CN105733392B - Submicron order polydivinylbenezene particle and its coating production with high temperature resistant and super-hydrophobicity - Google Patents
Submicron order polydivinylbenezene particle and its coating production with high temperature resistant and super-hydrophobicity Download PDFInfo
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- CN105733392B CN105733392B CN201610139418.XA CN201610139418A CN105733392B CN 105733392 B CN105733392 B CN 105733392B CN 201610139418 A CN201610139418 A CN 201610139418A CN 105733392 B CN105733392 B CN 105733392B
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- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 title claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 36
- 239000003999 initiator Substances 0.000 claims description 31
- 238000010792 warming Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- -1 neopelex Chemical compound 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 210000000481 breast Anatomy 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000010985 leather Substances 0.000 claims description 4
- 239000004579 marble Substances 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical group CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000003505 polymerization initiator Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 30
- 239000003643 water by type Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 235000019394 potassium persulphate Nutrition 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical class CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical class CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a kind of submicron order polydivinylbenezene particle and its coating production with high temperature resistant and super-hydrophobicity, including it is as follows：Step 1：Mini-emulsion polymerization, nanoscale emulsion I is made；Step 2：Seeded emulsion polymerization, submicron order emulsion II is made；Step 3：The medium of emulsion II is replaced as low boiling point solvent by centrifuging or being freeze-dried by water, then freshly prepd coating is cast or brushed on base material with certain solid content, after drying to be coated, obtains the super-hydrophobic coat that do not ftracture of certain thickness.Super-hydrophobic coat prepared by the present invention has good resistance to elevated temperatures, still have after high-temperature process compared with high contact angle and by controlling coating thickness that indehiscent super-hydrophobic coat can be made, the coating material production mild condition of the present invention simultaneously, it is green, involved low raw-material cost, and the required operating procedure of prepares coating is simple, it is not necessary to special machinery equipment.
Description
Technical field
The present invention relates to a kind of super hydrophobic coating, and in particular to a kind of submicron order polydivinylbenezene particle and its has
The coating production of high temperature resistant and super-hydrophobicity.
Background technology
When the contact angle of water droplet and the surface of solids is more than 150 °, the surface of solids is referred to as super hydrophobic surface.Due to super
Hydrophobic surface has special micro-rough structure with low surface energy, and dirt is not easy in surface aggregation, also holds even if aggregation
Easily depart from the presence of gravity, wind-force or rainwater, this assigns super hydrophobic material many excellent performances, such as waterproof, antifog, anti-
Frost, anti-corrosion, automatically cleaning etc., so that it is in automatically cleaning building coating, submerged structure anticorrosion, fabric is antifouling etc. to be had
Wide application prospect.
Due to super hydrophobic surface in theoretical research and actual industrial and agricultural production and daily life all have it is very important
Application prospect, therefore, the structure of the super-hydrophobic surface of solids cause extensive concern.The construction method of super hydrophobic surface mainly has
Two：One is low-surface energy substance is modified in coarse substrate, mostly fluorinated silicone modified resin；The second is in hydrophobic surface structure
Build the surface fine structure with certain roughness.Specific method mainly has electrochemical etching, vapour deposition, electrostatic spinning etc.,
Above method needs special equipment mostly, and process is complex, and energy consumption and cost are of a relatively high.
Existing method prepares poor resistance of the super hydrophobic surface to high temperature.Fluorine-containing material itself is expensive and contains
Fluorine material can be detrimental to health, environment is polluted, and the super-hydrophobic coat formed by micro-and nano-particles easily ftractures, and makes
Reduced into contact angle.
The content of the invention
The invention provides a kind of technique is simple, high temperature resistant, do not ftracture, free-floride is without silicon, and cost is cheap, and green is super-hydrophobic
The preparation method of coating.
The invention provides a kind of submicron order polydivinylbenezene particle and its painting with high temperature resistant and super-hydrophobicity
Layer preparation method, step are as follows：
Step 1：Mini-emulsion polymerization
Divinylbenzene is added drop-wise to the solution of emulsifying agent, co-stabilizer and deionized water composition under the conditions of -5-20 DEG C
In, 30-80 DEG C is warming up to after ultrasonic disperse, initiator is added in above-mentioned mixed solution, stirs 1-24 hours, nanometer is made
Level emulsion I；Divinylbenzene in described mini-emulsion polymerization：Emulsifying agent：Co-stabilizer：Initiator：The mass ratio of deionized water
For 1:0.01‐0.1:0.06‐1.0:0.001‐0.1:1‐20；
Step 2：Seeded emulsion polymerization
Divinylbenzene and emulsifying agent are subjected to pre-emulsification and obtain pre-emulsion, pre-emulsion and initiator solution difference
It is added drop-wise to simultaneously in nanoscale emulsion I and reacts 1-24 hours obtained submicron order emulsion II；It is pre- in described seeded emulsion polymerization
The divinylbenzene of emulsion：Emulsifying agent：The mass ratio of deionized water is 1:0.01-0.1:1-20；Described seed emulsion is gathered
Initiator in initiator solution in conjunction：The mass ratio of deionized water is 0.005-0.1:1-20；The volume of pre-emulsion：Trigger
The volume of the agent aqueous solution：The volume ratio 1 of nanoscale emulsion I：0.01-1：1-20；
Step 3：Water in submicron order emulsion II is replaced as low boiling point solvent by centrifuging or being freeze-dried, obtained new
The coating III of preparation, then freshly prepd coating III is cast or brushed on base material with 0.5-10wt% solid content, it is to be coated
After drying, the super-hydrophobic coat that do not ftracture that thickness is 5-10 μm, as submicron order polydivinylbenezene particle and its tool are obtained
There is the coating of high temperature resistant and super-hydrophobicity.
Described emulsifying agent is dodecyl sodium sulfate, neopelex, lauryl sodium sulfate or stearic acid
One or both of sodium is mixed above；
Described co-stabilizer be carbon number be 4-20 alkylol, carbon number be 4-20 fat alkane or polyvinyl alcohol one
Kind or two or more compound uses；
Described initiator is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate-sodium bisulfite or peroxidating
One kind in hydrogen-frerrous chloride.
Low boiling point solvent includes aliphatic hydrocarbon and aromatic hydrocarbon, chlorohydrocarbon, alkylol and alkyl ketone etc. in described step 3.
The base material is the conventional substrate materials such as quartz plate, alloy, glass, ceramics, leather, marble.
The preparation method of super-hydrophobic coat provided by the invention has advantages below：It is special using miniemulsion, seed emulsion
Poly- method prepare polydivinylbenezene submicron particles, equipment is simple, and energy consumption is low, and cost is low, it is not necessary to adds fluorine silicon etc.
Low-surface energy substance, it is green.
Super-hydrophobic coat provided by the invention has advantages below：The ultra-hydrophobicity of prepared super-hydrophobic coat is excellent
It is different, under the high temperature conditions can retention property it is stable and by controlling coating layer thickness coating can be controlled not ftracture.
Brief description of the drawings
The super-hydrophobic coat that the accompanying drawing embodiment of the present invention 1 provides.
Embodiment
Combination technology scheme and accompanying drawing are described in further details to the present invention.
Embodiment 1
By 0.2g dodecyl sodium sulfates, 0.9g hexadecanols are added in 80ml deionized waters, cold after 50 DEG C of stirring 30min
But to less than 10 DEG C, 10g divinylbenzenes are added dropwise, after being added dropwise, is cooled to 0 DEG C, ultrasonic disperse 3min, moves into 50 DEG C of oil baths
In pot, 0.05g potassium peroxydisulfates are dissolved in 5ml deionized waters, are added drop-wise in system, 50 DEG C of reaction 10h, obtain nanoscale breast
Liquid I.By 10g divinylbenzenes, 0.35g dodecyl sodium sulfates, which are dissolved in, to be stirred at room temperature 30min in 15ml water and obtains pre-emulsification
Liquid, initiator 0.05g potassium peroxydisulfates are dissolved in 10ml water, and emulsion I is warming up into 60 DEG C, by pre-emulsion, initiator solution
It is added drop-wise to simultaneously in reaction bulb, 5h is added dropwise, 75 DEG C of reaction 30min is warming up to after completion of dropwise addition, obtain submicron order emulsion II.Will
The medium of emulsion II is replaced as acetone by water by centrifugation, then freshly prepd coating is cast in into quartz plate with certain solid content
On, after drying to be coated, obtain the super-hydrophobic coat that do not ftracture of certain thickness.Contact angle is 151 °.Through 60 DEG C of placement 24h, connect
Feeler is still greater than 150 °.
Embodiment 2
By 0.15g lauryl sodium sulfate, 0.8g hexadecanols are added in 75ml deionized waters, after 70 DEG C of stirring 30min
Less than 10 DEG C are cooled to, 10g divinylbenzenes are added dropwise, after being added dropwise, 0 DEG C, ultrasonic disperse 3min is cooled to, moves into 70 DEG C of oil
In bath, 0.05g ammonium persulfate-sodium bisulfites are dissolved in 5ml deionized waters, are added drop-wise in system, 70 DEG C of reaction 8h,
Obtain nanoscale emulsion I.By 8g divinylbenzenes, 0.3g lauryl sodium sulfate is dissolved in 15ml water and 30min is stirred at room temperature
Pre-emulsion is obtained, initiator 0.06g ammonium persulfates-sodium hydrogensulfite is dissolved in 10ml water, and emulsion I is warming up into 80 DEG C,
Pre-emulsion, initiator solution are added drop-wise in reaction bulb simultaneously, 3h is added dropwise, 85 DEG C of reaction 30min are warming up to after completion of dropwise addition,
Obtain submicron order emulsion II.The medium of emulsion II is replaced as tetrahydrofuran by water by freeze-drying, then will be freshly prepd
Coating is cast on alloy with certain solid content, after drying to be coated, obtains the super-hydrophobic coat that do not ftracture of certain thickness.Connect
Feeler is 152 °.Through 70 DEG C of placement 24h, contact angle is still greater than 150 °.
Embodiment 3
By 0.2g neopelexes, 0.9g hexadecanols are added in 80ml deionized waters, after 80 DEG C of stirring 30min
Less than 10 DEG C are cooled to, 12g divinylbenzenes are added dropwise, are added dropwise, is cooled to 0 DEG C, ultrasonic 3min, moves into 80 DEG C of oil bath pans
In, 0.06g hydrogen peroxide-frerrous chloride is dissolved in 5ml deionized waters, is added drop-wise in system, 80 DEG C of reaction 8h, is obtained
Nanoscale emulsion I.By 9g divinylbenzenes, 0.35g neopelexes, which are dissolved in, to be stirred at room temperature 30min in 20ml water and obtains
To pre-emulsion, initiator 0.05g hydrogen peroxide-frerrous chloride is dissolved in 15ml water, emulsion I is warming up to 80 DEG C, will
Pre-emulsion, initiator solution are added drop-wise in reaction bulb simultaneously, and 3h is added dropwise, and 85 DEG C of reaction 30min are warming up to after completion of dropwise addition, are obtained
To submicron order emulsion II.The medium of emulsion II is replaced as acetone by water by freeze-drying, then by freshly prepd coating with
Certain solid content is brushed on glass, after drying to be coated, obtains the super-hydrophobic coat that do not ftracture of certain thickness.Contact angle is
151°.Through 80 DEG C of placement 24h, contact angle is still greater than 150 °.
Embodiment 4
By 0.1g lauryl sodium sulfate, 0.3g hexadecanols, 0.4g hexadecanes are added in 60ml deionized waters, and 60 DEG C are stirred
Less than 10 DEG C are cooled to after mixing 30min, 7g divinylbenzenes are added dropwise, are added dropwise, is cooled to 0 DEG C, ultrasonic 3min, moves into 60 DEG C
In oil bath pan, 0.05 potassium peroxydisulfate is dissolved in 5ml deionized waters, is added drop-wise in system, 60 DEG C of reaction 10h, obtain nanometer
Level emulsion I.By 7g divinylbenzenes, 0.35g lauryl sodium sulfate, which is dissolved in 20ml water, to be stirred at room temperature 30min and obtains pre- breast
Change liquid, initiator 0.05g potassium peroxydisulfates are dissolved in 10ml water, emulsion I are warming up to 70 DEG C, by pre-emulsion and initiator
Solution is added drop-wise in reaction bulb simultaneously, and 5h is added dropwise, and 75 DEG C of reaction 30min are warming up to after completion of dropwise addition, obtain submicron order emulsion
Ⅱ.The medium of emulsion II is replaced as ethanol by freeze-drying by water, then freshly prepd coating is poured with certain solid content
Casting after drying to be coated, obtains the super-hydrophobic coat that do not ftracture of certain thickness on quartz plate.Contact angle is 150 °.Through 100 DEG C
24h is placed, contact angle is still greater than 140 °.
Embodiment 5
By 0.2g odium stearate, 0.4g hexadecanols, 0.5g hexadecanes are added in 70ml deionized waters, 70 DEG C of stirrings
Less than 10 DEG C are cooled to after 30min, 13g divinylbenzenes are added dropwise, are added dropwise, is cooled to 0 DEG C, ultrasonic 3min, moves into 70 DEG C
In oil bath pan, 0.05g ammonium persulfates-sodium hydrogensulfite is dissolved in 5ml deionized waters, is added drop-wise in system, 70 DEG C of reactions
8h, obtain nanoscale emulsion I.By 7g divinylbenzenes, 0.35g lauryl sodium sulfate is dissolved in 20ml water and is stirred at room temperature
30min obtains pre-emulsion, and initiator 0.06g ammonium persulfates-sodium hydrogensulfite is dissolved in 15ml water, emulsion I is heated up
To 70 DEG C, and pre-emulsion and initiator solution are added drop-wise in reaction bulb simultaneously simultaneously, 4h is added dropwise, is warming up to after completion of dropwise addition
75 DEG C of reaction 30min, obtain submicron order emulsion II.The medium of emulsion II is replaced as methanol by water by centrifugation, then will be new
The coating of preparation is brushed on leather with certain solid content, and after drying to be coated, it is super-hydrophobic to obtain not ftractureing for certain thickness
Coating.Contact angle is 152 °.Through 60 DEG C of placement 24h, contact angle is still greater than 150 °.
Embodiment 6
By 0.1g neopelexes, 0.7g hexadecanes are added in 60ml deionized waters, after 60 DEG C of stirring 30min
Less than 10 DEG C are cooled to, 7g divinylbenzenes are added dropwise, are added dropwise, is cooled to 0 DEG C, ultrasonic 3min, is moved into 60 DEG C of oil bath pans,
0.05g ammonium persulfates are dissolved in 5ml deionized waters, are added drop-wise in system, 60 DEG C of reaction 10h, obtain nanoscale emulsion I.
By 6g divinylbenzenes, 0.4g neopelexes, which are dissolved in 20ml water, to be stirred at room temperature 30min and obtains pre-emulsion, will
Initiator 0.04g ammonium persulfates are dissolved in 15ml water, and emulsion I is warming up into 75 DEG C, and pre-emulsion and initiator solution is same
When be added drop-wise in reaction bulb, be added dropwise 4h, be warming up to after completion of dropwise addition 85 DEG C reaction 30min, obtain submicron order emulsion II.By breast
The medium of liquid II is replaced as toluene by water by centrifugation, then freshly prepd coating is brushed on ceramics with certain solid content,
After drying to be coated, the super-hydrophobic coat that do not ftracture of certain thickness is obtained.Contact angle is 151 °.Through 140 DEG C of placement 24h, contact
Angle is still greater than 130 °.
Embodiment 7
By 0.2g odium stearate, 0.8g hexadecanes are added in 85ml deionized waters, and 10 are cooled to after 70 DEG C of stirring 30min
Below DEG C, 12g divinylbenzenes are added dropwise, are added dropwise, be cooled to 0 DEG C, ultrasonic 3min, move into 70 DEG C of oil bath pans, by 0.05g
Hydrogen peroxide-frerrous chloride is dissolved in 8ml deionized waters, is added drop-wise in system, 70 DEG C of reaction 9h, obtains nanoscale emulsion
Ⅰ.By 10g divinylbenzenes, 0.35g odium stearate, which is dissolved in, to be stirred at room temperature 30min in 20ml water and obtains pre-emulsion, will be triggered
Agent 0.05g hydrogen peroxide-frerrous chloride is dissolved in 15ml water, emulsion I is warming up into 80 DEG C, by pre-emulsion and initiator
Solution is added drop-wise in reaction bulb simultaneously, and 3h is added dropwise, and 90 DEG C of reaction 30min are warming up to after completion of dropwise addition, obtain submicron order emulsion
Ⅱ.The medium of emulsion II is replaced as tetrahydrofuran by water by centrifugation, then by freshly prepd coating with certain solid content brush
It is coated on glass, after drying to be coated, obtains the super-hydrophobic coat that do not ftracture of certain thickness.Contact angle is 151 °.Put through 120 DEG C
24h is put, contact angle is still greater than 130 °.
Embodiment 8
By 0.2g neopelexes, 0.9g polyvinyl alcohol is added in 70ml deionized waters, 50 DEG C of stirring 30min
After be cooled to less than 10 DEG C, 13g divinylbenzenes are added dropwise, are added dropwise, are cooled to 0 DEG C, ultrasonic 3min, move into 50 DEG C of oil bath pans
In, by the molten potassium sulfate solution of 0.07g potassium peroxydisulfates in 10ml deionized waters, it is added drop-wise in system, 50 DEG C of reaction 10h, is received
Meter level emulsion I.By 7g divinylbenzenes, 0.35g neopelexes, which are dissolved in, to be stirred at room temperature 30min in 20ml water and obtains
Pre-emulsion, initiator 0.05g potassium peroxydisulfates are dissolved in 15ml water, and emulsion I is warming up into 70 DEG C, by pre-emulsion and are drawn
Hair agent solution is added drop-wise in reaction bulb simultaneously, and 4h is added dropwise, and 75 DEG C of reaction 30min are warming up to after completion of dropwise addition, obtain submicron order
Emulsion II.The medium of emulsion II is replaced as ethanol by centrifugation by water, then freshly prepd coating is poured with certain solid content
Casting after drying to be coated, obtains the super-hydrophobic coat that do not ftracture of certain thickness on marble.Contact angle is 151 °.Through 110 DEG C
24h is placed, contact angle is still greater than 130 °.
Embodiment 9
By 0.15g dodecyl sodium sulfates, 0.8g polyvinyl alcohol is added in 60ml deionized waters, 60 DEG C of stirring 30min
After be cooled to less than 10 DEG C, 10g divinylbenzenes are added dropwise, are added dropwise, are cooled to 0 DEG C, ultrasonic 3min, move into 60 DEG C of oil bath pans
In, 0.05g ammonium persulfates are dissolved in 8ml deionized waters, are added drop-wise in system, 60 DEG C of reaction 9h, obtain nanoscale emulsion
Ⅰ.By 8g divinylbenzenes, 0.3g dodecyl sodium sulfates, which are dissolved in 20ml water, to be stirred at room temperature 30min and obtains pre-emulsion, will
Initiator 0.05g ammonium persulfates are dissolved in 10ml water, and emulsion I is warming up into 80 DEG C, and pre-emulsion and initiator solution is same
When be added drop-wise in reaction bulb, be added dropwise 4h, be warming up to after completion of dropwise addition 85 DEG C reaction 30min, obtain submicron order emulsion II.By breast
The medium of liquid II is replaced as acetone by water by freeze-drying, then freshly prepd coating is cast in into quartz with certain solid content
On piece, after drying to be coated, the super-hydrophobic coat that do not ftracture of certain thickness is obtained.Contact angle is 151 °.24h are placed through 80 DEG C,
Contact angle is still greater than 150 °.
Embodiment 10
By 0.1g lauryl sodium sulfate, 0.6g polyvinyl alcohol is added in 60ml deionized waters, after 70 DEG C of stirring 30min
Less than 10 DEG C are cooled to, 6g divinylbenzenes are added dropwise, are added dropwise, is cooled to 0 DEG C, ultrasonic 3min, is moved into 70 DEG C of oil bath pans,
0.05g hydrogen peroxide-frerrous chloride is dissolved in 5ml deionized waters, is added drop-wise in system, 70 DEG C of reaction 8h, obtains nanometer
Level emulsion I.By 7g divinylbenzenes, 0.35g lauryl sodium sulfate, which is dissolved in 15ml water, to be stirred at room temperature 30min and obtains pre- breast
Change liquid, initiator 0.05g hydrogen peroxide-frerrous chloride is dissolved in 15ml water, emulsion I is warming up to 85 DEG C, by pre-emulsification
Liquid and initiator solution are added drop-wise in reaction bulb simultaneously, and 3h is added dropwise, and 90 DEG C of reaction 30min are warming up to after completion of dropwise addition, obtain Asia
Micron order emulsion II.The medium of emulsion II is replaced as chlorohydrocarbon by water by centrifugation, then by freshly prepd coating with certain
Solid content is brushed on glass, after drying to be coated, obtains the super-hydrophobic coat that do not ftracture of certain thickness.Contact angle is 152 °.
Through 130 DEG C of placement 24h, contact angle is still greater than 130 °.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by the embodiment of the invention
Limitation, other are any without departing from the change made under principles and Spirit Essence of the invention, are included in protection model of the invention
In enclosing.
Claims (10)
1. the coating production with high temperature resistant and super-hydrophobicity that a kind of submicron order polydivinylbenezene particle is formed, its
It is characterised by, step is as follows：
Step 1：Mini-emulsion polymerization
Divinylbenzene is added drop-wise in the solution of emulsifying agent, co-stabilizer and deionized water composition under the conditions of -5-20 DEG C, surpassed
30-80 DEG C is warming up to after sound is scattered, initiator is added in above-mentioned mixed solution, stirs 1-24 hours, nanoscale breast is made
Liquid I；Divinylbenzene in described mini-emulsion polymerization：Emulsifying agent：Co-stabilizer：Initiator：The mass ratio of deionized water is 1:
0.01‐0.1:0.06‐1.0:0.001‐0.1:1‐20；
Step 2：Seeded emulsion polymerization
Divinylbenzene and emulsifying agent are subjected to pre-emulsification and obtain pre-emulsion, pre-emulsion and initiator solution difference are simultaneously
It is added drop-wise in nanoscale emulsion I and reacts 1-24 hours obtained submicron order emulsion II；Pre-emulsification in described seeded emulsion polymerization
The divinylbenzene of liquid：Emulsifying agent：The mass ratio of deionized water is 1:0.01-0.1:1-20；In described seeded emulsion polymerization
Initiator in initiator solution：The mass ratio of deionized water is 0.005-0.1:1-20；The volume of pre-emulsion：Initiator water
The volume of solution：The volume ratio of nanoscale emulsion I is 1：0.01-1：1-20；
Step 3：Water in submicron order emulsion II is replaced as low boiling point solvent by centrifuging or being freeze-dried, obtained freshly prepared
Coating III, then freshly prepd coating III is cast or brushed on base material, drying to be coated with 0.5-10wt% solid content
Afterwards, the super-hydrophobic coat that do not ftracture that thickness is 5-10 μm is obtained, what as submicron order polydivinylbenezene particle was formed has
The coating of high temperature resistant and super-hydrophobicity.
2. coating production according to claim 1, it is characterised in that described emulsifying agent is dodecyl sodium sulfonate
One or both of sodium, neopelex, lauryl sodium sulfate or odium stearate are mixed above.
3. coating production according to claim 1 or 2, it is characterised in that described co-stabilizer is that carbon number is 4-
One or more kinds of compound uses of 20 alkylol, the fat alkane that carbon number is 4-20 or polyvinyl alcohol.
4. coating production according to claim 1 or 2, it is characterised in that described initiator is ammonium persulfate, mistake
One kind in potassium sulfate, sodium peroxydisulfate, ammonium persulfate-sodium bisulfite or hydrogen peroxide-frerrous chloride.
5. coating production according to claim 3, it is characterised in that described initiator is ammonium persulfate, over cure
One kind in sour potassium, sodium peroxydisulfate, ammonium persulfate-sodium bisulfite or hydrogen peroxide-frerrous chloride.
6. according to the coating production described in claim 1 or 2 or 5, it is characterised in that low boiling is molten in described step 3
Agent is tetrahydrofuran, aliphatic hydrocarbon and aromatic hydrocarbon, chlorohydrocarbon, alkylol or alkyl ketone.
7. coating production according to claim 3, it is characterised in that low boiling point solvent is four in described step 3
Hydrogen furans, aliphatic hydrocarbon and aromatic hydrocarbon, chlorohydrocarbon, alkylol or alkyl ketone.
8. coating production according to claim 4, it is characterised in that low boiling point solvent is four in described step 3
Hydrogen furans, aliphatic hydrocarbon and aromatic hydrocarbon, chlorohydrocarbon, alkylol or alkyl ketone.
9. according to the coating production described in claim 1,2,5,7 or 8, it is characterised in that the base material is quartz plate, closed
Gold, glass, ceramics, leather or marble.
10. coating production according to claim 6, it is characterised in that the base material be quartz plate, alloy, glass,
Ceramics, leather or marble.
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| CN108359344A (en) * | 2018-01-19 | 2018-08-03 | 大连理工大学 | A kind of preparation method of high hydrophobicity high temperature resistant fluoresent coating |
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