CN102634002A - Preparation method and application of flexible aminosilane curing agent - Google Patents
Preparation method and application of flexible aminosilane curing agent Download PDFInfo
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- CN102634002A CN102634002A CN201210118207XA CN201210118207A CN102634002A CN 102634002 A CN102634002 A CN 102634002A CN 201210118207X A CN201210118207X A CN 201210118207XA CN 201210118207 A CN201210118207 A CN 201210118207A CN 102634002 A CN102634002 A CN 102634002A
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Abstract
The invention discloses a preparation method and application of a flexible aminosilane curing agent. The preparation method is characterized in that polyether amine A and a silane coupling agent B react in a molar ratio of 1: (1-N) to obtain flexible aminosilane; the polyether amine A contains 1-N (N is a natural number more than or equal to 1) amino groups, such as amino group or imino group or amino group and imino group; the amino group can be positioned on the end group or the side chain of a molecular chain or positioned both on the end group and the side chain; the molecular chain contains a certain quantity of aliphatic ether chain links, and the molecular weight is 100-2000; the silane coupling agent B contains one group which can react with the amino group; the reaction temperature of the group and the amino group is 20-120DEG C; and the reaction time is 1-8 hours. The preparation method has the advantages of simple technology, high production efficiency and no side product. When aminosilane is used as the curing agent of epoxy/acrylate polysiloxane paint, the flexibility of the coating is obviously improved, the shock resistance of the coating is effectively improved, and the internal stress of the coating is lowered, so as to prolong the service life of the paint.
Description
Technical field
The invention belongs to field of fine chemical, be specifically related to a kind of preparation method and application in epoxy/acrylic acid ester polysiloxane coating materials of snappiness aminosilane solidifying agent.
Background technology
The protective system that is used for large scale industry steelwork such as offshore platform, wind-powered electricity generation tower, bridge belongs to ultra weather-proof heavy-duty coating, and work-ing life, this satisfied these harsh requirements with regard to needing the more outstanding coating of each item performance at least more than 10 years.
In the heavy duty system field, polysiloxane coating materials is because its low VOC, and height contains admittedly, does not contain isocyanic ester, and is less to the influence of HUMAN HEALTH and environment, has excellent performance such as ageing-resistant corrosion-resistant simultaneously and has obtained increasing application.Chinese patent CN 1618907, U.S. Pat 4250074 etc. have been announced the preparation method and the application of polysiloxane coating materials.
But a tangible deficiency of polysiloxane coating materials is that snappiness is not good, is prone to crisp.Therefore the stress concentration owing to coating may cause the damage of filming perhaps to come off in long application process, reduces the protection effect and the life-span of coating thus greatly.U.S. Pat 7125609 improves its snappiness through the solidifying agent that uses flexible good polyetheramine to do epoxy polysiloxane coating, if but use polyetheramine to make solidifying agent separately can only the cured epoxy component, and the ZGK 5 component is difficult to abundant curing.If polyetheramine and common aminosilane are mixed the change of piecing together,, will influence the raising of the crosslinked film forming of homogeneous with the final performance of resin because the speed of response of these two types of solidifying agent is different.
The present invention is through polyetheramine and the silane coupling agent pre-reaction that snappiness is splendid; Prepare the outstanding aminosilane solidifying agent of a kind of snappiness, wherein amino group can react with epoxide group or the acrylate group in the coating host, and siloxanes then can solidify the ZGK 5 component; Make full cross-linked film forming between epoxy/acrylic acid component and the ZGK 5 component like this; Can more effectively improve the snappiness of epoxy/acrylic acid ester polysiloxane coating materials, obviously improve shock-resistance, can not reduce simultaneously and improve abrasion property and hardness; And reduce the internal stress of coating, increase the service life.Can better meet the requirement of large scale industry steelwork heavy corrosion coating such as offshore platform atmospheric zone, oil tank, wind power plant, bridge, boats and ships.
Summary of the invention
The object of the invention is, a kind of preparation method and application thereof of snappiness aminosilane solidifying agent are provided.
For realizing above-mentioned purpose, technical scheme provided by the present invention is:
The preparation method of snappiness aminosilane solidifying agent may further comprise the steps:
At polyetheramine A and silane coupling agent B is that 1:1 ~ 1:N (N is the quantity of amido among the polyetheramine A) mixes in molar ratio, under heating condition, fully mixes, and the reaction of process certain hour obtains snappiness aminosilane solidifying agent.
Containing the individual amido of 1 ~ N (N is >=1 natural number) in the described polyetheramine A molecule, can be that amino also can be that imino-or existing amino have imino-again; Amido can be positioned at the end group of molecular chain or on the side chain of molecular backbone chain or both at end group also on side chain; The aliphatic ether chain link that contains some amount simultaneously in the molecular chain; Molecular weight is between 100-2000.
For guaranteeing reactive behavior preferably, preferably contain 2 amino groups, amino is positioned at the end group of molecular chain or the polyetheramine A on second carbon atom of molecular backbone chain.Contain a certain amount of aliphatic ether chain link among the polyetheramine A simultaneously, like T 46155, polyoxypropylene, polyoxy butylene, the perhaps arbitrary combination between them.The quantity of regulating the aliphatic ether chain link changes the molecular weight of polyetheramine A, and the molecular weight of polyetheramine A is too low to mean that the aliphatic ether chain link is less, and then snappiness reduces, and molecular weight is too high to mean that the aliphatic ether chain link is more, can cause resin too soft, and hardness is lower.The molecular weight of polyetheramine A is between 100-2000, preferably between 200-1000.Include but not limited to the JEFFAMINE series polyetheramine of HUNTSMAN, like D-230, D400, T403, THF-100, D-2000 etc.
The molecular formula of silane coupling agent B is Y
4-a-Si-(O-X)
aThe group that contains the reaction of 1 ability and amido; Comprise epoxide group or hydroxy-acid group or anhydride group or acid chloride groups or vinyl cyanide group or acrylate group or methacrylate based group or kiki alkenyl group or isocyanate groups; Preferred silane coupling agent B contains 1 epoxide group, like the glycidyl ether oxygen base; X is alkyl, hydroxyalkyl, alkoxyalkyl or the hydroxy alkoxy alkyl that is not more than 6 carbon atoms, and preferred X is methyl or ethyl; A>=1 wherein.Include but not limited to KH-560, KH-561 etc.
The reaction ratio of polyetheramine A and silane coupling agent B is to make among the silane coupling agent B to be consumed by amido fully with the group of amido reaction, like this can be with chemical bonded refractory altogether between polyetheramine A and the silane coupling agent B.For example as the polyetheramine A that contains 2 amino with contain when reacting between the silane coupling agent B of 1 glycidyl ether oxygen base, their mol ratio can be 1:1 or 1:2.When polyetheramine: during epoxy silane coupling agent=1:1,1 amino in the polyetheramine and epoxide group reaction contain an amino and an imino-in the product that obtains.When polyetheramine: during epoxy silane coupling agent=1:2,2 amino in the polyetheramine all by the epoxide group reaction, contain 2 imino-s in the product that obtains.
The temperature of reaction of polyetheramine A and silane coupling agent B is between 20-120 ℃, and the reaction times is 1-8 hour, can use rare gas element such as nitrogen or argon shield between the reaction period.
The snappiness aminosilane that the present invention prepares can be used as the solidifying agent of epoxy/acrylic acid ester polysiloxane coating materials, compares the snappiness that can obviously improve coating with conventional solidifying agent such as aminosilane, reduces internal stress.
The prepared snappiness aminosilane solidifying agent according to the present invention, its condition of cure can be a room temperature, is that 5～50 ℃, relative humidity are 10%～80% like temperature; Also can baking-curing, as 120 ℃ of bakings 1 hour down.Because the performance of baking-curing coating generally is superior to the coating of self-vulcanizing; So preferred baking-curing of the present invention; Baking condition toasted 10-60 minute down at 50-70 ℃ at first at room temperature placing 10-30 minute then, toasted 1-2 hour down at 100-120 ℃ at last.
Advantage of the present invention is: preparing method's technology provided by the invention is simple, and production efficiency is high, does not have by product; The snappiness aminosilane that utilizes the present invention to prepare can obviously improve impact resistance when making the solidifying agent of epoxy/acrylic acid ester polysiloxane coating materials, reduces the internal stress of coating, increases the service life greatly.Be suitable for the requirement for anticorrosion of large scale industry steelwork such as offshore platform, oil tank outer wall, wind-powered electricity generation tower, bridge, boats and ships.
Below in conjunction with several embodiments, further specify the present invention.
Embodiment
First embodiment: the preparation of snappiness aminosilane solidifying agent 1.
With 50 the gram polyetheramine D230, join in the 250ml round-bottomed flask, be warmed up to 65 ℃, turn on agitator, slowly drip 49 the gram KH-560, under the nitrogen protection, under 65 ℃ of conditions the reaction 3 hours, obtain the thick snappiness aminosilane 1 of transparent faint yellow.Wherein KH-560 has consumed 1 amino among the D230.
Second embodiment, the preparation of snappiness aminosilane solidifying agent 2.
With 50 the gram polyetheramine D230, join in the 250ml round-bottomed flask, be warmed up to 75 ℃, turn on agitator, slowly drip 98 the gram KH-560, under the nitrogen protection, under 75 ℃ of conditions the reaction 3 hours, obtain the thick snappiness aminosilane 2 of transparent faint yellow.Wherein KH-560 has consumed 2 amino among the D230.
The 3rd embodiment, the preparation of snappiness aminosilane solidifying agent 3.
Polyetheramine D400 with 50 grams joins in the 250ml round-bottomed flask, is warmed up to 85 ℃; Turn on agitator, slowly drip 25.7 the gram KH-560, under the nitrogen protection; Reaction is 4 hours under 85 ℃ of conditions, obtains the thick snappiness aminosilane 3 of transparent faint yellow.Wherein KH-560 has consumed 1 amino among the D400.
The 4th embodiment, the preparation of snappiness aminosilane solidifying agent 4.
Polyetheramine D400 with 50 grams joins in the 250ml round-bottomed flask, is warmed up to 95 ℃; Turn on agitator, the KH-560 of slow Dropwise 5 1.4 grams is under the nitrogen protection; Reaction is 4 hours under 95 ℃ of conditions, obtains the thick snappiness aminosilane 4 of transparent faint yellow.Wherein KH-560 has consumed 2 amino among the D400.
The chemical graft reaction has taken place in KH-560 and polyetheramine among each embodiment of FT-IR test shows.
Comparative Examples is to use conventional aminosilane solidifying agent KH-550.
Of the above embodiment of the present invention, adopt technical characterictic same or similar and other preparation method of obtaining, all in protection domain of the present invention with it.
Below be the The performance test results that adopts the inventive method to obtain, the test ground is the sandblast steel plate, and priming paint is epoxy zinc rich primer, and build is 40-50 μ m; Finish paint is an epoxy polysiloxane coating, and wherein Ahew in the solidifying agent and the epoxy equivalent (weight) ratio in the host are 1:1.The build of finish paint is at 40-50 μ m, and drying conditions is under the room temperature dry 20 minutes, 60 ℃ dry 20 minutes down, 120 ℃ dry 1 hour down.Carry out each item performance test after 7 days.The result is as shown in table 1.
Table 1 snappiness aminosilane curing agents test result
Of the above embodiment of the present invention, adopt technical characterictic same or similar and other preparation method and the coating that obtain, all in protection domain of the present invention with it.
Claims (5)
1. the preparation method of snappiness aminosilane solidifying agent is characterized in that the technological process of this method is following:
With polyetheramine A and silane coupling agent B is that 1:1 ~ 1:N mixes in molar ratio, and N is the quantity of amido among the polyetheramine A, under heating condition, fully stirs the mixture, and can obtain snappiness aminosilane solidifying agent through after the reaction of certain hour.
2. the preparation method of snappiness aminosilane solidifying agent according to claim 1 is characterized in that, comprises 1 ~ N amido in the described polyetheramine A molecule, N is >=1 natural number can be that amino also can be that imino-or existing amino have imino-again; Amido can be positioned on the side chain of end group or molecular backbone chain of molecular chain or both at end group also on side chain; The aliphatic ether chain link that contains some amount simultaneously in the molecular chain; The molecular weight that the aliphatic ether chain link of adjusting different quantities makes polyetheramine includes but not limited to JEFFAMINE series polyetheramine between 100-2000.
3. the preparation method of snappiness aminosilane solidifying agent according to claim 1 is characterized in that the molecular formula of described silane coupling agent B is Y
4-a-Si-(O-X)
a, contain 1 ability and the group that amido reacts, comprise epoxide group or hydroxy-acid group or anhydride group or acid chloride groups or vinyl cyanide group or acrylate group or methacrylate based group or kiki alkenyl group or isocyanate groups; X is alkyl, hydroxyalkyl, alkoxyalkyl or the hydroxy alkoxy alkyl that is not more than 6 carbon atoms; A>=1 wherein.
4. the preparation method of snappiness aminosilane solidifying agent according to claim 1 is characterized in that, described temperature of reaction is between 20-120 ℃, and the reaction times is 1-8 hour, can blanketing with inert gas between the reaction period.
5. the application of snappiness aminosilane solidifying agent; It is characterized in that; Prepared snappiness aminosilane can be used as the solidifying agent of epoxy/acrylic acid ester polysiloxane coating materials, and this coating can be used for preparing the long-acting coating of heavy anticorrosive of offshore oil platform, bridge, petroleum storage tank, industrial premises, wind-powered electricity generation tower, ship superstructure.
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| CN201210118207XA CN102634002A (en) | 2012-04-23 | 2012-04-23 | Preparation method and application of flexible aminosilane curing agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724368A (en) * | 2014-01-09 | 2014-04-16 | 嘉兴学院 | Preparation method of amino polyether-type silanization reagent |
| CN105255240A (en) * | 2015-11-05 | 2016-01-20 | 浩力森涂料（上海）有限公司 | Corrosion prevention additive and electrophoretic coating for highly preventing corrosion of edges |
| CN106637998A (en) * | 2016-10-18 | 2017-05-10 | 佛山市传化富联精细化工有限公司 | Hydrophilic ice-sense silicone oil and preparation method thereof |
| CN108504102A (en) * | 2018-04-24 | 2018-09-07 | 厦门万新橡胶有限公司 | A kind of low friction two-component crosslinked fluid silica gel |
| CN114672220A (en) * | 2022-04-07 | 2022-06-28 | 漳州鑫展旺化工有限公司 | Ultra-long salt-spray-resistant water-based epoxy primer and preparation method and use method thereof |
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| CN101977918A (en) * | 2008-03-20 | 2011-02-16 | 亨茨曼纺织货品（德国）有限责任公司 | Silanes and polysiloxanes |
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- 2012-04-23 CN CN201210118207XA patent/CN102634002A/en active Pending
Patent Citations (1)
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| CN101977918A (en) * | 2008-03-20 | 2011-02-16 | 亨茨曼纺织货品（德国）有限责任公司 | Silanes and polysiloxanes |
Non-Patent Citations (2)
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| 《涂料工业》 20110131 李宏静等 "有机硅聚醚胺增韧改性环氧树脂的研究" 9-12 1-5 第41卷, 第1期 * |
| 李宏静等: ""有机硅聚醚胺增韧改性环氧树脂的研究"", 《涂料工业》, vol. 41, no. 1, 31 January 2011 (2011-01-31), pages 9 - 12 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724368A (en) * | 2014-01-09 | 2014-04-16 | 嘉兴学院 | Preparation method of amino polyether-type silanization reagent |
| CN105255240A (en) * | 2015-11-05 | 2016-01-20 | 浩力森涂料（上海）有限公司 | Corrosion prevention additive and electrophoretic coating for highly preventing corrosion of edges |
| CN106637998A (en) * | 2016-10-18 | 2017-05-10 | 佛山市传化富联精细化工有限公司 | Hydrophilic ice-sense silicone oil and preparation method thereof |
| CN106637998B (en) * | 2016-10-18 | 2019-04-30 | 广东传化富联精细化工有限公司 | A kind of hydrophilic ice-feeling silicone oil and preparation method thereof |
| CN108504102A (en) * | 2018-04-24 | 2018-09-07 | 厦门万新橡胶有限公司 | A kind of low friction two-component crosslinked fluid silica gel |
| CN114672220A (en) * | 2022-04-07 | 2022-06-28 | 漳州鑫展旺化工有限公司 | Ultra-long salt-spray-resistant water-based epoxy primer and preparation method and use method thereof |
| CN114672220B (en) * | 2022-04-07 | 2022-11-15 | 漳州鑫展旺化工有限公司 | Ultra-long salt-spray-resistant water-based epoxy primer and preparation method and use method thereof |
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Application publication date: 20120815 |