CN107573797A - A kind of super-hydrophobic insulating film material of loose structure and preparation method thereof - Google Patents
A kind of super-hydrophobic insulating film material of loose structure and preparation method thereof Download PDFInfo
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- CN107573797A CN107573797A CN201710768079.6A CN201710768079A CN107573797A CN 107573797 A CN107573797 A CN 107573797A CN 201710768079 A CN201710768079 A CN 201710768079A CN 107573797 A CN107573797 A CN 107573797A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a kind of super-hydrophobic insulating film material of loose structure, component includes：Nanometer " organic/inorganic " nano particle that nano silicon outer wrap organic matter HMDS (hereinafter referred to as amine alkane) is formed, silica quality percentage is 50~80% in the nano particle, amine alkane mass percent is 10~40%, and bonding agent and curing agent mass percent amount to 10~40%.Simultaneously, present invention also offers the preparation method of above-mentioned porous super hydrophobic insulating film material, the material forms porous super hydrophobic structure on porcelain or glass substrate, 150 ° are up to the contact angle of water, its hydrophobic performance is significantly larger than existing RTV or PRTV classes product, and has the characteristics that spray coating constructing technique is simple, preparation approach is environment-friendly, product is nontoxic.Rub resistance, it is anti-aging, service life be up to more than 10 years, weatherability can, acid and alkali-resistance can meet the sub- requirement of power system insulation.
Description
Technical field
The present invention relates to power network manufacturing field, and in particular to a kind of super-hydrophobic insulating film material of loose structure and its preparation
Method, it is mainly used in power system insulation.
Background technology
At present, power system remove use traditional porcelain and glass insulator, it is relatively new, made of organic material silicon
Rubber-like external insulation product (including composite insulator, RTV coating and creeping-increasing skirt) is also received to a certain extent, and is sent out
Wave porcelain and the irreplaceable antifouling work effect of glass insulator.Composite insulator is as formal property product, it is considered that uses the longevity
Order as 20~30 years, it is suitable with the projected life of circuit and transformer station (30 years)；And porcelain, glass insulator surface coating RTV,
Up to the present PRTV coating is still only used as remedial or provisional measure due to many reasons such as material property, construction technology
Use, its service life time limit needs to be investigated all the time.
Meanwhile on transformer, it is most of still to be configured using traditional porcelain insulating, heavy tune is climbed and sweeper
Leave run unit for, or even the stage for being difficult to choose has been arrived in some new sites.In recent years " the close configuration external insulation of saturated salt is pressed "
The implementation of technical policy, fully rely on large distance porcelain insulating and would be more difficult to reach configuration needed for transformer, while porcelain is exhausted
Edge coating PRTV etc. can only in most cases be constructed using the of short duration interruption maintenance time, by construction condition shadow
Ring, part mass be present.
Glass insulator is primarily present following two problems at present：(1) antifouling property is poor；(2) existing antifouling products by
Construction technology influences, restricted lifetime, and pollution is poisonous.
The content of the invention
Present invention mainly solves the existing antifouling products antifouling property coated in porcelain or glass insulator is poor, short life, dirt
The problem of contaminating environment.The invention provides super-hydrophobic insulating film material of a kind of loose structure and preparation method thereof, pass through lifting
The easy-to-use preparation method plated films such as dipping, brushing are to porcelain or glass insulation surface, to improve insulator water repelling anti-fouling performance
And existing antifouling products are substituted, with more practicality.
First aspect present invention provides a kind of super-hydrophobic insulating film material of loose structure, and component includes：Nano-silica
The nano particle that SiClx outer wrap HMDS is formed, silica dioxide granule mass percent are 50~80%, amine
Alkane mass percent is 10~40%, and bonding agent and curing agent mass percent amount to 10~40%.
Second aspect of the present invention provides the preparation method of the super-hydrophobic insulating film material of above-mentioned loose structure, step bag
Include：
S1, hydrophobicity SiO2The preparation of nano particle：Ammoniacal liquor is added in ethanol and is warming up to 58~62 DEG C, is then added
Tetraethyl orthosilicate, cooled down after stirring 1-2h, be aged 22-26h, add HMDS, stirred 3~5h, be collected by centrifugation
Precipitation, is drying to obtain hydrophobicity SiO2Nano particle；
S2, super-hydrophobic insulating film material preparation：By hydrophobicity SiO2Nano particle is dispersed in solvent, ultrasonic 1-
20min, add bonding agent, ultrasonic 1-20min, add curing agent after shake up, be applied to after 20~40s on substrate produce it is super-hydrophobic
Insulating film material.
The beneficial effects of the invention are as follows：
Existing RTV or PRTV classes product average life 3-5 (organic material), environmental pollution is serious, hydrophobic
Property poor (only 110 degree of contact angle).It is super thin that material provided by the invention forms porous " organic/inorganic " on porcelain or glass substrate
The contact angle of water film, product and water is up to 150o, its hydrophobic performance is significantly larger than existing RTV or PRTV classes product, and has
The features such as spray coating constructing technique is simple, preparation approach is environment-friendly, product is nontoxic.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the gained sample 8 of embodiment 1.
Embodiment
First aspect present invention provides a kind of super-hydrophobic insulating film material of loose structure, and component includes：Nano-silica
The nano particle that SiClx outer wrap HMDS is formed, silica dioxide granule mass percent are 50~80%, amine
Alkane mass percent is 10~40%, and bonding agent and curing agent mass percent amount to 10~40%.
Nano level HMDS wraps up nano silicon, and it is super to form porous " organic/inorganic " through bonding agent
Hydrophobic film, there is multistage multilayer distributed architecture, hydrophobic performance is excellent, contact angle up to 150 °, compared to existing RTV or
PRTV classes product (only 110 ° of contact angle) hydrophobic effect is significantly improved.
Preferably, the bonding agent is Hydroxylated acrylic resin, and the curing agent is hexamethylene diisocyanate.
Preferably, the nano particle diameter is 200~800nm.
Second aspect of the present invention provides the preparation method of the super-hydrophobic insulating film material of above-mentioned loose structure, step bag
Include：
S1, hydrophobicity SiO2The preparation of nano particle：Ammoniacal liquor is added into ethanol and is warming up to 58~62 DEG C, is added just
Silester, cooled down after stirring 1-2h, be aged 22-26h, that is, obtain SiO2Nano dispersion fluid；HMDS is added, is stirred
3~5h is mixed, obtains hydrophobicity SiO2Dispersion liquid；High speed centrifugation collects precipitation, is drying to obtain hydrophobicity SiO2Nano particle；
S2, super-hydrophobic insulating film material preparation：By hydrophobicity SiO2Nano particle be dispersed to solvent (ethyl acetate or
Butyl acetate) in, ultrasonic 1-20min, bonding agent is added, ultrasonic 1-20min, shakes up after adding curing agent, is coated with after 20~40s
Super-hydrophobic insulating film material is produced on to substrate.
Described hydrophobicity SiO2Nano particle has unique loose structure, nano silicon outer wrap amine alkane shape
Into nano particle, there is loose structure and ultra-hydrophobicity using the film of the particle preparation.
Preferably, the bonding agent is Hydroxylated acrylic resin, and the curing agent is hexamethylene diisocyanate, described
Solvent is ethyl acetate or butyl acetate.
More preferred, with volume basis, ethanol volume parts are 50~150, and ammoniacal liquor volume parts are 4~12, positive silicon
Acetoacetic ester volume parts are 9~27, and HMDS volume parts are 1~20.
More preferred, in step S2, every 0.1~0.5g hydrophobicitys SiO2Nano particle is dispersed in 100mL solvents.
More preferred, in step S2, Hydroxylated acrylic resin addition is in every 100mL solvents plus 0.1~1g, and six is sub-
Methyl diisocyanate addition is in 100mL solvents plus 0.015~0.1mL.
In one embodiment of the invention, by adjusting hydrophobicity SiO2Nano particle, Hydroxylated acrylic resin, six Asias
The ratio of methyl diisocyanate has investigated the hydrophobic effect of the thin-film material ultimately formed.
More preferred, it is described to be applied to the film-forming temperature that super-hydrophobic insulating film material is produced on substrate in step S2
For 20~300 DEG C.It may be selected by plated film the methods of magnetron sputtering or vapor phase deposition or lifting dipping to porcelain or glass insulation table
Face, to improve insulator antifouling property and substitute existing antifouling products, with more practicality.
Below in conjunction with specific embodiment to a kind of super-hydrophobic insulating film material of loose structure provided by the invention and its
Preparation method is further described.The embodiments described below is exemplary, is only used for explaining the present invention, without being understood that
For limitation of the present invention.
Experimental method in following embodiments, it is conventional method unless otherwise specified.Reality used in following embodiments
Test material unless otherwise specified, be that market is commercially available.
Embodiment one
The super-hydrophobic insulating film material of loose structure of ten groups of different ratios is present embodiments provided, number consecutively is respectively
Sample 1~10, all samples are obtained by following preparation methods, and difference is hydrophobicity SiO2Nano particle, hydroxy acrylic acid
Resin, the ratio of hexamethylene diisocyanate are different.The preparation side of the super-hydrophobic insulating film material of loose structure includes
Following steps：
S1, hydrophobicity SiO2The preparation of nano particle：
(1) concentrated ammonia liquor (8mL) is added in 100mL ethanol, and is warming up to 60 DEG C.
(2) tetraethyl orthosilicate (TEOS) 24mL is added.
(3) continue to stir 1.5h, be cooled to room temperature, be aged 24h, that is, obtain SiO2Nano dispersion fluid.
(4) HMDS 10mL is added, 4h is stirred, obtains hydrophobicity SiO2Dispersion liquid.
(5) by above-mentioned product high speed centrifugation, precipitation drying to obtain hydrophobicity SiO is collected2Nano particle.
S2, the hydrophobic coating preparation (carrying out at room temperature) for preparing super-hydrophobic coat：
(1) by a certain amount of hydrophobicity SiO2Nano particle is distributed in 100mL ethyl acetate, hydrophobicity SiO2Nanometer
The amount of grain is 0.1~0.5, the hydrophobicity SiO of sample 1~102Nano particle dosage is different, and specific dosage is as shown in table 1.
(2) ultrasound 10 minutes.
(3) Hydroxylated acrylic resin is added as bonding agent, 0.1g to 1g, the hydroxy acrylic acid tree of sample 1~10
Fat dosage is different, and specific dosage is as shown in table 1.
(4) ultrasound is continued 10 minutes.
(5) hexamethylene diisocyanate that mass concentration is 10% is added to arrive in 0.015mL as curing agent, addition
0.1mL, the hexamethylene diisocyanate dosage of sample 1~10 is different, and specific dosage is as shown in table 1, then shakes up, and half
It can be applied to after minute on substrate, the film forming at 15~25 DEG C of room temperature, obtain required super-hydrophobic coat.
Contact angle test is carried out to sample 1~10, concrete outcome is as shown in table 1.
The contact angle and wiping effect of sample 1~10 obtained by the different ratio of table 1
Embodiment two
The super-hydrophobic insulating film material of loose structure that treatment of different temperature obtains is present embodiments provided, and it is carried out
Contact angle is tested before and after wiping.
Surpass specifically, method is prepared as follows from the component of sample in embodiment 7 and sample 8 proportioning and prepares loose structure
Hydrophobic insulating film material, specific steps include：
S1, hydrophobicity SiO2The preparation of nano particle：
(1) concentrated ammonia liquor (8mL) is added in 100mL ethanol, and is warming up to 60 DEG C.
(2) tetraethyl orthosilicate (TEOS) 24mL is added.
(3) continue to stir 1.5h, be cooled to room temperature, be aged 24h, that is, obtain SiO2Nano dispersion fluid.
(4) HMDS 10mL is added, 4h is stirred, obtains hydrophobicity SiO2Dispersion liquid.
(5) by above-mentioned product high speed centrifugation, precipitation drying to obtain hydrophobicity SiO is collected2Nano particle.
S2, the hydrophobic coating preparation for preparing super-hydrophobic coat are carried out at room temperature.
(1) by a certain amount of hydrophobicity SiO2Nano particle is distributed in 100mL ethyl acetate, hydrophobicity SiO2Nanometer
The amount of grain is 0.1~0.5, the hydrophobicity SiO of sample 7,82Nano particle dosage is different, in specific dosage and embodiment one
Sample 7,8 is identical.
(2) ultrasound 10 minutes.
(3) Hydroxylated acrylic resin is added as bonding agent, 0.1g to 1g, the Hydroxylated acrylic resin of sample 7,8
Dosage is different, and specific dosage is identical with sample in embodiment one 7,8.
(4) ultrasound is continued 10 minutes.
(5) hexamethylene diisocyanate that mass concentration is 10% is added to arrive in 0.015mL as curing agent, addition
0.1mL, the hexamethylene diisocyanate dosage of sample 7,8 is different, specific dosage and sample 7,8 phases in embodiment one
Together, then shake up, can be applied to after half a minute on substrate, respectively at 15~25 DEG C of room temperature, at 100 DEG C, at 200 DEG C, 300
Film forming at DEG C, obtain required super-hydrophobic coat.Contact angle is tested and friction effect test result is as shown in table 2.
Film forming characteristics under table 2, different temperatures
Embodiment three
The present embodiment uses butyl acetate to carry out the preparation of the super-hydrophobic insulating film material of loose structure for solvent, specifically
Preparation method and embodiment one are basically identical, and difference is that solvent be butyl acetate, contact angle test and wiping under different solvents
It is as shown in table 3 to wipe effectiveness results.
Table 3 changes the film forming characteristics under solvent
Example IV
A kind of preparation method of the super-hydrophobic insulating film material of loose structure is present embodiments provided, step includes：
S1, hydrophobicity SiO2The preparation of nano particle：
(1) concentrated ammonia liquor (12mL) is added in 150mL ethanol, and is warming up to 62 DEG C.
(2) tetraethyl orthosilicate (TEOS) 10mL is added.
(3) continue to stir 2h, be cooled to room temperature, be aged 22h, that is, obtain SiO2Nano dispersion fluid.
(4) HMDS 20mL is added, 5h is stirred, obtains hydrophobicity SiO2Dispersion liquid.
(5) by above-mentioned product high speed centrifugation, precipitation drying to obtain hydrophobicity SiO is collected2Nano particle.
S2, the hydrophobic coating preparation for preparing super-hydrophobic coat are carried out at room temperature.
(1) by 1g hydrophobicity SiO2Nano particle is distributed in 100mL ethyl acetate.
(2) ultrasound 15 minutes.
(3) 0.3g Hydroxylated acrylic resins are added as bonding agent.
(4) ultrasound is continued 15 minutes.
(5) hexamethylene diisocyanate that mass concentration is 10% is added as curing agent, addition 0.015mL,
Then shake up, can be applied to after half a minute on substrate, the film forming at 15~25 DEG C of room temperature, obtain required super-hydrophobic coat, institute
Film forming characteristics and the embodiment one for obtaining thin-film material are basically identical.
Embodiment five
A kind of preparation method of the super-hydrophobic insulating film material of loose structure is present embodiments provided, step includes：
S1, hydrophobicity SiO2 nano particles preparation：
(1) concentrated ammonia liquor (4mL) is added in 50mL ethanol, and is warming up to 62 DEG C.
(2) tetraethyl orthosilicate (TEOS) 15mL is added.
(3) continue to stir 2h, be cooled to room temperature, be aged 26h, that is, obtain SiO2Nano dispersion fluid.
(4) HMDS 5mL is added, 3h is stirred, obtains hydrophobicity SiO2Dispersion liquid.
(5) by above-mentioned product high speed centrifugation, precipitation drying to obtain hydrophobicity SiO is collected2Nano particle.
S2, the hydrophobic coating preparation for preparing super-hydrophobic coat are carried out at room temperature.
(1) by 1g hydrophobicity SiO2Nano particle is distributed in 100mL ethyl acetate.
(2) ultrasound 15 minutes.
(3) 0.3g Hydroxylated acrylic resins are added as bonding agent.
(4) ultrasound is continued 15 minutes.
(5) hexamethylene diisocyanate that mass concentration is 10% is added as curing agent, addition 0.015mL,
Then shake up, can be applied to after half a minute on substrate, the film forming at 15~25 DEG C of room temperature, obtain required super-hydrophobic coat, institute
Film forming characteristics and the embodiment one for obtaining thin-film material are basically identical.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (8)
- A kind of 1. super-hydrophobic insulating film material of loose structure, it is characterised in that：Component includes：Nano silicon outer wrap The nano particle that HMDS is formed, silica dioxide granule mass percent are 50~80%, amine alkane mass percent For 10~40%, bonding agent and curing agent mass percent amount to 10~40%.
- 2. the super-hydrophobic insulating film material of loose structure as claimed in claim 1, it is characterised in that：The bonding agent is hydroxyl Acrylic resin, the curing agent are hexamethylene diisocyanate.
- 3. the super-hydrophobic insulating film material of loose structure as claimed in claim 1, it is characterised in that：The nano particle diameter For 200~800nm.
- 4. a kind of preparation method of the super-hydrophobic insulating film material of loose structure, step include：S1, hydrophobicity SiO2The preparation of nano particle：Ammoniacal liquor is added in ethanol and is warming up to 58~62 DEG C, then adds positive silicon Acetoacetic ester, cooled down after stirring 1-2h, be aged 22-26h, add HMDS, stirred 3~5h, precipitation is collected by centrifugation, It is drying to obtain hydrophobicity SiO2Nano particle；S2, super-hydrophobic insulating film material preparation：By hydrophobicity SiO2Nano particle is dispersed in solvent, ultrasonic 1-20min, Add bonding agent, ultrasonic 1-20min, add curing agent after shake up, be applied to after 20~40s on substrate produce it is super-hydrophobic insulation it is thin Membrane material.
- 5. the preparation method of the super-hydrophobic insulating film material of loose structure as claimed in claim 4, it is characterised in that：It is described viscous It is Hydroxylated acrylic resin to connect agent, and the curing agent is hexamethylene diisocyanate, and the solvent is ethyl acetate or acetic acid Butyl ester.
- 6. the preparation method of the super-hydrophobic insulating film material of loose structure as claimed in claim 5, it is characterised in that：With volume Than meter, ethanol volume parts are 50~150, and ammoniacal liquor volume parts are 4~12, and tetraethyl orthosilicate volume parts are 9~27, pregnancy Base disilazane volume parts are 1~20.
- 7. the preparation method of the super-hydrophobic insulating film material of loose structure described in claim 5, it is characterised in that：Step S2 In, every 0.1~0.5g hydrophobicitys SiO2Nano particle is dispersed in 100mL solvents.
- 8. the preparation method of the super-hydrophobic insulating film material of loose structure described in claim 5, it is characterised in that：Step S2 In, Hydroxylated acrylic resin addition is in every 100mL solvents plus 0.1~1g, hexamethylene diisocyanate addition are Add 0.015~0.1mL in 100mL solvents.
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| CN201710768079.6A CN107573797A (en) | 2017-08-31 | 2017-08-31 | A kind of super-hydrophobic insulating film material of loose structure and preparation method thereof |
| CN201810242059.XA CN108610818A (en) | 2017-08-31 | 2018-03-22 | A kind of super-hydrophobic insulating film material of porous structure and its preparation method and application |
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| CN201710768079.6A CN107573797A (en) | 2017-08-31 | 2017-08-31 | A kind of super-hydrophobic insulating film material of loose structure and preparation method thereof |
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| CN201810242059.XA Pending CN108610818A (en) | 2017-08-31 | 2018-03-22 | A kind of super-hydrophobic insulating film material of porous structure and its preparation method and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610818A (en) * | 2017-08-31 | 2018-10-02 | 武汉疏能新材料有限公司 | A kind of super-hydrophobic insulating film material of porous structure and its preparation method and application |
| CN108948891A (en) * | 2018-07-28 | 2018-12-07 | 黄智慧 | A kind of preparation method of environment-friendly type resistance and fingerprint resistance coating material |
| CN109370418A (en) * | 2018-09-29 | 2019-02-22 | 武汉疏能新材料有限公司 | A kind of super hydrophobic coating, coating and its preparation method and application |
| CN112300648A (en) * | 2020-11-10 | 2021-02-02 | 中国矿业大学 | Transparent super-hydrophobic coating and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1826257A1 (en) * | 2006-02-24 | 2007-08-29 | sia Abrasives Industries AG | Nano functional abrasive |
| CN107573797A (en) * | 2017-08-31 | 2018-01-12 | 武汉疏能电力技术有限公司 | A kind of super-hydrophobic insulating film material of loose structure and preparation method thereof |
-
2017
- 2017-08-31 CN CN201710768079.6A patent/CN107573797A/en active Pending
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2018
- 2018-03-22 CN CN201810242059.XA patent/CN108610818A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610818A (en) * | 2017-08-31 | 2018-10-02 | 武汉疏能新材料有限公司 | A kind of super-hydrophobic insulating film material of porous structure and its preparation method and application |
| CN108948891A (en) * | 2018-07-28 | 2018-12-07 | 黄智慧 | A kind of preparation method of environment-friendly type resistance and fingerprint resistance coating material |
| CN109370418A (en) * | 2018-09-29 | 2019-02-22 | 武汉疏能新材料有限公司 | A kind of super hydrophobic coating, coating and its preparation method and application |
| CN112300648A (en) * | 2020-11-10 | 2021-02-02 | 中国矿业大学 | Transparent super-hydrophobic coating and preparation method thereof |
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| CN108610818A (en) | 2018-10-02 |
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Application publication date: 20180112 |