CN106554294A - Photo-curing material of fluorine-containing and tertiary amine structure and preparation method thereof - Google Patents
Photo-curing material of fluorine-containing and tertiary amine structure and preparation method thereof Download PDFInfo
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- CN106554294A CN106554294A CN201611001960.5A CN201611001960A CN106554294A CN 106554294 A CN106554294 A CN 106554294A CN 201611001960 A CN201611001960 A CN 201611001960A CN 106554294 A CN106554294 A CN 106554294A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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Abstract
The present invention relates to the preparation method of the photo-curing material of a kind of fluorine-containing and tertiary amine structure, carries out the intermediate product A that Michael additive reaction obtains fluorine-containing, tertiary amine structure by diethanolamine and fluorinated acrylate；Diisocyanate obtains the intermediate product B of isocyanate group end-blocking with crylic acid hydroxy ester reaction；The photo-curing material of fluorine-containing and tertiary amine structure is obtained by the hydroxyl of intermediate product A and the isocyanate group reaction of intermediate product B.The preparation method synthesis technique of the present invention is simple, without by-product, it is easily controllable, improve small molecule fluorochemical monomer problem that is fast, having little time participation solidification is migrated in Light Curing, introduce tertiary amine group and polymerizable acrylate group simultaneously, reduce the oxygen resistance effect of solidification process, it is to avoid the serious problem of xanthochromia that small molecule tertiary amine brings is directly added in photocureable coating.
Description
Technical field
The present invention relates to photo-curing material, particularly a kind of fluorine-containing ultraviolet photocureable material and preparation method thereof.
Background technology
Ultraviolet photocureable material is at home and abroad subject to weight with advantages such as low, the fast, efficient energy-savings of curing rate of its VOC content
Depending on being widely used in the top finishing of paper, timber, metal, plastic stool.With the fast development of functional material, ultraviolet
Fluorine-containing material is introduced in photocureable coating, the surface energy of material can be effectively reduced, improves the waterproof and oilproof soil resistance of coating, durable
Property and chemical corrosivity.Fluorine-containing material is introduced in photocureable coating most importantly directly to make existing fluorinated acrylate
Add for monomer.Have as being directly added on fluorinated acrylate in photocureable coating as monomer in CN103224722A
The resistance to acids and bases and stain resistance of photocureable coating are improved effect.But, the fluorochemical monomer of small molecule is due to molecular chain structure
Hydrophobic oleophobic characteristic to make which equably participate in solidification process relatively difficult, or even have some molecules to have little time to participate in solidification process
Just move to surface volatilization to walk, it is impossible to play its effect well.In recent years, fluorine-containing small molecule is grafted in polymer architecture
Solidification process is participated in photocureable coating is added to, the generation of this problem is greatly reduced.Such as CN102351981B systems
Standby fluorochemical urethane acrylate, hyperbranched polyester acrylic ester prepared by CN101367992A select to contain in these methods
Graft acrylic acid ester group participates in Light Curing to the copolymerization of perfluoroalkyl acrylate monomer elder generation again, or selects fluorine-containing alcohol to prepare, technique phase
To complexity, control of industrialization is difficult.And the fluorine element mobility in macromolecular structure is reduced, it is difficult to migrate to coating surface performance
Effect, especially the oxygen inhibition of Light Curing, has postponed top layer gel time, is difficult to obtain smooth, low-surface-energy
Coating.
The content of the invention
Present invention is primarily targeted at the photo-curing material of a kind of fluorine-containing and tertiary amine structure is provided and preparation method thereof, with
The molecular structure of fluorine material can at least be controlled so as to be easier to participate in Light Curing, and make fluorine move to top layer
Promote top layer fast setting simultaneously, obtain the light solidifying coating of low-surface-energy.
According to an aspect of the invention, there is provided the preparation method of the photo-curing material of a kind of fluorine-containing and tertiary amine structure,
The intermediate product A that Michael additive reaction obtains fluorine-containing, tertiary amine structure is carried out by diethanolamine and fluorinated acrylate；Two is different
Cyanate obtains the intermediate product B of isocyanate group end-blocking with crylic acid hydroxy ester reaction；By the hydroxyl and middle product of intermediate product A
The isocyanate group reaction of thing B obtains fluorine-containing and tertiary amine structure photo-curing material.
Preferably, the preparation method of the photo-curing material of a kind of fluorine-containing and tertiary amine structure includes step：At 25 ~ 60 DEG C, press
It is 1 according to mol ratio:（1~1.1）Diethanolamine reacts in adding fluorinated acrylate system and obtain completely intermediate product A；65~75
At DEG C, according to mol ratio it is（1~1.1）：1 crylic acid hydroxy ester is added in diisocyanate, and reaction obtains intermediate product completely
B；It is 1 according to the isocyanate group mol ratio in the hydroxyl in intermediate product A and product B:1, intermediate product A is added to into middle product
Thing B, reacts at 70 ~ 80 DEG C.
Preferably, fluorinated acrylate is selected from acrylic acid trifluoro ethyl ester, trifluoroethyl methacrylate, ten difluoro of acrylic acid
One kind in heptyl ester, dodecafluoroheptyl methacrylate, hexafluorobutyl acrylate and Hexafluorobutyl mathacrylate.
Preferably, diisocyanate is selected from isophorone diisocyanate, toluene di-isocyanate(TDI), dicyclohexyl methyl hydride two
In isocyanates, methyl diphenylene diisocyanate, hexamethylene diisocyanate and XDI one
Kind.
Preferably, crylic acid hydroxy ester is selected from 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, Hydroxypropyl acrylate and first
One kind in base hydroxypropyl acrylate.
According to another aspect of the present invention, additionally provide a kind of fluorine-containing and uncle prepared by above method of the present invention
The photo-curing material of amine structure.
Meanwhile, according to another aspect of the invention, the light that of the present invention fluorine-containing and tertiary amine structure is also claimed is solid
Change application of the material in UV photocureable coating is prepared.Can be used to prepare low-surface-energy, quick-setting metal, woodenware, plastics
Deng ultraviolet-curing paint in.
The preparation method synthesis technique of the present invention is simple, and no by-product, it is easy to control improves small molecule fluorochemical monomer
Problem that is fast, having little time participation solidification is migrated in Light Curing, while introducing tertiary amine group and polymerizable acrylate
Group, reduces the oxygen resistance effect of solidification process, it is to avoid be directly added into the Huang that small molecule tertiary amine brings in photocureable coating
Become serious problem.
Description of the drawings
Fig. 1 is fluorine-containing, the infrared spectrogram of tertiary amine structure photo-curing material prepared by the embodiment of the present invention 1.
Fig. 2 is fluorine-containing, tertiary amine structure photo-curing material prepared by the embodiment of the present invention 11H-NMR spectrum.
Specific embodiment
In a kind of typical embodiment of the present invention, the preparation side of the photo-curing material of a kind of fluorine-containing and tertiary amine structure
Method, carries out the intermediate product A that Michael additive reaction obtains fluorine-containing, tertiary amine structure by diethanolamine and fluorinated acrylate；Two
Isocyanates obtain the intermediate product B of isocyanate group end-blocking with crylic acid hydroxy ester reaction；By hydroxyl and the centre of intermediate product A
The isocyanate group reaction of product B obtains fluorine-containing and tertiary amine structure photo-curing material.
In a kind of relative specific embodiment, the preparation side of the photo-curing material of fluorine-containing and tertiary amine structure, including step
Suddenly：At 25 ~ 60 DEG C, it is 1 according to mol ratio:（1~1.1）During diethanolamine adds fluorinated acrylate system, react to infrared inspection
Till not detecting the characteristic peak of acrylate, reaction obtains intermediate product A completely；At 65 ~ 75 DEG C, according to mol ratio it is（1~
1.1）：1 crylic acid hydroxy ester is added in diisocyanate, and reacting to theoretical Carbimide. value nearby, reaction is obtained completely
Intermediate product B；It is 1 according to the isocyanate group mol ratio in the hydroxyl in intermediate product A and product B:1, intermediate product A is added
To intermediate product B, at 70 ~ 80 DEG C, reacting to infrared detection less than isocyanate group characteristic peak, reaction is contained completely
The photo-curing material of fluorine and tertiary amine structure.
Above-mentioned preparation method synthesis technique is simple, and no by-product, it is easy to control not only improves small molecule fluorochemical monomer
Problem that is fast, having little time participation solidification is migrated in Light Curing, while introducing tertiary amine group and polymerizable acrylate
Group, reduces the oxygen resistance effect of solidification process, it is to avoid be directly added into the Huang that small molecule tertiary amine brings in photocureable coating
Become serious problem.The molecular structure progressive of fluorinated acrylate, diisocyanate and crylic acid hydroxy ester can be passed through
Can modulation.
In a preferred embodiment, fluorinated acrylate is selected from acrylic acid trifluoro ethyl ester, methacrylic acid trifluoro
Ethyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, hexafluorobutyl acrylate and Hexafluorobutyl mathacrylate
In one kind.
In a preferred embodiment, diisocyanate is selected from isophorone diisocyanate, toluene diisocynate
Ester, dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, hexamethylene diisocyanate and phenylenedimethylidyne
One kind in diisocyanate.
In a preferred embodiment, crylic acid hydroxy ester selected from 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate,
One kind in Hydroxypropyl acrylate and Hydroxypropyl methacrylate.
Above method prepares fluorine-containing and tertiary amine structure photo-curing material.This photo-curing material is due to molecular structure
In contain fluorine element, the weatherability of light solidifying coating can be improved, especially soil resistance, and molecular structure has by many secondary responses
Effect control chain length and molecular weight so as to be easier to apply in light solidifying coating.Due to containing tertiary amine group in molecular structure, can
Effectively to reduce the oxygen inhibition of ultraviolet light polymerization process, thus more common fluorine-containing molecular structure is more conducive to ultraviolet light polymerization
Process, and coating shows that performance is more excellent.This photo-curing material contains the acrylate group that may participate in ultraviolet light polymerization, can
For preparing in the ultraviolet-curing paints such as low-surface-energy, quick-setting metal, woodenware, plastics.
1-5 is described further to the beneficial effect of invention preparation method and product with reference to embodiments.
Embodiment 1
In equipped with agitating device, nitrogen device, 500 mL four-hole boiling flasks of condensing tube, 211.0 g methacrylic acids ten are added
Difluoro heptyl ester, by 50.0 g diethanolamine in 60 DEG C of Deca such as four-hole bottle, reacts to infrared detection less than acrylate feature
Till peak, intermediate product A is obtained.
In equipped with agitating device, nitrogen device, 250 mL four-hole boiling flasks of condensing tube, 88.8 g isophorones are added
Diisocyanate, is warming up to 65 DEG C, and 46.4 g 2-(Acryloyloxy)ethanols are added drop-wise in four-hole bottle in 5h, 70 DEG C of guarantors after dripping
It is near 12.4%, that is, to obtain intermediate product B that temperature is reacted to isocyanide acid number.
The temperature of above-mentioned intermediate product B is risen to into 80 DEG C, 101.0 g intermediate product A is taken and is added drop-wise in B, reacted to infrared
Till spectrum monitoring is less than isocyanate group characteristic peak, that is, obtain the photo-curing material of fluorine-containing, tertiary amine structure.Building-up process and product
Structure is as follows.
Synthesis fluorine-containing, tertiary amine structure photo-curing material can using infrared spectrum,1H-NMR is analyzed table to which
Levy.
Products therefrom is evenly coated on KBr tablettings, its infrared spectrum is determined, as shown in Figure 1.From the infrared spectrum of product
As can be seen that 1185.0 cm in figure-1It is the absworption peak of C-F keys, 723.3 cm-1With 687. 5 cm-1It is-CF3Absorption
Peak, 1635cm-1It is-CH=CH2Characteristic absorption peak, and without significantly-NH-characteristic peak in infrared spectrum, illustrate to synthesize
Product structure in really contain fluorine, tertiary amine structure and polymerizable acrylate group.
By products therefrom with CDCl3For solvent, TMS is carried out as internal standard1H-NMR is analyzed, as shown in Figure 2.Can from figure
To find out positioned at 1 peak of 1.60ppm as methyl, it is connected with carbonyl positioned at 2 peaks of 2.11ppm and causes.Positioned at 3.65ppm3
Peak is the methylene being connected with hydroxyl.Show as positioned at 4 peaks of 3.80ppm it is unimodal, hydroxyl do not adjoin with other groups and not
It is impacted.It is the methylene being connected with nitrogen positioned at 5 peaks of 4.14-4.37ppm.6 peaks positioned at 5.09-5.30 are CF-CH2-O
Group, it shows as multimodal.Because the coupled in common effect between fluorine atom, the appearance of fluorine atom make which have slight with other peaks
Difference, due to being connected to-CF3With-CF（CF3）2Coupling, 7 peaks positioned at 5.5-5.8ppm equally show as multimodal, can
Target product has been obtained to determine.
Embodiment 2
In equipped with agitating device, nitrogen device, 500 mL four-hole boiling flasks of condensing tube, 73.3 g acrylic acid trifluoro second are added
Ester, by 50.0 g diethanolamine in 60 DEG C of Deca as in four-hole bottle, reacting to infrared detection less than acrylate characteristic peak,
Obtain intermediate product A.
In equipped with agitating device, nitrogen device, 250 mL four-hole boiling flasks of condensing tube, add 69.6 g toluene two different
Cyanate, is warming up to 65 DEG C, and 46.4 g 2-(Acryloyloxy)ethanols are added drop-wise in four-hole bottle in 5h, and after dripping, 70 DEG C of insulations are anti-
Should be near 14.4%, that is, to obtain intermediate product B to isocyanide acid number.
The temperature of above-mentioned intermediate product B is risen to into 80 DEG C, 51.8 g intermediate product A is taken and is added drop-wise in B, react to infrared light
Till spectrum monitoring is less than isocyanate group characteristic peak, that is, obtain the photo-curing material of fluorine-containing, tertiary amine structure.
Embodiment 3
In equipped with agitating device, nitrogen device, 500 mL four-hole boiling flasks of condensing tube, 83.8 g methacrylic acids three are added
Fluorine ethyl ester, by 50.0 g diethanolamine in 60 DEG C of Deca such as four-hole bottle, reacts to infrared detection less than acrylate characteristic peak
Till, obtain intermediate product A.
In equipped with agitating device, nitrogen device, 250 mL four-hole boiling flasks of condensing tube, 105.0 g dicyclohexyls are added
Methane diisocyanate, is warming up to 65 DEG C, 54.8 g hydroxyethyl methylacrylates is added drop-wise in four-hole bottle in 5h, is dripped
70 DEG C of insulation reaction to isocyanide acid number is near 10.5%, that is, to obtain intermediate product B afterwards.
The temperature of above-mentioned intermediate product B is risen to into 80 DEG C, 54.6 g intermediate product A is taken and is added drop-wise in B, react to infrared light
Till spectrum monitoring is less than isocyanate group characteristic peak, that is, obtain the photo-curing material of fluorine-containing, tertiary amine structure.
Embodiment 4
In equipped with agitating device, nitrogen device, 500 mL four-hole boiling flasks of condensing tube, 114.0 g acrylic acid hexafluoro fourths are added
Ester, by 50.0 g diethanolamine in 60 DEG C of Deca as in four-hole bottle, reacting to infrared detection less than acrylate characteristic peak,
Obtain intermediate product A.
In equipped with agitating device, nitrogen device, 250 mL four-hole boiling flasks of condensing tube, 66.8 g hexa-methylenes two are added
Isocyanates, are warming up to 65 DEG C, and 54.0 g Hydroxypropyl acrylates are added drop-wise in four-hole bottle in 5h, 70 DEG C of insulations after dripping
It is near 13.9%, that is, to obtain intermediate product B to react to isocyanide acid number.
The temperature of above-mentioned intermediate product B is risen to into 80 DEG C, 68.2 g intermediate product A is taken and is added drop-wise in B, react to infrared light
Till spectrum monitoring is less than isocyanate group characteristic peak, that is, obtain the photo-curing material of fluorine-containing, tertiary amine structure.
Embodiment 5
In equipped with agitating device, nitrogen device, 500 mL four-hole boiling flasks of condensing tube, 190.0 g methacrylic acids ten are added
Difluoro heptyl ester, by 50.0 g diethanolamine in 60 DEG C of Deca such as four-hole bottle, reacts to infrared detection less than acrylate feature
Till peak, intermediate product A is obtained.
In equipped with agitating device, nitrogen device, 250 mL four-hole boiling flasks of condensing tube, 66.8 g phenylenedimethylidynes are added
Diisocyanate, is warming up to 65 DEG C, and 57.0 g Hydroxypropyl methacrylates are added drop-wise in four-hole bottle in 5h, 70 after dripping
DEG C insulation reaction to isocyanide acid number is near 12.7%, that is, to obtain intermediate product B.
The temperature of above-mentioned intermediate product B is risen to into 80 DEG C, 101.0g intermediate product A is taken and is added drop-wise in B, react to infrared light
Till spectrum monitoring is less than isocyanate group characteristic peak, that is, obtain the photo-curing material of fluorine-containing, tertiary amine structure.
Products therefrom in embodiment 1 ~ 5 is added in ultraviolet-curing paint to curing rate, surface according to 10 wt.%
Water contact angle and resistance to oil stains tested.As a result it is as shown in table 1.
Curing rate is tested：Under 2 KW ultra violet lamps, ultraviolet-curing paint is coated on tinplate base material, thickness
For 50 um, its surface drying time is observed.
Water contact angle：According to GB/T23764-2009 standard testings.
Surface energy：According to water contact angle by obtained by computed in software.
It is resistance to oil stains：After soaking application product at room temperature 10 minutes using the diesel oil that main component is hexadecane, then survey
The water contact angle of examination coating surface.
Yellowing resistance：The chromatic aberration value △ E after 168 h of irradiation is determined according to GB/T 23983-2009.
Carried out with the conventional photocureable coating for being not added with synthesizing fluorine-containing, tertiary amine structure photo-curing material as a comparison case simultaneously
Performance test.
As shown in Table 1, the fluorine-containing of preparation, the photo-curing material of tertiary amine structure do not have attached to which in being added to photocureable coating
Put forth effort to bring impact with curing rate, and light prepared by fluorine-containing, tertiary amine structure the photo-curing material that different material is prepared
Coating material solidified water contact angle increase, shows good antifouling property.
Embodiment 6
Difference with embodiment 1 be the temperature control for preparing intermediate product A at 25 DEG C, prepare the temperature control of intermediate product B
At 75 DEG C, temperature control that final products are is prepared at 70 DEG C.
Embodiment 7
Difference with embodiment 3 be the temperature control for preparing intermediate product A at 30 DEG C, prepare the temperature control of intermediate product B
At 70 DEG C, temperature control that final products are is prepared at 75 DEG C.
Embodiment 8
Difference with embodiment 4 be the temperature control for preparing intermediate product A at 50 DEG C, prepare the temperature control of intermediate product B
At 75 DEG C, temperature control that final products are is prepared at 75 DEG C.
Obviously, it will be appreciated by those skilled in the art that, the fluorinated acrylate, diisocyanate and acrylic acid in the present invention
Hydroxy ester respectively has multiple choices and can be mutually combined.Preferably, fluorinated acrylate may be selected from acrylic acid trifluoro ethyl ester, first
Base acrylic acid trifluoro ethyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, hexafluorobutyl acrylate, methyl-prop
One kind in olefin(e) acid hexafluoro butyl ester.Diisocyanate may be selected from isophorone diisocyanate, toluene di-isocyanate(TDI), two hexamethylenes
Dicyclohexylmethane diisocyanate, methyl diphenylene diisocyanate, two Carbimide. of hexamethylene diisocyanate and phenylenedimethylidyne
One kind in ester.Crylic acid hydroxy ester may be selected from 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, Hydroxypropyl acrylate and methyl
One kind in Hydroxypropyl acrylate.In a reaction, any one specific fluorinated acrylate, diisocyanate and propylene
Sour hydroxy esters can be selected the raw material for being used as reacting.
The scope of protection of present invention is not limited to above specific embodiment, to those skilled in the art, this
Invention can have various deformation and a change, all designs in the present invention and any modification, improvement made within principle and be equal to
Replacement should be all included within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of the photo-curing material of fluorine-containing and tertiary amine structure, it is characterised in that：By diethanolamine and fluorine-containing third
Olefin(e) acid ester carries out the intermediate product A that Michael additive reaction obtains fluorine-containing, tertiary amine structure；Diisocyanate and dihydroxypropyl
Ester reaction obtains the intermediate product B of isocyanate group end-blocking；Reacted with the isocyanate group of intermediate product B by the hydroxyl of intermediate product A
Obtain fluorine-containing and tertiary amine structure photo-curing material.
2. method according to claim 1, it is characterised in that including step：At 25 ~ 60 DEG C, it is 1 according to mol ratio:（1~
1.1）Diethanolamine reacts in adding fluorinated acrylate system and obtain completely intermediate product A；At 65 ~ 75 DEG C, according to mol ratio
For（1~1.1）：1 crylic acid hydroxy ester is added in diisocyanate, and reaction obtains intermediate product B completely；According to intermediate product
Hydroxyl in A is 1 with the isocyanate group mol ratio in product B:1, intermediate product A is added to into intermediate product B, at 70 ~ 80 DEG C
Lower reaction obtains fluorine-containing and tertiary amine structure photo-curing material completely.
3. method according to claim 2, it is characterised in that：Fluorinated acrylate is selected from acrylic acid trifluoro ethyl ester, methyl
Acrylic acid trifluoro ethyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, hexafluorobutyl acrylate and metering system
One kind in sour hexafluoro butyl ester.
4. method according to claim 2, it is characterised in that：Diisocyanate is selected from isophorone diisocyanate, first
Phenylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, hexamethylene diisocyanate and
One kind in XDI.
5. method according to claim 2, it is characterised in that：Crylic acid hydroxy ester is selected from 2-(Acryloyloxy)ethanol, methyl-prop
One kind in olefin(e) acid hydroxyl ethyl ester, Hydroxypropyl acrylate and Hydroxypropyl methacrylate.
6. the photo-curing material of the fluorine-containing and tertiary amine structure for being prepared according to any one of claim 1-5.
7. application of the photo-curing material of the fluorine-containing and tertiary amine structure described in claim 6 in UV photocureable coating is prepared.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678761A (en) * | 2018-12-19 | 2019-04-26 | 上海维凯光电新材料有限公司 | A kind of high-modulus fluorochemical urethane acrylate and preparation method thereof |
| CN110734533A (en) * | 2019-10-10 | 2020-01-31 | 陕西科技大学 | terminal/side fluoroalkyl co-modified polyurethane nano hybrid emulsion and preparation method thereof |
| CN114133519A (en) * | 2020-09-04 | 2022-03-04 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer and preparation method and application thereof |
| CN114163605A (en) * | 2021-12-03 | 2022-03-11 | 万华化学集团股份有限公司 | Vegetable oil-based fluorinated hydroxy resin and preparation method and application thereof |
| CN114395125A (en) * | 2021-12-30 | 2022-04-26 | 江苏超力建材科技有限公司 | Fluorine-containing hyperbranched polymer viscosity reducer and preparation method and application thereof |
-
2016
- 2016-11-15 CN CN201611001960.5A patent/CN106554294A/en active Pending
Non-Patent Citations (6)
| Title |
|---|
| 孙常青等: "氟改性UV固化支化水性聚氨酯的制备与性能研究", 《涂料工业》 * |
| 李冠荣等: "水性UV固化含氟聚氨酯树脂的制备及性能研究", 《化工新型材料》 * |
| 李冠荣等: "阳离子型水性UV固化含氟聚氨酯树脂的制备及性能研究", 《涂料工业》 * |
| 樊淑兰: "聚氨酯丙烯酸酯合成及其UV固化涂料的制备及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 马国章等: "叔胺型聚氨酯丙烯酸酯的合成及其光固化性能研究", 《现代化工》 * |
| 马国章等: "叔胺型聚氨酯丙烯酸酯的合成和光固化性能", 《聚氨酯工业》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678761A (en) * | 2018-12-19 | 2019-04-26 | 上海维凯光电新材料有限公司 | A kind of high-modulus fluorochemical urethane acrylate and preparation method thereof |
| CN110734533A (en) * | 2019-10-10 | 2020-01-31 | 陕西科技大学 | terminal/side fluoroalkyl co-modified polyurethane nano hybrid emulsion and preparation method thereof |
| CN114133519A (en) * | 2020-09-04 | 2022-03-04 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer and preparation method and application thereof |
| CN114133519B (en) * | 2020-09-04 | 2023-10-17 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer and preparation method and application thereof |
| CN114163605A (en) * | 2021-12-03 | 2022-03-11 | 万华化学集团股份有限公司 | Vegetable oil-based fluorinated hydroxy resin and preparation method and application thereof |
| CN114395125A (en) * | 2021-12-30 | 2022-04-26 | 江苏超力建材科技有限公司 | Fluorine-containing hyperbranched polymer viscosity reducer and preparation method and application thereof |
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Application publication date: 20170405 |