CN107502127A - A kind of fluorine-containing lubricant coating and its preparation method and application - Google Patents

A kind of fluorine-containing lubricant coating and its preparation method and application Download PDF

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CN107502127A
CN107502127A CN201710793868.5A CN201710793868A CN107502127A CN 107502127 A CN107502127 A CN 107502127A CN 201710793868 A CN201710793868 A CN 201710793868A CN 107502127 A CN107502127 A CN 107502127A
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fluorine
preparation
lubricant coating
ether function
containing lubricant
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CN107502127B (en
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李辉
周翠平
石玉洁
赵小云
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • C08F299/0485—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters from polyesters with side or terminal unsaturations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters

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Abstract

The present invention relates to a kind of fluorine-containing lubricant coating and its preparation method and application, fluorine-containing lubricant coating of the invention is to be combined by copolymer porous surface with fluorine ether function oligomer by absorption and hydrogen bond action.Fluorine ether function oligomer is not easy to lose, deicing properties lasting stability because hydrogen bond action is adsorbed on porous surface.The fluorine-containing lubricant coating prepared, hydrophobic performance is strong, can be used for anti-icing coatings.The lubricant coating water contact angle is more than 100 °, and roll angle is less than 10 °, and has good deicing properties.

Description

A kind of fluorine-containing lubricant coating and its preparation method and application
Technical field
The present invention relates to a kind of fluorine-containing lubricant coating and its preparation method and application, belongs to coating preparation and application field.
Background technology
In fields such as communications and transportation, power communications, surface, which freezes, can bring significant damage and potential safety hazard, therefore prepare anti- Icing coating has great application value.Material surface freezing performance not only has with the chemical composition of material surface with structure Close, also influenceed by its microstructure.Therefore application study of the super hydrophobic surface with microstructure in freezing field is many It is more.But the microstructure of super hydrophobic surface is easily destroyed, the persistence of freezing performance is influenceed；And there are some researches show height The deicing properties of super hydrophobic surface are unsatisfactory under damp condition.In recent years, in freezing field, by adsorbing organic lubrication Liquid substitutes the air sheltered in super hydrophobic surface, and the lubricated surface formed turns into the focus of current research.
The content of the invention
It is an object of the present invention to it is directed to deficiency of the prior art, there is provided a kind of fluorine-containing lubricant coating and its preparation side Method.
Meanwhile present invention also offers the application of above-mentioned fluorine-containing lubricant coating.
Technical solution of the present invention is as follows：
A kind of preparation method of fluorine-containing lubricant coating, be by copolymer porous surface and fluorine ether function oligomer, by absorption and Hydrogen bond action is combined.
Further, described copolymer porous surface, preparation method are：First by fluorine-containing and/or silicon polyolefin-poly- Aromatic ester block copolymer, two mercaptan compounds and catalyst are dissolved in solvent, be configured to solvent quality fraction be 70~98% it is poly- Polymer solution；Then the solution is coated on base material using spraying or knife coating procedure, by 30~200min of ultraviolet light, Copolymer porous surface is produced after drying.
Preferably, above-mentioned copolymer porous surface, in preparation method：
The mass ratio of described fluorine-containing and/or silicon polyolefin-polyarylate block copolymer and two mercaptan compounds, catalyst is 100:2~10：0.01~0.05；
Described solvent is the mixing of one or both of chloroform, pentafluorodichloropropane, dimethylformamide and tetrahydrofuran Thing；
Two described mercaptan compounds are dithioglycol, dimercaptopropane, succinimide mercaptans or ethanthiol；
Described catalyst is diphenylethan, diphenylmethanone, 2,4 dihydroxyl benzophenone or 2- hydroxy-2-methyls -1- Phenylacetone.
Preferably, described fluorine-containing and/or silicon polyolefin-polyarylate block copolymer, its number-average molecular weight are 14000~150000, the water contact angle on its surface is more than 95o；Its structure is as shown in formula I：
In formula, n is 10~150 natural number, and m is 20~600 natural number；
R1 is：
；
R2 is：
。
Further, described fluorine ether function oligomer, preferably end carboxyl fluorine ether function oligomer（HFPO six Aggressiveness）, end diaminourea fluorine ether function oligomer（The HFPO tetramer）Or terminal hydroxy group fluorine ether function oligomer（Hexafluoro ring Ethylene Oxide dimer）.
Further, described fluorine ether function oligomer, it is using HFPO oligomer as raw material, to its acyl fluorides end Base is hydrolyzed, hydroxylating or aminating reaction, and the obtained fluorine ether function oligomer with different hydrogen bond receptors or donor, it is tied Structure is as shown in formula II：
In formula, x is 2~20 natural number；
Ra is：
。
Present invention additionally comprises a kind of fluorine-containing lubricant coating being prepared by the above method, the fluorine-containing lubricant coating water connects Feeler is more than 100 °, and roll angle is less than 10 °；Described fluorine-containing lubricant coating, fluorine ether function oligomer is in copolymer porous surface Adsorbance be 0.2~1.5L/m2。
The application of the fluorine-containing lubricant coating of the present invention, has good deicing properties, is preferred for anti-icing coatings.
Technical solution of the present invention, its advantage are：The present invention fluorine-containing lubricant coating be by copolymer porous surface with Fluorine ether function oligomer is combined by absorption and hydrogen bond action.Fluorine ether function oligomer is adsorbed porous due to hydrogen bond action On surface, therefore it is not easy to lose, deicing properties lasting stability.The fluorine-containing lubricant coating prepared, hydrophobic performance is strong, can be used to prevent Icing coating.The lubricant coating water contact angle is more than 100 °, and roll angle is less than 10 °, and has good deicing properties.
Embodiment
Illustrate the present invention below by way of instantiation, but the present invention is not only limited to these examples, it is impossible to be interpreted as pair The limitation of protection scope of the present invention, it is nonessential that person skilled in art can do some according to the content of the invention described above Modifications and adaptations.
Embodiment 1
1st, fluorine polyolefin-polyarylate block copolymer is prepared：
1）End group contains the preparation of the fluorine polyolefin of double bond：By 4.58g ENB carboxylic acids trifluoro ethyl ester, 100mg Grubbs II catalyst is dissolved in 20mL anhydrous methylene chlorides.After reacting 4h at 40 DEG C, cooling, stop reaction.Room temperature revolving removes dichloro Methane, dry, it is standby；
2）End group contains the preparation of the polyarylate of double bond：By 10g bisphenol A-types diallyl ether, 300mg Grubbs- Hoveyda II catalyst and 10g benzotrifluorides, add in reaction bulb, after stirring, be warming up to 80 DEG C, react 2h, cooling stops anti- Should.Revolving removes solvent, obtains brown solid；
3）Fluorine polyolefin-polyarylate block copolymer：The 4.2g end groups of above-mentioned preparation are contained to fluorine polyolefin, the 3.5g ends of double bond Base contains the polyarylate and 30mg Grubbs I catalyst and 20g toluene of double bond, adds in reaction bulb, leads to nitrogen, and stirring is equal After even, 60 DEG C are warming up to, reacts 3h.Precipitated with n-hexane, remove solvent, obtain brown solid, i.e. fluorine polyolefin-poly- virtue Ester block copolymer, structural formula are：
2nd, copolymer porous surface is prepared：By prepared fluorine polyolefin-polyarylate block copolymer 4g, (molecular weight is 14200), dithioglycol 0.08g and benzophenone 0.2g are dissolved in pentafluorodichloropropane, and 30% solution is made.Then will be made Standby solution spraying, in the ultraviolet light 40min using 365nm, after drying, obtains copolymer porous surface on base material.
3rd, fluorine-containing lubricant coating is prepared：By 2ml end carboxyl fluorine ether function oligomer（The aggressiveness of HFPO six） Even absorption is in copolymer porous surface（10cm×10cm）On, fluorine-containing lubricant coating is obtained, the contact angle of its surface water is 105 °, roll angle is 14 °.
Embodiment 2
1st, fluorine and silicon polyolefin-polyarylate block copolymer are prepared：
1）End group contains the preparation of the silicon polyolefin of double bond：By 10g cyclo-octene dimethyl silicone polymer esters（Molecular weight about 900）、 100mg Grubbs III catalyst is dissolved in 50mL anhydrous methylene chlorides.After reacting 6h at 40 DEG C, cooling, stop reaction.Room Temperature revolving removes dichloromethane, dries, standby；
2）End group contains the preparation of the polyarylate of double bond：By 10g bisphenol AF types diallyl ether, 15mg Grubbs-Hoveyda I catalyst and 30g toluene, add in reaction bulb, after stirring, be warming up to 105 DEG C, react 4h, cooling stops reaction.Rotation Solvent is evaporated off, obtains brown solid；
3）Fluorine-containing and silicon polyolefin-polyarylate block copolymer the 5.7g end groups of above-mentioned preparation are contained double bond silicon polyolefin, 7.2g end groups contain the polyarylate and 30mg Grubbs- Hoveyda II catalyst and 20g tetrahydrofurans of double bond, add anti- Answer in bottle, after stirring, be warming up to 40 DEG C, react 5h.Precipitated with n-hexane, remove solvent, obtain brown solid, i.e., Fluorine-containing and silicon polyolefin-polyarylate block copolymer, structural formula are：
2nd, copolymer porous surface is prepared：By prepared fluorine-containing and silicon polyolefin-polyarylate block copolymer 5g, (molecular weight is 135000), ethanthiol 0.5g and 2,4-DihydroxyBenzophenone 0.05g are dissolved in tetrahydrofuran alkane, and 15% solution is made. Then prepared solution is scratched on base material, in the ultraviolet light 80min using 365nm, is immersed in the water 20 minutes, takes Go out after drying, obtain copolymer porous surface.
3rd, fluorine-containing lubricant coating is prepared：By 15ml ends diaminourea fluorine ether function oligomer（The HFPO tetramer） Even absorption is in copolymer porous surface（10cm×10cm）On, fluorine-containing lubricant coating is obtained, the contact angle of its surface water is 112 °, roll angle is 4 °.
Embodiment 3
1st, fluorine polyolefin-polyarylate block copolymer is prepared：
1）End group contains the preparation of the fluorine polyolefin of double bond：By the difluoro heptyl ester of 9.16g ENBs carboxylic acid ten, 60mg Grubbs II catalyst is dissolved in 50mL anhydrous methylene chlorides.After reacting 6h at 40 DEG C, cooling, stop reaction.Room temperature revolving removes dichloro Methane, dry, it is standby；
2）End group contains the preparation of the polyarylate of double bond：By 10g bisphenol A-type diallyls benzoxazine, 50mg Grubbs- Hoveyda II catalyst and 50g dimethylformamides, add in reaction bulb, after stirring, be warming up to 85 DEG C, reaction 5h, cooling stop reaction.Revolving removes solvent, obtains sepia solid product；
3）Fluorine polyolefin-polyarylate block copolymer：The 2.7g end groups of above-mentioned preparation are contained to fluorine polyolefin, the 5.8g ends of double bond Base contains the polyarylate and 10mg Grubbs II catalyst and 20g chloroforms of double bond, adds in reaction bulb, stirs Afterwards, 50 DEG C are warming up to, reacts 6h.Precipitated with n-hexane, remove solvent, obtain brown solid, i.e. fluorine polyolefin-polyarylate Block copolymer, structural formula are：
2nd, copolymer porous surface is prepared：By prepared fluorine polyolefin-polyarylate block copolymer 6g, (molecular weight is 87000), succinimide mercaptans 0.048g and benzyl phenyl ketone 0.2g are dissolved in dichloromethane, and 10% solution is made.Then by prepared by Solution spraying on base material, using 365nm ultraviolet light 200min, dry after, obtain copolymer porous surface.
3rd, fluorine-containing lubricant coating is prepared：By 10ml terminal hydroxy group fluorine ether function oligomer（Dimerization of hexafluoropropene oxide body）Uniformly Absorption in copolymer porous surface（10cm×10cm）On, fluorine-containing lubricant coating is obtained, the contact angle of its surface water is 110 °, Roll angle is 6 °.
The deicing properties of fluorine-containing lubricant coating prepared by embodiment 1~3 are as shown in table 1：
The deicing properties of 1 fluorine-containing lubricant coating of table
Fluorine-containing lubricant coating prepared by the present invention is compared with metallic aluminum surface, the ice adhesion on anti-icing coatings surface of the present invention Intensity declines less than 95%；Under low temperature, ice cover reduces by less than 70%；During the water freezing delay on the fluorine-containing lubricant coating surface of the present invention Between be more than 40s.

Claims (10)

  1. A kind of 1. preparation method of fluorine-containing lubricant coating, it is characterised in that：It is oligomeric by copolymer porous surface and fluorine ether function Thing, it is combined by absorption and hydrogen bond action.
  2. 2. preparation method according to claim 1, it is characterised in that：Described copolymer porous surface, preparation method are： Fluorine-containing and/or silicon polyolefin-polyarylate block copolymer, two mercaptan compounds and catalyst are dissolved in solvent first, matched somebody with somebody The polymer solution that solvent quality fraction is 70~98% is made；Then the solution is coated on base using spraying or knife coating procedure On material, by 30~200min of ultraviolet light, copolymer porous surface is produced after drying.
  3. 3. preparation method according to claim 2, it is characterised in that：Described fluorine-containing and/or silicon polyolefin-polyarylate Block copolymer and two mercaptan compounds, the mass ratio of catalyst are 100:2~10：0.01~0.05；Described solvent is chlorine The mixture of one or both of imitative, pentafluorodichloropropane, dimethylformamide and tetrahydrofuran；Described two are Thiolation Compound is dithioglycol, dimercaptopropane, succinimide mercaptans or ethanthiol；Described catalyst is diphenylethan, diphenylmethyl Ketone, 2,4 dihydroxyl benzophenone or 2- hydroxy-2-methyl -1- phenylacetones.
  4. 4. preparation method according to claim 2, it is characterised in that：Described fluorine-containing and/or silicon polyolefin-polyarylate Block copolymer, its number-average molecular weight are 14000~150000, and the water contact angle on its surface is more than 95o；Its structure such as institute of formula I Show：
    In formula, n is 10~150 natural number, and m is 20~600 natural number；
    R1 is：
    ；
    R2 is：
    。
  5. 5. preparation method according to claim 1, it is characterised in that：Described fluorine ether function oligomer, it is end carboxyl fluorine Ether function oligomer, end diaminourea fluorine ether function oligomer or terminal hydroxy group fluorine ether function oligomer.
  6. 6. preparation method according to claim 1, it is characterised in that：Described fluorine ether function oligomer, is with hexafluoro ring Ethylene Oxide oligomer is raw material, its acyl fluorides end group is hydrolyzed, hydroxylating or aminating reaction, it is obtained have different hydrogen bonds by The fluorine ether function oligomer of body or donor, its structure is as shown in formula II：
    In formula, x is 2~20 natural number；
    Ra is：
    。
  7. 7. the fluorine-containing lubricant coating that a kind of any one of claim 1~6 methods described is prepared.
  8. 8. fluorine-containing lubricant coating according to claim 7, it is characterised in that：Water contact angle is more than 100 °, and roll angle is less than 10°。
  9. 9. fluorine-containing lubricant coating according to claim 7, it is characterised in that：Fluorine ether function oligomer is in the porous table of copolymer The adsorbance in face is 0.2~1.5L/m2。
  10. 10. the application for the fluorine-containing lubricant coating that a kind of any one of claim 1~6 methods described is prepared, it is characterised in that： With good deicing properties, for anti-icing coatings.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109232964A (en) * 2018-09-11 2019-01-18 济南大学 A kind of flexible lubrication coating and its preparation method and application
CN114656594A (en) * 2021-12-14 2022-06-24 济南大学 Preparation method and application of high-strength anti-icing organogel

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4301208A (en) * 1980-09-04 1981-11-17 The United States Of America As Represented By The Secretary Of The Army Method for reducing the adhesion of ice to the walls of navigation locks
CN105969178A (en) * 2016-05-24 2016-09-28 济南大学 Benzoxazine type super-hydrophobic nano silicon dioxide as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4301208A (en) * 1980-09-04 1981-11-17 The United States Of America As Represented By The Secretary Of The Army Method for reducing the adhesion of ice to the walls of navigation locks
CN105969178A (en) * 2016-05-24 2016-09-28 济南大学 Benzoxazine type super-hydrophobic nano silicon dioxide as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
毛昆朋等: "金属表面抗结冰研究进展", 《科技通报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109232964A (en) * 2018-09-11 2019-01-18 济南大学 A kind of flexible lubrication coating and its preparation method and application
CN109232964B (en) * 2018-09-11 2021-04-30 济南大学 Flexible lubricating coating and preparation method and application thereof
CN114656594A (en) * 2021-12-14 2022-06-24 济南大学 Preparation method and application of high-strength anti-icing organogel
CN114656594B (en) * 2021-12-14 2023-08-15 济南大学 Preparation method and application of high-strength anti-icing organogel

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