CN110343280A - A kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface - Google Patents
A kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface Download PDFInfo
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- CN110343280A CN110343280A CN201810306372.5A CN201810306372A CN110343280A CN 110343280 A CN110343280 A CN 110343280A CN 201810306372 A CN201810306372 A CN 201810306372A CN 110343280 A CN110343280 A CN 110343280A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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Abstract
A kind of super-hydrophilic coating that can be modified on hydrophobic material surface.It is directly modified in the surface of hydrophobic material by way of layer assembly.Less than 10 °, modification can make it obtain hydrophilicity behind hydrophobic material surface and have good permeability the super-hydrophilic coating contact angle.Prepared super-hydrophilic coating is easy to operate, can be applied in optical instrument or material after being made, and do not influence its optical property, and obtain hydrophily.
Description
Technical field:
The invention belongs to chemical field, it is related to a kind of preparing by way of layer assembly in hydrophobic material surface
The method of super-hydrophilic coating.
Background technique:
Plastics are materials indispensable in people's daily life, but frosting does not have hydrophily, so when modeling
When expecting that film two sides has certain temperature difference, steam will form small droplet in film surface, influence the permeability of plastic film, this
It has a certain impact in actual application tool.
Super-hydrophilic coating refers to water droplet in coating of the surface contact angle less than 10 °, at this point, water electrode is easily formed on its surface water
Film has high self-cleaning ability.Super-hydrophilic coating material in China's is flourishing at present, how on hydrophobic material surface
Hydrophilic coating, which is made, has important research significance.The super-hydrophilic film tool of common acid catalyzed sol-gel technique preparation
There is good wearability, and be conducive to industry and largely produced, there is centainly complementary for people's routine use, still
Its Penetration ration is lower, in optical material using not ideal enough.Since existing polyethylene film does not have super hydrophilicity,
Therefore it needs directly to modify its surface using a kind of simple method.
Chinese patent 201210211738.3 describes a kind of with acid catalyzed colloidal sol --- the high intensity of gel method production
Anti-reflection hydrophilic coating, outfit is less when preparation and material is simple, obtains solid nanometer by joined surfactant
Ball-type SiO2, and then obtain the super-hydrophilic film with good permeability.But it in its preparation process, needs using inertia
Gas sheet glass is carried out it is air-dried, and need to by precuring processing sheet glass quickly quenched in Muffle furnace,
And these improve cost of manufacture and operation difficulty.
Chinese patent 200510024941.X discloses a kind of using titanium oxide as the super hydrophilic painting of the titanium dioxide of presoma
The preparation method of layer, using titanium oxide as precursor preparation titanium dioxide hydrocolloid, and is covered on carrier surface.This method
The processing time is shorter, and photocatalytic activity is high, coating stable, and there is good photocatalytic to dry in the air the disadvantage is that cost of material is higher
Special light sources are needed to radiate when dry coating, coating hydrophilic performance is not ideal enough.
Summary of the invention:
Of the existing technology in order to solve the problems, such as, the present invention provides a kind of hydrophobic material surface and directly modifies super hydrophilic painting
The method of layer.
Chinese of the present invention in relation to abbreviation: bPEI is branched polyethylene imine, and PAA is polyacrylic acid, EDC 1-
(3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, PBS is phosphate buffer.
The method that super-hydrophilic coating is directly modified on a kind of hydrophobic material surface provided by the invention, step and condition are as follows:
(1) cation constructs the preparation of primitive A-C solution
At room temperature, 0.01-1g A is dissolved in 10-100mL deionized waters, the pH for adjusting solution is 7.0-13.0, is obtained
To solution A.By 0.01-1g C in 10-100mL deionized waters, 0.01-1g EDC is then added, reacts 1-48h.Finally will
Solution A made from the first step is added in second step obtained solution, reacts 1-48h, and can be prepared by cation, to construct primitive A-C molten
Liquid.The A is the water soluble polymer containing amino in strand, and preferred A is bPEI, PAH, CHI or PDDA, molecular weight
It is 2.5 × 105–7.5×105；The C is the pyrocatechol substance containing carboxyl in molecule.
(2) anion constructs the preparation of primitive B-D solution
At room temperature, 0.01-1g B is dissolved in 10-100mL, the PBS that pH is 5.7-8.0, concentration is 0.01-0.2moL/L
In, the pH for adjusting solution is 5.0-10.0, and 0.01-10g EDC is then added.React 1-48h.Finally 0.01-10g D is added
Above-mentioned solution, 1-48h of reaction can be prepared by B-D solution.The B is the water soluble polymer containing carboxyl in strand, excellent
The B of choosing is PAA, HA, and the molecular weight of B is 1.0 × 105–3.0×106；The D is the pyrocatechol object containing amino in molecule
Matter.
(3) preparation of super-hydrophilic coating
1) processing of hydrophobic material substrate
At room temperature, with dehydrated alcohol by material surface wiped clean, preferred hydrophobic material is polyethylene (PE), linear low
Density polyethylene (LLDPE), polypropylene (PP), polystyrene (PS), polytetrafluoroethylene (PTFE) (PTFE).Selected hydrophobic material can
To be arbitrary shape.
2) it is deposited with the preparation of the super-hydrophilic coating of different cycles
At room temperature, processed substrate is successively subjected in A-C and B-D solution alternating deposit, deposits 0.1-respectively
10h repeats n period as a deposition cycle, obtains (A-C/B-D) * n coating, and the n is natural number.
The utility model has the advantages that the present invention provides a kind of methods that super-hydrophilic coating is directly modified on hydrophobic material surface, including dredge
The processing of water material is grafted with the preparation of the solution of catechol group, using the method for alternating deposit in hydrophobic material surface system
For super-hydrophilic coating.It is 0 °, the i.e. coating of total hydrophilic by adjusting deposition cycle contact angle can be made.
Hydrophilic coating prepared by the present invention is not limited by the shape of hydrophobic material, size, for plane and curved surface etc.
Irregular surface can carry out the attachment of hydrophilic coating.
Raw material of the invention is easy to get, simple process, and solvent is water, mild condition environmental protection.
Detailed description of the invention:
Fig. 1 is super-hydrophilic coating prepared by the present invention.
Specific embodiment
Carry out the specific implementation that the present invention is furture elucidated below by way of some examples and as a result, rather than with these examples
To limit the present invention.
Embodiment 1: a kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface, the coating are (bPEI-C/
PAA-D), the step of A bPEI, B PAA, C 3,4- dihydroxypropionic acid, D are dopamine, preparation and condition are as follows:
(1) preparation of bPEI-C solution
It at room temperature, is 2.5 × 10 by 0.4g molecular weight5BPEI be dissolved in 50mL deionized water, the pH of solution is uncomfortable,
Obtain bPEI solution.By 0.04g 3,4- dihydroxypropionic acid is dissolved in 50mL deionized water, and 0.0717g EDC is then added,
React 3h.Finally bPEI solution made from the first step is added in second step obtained solution, reacts 3h, bPEI-C solution is made.
(2) preparation of PAA-D solution
It at room temperature, is 1.0 × 10 by 0.1416g molecular weight5PAA be dissolved in 100mL, pH 6.0, concentration is
In the PBS of 0.01moL/L, the pH for adjusting solution is 7.0, and 0.129g EDC is then added.React 3h.Finally by 0.158g DOPA
Amine is added in above-mentioned solution, and PAA-D solution is made in reaction 3h.
(3) preparation of super-hydrophilic coating
1) it is deposited with the preparation of the super-hydrophilic coating of different cycles
At room temperature, processed rectangle LLDPE is successively subjected to alternating deposit in bPEI-C and PAA-D solution, point
Not Chen Ji 0.5h repeat 4 periods, obtain (bPEI-C/PAA-D) * 4 coating as a deposition cycle.
Contact-angle measurement is carried out with the Drop Shape Analyzer of DSA100, measures and above-mentioned is deposited with (bPEI-C/PAA-D) * 4
The contact angle of the rectangular LLDPE of coating is 0 °, i.e. total hydrophilic.
Embodiment 2
A kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface, the coating are (bPEI-C/PAA-D), A
For bPEI, the step of B PAA, C 3,4- dihydroxypropionic acid, D is dopamine, preparation and condition are as follows:
(1) preparation of bPEI-C solution
At room temperature, 0.4g bPEI is dissolved in 50mL deionized water, the pH of solution is uncomfortable, obtains bPEI solution.It will
0.04g 3,4- dihydroxypropionic acid are dissolved in 50mL deionized water, and 0.0717g EDC is then added, and react 3h.Finally by
BPEI solution made from one step is added in second step obtained solution, reacts 3h, and bPEI-C solution is made.Above-mentioned bPEI molecule used
Amount is 250000.
(2) preparation of PAA-D solution
At room temperature, 0.1416g PAA is dissolved in 100mL, pH 6.0, concentration is to adjust molten in the PBS of 0.01moL/L
The pH of liquid is 7.0, and 0.129g EDC is then added.React 3h.Finally 0.158g DA is added in above-mentioned solution, reacts 3h system
Obtain PAA-D solution.The molecular weight of above-mentioned PAA used is 100000.
(3) preparation of super-hydrophilic coating
1) it is deposited with the preparation of the super-hydrophilic coating of different cycles
At room temperature, the PP of processed triangle is successively subjected to alternating deposit in bPEI-C and PAA-D solution, respectively
1h is deposited, as a deposition cycle, 5 periods is repeated, obtains (bPEI-C/PAA-D) * 5 coating.
Contact-angle measurement is carried out with the Drop Shape Analyzer of DSA100, measures and above-mentioned is deposited with (bPEI-C/PAA-D) * 5
The contact angle of the PP of the triangle of coating is 0 °, i.e. total hydrophilic.
Claims (9)
1. a kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface, feature, step and condition are as follows:
(1) cation constructs the preparation of primitive A-C solution
At room temperature, 0.01-1g A is dissolved in 10-100mL deionized waters, the pH for adjusting solution is 7.0-13.0, and it is molten to obtain A
Liquid.0.01-1g C is dissolved in 10-100mL deionized waters, 0.01-1g EDC is then added, 1-48h is reacted, it is molten to obtain C
Liquid.Second step finally is added in solution A made from the first step to be made in C solution, 1-48h is reacted, can be prepared by cation and construct
Primitive A-C solution.The A is the water soluble polymer containing amino in strand.
(2) anion constructs the preparation of primitive B-D solution
At room temperature, 0.01-1g B being dissolved in 10-100mL, pH is 5.7-8.0, and concentration is in the PBS of 0.01-0.2moL/L,
The pH for adjusting solution is 5.0-10.0, and 0.01-10g EDC is then added.React 1-48h.It finally will be in 0.01-10g D addition
Solution is stated, 1-48h of reaction can be prepared by anion and construct primitive B-D solution.The B is to contain the water-soluble of carboxyl in strand
Property macromolecule, preferred B be PAA or HA, the D be molecule in the pyrocatechol substance containing amino.
(3) preparation of super-hydrophilic coating
1) processing of hydrophobic material substrate
At room temperature, with dehydrated alcohol by material surface wiped clean.The hydrophobic material can be arbitrary shape.
2) it is deposited with the preparation of the super-hydrophilic coating of different cycles
At room temperature, processed substrate is successively subjected in A-C and B-D solution alternating deposit, deposits 0.1-10h respectively, made
For a deposition cycle, n period is repeated, obtains (A-C/B-D) * n coating, the n is natural number.
2. a kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface as described in claim 1, which is characterized in that institute
It is bPEI, PAH, CHI or PDDA that the cation stated, which constructs A in primitive A-C solution,.The anion constructs primitive solution B-D
Middle B is PAA or HA.
3. a kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface as described in claim 1, which is characterized in that institute
It is respectively 2.5 × 10 that the cation stated, which constructs A and anion in primitive and constructs B molecular weight ranges in primitive,5–7.5×105With 1.0
×105–3.0×106。
4. a kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface as described in claim 1, which is characterized in that
Cation constructs pyrocatechol substance of the grafting containing carboxyl in primitive, and the C is 3,4- dihydroxyphenyl propionic acid.
5. a kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface as described in claim 1, which is characterized in that
Anion constructs pyrocatechol substance of the grafting containing amino in primitive, and the D is dopamine.
6. a kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface as described in claim 1, which is characterized in that institute
The pH range that the cation stated constructs solution A-C is 7.0-13.0, and the pH range that anion constructs solution B-D is 5.0-10.0.
7. a kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface as described in claim 1, which is characterized in that institute
The first layer that super-hydrophilic coating is directly modified on a kind of hydrophobic material surface stated is bPEI-C, and number of plies range should be controlled 1-
10。
8. a kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface as described in claim 1, which is characterized in that institute
The hydrophobic material stated is PE, LLDPE, PP, PS, PTFE.
9. a kind of method that super-hydrophilic coating is directly modified on hydrophobic material surface as described in claim 1, which is characterized in that institute
The solvent that the cation stated constructs primitive A-C solution is water, and the solvent that the anion constructs primitive B-D solution is PBS.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745327A (en) * | 2009-12-29 | 2010-06-23 | 浙江大学 | Method for fixing biological molecules on polymer microporous membrane surface |
| CN102319662A (en) * | 2011-09-26 | 2012-01-18 | 吉林大学 | Method for preparing self-repairing polyelectrolyte coating based on layer-by-layer assembly technology |
| CN107486021A (en) * | 2017-09-26 | 2017-12-19 | 南京理工大学 | Preparation method for the self assembly composite nanometer filtering film of water softening |
-
2018
- 2018-04-08 CN CN201810306372.5A patent/CN110343280A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745327A (en) * | 2009-12-29 | 2010-06-23 | 浙江大学 | Method for fixing biological molecules on polymer microporous membrane surface |
| CN102319662A (en) * | 2011-09-26 | 2012-01-18 | 吉林大学 | Method for preparing self-repairing polyelectrolyte coating based on layer-by-layer assembly technology |
| CN107486021A (en) * | 2017-09-26 | 2017-12-19 | 南京理工大学 | Preparation method for the self assembly composite nanometer filtering film of water softening |
Non-Patent Citations (2)
| Title |
|---|
| BAILIANG WANG ET AL.: ""Loading of Antibiotics into Polyelectrolyte Multilayers after Self-Assembly and Tunable Release by Catechol Reaction"", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| HAESHIN LEE ET AL.: ""Substrate-Independent Layer-by-Layer Assembly by Using Mussel-Adhesive-Inspired Polymers"", 《ADVANCED MATERIALS》 * |
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Application publication date: 20191018 |