CN101235186B - Solvent-free epoxy-organic silicon composition capable of self-layering and curing - Google Patents
Solvent-free epoxy-organic silicon composition capable of self-layering and curing Download PDFInfo
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- CN101235186B CN101235186B CN2008100490700A CN200810049070A CN101235186B CN 101235186 B CN101235186 B CN 101235186B CN 2008100490700 A CN2008100490700 A CN 2008100490700A CN 200810049070 A CN200810049070 A CN 200810049070A CN 101235186 B CN101235186 B CN 101235186B
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Abstract
The invention belongs to the chemical material technology field, providing an epoxy-organosilicon composition which does not comprises solvent, and can automatically stratified and solidified, which comprises two components, wherein the first component is formed by 100-0 parts of epoxy resin, 0-100 parts of polyether modification epoxy resin and 20-240 parts of organosilicon resin, and the secondcomponent comprises 5-40 parts of amine curing agent, 1-16 parts of organosilicon cross linker and 0-0.05 parts of organosilicon cross-linking catalyst, wherein the parts which are added are parts byweight. The epoxy-organosilicon composition utilizes the exclusion principle between epoxy resin and organosilicon resin, and can automatically stratify in the film forming process, and the epoxy resin is deposited to the bottom and the organosilicon is exposed on the outer surface. The composition does not comprises solvent, and has the advantages of non toxic and environmental protection, and solidified products share the characteristics of distinct adhesive force of epoxy resin and low weatherability and surface property of organosilicon.
Description
Technical field
The invention belongs to chemical material technical field, relate generally to a kind of solvent-free can be from the epoxy-organic silicon composition of multi-shell curing.
Background technology
In coatings industry, because most single layer coatings can not reach excellent protection and decorative effect, common coated article surface will be covered with paint, lacquer, colour wash, etc. multilayer film and just can be met the demands.Yet every layer of need are constructed respectively, and working procedure is many, the time is long, expense is high, may have short shortcoming of poor adhesive force, work-ing life between two-layer.Funke in 1976 etc. present a new concept---self stratifying coating.Self stratifying coating is made up of two kinds of (or multiple) inconsistent superpolymer, after coating is once constructed on ground, can spontaneously directly produce and be separated, the coating that in film process, is divided into two (or a plurality of) successive difference in functionalitys, form the different composite coating systems of forming, every layer demonstrates different characteristics.This once multilayer film of construction has not only reduced production cost, the more important thing is the ply adhesion problem that has solved the multiple pass coat system.
Since Funke in 1976 etc. at first develop the powder self stratifying coating, obtained extensive concern from theory of hierarchies.The Soviet Union was applied to solvent based coating to self stratifying coating in 1987, began to produce the solvent-borne type self stratifying coating, was used as having the two-layer enamel paint in bottom surface; 1989-1993, European Commission and European coating polymer company have carried out large-scale research to the theory and the application of self stratifying coating jointly, relate to the field and be mainly the solvent-borne type self stratifying coating, develop solvent-borne type epoxy-vinylformic acid, epoxy-chlorinated rubber, epoxy-self stratifying coatings such as fluoro-chloromethylated copolymer.And the posttension people hide etc. development from developments such as layering water-borne coatings, Hu Jianqing from the layering cathode electrophoresis dope.Do not see as yet from the layering epoxy. the report of organosilicon coating and no-solvent type self stratifying coating.
Summary of the invention
The objective of the invention is to utilize from demixing technology, develop a kind of solvent-free can be from the epoxy-organic silicon composition of multi-shell curing, this composition utilizes AUTOMATIC ZONING in the solidification process, Resins, epoxy sinks to the bottom, silicone resin is exposed to outside surface.This composition does not contain solvent, cured product have concurrently excellent adhesion of epoxy resin and organosilicon weather-proof with the low characteristics of surface energy, on the anticorrosion weather-proof and anticorrosion and antifouling coating of exploitation, have the potential application prospect.
The present invention is achieved through the following technical solutions: disclosed in this invention solvent-free can be from the epoxy of multi-shell curing. silicon composition is a two-pack, and the first component is made up of 20～240 parts of institutes of 100～0 parts of Resins, epoxy, 0～100 part of polyether modified epoxy epoxy resins, silicone resin; The second component is made up of 5～40 parts of amine curing agents, 1～16 part of organosilicon cross-linking agent and 0～0.05 part of institute of organosilicon crosslinked catalyzer, and wherein said adding umber is a weight part.
Described silicone resin is the poly-diorganosiloxane of terminal hydroxy group, and wherein, organic radical comprises: methyl, CF
3CH
2CH
2, phenyl etc.
The total add-on ratio range of described silicone resin add-on and Resins, epoxy and polyether modified epoxy epoxy resins is 1: 5～5: 1.
Described amine curing agent is amidoamines or polyetheramine or epoxy hardeners such as aromatic amine or ring grease amine, and preferred viscosities is lower than 3000cps/25 ℃, reactive hydrogen equivalent at 20～200 solidifying agent.
Described organosilicon cross-linking agent is siloxanes or the polysiloxane that contains three and three above functional groups.
Described organosilicon crosslinked catalyzer is a dibutyl tin dilaurate.
Described Resins, epoxy is not solvent-laden liquid-type Resins, epoxy, oxirane value 0.20～0.60eq/100g;
Oxirane value 0.20～the 0.60eq/100g of described polyether modified epoxy epoxy resins;
Described Resins, epoxy and polyether modified epoxy epoxy resins can be composite, also can use separately;
It is of the present invention that solvent-free can to form the invention effect from the epoxy-organic silicon of multi-shell curing as follows:
(1) can not contain solvent from the epoxy-organic silicon composition of multi-shell curing, have the asepsis environment-protecting advantage.
(2) after once constructing on ground, the curing along with filming is separated and spontaneous layering in wet film, and the transition layer of a gradual change is arranged.In the delaminating process, Resins, epoxy sinks to the bottom, and silicone resin is exposed to outside surface.
(3) after the curing, Resins, epoxy and solidifying agent generation crosslinking reaction form the superpolymer of tridimensional network, and molecular structure is comparatively tight, has good chemical-resistant, erosion resistance, and to base material sticking power excellence; Crosslinking reaction also takes place in silicone resin and its solidifying agent, has weather-proof and the low characteristics of surface energy.
Embodiment
The present invention is further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1:
Material proportion:
(1) first component:
Resins, epoxy: 100
Hydroxyl-terminated injecting two methyl siloxane: 120
(2) second component:
Amido amine: 30
Tetraethoxy: 8
Dibutyl tin dilaurate: 0.05
First component and second component (by above-mentioned weight ratio) are mixed, slaking half an hour (25 ℃) but after both applications.
Embodiment 2:
Material proportion:
(1) first component:
Polyether modified epoxy epoxy resins: 100
Hydroxyl-terminated injecting two methyl siloxane: 20
(2) second component:
Amido amine: 25
Ketoximinosilanes: 1
Dibutyl tin dilaurate: 0.02
First component and second component (by above-mentioned weight ratio) are mixed, slaking half an hour (25 ℃) but after both applications.
Embodiment 3:
Material proportion:
(1) first component:
Polyether modified epoxy epoxy resins: 20
Hydroxyl-terminated injecting two methyl siloxane: 100
(2) second component:
Amido amine: 5
Ketoximinosilanes: 5
Dibutyl tin dilaurate: 0.02
First component and second component (by above-mentioned weight ratio) are mixed, slaking half an hour (25 ℃) but after both applications.
Embodiment 4:
Material proportion:
(1) first component:
Resins, epoxy: 50
Polyether modified epoxy epoxy resins: 50
Hydroxyl-terminated injecting two methyl siloxane: 120
(2) second component:
Polyetheramine: 27.5
Ketoximinosilanes: 8
First component and second component (by above-mentioned weight ratio) are mixed, slaking half an hour (25 ℃) but after both applications.
Embodiment 5:
Material proportion:
(1) first component:
Resins, epoxy: 50
Polyether modified epoxy epoxy resins: 50
Hydroxyl-terminated injecting two methyl siloxane: 60
(2) second component:
Polyetheramine: 27.5
Methoxy silane: 4
Dibutyl tin dilaurate: 0.04
First component and second component (by above-mentioned weight ratio) are mixed, slaking half an hour (25 ℃) but after both applications.
Embodiment 6:
Material proportion:
(1) first component:
Resins, epoxy: 50
Polyether modified epoxy epoxy resins: 50
Hydroxyl-terminated injecting two methyl siloxane: 240
(2) second component:
Polyetheramine: 27.5
Ethoxysilane: 16
Dibutyl tin dilaurate: 0.05
First component and second component (by above-mentioned weight ratio) are mixed, get final product application after slaking half an hour (25 ℃).
Embodiment 7:
Material proportion:
(1) first component:
Resins, epoxy: 50
Polyether modified epoxy epoxy resins: 50
Terminal hydroxy group gathers diphenyl siloxane: 240
(2) second component:
Aromatic amine: 40
Ethoxysilane: 16
Dibutyl tin dilaurate: 0.05
First component and second component (by above-mentioned weight ratio) are mixed, get final product application after slaking half an hour (25 ℃).
Embodiment 8:
Material proportion:
(1) first component:
Resins, epoxy: 50
Polyether modified epoxy epoxy resins: 50
Terminal hydroxy group gathers diphenyl siloxane: 60
(2) second component:
Polyetheramine: 27.5
Tetraethoxy: 4
Dibutyl tin dilaurate: 0.04
First component and second component (by above-mentioned weight ratio) are mixed, slaking half an hour (25 ℃) but after both applications.
Embodiment 9:
Material proportion:
(1) first component:
Polyether modified epoxy epoxy resins: 50
Terminal hydroxy group gathers two (CF
3CH
2CH
2) siloxanes: 60
(2) second component:
Ring grease amine: 23
Ketoximinosilanes: 4
Dibutyl tin dilaurate: 0.02
First component and second component (by above-mentioned weight ratio) are mixed, slaking half an hour (25 ℃) but after both applications.
Embodiment 10:
Material proportion:
(1) first component:
Resins, epoxy: 50
Polyether modified epoxy epoxy resins: 50
Terminal hydroxy group gathers two (CF
3CH
2CH
2) siloxanes: 120
(2) second component:
Aromatic amine: 40
Ketoximinosilanes: 8
Claims (4)
- One kind solvent-free can be from the epoxy-organic silicon composition of multi-shell curing, it is characterized in that: described solvent-free can be two-pack from the epoxy-organic silicon composition of multi-shell curing, the first component is made up of 20～240 parts of institutes of 100～0 parts of Resins, epoxy, 0～100 part of polyether modified epoxy epoxy resins, silicone resin; The total add-on ratio range of described silicone resin add-on and Resins, epoxy and polyether modified epoxy epoxy resins is 1: 5～5: 1; Described silicone resin is the poly-diorganosiloxane of terminal hydroxy group, and wherein, organic radical comprises: methyl or CF 3CH 2CH 2Or phenyl; The second component is made up of 5～40 parts of amine curing agents, 1～16 part of organosilicon cross-linking agent and 0～0.05 part of institute of organosilicon crosslinked catalyzer, and wherein said adding umber is a weight part.
- 2. solvent-free can it is characterized in that from the epoxy-organic silicon composition of multi-shell curing according to claim 1: described amine curing agent is amidoamines or polyetheramine or aromatic amine or ring grease amine epoxy curing agent.
- 3. solvent-free can it is characterized in that from the epoxy-organic silicon composition of multi-shell curing according to claim 1: described organosilicon cross-linking agent is siloxanes or the polysiloxane that contains three and three above functional groups.
- 4. solvent-free can it is characterized in that from the epoxy-organic silicon composition of multi-shell curing according to claim 1: described organosilicon crosslinked catalyzer is a dibutyl tin dilaurate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100490700A CN101235186B (en) | 2008-01-03 | 2008-01-03 | Solvent-free epoxy-organic silicon composition capable of self-layering and curing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100490700A CN101235186B (en) | 2008-01-03 | 2008-01-03 | Solvent-free epoxy-organic silicon composition capable of self-layering and curing |
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| CN101235186A CN101235186A (en) | 2008-08-06 |
| CN101235186B true CN101235186B (en) | 2010-08-11 |
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| US8093423B2 (en) | 2003-02-19 | 2012-01-10 | Globoasia, Llc | Pharmaceutical-grade ferric organic compounds, uses thereof and method of making same |
| TWI335218B (en) | 2003-02-19 | 2011-01-01 | Panion & Bf Biotech Inc | Ferric organic compounds, uses thereof and methods of making same |
| CN105616397A (en) | 2006-01-30 | 2016-06-01 | 宝龄富锦生技股份有限公司 | Method of treating chronic kidney disease |
| CN102573807A (en) | 2009-07-21 | 2012-07-11 | 凯克斯生物制药公司 | Ferric citrate dosage forms |
| CN102532809A (en) * | 2011-11-17 | 2012-07-04 | 杭州师范大学 | Organosilicon-epoxy resin composition and preparation method thereof |
| CN103805028B (en) * | 2014-02-20 | 2015-12-30 | 中国船舶重工集团公司第七二五研究所 | A kind of solvent-free antifouling paint compound method for underwater construction |
| CN107760167B (en) * | 2017-11-27 | 2020-04-17 | 中科院广州化学有限公司南雄材料生产基地 | Water-based epoxy coating containing polyether modified water-based epoxy resin and preparation method thereof |
| CN107964333B (en) * | 2017-12-29 | 2020-01-17 | 中科院广州化学有限公司 | Amino-terminated reactive fluorine-containing polymer modified waterborne epoxy coating and preparation and application thereof |
| CN110964407B (en) * | 2019-11-15 | 2022-01-28 | 中国船舶重工集团公司第七二五研究所 | Anticorrosion and antifouling integrated coating for coating repair and preparation method thereof |
| CN111645371A (en) * | 2020-06-12 | 2020-09-11 | 安徽名士达新材料有限公司 | High-wear-resistance water-based paint film and preparation method thereof |
| CN115466533B (en) * | 2022-08-25 | 2023-11-10 | 中远关西涂料（上海）有限公司 | Preparation method of elastic self-layering methyl methacrylate protective material |
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