CN101270202B - Polymethyl methacrylate with superhydrophobic surface and preparation method thereof - Google Patents
Polymethyl methacrylate with superhydrophobic surface and preparation method thereof Download PDFInfo
- Publication number
- CN101270202B CN101270202B CN2007100647562A CN200710064756A CN101270202B CN 101270202 B CN101270202 B CN 101270202B CN 2007100647562 A CN2007100647562 A CN 2007100647562A CN 200710064756 A CN200710064756 A CN 200710064756A CN 101270202 B CN101270202 B CN 101270202B
- Authority
- CN
- China
- Prior art keywords
- polymethyl methacrylate
- pmma
- solvent
- hydrophobic surface
- super
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses polymethyl methacrylate with super-hydrophobic surface and a preparation method thereof. The polymethyl methacrylate material with super-hydrophobic surface of the invention is prepared in the following steps: 1) the polymethyl methacrylate material is first put into diamine solution, so that the ester group on the surface of the material has ammonolysis reaction with diamine molecules; 2) and then, the product of the step 1) is put into long chain fatty acid solution to be treated and the solvent is volatilized, so as to obtain the polymethyl methacrylate material with super-hydrophobic surface. The method of the invention chemically modifies the PMMA surface and builds a three-dimensional micro structure similar to the lotus leaf surface on the PMMA surface; the obtained PMMA material is super-hydrophobic, has a contact angle with the surface of pure water of up to 170 degrees at most, and is widely applicable in the fields, such as architecture, medical science, etc.
Description
Technical field
The present invention relates to material modifiedly and preparation method thereof, particularly relate to a kind of polymethylmethacrylate and preparation method thereof with super hydrophobic surface.
Background technology
Have super hydrophobic surface material (with the contact angle of water greater than 150 °) produce and life in great application prospect is all arranged.Because the surface of these materials and the contact area of water are less, on super hydrophobic surface, just can not take place like this to have chemical reaction that water could take place and with water formation chemical bond, corresponding image surface is to the absorption of snow and rainwater, the oxidation and the various phenomenons such as examining resistance of rubbing on surface can reduce or stop accordingly at super hydrophobic surface, therefore, these materials with super hydrophobic surface have self-cleaning function.Super-hydrophobicization material of construction and exterior coating with self-cleaning function are the effective ways that solves sleet adhesion and contamination by dust.
The wetting property of solid surface is made up of the solid surface chemistry and the decision of surface three dimension microstructure.In order to obtain the super-hydrophobic surface of solid, people often carry out surface treatment with fluoro-containing group.Can't reach good hydrophobic effect but only carry out surface treatment with the low surface energy material, the wetting property of solid surface is also closely related with the surface three dimension microstructure.1949, Wenzel proposed the contact angle θ ' type of a describing roughness surface, and equation is as follows:
coaθ′＝r(γ
SV-γ
SL)/γ
LV＝rcosθ (1)
In following formula, r is a roughness factor, is defined as the long-pending ratio with its geometrical projection zone of the real surface of uneven surface; θ is the intrinsic contact angle of material.Because r always greater than 1, therefore, improves the hydrophobicity that surfaceness can improve hydrophobic surface.As seen, the surface three dimension microstructure is infiltrating another important factor of decision solid surface, particularly when material surface be the yardstick of 3-D solid structure and this structure during in micron and nanometer range (10-5000nm), tend to present the common specific performance that does not have.
But, up till now for this reason, the preparation of existing bibliographical information has the method for super-hydrophobic effect uneven surface, because its condition harshness, often will use reagent such as silicon fluoride to carry out finishing, this can pollute human body and environment, and, these method stepss are various, are difficult in and obtain practical application in the industrial production.
Summary of the invention
The purpose of this invention is to provide a kind of polymethyl methacrylate materials and preparation method thereof with super hydrophobic surface.
The present invention has the polymethyl methacrylate materials of super hydrophobic surface, is prepared according to following steps:
1) polymethyl methacrylate materials is placed two amine aqueous solutions make the ester group and the two amine molecule generation ammonolysis reactions on polymethyl methacrylate materials surface earlier;
2) then, be placed in the long-chain fat acid solution and handle, vapor away solvent, obtain having the polymethyl methacrylate materials of super hydrophobic surface.
In the present invention, ester group generation ammonolysis reaction in two amine molecules and the PMMA material, then be fixed on the lip-deep active amine of PMMA and induce the long-chain fat acid crystal, the carboxyl of longer chain fatty acid is preferentially arranged in the PMMA substrate, and hydrophobic alkyl chain is inclined to and is arranged on the gas-solid interface, the PMMA surface is covered by hydrophobic alkyl chain, thereby make the PMMA material have super hydrophobic surface.
Wherein, a variety of diamines all can be applied to the present invention, and, can also use various hybrid diamines, common, the diamines structural formula is suc as formula I,
NH
2-Ra-NH
2(formula I)
Wherein, Ra is C
1-14The straight or branched alkyl, perhaps, aryl.
These straight or branched alkyl and aryl, can be that replace or unsubstituted, perhaps, this aryl comprises five yuan, the carbocyclic ring of hexa-atomic or ten-ring system and closes heterocyclic group, it by covalent linkage or at interval the alkyl of the straight or branched of unit such as 1-8 carbon atom link to each other with amido.Among the present invention, do not have particular restriction for the solvent of diamines, solvent commonly used is selected from the poor solvent of water, methyl alcohol, ethanol, acetonitrile and other PMMA, and the volume ratio of solvent and diamines is 0-30: 1.The temperature of step 1) ammonolysis reaction is 0-50 ℃; Time is 0.5-10h.
In the present invention, the surface hydrophobicity group of modified PMMA material comes from longer chain fatty acid, and the carbonatoms of longer chain fatty acid is 3-30; Its common solvent is selected from the poor solvent of water, methyl alcohol, ethanol and other PMMA; The mass percentage concentration of longer chain fatty acid is 0.01-15%.Step 2) temperature of Chu Liing is 0-90 ℃; Treatment time is 0.1-30 hour.
In general, the lipid acid of the carbon chain length lipid acid shorter than carbochain helps the raising of contact angle, and in addition for different diamines and lipid acid, the suitable solvent and the selection of treatment temp also help the raising of surface hydrophobicity.
Polymethylmethacrylate (PMMA) is commonly called as synthetic glass, because its good transparency, stable physical property and extremely strong machinability are a kind of macromolecular materials that has wide range of applications, the contact angle of itself and pure water is about 66 °.The present invention utilizes ester group and diamines generation ammonolysis reaction in the PMMA material, then make active amine induce the long-chain fat acid crystal again, the carboxyl of longer chain fatty acid is preferentially arranged in the PMMA substrate, and hydrophobic alkyl chain is inclined to and is arranged on the gas-solid interface (top layer of PMMA), the PMMA surface is covered by hydrophobic alkyl chain, thereby, make PMMA material of the present invention have super hydrophobic surface.The inventive method is simple to operate, the treatment condition gentleness, low cost of raw materials, and when being carried out chemical modification, the PMMA surface also constructed the three-dimensional microcosmic structure that is similar to lotus leaf surface at the PMMA material surface, prepared modified PMMA material has superhydrophobic property, the surface contact angle of itself and pure water reaches as high as 170 °, has greatly improved the surface of PMMA material
Embodiment
Embodiment 1,
Commercial PMMA sheet material is cleaned up, be placed on the methanol solution (methyl alcohol: Ursol D=2 of Ursol D, volume ratio) under normal temperature, shelves 0.5h in, take out the hexane solution (1% that is placed on capric acid again, quality) handles 30h down in certain temperature (5 ℃) in, take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measure the contact angle of itself and pure water, be 90-110 °.
Embodiment 2,
Commercial PMMA sheet material is cleaned up, be placed on 1, the methanol solution of 4-butanediamine (methyl alcohol: 1,4-butanediamine=4, volume ratio) under normal temperature, shelves 2h in, take out in the tetrahydrofuran solution (0.5%, quality) that is placed on caproic acid again and handle 30h down in certain temperature (20 ℃), take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measure the contact angle of itself and pure water, be 110-130 °.
Embodiment 3
Commercial PMMA sheet material is cleaned up, be placed in the pure quadrol and under normal temperature, shelve 0.5h, take out to be placed on again in the stearic hexane solution (1%, quality) and handle 30h down in certain temperature (30 ℃), take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measuring the contact angle of itself and pure water, is 100～120 °.
Embodiment 4
Commercial PMMA sheet material is cleaned up, be placed on 1,4-butanediamine ethanolic soln (ethanol: 1,4-butanediamine=10, volume ratio) under normal temperature, shelves 6h in, take out in the cyclohexane solution (4%, quality) that is placed on moon silicic acid again and handle 15h down in certain temperature (30 ℃), take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measure the contact angle of itself and pure water, be 120-140 °.
Embodiment 5
Commercial PMMA sheet material is cleaned up, be placed on 1, the ethanolic soln of 4-butanediamine (ethanol: 1,4-butanediamine=2, volume ratio) under normal temperature, shelves 2h in, take out in the cyclohexane solution (4%, quality) that is placed on moon silicic acid again and handle 15h down in certain temperature (40 ℃), take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measure the contact angle of itself and pure water, be 90-100 °.
Embodiment 6
Commercial PMMA sheet material is cleaned up, be placed on the ethanolic soln (ethanol: hexanediamine=30 of hexanediamine, volume ratio) under normal temperature, shelves 10h in, take out the cyclohexane solution (10% that is placed on moon silicic acid again, quality) handles 12h down in certain temperature (50 ℃) in, take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measuring the contact angle of itself and pure water, is 130～158 °.
Embodiment 7
Commercial PMMA sheet material is cleaned up, be placed on the aqueous solution (water: Tetramethyl Ethylene Diamine=6 of Tetramethyl Ethylene Diamine, volume ratio) under normal temperature, shelves 2h in, take out the cyclohexane solution (15% that is placed on moon silicic acid again, quality) handles 10h down in certain temperature (60 ℃) in, take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measure the contact angle of itself and pure water, be 120-130 °.
Embodiment 8
Commercial PMMA sheet material is cleaned up, be placed on the ethanolic soln (ethanol: hexanediamine=2 of hexanediamine, volume ratio) under normal temperature, shelves 1h in, take out the cyclohexane solution (8% that is placed on moon silicic acid again, quality) handles 5h down in certain temperature (80 ℃) in, take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measuring the contact angle of itself and pure water, is about 120 °.
Embodiment 9
Commercial PMMA sheet material is cleaned up, be placed on the ethanolic soln (ethanol: hexanediamine=1 of hexanediamine, volume ratio) under normal temperature, shelves 1h in, take out the cyclohexane solution (8% that is placed on pentadecylic acid again, quality) handles 5h down in certain temperature (80 ℃) in, take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measuring the contact angle of itself and pure water, is 120～150 °.
Embodiment 10
Commercial PMMA sheet material is cleaned up, be placed in the pure hexanediamine and under normal temperature, shelve 0.5h, take out in the cyclohexane solution (5%, quality) that is placed on pentadecylic acid again and handle 2h down in certain temperature (90 ℃), take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measuring the contact angle of itself and pure water, is 100～130 °
Embodiment 11
Commercial PMMA sheet material is cleaned up, be placed on the ethanolic soln (ethanol: hexanediamine=2 of hexanediamine, volume ratio) under normal temperature, shelves 4h in, take out the ethanolic soln (10% that is placed on Lignoceric acid again, quality) handles 20h down in certain temperature (60 ℃) in, take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measure the contact angle of itself and pure water, be 130-160 °.
Embodiment 12
Commercial PMMA sheet material is cleaned up, be placed in the pure pentamethylene diamine and under normal temperature, shelve 1h, take out in the ethanolic soln (4%, quality) that is placed on Lignoceric acid again and handle 30h down in certain temperature (40 ℃), take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measuring the contact angle of itself and pure water, is 130 °-140 °.
Embodiment 13
Commercial PMMA sheet material is cleaned up, be placed on the mixing solutions (pentamethylene diamine: quadrol=1 of pentamethylene diamine and quadrol, volume ratio) under normal temperature, shelves 1-3h in, take out the ethanolic soln (4% that is placed on Lignoceric acid again, quality) handles 30h down in certain temperature (40 ℃) in, take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measure the contact angle of itself and pure water, be 140-170 °.
Embodiment 14
Commercial PMMA sheet material is cleaned up, be placed on the mixing solutions (Ursol D: hexanediamine=1 of Ursol D and hexanediamine, volume ratio) under normal temperature, shelves 1h in, take out the ethanolic soln (10% that is placed on Lignoceric acid again, quality) handles 20h down in certain temperature (50 ℃) in, take out, removing desolvates promptly gets the PMMA material with super hydrophobic surface.
Measuring the contact angle of itself and pure water, is 120～140 °.
Claims (8)
1. a method for preparing the polymethyl methacrylate materials with super hydrophobic surface comprises the steps:
1) polymethyl methacrylate materials is placed two amine aqueous solutions make the ester group and the two amine molecule generation ammonolysis reactions on polymethyl methacrylate materials surface earlier;
2) then, be placed in the long-chain fat acid solution and handle, vapor away solvent, obtain having the polymethyl methacrylate materials of super hydrophobic surface.
2. method according to claim 1 is characterized in that: described diamines is selected from structural formula suc as formula in the diamines of I one or more,
NH
2-Ra-NH
2(formula I)
Wherein, Ra is C
1-14The straight or branched alkyl, perhaps, aryl.
3. method according to claim 2 is characterized in that: the solvent of described two amine aqueous solutions is selected from the poor solvent of water, methyl alcohol, ethanol and other PMMA, and the volume ratio of solvent and diamines is 0-30: 1.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: the temperature of step 1) ammonolysis reaction is 0-50 ℃; Time is 0.5-10h.
5. method according to claim 1 is characterized in that: the carbonatoms of described longer chain fatty acid is 3-30.
6. method according to claim 5 is characterized in that: the solvent of described long-chain fat acid solution is selected from water, methyl alcohol, ethanol; The mass percentage concentration of longer chain fatty acid is 0.01-15%.
7. according to claim 1 or 5 or 6 described methods, it is characterized in that: step 2) temperature handled is 0-90 ℃; Treatment time is 0.1-30 hour.
8. the preparation-obtained polymethyl methacrylate materials of the arbitrary described method of claim 1-7 with super hydrophobic surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100647562A CN101270202B (en) | 2007-03-23 | 2007-03-23 | Polymethyl methacrylate with superhydrophobic surface and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100647562A CN101270202B (en) | 2007-03-23 | 2007-03-23 | Polymethyl methacrylate with superhydrophobic surface and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101270202A CN101270202A (en) | 2008-09-24 |
| CN101270202B true CN101270202B (en) | 2010-08-11 |
Family
ID=40004446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100647562A Expired - Fee Related CN101270202B (en) | 2007-03-23 | 2007-03-23 | Polymethyl methacrylate with superhydrophobic surface and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101270202B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059228B (en) * | 2011-10-24 | 2015-05-13 | 中国石油化工股份有限公司 | Modified acrylonitrile-styrene-acrylate terpolymer resin, and preparation method and product thereof |
| CN103059332A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Modified acrylonitrile-styrene-acrylate terpolymer product and preparation method thereof |
| CN114381941B (en) * | 2021-12-31 | 2024-03-01 | 金华洁灵家居用品有限公司 | Stable hydrophobic denier material and modification method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006282871A (en) * | 2005-03-31 | 2006-10-19 | Univ Nagoya | Method for keeping hydrophilic property of surface of hydrophobic polymer substrate |
| CN1858079A (en) * | 2006-04-17 | 2006-11-08 | 江南大学 | Process for preparing hydrophilic-hydrophobic graft polymer with controllable main and side chain length |
| CN1919429A (en) * | 2005-08-24 | 2007-02-28 | 中国石油天然气股份有限公司 | Graft phenylethene modified film and preparation method and application thereof |
-
2007
- 2007-03-23 CN CN2007100647562A patent/CN101270202B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006282871A (en) * | 2005-03-31 | 2006-10-19 | Univ Nagoya | Method for keeping hydrophilic property of surface of hydrophobic polymer substrate |
| CN1919429A (en) * | 2005-08-24 | 2007-02-28 | 中国石油天然气股份有限公司 | Graft phenylethene modified film and preparation method and application thereof |
| CN1858079A (en) * | 2006-04-17 | 2006-11-08 | 江南大学 | Process for preparing hydrophilic-hydrophobic graft polymer with controllable main and side chain length |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101270202A (en) | 2008-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ye et al. | Constructing fluorine-free and cost-effective superhydrophobic surface with normal-alcohol-modified hydrophobic SiO2 nanoparticles | |
| Mian et al. | A fundamental understanding of catechol and water adsorption on a hydrophilic silica surface: exploring the underwater adhesion mechanism of mussels on an atomic scale | |
| Sowerby et al. | Self-assembly at the prebiotic solid− liquid interface: Structures of self-assembled monolayers of adenine and guanine bases formed on inorganic surfaces | |
| Loget et al. | Electrodeposition of polydopamine thin films for DNA patterning and microarrays | |
| Xiu et al. | Hierarchical silicon etched structures for controlled hydrophobicity/superhydrophobicity | |
| CN103421423B (en) | A kind of in-situ preparation method of resistant to elevated temperatures super-hydrophobic coat | |
| Ou et al. | Self-assembly of octadecyltrichlorosilane on graphene oxide and the tribological performances of the resultant film | |
| Wang et al. | Self-assembly of catecholic macroinitiator on various substrates and surface-initiated polymerization | |
| Xue et al. | Importance of hierarchical structures in wetting stability on submersed superhydrophobic surfaces | |
| Kim et al. | Biomimetic formation of silica thin films by surface-initiated polymerization of 2-(dimethylamino) ethyl methacrylate and silicic acid | |
| Zhang et al. | Solvothermal synthesis of nanoporous polymer chalk for painting superhydrophobic surfaces | |
| CN101270202B (en) | Polymethyl methacrylate with superhydrophobic surface and preparation method thereof | |
| PT1618153E (en) | Use of polysilazane for the production of hydrophobically and oleophobically modified surfaces | |
| WO2007052260A3 (en) | Use of poss nanostructured molecules for hydrophobic and self cleaning coatings | |
| CN108504284A (en) | A kind of preparation method of nano superhydrophobic material | |
| CN104057670A (en) | Double-layer coating and coating method thereof | |
| CN103412019A (en) | Bioelectrode formed by three-dimensional ordered porous oxide modified conductive film and preparation method of bioelectrode | |
| CN108102541A (en) | Efficient hydrophobing agent and preparation method thereof | |
| Zhang et al. | Effect of morphology evolution on the anticorrosion performance of superhydrophobic surfaces and lubricant-infused surfaces | |
| WO2009025247A1 (en) | Hydrophilic film-forming composition, spray composition, and hydrophilic member using the same | |
| CN104231274A (en) | Surface activity organosilicon room-temperature ionic liquid and synthetic method thereof | |
| Etha et al. | Wetting dynamics on solvophilic, soft, porous, and responsive surfaces | |
| WO2009041550A1 (en) | Adhesive set and bonding method using the same | |
| CN103709934B (en) | magnetic hydrophobic self-cleaning coating and preparation method thereof | |
| CN106811957B (en) | A kind of preparation method of the super hydrophobic surface for lotion separation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100811 Termination date: 20140323 |