CN105713181B - Water paint self-emulsifying epoxy resin emulsion and preparation method thereof - Google Patents
Water paint self-emulsifying epoxy resin emulsion and preparation method thereof Download PDFInfo
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- CN105713181B CN105713181B CN201610241815.8A CN201610241815A CN105713181B CN 105713181 B CN105713181 B CN 105713181B CN 201610241815 A CN201610241815 A CN 201610241815A CN 105713181 B CN105713181 B CN 105713181B
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 81
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000000839 emulsion Substances 0.000 title claims abstract description 35
- 239000003973 paint Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000004945 emulsification Methods 0.000 title description 6
- 239000004593 Epoxy Substances 0.000 claims abstract description 53
- -1 alkyl phenol Chemical compound 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 23
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 6
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 4
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical group CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000004848 polyfunctional curative Substances 0.000 abstract description 3
- 230000013011 mating Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 description 20
- 239000003995 emulsifying agent Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 2
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 2
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229940085675 polyethylene glycol 800 Drugs 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229950009789 cetomacrogol 1000 Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- 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
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of water paint self-emulsifying epoxy resin emulsions, including following components in percentage by weight：Modified epoxy 40%~75%, deionized water 25%~60%；The modified epoxy is made of the raw material of following weight percent：Epoxy resin 20%~50%, polyether polyol 10%~30%, alkyl phenol polyoxyethylene ether 1%~15%, C12~C14 alkyl glycidyl ethers epoxy resin 2%~15%, chain extender 5%~20%, catalyst 0.16%~0.4%, organic solvent 20%~50%.The self-emulsifying epoxy resin emulsion storage stability of the present invention is good, and good with mating emulsion type epoxy hardener compatibility, paint film property is excellent.
Description
Technical field
The present invention relates to a kind of water paint self-emulsifying epoxy resin emulsions and preparation method thereof.
Background technology
Epoxy resin has adhesive property good, and solidfied material stability is good, high mechanical strength, and shrinking percentage and water absorption rate are low, electricity
The advantages that insulation performance is splendid, to be widely used in the industries such as coating, adhesive and macromolecule manufacture.Epoxy resin coating
It is one of the pillar product of coating industry.It is reported that the dosage of China's coating epoxy resin accounts for about the total dosage of epoxy resin
40%, it is contemplated that following country's epoxy resin industry remains to steady growth.On the one hand it is that global industrial shift makes electronics, ship etc.
Downstream industry is transferred to domestic product, has pulled the demand to epoxy resin；On the other hand it is domestic enterprise's production product
Quality is being continuously improved, and gradually has comparative advantages compared with overseas enterprise.However, traditional epoxy resin is dissolved only in aromatic hydrocarbon
And the organic solvents such as ketone.Coating industry with the topic in " water " generation " oil " always by discussing warmly, the country from 2 1st, 2015
To VOC content be more than 420 grams per liters coating impose 4% consumption tax policy landing after, traditional solvent-borne industrial coating enterprise to
The process of the environmental protections such as aqueous, powder direction transition and upgrade is irreversible.
The Water-borne modification technology of epoxy resin experienced the development course from additional emulsifier method to self-emulsification.It is general next
It says, additional emulsifier method is primarily referred to as Mechanical Method and phase inversion, and the aqueous epoxy resins prepared by the method belong to first generation water
Property epoxy-resin systems.2002, upper sea green good water paint Co., Ltd Shi Xuezhen et al. reported a kind of water-base epoxy breast
The preparation method of liquid is characterized in that and is prepared for a kind of reactive emulsifier, is then prepared as in conjunction with phase inversion aqueous
Epoxy emulsion.But additional emulsifier method, generally there are paint film chemical resistance is poor, solidfied material molecular weight is low, easily extracts from paint film
The shortcomings of taking out.
The aqueous epoxy emulsion prepared using water soluble solid agent oil emulsion soluble epoxy belongs to the aqueous ring of the second generation
The product of oxygen system.Zhou Jiliang et al. reports a kind of synthesis of nonionic waterborne epoxy curing agent, and the curing agent is in room temperature
Has the function of good emulsifying liquid epoxy resin down, after being cured at room temperature by the double-component aqueous epoxy coating of its preparation
The film of function admirable is obtained, there is good flexibility and impact resistance.But the system initial viscosity is big, constructs the time limit
Short, curing rate is slow, and certain difficulty is brought to Practical Project construction.
Self-emulsification, that is, chemic modified method, be using the active reactive group on epoxy resin, as epoxy group, secondary hydroxyl,
Methylene hydrogen etc., thus by hydrophilic radical（Amino, polyoxyethylene segment, carboxyl）It is introduced into epoxy molecule structure, makes ring
Oxygen resin has the amphiphilic performance of hydrophilic and oleophilic.The a variety of water-base epoxy products released domestic before this, technology also rest on the
On two generation water-base epoxies, the performance of solvent based coating product is also much not achieved in the coating products prepared in performance.Through inspection
Suo Faxian, the Chinese patent of Patent No. 2006100498972 disclose a kind of propylene oxide acids emulsifiers and by the emulsifiers
The preparation method of acrylic acid epoxy lotion made from emulsion acrylic epoxy ester series monomer, the method using toluene di-isocyanate(TDI) or
Triphenylphosphine is as coupling agent, and toluene di-isocyanate(TDI) at normal temperatures will be secondary anti-with the reaction of moisture in raw material and air
Product should be caused impure, and raw material not only needs dehydration, free isocyanates that can cause environment and paint film property more
Adverse effect, and the present invention is only to be prepared for a kind of emulsifier, then be prepared as lotion by emulsifier monomer, is still fallen within
Give an account of the scope of the first generation water-base epoxy to continue；The Chinese patent of Patent No. 2008100274947 discloses a kind of nonionic
The preparation method of type solid epoxy and its lotion, the method is by the catalysis of LEWIS acid boron trifluoride ether, in epoxy resin
Polyether segment has been accessed on molecule, to realize the Water-borne modification of epoxy resin, but has been difficult to after the completion of the reaction of LEWIS acid catalysts
It removes, being used for a long time can also etching apparatus, it is most important that catalyst is used as using boron trifluoride ether, reacts more violent,
The autohemagglutination of epoxy group can be caused, reaction is not easy to control.
Invention content
It is an object of the invention to：In view of the above-mentioned problems of the prior art, proposing a kind of water paint self-emulsifying
Epoxy resin latex, while giving preparation method.
In order to reach object above, of the invention technical solution provides
The water paint self-emulsifying epoxy resin emulsion of the present invention, including following components in percentage by weight：Modified ring
Oxygen resin 40%~75%, deionized water 25%~60%；The modified epoxy is made of the raw material of following weight percent：Ring
Oxygen resin 20%~50%, polyether polyol 10%~30%, alkyl phenol polyoxyethylene ether 1%~15%, C12~C14 alkyl shrink sweet
Oily ether epoxy resin 2%~15%, chain extender 5%~20%, catalyst 0.16%~0.4%, organic solvent 20%~50%.
The modified epoxy of the present invention refers to the grafting alkyl phenol polyoxy in epoxy molecule structure not soluble in water
The hydrophilic substances such as vinethene and polyether polyol, alkyl phenol polyoxyethylene ether itself can be used as a kind of emulsifier, by alkane
Base phenol polyethenoxy ether, which is grafted to the modified epoxy obtained in epoxy resin, has the function of self-emulsifying.In addition, being added small point
C12~C14 alkyl glycidyl ether epoxy resin of son, acts not only as macromolecular epoxy resin such as E-20, E-44, E-
51 equal diluents use, and the epoxy resin for being also used as participating in reaction uses（Epoxy resin be E-20, E-44, E-51,
One or more of C12~C14 alkyl glycidyl ether epoxy resin）, the use of a large amount of organic solvents is avoided, is rationally controlled
Reaction viscosity is made, it is ensured that reaction will not cause to stir uneven because of excessively glutinous, and then avoid and occur gel in preparation process
Phenomenon.
Preferably, the modified epoxy is made of the raw material of following weight percent：Epoxy resin 20%~50% gathers
Ethoxylated polyhydric alcohol 20%~30%, alkyl phenol polyoxyethylene ether 1%~5%, C12~C14 alkyl glycidyl ethers epoxy resin 2%~5%,
Chain extender 5%~20%, catalyst 0.16%~0.4%, organic solvent 20%~50%.
Preferably, the modified epoxy is made of the raw material of following weight percent：Epoxy resin 20%~50% gathers
Ethoxylated polyhydric alcohol 15%~20%, alkyl phenol polyoxyethylene ether 5%~10%, C12~C14 alkyl glycidyl ethers epoxy resin 5%~
10%, chain extender 5%~20%, catalyst 0.16%~0.4%, organic solvent 20%~50%.
Preferably, the modified epoxy is made of the raw material of following weight percent：Epoxy resin 20%~50% gathers
Ethoxylated polyhydric alcohol 10%~15%, alkyl phenol polyoxyethylene ether 10%~15%, C12~C14 alkyl glycidyl ethers epoxy resin 10%~
15%, chain extender 5%~20%, catalyst 0.16%~0.4%, organic solvent 20%~50%.
Preferably, the epoxy resin is in E-20, E-44, E-51, C12~C14 alkyl glycidyl ether epoxy resin
One or more；The molecular weight of the preferred polyethylene glycol of polyether polyol, the polyethylene glycol is 400~1000；It is described
Alkyl phenol polyoxyethylene ether is one or both of nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether.
It is further preferred that C12~C14 alkyl glycidyl ethers epoxy resin is reactive diluent AGE or activity
Diluent BGE.
Preferably, the chain extender is phthalic anhydride, methyl tetrahydro phthalic anhydride, one kind in methyl hexahydrophthalic anhydride or more
Kind；The catalyst is quaternary ammonium salts catalyst, the preferred tetrabutylammonium bromide of quaternary ammonium salts catalyst；The organic solvent is third
One or more of glycol butyl ether, propylene glycol monomethyl ether, n-butanol.
In order to reach object above, the present invention also provides the preparation sides of water paint self-emulsifying epoxy resin emulsion
Method, characterized in that include the following steps：
One, modified epoxy is prepared：
（1）The half of 5%~20% chain extender and 20%~50% organic solvent is added by required raw material weight percentage
Enter into container, after stirring evenly, be warming up to 105 ± 15 DEG C, into next step；
（2）10%~30% polyether polyol and 1%~15% alkyl phenol polyoxyethylene ether are taken by required raw material weight percentage
It is uniformly mixed and obtains mixture, then mixture is added drop-wise in container, mixture time for adding is controlled in 1~2h, mixture
After being added dropwise to complete under the conditions of 105 ± 15 DEG C keep the temperature 2~3h obtain prepolymer, prepolymer is poured out it is spare, into next step；
（3）The half of 20%~50% organic solvent, 0.16%~0.4% is catalyzed by required raw material weight percentage
Agent, 20%~50% epoxy resin and 2%~15% C12~C14 alkyl glycidyl ether epoxy resin are added in container, stirring
120 ± 10 DEG C are warming up to after uniformly, prepolymer then is added dropwise to container, prepolymer time for adding is controlled in 2 ± 0.5h, prepolymer
2~4h is kept the temperature after being added dropwise to complete under the conditions of 120 ± 10 DEG C, vacuum distillation obtains modified epoxy；
Two, self-emulsifying epoxy resin emulsion is prepared：
40%~75% modified epoxy is added in container by required weight percentages of components, then temperature 50 ±
5 DEG C, to container 25%~60% deionized water, deionized water time for adding control is added dropwise under conditions of 1000~1200r/min of rotating speed
For system in 0.5~1h, deionized water is uniformly mixing to obtain self-emulsifying epoxy after dripping under 300 ± 50r/min speed conditions
Resin emulsion.
The preparation method of the present invention does not need additional the advantage is that during preparing self-emulsifying epoxy resin emulsion
Emulsifier realizes its own emulsification, and the grain size of self-emulsifying epoxy resin emulsion by being modified to oil-soluble epoxy resin
For 100~200nm, blue light is apparent, with common emulsion type epoxy hardener room temperature rapid curing, and paint film property in the market
It is good.
Preferably, the epoxy resin is in E-20, E-44, E-51, C12~C14 alkyl glycidyl ether epoxy resin
One or more；The molecular weight of the preferred polyethylene glycol of polyether polyol, the polyethylene glycol is 400~1000；It is described
Alkyl phenol polyoxyethylene ether is one or both of nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether.
Preferably, the chain extender is phthalic anhydride, methyl tetrahydro phthalic anhydride, one kind in methyl hexahydrophthalic anhydride or more
Kind；The catalyst is quaternary ammonium salts catalyst, the preferred tetrabutylammonium bromide of quaternary ammonium salts catalyst；The organic solvent is third
One or more of glycol butyl ether, propylene glycol monomethyl ether, n-butanol.This patent has selected the anhydride object for being not susceptible to side reaction
Matter can introduce polyoxyethylene ether segment as chain extender, without catalyst action in epoxy molecule structure, by oiliness
It is epoxy-modified for can self-emulsifying water-base epoxy.
It is an advantage of the invention that：The self-emulsifying epoxy resin emulsion storage stability of the present invention is good, with mating emulsion type
Epoxy hardener compatibility is good, and paint film property is excellent.
Specific implementation mode
Chemical reagent and material used in the present invention are purchased in market.The wherein model 748 of reactive diluent AGE, purchase
From Foshan Hong Shuo Chemical Co., Ltd.s；The model 501 of reactive diluent BGE is purchased from Foshan Hong Shuo Chemical Co., Ltd.s.
Embodiment one
Prepare modified epoxy：
The half of 5% phthalic anhydride and 20% propylene glycol monomethyl ether is taken to be added to dress by required raw material weight percentage
In the four-hole boiling flask for having blender, thermometer and condensing unit, after stirring evenly, it is to slowly warm up to 105 DEG C.Then it first presses required
Raw material weight percentage takes 30% polyethylene glycol 400 and 15% nonylphenol polyoxyethylene ether to be uniformly mixed and obtains mixture, then will mix
It closes object to be added drop-wise in four-hole boiling flask, mixture time for adding is controlled in 1h, and mixture is kept the temperature after being added dropwise to complete under the conditions of 105 DEG C
2h obtains prepolymer, prepolymer is poured out spare.By required raw material weight percentage by two points of remaining 20% propylene glycol monomethyl ether
One of, 0.16% tetrabutylammonium bromide, 20% epoxy resin E-51 and 9.84% reactive diluent AGE are added in four-hole boiling flask,
It is to slowly warm up to 120 DEG C after stirring evenly, and prepolymer is added dropwise to container, the control of prepolymer time for adding is in 2h, prepolymer drop
2h is kept the temperature after the completion of adding under the conditions of 120 DEG C, vacuum distillation obtains modified epoxy.
Prepare self-emulsifying epoxy resin emulsion：
Take 40% modified epoxy to be added in four-hole boiling flask by required weight percentages of components, then temperature 50 C,
60% deionized water is added dropwise to container under the conditions of rotating speed 1000r/min, deionized water time for adding is controlled in 1h, deionized water drop
After the completion of adding self-emulsifying epoxy resin emulsion is uniformly mixing to obtain under 300r/min speed conditions.
Embodiment two
Prepare modified epoxy：
6.6% methyl tetrahydro phthalic anhydride and the half of 30% propandiol butyl ether is taken to be added to by required raw material weight percentage
In four-hole boiling flask equipped with blender, thermometer and condensing unit, after stirring evenly, it is to slowly warm up to 120 DEG C.Then institute is first pressed
It needs raw material weight percentage that 10% Macrogol 600 and 1% octyl phenol polyoxyethylene ether is taken to be uniformly mixed and obtains mixture, then will mix
It closes object to be added drop-wise in four-hole boiling flask, mixture time for adding is controlled in 2h, and mixture is kept the temperature after being added dropwise to complete under the conditions of 120 DEG C
3h obtains prepolymer, prepolymer is poured out spare.By required raw material weight percentage by two points of remaining 30% propandiol butyl ether
One of, 0.4% tetrabutylammonium bromide, 50% epoxy resin E-20 and 2% reactive diluent BGE are added in four-hole boiling flask, stirring
It is to slowly warm up to 130 DEG C after uniformly, and prepolymer is added dropwise to container, the control of prepolymer time for adding is added dropwise in 2.5h, prepolymer
4h is kept the temperature under the conditions of 130 DEG C after the completion, vacuum distillation obtains modified epoxy.
Prepare self-emulsifying epoxy resin emulsion：
Take 40% modified epoxy to be added in four-hole boiling flask by required weight percentages of components, then 55 DEG C of temperature,
60% deionized water is added dropwise to container under the conditions of rotating speed 1050r/min, deionized water time for adding is controlled in 0.5h, deionized water
After being added dropwise to complete self-emulsifying epoxy resin emulsion is uniformly mixing to obtain under 350r/min speed conditions.
Embodiment three
Prepare modified epoxy：
It takes the half of 20% methyl hexahydrophthalic anhydride and 20% n-butanol to be added to by required raw material weight percentage to be equipped with
In the four-hole boiling flask of blender, thermometer and condensing unit, after stirring evenly, it is to slowly warm up to 100 DEG C.Then required original is first pressed
Material weight percent takes 15% polyethylene glycol-800 and 9.72% nonylphenol polyoxyethylene ether to be uniformly mixed and obtains mixture, then will mix
It closes object to be added drop-wise in four-hole boiling flask, mixture time for adding is controlled in 1.5h, and mixture is protected after being added dropwise to complete under the conditions of 100 DEG C
Warm 2.5h obtains prepolymer, prepolymer is poured out spare.By required raw material weight percentage by two points of remaining 20% n-butanol
One of, 0.28% tetrabutylammonium bromide, 30% epoxy resin E-44 and 5% reactive diluent AGE are added in four-hole boiling flask, stirring
It is to slowly warm up to 110 DEG C after uniformly, and prepolymer is added dropwise to container, the control of prepolymer time for adding is added dropwise in 1.5h, prepolymer
3h is kept the temperature under the conditions of 110 DEG C after the completion, vacuum distillation obtains modified epoxy.
Prepare self-emulsifying epoxy resin emulsion：
Take 40% modified epoxy to be added in four-hole boiling flask by required weight percentages of components, then temperature 45 C,
60% deionized water is added dropwise to container under the conditions of rotating speed 1200r/min, deionized water time for adding is controlled in 1h, deionized water drop
After the completion of adding self-emulsifying epoxy resin emulsion is uniformly mixing to obtain under 300r/min speed conditions.
Example IV
Prepare modified epoxy：
10% phthalic anhydride and the half of 50% propylene glycol monomethyl ether is taken to be added to by required raw material weight percentage
In four-hole boiling flask equipped with blender, thermometer and condensing unit, after stirring evenly, it is to slowly warm up to 90 DEG C.Then institute is first pressed
It needs raw material weight percentage that 12.78% cetomacrogol 1000 and 5% octyl phenol polyoxyethylene ether is taken to be uniformly mixed and obtains mixture, then
Mixture is added drop-wise in four-hole boiling flask, mixture time for adding control in 2h, mixture be added dropwise to complete after under the conditions of 90 DEG C
Heat preservation 3h obtains prepolymer, prepolymer is poured out spare.By required raw material weight percentage by remaining 50% propylene glycol monomethyl ether
Half, 0.22% tetrabutylammonium bromide, 20%AGE and 2% reactive diluent BGE are added in four-hole boiling flask, are stirred evenly
After be to slowly warm up to 120 DEG C, and prepolymer is added dropwise to container, prepolymer time for adding is controlled in 2h, after prepolymer is added dropwise to complete
4h is kept the temperature under the conditions of 120 DEG C, vacuum distillation obtains modified epoxy.
Prepare self-emulsifying epoxy resin emulsion：
Take 40% modified epoxy to be added in four-hole boiling flask by required weight percentages of components, then temperature 50 C,
60% deionized water is added dropwise to container under the conditions of rotating speed 1100r/min, deionized water time for adding is controlled in 1h, deionized water drop
After the completion of adding self-emulsifying epoxy resin emulsion is uniformly mixing to obtain under 250r/min speed conditions.
Embodiment five
Prepare modified epoxy：
The half of 14.66% methyl tetrahydro phthalic anhydride and 20% n-butanol is taken to be added to dress by required raw material weight percentage
In the four-hole boiling flask for having blender, thermometer and condensing unit, after stirring evenly, it is to slowly warm up to 115 DEG C.Then it first presses required
Raw material weight percentage takes 20% polyethylene glycol-800 and 10% octyl phenol polyoxyethylene ether to be uniformly mixed and obtains mixture, then will mix
It closes object to be added drop-wise in four-hole boiling flask, mixture time for adding is controlled in 1.5h, and mixture is protected after being added dropwise to complete under the conditions of 115 DEG C
Warm 2.5h obtains prepolymer, prepolymer is poured out spare.By required raw material weight percentage by two points of remaining 20% n-butanol
One of, 0.34% tetrabutylammonium bromide, 20%BGE and 15% reactive diluent AGE are added in four-hole boiling flask, are delayed after stirring evenly
Slow to be warming up to 125 DEG C, and prepolymer is added dropwise to container, prepolymer time for adding is controlled in 2h, prepolymer be added dropwise to complete after 125
3h is kept the temperature under the conditions of DEG C, vacuum distillation obtains modified epoxy.
Prepare self-emulsifying epoxy resin emulsion：
Take 40% modified epoxy to be added in four-hole boiling flask by required weight percentages of components, then 55 DEG C of temperature,
60% deionized water is added dropwise to container under the conditions of rotating speed 1200r/min, deionized water time for adding is controlled in 1h, deionized water drop
After the completion of adding self-emulsifying epoxy resin emulsion is uniformly mixing to obtain under 300r/min speed conditions.
In addition to the implementation, the present invention can also have other embodiment.It is all to be formed using equivalent substitution or equivalent transformation
Technical solution, fall the present invention claims protection domain.
Claims (5)
1. water paint self-emulsifying epoxy resin emulsion, characterized in that including following components in percentage by weight：Modified epoxy
Resin 40%~75%, deionized water 25%~60%；The modified epoxy is made of the raw material of following weight percent：
Epoxy resin 20%~50%, polyether polyol 10%~30%, alkyl phenol polyoxyethylene ether 1%~15%, C12~C14 alkane
Base tetraglycidel ether epoxy resin 2%~15%, chain extender 5%~20%, catalyst 0.16%~0.4%, organic solvent
20%~50%；The epoxy resin is one or more of E-20, E-44, E-51；The polyether polyol is poly- second two
The molecular weight of alcohol, the polyethylene glycol is 400~1000；The alkyl phenol polyoxyethylene ether is nonylphenol polyoxyethylene ether, pungent
One or both of base phenol polyethenoxy ether；C12~C14 alkyl glycidyl ethers epoxy resin is reactive diluent
AGE；The chain extender is one or more in phthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride；The catalysis
Agent is quaternary ammonium salts catalyst, and quaternary ammonium salts catalyst is tetrabutylammonium bromide；The organic solvent is propandiol butyl ether, the third two
One or more of alcohol methyl ether, n-butanol.
2. water paint self-emulsifying epoxy resin emulsion according to claim 1, characterized in that the modified epoxy tree
Fat is made of the raw material of following weight percent：Epoxy resin 20%~50%, polyether polyol 20%~30%, alkyl phenol are poly-
Ethylene oxide ether 1%~5%, C12~C14 alkyl glycidyl ethers epoxy resin 2%~5%, chain extender 5%~20%, catalysis
Agent 0.16%~0.4%, organic solvent 20%~50%.
3. water paint self-emulsifying epoxy resin emulsion according to claim 1, characterized in that the modified epoxy tree
Fat is made of the raw material of following weight percent：Epoxy resin 20%~50%, polyether polyol 15%~20%, alkyl phenol are poly-
Ethylene oxide ether 5%~10%, C12~C14 alkyl glycidyl ethers epoxy resin 5%~10%, chain extender 5%~20% are urged
Agent 0.16%~0.4%, organic solvent 20%~50%.
4. water paint self-emulsifying epoxy resin emulsion according to claim 1, characterized in that the modified epoxy tree
Fat is made of the raw material of following weight percent：Epoxy resin 20%~50%, polyether polyol 10%~15%, alkyl phenol are poly-
Ethylene oxide ether 10%~15%, C12~C14 alkyl glycidyl ethers epoxy resin 10%~15%, chain extender 5%~20%,
Catalyst 0.16%~0.4%, organic solvent 20%~50%.
5. the preparation method of water paint self-emulsifying epoxy resin emulsion according to claim 1, characterized in that including
Following steps：
One, modified epoxy is prepared：
(1) half of 5%~20% chain extender and 20%~50% organic solvent is added by required raw material weight percentage
Enter into container, after stirring evenly, be warming up to 105 ± 15 DEG C, into next step；
(2) 10%~30% polyether polyol and 1%~15% alkyl phenol polyoxyethylene ether are taken by required raw material weight percentage
It is uniformly mixed and obtains mixture, then mixture is added drop-wise in container, mixture time for adding is controlled in 1~2h, mixture
After being added dropwise to complete under the conditions of 105 ± 15 DEG C keep the temperature 2~3h obtain prepolymer, prepolymer is poured out it is spare, into next step；
(3) required raw material weight percentage is pressed by the half of 20%~50% organic solvent, 0.16%~0.4% catalysis
Agent, 20%~50% epoxy resin and 2%~15%C12~C14 alkyl glycidyl ether epoxy resin are added in container, are stirred
120 ± 10 DEG C are warming up to after mixing uniformly, prepolymer then is added dropwise to container, prepolymer time for adding is controlled in 2 ± 0.5h, pre-polymerization
Object keeps the temperature 2~4h under the conditions of 120 ± 10 DEG C after being added dropwise to complete, vacuum distillation obtains modified epoxy；
Two, self-emulsifying epoxy resin emulsion is prepared：
40%~75% modified epoxy is added in container by required weight percentages of components, then in temperature 50 ± 5
DEG C, to container 25%~60% deionized water, deionized water time for adding control is added dropwise under conditions of 1000~1200r/min of rotating speed
For system in 0.5~1h, deionized water is uniformly mixing to obtain self-emulsifying epoxy after dripping under 300 ± 50r/min speed conditions
Resin emulsion.
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| CN107603410A (en) * | 2017-10-13 | 2018-01-19 | 武汉工程大学 | Floor coatings aqueous epoxy resin emulsion and preparation method thereof |
| CN107955108B (en) * | 2017-10-26 | 2019-10-25 | 无锡洪汇新材料科技股份有限公司 | A kind of preparation method of epoxy-modified vinyl chloride acrylate copolymer emulsion |
| CN108503846B (en) * | 2018-05-02 | 2021-04-02 | 北京化工大学 | Method for synthesizing nonionic emulsifier by solid acid catalysis and application thereof |
| CN109809732A (en) * | 2019-01-08 | 2019-05-28 | 中海油常州涂料化工研究院有限公司 | A kind of silicate grout polyepoxy aqueous epoxy emulsion and preparation method thereof |
| WO2021237404A1 (en) * | 2020-05-25 | 2021-12-02 | 厦门双瑞船舶涂料有限公司 | Aqueous epoxy anticorrosive coating and preparation method therefor |
| CN112662205B (en) * | 2020-11-12 | 2022-06-28 | 广东至道先进土木工程材料技术研究有限公司 | Anti-aging luminous inorganic coating for building exterior wall and preparation method thereof |
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| CN1891772B (en) * | 2005-07-05 | 2010-05-26 | 浙江安邦新材料发展有限公司 | Epoxy resin emulsion for water-based coating, and its preparing method |
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Address after: No. 449, Xiongzhou South Road, Liuhe Economic Development Zone, Nanjing City, Jiangsu Province Patentee after: Jiangsu Fengcai building materials (Group) Co.,Ltd. Patentee after: Jiangsu Fengcai Architectural Technology Development Co.,Ltd. Patentee after: JIANGSU FENGCAI THERMAL INSULATION DECORATIVE BOARD Co.,Ltd. Address before: 211500 No.449, Xiongzhou South Road, Liuhe District, Nanjing, Jiangsu Province Patentee before: JIANGSU COLOURFUL NEW BUILDING MATERIAL INDUSTRY Co.,Ltd. Patentee before: Jiangsu Fengcai Architectural Technology Development Co.,Ltd. Patentee before: JIANGSU FENGCAI THERMAL INSULATION DECORATIVE BOARD Co.,Ltd. |