CN103435741A - POSS (Polyhedral Oligomeric Silsesquioxane) based hybridized fluorinated acrylate resin, and preparation method and application thereof - Google Patents
POSS (Polyhedral Oligomeric Silsesquioxane) based hybridized fluorinated acrylate resin, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a POSS (Polyhedral Oligomeric Silsesquioxane) based hybridized fluorinated acrylate resin, and a preparation method and an application thereof. The formula of the resin comprises the following components by weight percent: 0.9-14% of POSS based monomer, 1.5-10% of hard monomer, 2.5-14% of soft monomer, 4-10.5% of acrylic higher ester monomer, 1.8-6% of fluoridized acrylate monomer, 1.8-9% of cross-linked monomer, 0.4-1.5% of initiator and 50-80% of solvent. According to the invention, the acrylic higher ester monomer is introduced as an oleophilic monomer into a fluorinated acrylate copolymer and then a hydrophobic and oleophilic compound multi-scale structure is established on filter paper or a metal filter screen by virtue of aggregating self-assembly of the POSS base in the copolymer; therefore, a hydrophobic and oleophilic coating is prepared. The resin coating prepared from the resin provided by the invention is applicable to the oil-water separation field and capable of removing trace moisture in the fuel oil, and has great practical application significance.
Description
Technical field
The present invention relates to a kind of acrylate resin, particularly relate to a kind of POSS base hydridization fluorinated acrylate resin with super-hydrophobic super-oleophilic performance and preparation method thereof and application; Belong to organic/inorganic hybridization material.
Background technology
Along with the development of aviation, automotive industry, people are more and more higher to the requirement of aircraft, motor car engine, and, as " blood "-fuel oil and the hydraulic efficiency oil of engine, their quality directly affects the performance of engine.The fluid water content is an important indicator of Oil Quality, is the one of the main reasons that causes motor fault.Purifier in engine utilizes coarse separation to remove the impurity such as particle in fluid and water, selects the moisture in filter screen (filter paper) oil and water separation with good hydrophilic oleophobic property, has great practical application meaning.
In recent years, the screen surface study on the modification mainly concentrates on the wettability intrinsic by adjustment interface and improves the flow behavior of liquid phase at solid surface, changes the resistance of filtration medium to oil and water, realizes oily water separation.Chinese utility model patent CN2598612Y adopts wire netting as framing structural member, all apply polytetrafluorethylepowder powder (teflon) coating of layer of hydrophobic in the both side surface of wire netting, although teflon has good hydrophobic performance, but lipophilicity is not good, be insoluble to organic solvent, need to adopt after powder coating and their application high-temperature fusion again, complicated operation, conditional request harshness, and teflon coating is thicker, easily stop up the wire netting hole after spraying, increase the fluid resistance to flow, reduce oily water separation efficiency.The Chinese invention patent application that publication number is CN1O1696312A and publication number CN1O160194OA is carried out dipping coating by add the inorganic silicon dioxide particle in fluorine resin to filter screen, reach ultra-hydrophobicity, but the inorganic particulate in this polymkeric substance easily comes off, thereby engine is caused to wearing and tearing, can not be applied in engine filter.
The filter structure of two-way heat power expansion that further the exploitation separation efficiency is high, mechanical property is strong, have important practical application meaning.In recent years, the organic-inorganic nano hybrid composite material based on polyhedral oligomeric silsesquioxane (Polyhedral Oligomeric Silsesquioxane is called for short POSS) has been subject to paying close attention to widely.The core of the inorganic cage structure that the Si-O-Si key of POSS forms, have good mechanical property and thermostability.Between POSS inorganic particle and organic polymer in conjunction with belonging to chemical bonds, make surface bonding power between inorganic particle and matrix be better than the surface bonding of traditional physical mechanical blending far away; Can control the size of inorganic nanoparticles simultaneously by controlling synthesis condition, carry out the molecule assembling, thereby reach the purpose of controlling the material requested macroscopic property.The Chinese invention patent application that publication number is CN102775567A discloses a kind of containing POSS polyacrylic ester one polysiloxane block copolymers and preparation thereof.This invents the surface energy hydrophobicity that prepared coated material has, can be for the preparation of Anti-ice-and-snow, antifouling paint.This application is incorporated into the POSS base in traditional polymer, prepared respectively hydrophobic, parents, the hydrophobic oleophobic coating, but do not have at present bibliographical information that POSS base applications of fluoropolymers is constructed to the micro-nano pair of compound coarse structure of yardstick and reached the super oily effect of super-hydrophobic parent on metal screen, with the high efficiency separation that realizes profit and the efficient conveying of fluid.
Summary of the invention
One of purpose of the present invention is to provide a kind of super-hydrophobic super-oleophilic that has, the POSS base hydridization fluorinated acrylate resin that mechanical property is good.
Another object of the present invention is to provide synthesis condition simple, reaction scheme is short, the preparation method of the POSS base hydridization fluorinated acrylate resin that raw material is simple and easy to get.
The present invention also has a purpose to be to provide the application of POSS base hydridization fluorinated acrylate resin in the hydrophobic oleophylic of preparation is filmed.
The object of the invention is achieved through the following technical solutions:
A kind of POSS base hydridization fluorinated acrylate resin, by weight percentage, this resin formula is: POSS base monomer accounts for 0.9～14%, hard monomer accounts for 1.5～10%, and soft monomer accounts for 2.5～14%, and higher hydrocarbyl acrylate class monomer accounts for 4～10.5%, the fluoroacrylate monomer accounts for 1.8～6%, cross-linking monomer accounts for 1.8～9%, and initiator accounts for 0.4～1.5%, and solvent accounts for 50～80%;
Described POSS base monomer structure formula is:
Wherein: R=-C
2h
5,-CH
2cH(CH
3) CH
3,-C
6h
5,-C
8h
17,
R '=-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;
Described higher hydrocarbyl acrylate class monomer is Octyl acrylate, dodecyl acrylate, Process Conditions of Cetane Acrylate or stearyl methacrylate;
The molecular 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 vinylformic acid hydroxy butyl ester;
Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate;
Described solvent is butylacetate and/or dimethylbenzene;
During preparation, the solvent that first will account for solvent quality 30～68% joins in reactor and is heated at 70～110 ℃ of temperature, 0.5～1h refluxes, then by hard monomer, soft monomer, higher hydrocarbyl acrylate class monomer, cross-linking monomer, account for initiator quality 48～90% initiator even with the solvent that accounts for solvent quality 4～27%, at the uniform velocity be added drop-wise to reactor in nitrogen atmosphere protection situation in, insulation reaction 0.5～4h, obtain reaction system; Then by the fluoroacrylate monomer, account for initiator quality 4～16% initiator even with the solvent that accounts for solvent quality 2.5～20%, be added drop-wise in reaction system, drip rear continuation reaction 0.5～4h, obtain mixed system; By POSS base monomer, remaining initiator and remaining solvent are even, are added drop-wise in mixed system again, drip rear continuation reaction 0.5～4h, and cooling discharge obtains hydrophobic lipophilicity POSS base hydridization fluorinated acrylate resin.
For further realizing the object of the invention, described POSS base monomer is (SiO
1.5)
8r
7(CH
2)
3oOCC (CH
3) CH
2; R=-C wherein
2h
5, R=-CH
2cH (CH
3) CH
3, R=-C
8h
17or R=-C
6h
5; Or described POSS base monomer 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; R=-C wherein
2h
5, R=-CH
2cH (CH
3) CH
3, R=-C
8h
17or
Described fluoroacrylate monomer is trifluoroethyl methacrylate, 2-(perfluoro capryl) ethyl-methyl acrylate, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl esters, vinylformic acid ten trifluoro monooctyl esters, Hexafluorobutyl mathacrylate or vinylformic acid hexafluoro butyl ester.
By weight percentage, preferably, described POSS base monomer accounts for 3～40% of composition of raw materials material mass.
The preparation method of described POSS base hydridization fluorinated acrylate resin, comprise the steps:
The first step, join in reactor by the solvent that accounts for solvent total amount 30～68% and be heated at 70～110 ℃ of temperature, 0.5～1h refluxes, then by hard monomer, soft monomer, higher hydrocarbyl acrylate class monomer, cross-linking monomer, account for initiator total amount 48～90% initiator even with the solvent that accounts for solvent total amount 4～27%, at the uniform velocity be added drop-wise to reactor in nitrogen atmosphere protection situation in, the control time for adding is 2～3h, stirring velocity is 350 rev/mins, drips follow-up continuation of insurance temperature reaction 0.5～4h;
Second step, by the fluoroacrylate monomer, account for the initiator total amount 4～16% initiator even with the solvent that accounts for solvent total amount 2.5～20%, then at the uniform velocity be added drop-wise in the reaction system of the first step, the control time for adding is 5min～3h, drips rear continuation reaction 0.5～4h;
The 3rd step, by POSS base monomer, the initiator that accounts for initiator total amount 3～41% is even with 9～49% the solvent that accounts for the solvent total amount, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 0.5～3h, drip rear continuation reaction 0.5～4h, cooling discharge obtains hydrophobic lipophilicity POSS base hydridization fluorinated acrylate resin.
The application of described POSS base hydridization fluorinated acrylate resin in the hydrophobic oleophylic of preparation is filmed: described 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 is assembled self-assembly in film forming solvent, the micellar solution that the formation median size is 50～900nm, then described micellar solution is mixed with solidifying agent, adopt dip-coating method at stainless steel plate, make one deck uniform coating on filter paper or metal screen, react 1～3h and obtain hydrophobic oleophylic coating at 20～150 ℃ of temperature,
Described film forming solvent is one or both mixtures in Freon 113, dimethylbenzene, toluene, acetone, methyl alcohol, ethanol, trichloromethane, acetonitrile, pimelinketone, hexanaphthene, butylacetate and tetrahydrofuran (THF);
Described solidifying agent is the isocyanates solidifying agent; For HDI biuret, TDI-HDI tripolymer, HDI tripolymer or IPDI tripolymer; With molar ratio computing, the NCO/OH of solidifying agent and POSS base hydridization fluorinated acrylate resin is (0.7～1.9): 1.
The present invention has following advantage and effect with respect to prior art:
1) in resin of the present invention, fluorine segment hydrophobic property, chain alkyl segment are given lipophilicity, at this hydrophobic oil-wetted surface, micro-nano pair of yardstick coarse structure of structure assembled in the self-assembly of recycling POSS base on filter screen, thereby constructs out super-hydrophobic super-oleophilic surface.Utilize the standby coating of this resin to reach 152 ° with the static contact angle of water on filter paper or metal screen, with oily static contact angle be 0 °; This super-hydrophobic super oil-wetted surface has efficient oily water separation characteristic, can remove the micro-moisture in fuel oil, has great real world applications meaning.
2) in resin of the present invention, the active function groups on the POSS base reacts with the intermolecular generation chemical copolymerization of organic group, chemical bonded refractory between this inorganic particulate and matrix is better than the bonding force of traditional physical mechanical blending with joint efforts far away, there is extremely strong mechanical property, the sticking power of the coating of utilizing this resin to prepare on stainless steel plate is 0～1 grade, pencil hardness is 1～3H, and the mechanical use properties of filming reaches requirement on industrial application.
3) POSS base hydridization fluorinated acrylate resin of the present invention adopts the preparation of free radical solution polymerization method, 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.
Embodiment
For understanding better the present invention, below in conjunction with embodiment, the invention will be further described, but embodiments of the present invention are not limited to this.
Embodiment 1
The first step, be equipped with electric blender, N
2in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel, add the 12g butylacetate as solvent, be warming up to 75 ℃ of backflow 30min, and pass into N
2then by the 1.2g methyl methacrylate, 1.9g butyl acrylate, 2.1g dodecyl acrylate, 1.5g methacrylic acid-β-hydroxyl ethyl ester, join constant pressure funnel after 0.135g Diisopropyl azodicarboxylate and 4g butylacetate mix, and stirs with 350 rev/mins of speed, 2.5h inside drip off continuously, drip follow-up continuation of insurance temperature reaction 3h;
Second step, by 1.0g methacrylic acid ten trifluoro monooctyl esters, the 0.019g Diisopropyl azodicarboxylate with join constant pressure funnel after the 2g butylacetate mixes, then at the uniform velocity be added drop-wise in the reaction system of the first step, 1.5h inside drip off continuously, drip follow-up continuation of insurance temperature reaction 3h;
The 3rd step, by 2.7g POSS base monomer (R=-CH wherein
2cH(CH
3) CH
3; P=3), 0.05g join in constant pressure funnel after Diisopropyl azodicarboxylate and 8g butylacetate mix, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 1h, drip follow-up continuation of insurance temperature reaction 2h, cooling discharge obtains hydrophobic lipophilicity POSS base hydridization fluorinated acrylate resin;
The 4th step, getting the hydrophobic lipophilicity POSS base of 1g hydridization fluorinated acrylate resin mixes with 0.089g HDI tripolymer (N3300), configuration 1.5% concentration resin solution in Freon 113/dimethylbenzene (V/V=1/1) solvent, after mixing, on stainless steel plate, filter paper and metal screen, adopt dip-coating method to film, at 100 ℃ of temperature, reaction 2h makes coating.
Embodiment 2
The first step, be equipped with electric blender, N
2in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel, add the 10g butylacetate as solvent, be warming up to 90 ℃ of backflow 30min, and pass into N
2then by the 0.8g Tert-butyl Methacrylate, 1.2g Isooctyl acrylate monomer, 1.8g Process Conditions of Cetane Acrylate, 1.4g the methacrylic acid hydroxy butyl ester, join constant pressure funnel after 0.104g benzoyl peroxide and 3g butylacetate mix, and stirs with 350 rev/mins of speed, drip off continuously in 3h, drip follow-up continuation of insurance temperature reaction 3.5h;
Second step, by 0.8g vinylformic acid hexafluoro butyl ester, the 0.015g benzoyl peroxide with join constant pressure funnel after the 2g butylacetate mixes, then at the uniform velocity be added drop-wise in the reaction system of the first step, in 0.5h, drip off continuously, drip follow-up continuation of insurance temperature reaction 2h;
The 3rd step, by 4g POSS base monomer (R=-CH wherein
2cH(CH
3) CH
3; P=2), 0.09g join in constant pressure funnel after benzoyl peroxide and 12g butylacetate mix, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 3h, drip follow-up continuation of insurance temperature reaction 4h, cooling discharge obtains hydrophobic lipophilicity POSS base hydridization fluorinated acrylate resin;
The 4th step, getting the hydrophobic lipophilicity POSS base of 1g hydridization fluorinated acrylate resin mixes with 0.099g IPDI tripolymer, configuration 2% concentration resin solution in the Freon 113 solvent, after mixing, on stainless steel plate, filter paper and metal screen, adopt dip-coating method to film, at 50 ℃ of temperature, reaction 2h makes coating.
Embodiment 3
The first step, be equipped with electric blender, N
2in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel, add the 11g butylacetate as solvent, be warming up to 80 ℃ of backflow 30min, and pass into N
2then by the 1.8g methyl methacrylate, 2.7g Isooctyl acrylate monomer, 2.4g stearyl methacrylate, 1.7g Rocryl 410, join constant pressure funnel after 0.184g Diisopropyl azodicarboxylate and 3g butylacetate mix, and stirs with 350 rev/mins of speed, 2.5h inside drip off continuously, drip follow-up continuation of insurance temperature reaction 4h;
Second step, by 1.2g 2-(perfluoro capryl) ethyl-methyl acrylate, the 0.02g Diisopropyl azodicarboxylate with join constant pressure funnel after the 2g butylacetate mixes, then at the uniform velocity be added drop-wise in the reaction system of the first step, 1.5h inside drip off continuously, drip follow-up continuation of insurance temperature reaction 2h;
The 3rd step, by 0.3g POSS base monomer (wherein
p=4), 0.005g join in constant pressure funnel after Diisopropyl azodicarboxylate and 3g butylacetate mix, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 2h, drip follow-up continuation of insurance temperature reaction 4h, cooling discharge obtains hydrophobic lipophilicity POSS base hydridization fluorinated acrylate resin;
The 4th step, getting the hydrophobic lipophilicity POSS base of 1.5g hydridization fluorinated acrylate resin mixes with 0.154g HDI tripolymer (N3300), configuration 1% concentration resin solution in Freon 113/dimethylbenzene (V/V=1/1) solvent, after mixing, on stainless steel plate, filter paper and metal screen, adopt dip-coating method to film, at 35 ℃ of temperature, reaction 2h makes coating.
Embodiment 4
The first step, be equipped with electric blender, N
2in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel, add 9g dimethylbenzene as solvent, be warming up to 90 ℃ of backflow 30min, and pass into N
2then by the 1.4g isopropyl methacrylate, 2.1g butyl acrylate, 2.6g Octyl acrylate, the 1g Rocryl 410, join constant pressure funnel after 0.142g Diisopropyl azodicarboxylate and 3g dimethylbenzene mix, and with 350 rev/mins of speed, stirs, drip off continuously in 3h, drip follow-up continuation of insurance temperature reaction 3h;
Second step, by 1.5g vinylformic acid ten trifluoro monooctyl esters, the 0.03g Diisopropyl azodicarboxylate with join constant pressure funnel after 4g dimethylbenzene mixes, then at the uniform velocity be added drop-wise in the reaction system of the first step, in 2.5h, drip off continuously, drip follow-up continuation of insurance temperature reaction 2.5h;
The 3rd step, by 1.4g POSS base monomer (R=-CH wherein
2cH(CH
3) CH
3; P=2), 0.03g join in constant pressure funnel after Diisopropyl azodicarboxylate and 5g dimethylbenzene mix, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 2h, drip follow-up continuation of insurance temperature reaction 3h, cooling discharge obtains hydrophobic lipophilicity POSS base hydridization fluorinated acrylate resin;
The 4th step, getting the hydrophobic lipophilicity POSS base of 1g hydridization fluorinated acrylate resin mixes with 0.079g HDI tripolymer (N3300), configuration 1% concentration resin solution in acetone/hexanaphthene (V/V=2/1) solvent, after mixing, on stainless steel plate, filter paper and metal screen, adopt dip-coating method to film, at 80 ℃ of temperature, reaction 2h makes coating.
Embodiment 5
The first step, be equipped with electric blender, N
2in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel, add 13g butylacetate/dimethylbenzene (V/V=1/1) as solvent, be warming up to 100 ℃ of backflow 30min, and pass into N
2then by the just own ester of 1.2g methacrylic acid, 1.6g ethyl propenoate, 1.7g Process Conditions of Cetane Acrylate, 1.9g Hydroxyethyl acrylate, join constant pressure funnel after 0.122g benzoyl peroxide and 4g butylacetate/dimethylbenzene (V/V=1/1) mix, and stirs with 350 rev/mins of speed, 2.5h inside drip off continuously, drip follow-up continuation of insurance temperature reaction 4h;
Second step, by the 1.5g dodecafluoroheptyl methacrylate, 0.03g benzoyl peroxide with join constant pressure funnel after 4g butylacetate/dimethylbenzene (V/V=1/1) mixes, then at the uniform velocity be added drop-wise in the reaction system of the first step, drip off continuously in 5min, drip follow-up continuation of insurance temperature reaction 0.5h;
The 3rd step, by 2.4g POSS base monomer (R=-C wherein
6h
5; P=2), 0.05g join in constant pressure funnel after benzoyl peroxide and 8g butylacetate/dimethylbenzene (V/V=1/1) mix, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 1h, drip follow-up continuation of insurance temperature reaction 4h, cooling discharge obtains hydrophobic lipophilicity POSS base hydridization fluorinated acrylate resin;
The 4th step, getting the hydrophobic lipophilicity POSS base of 1g hydridization fluorinated acrylate resin mixes with 0.105g HDI biuret, configuration 2% concentration resin solution in Freon 113/methyl alcohol (V/V=1/1) solvent, after mixing, on stainless steel plate, filter paper and metal screen, adopt dip-coating method to film, at 80 ℃ of temperature, reaction 2h makes coating.
Embodiment 6
The OCA mono-40 type contact angle instruments that adopt German Dataphysics company to the hydrophobic lipophilicity POSS base hydridization fluorinated acrylate resin coating of embodiment 1～5 preparation carry out Static Water, the kerosene contact angle is measured, the situation that records Static Water contact angle on stainless steel plate, filter paper and metal screen is as shown in table 1 below; The situation that records static kerosene contact angle on different grounds is as shown in table 2 below; The sticking power (GB/T1720 1), the pencil hardness (GB/T6739 1) that record coating on stainless steel plate are as shown in table 3 below.
The Static Water contact angle of the hydrophobic oleophylic coating of table 1 embodiment 1～5
| Ground | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Stainless steel plate ° | 131 | 127 | 135 | 139 | 129 |
| Filter paper ° | 146 | 143 | 145 | 149 | 143 |
| Metal screen ° | 150 | 148 | 152 | 151 | 144 |
The static kerosene contact angle of the hydrophobic oleophylic coating of table 2 embodiment 1～5
| Ground | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Stainless steel plate ° | 21 | 29 | 17 | 13 | 29 |
| Filter paper ° | 9 | 8 | 0 | 0 | 7 |
| Metal screen ° | 7 | 8 | 0 | 0 | 5 |
Sticking power and the pencil hardness of table 3 embodiment 1～5 coating on stainless steel plate
| Ground | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Sticking power | 1 grade | 0 grade | 1 grade | 0 grade | 1 grade |
| Pencil hardness | 2H | 1H | 3H | 1H | 2H |
From table 1 and table 2, the coating that the present invention constructs utilizes the coarse structure of the micron level on metal screen and the nano level roughness of POSS base monomer aggregation self-assembly structure jointly to form micro-nano pair of yardstick coarse structure, and then has been issued to super-hydrophobic super oleophylic effect in the modification of fluorochemical monomer low surface energy.Compared obvious advantage with the filming of resin formation of the POSS base monomer that undopes, as the Chinese patent of application publication number CN101696312A discloses a kind of hydrophobic oleophyllic bi-component acrylic resin, the static contact angle of this resin coating and water is greater than 110 °, and maximum has 132 °.Some reports of introducing other POSS base monomers in resin are also arranged, but hydrophobic effect is inadequate, lipophilicity is not discussed more, as the Chinese patent of publication number CN101029137A discloses a kind of synthetic resin of atom transfer radical polymerization method that adopts, the contact angle of its coating and water is 85～120 °; The Chinese patent of application publication number CN103012700A and CN102775567A, all adopt reversible addition one fragmentation chain transfer free radical polymerization method (RAFT) structure low surface energy, preparation technology's more complicated, hydrophobic effect is remarkable not, does not reach super-hydrophobic effect.
As known from Table 3, the coating that resin of the present invention is constructed has stronger sticking power and hardness, this is because the rigid structure of POSS self, and the bonding force of POSS base monomer and resin chemical bond increased the bonding force of inorganic particle and ground greatly, thereby substantially meets application requiring.Not introducing POSS base monomer system with other compares, it is with the obvious advantage: as the Chinese patent of publication number CN1721030A discloses a kind of oil-water separating net of super-hydrophobic super oleophylic, it adopts acid etch and surface-coated one strata perfluoroalkyl silicone film, but obtain roughness owing to need base material being carried out to acid etch, make woven mesh structure change and physical strength decline.
Claims (7)
1. a POSS base hydridization fluorinated acrylate resin, it is characterized in that, by weight percentage, this resin formula is: POSS base monomer accounts for 0.9～14%, and hard monomer accounts for 1.5～10%, soft monomer accounts for 2.5～14%, higher hydrocarbyl acrylate class monomer accounts for 4～10.5%, and the fluoroacrylate monomer accounts for 1.8～6%, and cross-linking monomer accounts for 1.8～9%, initiator accounts for 0.4～1.5%, and solvent accounts for 50～80%;
Described POSS base monomer structure formula is:
Wherein: R=-C
2h
5,-CH
2cH(CH
3) CH
3,-C
6h
5,-C
8h
17,
R '=-CH
2(CH2
) 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;
Described higher hydrocarbyl acrylate class monomer is Octyl acrylate, dodecyl acrylate, Process Conditions of Cetane Acrylate or stearyl methacrylate;
The molecular structural formula of described fluoroacrylate monomer is CF
3(CFX)
p(CH
2)
noOCCYCH
2, wherein, X is H, F, F
2or not containing any group; Y is H or CH
3; P=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 vinylformic acid hydroxy butyl ester;
Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate;
Described solvent is butylacetate and/or dimethylbenzene;
During preparation, the solvent that first will account for solvent quality 30～68% joins in reactor and is heated at 70～110 ℃ of temperature, 0.5～1h refluxes, then by hard monomer, soft monomer, higher hydrocarbyl acrylate class monomer, cross-linking monomer, account for initiator quality 48～90% initiator even with the solvent that accounts for solvent quality 4～27%, at the uniform velocity be added drop-wise to reactor in nitrogen atmosphere protection situation in, insulation reaction 0.5～4h, obtain reaction system; Then by the fluoroacrylate monomer, account for initiator quality 4～16% initiator even with the solvent that accounts for solvent quality 2.5～20%, be added drop-wise in reaction system, drip rear continuation reaction 0.5～4h, obtain mixed system; By POSS base monomer, remaining initiator and remaining solvent are even, are added drop-wise in mixed system again, drip rear continuation reaction 0.5～4h, and cooling discharge obtains hydrophobic lipophilicity POSS base hydridization fluorinated acrylate resin.
2. POSS base hydridization fluorinated acrylate resin according to claim 1, is characterized in that, described POSS base monomer is (SiO
1.5)
8r
7(CH
2)
3oOCC (CH
3) CH
2; R=-C wherein
2h
5, R=-CH
2cH (CH
3) CH
3, R=-C
8h
17or R=-C
6h
5; Or described POSS base monomer 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; R=-C wherein
2h
5, R=-CH
2cH (CH
3) CH
3, R=-C
8h
17or
3. POSS base hydridization fluorinated acrylate resin according to claim 1, it is characterized in that, described fluoroacrylate monomer is trifluoroethyl methacrylate, 2-(perfluoro capryl) ethyl-methyl acrylate, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl esters, vinylformic acid ten trifluoro monooctyl esters, Hexafluorobutyl mathacrylate or vinylformic acid hexafluoro butyl ester.
4. POSS base hydridization fluorinated acrylate resin according to claim 1, is characterized in that, by weight percentage, described POSS base monomer accounts for 3～40% of composition of raw materials material mass.
5. according to the preparation method of the described POSS base of claim 1-4 any one hydridization fluorinated acrylate resin, it is characterized in that comprising the steps:
The first step, join in reactor by the solvent that accounts for solvent total amount 30～68% and be heated at 70～110 ℃ of temperature, 0.5～1h refluxes, then by hard monomer, soft monomer, higher hydrocarbyl acrylate class monomer, cross-linking monomer, account for initiator total amount 48～90% initiator even with the solvent that accounts for solvent total amount 4～27%, at the uniform velocity be added drop-wise to reactor in nitrogen atmosphere protection situation in, the control time for adding is 2～3h, stirring velocity is 350 rev/mins, drips follow-up continuation of insurance temperature reaction 0.5～4h;
Second step, by the fluoroacrylate monomer, account for the initiator total amount 4～16% initiator even with the solvent that accounts for solvent total amount 2.5～20%, then at the uniform velocity be added drop-wise in the reaction system of the first step, the control time for adding is 5min～3h, drips rear continuation reaction 0.5～4h;
The 3rd step, by POSS base monomer, the initiator that accounts for initiator total amount 3～41% is even with 9～49% the solvent that accounts for the solvent total amount, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 0.5～3h, drip rear continuation reaction 0.5～4h, cooling discharge obtains hydrophobic lipophilicity POSS base hydridization fluorinated acrylate resin.
6. the application of POSS base hydridization fluorinated acrylate resin claimed in claim 1 in the hydrophobic oleophylic of preparation is filmed: described 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 is assembled self-assembly in film forming solvent, the micellar solution that the formation median size is 50～900nm, then described micellar solution is mixed with solidifying agent, adopt dip-coating method at stainless steel plate, make one deck uniform coating on filter paper or metal screen, react 1～3h and obtain hydrophobic oleophylic coating at 20～150 ℃ of temperature,
Described film forming solvent is one or both mixtures in Freon 113, dimethylbenzene, toluene, acetone, methyl alcohol, ethanol, trichloromethane, acetonitrile, pimelinketone, hexanaphthene, butylacetate and tetrahydrofuran (THF);
Described solidifying agent is the isocyanates solidifying agent; For HDI biuret, TDI-HDI tripolymer, HDI tripolymer or IPDI tripolymer; With molar ratio computing, the NCO/OH of solidifying agent and POSS base hydridization fluorinated acrylate resin is (0.7～1.9): 1.
7. the application of POSS base hydridization fluorinated acrylate resin in the hydrophobic oleophylic of preparation is filmed according to claim 6, it is characterized in that: the coating on described stainless steel plate and the static contact angle of water are 120～140 °, with the static contact angle of kerosene be 30～10 °; Coating on described filter paper or metal screen and the static contact angle of water are 143～152 °, with the static contact angle of kerosene be 10～0 °; On described stainless steel plate, the sticking power of coating is 0～1 grade, and pencil hardness is 1～3H.
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| CN105749770A (en) * | 2016-03-28 | 2016-07-13 | 无锡市绿之星环保有限公司 | Preparation method of novel super-oleophylic and super-hydrophobic separation membrane |
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