtain the hydroxyl coumarone resin emulsion with the solid content of 62%; the solid content of the hydroxyl coumarone resin emulsion product is 62%, the stability is good, the average particle diameter is 0.683 μm, and the results are shown in Table 1.
Table 1 preparation parameters and properties
| Examples | Mass ratio of emulsifier to resin | Temperature/. Degree.C | Water addition per gram | Solids content/% | Stability of | Particle size/. Mu.m |
| Example 1 | 0.04:1 | 60 | 20 | 50 | Good (good) | 0.583 |
| Example 2 | 0.04:1 | 80 | 20 | 50 | Good (good) | 0.629 |
| Example 3 | 0.05:1 | 60 | 16.4 | 55 | Good (good) | 0.437 |
| Example 4 | 0.06:1 | 80 | 16.4 | 55 | Good (good) | 0.386 |
| Example 5 | 0.07:1 | 80 | 10.7 | 65 | Good (good) | 0.318 |
| Example 6 | 0.05:1 | 70 | 10 | 63 | Good (good) | 0.611 |
| Example 7 | 0.04:1 | 80 | 10 | 62 | Good (good) | 0.683 |
Note that: (1) the solids content is determined according to GB/T20623;
(2) Standing for 30 days according to the stability standard at room temperature, and visually observing no sedimentation and layering;
(3) Particle size was measured using a malvern 2000 particle size tester.
In summary, in the production method of the hydroxyl coumarone resin emulsion, the emulsifier is added into the hydroxyl coumarone resin, the mixture is heated to a certain temperature, and the mixture is stirred uniformly, so that deionized water is heated to the same temperature as the hydroxyl coumarone resin; then slowly adding deionized water into the hydroxyl coumarone resin, and preparing an oil-in-water hydroxyl coumarone resin emulsion by a phase inversion method, so that the hydroxyl coumarone resin is uniformly distributed in water, and the emulsion product has good stability, small particle size, high solid content and high added value, is simple and convenient to operate in the preparation process, and is suitable for industrial production; according to the production method of the hydroxyl coumarone resin emulsion, the hydroxyl coumarone resin emulsion product meeting the market demand is obtained by selecting proper parameters such as the emulsifier, the temperature, the emulsifier proportion, the stirring speed and the like, the hydroxyl coumarone resin emulsion with the functional group meets the requirements of the market on the polar resin emulsion while meeting the environmental protection requirements, the water resistance, the chemical resistance, the flexibility and the like can be improved in an epoxy, polyurethane and acrylic coating system, and the application field of the product is wide.
It will be appreciated by persons skilled in the art that the above embodiments are provided for illustration only and not for limitation of the invention, and that variations and modifications of the above described embodiments are intended to fall within the scope of the claims of the invention as long as they fall within the true spirit of the invention.
Claims (10)
1. The production method of the hydroxyl coumarone resin emulsion is characterized by comprising the following steps of:
s1, preparing hydroxyl coumarone resin by taking coumarone-indene fraction as a raw material;
s2, adding an emulsifying agent into the hydroxyl coumarone resin, and uniformly stirring at a preset temperature to form a mixed solution;
s3, heating deionized water to the same preset temperature as the mixed solution, slowly adding the deionized water into the mixed solution, and keeping high-speed stirring, wherein the mixed solution gradually forms water-in-oil emulsion, the viscosity gradually increases to a phase inversion point, when the viscosity of the emulsion suddenly decreases, stopping adding the deionized water, and continuously adding the deionized water for dilution after full stirring to obtain the oil-in-water emulsion;
s4, adding the defoamer and the stabilizer into the oil-in-water emulsion, uniformly stirring, and then reducing the temperature to room temperature to obtain the hydroxyl coumarone resin emulsion.
2. The method for producing the hydroxyl coumarone resin emulsion according to claim 1, wherein in the step S1, the hydroxyl coumarone resin is prepared by:
preparing raw materials, namely preparing coumarone-indene fraction and a solvent into raw oil with indene content of 1-55%;
the crude coumarone fraction is depyridine dephenolized, the raw oil is subjected to conventional acid washing and alkali washing to remove pyridine dephenolization, and the dephenolized and depyridine coumarone fraction is further obtained through neutralization;
decolorizing and distilling, namely passing the dephenolized and depyridine coumarone fraction through a decolorizing tower, separating heavy fraction from the bottom of the tower, and distilling decolorizing raw oil from the top of the tower;
polymerizing, namely mixing the decolorized raw oil with a phenolic compound, alpha-methylstyrene and a catalyst, and obtaining polymerized oil through a polymerization reaction;
and (3) distilling, namely washing the polymerized oil with water, and removing impurities without polymerization through distillation to obtain the hydroxyl coumarone resin.
3. The method for producing the hydroxyl coumarone resin emulsion according to claim 2, wherein in the preparation process of the hydroxyl coumarone resin:
in the raw material preparation, the solvent is one or more of toluene, xylene, para-toluene and flash oil; and/or
In the decoloring and distilling process, the heavy fraction comprises naphthalene, acid tar and asphalt; and/or
In the polymerization process, the mass ratio of the phenolic compound to the alpha-methylstyrene to the decolored raw oil is 1:1 to 8:1 to 6; and/or
In the polymerization process, the phenolic compound is selected from one of phenol, o-cresol, m-cresol, p-cresol and xylenol; and/or
In the polymerization process, the catalyst is selected from one or more of aluminum trichloride, boron trifluoride, cation exchange resin, activated clay and titanium tetrachloride; and/or
In the polymerization process, the mass of the catalyst is 0.3-10wt% of the mass of the decolorized oil raw oil;
in the polymerization process, the polymerization reaction temperature is 5-60 ℃ and the polymerization reaction time is 1-5 h.
4. The method for producing a hydroxyl coumarone resin emulsion according to claim 3, wherein in the polymerization process:
the mass of the catalyst is 2-5 wt% of the mass of the decolorized oil raw oil; and/or
The polymerization reaction temperature is 20-40 ℃, and the polymerization reaction time is 2-3 h.
5. The method for producing a hydroxyl coumarone resin emulsion according to claim 1, wherein in the step S2:
the emulsifier adopts an anionic emulsifier; and/or
The mass ratio of the emulsifying agent to the hydroxyl coumarone resin is 0.01-0.1: 1, a step of; and/or
The preset temperature is 30-80 ℃; and/or
The stirring speed is 500-2500 rpm.
6. The method for producing a hydroxyl coumarone resin emulsion according to claim 5, wherein in the step S1:
the mass ratio of the hydroxyl coumarone resin to the emulsifier is 0.04-0.07: 1, a step of; and/or
The anionic emulsifier is selected from one of carboxylate type emulsifier, sulfate type emulsifier, sulfonate type emulsifier and phosphate type emulsifier; and/or
The preset temperature is 40-70 ℃.
7. The method for producing a hydroxyl coumarone resin emulsion according to claim 6, wherein the anionic emulsifier is one selected from fatty alcohol polyoxyethylene ether sodium sulfate, sodium alkylbenzenesulfonate and sodium alkylpolyoxyethylene ether sodium sulfate.
8. The method for producing a hydroxyl coumarone resin emulsion according to claim 1, wherein in the step S3:
the total addition of the deionized water accounts for 50-100 wt% of the mass of the hydroxyl coumarone resin; and/or
The solid content of the oil-in-water emulsion is more than or equal to 50wt%.
9. The method for producing a hydroxyl coumarone resin emulsion according to claim 1, wherein in the step S4:
the defoaming agent adopts mineral oil defoaming agent; and/or
The stabilizer adopts a high molecular weight polyethylene glycol stabilizer.
10. The method for producing a hydroxyl coumarone resin emulsion according to any one of claims 1 to 9, wherein the hydroxyl coumarone resin emulsion has a solid content of 50wt% or more and an average particle diameter of 0.30 to 0.70 μm.
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