CN103435742B - Hydrophobicity POSS base hydridization fluorinated acrylate resin and preparation method thereof and application - Google Patents
Hydrophobicity POSS base hydridization fluorinated acrylate resin and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses hydrophobicity POSS base hydridization fluorinated acrylate resin and preparation method thereof and application.By weight percentage, this resin raw material formula consists of: POSS base monomer accounts for 2 ~ 12%, and hard monomer accounts for 2 ~ 11%, soft monomer accounts for 3 ~ 16%, and fluoroacrylate monomer accounts for 1.5 ~ 7%, and cross-linking monomer accounts for 3 ~ 11%, initiator accounts for 0.4 ~ 1.3%, and solvent accounts for 50 ~ 79%; The present invention adopts cross-linking type multipolymer to mix with solidifying agent, assembles self-assembly and form micellar solution in film forming solvent, and recycling phase detachment technique, makes solvent on filter paper or metal screen, volatilize film forming to construct compound Multi-scale model, prepare super-hydrophobic film.The present invention adopts the method for free radical solution polymerization, and synthesis condition is simple, and reaction scheme is short, and raw material is simple and easy to get, greatly simplifies the preparation flow of organic/inorganic hybridization material, is with a wide range of applications in the paint field such as waterproof and dampproof.
Description
Technical field
The present invention relates to a kind of fluorinated acrylate resin, particularly relate to a kind of hydrophobicity POSS base hydridization fluorinated acrylate resin and preparation method thereof and application; Belong to the technology of preparing of organic/inorganic hybridization material.This resin is a kind of fluorinated acrylate super hydrophobic material containing polyhedral oligomeric silsesquioxane structure adopting free radical solution polymerization reaction method to prepare.
Background technology
Polyhedral oligomeric silsesquioxane (PolyhedralOligomericSilsesquioxane is called for short POSS) is a kind of novel nano-material occurred in recent years.Its molecular formula can be expressed as (RSiO
1.5)
n(n generally can be 6,8,10 etc.), the organic group R that the nano grade inorganic kernel that the rigidity that it is made up of silicon and oxygen, structure are determined is connected with by covalent linkage is the hybrid molecule that shell forms.Can by stronger chemical bonds between it and organic phase, the consistency between both improvement, effectively prevent the easy reunion of common inorganic particle and the weak problem of two-phase interface bonding force.The core of the inorganic cage structure of the Si-O-Si key formation of POSS, has good mechanical property and thermostability.POSS introduced traditional polymer, polymkeric substance use temperature can be improved, reduce Polymeric dielectric constant, improve system mechanical property etc.The domestic and international research to POSS at present, the overwhelming majority concentrates on and improves second-order transition temperature by adding POSS in system, improves decomposition temperature, improves mechanical property, reduces specific inductivity, reduces thermal conductivity etc.Publication number is that the Chinese patent application of CN102643433A discloses a kind of epoxidation POSS silicone resin and preparation method thereof.The epoxidation silicone resin that this invention obtains has good high thermal resistance.Publication number is the hybrid resin and its production and use that the Chinese patent application of CN101139442A discloses containing silsesquioxane.This resin is used as high temperature resistant, wave transparent, radiation hardness matrix material resin matrix, has excellent normal mechanical behavior under high temperature and excellent dielectric properties.The Chinese invention patent application of publication number CN102443330A discloses a kind of coated material and preparation method thereof.The coated material of this invention, with the resin matrix of the polyhedral oligomeric silsesquioxane POSS containing hydroxyl and acrylic resin, silicone resin for raw material obtains.Pencil hardness 3 ~ the 6H of coating, snappiness 1 ~ 3mm, shock strength 60 ~ 80kg/cm.Publication number is that the Chinese invention patent application of CN101024751A discloses a kind of coated material containing POSS acrylate copolymer and preparation method thereof.This coated material can be applicable to woodenware, hardware equipment, optical fiber surface, building material surface and the application of optical storage equipment high surface hardness, and coating hardness is up to pencil hardness 6H.
In prior art, also to have and construct hydrophobic surface by adding POSS.The Chinese invention patent application being CN101029137A as publication number discloses a kind of fluorine-containing POSS acrylate block copolymer resin and synthetic method thereof.This resin adopts atom transfer radical polymerization method (ATRP) synthesis, and after film forming, the contact angle of coating and water is 85 ~ 120 °, and wherein POSS is fluorine-containing polyhedral oligomeric silsesquioxane.But the atom transfer radical polymerization method that this invention adopts, process is more loaded down with trivial details, and the fluorine-containing POSS preparation technology more complicated of employing, the Static water contact angles reached is maximum also only has 120 ° simultaneously.Publication number is the Chinese invention patent application of CN103012700A and CN102775567A is all adopt reversible addition one fragmentation chain transfer free radical polymerization method (RAFT) to construct low surface energy, preparation technology's more complicated, and hydrophobic effect is remarkable not.
Summary of the invention
The object of the present invention is to provide and a kind ofly there is applicable multipolymer second-order transition temperature, the hydrophobicity POSS base hydridization fluorinated acrylate resin of resin-bonded excellent performance.
Another object of the present invention is to provide a kind of synthesis condition simple, reaction scheme is short, the preparation method of the hydrophobicity POSS base hydridization fluorinated acrylate resin that raw material is simple and easy to get.
The present invention also has an object to be to provide described hydrophobicity POSS base hydridization fluorinated acrylate resin in the application of the hydrophobic or super-hydrophobic film of preparation.
The present invention utilizes the strong self aggregation trend existed between POSS, assembles self-assembly and form micellar solution in film forming solvent, recycling phase detachment technique, and film forming that filter paper or metal screen volatilize is to construct micro-nano coarse structure; Utilize fluorine segment in fluorinated acrylic ester to form low surface energy to the migration of film-Air Interface, comprehensive micro-nano coarse structure and low-surface energy substance carry out constructing super-drainage coating simultaneously.The present invention adopts the method for free radical solution polymerization to prepare hybrid resin (hydrophobicity POSS base hydridization fluorinated acrylate resin), synthesis condition is simple, reaction scheme is short, raw material is simple and easy to get, greatly simplify the preparation flow of organic/inorganic hybridization material, on metal screen, static contact angle reaches more than 150 °.
A kind of hydrophobicity POSS base hydridization fluorinated acrylate resin, by weight percentage, this resin raw material formula is: POSS base monomer accounts for 2 ~ 12%, hard monomer accounts for 2 ~ 11%, soft monomer accounts for 3 ~ 16%, and fluoroacrylate monomer accounts for 1.5 ~ 7%, and cross-linking monomer accounts for 3 ~ 11%, initiator accounts for 0.4 ~ 1.3%, and solvent accounts for 50 ~ 79%;
The structural formula of described POSS base monomer is:
Wherein: R=mono-C
2h
5, a CH
2cH(CH
3) CH
3, a C
6h
5, a C
8h
17,
R'=mono-CH
2(CH
2)
poOCC (CH
3) CH
2; P=2,3 or 4;
Described hard monomer is the just own ester of methyl methacrylate, Tert-butyl Methacrylate, isopropyl methacrylate or methacrylic acid;
Described soft monomer is butyl acrylate, Isooctyl acrylate monomer or ethyl propenoate;
The structural formula of described fluoroacrylate monomer is CF
3(CFX)
m(CH
2)
noOCCYCH
2,; Wherein, X is H, F, F
2or not containing any group; Y is H or CH
3; M=2,5,6,8,10; N=1,2;
Described cross-linking monomer is methacrylic acid-β-hydroxyl ethyl ester, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate or hy-droxybutyl;
Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate;
Described solvent is butylacetate and/or dimethylbenzene
For realizing the object of the invention further, preferably, described POSS base monomer structure formula is: (SiO
1.5)
8r
7(CH
2)
3oOCC (CH
3) CH
2; Wherein R=-C
2h
5, R=-CH
2cH (CH
3) CH
3,r=-C
8h
17or R=-C
6h
5.
Or described POSS base monomer structure formula is: (SiO
1.5)
8r
7(CH
2)
4oOCC (CH
3) CH
2or (SiO
1.5)
8r
7(CH
2)
5oOCC (CH
3) CH
2; Wherein R=-C
2h
5, R=-CH
2cH (CH
3) CH
3,r=-C
8h
17or
Described fluoroacrylate monomer is trifluoroethyl methacrylate, 2-(perfluoro capryl) ethylmethyl acrylate, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl ester, vinylformic acid ten trifluoro monooctyl ester, Hexafluorobutyl mathacrylate or vinylformic acid hexafluoro butyl ester.
The preparation method of described hydrophobicity POSS base hydridization fluorinated acrylate resin, comprises the steps:
The first step, the solvent accounting for solvent quality 29 ~ 58% to be joined in reactor and under being heated to 70 ~ 110 DEG C of temperature, backflow 0.5 ~ 1h, then by hard monomer, soft monomer, cross-linking monomer, account for initiator quality 40 ~ 89% initiator even with the solvent accounting for solvent quality 5 ~ 25%, at the uniform velocity be added drop-wise in reactor in nitrogen atmosphere protection situation, control time for adding is 2 ~ 3h, and stirring velocity is (300-400) rev/min, drips follow-up continuous insulation reaction 0.5 ~ 4h;
Second step, by fluoroacrylate monomer, account for initiator quality 9 ~ 22% initiator even with the solvent accounting for solvent quality 5 ~ 13%, then be at the uniform velocity added drop-wise in the reaction system of the first step, control time for adding is 5min ~ 3h, drips rear continuation reaction 0.5 ~ 4h;
3rd step, POSS base monomer, remaining initiator and remaining solvent is even, and be then at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 0.5 ~ 3h, drip rear continuation reaction 0.5 ~ 4h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin
Described hydrophobicity POSS base hydridization fluorinated acrylate resin is in the application of the hydrophobic or super-hydrophobic film of preparation: mixed with film forming solvent by POSS base hydridization fluorinated acrylate resin, be configured to the solution of 0.1 ~ 30% concentration, POSS base hydridization fluorinated acrylate resin assembles self-assembly in film forming solvent, forming median size is the micellar solution of 100 ~ 800nm, then described micellar solution is mixed with solidifying agent, adopt dip-coating method at stainless steel plate, filter paper or metal screen obtain one deck uniform coating, at 20 ~ 150 DEG C of temperature, react 1 ~ 3h obtain hydrophobic/super-hydrophobic coat,
Described film forming solvent is one or both in Freon 113, dimethylbenzene, toluene, acetone, methyl alcohol, ethanol, trichloromethane, acetonitrile, pimelinketone, hexanaphthene, butylacetate and tetrahydrofuran (THF);
Described solidifying agent is isocyanates solidifying agent; Ratio, the NCO/OH in isocyanates solidifying agent and resin is (0.7 ~ 1.9): 1.
Described isocyanates solidifying agent is HDI biuret, TDI-HDI tripolymer, HDI tripolymer or IPDI tripolymer.
Coating on described stainless steel plate and the static contact angle of water are 120 ~ 140 °, and the coating on described filter paper or metal screen and the static contact angle of water are 145 ~ 154 °.
The present invention has following advantage and effect relative to prior art:
1) POSS base fluorinated acrylate resin of the present invention self-assembly in film forming solvent, recycling solvent evaporates membrane formation process prepares the uneven surface of micro nano structure, and prepare super-hydrophobic film, the film Static water contact angles on metal screen reaches more than 150 °.
2) resin of the present invention adopts hard monomer and soft monomer simultaneously, has applicable multipolymer second-order transition temperature, resin-bonded excellent performance, is conducive to the attachment of film, extends range of application.
3) POSS base fluorinated acrylate resin of the present invention adopts the preparation of free radical solution polymerization method, and this preparation method's synthesis condition is simple, and reaction scheme is short, and raw material is simple and easy to get, greatly simplifies the preparation flow of organic/inorganic hybridization material.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The first step, is being equipped with electric blender, N
211g butylacetate is added as solvent in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel, be warming up to 85 DEG C of backflow 30min, and pass into N2, then by 1.9g methyl methacrylate, 2.8g butyl acrylate, 1.9g methacrylic acid-β-hydroxyl ethyl ester, constant pressure funnel is joined after 0.14g Diisopropyl azodicarboxylate and 4g butylacetate mix, stir with 350 revs/min of speed, drip off continuously in 2.5h, drip follow-up continuous insulation reaction 3.5h;
Second step, by 1.4g2-(perfluoro capryl) ethylmethyl acrylate, 0.03g Diisopropyl azodicarboxylate and 2g solvent evenly after join constant pressure funnel, be at the uniform velocity added drop-wise in the reaction system of the first step, drip off continuously in 0.5h, drip follow-up continuous insulation reaction 2h;
3rd step, by 1.9gPOSS(wherein R=mono-CH
2cH(CH
3) CH
3; P=2), join in constant pressure funnel after 0.04g Diisopropyl azodicarboxylate and 8g butylacetate mix, then be at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 1h, drip follow-up continuous insulation reaction 2h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin;
4th step, get 1g hydrophobicity POSS base hydridization fluorinated acrylate resin to mix with 0.093gHDI tripolymer (N3300), 0.5% concentration resin solution is configured in Freon 113/dimethylbenzene (V/V=1/2) solvent, on stainless steel plate, filter paper and metal screen, adopt dip-coating method film after mixing, react 2h at 100 DEG C of temperature and obtain coating.
Embodiment 2
The first step, 10g dimethylbenzene is added as solvent in the four-hole boiling flask that electric blender, N2 airway, condensing reflux pipe and constant pressure funnel are housed, be warming up to 80 DEG C of backflow 30min, and pass into N2, then by 1.2g isopropyl methacrylate, 1.7g butyl acrylate, 2.1g Rocryl 410,0.1g Diisopropyl azodicarboxylate and 2g solvent evenly after join constant pressure funnel, stir with 350 revs/min of speed, drip off continuously in 2.5h, drip follow-up continuous insulation reaction 3h;
Second step, by 0.9g dodecafluoroheptyl methacrylate, 0.02g Diisopropyl azodicarboxylate and 2g solvent join in constant pressure funnel, are at the uniform velocity added drop-wise in the reaction system of the first step, drip off continuously in 2h, drip follow-up continuous insulation reaction 3h;
3rd step, gets 4.1gPOSS(wherein R=mono-CH
2cH(CH
3) CH
3; P=3), 0.08g Diisopropyl azodicarboxylate and 16g solvent evenly after join in constant pressure funnel, be then at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 1h, drip follow-up continuous insulation reaction 2h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin;
4th step, get 1g hydrophobicity POSS base hydridization fluorinated acrylate resin to mix with 0.089gHDI tripolymer (N3300), 1% concentration resin solution is configured in acetone/hexanaphthene (V/V=2/1) solvent, on stainless steel plate, filter paper and metal screen, adopt dip-coating method film after mixing, react 2h at 80 DEG C of temperature and obtain coating.
Embodiment 3
The first step, 11g dimethylbenzene is added as solvent in the four-hole boiling flask that electric blender, N2 airway, condensing reflux pipe and constant pressure funnel are housed, be warming up to 90 DEG C of backflow 45min, and pass into N2, then by 2.4g Tert-butyl Methacrylate, 3.6g Isooctyl acrylate monomer, 2.4g methacrylate, 0.18g benzoyl peroxide and 4g solvent evenly after join constant pressure funnel, stir with 350 revs/min of speed, drip off continuously in 1.5h, drip follow-up continuous insulation reaction 2h;
Second step, by 1.3g methacrylic acid ten trifluoro monooctyl ester, 0.03g benzoyl peroxide and 2g solvent evenly after join constant pressure funnel, be at the uniform velocity added drop-wise in the reaction system of the first step, drip off continuously in 1h, drip follow-up continuous insulation reaction 1h;
3rd step, by 0.1gPOSS(wherein R=mono-C
2h
5; P=2), 0.01g benzoyl peroxide and 2g solvent evenly after join in constant pressure funnel, be then at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 1.5h, drip follow-up continuous insulation reaction 2h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin;
4th step, get 1g hydrophobicity POSS base hydridization fluorinated acrylate resin to mix with 0.09gIPDI tripolymer, 2% concentration resin solution is configured in Freon 113 solvent, on stainless steel plate, filter paper and metal screen, adopt dip-coating method film after mixing, react 2h at 50 DEG C of temperature and obtain coating.
Embodiment 4
The first step, is being equipped with electric blender, N
211g butylacetate/dimethylbenzene (V/V=1/1) is added as solvent in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel, be warming up to 110 DEG C of backflow 30min, and pass into N2, then by just own for 1.4g methacrylic acid ester, 2.1g ethyl propenoate, 1.4g Hydroxyethyl acrylate, 0.1g benzoyl peroxide and 2g solvent evenly after join constant pressure funnel, stir with 350 revs/min of speed, drip off continuously in 2.5h, drip follow-up continuous insulation reaction 3h;
Second step, by 2g trifluoroethyl methacrylate, 0.04g benzoyl peroxide, joins constant pressure funnel after even with 2g solvent, is at the uniform velocity added drop-wise in the reaction system of the first step, drips off continuously in 5min, drip follow-up continuous insulation reaction 1h;
3rd step, gets 3gPOSS(wherein R=mono-C
6h
5; P=2), 0.07g benzoyl peroxide and 12g solvent evenly after join in constant pressure funnel, then be at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 2.5h, drip follow-up continuous insulation reaction 3h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin;
4th step, get 1g hydrophobicity POSS base hydridization fluorinated acrylate resin to mix with 0.1gHDI biuret, 2% concentration resin solution is configured in Freon 113/methyl alcohol (V/V=1/1) solvent, on stainless steel plate, filter paper and metal screen, adopt dip-coating method film after mixing, react 2h at 80 DEG C of temperature and obtain coating.
Embodiment 5
The first step, 10g butylacetate is added as solvent in the four-hole boiling flask that electric blender, N2 airway, condensing reflux pipe and constant pressure funnel are housed, be warming up to 95 DEG C of backflow 30min, and pass into N2, then by 2.4g methyl methacrylate, 3.5g Isooctyl acrylate monomer, 1.6g Rocryl 410,0.14g Diisopropyl azodicarboxylate and 4g solvent evenly after join constant pressure funnel, stir with 350 revs/min of speed, drip off continuously in 1.5h, drip follow-up continuous insulation reaction 2h;
Second step, by 1.5g vinylformic acid hexafluoro butyl ester, 0.03g Diisopropyl azodicarboxylate and 2g solvent evenly after join constant pressure funnel, be at the uniform velocity added drop-wise in the reaction system of the first step, drip off continuously in 5min, drip follow-up continuous insulation reaction 1h;
3rd step, gets 1gPOSS(wherein
p=4), 0.02g Diisopropyl azodicarboxylate and 6g solvent evenly after join in constant pressure funnel, be then at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 1.5h, drip follow-up continuous insulation reaction 4h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin;
4th step, get 1g hydrophobicity POSS base hydridization fluorinated acrylate resin to mix with 0.09gHDI tripolymer (N3300), 1% concentration resin solution is configured in Freon 113/dimethylbenzene (V/V=1/1) solvent, on stainless steel plate, filter paper and metal screen, adopt dip-coating method film after mixing, react 2h at 35 DEG C of temperature and obtain coating.
Embodiment 6
Adopt the OCA 1 type contact angle instrument of German Dataphysics company to carry out Static water contact angular measurement to hydrophobicity POSS base hydridization fluorinated acrylate resin coating prepared by embodiment 1 ~ 5, the situation recording Static water contact angles on stainless steel plate, filter paper and metal screen is as shown in table 1 below:
Table 1
| Sample | Stainless steel plate ° | Filter paper ° | Metal screen ° |
| Embodiment 1 | 132 | 152 | 154 |
| Embodiment 2 | 127 | 148 | 151 |
| Embodiment 3 | 137 | 149 | 152 |
| Embodiment 4 | 131 | 151 | 149 |
| Embodiment 5 | 138 | 153 | 154 |
As known from Table 1, Static water contact angles on metal screen and filter paper is than the height on stainless steel plate, reach super-hydrophobicity, this is because the vesicular structure on metal screen and filter paper has all constructed micron order coarse scale, they and nano level POSS base monomer have constructed micro-nano pair of yardstick coarse structure jointly, simultaneously under the acting in conjunction of the fluorine monomer of low surface energy, thus obtain super-hydrophobicity film; And coarse scale single on stainless steel plate is also not enough to construct super-hydrophobicity film.
Claims (7)
1. a hydrophobicity POSS base hydridization fluorinated acrylate resin, it is characterized in that, by weight percentage, this resin raw material formula consists of: POSS base monomer accounts for 2 ~ 12%, and hard monomer accounts for 2 ~ 11%, and soft monomer accounts for 3 ~ 16%, fluoroacrylate monomer accounts for 1.5 ~ 7%, cross-linking monomer accounts for 3 ~ 11%, and initiator accounts for 0.4 ~ 1.3%, and solvent accounts for 50 ~ 79%;
The structural formula of described POSS base monomer is:
Wherein: R=mono-C
2h
5, a CH
2cH (CH
3) CH
3, a C
6h
5, a C
8h
17or
R'=mono-CH
2(CH
2)
poOCC (CH
3) CH
2; P=2,3 or 4;
Described hard monomer is the just own ester of methyl methacrylate, Tert-butyl Methacrylate, isopropyl methacrylate or methacrylic acid;
Described soft monomer is butyl acrylate, Isooctyl acrylate monomer or ethyl propenoate;
The structural formula of described fluoroacrylate monomer is CF
3(CFX)
m(CH
2)
noOCCYCH
2,; Wherein, X is H or F; Y is H or CH
3; M=2,5,6,8,10; N=1,2;
Described cross-linking monomer is methacrylic acid-β-hydroxyl ethyl ester, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate or hy-droxybutyl;
Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate;
Described solvent is butylacetate and/or dimethylbenzene;
Described hydrophobicity POSS base hydridization fluorinated acrylate resin is prepared in accordance with the following steps:
The first step, the solvent accounting for solvent quality 29 ~ 58% to be joined in reactor and under being heated to 70 ~ 110 DEG C of temperature, backflow 0.5 ~ 1h, then by hard monomer, soft monomer, cross-linking monomer, account for initiator quality 40 ~ 89% initiator even with the solvent accounting for solvent quality 5 ~ 25%, at the uniform velocity be added drop-wise in reactor in nitrogen atmosphere protection situation, control time for adding is 2 ~ 3h, stirring velocity is (300-400) rev/min, drips follow-up continuous insulation reaction 0.5 ~ 4h;
Second step, by fluoroacrylate monomer, account for initiator quality 9 ~ 22% initiator even with the solvent accounting for solvent quality 5 ~ 13%, then be at the uniform velocity added drop-wise in the reaction system of the first step, control time for adding is 5min ~ 3h, drips rear continuation reaction 0.5 ~ 4h;
3rd step, POSS base monomer, remaining initiator and remaining solvent is even, and be then at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 0.5 ~ 3h, drip rear continuation reaction 0.5 ~ 4h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin.
2. hydrophobicity POSS base hydridization fluorinated acrylate resin according to claim 1, is characterized in that, described POSS base monomer structure formula is: (SiO
1.5)
8r
7(CH
2)
3oOCC (CH
3) CH
2; Wherein R=-C
2h
5, R=-CH
2cH (CH
3) CH
3,r=-C
8h
17or R=-C
6h
5.
3. hydrophobicity POSS base hydridization fluorinated acrylate resin according to claim 1, is characterized in that, described POSS base monomer structure formula is: (SiO
1.5)
8r
7(CH
2)
4oOCC (CH
3) CH
2or (SiO
1.5)
8r
7(CH
2)
5oOCC (CH
3) CH
2; Wherein R=-C
2h
5, R=-CH
2cH (CH
3) CH
3, R=-C
8h
17or R=
4. the preparation method of hydrophobicity POSS base hydridization fluorinated acrylate resin described in any one of claim 1-3, is characterized in that comprising the steps:
The first step, the solvent accounting for solvent quality 29 ~ 58% to be joined in reactor and under being heated to 70 ~ 110 DEG C of temperature, backflow 0.5 ~ 1h, then by hard monomer, soft monomer, cross-linking monomer, account for initiator quality 40 ~ 89% initiator even with the solvent accounting for solvent quality 5 ~ 25%, at the uniform velocity be added drop-wise in reactor in nitrogen atmosphere protection situation, control time for adding is 2 ~ 3h, stirring velocity is (300-400) rev/min, drips follow-up continuous insulation reaction 0.5 ~ 4h;
Second step, by fluoroacrylate monomer, account for initiator quality 9 ~ 22% initiator even with the solvent accounting for solvent quality 5 ~ 13%, then be at the uniform velocity added drop-wise in the reaction system of the first step, control time for adding is 5min ~ 3h, drips rear continuation reaction 0.5 ~ 4h;
3rd step, POSS base monomer, remaining initiator and remaining solvent is even, and be then at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 0.5 ~ 3h, drip rear continuation reaction 0.5 ~ 4h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin.
5. the hydrophobicity POSS base hydridization fluorinated acrylate resin described in any one of claim 1-3 is in the application of the hydrophobic or super-hydrophobic film of preparation, it is characterized in that: POSS base hydridization fluorinated acrylate resin is mixed with film forming solvent, be configured to the solution of 0.1 ~ 30% concentration, POSS base hydridization fluorinated acrylate resin assembles self-assembly in film forming solvent, forming median size is the micellar solution of 100 ~ 800nm, then described micellar solution is mixed with solidifying agent, adopt dip-coating method at stainless steel plate, filter paper or metal screen obtain one deck uniform coating, at 20 ~ 150 DEG C of temperature, react 1 ~ 3h obtain hydrophobic/super-hydrophobic coat,
Described film forming solvent is one or both in Freon 113, dimethylbenzene, toluene, acetone, methyl alcohol, ethanol, trichloromethane, acetonitrile, pimelinketone, hexanaphthene, butylacetate and tetrahydrofuran (THF);
Described solidifying agent is isocyanates solidifying agent; Ratio, the NCO/OH in isocyanates solidifying agent and resin is (0.7 ~ 1.9): 1.
6. hydrophobicity POSS base hydridization fluorinated acrylate resin according to claim 5 is in the application of the hydrophobic or super-hydrophobic film of preparation, it is characterized in that: described isocyanates solidifying agent is HDI biuret, TDI-HDI tripolymer, HDI tripolymer or IPDI tripolymer.
7. hydrophobicity POSS base hydridization fluorinated acrylate resin according to claim 5 is in the application of the hydrophobic or super-hydrophobic film of preparation, it is characterized in that: the coating on described stainless steel plate and the static contact angle of water are 120 ~ 140 °, the coating on described filter paper or metal screen and the static contact angle of water are 145 ~ 154 °.
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|---|---|---|---|---|
| CN104263238B (en) | 2014-09-11 | 2016-09-07 | 天津大学 | One is fluorinated POSS composite organic coating and preparation method and ice-covering-proof application |
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| CN112094588B (en) * | 2020-11-02 | 2021-02-19 | 宁波富纳新材料科技有限公司 | Fingerprint-preventing and anti-glare coating, protective film comprising same and preparation method of protective film |
| CN115537135B (en) * | 2022-10-10 | 2023-06-06 | 广东皇冠新材料科技有限公司 | High-temperature-resistant pressure-sensitive adhesive tape protective film and preparation method thereof |
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