CN107814914A - A kind of organic silicon modified aqueous epoxy hardener and preparation method thereof - Google Patents
A kind of organic silicon modified aqueous epoxy hardener and preparation method thereof Download PDFInfo
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- CN107814914A CN107814914A CN201711010273.4A CN201711010273A CN107814914A CN 107814914 A CN107814914 A CN 107814914A CN 201711010273 A CN201711010273 A CN 201711010273A CN 107814914 A CN107814914 A CN 107814914A
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- epoxy
- silicon modified
- organic silicon
- modified aqueous
- silicone oil
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 33
- 239000010703 silicon Substances 0.000 title claims abstract description 33
- 239000004848 polyfunctional curative Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 claims abstract description 30
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 30
- 229920002545 silicone oil Polymers 0.000 claims abstract description 28
- 229920000768 polyamine Polymers 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 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 abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 11
- -1 alcohol ethers Chemical class 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 16
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 12
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 3
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 4
- 229920006334 epoxy coating Polymers 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 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
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 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
- C08G59/62—Alcohols or phenols
-
- 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
-
- 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
- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention discloses a kind of preparation method of organic silicon modified aqueous epoxy hardener, comprises the following steps：Polyamine and epoxy-terminated silicone oil are dissolved in alcohol ethers organic solvent respectively, stirs, epoxy-terminated silicone oil is added drop-wise in polyamine under nitrogen protection, heating is reacted；Bisphenol A type epoxy resin is added into above-mentioned reaction product, heating response；Add organic acid and carry out water-solubility modifying, be eventually adding water and the organic silicon modified aqueous epoxy curing agent that solid content is 30 90% is made.The ring-opening reaction that the present invention carries out amino-epoxy base using epoxy-terminated silicone oil with polyamine carries out the organosilicon grafted and modified of curing agent, improves the hydrophobicity and toughness of epoxy resin film；Carry out the open loop graft reaction of amino-epoxy base at high temperature using the epoxy radicals in epoxy resin and the amino being grafted on the polyamines of organosilicon, improving curing agent has the compatibility of epoxy resin；Water-solubility modifying then can solve the problem that the shortcomings that traditional organic coating high VOC.
Description
Technical field
The present invention relates to technical field of coatings, specifically a kind of organic silicon modified aqueous epoxy hardener and its preparation side
Method.
Background technology
Current epoxy hardener uses polyethylene polyamine system more.But also there are some defects in the system：Two-component
Stability is poor, the trial period is short, the hydrophobicity of film is poor, pliability is poor, easy scuffing, not resistant and impact resistance difference etc..
The conventional method of modifying of polyamine has following three kinds：(1) amidatioon as made from polyamine and mono fatty acid reaction
Polyamines；(2) there is the polyamide that dimeric dibasic acid closes with polyamine progress；(3) polyamine is obtained with epoxy resin addition
Epoxy-more amine additives.These three methods use and introduce non-polar group in polyamine strand so that modified
Polyamine curing agent has amphipathic structure, to improve the compatibility with epoxy resin.
At present, already turn into the focus studied both at home and abroad on the organic-silicon-modified of epoxy resin, but be with poly- silica mostly
Alkane is curing agent of the main chain as epoxy resin, also has part to be used as by the use of organosilicon and applies film additive.With organic-silicon-modified more
The document report of amine hardener is seldom.Patent CN201310418041 employ hydrosilylation be prepared for it is organic-silicon-modified more
Amine hardener；Patent CN20120327859 prepares organosilicon curing agent using organosilicon hydrolyzation condensation.But above-mentioned prepared consolidates
Agent and the compatibility of epoxy resin are poor, can influence epoxy resin film forming and film properties.
The ring-opening reaction that the present invention carries out amino-epoxy base using epoxy-terminated silicone oil with polyamines carries out the organic of curing agent
Silicon graft modification, improve the hydrophobicity and toughness of epoxy resin film；Using the epoxy radicals in epoxy resin with being grafted
Amino on the polyamines of machine silicon carries out the open loop graft reaction of amino-epoxy base at high temperature, and improving curing agent has epoxy resin
Compatibility；Water-solubility modifying then can solve the problem that the shortcomings that traditional organic coating high VOC.
The content of the invention
The technical problem solved needed for of the invention is in existing epoxy curing agent or epoxy coating
Weak point, there is provided it is a kind of to have fine compatibility with epoxy resin, epoxy coating hydrophobicity and toughness can be improved, and have
There is low VOC organic silicon modified aqueous epoxy curing agent.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of organic silicon modified aqueous epoxy hardener, the organic silicon modified aqueous epoxy hardener general structure such as formula
(I) shown in：
In formula, n1 values are 1-5 integer；
N2 values are 0-2；
R1 is for methyl, ethyl or without group；
R2 is chain alkyl or phenyl with secondary amino group；
It is another object of the present invention to provide a kind of preparation method of organic silicon modified aqueous epoxy hardener, including
Following steps：Polyamine and epoxy-terminated silicone oil are dissolved in alcohol ethers organic solvent respectively, stirred, under nitrogen protection will
Epoxy-terminated silicone oil is added drop-wise in polyamine, is heated to 50-100 DEG C, reacts 2.5-4.5h；Bisphenol A type epoxy resin is added to arrive
In above-mentioned reaction product, 3-5h is reacted at a temperature of 100-150 DEG C；Add a certain amount of organic acid and carry out water-solubility modifying, most
Water being added afterwards the organic silicon modified aqueous epoxy curing agent that solid content is 30-90% being made, reaction expression is as follows：
In formula, n1 values are 1-5 integer；
N2 values are 0-2；
R1 is for methyl, ethyl or without group；
R2 is chain alkyl or phenyl with secondary amino group.
Further, the polyamine, epoxy-terminated silicone oil, alcohol ethers organic solvent, bisphenol A type epoxy resin, organic acid
Mol ratio be 100:50-99:70-100:40-70:30-60.
Further, the polyamine is that the one or more in diethylenetriamine, triethylene tetramine and m-phenylene diamine (MPD) are mixed
Compound；The epoxy-terminated silicone oil is that epoxy ethyl blocks poly- methyl-silicone oil, glycidyl capped poly- methyl-silicone oil, epoxybutyl
Block at least one of poly- methyl-silicone oil.
Further, the alcohol ethers organic solvent is propylene glycol monomethyl ether, ethylene glycol ethyl ether or butyl glycol ether.
Further, the bisphenol A type epoxy resin is bisphenol type epoxy of the epoxide number between 0.4-0.6mol/100g
Resin, preferably E42, E44 or E51.
Further, the organic acid is acetic acid or propionic acid.
Further, the epoxy-terminated silicone oil is loaded using at the uniform velocity dropwise addition mode, loading time 1-2h；The phenol
A types epoxy resin is loaded using at the uniform velocity dropwise addition mode, loading time 2-3h.
Further, organic acid is loaded using at the uniform velocity dropwise addition mode, loading time 0.5-1h.
Further, the water is loaded using at the uniform velocity dropwise addition mode, loading time 0.5-1h.
Beneficial effects of the present invention：The open loop that the present invention carries out amino-epoxy base using epoxy-terminated silicone oil with polyamine is anti-
The organosilicon grafted and modified of curing agent should be carried out, improves the hydrophobicity and toughness of epoxy resin film；Using in epoxy resin
Epoxy radicals and the amino that has been grafted on the polyamines of organosilicon carry out the open loop graft reaction of amino-epoxy base at high temperature, improve
Curing agent has the compatibility of epoxy resin；Water-solubility modifying then can solve the problem that the shortcomings that traditional organic coating high VOC；The present invention's
Synthetic method need not use various catalyst, possess safety, easy-operating advantage.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
Unless otherwise instructed, " part " refers to mole in following embodiments.
Embodiment 1
100 parts of diethylenetriamine is dissolved into 30 parts of propylene glycol monomethyl ethers, under 300r/min mixing speed, stirring
Uniformly, then 50 DEG C of reactant constant temperature water bath is at the uniform velocity added dropwise has dissolved 50 parts of poly- first of epoxy ethyls end-blocking under nitrogen protection
20 parts of propylene glycol monomethyl ether solution of base silicone oil, time for adding 1h, after completion of dropwise addition at 50 DEG C, continue to react 1.5h.In nitrogen
At the uniform velocity it is added dropwise during atmosphere is enclosed, under the conditions of 100 DEG C and has dissolved 40 parts of E42 20 parts of propylene glycol monomethyl ether solution, time for adding 2h, after
100 DEG C of reaction 1h of continuation of insurance temperature.60 DEG C are cooled to, 30 parts of propionic acid is added and neutralizes, time for adding 0.5h, water stirring is finally added dropwise, matches somebody with somebody
Into the organic silicon modified aqueous epoxy hardener aqueous solution that solid content is 30%.
Embodiment 2
100 parts of triethylene tetramine is dissolved into 40 parts of propylene glycol monomethyl ethers, under 300r/min mixing speed, stirring
Uniformly, then 75 DEG C of reactant constant temperature water bath is at the uniform velocity added dropwise has dissolved 50 parts of poly- first of epoxy ethyls end-blocking under nitrogen protection
20 parts of propylene glycol monomethyl ether solution of base silicone oil, time for adding 1.5h, after being added dropwise to complete at 75 DEG C, continue to react 2h.In nitrogen
At the uniform velocity it is added dropwise during atmosphere is enclosed, under the conditions of 120 DEG C and has dissolved 50 parts of E42 20 parts of propylene glycol monomethyl ether solution, time for adding 2h, after
120 DEG C of reaction 2h of continuation of insurance temperature.60 DEG C are cooled to, 60 parts of propionic acid is added and neutralizes, time for adding 0.5h, water stirring is finally added dropwise,
It is made into the organic silicon modified aqueous epoxy hardener aqueous solution that solid content is 30%.
Embodiment 3
100 parts of triethylene tetramine is dissolved into 40 parts of propylene glycol monomethyl ethers, under 400r/min mixing speed, stirring
Uniformly, then 100 DEG C of reactant constant temperature water bath is at the uniform velocity added dropwise has dissolved 50 parts of glycidyl capped poly- first under nitrogen protection
30 parts of propylene glycol monomethyl ether solution of base silicone oil, time for adding 2h, after being added dropwise to complete at 100 DEG C, continue to react 2h.In nitrogen
At the uniform velocity it is added dropwise in atmosphere, under the conditions of 120 DEG C and has dissolved 50 parts of E44 20 parts of propylene glycol monomethyl ether solution, time for adding 2.5h, after
120 DEG C of reaction 2h of continuation of insurance temperature.60 DEG C are cooled to, 40 parts of propionic acid is added and neutralizes, time for adding 1h, water stirring is finally added dropwise, matches somebody with somebody
Into the organic silicon modified aqueous epoxy hardener aqueous solution that solid content is 30%.
Embodiment 4
100 parts of m-phenylene diamine (MPD) is dissolved into 50 parts of ethylene glycol ethyl ethers, under 500r/min mixing speed, stirring is equal
It is even, then by 100 DEG C of reactant constant temperature water bath, at the uniform velocity it is added dropwise has dissolved 60 parts of glycidyl capped poly- methyl under nitrogen protection
30 parts of ethylene glycol ethyl ethers ethereal solutions of silicone oil, time for adding be 2h be added dropwise to complete after at 100 DEG C, continue react 2h.In blanket of nitrogen
In enclosing, 20 parts of ethylene glycol ethyl ethers ethereal solutions for having dissolved 40 parts of E51 are at the uniform velocity added dropwise under the conditions of 150 DEG C, time for adding 3h, continue to protect
150 DEG C of reaction 2h of temperature.60 DEG C are cooled to, 60 parts of acetic acid is added and neutralizes, time for adding 1h, water stirring is finally added dropwise, is made into solid
Content is the 50% organic silicon modified aqueous epoxy hardener aqueous solution.
Embodiment 5
100 parts of m-phenylene diamine (MPD) is dissolved into 50 parts of butyl glycol ethers, under 300r/min mixing speed, stirring is equal
It is even, then by 100 DEG C of reactant constant temperature water bath, at the uniform velocity it is added dropwise has dissolved 70 parts of poly- methyl of epoxybutyls end-blocking under nitrogen protection
30 parts of butyl glycol ether solution of silicone oil, time for adding 2h, after being added dropwise to complete, at 100 DEG C, continue to react 2.5h.In nitrogen
At the uniform velocity it is added dropwise during atmosphere is enclosed, under the conditions of 150 DEG C and has dissolved 60 parts of E51 20 parts of butyl glycol ether solution, time for adding 3h, after
150 DEG C of reaction 2h of continuation of insurance temperature.60 DEG C are cooled to, 60 parts of acetic acid is added and neutralizes, time for adding 0.5h, water stirring is finally added dropwise,
It is made into the organic silicon modified aqueous epoxy hardener aqueous solution that solid content is 70%.
Embodiment 6
100 parts of m-phenylene diamine (MPD) is dissolved into 50 parts of propylene glycol monomethyl ethers, under 300r/min mixing speed, stirring is equal
It is even, then by 100 DEG C of reactant constant temperature water bath, at the uniform velocity it is added dropwise has dissolved 99 parts of glycidyl capped poly- methyl under nitrogen protection
20 parts of propylene glycol monomethyl ether solution of silicone oil, time for adding 2h, after being added dropwise to complete, at 100 DEG C, continue to react 2h.In nitrogen
In atmosphere, 20 parts of propylene glycol monomethyl ether solution for having dissolved 70 parts of E51 are at the uniform velocity added dropwise under the conditions of 150 DEG C, time for adding 3h, continue
150 DEG C of reaction 2h of insulation.60 DEG C are cooled to, 60 parts of acetic acid is added and neutralizes, time for adding 1h, water stirring is finally added dropwise, is made into
Solid content is the 90% organic silicon modified aqueous epoxy hardener aqueous solution.
Comparative example 1
100 parts of triethylene tetramine is dissolved into 40 parts of propylene glycol monomethyl ethers, under 300r/min mixing speed, stirring
Uniformly, then 75 DEG C of reactant constant temperature water bath is at the uniform velocity added dropwise has dissolved 70 parts of poly- first of epoxy ethyls end-blocking under nitrogen protection
20 parts of propylene glycol monomethyl ether solution of base silicone oil, time for adding continue to react 2.5h, cooling after the completion of being 2h under conditions of 75 DEG C
To 60 DEG C, add 60 parts of acetic acid and neutralize, time for adding 0.5h, water stirring is finally added dropwise, be made into solid content be 50% it is organic
The silicon modified aqueous epoxy hardener aqueous solution.
Comparative example 2
Diethylenetriamine
Comparative example 3
Triethylene tetramine
Comparative example 4
M-phenylene diamine (MPD)
Curing agent in above-described embodiment and comparative example is diluted into same solid content and Shanghai profit carbon new material science and technology has
The aqueous epoxy resin emulsion MU601A of limit company is 1 than epoxide number by amine value:1 amount is compounded, after reserved sample observing 4h
Mixture state, then test its performance after unnecessary sample is carried out into curing of coating on concrete test block.Paint adhesion intensity is pressed
Method of testing measure in GB/T9779-1988；Coating hardness is determined by standard GB/T6739-1996；Wearability presses standard GB/
T1768-2006 is determined；Impact resistance presses the method measure in standard GB/T22374-2008；Coating weatherability presses GB/
Method in T1865-2009 is tested and (evaluated by 1000h coating mechanical properties decrease degree)；The hydrophobicity of coating uses
The CA100A of Shanghai Ying Nuo precision instruments Co., Ltd is measured.
The epoxy coating paint film property test result of 1 each embodiment of table and comparative example.
Table 1
It is can be seen that by the embodiment in table 1 and the correction data of comparative example via the curing agent and ring after organic-silicon-modified
Formed film after the mixing of oxygen tree fat, relative to unmodified curing agent, is obtained in terms of toughness, weatherability and hydrophobicity
Larger raising.Embodiment 1-6 understands that the introducing of organic-silicon-modified curing agent epoxy resin has improved compared with comparative example 1
The compatibility of machine silicon curing agent and epoxy resin.Therefore, organic silicon modified aqueous epoxy hardener disclosed in this invention is relative
The curing agent of conventional and the mixed formed film of asphalt mixtures modified by epoxy resin lipid phase, have more preferable toughness, weatherability, hydrophobicity, compatibility with
And the characteristic of low stain.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously can easily make various modifications to case study on implementation, and described herein one
As principle be applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation case here
Example, for those skilled in the art according to the announcement of the present invention, not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (10)
- A kind of 1. organic silicon modified aqueous epoxy hardener, it is characterised in that the organic silicon modified aqueous epoxy hardener knot Shown in structure formula such as formula (I)：In formula, n1 values are 1-5 integer；N2 values are 0-2；R1 is for methyl, ethyl or without group；R2 is chain alkyl or phenyl with secondary amino group.
- 2. the preparation method of the organic silicon modified aqueous epoxy hardener described in claim 1, it is characterised in that including following step Suddenly：Polyamine and epoxy-terminated silicone oil are dissolved in alcohol ethers organic solvent respectively, stirred, under nitrogen protection by end ring oxygen Base silicone oil is added drop-wise in polyamine, is heated to 50-100 DEG C, reacts 2.5-4.5h；Add bisphenol A type epoxy resin to it is above-mentioned instead Answer in product, 3-5h is reacted at a temperature of 100-150 DEG C；Add a certain amount of organic acid and carry out water-solubility modifying, be eventually adding The organic silicon modified aqueous epoxy curing agent that solid content is 30-90% is made in water.
- 3. the preparation method of organic silicon modified aqueous epoxy hardener according to claim 1, it is characterised in that described more First amine, epoxy-terminated silicone oil, alcohol ethers organic solvent, bisphenol A type epoxy resin, the mol ratio of organic acid are 100:50-99: 70-100:40-70:30-60。
- 4. the preparation method of organic silicon modified aqueous epoxy hardener according to claim 1, it is characterised in that described more First amine is one or more mixtures in diethylenetriamine, triethylene tetramine and m-phenylene diamine (MPD)；The epoxy-terminated silicone oil Poly- methyl-silicone oil, glycidyl capped poly- methyl-silicone oil, epoxybutyl are blocked for epoxy ethyl to block in poly- methyl-silicone oil extremely Few one kind.
- 5. the preparation method of organic silicon modified aqueous epoxy hardener according to claim 1, it is characterised in that the alcohol Ether organic solvent is propylene glycol monomethyl ether, ethylene glycol ethyl ether or butyl glycol ether.
- 6. the preparation method of organic silicon modified aqueous epoxy hardener according to claim 1, it is characterised in that described double Phenol A types epoxy resin is bisphenol A type epoxy resin of the epoxide number between 0.4-0.6mol/100g, preferably E42, E44 or E51.
- 7. the preparation method of organic silicon modified aqueous epoxy hardener according to claim 1, it is characterised in that described to have Machine acid is acetic acid or propionic acid.
- 8. the preparation method of organic silicon modified aqueous epoxy hardener according to claim 1, it is characterised in that the end Epoxy radicals silicone oil is loaded using at the uniform velocity dropwise addition mode, loading time 1-2h；The bisphenol A type epoxy resin is using at the uniform velocity Dropwise addition mode is loaded, loading time 2-3h.
- 9. the preparation method of organic silicon modified aqueous epoxy hardener according to claim 1, it is characterised in that described to have Machine acid is loaded using at the uniform velocity dropwise addition mode, loading time 0.5-1h.
- 10. organic silicon modified aqueous epoxy hardener according to claim 1 and preparation method thereof, it is characterised in that institute State water to be loaded using at the uniform velocity dropwise addition mode, loading time 0.5-1h.
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| CN110511356A (en) * | 2019-08-30 | 2019-11-29 | 华南理工大学 | A kind of silicon oil modified aqueous epoxy curing agent of epoxy and phenyl and preparation method thereof |
| CN111234178A (en) * | 2020-03-31 | 2020-06-05 | 陕西立高涂料有限公司 | Self-emulsifying water-based epoxy resin curing agent and preparation method thereof |
| CN112851915A (en) * | 2021-01-13 | 2021-05-28 | 山东硅科新材料有限公司 | Preparation method of waterborne organic silicon modified aliphatic polyamine epoxy curing agent |
| CN113527634A (en) * | 2021-08-10 | 2021-10-22 | 广东花果山环保科技有限公司 | Reactive flame-retardant epoxy resin curing agent and preparation technology thereof |
| CN113912850A (en) * | 2021-10-29 | 2022-01-11 | 珠海三臻新材料科技有限公司 | Dicyandiamide derivative, high-toughness epoxy resin and corresponding preparation method |
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| CN110511356A (en) * | 2019-08-30 | 2019-11-29 | 华南理工大学 | A kind of silicon oil modified aqueous epoxy curing agent of epoxy and phenyl and preparation method thereof |
| CN110511356B (en) * | 2019-08-30 | 2021-08-06 | 华南理工大学 | Epoxy phenyl silicone oil modified waterborne epoxy curing agent and preparation method thereof |
| CN111234178A (en) * | 2020-03-31 | 2020-06-05 | 陕西立高涂料有限公司 | Self-emulsifying water-based epoxy resin curing agent and preparation method thereof |
| CN112851915A (en) * | 2021-01-13 | 2021-05-28 | 山东硅科新材料有限公司 | Preparation method of waterborne organic silicon modified aliphatic polyamine epoxy curing agent |
| CN112851915B (en) * | 2021-01-13 | 2022-05-31 | 山东硅科新材料有限公司 | Preparation method of waterborne organic silicon modified aliphatic polyamine epoxy curing agent |
| CN113527634A (en) * | 2021-08-10 | 2021-10-22 | 广东花果山环保科技有限公司 | Reactive flame-retardant epoxy resin curing agent and preparation technology thereof |
| CN113912850A (en) * | 2021-10-29 | 2022-01-11 | 珠海三臻新材料科技有限公司 | Dicyandiamide derivative, high-toughness epoxy resin and corresponding preparation method |
| CN113912850B (en) * | 2021-10-29 | 2023-03-14 | 珠海三臻新材料科技有限公司 | Preparation method of dicyandiamide derivative and preparation method of high-toughness epoxy resin |
| CN114854349A (en) * | 2022-05-20 | 2022-08-05 | 长春艾德斯新材料有限公司 | Mini LED, micro LED packaging adhesive and preparation method thereof |
| CN116284800A (en) * | 2023-05-18 | 2023-06-23 | 广州恒峰新材料科技有限公司 | Water-based epoxy resin curing agent and preparation method of water-based epoxy paint |
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Application publication date: 20180320 |