CN104910203B - A kind of glass surface hydrophobic modifier and its synthetic method - Google Patents
A kind of glass surface hydrophobic modifier and its synthetic method Download PDFInfo
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- CN104910203B CN104910203B CN201510246902.8A CN201510246902A CN104910203B CN 104910203 B CN104910203 B CN 104910203B CN 201510246902 A CN201510246902 A CN 201510246902A CN 104910203 B CN104910203 B CN 104910203B
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- glass surface
- glass
- hydrophobic modifier
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Abstract
A kind of glass surface hydrophobic modifier of the present invention, using s-triazine as core, peripheral end group is six hydrophobic alkyl end groups and a coupled base, its structural formula are：In formula：R1For the alkyl of 4 12 carbon；R2For methyl or ethyl；The synthetic method of the glass surface hydrophobic modifier contains following steps：(1) component prepares；(2) react；(3) add 3 aminopropyltrialkoxy silanes and continue back flow reaction；(4) remove organic solvent and wash, obtain glass surface hydrophobic modifier.The hydrophobic modifier of the present invention is using Cyanuric Chloride cheap and easy to get as raw material, six alkyl chains are successively introduced as hydrophobic ending group and an organosiloxane as the coupling end group with glass, the hydrophobically modified of glass surface can be carried out under the conditions of simplicity, contact angle of the water on its surface can reach 90oMore than, there is good hydrophobicity and glass transmission rate.Synthetic method raw material of the invention is cheap, synthesis condition is gentle, the simple yield of technique is high, and application prospect is good.
Description
Technical field
The invention belongs to technical field of fine, and in particular to a kind of glass surface hydrophobic modifier and its synthesis side
Method.
Background technology
Glass is the very extensive a kind of material used at present, available for build, building decoration, automobile making, electronics
Many fields such as display and photovoltaic device.The surface of simple glass is usually the water-wetted surface of high surface energy.It is general after being contacted with water
The surface energy of logical glass has larger reduction, thus can be soaked by water.It is but rough, no due to simple glass
Uniformly so that water droplet on the surface of inclined simple glass after advancing angle occurs and laggard angle is unequal sticks.Water droplet
Stick can cause the translucency of glass it is poor, flash of light, pickup situations such as, influence glass automobile, building decoration, electronical display and
The application in the fields such as photovoltaic device.
Produced to solve the problems, such as water droplet to be attached on glass, typically now using the method for the plated film on glass.Glass
Glass plated film makes to carry hydrophobic film on glass, turns into Hydrophobic glass.After water is dropped on inclined Hydrophobic glass, due to hydrophobic thin
Film reduces the adhesion between glass and water droplet, it is thus possible to water droplet is slided rapidly from glass in the presence of self gravitation
Fall.Present coating technique has：Alumina formwork method, chemical vapour deposition technique, sol-gel process etc..Due to after coating film on glass its
Translucency can reduce, and can influence its application in some fields；Or need to take special anti-reflection technology, such production cost
Improve again.It can so accomplish simple glass being converted into Hydrophobic glass, carry out the same of surface of ordinary glass hydrophobically modified
When do not influence the translucency of glass againHere, just turn into simple glass using suitable glass surface hydrophobic modifier to convert
For the key of Hydrophobic glass.
The content of the invention
It is an object of the invention to solve the above problems, there is provided a kind of glass surface hydrophobic modifier --- s-triazine is dredged
Water modifying agent, it successively introduces six alkyl chains as hydrophobic ending group and one using Cyanuric Chloride cheap and easy to get as raw material
Organosiloxane can carry out glass surface hydrophobically modified as the coupling end group with glass under the conditions of simplicity, modified
Glass, contact angle of the water on its surface can reach 90oMore than, there is good hydrophobicity.The second object of the present invention is to carry
For the synthetic method of the glass surface hydrophobic modifier.
To achieve the above object, this invention takes following technical scheme.
A kind of glass surface hydrophobic modifier, it is characterised in that using s-triazine as core, peripheral end group is six hydrophobic alkyls
End group and a coupled base, its structural formula are：
In formula：
R1For the alkyl of 4-12 carbon；
R2For methyl or ethyl.
To realize above-mentioned second purpose, this invention takes following technical scheme.
A kind of synthetic method of glass surface hydrophobic modifier, it is characterised in that contain following steps：
（1）Component prepares
Under nitrogen atmosphere, into the reactor with reflux add 1 times of mole Cyanuric Chloride, 2 times moles
The three of amount-（2- alkoxy carbonyl group ethoxymethyls）- methylamine, the potassium carbonate of 4 times of moles and dioxane are as solvent, by above-mentioned original
Material mixing；
（2）Reaction
By step（1）Mixed material first under 0 DEG C of ice-water bath react 1h；Then 2h is reacted at room temperature；Back flow reaction again
20h；
（3）Add 3- aminopropyltrialkoxy silanes and continue back flow reaction
In step（2）The 3- aminopropyltrialkoxy silanes of 5 times of moles are added on the basis of reactant, continue to flow back
React 10h；
（4）Remove organic solvent and wash
Decompression boils off organic solvent and dioxane and the 3- aminopropyltrialkoxy silanes of excess, then successively uses water
Impurity is removed with petroleum ether, obtains glass surface hydrophobic modifier --- 2-（3- alkoxy silane Propylaminos）- 4,6- two-
[three-（2- alkoxy carbonyl group ethoxyl methyls）- methylamino]-[1,3,5]-triazine；
The chemical equation of the synthetic method is：
。
Further, step（1）Described three-（2- alkoxy carbonyl group ethoxymethyls）- methylamine is the tert-butyl alcohol in C4-C12 alcohol esters
Ester, hexamethylene alcohol ester, one kind of isooctanol ester or lauryl alcohol ester.
Further, step（3）Described 3- aminopropyltrialkoxy silanes are one in methoxyl group or ethyoxyl
Kind.
The positive effect of the present invention is：
（1）The glass surface hydrophobic modifier of the present invention successively introduces six using Cyanuric Chloride cheap and easy to get as raw material
Alkyl chain, as the coupling end group with glass, can be carried out as hydrophobic ending group and an organosiloxane under the conditions of simplicity
The hydrophobically modified of glass surface.
（2）Using the modified glass of the glass surface hydrophobic modifier of the present invention, light transmittance is unaffected, and water is in its table
The contact angle in face can reach 90oMore than, there is good hydrophobicity.
（3）Synthetic method raw material of the invention is cheap, synthesis condition is gentle, technique is simple, yield is high, has applications well
Prospect.
Brief description of the drawings
Fig. 1 is a kind of FB(flow block) of the synthetic method of glass surface hydrophobic modifier of the present invention.
Fig. 2 is water in the contact angle without modifying agent glass surface.
Fig. 3 is contact angle of the water on modifying agent I-1 modified glass surface.
Fig. 4 is contact angle of the water on modifying agent I-2 modified glass surface.
Fig. 5 is contact angle of the water on modifying agent I-3 modified glass surface.
Fig. 6 is contact angle of the water on modifying agent I-4 modified glass surface.
Fig. 7 is contact angle of the water on modifying agent I-5 modified glass surface.
Embodiment
The specific embodiment party of a kind of glass surface hydrophobic modifier of the present invention and its synthetic method is provided below in conjunction with accompanying drawing
Formula, there is provided 5 embodiments and 1 Application Example.It should be noted that the implementation of the present invention is not limited to following embodiment party
Formula.
Embodiment 1
A kind of synthetic method of glass surface hydrophobic modifier, contains following steps：
（1）Component prepares
3.69g is sequentially added in 1000mL three-necked flasks（20mmol）Cyanuric Chloride, 11.2g（80mmol）Carbon Dioxide
Potassium, then 400mL dioxane is added under nitrogen protection, under ice-water bath cooling, then 20.2g is added dropwise（40mmol）Three-[（2-
Tert-butoxycarbonyl ethyoxyl）- methyl]-methylamine dioxane（100mL）Solution, above-mentioned raw materials are mixed.
（2）Reaction
By step（1）Mixed material first under 0 DEG C of ice-water bath react 1h；Then 2h is reacted at room temperature；Back flow reaction again
20h。
（3）Add 3- aminopropyltrialkoxy silanes and continue back flow reaction
In step（2）3- aminopropyls three are added on the basis of reactant（Ethyoxyl）Silane 22.5g（100mmol）'s
100mL dioxane solutions, back flow reaction 10h.
（4）Remove organic solvent and wash
Organic solvent and dioxane and the 3- aminopropyl triethoxysilanes of excess is removed under reduced pressure, then successively uses water
No longer reduced with petroleum ether residue to weight, obtain the glass surface hydrophobic modifier 20.1g of yellow mucus shape, yield
For 77%, numbering is modifying agent I-1.
The chemical equation of the synthetic method is：
。
The glass surface hydrophobic modifier synthesized using NMR spectrum method to embodiment 1 is detected, detection knot
Fruit is：
1H NMR(CDCl3, 400MHz, 25℃), δ(ppm): 3.86-3.78(m, 18H), 3.64(t, J =
6.4Hz, 12H), 3.31(d, J = 4.8Hz, 2H), 2.45(t, J = 10.4Hz, 12H), 1.44(s, 56H),
1.23(t, J = 7.2Hz, 9H), 0.53(t, J=7.0Hz, 2H)。
13C NMR(CDCl3, 100MHz, 25℃), δ(ppm): 171.9, 165.4, 80.3, 69.6, 67.0,
59.3, 58.4, 36.3, 28.3, 28.1, 23.2, 18.3, 7.8, 0.01。
Embodiment 2
A kind of synthetic method of glass surface hydrophobic modifier, contains following steps：
（1）Component prepares
Substantially it is distinguishing to be with embodiment 1：
Described three-（2- alkoxy carbonyl group ethoxymethyls）- methylamine is tert-butyl alcohol ester 22.5g.
（2）Reaction（With embodiment 1）.
（3）Add 3- aminopropyltrialkoxy silanes and continue back flow reaction
Substantially it is distinguishing to be with embodiment 1：
In step（2）3- aminopropyl trimethoxy silane 17.8g is added on the basis of reactant.
（4）Remove organic solvent and wash
Substantially with embodiment 1, the glass surface hydrophobic modifier 19.2g of yellow mucus shape is obtained, yield 76%, is numbered
For modifying agent I-2.
Embodiment 3
A kind of synthetic method of glass surface hydrophobic modifier, contains following steps：
（1）Component prepares
Substantially it is distinguishing to be with embodiment 1：
Described three-（2- alkoxy carbonyl group ethoxymethyls）- methylamine is hexamethylene alcohol ester 23.4g.
（2）Reaction（With embodiment 1）.
（3）Add 3- aminopropyltrialkoxy silanes and continue back flow reaction（With embodiment 1）.
（4）Remove organic solvent and wash
Substantially with embodiment 1, the glass surface hydrophobic modifier 21.5g of yellow mucus shape is obtained, yield 73%, is numbered
For modifying agent I-3.
Embodiment 4
A kind of synthetic method of glass surface hydrophobic modifier, contains following steps：
（1）Component prepares
Substantially it is distinguishing to be with embodiment 1：
600mL dioxane is added under nitrogen protection；
Described three-（2- alkoxy carbonyl group ethoxymethyls）- methylamine is isooctanol ester 27.0g.
（2）Reaction（With embodiment 1）.
（3）Add 3- aminopropyltrialkoxy silanes and continue back flow reaction（With embodiment 1）.
（4）Remove organic solvent and wash
Substantially with embodiment 1, the glass surface hydrophobic modifier 24.6g of yellow mucus shape is obtained, yield 75%, is numbered
For modifying agent I-4.
Embodiment 5
A kind of synthetic method of glass surface hydrophobic modifier, contains following steps：
（1）Component prepares
Substantially it is distinguishing to be with embodiment 1：
600mL dioxane is added under nitrogen protection；
Described three-（2- alkoxy carbonyl group ethoxymethyls）- methylamine is lauryl alcohol ester 33.5g.
（2）Reaction（With embodiment 1）.
（3）Add 3- aminopropyltrialkoxy silanes and continue back flow reaction（With embodiment 1）.
（4）Remove organic solvent and wash
Substantially with embodiment 1, the glass surface hydrophobic modifier 26.5g of yellow mucus shape is obtained, yield 67%, is numbered
For modifying agent I-5.
Embodiment 1-5 composite result is shown in Table 1.
The synthesis list of the glass surface hydrophobic modifier of 1. embodiment of table 1~5
。
Application Example 1
The application for the glass surface hydrophobic modifier that the present invention synthesizes, comprises the following steps：
（1）First, with alternately cleaning surface of ordinary glass 3 times of absolute ethyl alcohol and acetone, each scavenging period is 3 minutes.
（2）Then, by step（1）The glass of cleaning is placed in volume ratio as 1:3 hydrogen peroxide（30%）With the concentrated sulfuric acid（98%）
Mixed solution in clean 15 minutes；It is cleaned by ultrasonic 3 times with deionized water again, then hot blast drying.
（3）Again by step（2）The glass immersion of drying pH value be 6, glass that the present invention containing 0.1mol/L synthesizes
1 hour in glass surface hydrophobicity modifying agent numbering I-1~I-5 dioxane solution.
（4）Finally, by step（3）The sheet glass handled well takes out, clear with dichloromethane, ethanol and deionized water successively
Glass surface is washed, hot blast drying, obtains the glass of surface hydrophobicity modification.
The test result for the glass that the surface hydrophobicity that is obtained to Application Example 1 is modified is：
With the contact angle of the modified glass surface of the glass surface hydrophobic modifier of invention synthesis 75.5~95.1oIt
Between, and contact angle before modified is 21.4o；The light transmittance of 550nm visible light wavelengths is basically unchanged afterwards before modification, referring to table 2.
The reclaimed water of 2. Application Example of table 1 and the contact angle and glass transmission rate on modified glass surface
。
Application Example 1 proves：The modified surface of glass surface hydrophobic modifier of the simple glass through the present invention is thin
Aqueous surface simultaneously has preferable glass transmission rate.
Claims (2)
1. a kind of glass surface hydrophobic modifier, it is characterised in that using s-triazine as core, peripheral end group is six hydrophobic alkyl ends
Base and a coupled base, its structural formula are：
In formula：
R1For the alkyl of 4-12 carbon；
R2For methyl or ethyl.
2. a kind of synthetic method of glass surface hydrophobic modifier as claimed in claim 1, it is characterised in that contain following step
Suddenly：
(1) component prepares
Under nitrogen atmosphere, the Cyanuric Chloride of 1 times of mole, 2 times of moles are added into the reactor with reflux
Three-(2- alkoxy carbonyl groups ethoxymethyl)-methylamines, the potassium carbonate of 4 times of moles and dioxane mix above-mentioned raw materials as solvent
Close；
Described three-(2- alkoxy carbonyl groups ethoxymethyl)-methylamine is tert-butyl alcohol ester in C4-C12 alcohol esters, hexamethylene alcohol ester, isooctanol
One kind of ester or lauryl alcohol ester；
(2) react
The mixed material of step (1) is first reacted into 1h under 0 DEG C of ice-water bath；Then 2h is reacted at room temperature；Back flow reaction 20h again；
(3) 3- aminopropyltrialkoxy silanes are added and continues back flow reaction
The 3- aminopropyltrialkoxy silanes of 5 times of moles are added on the basis of step (2) reactant, continue back flow reaction
10h；
(4) remove organic solvent and wash
Decompression boils off organic solvent and dioxane and the 3- aminopropyltrialkoxy silanes of excess, then priority water and stone
Oily ether washing removes impurity, obtains glass surface hydrophobic modifier --- and 2- (3- alkoxy silanes Propylamino) -4,6- bis--[three -
(2- alkoxy carbonyl groups ethoxyl methyl)-methylamino]-[1,3,5]-triazine；
The chemical equation of the synthetic method is：
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| CN201510246902.8A CN104910203B (en) | 2015-05-13 | 2015-05-13 | A kind of glass surface hydrophobic modifier and its synthetic method |
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| CN104910203A CN104910203A (en) | 2015-09-16 |
| CN104910203B true CN104910203B (en) | 2018-03-06 |
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| CN116143728A (en) * | 2022-10-18 | 2023-05-23 | 智仑超纯环氧树脂(西安)有限公司 | Reactive epoxy hydrophobic modifier and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158364A (en) * | 1995-10-26 | 1997-09-03 | 默克专利股份有限公司 | Material for and method of preparing water-repellent coatings on optical substrates |
| US20050106068A1 (en) * | 2003-11-18 | 2005-05-19 | Abdul Malik | Sol-gel dendron separation and extraction capillary column |
| CN102952158A (en) * | 2012-10-26 | 2013-03-06 | 大连理工大学 | Triazine type siloxane surface modifier and preparation method thereof |
-
2015
- 2015-05-13 CN CN201510246902.8A patent/CN104910203B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158364A (en) * | 1995-10-26 | 1997-09-03 | 默克专利股份有限公司 | Material for and method of preparing water-repellent coatings on optical substrates |
| US20050106068A1 (en) * | 2003-11-18 | 2005-05-19 | Abdul Malik | Sol-gel dendron separation and extraction capillary column |
| CN102952158A (en) * | 2012-10-26 | 2013-03-06 | 大连理工大学 | Triazine type siloxane surface modifier and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Electrochemical Study of a Dendritic Family at the Water/1,2-Dichloroethane Interface;Marcelo Calderon等，;《Langmuir》;20080521;第6343-6350页，尤其是第6344页图1，第6347页左栏，第6350页左栏第2段 * |
| Photophysical properties of Newkome-type dendrimers in aqueous medium;Subhendu K. Mohanty等，;《Photochem. Photobiol. Sci.》;20070828;第1164-1169页，尤其是第1164-1165页 * |
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