CN103435741B - POSS base hydridization fluorinated acrylate resin and preparation method thereof and application - Google Patents
POSS base hydridization fluorinated acrylate resin and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses POSS base hydridization fluorinated acrylate resin and preparation method thereof and application.By weight percentage, this resin formula is: POSS base monomer accounts for 0.9 ~ 14%, 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 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%.The present invention introduces higher hydrocarbyl acrylate class monomer as oleophylic monomer in fluoro-acrylate copolymer, the gathering self-assembly of POSS base in recycling multipolymer, filter paper or metal screen are constructed hydrophobic oleophilic oil compound Multi-scale model, thus prepares hydrophobic oleophilic oil film.Resin coating film prepared by the present invention is applicable to oily water separation field, can remove the micro-moisture in fuel oil, has great real world applications meaning.
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-oleophylic performance and preparation method thereof and application; Belong to organic/inorganic hybridization material.
Background technology
Along with the development of aviation, automotive industry, the requirement of people to aircraft, motor car engine is more and more higher, and as " the blood "-fuel oil of engine and hydraulic efficiency oil, their quality directly affects the performance of engine.Fluid water content is an important indicator of Oil Quality, is the one of the main reasons causing motor fault.Purifier in engine utilizes coarse separation to remove the impurity such as particle and water in fluid, selects the moisture had in filter screen (filter paper) oil and water separation of good hydrophilic oleophobic property, has great practical application meaning.
In recent years, screen surface study on the modification mainly concentrates on and improves the flow behavior of liquid phase at solid surface by the wettability that adjustment interface is intrinsic, and modified filter medium, to resistance that is oily and water, realizes oily water separation.Chinese utility model patent CN2598612Y adopts wire netting as framing structural member, polytetrafluorethylepowder powder (teflon) coating of layer of hydrophobic is all applied in the both side surface of wire netting, although teflon has excellent hydrophobic performance, but lipophilicity is not good, be insoluble to organic solvent, high-temperature fusion again need to be adopted after powder coating and their application, complicated operation, conditional request are harsh, and teflon coating is thicker, easily wire netting hole is blocked after spraying, increase fluid resistance to flow, reduce oily water separation efficiency.Publication number is that the Chinese invention patent application of CN1O1696312A and publication number CN1O160194OA carries out dipping coating by adding inorganic silicon dioxide particle in fluorine resin to filter screen, reach ultra-hydrophobicity, but the inorganic particulate in this polymkeric substance easily comes off, thus wearing and tearing are caused to engine, can not be applied in engine filter.
The filter structure of two-way heat power expansion that further exploitation separation efficiency is high, mechanical property is strong, has important practical application meaning.In recent years, receive based on the organic-inorganic nano hybrid composite material of polyhedral oligomeric silsesquioxane (PolyhedralOligomericSilsesquioxane, be called for short POSS) and pay close attention to widely.The core of the inorganic cage structure of the Si-O-Si key formation of POSS, has good mechanical property and thermostability.Combination between POSS inorganic particle and organic polymer belongs to chemical bonds, makes the surface bonding power between inorganic particle and matrix be better than the surface bonding of traditional physical mechanical blending far away; The size of inorganic nanoparticles can be controlled simultaneously by controlling synthesis condition, carrying out molecule assembling, thus reach the object controlling material requested macroscopic property.Publication number is that the Chinese invention patent application of CN102775567A discloses one containing POSS polyacrylic ester one polysiloxane block copolymers and preparation thereof.The surface energy hydrophobicity that coated material prepared by this invention has, may be used for preparing Anti-ice-and-snow, antifouling paint.POSS base is incorporated in traditional polymer by this application, to prepare hydrophobic respectively, parents, hydrophobic oleophobic coating, but do not have bibliographical information POSS base applications of fluoropolymers is constructed micro-nano pair of yardstick compound coarse structure on metal screen and reaches the super oily effect of super-hydrophobic parent, with the efficient conveying of the high efficiency separation and fluid that realize profit at present.
Summary of the invention
An object of the present invention is to provide one to have super-hydrophobic super-oleophylic, the POSS base hydridization fluorinated acrylate resin of good mechanical performance.
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 an object to be to provide POSS base hydridization fluorinated acrylate resin preparing the application in hydrophobic oleophilic oil film.
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%, 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 hy-droxybutyl;
Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate;
Described solvent is butylacetate and/or dimethylbenzene;
During preparation, first the solvent accounting for solvent quality 30 ~ 68% 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, higher hydrocarbyl acrylate class monomer, cross-linking monomer, account for initiator quality 48 ~ 90% initiator even with the solvent accounting for solvent quality 4 ~ 27%, at the uniform velocity be added drop-wise in reactor in nitrogen atmosphere protection situation, insulation reaction 0.5 ~ 4h, obtains reaction system; Then by fluoroacrylate monomer, account for initiator quality 4 ~ 16% initiator even with the solvent accounting for solvent quality 2.5 ~ 20%, be added drop-wise in reaction system, drip rear continuation reaction 0.5 ~ 4h, obtain mixed system; Again by POSS base monomer, evenly, be added drop-wise in mixed system, drip rear continuation reaction 0.5 ~ 4h, cooling discharge obtains hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin for remaining initiator and remaining solvent.
For realizing the object of the invention further, described POSS base monomer 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 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.
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, comprises the steps:
The first step, the solvent accounting for solvent total amount 30 ~ 68% 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, higher hydrocarbyl acrylate class monomer, cross-linking monomer, account for initiator total amount 48 ~ 90% initiator even with the solvent accounting for solvent total amount 4 ~ 27%, 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 350 revs/min, drips follow-up continuous insulation reaction 0.5 ~ 4h;
Second step, by fluoroacrylate monomer, account for initiator total amount 4 ~ 16% initiator with to account for the solvent of solvent total amount 2.5 ~ 20% even, 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, by POSS base monomer, the initiator accounting for initiator total amount 3 ~ 41% is even with the solvent of account for solvent total amount 9 ~ 49%, then be 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 hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin.
The application in hydrophobic oleophilic oil film prepared by described POSS base hydridization fluorinated acrylate resin: mixed with film forming solvent by described 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 50 ~ 900nm, 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 oleophilic oil coating,
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 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 relative to prior art:
1) in resin of the present invention, fluorine segment hydrophobic property, chain alkyl segment give lipophilicity, on this hydrophobic oleophilic oil surface, structure micro-nano pair of yardstick coarse structure is assembled in the self-assembly of recycling POSS base on filter screen, thus constructs out super-hydrophobic super-oleophilic surface.Utilizing the standby coating of this resin-made to reach 152 ° with the static contact angle of water on filter paper or metal screen, is 0 ° with the static contact angle of oil; This super-hydrophobic super-oleophylic surface has efficient oily water separation characteristic, can remove the micro-moisture in fuel oil, has great real world applications meaning.
2) active function groups in resin of the present invention on POSS base and between organic group Molecule, chemical copolymerization occurs and react, 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 utilizing this resin to prepare on stainless steel is 0 ~ 1 grade, pencil hardness is 1 ~ 3H, and film machinery use properties 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 the present invention better, below in conjunction with embodiment, the invention will be further described, but embodiments of the present invention are not limited thereto.
Embodiment 1
The first step, is being equipped with electric blender, N
2add 12g butylacetate in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel as solvent, be warming up to 75 DEG C of backflow 30min, and pass into N
2then by 1.2g methyl methacrylate, 1.9g butyl acrylate, 2.1g dodecyl acrylate, 1.5g methacrylic acid-β-hydroxyl ethyl ester, joins constant pressure funnel after 0.135g Diisopropyl azodicarboxylate and 4g butylacetate mix, and stirs with 350 revs/min of speed, drip off continuously in 2.5h, drip follow-up continuous insulation reaction 3h;
Second step, by 1.0g methacrylic acid ten trifluoro monooctyl ester, 0.019g Diisopropyl azodicarboxylate joins constant pressure funnel after mixing with 2g butylacetate, is then at the uniform velocity added drop-wise in the reaction system of the first step, drip off continuously in 1.5h, drip follow-up continuous insulation reaction 3h;
3rd step, by 2.7gPOSS base monomer (wherein R=-CH
2cH(CH
3) CH
3; P=3), join in constant pressure funnel after 0.05g 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 hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin;
4th step, get 1g hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin to mix with 0.089gHDI tripolymer (N3300), 1.5% 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 100 DEG C of temperature and obtain coating.
Embodiment 2
The first step, is being equipped with electric blender, N
2add 10g butylacetate in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel as solvent, be warming up to 90 DEG C of backflow 30min, and pass into N
2then by 0.8g Tert-butyl Methacrylate, 1.2g Isooctyl acrylate monomer, 1.8g Process Conditions of Cetane Acrylate, 1.4g methacrylate, joins constant pressure funnel after 0.104g benzoyl peroxide and 3g butylacetate mix, and stirs with 350 revs/min of speed, drip off continuously in 3h, drip follow-up continuous insulation reaction 3.5h;
Second step, by 0.8g vinylformic acid hexafluoro butyl ester, 0.015g benzoyl peroxide joins constant pressure funnel after mixing with 2g butylacetate, is then at the uniform velocity added drop-wise in the reaction system of the first step, drips off continuously in 0.5h, drips follow-up continuous insulation reaction 2h;
3rd step, by 4gPOSS base monomer (wherein R=-CH
2cH(CH
3) CH
3; P=2), join in constant pressure funnel after 0.09g benzoyl peroxide and 12g butylacetate mix, then be at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 3h, drip follow-up continuous insulation reaction 4h, cooling discharge obtains hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin;
4th step, get 1g hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin to mix with 0.099gIPDI 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 3
The first step, is being equipped with electric blender, N
2add 11g butylacetate in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel as solvent, be warming up to 80 DEG C of backflow 30min, and pass into N
2then by 1.8g methyl methacrylate, 2.7g Isooctyl acrylate monomer, 2.4g stearyl methacrylate, 1.7g Rocryl 410, joins constant pressure funnel after 0.184g Diisopropyl azodicarboxylate and 3g butylacetate mix, and stirs with 350 revs/min of speed, drip off continuously in 2.5h, drip follow-up continuous insulation reaction 4h;
Second step, by 1.2g2-(perfluoro capryl) ethylmethyl acrylate, 0.02g Diisopropyl azodicarboxylate joins constant pressure funnel after mixing with 2g butylacetate, is then at the uniform velocity added drop-wise in the reaction system of the first step, drip off continuously in 1.5h, drip follow-up continuous insulation reaction 2h;
3rd step, by 0.3gPOSS base monomer (wherein
p=4), join in constant pressure funnel after 0.005g Diisopropyl azodicarboxylate and 3g butylacetate mix, then be at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 2h, drip follow-up continuous insulation reaction 4h, cooling discharge obtains hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin;
4th step, get 1.5g hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin to mix with 0.154gHDI 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 4
The first step, is being equipped with electric blender, N
2add 9g dimethylbenzene in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel as solvent, be warming up to 90 DEG C of backflow 30min, and pass into N
2then by 1.4g isopropyl methacrylate, 2.1g butyl acrylate, 2.6g Octyl acrylate, 1g Rocryl 410, joins constant pressure funnel after 0.142g Diisopropyl azodicarboxylate and 3g dimethylbenzene mix, and stirs with 350 revs/min of speed, drip off continuously in 3h, drip follow-up continuous insulation reaction 3h;
Second step, by 1.5g vinylformic acid ten trifluoro monooctyl ester, 0.03g Diisopropyl azodicarboxylate joins constant pressure funnel after mixing with 4g dimethylbenzene, is then at the uniform velocity added drop-wise in the reaction system of the first step, drips off continuously in 2.5h, drips follow-up continuous insulation reaction 2.5h;
3rd step, by 1.4gPOSS base monomer (wherein R=-CH
2cH(CH
3) CH
3; P=2), join in constant pressure funnel after 0.03g Diisopropyl azodicarboxylate and 5g dimethylbenzene mix, then be at the uniform velocity added drop-wise in the reaction system of second step, control time for adding is 2h, drip follow-up continuous insulation reaction 3h, cooling discharge obtains hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin;
4th step, get 1g hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin to mix with 0.079gHDI 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 5
The first step, is being equipped with electric blender, N
2add 13g butylacetate/dimethylbenzene (V/V=1/1) in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel as solvent, be warming up to 100 DEG C of backflow 30min, and pass into N
2then by just own for 1.2g methacrylic acid ester, 1.6g ethyl propenoate, 1.7g Process Conditions of Cetane Acrylate, 1.9g Hydroxyethyl acrylate, joins constant pressure funnel after 0.122g benzoyl peroxide and 4g butylacetate/dimethylbenzene (V/V=1/1) mix, and stirs with 350 revs/min of speed, drip off continuously in 2.5h, drip follow-up continuous insulation reaction 4h;
Second step, by 1.5g dodecafluoroheptyl methacrylate, 0.03g benzoyl peroxide joins constant pressure funnel after mixing with 4g butylacetate/dimethylbenzene (V/V=1/1), then 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 0.5h;
3rd step, by 2.4gPOSS base monomer (wherein R=-C
6h
5; P=2), join in constant pressure funnel after 0.05g benzoyl peroxide and 8g butylacetate/dimethylbenzene (V/V=1/1) 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 4h, cooling discharge obtains hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin;
4th step, get 1g hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin to mix with 0.105gHDI 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 6
Adopt the OCA 1 type contact angle instrument of German Dataphysics company to carry out Static Water, kerosene Contact-angle measurement to hydrophobic oleophilic oil 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; The situation recording static kerosene contact angle on different ground 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 angles of table 1 embodiment 1 ~ 5 hydrophobic oleophilic oil coating
| 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 table 2 embodiment 1 ~ 5 hydrophobic oleophilic oil coating
| 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 |
Table 3 embodiment 1 ~ 5 coating sticking power on stainless steel and pencil hardness
| 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 nanoscale rough degree of the coarse structure of the micron level on metal screen and POSS base monomer aggregation self-assembly structure to together 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.Obvious advantage is had compared with the film of the resin formation of the POSS base monomer that undopes, Chinese patent as application publication number CN101696312A discloses a kind of hydrophobic oleophilic oil bi-component acrylic resin, the static contact angle of this resin coating and water is greater than 110 °, and maximum have 132 °.Also some reports introducing other POSS base monomers in resin are had, but hydrophobic effect is inadequate, lipophilicity is not discussed more, Chinese patent as publication number CN101029137A discloses a kind of resin adopting atom transfer radical polymerization method to synthesize, and the contact angle of its coating and water is 85 ~ 120 °; The Chinese patent of application publication number CN103012700A and CN102775567A, reversible addition one fragmentation chain transfer free radical polymerization method (RAFT) is all adopted to construct 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 constructs 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 key considerably increases the bonding force of inorganic particle and ground, thus substantially meets application requiring.Compared with other do not introduce POSS base monomer system, with the obvious advantage: the Chinese patent as 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 perfluoroalkylsilane film, but due to acid etch need be carried out to obtain roughness to base material, woven mesh structure is changed and physical strength decline.
Claims (6)
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 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(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)
p(CH
2)
noOCCYCH
2,wherein, X is H or F; 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 hy-droxybutyl;
Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate;
Described solvent is butylacetate and/or dimethylbenzene;
During preparation, first the solvent accounting for solvent quality 30 ~ 68% 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, higher hydrocarbyl acrylate class monomer, cross-linking monomer, account for initiator quality 48 ~ 90% initiator even with the solvent accounting for solvent quality 4 ~ 27%, at the uniform velocity be added drop-wise in reactor in nitrogen atmosphere protection situation, insulation reaction 0.5 ~ 4h, obtains reaction system; Then by fluoroacrylate monomer, account for initiator quality 4 ~ 16% initiator even with the solvent accounting for solvent quality 2.5 ~ 20%, be added drop-wise in reaction system, drip rear continuation reaction 0.5 ~ 4h, obtain mixed system; Again by POSS base monomer, evenly, be added drop-wise in mixed system, drip rear continuation reaction 0.5 ~ 4h, cooling discharge obtains hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin for remaining initiator and remaining solvent.
2. POSS base hydridization fluorinated acrylate resin according to claim 1, it is characterized in that, described POSS base monomer 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 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
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) 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.
4. the preparation method of the POSS base hydridization fluorinated acrylate resin according to any one of claim 1-3, is characterized in that comprising the steps:
The first step, the solvent accounting for solvent total amount 30 ~ 68% 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, higher hydrocarbyl acrylate class monomer, cross-linking monomer, account for initiator total amount 48 ~ 90% initiator even with the solvent accounting for solvent total amount 4 ~ 27%, 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 350 revs/min, drips follow-up continuous insulation reaction 0.5 ~ 4h;
Second step, by fluoroacrylate monomer, account for initiator total amount 4 ~ 16% initiator with to account for the solvent of solvent total amount 2.5 ~ 20% even, 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, by POSS base monomer, the initiator accounting for initiator total amount 3 ~ 41% is even with the solvent of account for solvent total amount 9 ~ 49%, then be 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 hydrophobic oleophilic oil POSS base hydridization fluorinated acrylate resin.
5. the application in hydrophobic oleophilic oil film prepared by POSS base hydridization fluorinated acrylate resin according to claim 1: mixed with film forming solvent by described 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 50 ~ 900nm, 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 oleophilic oil coating,
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 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.
6. the application in hydrophobic oleophilic oil film prepared by POSS base hydridization fluorinated acrylate resin according to claim 5, it is characterized in that: the coating on described stainless steel plate and the static contact angle of water are 120 ~ 140 °, is 30 ~ 10 ° with the static contact angle of kerosene; Coating on described filter paper or metal screen and the static contact angle of water are 143 ~ 152 °, are 10 ~ 0 ° with the static contact angle of kerosene; 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 |
| CN108641257B (en) * | 2016-07-22 | 2020-06-12 | 广州连达橡塑有限公司 | High-temperature-resistant acrylate rubber |
| CN106700809A (en) * | 2016-12-13 | 2017-05-24 | 中国人民解放军61489部队 | POSS (Posspolyhedral Oligomeric Silsesquioxane) containing construction engineering waterproof coating and preparation method thereof |
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| CN109289559B (en) * | 2018-10-09 | 2021-05-07 | 西北工业大学 | Preparation method of hydrophobic oleophylic self-supporting membrane polymer porous membrane and composite hydrophobic oleophylic separation material |
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| CN110452490B (en) * | 2019-08-29 | 2021-09-17 | 安徽立兴化工有限公司 | Dual POSS polyether hybrid water-based acrylic resin dispersion, preparation method and composition for preparing resin coating film |
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| CN112961602B (en) * | 2021-03-04 | 2022-09-23 | 宁波市金象厨具有限公司 | Non-stick pan coating based on interpenetrating network structure and preparation method thereof |
| CN114381172A (en) * | 2021-12-31 | 2022-04-22 | 山东东岳未来氢能材料股份有限公司 | Stripping-resistant ethylene-tetrafluoroethylene copolymer powder coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696312A (en) * | 2009-10-27 | 2010-04-21 | 华南理工大学 | Hydrophobic and oleophyllic bi-component acrylic resin and preparation method and application thereof |
| CN101875707A (en) * | 2009-04-30 | 2010-11-03 | 比亚迪股份有限公司 | Fluorin-containing POSS acrylate polymer, preparation method thereof and paint |
| CN102351983A (en) * | 2011-08-10 | 2012-02-15 | 天津大学 | Fluorine silicon acrylate copolymer, preparation process thereof and application thereof |
-
2013
- 2013-08-27 CN CN201310378732.XA patent/CN103435741B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875707A (en) * | 2009-04-30 | 2010-11-03 | 比亚迪股份有限公司 | Fluorin-containing POSS acrylate polymer, preparation method thereof and paint |
| CN101696312A (en) * | 2009-10-27 | 2010-04-21 | 华南理工大学 | Hydrophobic and oleophyllic bi-component acrylic resin and preparation method and application thereof |
| CN102351983A (en) * | 2011-08-10 | 2012-02-15 | 天津大学 | Fluorine silicon acrylate copolymer, preparation process thereof and application thereof |
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