CN108003327A - A kind of anionic modifying epoxy resin by organosilicon waterborne curing agent and preparation method thereof - Google Patents
A kind of anionic modifying epoxy resin by organosilicon waterborne curing agent and preparation method thereof Download PDFInfo
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- CN108003327A CN108003327A CN201711451565.1A CN201711451565A CN108003327A CN 108003327 A CN108003327 A CN 108003327A CN 201711451565 A CN201711451565 A CN 201711451565A CN 108003327 A CN108003327 A CN 108003327A
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- epoxy resin
- curing agent
- waterborne curing
- anionic modifying
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 45
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 45
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 3
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 3
- 238000007711 solidification Methods 0.000 claims abstract description 3
- 230000008023 solidification Effects 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 229920000768 polyamine Polymers 0.000 claims description 23
- -1 polyethylene Polymers 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical class OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical class CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 2
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical class CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 claims description 2
- GLBHAWAMATUOBB-UHFFFAOYSA-N 6,6-dimethylheptane-1,1-diamine Chemical compound CC(C)(C)CCCCC(N)N GLBHAWAMATUOBB-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910008051 Si-OH Inorganic materials 0.000 claims description 2
- 229910006358 Si—OH Inorganic materials 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008053 sultones Chemical class 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- LMVLVUPTDRWATB-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-ol Chemical compound CO[Si](C)(OC)CCCO LMVLVUPTDRWATB-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001412 amines Chemical class 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 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
- 231100001244 hazardous air pollutant Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000007964 self emulsifier Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of anionic modifying epoxy resin by organosilicon waterborne curing agent and preparation method thereof, is made for polynary amine by nucleophilic substitution twice, with‑Si‑OCH2CH3For Water-borne modification group, nucleophilic substitution occurs and plays solidification effect by curing groups and epoxy group of NH, while because of Si OCH2CH3Easily with the hydroxyl after epoxy ring-opening, substrate surface hydroxyl deep-crosslinked reaction occurs for the Si OH formed after hydrolysis, though therefore the anionic modifying epoxy resin by organosilicon waterborne curing agent of the present invention is water-based, hardness height, strong adhesive force, wearability are good after curing with cross linking of epoxy resin.
Description
Technical field
The present invention relates to a kind of waterborne curing agent, more particularly to a kind of anionic modifying epoxy resin by organosilicon are water-based
Curing agent and preparation method thereof, belongs to environmental technology field.
Technical background
Epoxy resin product is widely used in life with its excellent mechanical property and chemical resistance and industry is led
Domain, epoxy curing agent are the products for epoxy cure, curable epoxy resin can be had a major impact, wherein can
Mainly amine curing agent for room temperature curing epoxy.Improved with the environmental consciousness of society, many countries issue
Compare the regulation of stringent limitation volatile organic solvent, Water-borne modification product becomes trend already.
Water-borne epoxy systems are retaining adhesion excellent possessed by conventional epoxy system, heat endurance, chemicals-resistant
Property, on the basis of the characteristic such as insulating properties, using water as decentralized medium, be free of or comprise only a small amount of organic solvent, be a kind of environment friend
Good high molecular material.As the requirement to environmental protection is increasingly urgent and stringent, without volatile organic solvent or low volatilization
Property organic solvent, the water-borne epoxy systems without hazardous air pollutants become current research hot spot.
Chinese patent CN102432830A discloses a kind of Water-based epoxy resin curing agent emulsion and preparation method thereof.The party
Novolac epoxy resin and organic solvent are added in reactor by method first, after being completely dissolved under the conditions of 50~80 DEG C, then are added
Enter modifying agent, 0.5~2h of reaction obtains the novolac epoxy resin of amine modification；Organic polyamine and organic solvent are taken at the same time, after mixing
Organic polyamine is completely dissolved under the conditions of 50~90 DEG C, organic acid is then added dropwise, reacts 10~60min, obtains having for modification
Machine polyamines；The novolac epoxy resin of Water-borne modification is added into again in the organic polyamine after salt, 40~100 DEG C of 1~3h of reaction are made
A kind of modification organic polyamine class aqueous epoxy curing agent with self-emulsifying.
Chinese patent CN1958639A discloses a kind of aqueous epoxy resin curing agent and preparation method thereof.This method be through
Cross epoxy resin and polyether Glycols condensation reaction, to polyethylene polyamine addition modification, end-blocking and into salt and etc. water is made
Property epoxy curing agent, it is by itrile group and primary amine by acrylonitrile and polyethylene polyamine modifier obtained by addition modification that it, which is blocked,
Hydrogen is with 1.1~1.2: 1.0 mixed in molar ratio, when reaction 1.5~2.0 is small under the conditions of temperature is 65~70 DEG C.The invention system
Standby curing agent can substantially reduce irritation of the modified multicomponent amine to skin, and substantially eliminate volatile flavor.
Chinese patent CN104098757A discloses a kind of organic silicon-phosphorus hydridization extinguishing waterborn self-emulsifying epoxy resin and cures
The preparation method of agent, comprises the following steps：A) silicon phospha compound synthesizes；B) prepared by non-ion aqueous epoxy self-emulsifier；c)
Melted ash corrosion prepares organic silicon-phosphorus hydridization extinguishing waterborn self-emulsifying epoxy resin curing agent.
Although aqueous epoxy resin curing agent is the hot spot of recent research, cure in the prior art with cross linking of epoxy resin
All there are performance deficiency for rear hardness, adhesive force, wearability etc..Meanwhile on anionic modifying epoxy resin by organosilicon water
Property curing agent and its preparation process do not have been reported that temporarily.
The content of the invention
A kind of the present invention is intended to provide anionic modifying epoxy resin by organosilicon waterborne curing agent.
A kind of molecular formula of anionic modifying epoxy resin by organosilicon waterborne curing agent of the present invention is as follows,
Be made for polynary amine by nucleophilic substitution twice, the modified epoxy waterborne curing agent with-Si-
OCH2CH3For Water-borne modification group, nucleophilic substitution is occurred as curing groups and epoxy group using-NH and plays solidification effect, while because-
Si-OCH2CH3- the Si-OH formed after hydrolysis is easily anti-with the hydroxyl after epoxy ring-opening, substrate surface hydroxyl generation deep-crosslinked
Should, though therefore the present invention anionic modifying epoxy resin by organosilicon waterborne curing agent to be water-based, and cross linking of epoxy resin
Hardness height, strong adhesive force, wearability are good after curing.
The shortcomings that to overcome the prior art and deficiency, the present invention take following technical scheme, a kind of anionic
Modifying epoxy resin by organosilicon waterborne curing agent, is prepared by following methods：
(1) it is anion-modified：Polyamine and ring-type sultones are mixed and have been dissolved in molar ratio at 1: 1~1.5: 1
In solvent, when 50~90 DEG C of reactions 4~8 are small, add neutralizer, it is to be precipitated separate out it is complete, it is filtering, washing, drying precipitated, obtain
Anionic polyamine；
(2) it is organic-silicon-modified：60.0 parts of anionic polyamines, 20.0~40.0 in step (1) are added in the reactor
Part silane coupling agent containing epoxy group, 20.0~50.0 parts of alcohols, it is uniform by material stirring to open stirring, it is heated to 50~
After 90 DEG C of 3~6h of reaction, up to anionic modifying epoxy resin by organosilicon waterborne curing agent.
The anionic modifying epoxy resin by organosilicon waterborne curing agent, is stirred with epoxy resin latex when in use
Film after mixing, about 24h completion of cures.
The polyamine is ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, diethylenetriamine, triethylene four
At least one of amine, tetraethylenepentamine, polyethylene polyamine, m-xylene diamine, trimethylhexane diamine.
The ring-type propane sultone is 1,3- propane sultones, 1- methyl isophthalic acids, 3-N-morpholinopropanesulfonic acid lactone, 2- methyl isophthalic acids,
3-N-morpholinopropanesulfonic acid lactone, 3- methyl isophthalic acids, 3-N-morpholinopropanesulfonic acid lactone, 1,4- butyl sultones, 1- methyl isophthalic acids, 4- butyl sultones, 2- first
Base -1,4- butyl sultones, 3- methyl isophthalic acids, 4- butyl sultones, at least one of 4- methyl isophthalic acids, 4- butyl sultones.
The organic solvent for n,N-dimethylacetamide, dimethyl sulfoxide, n,N-Dimethylformamide, acetone, butanone,
At least one of cyclohexanone.
The neutralizer is ammonia, triethylamine, triethanolamine, N- methylpyrroles, N- methyl piperidines, in trimethylamine extremely
Few one kind.
The silane coupling agent containing epoxy group is 3- [the third oxygen of (2,3)-epoxy] hydroxypropyl methyl dimethoxy silicon
Alkane, KH560,3- glycydoxy trimethoxy silane, 2- (3,4- 7-oxa-bicyclo[4.1.0s) ethyl trimethoxy silane
At least one of.
The alcohols is at least one of methanol, ethanol, normal propyl alcohol, 2- propyl alcohol.
The anionic modifying epoxy resin by organosilicon waterborne curing agent preparation principle signal equation of the present invention
(by taking triethylene tetramine, 1,3- propane sultones, KH560 as an example) is as follows：
Embodiment
With reference to embodiment to the present invention a kind of anionic modifying epoxy resin by organosilicon waterborne curing agent do into
The description of one step.It is understood that specific embodiment described herein is used only for explaining related invention, rather than to the hair
Bright restriction.
Embodiment 1
A kind of anionic modifying epoxy resin by organosilicon waterborne curing agent, is prepared by following methods：
(1) it is anion-modified：Triethylene tetramine and 1,3- propane sultones are mixed in molar ratio and are dissolved in third at 1: 1.1
In ketone, when 50 DEG C of stirring reactions 5 are small, add triethylamine, it is to be precipitated separate out it is complete, it is filtering, washing, drying precipitated, obtain anion
Type polyamine；
(2) it is organic-silicon-modified：Add in the reactor 60.0 parts of anionic polyamines in step (1), 30.0 parts
KH560,35.0 parts of ethanol, unlatching stirring is uniform by material stirring, after being heated to 70 DEG C of reaction 5h, up to anionic organosilicon
Modified epoxy waterborne curing agent.
Embodiment 2
A kind of anionic modifying epoxy resin by organosilicon waterborne curing agent, is prepared by following methods：
(1) it is anion-modified：Diethylenetriamine and 2- methyl isophthalic acids, 1: 1 mixing in molar ratio of 4- butyl sultones is simultaneously molten
Solution is in butanone, when 70 DEG C of stirring reactions 4 are small, adds triethanolamine, it is to be precipitated separate out it is complete, it is filtering, washing, drying precipitated,
Obtain anionic polyamine；
(2) it is organic-silicon-modified：60.0 parts of anionic polyamines, 45.0 parts of 2- in step (1) are added in the reactor
(3,4- 7-oxa-bicyclo[4.1.0) ethyl trimethoxy silane, 30.0 parts of methanol, unlatching stirring is uniform by material stirring, is heated to 60 DEG C
After reacting 5h, up to anionic modifying epoxy resin by organosilicon waterborne curing agent.
Embodiment 3
A kind of anionic modifying epoxy resin by organosilicon waterborne curing agent, is prepared by following methods：
(1) it is anion-modified：Tetraethylenepentamine and 1,4- butyl sultones are mixed and are dissolved in molar ratio at 1: 1.05
In DMF, when 90 DEG C of stirring reactions 4 are small, be passed through ammonia, it is to be precipitated separate out it is complete, it is filtering, washing, drying precipitated, obtain anionic
Polyamine；
(2) it is organic-silicon-modified：60.0 parts of anionic polyamines in step (1), 20.0 parts of 3- contractings are added in the reactor
Water glycerin ether epoxide propyl trimethoxy silicane, 35.0 parts of normal propyl alcohols, unlatching stirring is uniform by material stirring, is heated to 80 DEG C instead
After answering 4h, up to anionic modifying epoxy resin by organosilicon waterborne curing agent.
According to embodiment 1,2,3, obtained anionic modifying epoxy resin by organosilicon waterborne curing agent, its molecular formula
For：
Anionic modifying epoxy resin by organosilicon waterborne curing agent, commercially available water-base epoxy in embodiment 1,2,3 are cured
Agent, when in use according to curing agent：Commercial epoxy resins lotion=0.3:After 1 is mixed thoroughly, cement surface is painted on,
Performance parameter such as following table after 24h：
Although the present invention has been explained in detail and refer to embodiment, for those of ordinary skill in the art, show
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of claim.
Claims (9)
1. a kind of anionic modifying epoxy resin by organosilicon waterborne curing agent, it is characterised in that molecular structural formula is as follows：
Its with-Si-OCH2CH3For Water-borne modification group, nucleophilic substitution occurs by curing groups and epoxy group of-NH
Play solidification effect ,-Si-OCH2CH3- the Si-OH formed after hydrolysis is easily sent out with the hydroxyl after epoxy ring-opening, substrate surface hydroxyl
Raw deep-crosslinked reaction.
2. a kind of preparation method of anionic modifying epoxy resin by organosilicon waterborne curing agent as claimed in claim 1, its
It is characterized in that, includes the following steps：
(1) it is anion-modified：Polyamine and ring-type sultones are mixed and are dissolved in organic molten in molar ratio at 1: 1~1.5: 1
In agent, when 50~90 DEG C of reactions 4~8 are small, add neutralizer, it is to be precipitated separate out it is complete, it is filtering, washing, drying precipitated, obtain it is cloudy from
Subtype polyamine；
(2) it is organic-silicon-modified：Add in the reactor 60.0 parts of anionic polyamines in step (1), 20.0~40.0 parts contain
There are silane coupling agent, 20.0~50.0 parts of alcohols of epoxy group, unlatching stirring is uniform by material stirring, is heated to 50~90 DEG C
After reacting 3~6h, up to anionic modifying epoxy resin by organosilicon waterborne curing agent.
3. a kind of preparation method of anionic modifying epoxy resin by organosilicon waterborne curing agent according to claim 2,
It is characterized in that, the polyamine is ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, diethylenetriamine, triethylene
At least one of tetramine, tetraethylenepentamine, polyethylene polyamine, m-xylene diamine, trimethylhexane diamine.
4. a kind of preparation method of anionic modifying epoxy resin by organosilicon waterborne curing agent according to claim 2,
It is characterized in that, the ring-type propane sultone is 1,3-propane sultone, 1- methyl isophthalic acids, 3-N-morpholinopropanesulfonic acid lactone, 2- methyl-
1,3- propane sultones, 3- methyl isophthalic acids, 3-N-morpholinopropanesulfonic acid lactone, 1,4- butyl sultones, 1- methyl isophthalic acids, 4- butyl sultones, 2-
Methyl isophthalic acid, 4- butyl sultones, 3- methyl isophthalic acids, 4- butyl sultones, at least one of 4- methyl isophthalic acids, 4- butyl sultones.
5. a kind of preparation method of anionic modifying epoxy resin by organosilicon waterborne curing agent according to claim 2,
It is characterized in that, the organic solvent is n,N-dimethylacetamide, dimethyl sulfoxide, n,N-Dimethylformamide, acetone, fourth
At least one of ketone, cyclohexanone.
6. a kind of preparation method of anionic modifying epoxy resin by organosilicon waterborne curing agent according to claim 2,
It is characterized in that, the neutralizer is ammonia, in triethylamine, triethanolamine, N- methylpyrroles, N- methyl piperidines, trimethylamine
At least one.
7. a kind of preparation method of anionic modifying epoxy resin by organosilicon waterborne curing agent according to claim 2,
It is characterized in that, the silane coupling agent containing epoxy group is 3- [the third oxygen of (2,3)-epoxy] hydroxypropyl methyl dimethoxy
Silane, KH560,3- glycydoxy trimethoxy silane, 2- (3,4- 7-oxa-bicyclo[4.1.0s) ethyl trimethoxy silicon
At least one of alkane.
8. a kind of preparation method of anionic modifying epoxy resin by organosilicon waterborne curing agent according to claim 2,
It is characterized in that, the alcohols is at least one of methanol, ethanol, normal propyl alcohol, 2- propyl alcohol.
9. a kind of application process of anionic modifying epoxy resin by organosilicon waterborne curing agent as claimed in claim 1, its
It is characterized in that, itself and epoxy resin latex is uniformly mixed rear film, about 24h completion of cures when in use.
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| CN112745483A (en) * | 2021-01-15 | 2021-05-04 | 万华化学集团股份有限公司 | Epoxy resin curing agent, preparation method thereof, epoxy resin composition and application |
| US20210340404A1 (en) * | 2018-10-18 | 2021-11-04 | 3M Innovative Properties Company | Silanol compositions and methods of use |
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