CN106032396B - Fluororesin and the preparation method and application thereof with photoinitiator group - Google Patents
Fluororesin and the preparation method and application thereof with photoinitiator group Download PDFInfo
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- CN106032396B CN106032396B CN201510108933.7A CN201510108933A CN106032396B CN 106032396 B CN106032396 B CN 106032396B CN 201510108933 A CN201510108933 A CN 201510108933A CN 106032396 B CN106032396 B CN 106032396B
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Abstract
The present invention provides a kind of fluororesin with photoinitiator group and its preparation and application.Photoinitiator group is in the side chain of fluororesin in fluororesin with photoinitiator group, and preparation method is synthesized by the fluororesin containing hydroxyl and the photoinitiator esterification containing carboxyl.The present invention also provides a kind of Photocurable compositions, by 0.1%~5% fluororesin with photoinitiator group, 87~98.9% reaction resin or activated monomer and 1~8% photoinitiator composition.The photo-curing paint of waterproof and oilproof soil resistance is significantly improved the present invention provides a kind of.
Description
Technical field:
The present invention relates to a kind of functional fluororesins, especially with the fluororesin and preparation method thereof of photoinitiator group
With application.
Background technique:
In paint field, weatherability is one of the important performance of outdoor coating, industrial at present main by directly adding
The method of fluorine material is modified coating, in coating add fluorine material can effectively improve coating waterproof and oilproof it is antifouling
Property, weatherability and chemical corrosion resistance.F-C paint is one of the kind of best performance show in the prior art.
Since fluorine material has the performances such as excellent thermal stability, corrosion resistance, low surface tension, answered extensively
With.In Chinese patent CN103059316A, fluorine-containing modified polyurethane is introduced into photocureable coating, for enhancing the resistance to of coating
Water anti-pollution characteristic；And in Chinese patent CN103589320A, fluorine-containing acrylate is added in pcb board three-proofing coating and participates in altogether
Poly-, to reduce the surface energy of film surface, but these schemes also bring the decline of film Yu substrate adhesive force, so that it is durable to influence its
Property.
Most common F-C paint is all the isocyanates and hydroxyl fluororesin catalytic crosslinking of two-component, needs high-temperature process item
Part, production efficiency is low, is unfavorable for outdoor site operation.
Light lnduced Free Radicals polymerization is also known as photocuring technology and is existed with its rapid curing, low pollution and the advantages such as energy-efficient
It is taken seriously both at home and abroad, is widely used in metal, timber, plastic coating, ink printing, textile printing, fibre coating etc.,
It is one of the cutting edge technology in coating, ink area.But photocuring technology is mainly drawn using acrylate and monomer and light
Agent composition is sent out, the cured film that they are formed does not have ideal waterproof, antifouling, weatherability also.
It is one of the method for improving photocureable coating performance that fluorine material, which is introduced into photocuring technology,.
Fluoride is introduced into initiator, the fluorine-containing photoinitiator as described in Chinese patent CN101812143A, it will
Photoinitiator is connected with small molecule perfluoro alkane synthesizes fluorine-containing photoinitiator.N- ethylperfluoro octyl sulphonyl is used in embodiment
The fluorine richness light that amine ethyl alcohol and UVINUL MS 40-carboxylic acid are reacted to obtain the small-molecular-weight for containing only an initiator group draws
Agent is sent out, and using the surface migration of fluorine material, causes gradient polymeric.And small molecule compound moves to surface and can both damage
The performance of film can also pollute the contactant of film, the toxicity of all-fluoroalkyl compound be exactly it is very troubling, as
Persistence organic pollutant has been put into the short-list of Convention of Stockholm (Shi Yali etc. the, " environment of perfluorochemical
Problem ", chemical progress, 2009,21 (3), 369).
The paper (Li Wei, Zou Yingquan, information-recording material, 2011,12 (5), 38) of Zou Yingquan summarize fluorochemical monomer or
Application study of the fluorine resin in Photocurable composition, the problem is that as compound fluorine content improves, with other groups
The intermiscibility divided is poorer, and formulation cost is also increase accordingly.Because of the difficulty of preparation, these fluorochemical monomers or resin also rarely seen quotient
Product.
Summary of the invention:
In order to solve above-mentioned the shortcomings of the prior art, the present invention provides a kind of fluorine trees with initiator group
Rouge, wherein photoinitiator group is connected on the side chain of fluororesin with chemical bond.Especially photoinitiator is connected to tree with ester bond
On rouge side chain.Wherein initiator is by the fluororesin with hydroxyl and the warp of the initiator with carboxyl with the fluororesin that ester bond connects
Esterification synthesis, hydroxy ester rate is 1~100%.
One of the synthesis material that the present invention uses, the fluororesin with hydroxyl, it is characterised in that weight average molecular weight 2000
~200000, hydroxyl value is 10~100mg/g, and fluorine atom mass content is 5~35%.
One of the raw material that the present invention uses, the photoinitiator with carboxyl are chosen in particular from following formula (I), formula (II), formula
(III), the structure of formula (IV), formula (V) or (VI):
The present invention also provides a kind of preparation methods of fluororesin with photoinitiator group.Specific method is: having
The fluororesin of hydroxyl and photoinitiator with carboxyl are dissolved in solvent, using the acid of catalytic amount as the catalyst of esterification, one
It plays heating and esterification occurs, after the reaction was completed, obtain the fluororesin solution with photoinitiator group.
The present invention also provides a kind of Photocurable compositions, are made of following components:
A. the fluororesin of photoinitiator group is had, mass ratio is 0.1%~5%；
B. reaction resin or monomer.Mass ratio is 87~98.9%；
C. photoinitiator, mass ratio are 1~8%.
Reaction resin described in Photocurable composition be selected from Epocryl, polyurethane acrylate resin,
Polyester acrylate resin, polyether acrylate resins, acroleic acid esterification polyacrylate, epoxy methacrylates resin,
Urethane methacylate resins, polyester methacrylate resin, methacrylates resin, acroleic acid esterification are poly-
Methacrylate, allyl ether compound, the monomer be simple function group, difunctional or multi-functional acrylate or
Methacrylate monomers.
Photoinitiator described in Photocurable composition is commercial goods, is selected from: 2- hydroxy-2-methyl -1- phenylacetone,
1- hydroxycyclohexyl phenyl ketone, 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6- front three
Base benzoyl-diphenyl phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester, 2- dimethylamino -2- benzyl -1-
[4- (4- morpholinyl) phenyl] -1- butanone, 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- acetone, hexichol
Ketone, 4- phenyl benzophenone, o-benzoyl yl benzoic acid methyl esters.
On the basis of above-mentioned Photocurable composition, organic amine is added as auxiliary agent, additive amount is with photoinitiator group
0.1~5 times of fluororesin quality, organic amine auxiliary agent is selected from: triethylamine, triethanolamine, N methyldiethanol amine, N, N- diethyl
Ethanol amine, N, N- mesitylenic acid ethyl ester, N, N- mesitylenic acid -2- ethylhexyl, benzoic acid dimethylaminoethyl, 4-
The own ester of (dimethylamino)-benzoic acid-(2- ethyl), ethyl 4-dimethylaminobenzoate, polyethylene glycol two-(p- dimethylamino
Yl benzoic acid) ester, reactive amines.Wherein reactive amines are the P115 or di-n-butylamine and trimethylolpropane tris third of such as Qing Te company
The addition product of olefin(e) acid ester.
Above-mentioned Photocurable composition can be diluted with solvent, and amount of solvent is the fluorine-containing tree with photoinitiator group
0.5~5 times of rouge, reaction resin or activated monomer and organic amine auxiliary agent gross mass.Solvent is selected from: propylene glycol monomethyl ether acetic acid
Ester, dipropylene glycol methyl ether acetate, ethylene glycol ether acetate, toluene, dimethylbenzene, durol, methylisobutylketone, hexamethylene
Ketone, ethyl acetate, butyl acetate, gamma-butyrolacton, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, acetone, butanone.
The present invention provides a kind of curing method of Photocurable composition, and above-mentioned Photocurable composition is coated on substrate, such as
Fruit has solvent, and just first dry out solvent, is placed under ultraviolet lamp and irradiates, be allowed to solidify.
Substrate as Photocurable composition of the present invention coating object can be timber, paper, plastics, coating, metal etc..
The method of coating can be spray coating method, stick coating method, scraper for coating method, rolling method, scraper coating method to form figure layer.Then in purple
Solidify under outer light.It is on base material to obtain cured film, it shields to substrate.
The beneficial effects of the present invention are: the fluororesin with photoinitiator of the invention is used in Photocurable composition,
The waterproof and oilproof soil resistance for improving film, improves the weatherability of film, while not influencing cured film to the adhesive force of substrate.
Specific implementation method
Embodiment 1 has the fluororesin FR01 of photoinitiator group
Under nitrogen protection, 400g fluororesin (model SRF-350, resin solid content 60%, hydroxyl are put into 1L four-hole bottle
Value 50mg/g, Beijing Hua Tongrui speed Science and Technology Ltd. production), 48.4g neighbour's carboxyl benzophenone, 2g p-methyl benzenesulfonic acid, 400g
Toluene is warming up to 114 DEG C of back flow reaction 15h.After the reaction was completed, reaction solution precipitation obtains 290g with photoinitiator group
Fluororesin FR01.It is added and dissolves with the butanone of the quality such as product to get the butanone solution of target product FR01 is arrived thereto.
Embodiment 2 has the fluororesin FR02 of photoinitiator group
Using the synthetic method of embodiment 1,48.4g neighbour's carboxyl two is substituted with 54.87g 4- Carboxymethoxybenzophenone
The butanone solution of target product FR02 is made in Benzophenone.
Embodiment 3
1. the preparation of composition:
Each component is added by ingredient shown in table 1 and its mass fraction, stirs to dissolve uniformly, respectively obtains experimental example
1, experimental example 2, experimental example 3, reference examples 1, reference examples 2 and reference examples 3 totally six groups of compositions.
Table 1
2. film curing process
Above-mentioned each composition is coated in white PC version with 25 μm of bars, 10min is toasted at 60 DEG C, is then passed through
600mW/cm2Ultraviolet light 25S (surface drying test and gel conversion rate test except), obtain the paint film with a thickness of 10 μm,
Paint film is tested as follows, the results are shown in Table 2.
3. surface drying is tested
400mJ/cm is used respectively2、300mJ/cm2、200mJ/cm2Ultraviolet light applies the PC plate of above-mentioned paint film, uses touch dry
Method checks whether viscous hand, is recorded in table 2.
4. adhesive force is tested
The square lattice of 100 1mm*1mm, the type produced with Minnesota Mining and Manufacturing Company are drawn in above-mentioned each surface of the paint film with cross hatch device
Number for 600 adhesive tape it is smooth be bonded on grid, do not interspace, then uncover adhesive tape rapidly with 60 degree angles, observation scratch
Whether edge has depainting, is as a result recorded in table 2.
If being 5B without any depainting, it is 4B that depainting amount, which is the 0~5% of the gross area, depainting amount be the gross area 5~
15% is 3B, and it is 2B that depainting amount, which is the 15~35% of the gross area,.It is 1B that depainting amount, which is the 35~65% of the gross area, and depainting amount is total
65% or more of area is 0B.
5. gel conversion rate
Above-mentioned each paint film is exposed with the ultraviolet light of different-energy, the paint film after solidification wraps up sample with stainless (steel) wire
Plate, weighing and surveying film weight is W1, acetone soak 72 hours, drying measurement residual film weight W2, W1/W2For gel conversion rate
Gel%.Data are listed in table 2.
6. water surface Contact-angle measurement
By 6 μ l distillation water droplet on above-mentioned each cured paint film surface, surveyed using the company OCA collection of contact angle Data physics
Amount instrument measures water surface contact angle, and data are listed in table 2.
Table 2
From the test result of table 2 it can be seen that
A. using the experimental example of the fluororesin FR with photoinitiator group, the surface drying of cured film, which is better than, all does not add FR
Reference examples；
B. using the experimental example of the fluororesin FR with photoinitiator group, the surface drying of cured film, which is better than, has been used without light
The reference examples of the fluororesin of initiator；
C. the composition of fluororesin FR of the addition with photoinitiator group, does not have bad shadow to the adhesive force of cured film
It rings；And the cured film adhesive force for being used without the fluororesin of photoinitiator reduces；
D. using the experimental example of the fluororesin FR with photoinitiator group, the gel conversion rate of cured film, which is higher than, is not added
The reference examples of fluororesin；
E. using the experimental example of the fluororesin FR with photoinitiator group, the water surface contact angle of cured film, which is greater than, not to be added
The reference examples of fluororesin have better waterproof effect.
Claims (14)
1. a kind of fluororesin with photoinitiator group, it is characterised in that: be by the fluororesin containing hydroxyl and to contain carboxyl
Initiator synthesized through esterification, the esterification yield of hydroxyl is 1~100%；The wherein fluororesin Weight-average molecular containing hydroxyl
Amount is 2000~200000, and hydroxyl value is 10~100mg/g, and fluorine atom mass content is 5~35%, and photoinitiator group is with ester bond
It is connected on the side chain of fluororesin.
2. the synthesis of the fluororesin described in claim 1 with photoinitiator group, wherein raw material contains the light-initiated of carboxyl
Agent, selected from following formula (I), formula (II), formula (III), formula (IV), the structure of formula (V) or (VI):
3. the preparation method of the fluororesin described in claim 1 with photoinitiator group is: fluororesin with hydroxyl and
Photoinitiator with carboxyl is dissolved in solvent, and using the acid of catalytic amount as the catalyst of esterification, heating is esterified together
Reaction obtains the fluororesin solution with photoinitiator group.
4. a kind of Photocurable composition, is made of following components:
A. the fluororesin of photoinitiator group is had described in claim 1, mass ratio is 0.1%~5%；
B. reaction resin or monomer, mass ratio are 87~98.9%；
C. photoinitiator, mass ratio are 1~8%.
5. Photocurable composition described in claim 4, wherein reaction resin is selected from Epocryl, polyurethane propylene
Acid ester resin, polyester acrylate resin, polyether acrylate resins, acroleic acid esterification polyacrylate, epoxy metering system
Acid ester resin, urethane methacylate resins, polyester methacrylate resin, methacrylates resin, third
Olefin(e) acid is esterified polymethacrylates, allyl ether compound；Monomer is simple function group or multi-functional acrylate or first
Base acrylate.
6. Photocurable composition as claimed in claim 4, wherein photoinitiator is selected from: 2- hydroxy-2-methyl -1- phenylacetone,
1- hydroxycyclohexyl phenyl ketone, 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6- front three
Base benzoyl-diphenyl phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester, 2- dimethylamino -2- benzyl -1-
[4- (4- morpholinyl) phenyl] -1- butanone, 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- acetone, hexichol
Ketone, 4- phenyl benzophenone, o-benzoyl yl benzoic acid methyl esters.
7. Photocurable composition as claimed in claim 4, it is characterized in that separately containing organic amine as auxiliary agent, additive amount is with light
0.1~5 times of the fluororesin quality of initiator group.
8. Photocurable composition described in claim 7, the organic amine auxiliary agent is selected from: triethylamine, triethanolamine, N- first
Base diethanol amine, N, N- diethyl ethylene diamine, benzoic acid dimethylaminoethyl, 4- (dimethylamino)-benzoic acid-(2- ethyl) oneself
Ester, ethyl 4-dimethylaminobenzoate, polyethylene glycol two-(p- dimethylaminobenzoic acid) ester or reactive amines.
9. Photocurable composition described in claim 4 or 7, it is characterized in that separately contain solvent, additive amount be reaction resin or
0.5~5 times of monomer gross mass.
10. Photocurable composition as claimed in claim 9, wherein solvent is selected from: propylene glycol methyl ether acetate, dipropylene glycol methyl ether
Acetate, ethylene glycol ether acetate, toluene, dimethylbenzene, durol, methylisobutylketone, cyclohexanone, ethyl acetate, acetic acid
Butyl ester, gamma-butyrolacton, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, acetone, butanone.
11. a kind of curing method of Photocurable composition, it is characterised in that by claim 4, claim 7 or claim 9
The Photocurable composition, is coated on substrate, after carrying out drying operation, is placed under ultraviolet lamp and irradiates, be allowed to solidify.
12. a kind of curing method of Photocurable composition described in claim 11, wherein coating method is spraying.
13. a kind of curing method of Photocurable composition according to claim 11 is obtained playing substrate on substrate and be protected
The cured film of shield effect.
14. a kind of curing method of Photocurable composition described in claim 11, wherein substrate is selected from: timber, paper, modeling
Material, coating, metal.
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| CN201510108933.7A CN106032396B (en) | 2015-03-12 | 2015-03-12 | Fluororesin and the preparation method and application thereof with photoinitiator group |
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| CN201510108933.7A CN106032396B (en) | 2015-03-12 | 2015-03-12 | Fluororesin and the preparation method and application thereof with photoinitiator group |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391587A (en) * | 1991-12-11 | 1995-02-21 | Alliedsignal Inc. | Fluorinated photoinitiators and their application in UV curing of fluorinated monomers |
| CN101121660A (en) * | 2006-08-08 | 2008-02-13 | 北京英力科技发展有限公司 | Phenyl benzophenone derivates and uses as photoinitiators |
-
2015
- 2015-03-12 CN CN201510108933.7A patent/CN106032396B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391587A (en) * | 1991-12-11 | 1995-02-21 | Alliedsignal Inc. | Fluorinated photoinitiators and their application in UV curing of fluorinated monomers |
| CN101121660A (en) * | 2006-08-08 | 2008-02-13 | 北京英力科技发展有限公司 | Phenyl benzophenone derivates and uses as photoinitiators |
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