CN107603475B - A kind of bisphenol AF-PEG block copolymer hydrophilic surface coating and preparation method thereof - Google Patents
A kind of bisphenol AF-PEG block copolymer hydrophilic surface coating and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of bisphenol AF-PEG block copolymer hydrophilic surface coatings and preparation method thereof, prepare bisphenol AF-PEG block copolymer by olefin metathesis polymerisation first, then construct hydrophilic freezing surface covering with prepared block copolymer.The bisphenol AF of preparation-PEG block copolymer, molecular weight is controllable, and surface can generate micro phase separation structure, hydrophilic strong；Preparation method is simple, and reaction condition is mild, and the reaction time is short, is conducive to industrialize.Water-wetted surface is formed by using the block copolymer, water contact angle is less than 20 °.May interfere with aggregation of the hydrone on the copolymer surface under low temperature since though fluorine-containing groups are different from the interaction force of PEG chain segment hydrone, between -7~0 DEG C can anti-stagnant ice adherency, extend freezing time.There is good wide application prospect in anti-freeze field.
Description
Technical field
The present invention relates to a kind of bisphenol AF-PEG block copolymer hydrophilic surface coatings and preparation method thereof, belong to coating system
Standby and applied technical field.
Background technique
Ice damage brings great harm to the mankind and society, how effectively to prevent water droplet under low temperature on the substrate surface
Icing has become an important and urgent project.Currently, that there are types is few for used freezing coating, application limitation is big
Etc. problems, be not able to satisfy the requirement of society, be badly in need of developing the freezing coating material of high comprehensive performance a kind of
Material (Progress in Chemistry, 2012 24:2087-2096).In recent years, the freezing coating of water-wetted surface by
Extensive concern.Block copolymer is one kind functional polymer made of chemical structure difference segment alternating polymerization.With specific
The block polymer of structure can be shown and simple wire-form polymer and many random copolymers even mixture of homopolymer
Different property, it is anti-icing, antifouling, in terms of have great application prospect.
Summary of the invention
It is an object of the present invention to aiming at the shortcomings in the prior art, provide a kind of bisphenol AF-PEG block copolymer parent
Water meter finishing coat and preparation method thereof.Bisphenol AF-PEG block copolymer is prepared by olefin metathesis polymerisation first, then with institute
The block copolymer of preparation constructs hydrophilic freezing surface covering.
Technical solution of the present invention is as follows:
A kind of bisphenol AF-PEG block copolymer hydrophilic surface coating is with main chain bisphenol AF-PEG block containing double bonds
Copolymer and the bis- mercapto-polyglycols of HS-PEG-SH() it is raw material, under the action of catalyst, room temperature is reacted by ultraviolet light
30~200min is formed；The hydrophilic surface coating water contact angle is less than 20 °.
Further, main chain bisphenol AF containing double bonds-PEG block copolymer, number-average molecular weight be 4000~
96000, the water contact angle on surface is less than 40 °, and structure is as shown in formula I:
In formula, the natural number that n is 8~150, the natural number that m is 5~100；
R1 are as follows:
；
R2 are as follows:
,
In formula, x be 10~120 natural number.
Preferably, main chain bisphenol AF containing double bonds-PEG block copolymer, preparation method are as follows: contain end group
The bisphenol AF polyarylate and end group polyethylene glycol containing double bonds for having double bond are dissolved in solvent, after mixing, are made in catalyst
In 30~105 DEG C of 1~6h of reaction under, remove solvent after having reacted to obtain the final product.
Above-mentioned main chain bisphenol AF containing double bonds-PEG block copolymer, during the preparation process, preferably:
The molar ratio of the end group bisphenol AF polyarylate containing double bonds and end group polyethylene glycol containing double bonds, catalyst
For 1:1.5~4:0.002~0.1；
The end group polyethylene glycol containing double bonds, number-average molecular weight are 1000~20000, are the double acrylic acid of polyethylene glycol
Or mixtures thereof one kind in ester or polyethylene glycol bi-vinyl ether；
The solvent is or mixtures thereof one of tetrahydrofuran or dimethylformamide；
The catalyst is one of Gruubs ruthenium catalyst；Preferably Gruubs I, Gruubs II, Gruubs
III, Gruubs-Hoveyda I or Gruubs-Hoveyda II, structural formula is as follows:
。
Preferably, end group bisphenol AF polyarylate containing double bonds is prepared by acyclic diene hydrocarbon metathesis polymerization, number
Average molecular weight is 2000~32000, the preparation method comprises the following steps: reaction monomers, solvent and catalyst are mixed, reacts 1 in 60~95 DEG C
After~6h, it is down to room temperature；Remove solvent to obtain the final product.
Above-mentioned end group bisphenol AF polyarylate containing double bonds, during the preparation process, preferably:
The mass ratio of the reaction monomers and solvent, catalyst is 1~10:1~40:0.004~0.03；
The reaction monomers are that bisphenol AF diallyl ether, bisphenol AF diacrylate and bisphenol AF diallyl benzo are disliked
The mixture of one or both of piperazine, structural formula are respectively as follows:
；
The solvent is one of pentafluorodichloropropane, tetrahydrofuran, benzotrifluoride, toluene, dimethylformamide
Or mixtures thereof；
The catalyst is ruthenium catalyst Gruubs-Hoveyda I or Gruubs-Hoveyda II.
A kind of preparation method of bisphenol AF-PEG block copolymer hydrophilic surface coating, step include:
1) at 10~40 DEG C, by main chain bisphenol AF containing double bonds-PEG block copolymer, HS-PEG-SH and photocatalysis
Agent is dissolved in solvent, is formulated as the solution that solvent quality score is 30~60%；
2) coating that thickness is greater than 2mm is made by knife coating, then using 365nm's in the solution for preparing step 1)
30~120min of ultraviolet light removes solvent, obtains bisphenol AF-PEG block copolymer hydrophilic surface coating.
Further, main chain bisphenol AF containing double bonds-PEG block copolymer and HS-PEG-SH, photochemical catalyst
Mass ratio is 1:0.05~0.2:0.005~0.02；
Further, the HS-PEG-SH, number-average molecular weight are 200~2000；
Further, the photochemical catalyst is diphenylethan, diphenylmethanone, 2,4-DihydroxyBenzophenone or 2- hydroxyl
Base-2- methyl-1-phenylacetone；
Further, the solvent is or mixtures thereof one of tetrahydrofuran or dimethylformamide.
Above-mentioned bisphenol AF-application of the PEG block copolymer water-wetted surface as freezing coating.
Technical solution of the present invention, it has the advantage that: bisphenol AF-PEG block copolymer of preparation, molecular weight is controllable,
Surface can generate micro phase separation structure, hydrophilic strong；Preparation method is simple, and reaction condition is mild, and the reaction time is short, is conducive to work
Industry.Water-wetted surface is formed by using the block copolymer, water contact angle is less than 20 °.Due to fluorine-containing groups and PEG chain segment
Though the interaction force of hydrone is different, may interfere with aggregation of the hydrone on the copolymer surface under low temperature, -7~0 DEG C it
Between can anti-stagnant ice adherency, extend freezing time.There is good wide application prospect in anti-freeze field.
Specific embodiment
Illustrate the present invention below by way of specific example, but the present invention is not only limited to these examples, should not be understood as pair
The limitation of protection scope of the present invention, person skilled in art can do some nonessential according to the content of aforementioned present invention
Modifications and adaptations.
Embodiment 1:
1) preparation of end group bisphenol AF polyarylate containing double bonds:
By 5g bisphenol AF type diallyl ether, 0.15g Grubbs- Hoveyda II catalyst and 10g benzotrifluoride,
It is added in reaction flask, after mixing evenly, is warming up to 80 DEG C, react 2h, it is cooling to stop reaction.Revolving removes solvent, obtains brown
Solid product, number-average molecular weight 2700.
2) main chain bisphenol AF containing double bonds-PEG block copolymer preparation:
By above-mentioned steps 1) preparation 5.4g(0.002mol) end group bisphenol AF polyarylate containing double bonds, 6g
(0.003mol) polyethyleneglycol diacrylate (number-average molecular weight 2000) and 0.041g (0.00005mol) Grubbs I are urged
Agent and 20g tetrahydrofuran are added in reaction flask, lead to nitrogen, after mixing evenly, are warming up to 60 DEG C, react 3h, remove molten
Agent, obtains brown product, number-average molecular weight 7800, and the water contact angle on surface is 32 °.
3) bisphenol AF-PEG block copolymer hydrophilic surface coating preparation:
Prepared bisphenol AF-PEG block copolymer 7.8g, HS-PEG-HS 0.39g and benzophenone 0.04g is dissolved in four
In hydrogen furans, 70% solution is made；Then the coating that thickness is greater than 2mm is made by knife coating in prepared solution, then led to
The ultraviolet light 120min of 365nm is crossed, after removing solvent, obtains bisphenol AF-PEG block copolymer hydrophilic surface coating,
19 ° of surface water contact angle.
Embodiment 2:
1) preparation of end group bisphenol AF polyarylate containing double bonds:
By 5g bisphenol AF diacrylate, 0.05g Grubbs- Hoveyda I catalyst and 20g dimethyl formyl
Amine is added in reaction flask, after mixing evenly, is warming up to 90 DEG C, reacts 6h, cooling to stop reaction.Revolving removes solvent, obtains palm fibre
Color solid product, number-average molecular weight 31000.
2) main chain bisphenol AF containing double bonds-PEG block copolymer preparation:
By above-mentioned steps 1) preparation 3.1g(0.0001mol) end group bisphenol AF polyarylate containing double bonds, 4g
(0.0004mol) polyethyleneglycol diacrylate (number-average molecular weight 10000) and 0.0042g (0.000005mol) Grubbs
II catalyst and 20g dimethylformamide are added in reaction flask, lead to nitrogen, after mixing evenly, are warming up to 80 DEG C, react 6h,
Solvent is removed, brown product, number-average molecular weight 96000 are obtained, the water contact angle on surface is 24 °.
3) bisphenol AF-PEG block copolymer water-wetted surface preparation:
Prepared bisphenol AF-PEG block copolymer 4.8g, HS-PEG-HS 0.96g and hexichol methyl ethyl ketone 0.0024g is molten
In tetrahydrofuran, 40% solution is made.Then the painting that thickness is greater than 2mm is made by knife coating in prepared solution
Layer, then pass through the ultraviolet light 60min of 365nm, after removing solvent, bisphenol AF-PEG block copolymer water-wetted surface is obtained,
11 ° of its surface water contact angle.
Embodiment 3:
1) preparation of end group bisphenol AF polyarylate containing double bonds:
By 5g bisphenol AF type diallyl benzoxazine, five fluorine of 0.02g Grubbs- Hoveyda II catalyst and 5g
Dichloropropane is added in reaction flask, after mixing evenly, is warming up to 60 DEG C, reacts 2h, cooling to stop reaction.Revolving removes solvent,
Obtain brown solid, number-average molecular weight 11000.
2) main chain bisphenol AF containing double bonds-PEG block copolymer preparation:
By above-mentioned steps 1) preparation 2.2g(0.0002mol) end group bisphenol AF polyarylate containing double bonds, 0.4g
(0.0004mol) polyethylene glycol bi-vinyl ether (number-average molecular weight 1000) and 0.044g (0.00005mol) Grubbs
III catalyst and 10g tetrahydrofuran are added in reaction flask, lead to nitrogen, after mixing evenly, are warming up to 60 DEG C, react 3h, remove
Solvent is removed, brown product, number-average molecular weight 39800 are obtained, the water contact angle on surface is 37 °.
3) bisphenol AF-PEG block copolymer water-wetted surface preparation:
By prepared bisphenol AF-PEG block copolymer 3.98g, HS-PEG-HS 0.398g and 2,4- dihydroxy hexichol first
Ketone 0.042g is dissolved in dimethylformamide, and 60% solution is made.Then thickness is made by knife coating in prepared solution
Coating greater than 2mm, then pass through the ultraviolet light 30min of 365nm, after removing solvent, obtain bisphenol AF-PEG block copolymerization
Object water-wetted surface, 15 ° of surface water contact angle.
Claims (10)
1. a kind of bisphenol AF-PEG block copolymer hydrophilic surface coating, it is characterised in that: be with main chain bis-phenol containing double bonds
AF-PEG block copolymer and HS-PEG-SH are raw material, under the action of catalyst, room temperature reacts 30 by ultraviolet light~
200min is formed；The hydrophilic surface coating water contact angle is less than 20 °.
2. hydrophilic surface coating according to claim 1, it is characterised in that: main chain bisphenol AF-containing double bonds
PEG block copolymer, number-average molecular weight are 4000~96000, and the water contact angle on surface is less than 40 °, structure such as I institute of formula
Show:
In formula, the natural number that n is 8~150, the natural number that m is 5~100；
R1Are as follows:
；
R2Are as follows:
, in formula, natural number that x is 10~120.
3. hydrophilic surface coating according to claim 1, it is characterised in that: main chain bisphenol AF-containing double bonds
PEG block copolymer, preparation method are as follows: by end group bisphenol AF polyarylate containing double bonds and end group poly- second two containing double bonds
Alcohol is dissolved in solvent, after mixing, under the action of catalyst in 30~105 DEG C of 1~6h of reaction, removes solvent after the reaction was completed
To obtain the final product.
4. hydrophilic surface coating according to claim 3, it is characterised in that: the end group bisphenol AF containing double bonds is poly-
The molar ratio of aromatic ester and end group polyethylene glycol containing double bonds, catalyst is 1:1.5~4:0.002~0.1；The end group contains
The polyethylene glycol of double bond, number-average molecular weight are 1000~20000, are polyethyleneglycol diacrylate or polyethylene glycol bi-vinyl
Or mixtures thereof one kind in ether；The solvent is or mixtures thereof one of tetrahydrofuran or dimethylformamide；It is described to urge
Agent is one of Grubbs ruthenium catalyst.
5. hydrophilic surface coating according to claim 4, it is characterised in that: the catalyst is Grubbs I, Grubbs
II, one of Grubbs III, Grubbs-Hoveyda I or Grubbs-Hoveyda II, structural formula is as follows:
。
6. hydrophilic surface coating according to claim 3, it is characterised in that: the poly- virtue of the end group bisphenol AF containing double bonds
Ester is prepared by acyclic diene hydrocarbon metathesis polymerization, and number-average molecular weight is 2000~32000, the preparation method comprises the following steps: will reaction list
Body, solvent and catalyst mixing, after 60~95 DEG C of 1~6h of reaction, are down to room temperature；Remove solvent to obtain the final product.
7. hydrophilic surface coating according to claim 6, it is characterised in that: the reaction monomers and solvent, catalyst
Mass ratio is 1~10:1~40:0.004~0.03；The reaction monomers are bisphenol AF diallyl ether, bisphenol AF diacrylate
The mixture of one or both of ester and bisphenol AF diallyl benzoxazine, structural formula are respectively as follows:
；
The solvent be one of pentafluorodichloropropane, tetrahydrofuran, benzotrifluoride, toluene, dimethylformamide or its
Mixture；The catalyst is ruthenium catalyst Grubbs-Hoveyda I or Grubbs-Hoveyda II.
8. described in any item hydrophilic surface coatings according to claim 1~7, it is characterised in that: its water-wetted surface is as resistive connection
Ice coating.
9. a kind of bisphenol AF-PEG block copolymer hydrophilic surface coating preparation method, which is characterized in that step includes:
1) at 10~40 DEG C, main chain bisphenol AF containing double bonds-PEG block copolymer, HS-PEG-SH and photochemical catalyst is molten
In solvent, the solution that mass percentage concentration is 40~70% is prepared；
2) coating that thickness is greater than 2mm is made by knife coating, then using the ultraviolet of 365nm in the solution for preparing step 1)
Light irradiates 30~120min and removes solvent, obtains bisphenol AF-PEG block copolymer hydrophilic surface coating.
10. preparation method according to claim 9, it is characterised in that: the main chain bisphenol AF-PEG containing double bonds is embedding
The mass ratio of section copolymer and HS-PEG-SH, photochemical catalyst are 1:0.05~0.2:0.005~0.02；The HS-PEG-SH,
Number-average molecular weight is 200~2000；The photochemical catalyst is diphenylethan, diphenylmethanone, 2,4 dihydroxyl benzophenone
Or 2- hydroxy-2-methyl -1- phenylacetone；The solvent is one of tetrahydrofuran or dimethylformamide or its mixing
Object.
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