CN109554927A - A kind of preparation method of aqueous epoxy resin emulsion - Google Patents
A kind of preparation method of aqueous epoxy resin emulsion Download PDFInfo
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- CN109554927A CN109554927A CN201811354510.3A CN201811354510A CN109554927A CN 109554927 A CN109554927 A CN 109554927A CN 201811354510 A CN201811354510 A CN 201811354510A CN 109554927 A CN109554927 A CN 109554927A
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- China
- Prior art keywords
- epoxy resin
- added
- resin emulsion
- aqueous epoxy
- preparation
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- Granted
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 95
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 95
- 239000000839 emulsion Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000004593 Epoxy Substances 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 23
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 6
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 58
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 45
- 238000009835 boiling Methods 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 19
- 238000010792 warming Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical group [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 11
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 10
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical group NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000004513 sizing Methods 0.000 abstract description 29
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 23
- 239000004917 carbon fiber Substances 0.000 abstract description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 23
- 239000012855 volatile organic compound Substances 0.000 abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 78
- 230000000052 comparative effect Effects 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 238000009955 starching Methods 0.000 description 12
- 238000005352 clarification Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- 230000001376 precipitating effect Effects 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 230000006837 decompression Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000002479 acid--base titration Methods 0.000 description 6
- -1 alkyl phenol Chemical compound 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 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 5
- 239000006210 lotion Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- XTBMQKZEIICCCS-UHFFFAOYSA-N hexane-1,5-diamine Chemical compound CC(N)CCCCN XTBMQKZEIICCCS-UHFFFAOYSA-N 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 230000003252 repetitive effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000003141 primary amines Chemical group 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002552 dosage form Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Epoxy Resins (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to the technical field of aqueous epoxy resin emulsion, specially a kind of preparation method of aqueous epoxy resin emulsion.Polyether polyol and bromo-acetic acid tert-butyl dissolve in a solvent, and bromo-reaction occurs under the action of catalyst, and the sodium hydroxide solution of mass concentration 20% ~ 40% is added, and hydrolyzed under basic conditions obtains substance A；It takes above-mentioned substance A to react with diamine, end-capping reagent is added and obtains substance B；It takes above-mentioned substance B to react to obtain epoxy terminated surfactant with epoxy resin, deionized water is slowly added dropwise under strong stirring and then continues to emulsify epoxy resin to obtain aqueous epoxy resin emulsion；The problem of surfactant is precipitated when the wellability of present invention improves aqueous epoxy resin emulsion stability poor, epoxy resin-base and carbon fiber difference and film forming, the epoxy resin sizing agent is free of volatile organic compound simultaneously, greatly reduces the pollution to environment.
Description
Technical field
The present invention relates to the technical field of aqueous epoxy resin emulsion, specially a kind of preparation of aqueous epoxy resin emulsion
Method.
Background technique
Carbon fiber is a kind of fibrous material for the excellent combination property that carbon element content is up to 90% or more, has height
A series of excellent performances such as specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, conductive, damping, noise reduction, are widely used in aviation
Space flight and military field, sports field, medical and health care field, civil construction field, textile garment field etc. are modern
Industrially.But there are a plurality of types of defects such as mechanical damage, radial cracking, central cavity for carbon fiber, when by external force
Crack tip be also easy to produce stress concentrate, therefore in process it is rubbed easily fracture generate lousiness, influence carbon fiber with
The compatibility of matrix resin reduces composite property.Therefore, one layer of finish, referred to as starching usually are coated in carbon fiber surface
Agent.Sizing agent improves the convergence of carbon fiber, reduces relative friction, to reduce lousiness amount and single wire fracture phenomenon, is promoted multiple
Condensation material comprehensive performance.
The development course of sizing agent is broadly divided into three phases: solvent type, additional emulsification dosage form, self-emulsifying type sizing agent.
Solvent-borne type sizing agent is resin to be dissolved in acetone and other organic solvent to be formulated, but since organic solvent is volatile, cause
Starching amount is discrete big and generates larger pollution to ambient enviroment.Additional emulsification dosage form sizing agent is using Small molecular surfactant
Make resin evenly dispersed water-based emulsion obtained in water, reduces environmental pollution, but Small molecular surfactant is in film forming
It is easily precipitated, while also will increase composite material water absorption rate causes intensity to decline.Self-emulsifying type sizing agent is using modified surface
Activating agent makes it participate in the reaction of resin, surfactant can not only be effectively reduced, problem, while water-based emulsion obtained is precipitated
Partial size is small, improves the wellability of carbon fiber and resin matrix.For different types of carbon fiber enhancement resin base body, sizing agent
Also it is matching accordingly to produce each veriety, mainly includes epoxide resin type, polyurethane-type and compound.Wherein, aqueous ring
Oxygen resin sizing agent is quickly grown in recent years, is most widely used.
The Chinese invention patent application of 103572608 A of Publication No. CN discloses a kind of aqueous epoxy resin emulsion type
Carbon fiber sizing agent and its preparation, component include epoxy resin 15% ~ 35%, surfactant 5% ~ 20%, and lubricant 0.1% ~
0.5%, defoaming agent 0.1% ~ 0.5%, deionized water 55% ~ 65%；Aqueous epoxy resin emulsion type carbon fiber sizing agent in this document
Without containing volatile organic compounds such as acetone, toluene in preparation process, be conducive to environmental protection.But used surface-active
Agent is alkyl phenol polyoxyethylene ether type surfactant, is not involved in the reaction of epoxy resin, and when film forming, which is easily precipitated, influences processability
Can, for this sizing agent partial size in 200 ~ 400nm, partial size is larger, is unfavorable for the groove on filling carbon fiber surface, leads to fiber after starching
Play that gross weight is big, convergence is poor.
The Chinese invention patent application of 101858038 A of Publication No. CN disclose a kind of carbon fiber emulsion pasting agent and
Preparation method and application, the preparation method is easy to operate, but uses a large amount of volatile organic solvent, to ecological environment and
The health of human body of operator causes centainly to threaten, and organic solvent is volatile, and sizing agent concentration changes greatly, and leads to starching
Unevenly, fiber comprehensive performance is influenced.
Summary of the invention
The present invention for aqueous epoxy resin emulsion stability is poor, the wellability of epoxy resin-base and carbon fiber is poor and
The problem of surfactant is precipitated when film forming, provides a kind of preparation method of aqueous epoxy resin emulsion, made from this method
For carbon fiber sizing agent emulsion particle diameter made of aqueous epoxy resin emulsion in 80 ~ 100nm, partial size is smaller, is conducive to filling carbon fiber
Surface grooves, form a kind of mechanical interlock, and reinforcing fiber convergence has reduced gross weight；Sizing agent emulsion is without acetone etc.
Volatile organic solvent, using water as dispersing agent, less, starching is uniform, and will not be to operator for concentration variation in sizing process
Health threat is caused, ecological environmental protection is conducive to；Generation prepares the epoxy terminated surface-active of intermediate product in the preparation method
The polyethylene glycol of small molecule can be modified and then be introduced into epoxy molecule chain by agent, the epoxy terminated surfactant,
The curing reaction of epoxy resin is participated in, processing is not precipitated when forming a film, and does not influence product appearance and comprehensive performance.
The technical solution of the present invention is as follows:
A kind of preparation method of aqueous epoxy resin emulsion, includes the following steps:
(1) polyether polyol and bromo-acetic acid tert-butyl dissolve in a solvent, and bromo-reaction occurs under the action of catalyst, and matter is added
The sodium hydroxide solution of concentration 20% ~ 40% is measured, hydrolyzed under basic conditions obtains substance A；Mass percent shared by each raw material is molten
10 ~ 15 parts of agent, 3 ~ 10 parts of bromo-acetic acid tert-butyl, 2 ~ 5 parts of catalyst, 5 ~ 10 parts of 20% ~ 40% sodium hydroxide solution, surplus is poly-
Ethoxylated polyhydric alcohol；
(2) it takes above-mentioned substance A to react with diamine, end-capping reagent is added and obtains substance B；Mass percent shared by each raw material is to produce
Object A is 80 ~ 90 parts, and diamine is 10 ~ 15 parts, and end-capping reagent is 2 ~ 5 parts；
(3) it takes above-mentioned substance B to react to obtain epoxy terminated surfactant with epoxy resin, is slowly added dropwise under strong stirring
Ionized water continues to emulsify epoxy resin to obtain aqueous epoxy resin emulsion in turn；Mass percent shared by each raw material is that B is 5
~ 10 parts, 30 ~ 40 parts of epoxy resin, 50 ~ 60 parts of deionized water.
Preferably, step (1) is, equipped with blender, reflux condenser, thermometer, nitrogen 500mL four-hole boiling flask
In, the pure and mild solvent of polyether polyols is added, sequentially adds catalyst and bromo-acetic acid tert-butyl after stirring and dissolving at 40 ~ 50 DEG C, rises
Solvent is removed under reduced pressure to 60 ~ 65 DEG C of 10 ~ 12h of reaction in temperature, is down to room temperature, and it is anti-that 20% ~ 40% sodium hydroxide solution of mass concentration is added
Answer 8 ~ 10h, suitable deionized water dissolving is added and is transferred in separatory funnel, be added methylene chloride extraction remove impurity until
Supernatant liquid clarification, revolving remove methylene chloride, obtain product A.
Preferably, step (2) is specifically, in tetra- mouthfuls of the 500mL burnings equipped with blender, reflux condenser, thermometer, nitrogen
In bottle, product A is added and depressurizes the remaining moisture content of suction filtration removing at 85 ~ 95 DEG C, is added after diamine mixes and rises to 160 ~ 180 DEG C
1 ~ 2h is reacted, vacuumizes and removes extra diamine, is down to 60 ~ 65 DEG C, 2 ~ 3h of blocking agent reaction is added and obtains substance B.
Preferably, in step (3), in the 500mL tetra- that blender, reflux condenser, thermometer, constant pressure funnel are housed
In mouth flask, substance B, epoxy resin and diluent propylene glycol monomethyl ether is added, is warming up to 90 ~ 100 DEG C of 2 ~ 3h of reaction, cools to 40
~ 50 DEG C, deionized water is dropped evenly under 1000 ~ 1500r/min strong stirring, the water-base epoxy that solid content is 40 ~ 50% is made
Resin emulsion.
Preferably, polyether polyol is polyethylene glycol, any one in polypropylene glycol in step (1).
Preferably, solvent is dimethylbenzene or toluene in step (1)；Catalyst is potassium tert-butoxide.
Preferably, diamine is 2- methyl-1,5- pentanediamine, m-phenylene diamine (MPD), hexamethylene diamine in step (2)；End-capping reagent is single
The tertiary carbonic acid glycidyl ester of epoxy.
Preferably, epoxy resin is the epoxy resin containing two or more epoxy-functionals in step (3), most preferably
For bisphenol A type epoxy resin.
The preparation of aqueous epoxy resins sizing agent: it is 3% that obtained aqueous epoxy resin emulsion, which is diluted to solid content, is pressed
0.5% ~ 2% wetting agent TEGO4100,0.5% ~ 2% coalescing agent Tao Shi is added in aqueous epoxy resin emulsion quality before diluting
DPM is configured to aqueous epoxy resins sizing agent, the preparation of aqueous epoxy resins sizing agent can also be used commonly used in the art
Preparation proportion, meet different demands.
The beneficial effects of the present invention are:
(1) aqueous epoxy resin emulsion of the invention is that the hydrophilic segment of surfactant is introduced asphalt mixtures modified by epoxy resin by chemically reacting
The sizing agent partial size of aqueous epoxy resin emulsion obtained in rouge strand, preparation is 80 ~ 100nm, and particle diameter distribution is relatively narrow, is conducive to
Filling carbon fiber surface grooves form a kind of mechanical interlock, and reinforcing fiber convergence has reduced gross weight, have good
Storage stability, dilution stability, freeze-thaw stability, mechanical stability.
(2) the epoxy terminated surfactant of intermediate product of the present invention may participate in the curing reaction of resin, no longer with small molecule
State exists, and processing is not precipitated when forming a film, and does not influence product appearance and comprehensive performance.
(3) sizing agent produced by the present invention is free of volatile organic compounds, using water as dispersing agent, concentration in sizing process
Less, starching is uniform, and will not cause health threat to operator, is conducive to ecological environmental protection for variation.
Detailed description of the invention
Fig. 1 is the SEM figure without the carbon fiber of starching processing.
Fig. 2 is the SEM figure without the carbon fiber of starching processing.
Fig. 3 is the SEM figure without the carbon fiber of starching processing.
Fig. 4 is the carbon fiber SEM figure of the sizing agent starching processing prepared using the embodiment of the present invention 1.
Fig. 5 is the carbon fiber SEM figure of the sizing agent starching processing prepared using the embodiment of the present invention 1.
Fig. 6 is the carbon fiber SEM figure of the sizing agent starching processing prepared using the embodiment of the present invention 1.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without this hair described in claims should will not be limited
It is bright.
Embodiment 1
In the 500mL four-hole boiling flask that blender, reflux condenser, thermometer, nitrogen are housed, 100g polyethylene glycol is added
PEG4000 and toluene 20g, and 40 DEG C of dissolutions are risen to, it is kept stirring speed 60r/min, sequentially adds bromo-acetic acid tert-butyl 9.5g
With potassium tert-butoxide 5.5g and rise to 65 DEG C of reaction 10h, revolving removes toluene, after 20g deionized water dissolving is added, is added 40%
Sodium hydrate aqueous solution 10g reacts at room temperature 8h, and q. s. methylene chloride is added and is extracted to upper liquid clarification, revolving removes dichloromethane
Alkane obtains product A.
The acid value that product A is surveyed by acid-base titration is 22.50mgKOH/g, and product A is transferred in four-hole boiling flask, is risen
Temperature filters to 91 DEG C of decompressions and removes residual moisture, is kept stirring speed 100r/min, and the 2- of 4.65g is added under a nitrogen atmosphere
Methyl-1,5- pentanediamine, and 170 DEG C of reaction 1h are warming up to, decompression, which filters, removes 2- methyl-1, and 5- pentanediamine is simultaneously cooled to 65
DEG C, the tertiary carbonic acid glycidyl ester 4.1g reaction 2h that monocycle oxygen is added obtains product B.
It takes the above-mentioned product B of 20g and 95g bisphenol A type epoxy resin E-51 in four-hole boiling flask, propylene glycol monomethyl ether 5g is added,
It is kept stirring speed 200r/min, 98 DEG C of reaction 2h is warming up to and obtains epoxy terminated surfactant, and further emulsify and do not change
Property epoxy resin, be cooled to 40 DEG C, promote revolving speed to 1500r/min, deionized water is added dropwise with the speed of 3mL/min
167.5g obtains aqueous epoxy resin emulsion until emulsion solid content is 40%.
Embodiment 2
In the 500mL four-hole boiling flask that blender, reflux condenser, thermometer, nitrogen are housed, 120g polyethylene glycol is added
PEG4000 and dimethylbenzene 15g, and 50 DEG C of dissolutions are risen to, it is kept stirring speed 60r/min, sequentially adds bromo-acetic acid tert-butyl
4.5g and potassium tert-butoxide 3g simultaneously rises to 65 DEG C of reaction 12h, and revolving removes removal xylene, after 20g deionized water dissolving is added, is added
40% sodium hydrate aqueous solution 7.5g reacts at room temperature 10h, and q. s. methylene chloride is added and is extracted to upper liquid clarification, revolving removes
Methylene chloride obtains product A.
The acid value that product A is surveyed by acid-base titration is 19.75mgKOH/g, and product A is transferred in four-hole boiling flask, is risen
Temperature filters to 91 DEG C of decompressions and removes residual moisture, is kept stirring speed 100r/min, and 5.75g isophthalic two is added under a nitrogen atmosphere
Amine is simultaneously warming up to 180 DEG C of reaction 2h, vacuumizes and m-phenylene diamine (MPD) is removed under reduced pressure and is cooled to 65 DEG C, the versatic acid contracting of addition monocycle oxygen
Water glyceride 6.2g reaction 2h obtains product B.
It takes the above-mentioned product B of 15g and 100g bisphenol A type epoxy resin E-51 in four-hole boiling flask, propylene glycol monomethyl ether 5g is added,
It is kept stirring speed 200r/min, 98 DEG C of reaction 2h is warming up to and obtains epoxy terminated surfactant and further emulsify unmodified
Epoxy resin is cooled to 40 DEG C, promotes revolving speed to 1500r/min, deionized water 110g is added dropwise extremely with the speed of 3mL/min
Emulsion solid content obtains aqueous epoxy resin emulsion for 50%.
Embodiment 3
In the 500mL four-hole boiling flask that blender, reflux condenser, thermometer, nitrogen are housed, 90g polyethylene glycol is added
PEG4000 and toluene 22.5g, and 40 DEG C of dissolutions are risen to, it is kept stirring speed 60r/min, sequentially adds bromo-acetic acid tert-butyl 15g
With potassium tert-butoxide 7.5g and rise to 65 DEG C of reaction 10h, revolving removes toluene, after 20g deionized water dissolving is added, is added 40%
Sodium hydrate aqueous solution 15g reacts at room temperature 8h, and q. s. methylene chloride water is added and is extracted to upper liquid clarification, revolving removes dichloro
Methane obtains product A.
The acid value that product A is surveyed by acid-base titration is 26.37mgKOH/g, and product A is transferred in four-hole boiling flask, is risen
Temperature filters to 91 DEG C of decompressions and removes residual moisture, is kept stirring speed 100r/min, and the 2- of 4.90g is added under a nitrogen atmosphere
Methyl-1,5- pentanediamine are simultaneously warming up to 160 DEG C of reaction 2h, vacuumize and extra 2- methyl-1 is removed under reduced pressure, 5- pentanediamine simultaneously drops
For temperature to 65 DEG C, the tertiary carbonic acid glycidyl ester 3.7g reaction 2h that monocycle oxygen is added obtains product B.
It takes the above-mentioned product B of 30g and 110g bisphenol A-type solid epoxy E-20 in four-hole boiling flask, propylene glycol first is added
Ether 10g is kept stirring speed 200r/min after heating for dissolving, is warming up to 98 DEG C of reaction 2h and obtains epoxy terminated surfactant simultaneously
Unmodified epoxy resin is further emulsified, is cooled to 40 DEG C, revolving speed is promoted to 1500r/min, is added dropwise with the speed of 3mL/min
Enter deionized water 200g and obtains aqueous epoxy resin emulsion to emulsion solid content for 40%.
Comparative example 1
In the 500mL four-hole boiling flask that blender, reflux condenser, thermometer, nitrogen are housed, 100g polyethylene glycol is added
PEG4000 and toluene 20g, and 40 DEG C of dissolutions are risen to, it is kept stirring speed 60r/min, sequentially adds bromo-acetic acid tert-butyl 9.5g
With potassium tert-butoxide 5.5g and rise to 65 DEG C of reaction 10h, revolving removes toluene, after 20g deionized water dissolving is added, is added 40%
Sodium hydrate aqueous solution 10g reacts at room temperature 8h, and q. s. methylene chloride is added and is extracted to upper liquid clarification, revolving removes dichloromethane
Alkane obtains product A.
It takes the above-mentioned product A of 20g and 95g bisphenol A type epoxy resin E-51 in four-hole boiling flask, propylene glycol monomethyl ether 5g is added,
It is kept stirring speed 200r/min, 98 DEG C of reaction 2h is warming up to and obtains epoxy terminated surfactant, and further emulsify and do not change
Property epoxy resin, be cooled to 40 DEG C, promote revolving speed to 1500r/min, deionized water is added dropwise with the speed of 3mL/min
167.5g obtains aqueous epoxy resin emulsion until emulsion solid content is 40%.
This comparative example 1 is compared with embodiment 1, and the carboxyl and epoxy group reactivity of the end product A are poor, grafting rate
It is lower, cause finally obtained emulsion particle diameter larger, stability is poor, and specific experiment result is as shown in table 2 below.
Comparative example 2
In the 500mL four-hole boiling flask that blender, reflux condenser, thermometer, nitrogen are housed, 100g polyethylene glycol is added
PEG4000 and toluene 20g, and 40 DEG C of dissolutions are risen to, it is kept stirring speed 60r/min, sequentially adds bromo-acetic acid tert-butyl 9.5g
With potassium tert-butoxide 5.5g and rise to 65 DEG C of reaction 10h, revolving removes toluene, after 20g deionized water dissolving is added, is added 40%
Sodium hydrate aqueous solution 10g reacts at room temperature 8h, and q. s. methylene chloride is added and is extracted to upper liquid clarification, revolving removes dichloromethane
Alkane obtains product A.
The acid value that product A is surveyed by acid-base titration is 22.50mgKOH/g, and product A is transferred in four-hole boiling flask, is risen
Temperature filters to 91 DEG C of decompressions and removes residual moisture, is kept stirring speed 100r/min, and the 2- of 4.65g is added under a nitrogen atmosphere
Methyl-1,5- pentanediamine are simultaneously warming up to 170 DEG C of reaction 1h, vacuumize and remaining 2- methyl-1 is removed under reduced pressure, 5- pentanediamine simultaneously drops
Temperature obtains product B to 65 DEG C.
It takes the above-mentioned product B of 20g and 95g bisphenol A type epoxy resin E-51 in four-hole boiling flask, propylene glycol monomethyl ether 5g is added,
It is kept stirring speed 200r/min, 98 DEG C of reaction 2h is warming up to and obtains epoxy terminated surfactant and further emulsify unmodified
Epoxy resin is cooled to 40 DEG C, promotes revolving speed to 1500r/min, deionized water 167.5g is added dropwise with the speed of 3mL/min
Aqueous epoxy resin emulsion is obtained to emulsion solid content for 40%.
This comparative example 2 compared with embodiment 1, though obtained product A further with 2- methyl-1,5- pentanediamine reaction with
Improve its reactivity with epoxy group, but without termination process, the primary amine group at strand both ends easily with it is epoxy functionalized
Group's reaction, the lotion mobility caused is poor, and partial size is larger, and storage stability is poor or even is long placed in generation precipitating, specifically
Experimental result is as shown in table 2 below.
In the 500mL four-hole boiling flask that blender, reflux condenser, thermometer, nitrogen are housed, 120g polyethylene glycol is added
PEG4000 and dimethylbenzene 15g, and 50 DEG C of dissolutions are risen to, it is kept stirring speed 60r/min, sequentially adds bromo-acetic acid tert-butyl
4.5g and potassium tert-butoxide 3g simultaneously rises to 65 DEG C of reaction 12h, and revolving removes removal xylene, after 20g deionized water dissolving is added, is added
40% sodium hydrate aqueous solution 7.5g reacts at room temperature 10h, and q. s. methylene chloride is added and is extracted to upper liquid clarification, revolving removes
Methylene chloride obtains product A.
It takes the above-mentioned product A of 15g and 100g bisphenol A type epoxy resin E-51 in four-hole boiling flask, propylene glycol monomethyl ether 5g is added,
It is kept stirring speed 200r/min, 98 DEG C of reaction 2h is warming up to and obtains epoxy terminated surfactant and further emulsify unmodified
Epoxy resin is cooled to 40 DEG C, promotes revolving speed to 1500r/min, deionized water 110g is added dropwise extremely with the speed of 3mL/min
Emulsion solid content obtains aqueous epoxy resin emulsion for 50%.
This comparative example 3 is compared with embodiment 2, and the carboxyl and epoxy group reactivity of the end product A are poor, grafting rate
It is lower, cause finally obtained emulsion particle diameter larger, stability is poor, and specific experiment result is as shown in table 2 below.
Comparative example 4
In the 500mL four-hole boiling flask that blender, reflux condenser, thermometer, nitrogen are housed, 120g polyethylene glycol is added
PEG4000 and dimethylbenzene 15g, and 50 DEG C of dissolutions are risen to, it is kept stirring speed 60r/min, sequentially adds bromo-acetic acid tert-butyl
4.5g and potassium tert-butoxide 3g simultaneously rises to 65 DEG C of reaction 12h, and revolving removes removal xylene, after 20g deionized water dissolving is added, is added
40% sodium hydrate aqueous solution 7.5g reacts at room temperature 10h, and q. s. methylene chloride is added and is extracted to upper liquid clarification, revolving removes
Methylene chloride obtains product A.
The acid value that product A is surveyed by acid-base titration is 19.75mgKOH/g, and product A is transferred in four-hole boiling flask, is risen
Temperature filters to 91 DEG C of decompressions and removes residual moisture, is kept stirring speed 100r/min, and 5.75g isophthalic two is added under a nitrogen atmosphere
Amine is simultaneously warming up to 180 DEG C of reaction 2h, vacuumizes that m-phenylene diamine (MPD) is removed under reduced pressure and is cooled to 65 DEG C and obtains product B.
It takes the above-mentioned product B of 15g and 100g bisphenol A type epoxy resin E-51 in four-hole boiling flask, propylene glycol monomethyl ether 5g is added,
It is kept stirring speed 200r/min, 98 DEG C of reaction 2h is warming up to and obtains epoxy terminated surfactant and further emulsify unmodified
Epoxy resin is cooled to 40 DEG C, promotes revolving speed to 1500r/min, deionized water 110g is added dropwise extremely with the speed of 3mL/min
Emulsion solid content obtains aqueous epoxy resin emulsion for 50%.
This comparative example 4 compared with embodiment 2, though obtained product A further reacted with m-phenylene diamine (MPD) with improve its with
The reactivity of epoxy group, but without termination process, the primary amine group at strand both ends is easily reacted with epoxy-functional, is led
Cause obtained lotion mobility poor, partial size is larger, and storage stability is poor or even is long placed in generation precipitating, and specific experiment result is such as
Shown in the following table 2.
Comparative example 5
In the 500mL four-hole boiling flask that blender, reflux condenser, thermometer, nitrogen are housed, 90g polyethylene glycol is added
PEG4000 and toluene 22.5g, and 40 DEG C of dissolutions are risen to, it is kept stirring speed 60r/min, sequentially adds bromo-acetic acid tert-butyl 15g
With potassium tert-butoxide 7.5g and rise to 65 DEG C of reaction 10h, revolving removes toluene, after 20g deionized water dissolving is added, is added 40%
Sodium hydrate aqueous solution 15g reacts at room temperature 8h, and q. s. methylene chloride is added and is extracted to upper liquid clarification, revolving removes dichloromethane
Alkane obtains product A.
It takes the above-mentioned product A of 30g and 110g bisphenol A-type solid epoxy E-20 in four-hole boiling flask, propylene glycol first is added
Ether 10g is kept stirring speed 200r/min after heating for dissolving, is warming up to 98 DEG C of reaction 2h and obtains epoxy terminated surfactant simultaneously
Unmodified epoxy resin is further emulsified, is cooled to 40 DEG C, revolving speed is promoted to 1500r/min, is added dropwise with the speed of 3mL/min
Enter deionized water 200g and obtains aqueous epoxy resin emulsion to emulsion solid content for 40%.
This comparative example 5 is compared with embodiment 3, and the carboxyl and epoxy group reactivity of the end product A are poor, grafting rate
It is lower, cause finally obtained emulsion particle diameter larger, stability is poor, and specific experiment result is as shown in table 2 below.
Comparative example 6
In the 500mL four-hole boiling flask that blender, reflux condenser, thermometer, nitrogen are housed, 90g polyethylene glycol is added
PEG4000 and toluene 22.5g, and 40 DEG C of dissolutions are risen to, it is kept stirring speed 60r/min, sequentially adds bromo-acetic acid tert-butyl 15g
With potassium tert-butoxide 7.5g and rise to 65 DEG C of reaction 10h, revolving removes toluene, after 20g deionized water dissolving is added, is added 40%
Sodium hydrate aqueous solution 15g reacts at room temperature 8h, and q. s. methylene chloride is added and is extracted to upper liquid clarification, revolving removes dichloromethane
Alkane obtains product A.
The acid value that product A is surveyed by acid-base titration is 26.37mgKOH/g, and product A is transferred in four-hole boiling flask, is risen
Temperature filters to 91 DEG C of decompressions and removes residual moisture, is kept stirring speed 100r/min, and the 2- of 4.90g is added under a nitrogen atmosphere
Methyl-1,5- pentanediamine are simultaneously warming up to 160 DEG C of reaction 2h, vacuumize and remaining 2- methyl-1 is removed under reduced pressure, 5- pentanediamine simultaneously drops
Temperature obtains product B to 65 DEG C.
It takes the above-mentioned product B of 30g and 110g bisphenol A-type solid epoxy E-20 in four-hole boiling flask, propylene glycol first is added
Ether 10g is kept stirring speed 200r/min after heating for dissolving, is warming up to 98 DEG C of reaction 2h and obtains epoxy terminated surfactant simultaneously
Unmodified epoxy resin is further emulsified, is cooled to 40 DEG C, revolving speed is promoted to 1500r/min, is added dropwise with the speed of 3mL/min
Enter deionized water 200g and obtains aqueous epoxy resin emulsion to emulsion solid content for 40%.
This comparative example 6 compared with embodiment 3, though obtained product A further with 2- methyl-1,5- pentanediamine reaction with
Improve its reactivity with epoxy group, but without termination process, the primary amine group at strand both ends easily with it is epoxy functionalized
Group's reaction, the lotion mobility caused is poor, and partial size is larger, and storage stability is poor or even is long placed in generation precipitating, specifically
Experimental result is as shown in table 2 below.
The preparation of two, aqueous epoxy resins sizing agents
Obtained all kinds of aqueous epoxy resin emulsions are diluted to admittedly containing being 3%, by the quality of aqueous epoxy resin emulsion before diluting
The DPM of 1% wetting agent TEGO4100,1% coalescing agent Tao Shi is added, is configured to aqueous epoxy resins sizing agent.Using English
The nano particle size analyzer of the model EanoZS of Malvern Instr Ltd., state production carries out grain diameter measurement to sizing agent, uses
The microVISC viscosity apparatus of Beijing Lei Ou development in science and technology Co., Ltd production carries out viscosity test to sizing agent.
Self-emulsification aqueous epoxy resin emulsion performance such as the following table 1 prepared by the present embodiment 1 ~ 3, implements as can be seen from the table
The aqueous epoxy resin emulsion partial size that example 1-3 is obtained is distributed between 70 ~ 100nm, and partial size is smaller, narrow distribution, and storage is steady
Qualitative, centrifugal stability, high-temperature stability, dilution stability are preferable.
1 performance data table of table
Note: aqueous epoxy resin emulsion epoxide number epoxide number: is measured according to national standard GB-T1677-2008 hydrochloric acid-acetone method；Storage
Stability: standing under the conditions of 15 ~ 30 DEG C, sees whether to precipitate；Centrifugal stability: take 30mL aqueous epoxy resin emulsion in
In centrifuge, aqueous epoxy resin emulsion centrifugal stability is tested under the conditions of 3000r/min, 30min；High-temperature stability:
100mL aqueous epoxy resin emulsion heats at 60 DEG C and stores 12h under the conditions of 12h is cooled to room temperature, repetitive operation observation whether there is or not
Precipitating；Freeze-thaw stability: taking 50mL lotion in -5 ± 2 DEG C of cryogenic boxes, take out after 18h, places 6h under the conditions of 23 ± 2 DEG C,
Whether there is or not precipitatings for repetitive operation observation；Dilution stability: it is 2% ~ 3% that aqueous epoxy resin latex 10mL, which is diluted to solid content, room
Temperature stands 48h, and whether there is or not precipitatings for observation.
The self-emulsification aqueous epoxy resin emulsion of this comparative example preparation, performance such as the following table 2, as can be seen from the table, comparison
The aqueous epoxy resin emulsion partial size that example 1 ~ 6 obtains is larger, and then leads to its storage stability, centrifugal stability, high-temperature stable
Property, dilution stability performance are poor, to influence the starch finishing effect of carbon fiber.
2 performance data table of table
Note: aqueous epoxy resin emulsion epoxide number epoxide number: is measured according to national standard GB-T1677-2008 hydrochloric acid-acetone method；Storage
Stability: standing under the conditions of 15 ~ 30 DEG C, sees whether to precipitate；Centrifugal stability: take 30mL aqueous epoxy resin emulsion in
In centrifuge, aqueous epoxy resin emulsion centrifugal stability is tested under the conditions of 3000r/min, 30min；High-temperature stability:
100mL aqueous epoxy resin emulsion heats at 60 DEG C and stores 12h under the conditions of 12h is cooled to room temperature, repetitive operation observation whether there is or not
Precipitating；Freeze-thaw stability: taking 50mL lotion in -5 ± 2 DEG C of cryogenic boxes, take out after 18h, places 6h under the conditions of 23 ± 2 DEG C,
Whether there is or not precipitatings for repetitive operation observation；Dilution stability: it is 2% ~ 3% that aqueous epoxy resin latex 10mL, which is diluted to solid content, room
Temperature stands 48h, and whether there is or not precipitatings for observation.
The bound of each raw material cited by the present invention and each raw material of the present invention, section value and technological parameter are (such as
Temperature, time, revolving speed etc.) bound, section value can realize of the invention (reaching the same effect of illustrated embodiment),
Embodiment is not listed one by one in this.
Claims (8)
1. a kind of preparation method of aqueous epoxy resin emulsion, includes the following steps:
(1) polyether polyol and bromo-acetic acid tert-butyl dissolve in a solvent, and bromo-reaction occurs under the action of catalyst, and matter is added
The sodium hydroxide solution of concentration 20% ~ 40% is measured, hydrolyzed under basic conditions obtains substance A；Mass percent shared by each raw material is molten
10 ~ 15 parts of agent, 3 ~ 10 parts of bromo-acetic acid tert-butyl, 2 ~ 5 parts of catalyst, 5 ~ 10 parts of 20% ~ 40% sodium hydroxide solution, surplus is poly-
Ethoxylated polyhydric alcohol；
(2) it takes above-mentioned substance A to react with diamine, end-capping reagent is added and obtains substance B；Mass percent shared by each raw material is to produce
Object A is 80 ~ 90 parts, and diamine is 10 ~ 15 parts, and end-capping reagent is 2 ~ 5 parts；
(3) it takes above-mentioned substance B to react to obtain epoxy terminated surfactant with epoxy resin, is slowly added dropwise under strong stirring
Ionized water continues to emulsify epoxy resin to obtain aqueous epoxy resin emulsion in turn；Mass percent shared by each raw material is that B is 5
~ 10 parts, 30 ~ 40 parts of epoxy resin, 50 ~ 60 parts of deionized water.
2. the preparation method of aqueous epoxy resin emulsion according to claim 1, which is characterized in that step (1) is to fill
In the 500mL four-hole boiling flask for having blender, reflux condenser, thermometer, nitrogen, the pure and mild solvent of polyether polyols is added, 40 ~ 50
Catalyst and bromo-acetic acid tert-butyl are sequentially added at DEG C after stirring and dissolving, 60 ~ 65 DEG C of 10 ~ 12h of reaction is warming up to, is removed under reduced pressure molten
Room temperature is down in agent, and 20% ~ 40% sodium hydroxide solution of mass concentration is added and reacts 8 ~ 10h, suitable deionized water dissolving is added simultaneously
It is transferred in separatory funnel, methylene chloride extraction is added and removes impurity until supernatant liquid is clarified, revolving removes methylene chloride, obtains
To product A.
3. the preparation method of aqueous epoxy resin emulsion according to claim 1, which is characterized in that step (2) specifically,
In the 500mL four-hole boiling flask that blender, reflux condenser, thermometer, nitrogen are housed, product A is added and is depressurized at 85 ~ 95 DEG C
It filters and removes remaining moisture content, be added after diamine mixes and rise to 160 ~ 180 DEG C of 1 ~ 2h of reaction, vacuumize and remove extra binary
Amine is down to 60 ~ 65 DEG C, and 2 ~ 3h of blocking agent reaction is added and obtains substance B.
4. the preparation method of aqueous epoxy resin emulsion according to claim 1, which is characterized in that in step (3), filling
In the 500mL four-hole boiling flask for having blender, reflux condenser, thermometer, constant pressure funnel, be added substance B, epoxy resin with
Diluent propylene glycol monomethyl ether is warming up to 90 ~ 100 DEG C of 2 ~ 3h of reaction, cools to 40 ~ 50 DEG C, stirs in 1000 ~ 1500r/min strength
It mixes down and drops evenly deionized water, the aqueous epoxy resin emulsion that solid content is 40 ~ 50% is made.
5. the preparation method of aqueous epoxy resin emulsion according to claim 1, which is characterized in that polyethers in step (1)
Polyalcohol is polyethylene glycol, any one in polypropylene glycol.
6. the preparation method of aqueous epoxy resin emulsion according to claim 1, which is characterized in that solvent in step (1)
For dimethylbenzene or toluene；Catalyst is potassium tert-butoxide.
7. the preparation method of aqueous epoxy resin emulsion according to claim 1, which is characterized in that binary in step (2)
Amine is 2- methyl-1,5- pentanediamine, m-phenylene diamine (MPD), hexamethylene diamine；End-capping reagent is the tertiary carbonic acid glycidyl ester of monocycle oxygen.
8. the preparation method of aqueous epoxy resin emulsion according to claim 1, which is characterized in that epoxy in step (3)
Resin is the epoxy resin containing two or more epoxy-functionals, most preferably bisphenol A type epoxy resin.
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