CN104628928B - Photochromic fluorocarbon resin as well as preparation method and application thereof - Google Patents
Photochromic fluorocarbon resin as well as preparation method and application thereof Download PDFInfo
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- CN104628928B CN104628928B CN201510047786.7A CN201510047786A CN104628928B CN 104628928 B CN104628928 B CN 104628928B CN 201510047786 A CN201510047786 A CN 201510047786A CN 104628928 B CN104628928 B CN 104628928B
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Abstract
The invention belongs to the field of photochromic high polymer materials and discloses a photochromic fluorocarbon resin as well as a preparation method and application thereof. The photochromic fluorocarbon resin is prepared by carrying out graft modification on fluorocarbon resin by a diarylethene photochromic material. The photochromic fluorocarbon resin can form polyurethane high polymer under action of isocyanate and the polyurethane high polymer is solidified to prepare a photochromic fluorocarbon resin film. The photochromic fluorocarbon resin film can smoothly realize photochromic reaction, and then characters can be written through metachromatism. The photochromic fluorocarbon resin is especially suitable for preparing a coating material requiring photochromic characteristic, is used for the fields of information writing, real-time monitoring of leakage of ultraviolet light and the like, and can be used for places needing a plurality of writing method requirements.
Description
Technical field
The invention belongs to Photochromic Polymers field is and in particular to a kind of photochromic fluorocarbon resin and its preparation
Method and application.
Background technology
Fluorocarbon resin (FEVE) is fluorine organic high molecular polymer, has superpower chemical stability and ageing-resistant
Performance, thus be widely used in resistant, the manufacturing of weather-proof sapecial coating.
Organic photochromic material is that a class can control its absorption spectrum under different illumination conditions, and and then adjusts it
The organic compound of color.Photochromic material has many kinds, has (the Satoshi such as spiro-pyrans, fulgide and oxazines
Kawata, et al, Chem.Rev.2000,100,1777-1788, patent CN100434430C and CN101671467B), two virtues
Base ethylene photochromic compound because having good heat stability and fatigue durability, by the extensive concern of researcher and open
A large amount of derivants (Masahiro Irie et al, Bull.Chem.Soc., Jpn.71,985-996) are sent out.
At present, existing photochromic resin framework material is polyvinyl alcohol, and this resin is not suitable for blank coating,
Because its not organic solvent-resistant, intolerant to wipe it is impossible to repeatedly writing for oil pen and wiping；Or it is photochromic due to use
The heat stability of compound is poor, and the word of illumination write can quickly fade, and do not reach and use up write word and exchanged
Purpose.The product that be grafted to diarylethene on fluorocarbon resin skeleton is there is not yet occur.In addition, having of current report is photic
The resin of discoloration, polymer are all not directed to fluorocarbon resin.
Content of the invention
In order to overcome shortcoming and the deficiency of prior art, the primary and foremost purpose of the present invention is to provide a kind of photochromic fluorine carbon
Resin；
Another object of the present invention is to providing the preparation method of above-mentioned photochromic fluorocarbon resin；
It is still another object of the present invention to provide the application of above-mentioned photochromic fluorocarbon resin.
The purpose of the present invention is achieved through the following technical solutions：
A kind of photochromic fluorocarbon resin, carries out graft modification by diaryl ethylene photochromic material to fluorocarbon resin
It is prepared；Wherein, in parts by weight, fluorocarbon resin is 10～20 weight portions to each raw material, diaryl ethylene photochromic material
Expect for 0.001～0.01 weight portion.
Preferably, described diaryl ethylene photochromic material is 9,10- bis- (2,5- thioxene) phenanthrene light-induced variable
Color material；
It is furthermore preferred that described diaryl ethylene photochromic material is 9,10- bis- (2,5- thioxene) luxuriant and rich with fragrance -2,7-
Dimethyl chloride；
Described 9,10- bis- (2,5- thioxene) phenanthrene -2,7- dimethyl chloride reference literature (Junjie He et al,
J.Mater.Chem.C, 2014,2,7531-7540) it is prepared and obtain, comprise the steps：By the 9 of 0.1～0.5mmol,
10- bis- (2,5- thioxene) phenanthrene -2,7- dioctyl phthalate adds in single-necked flask, adds 20～50mL dichloromethane, then Deca
The oxalyl chloride of 0.4～1mmol or thionyl chloride, and the DMF of catalytic amount, react 3～5h under room temperature；So
Evaporated under reduced pressure solvent afterwards, repeatedly adds dichloromethane to be dissolved and be evaporated, removes unreacted oxalyl chloride, finally it is dissolved in 20～
In 50mL dichloromethane solution, obtain 9,10- bis- (2,5- thioxene) phenanthrene -2,7- dimethyl chloride solution.
The preparation method of above-mentioned photochromic fluorocarbon resin, comprises the steps：
(1) dichloromethane solution of diaryl ethylene photochromic material is added drop-wise to the toluene solution of fluorocarbon resin
In, stirring reaction under room temperature；
(2) step (1) is reacted resulting material pressurization and steam the hydrogen chloride that solvent and reaction produce, repeat addition dichloro
Methane, so that solvent and hydrogen chloride are evaporated off, are subsequently adding toluene solvant and adjust solid content, obtain described photochromic fluorocarbon resin.
Preferably, under the described room temperature of step (1), the response time of stirring reaction is 12～24 hours；
Preferably, the described solid content of step (2) is 40%～60%.
Graft modification preparation is carried out to fluorocarbon resin using 9,10- bis- (2,5- thioxene) phenanthrene -2,7- dimethyl chloride
During photochromic fluorocarbon resin, its reaction equation is as follows：
The change of structural formula in photochromism processes of the photochromic fluorocarbon resin of gained is as follows：
Wherein, UV represents ultraviolet light, and Vis represents visible ray.
Above-mentioned photochromic fluorocarbon resin can be applicable to preparation and reveals monitoring technology field for information write or ultraviolet light
Photochromic characteristic coating material.
The method that above-mentioned photochromic fluorocarbon resin prepares photochromic fluorocarbon resin film, comprises the steps：
A () adds isocyanates in photochromic fluorocarbon resin and stirs；
The addition of described isocyanates is 1.1～1.2 times amount of photochromic fluorocarbon resin middle hydroxyl value content；
Preferably, described isocyanates are toluene di-isocyanate(TDI), hexamethylene diisocyanate or isophorone two
Isocyanates；
For to strengthen performance, again reinforcer can be added in photochromic fluorocarbon resin in step (a) and be stirred；Excellent
Choosing, described reinforcer is triple superphosphate or Griffith's zinc white.；
B () is by step (a) resulting material evacuation until removing bubble completely；
C () step (b) resulting material is scraped in clean substrate surface and is painted thin film, horizontal positioned levelling film forming；
D step (c) gained film aeration-drying is solidified by (), obtain described photochromic fluorocarbon resin film.
The present invention has such advantages as with respect to prior art and effect：
(1) photochromic functionalities are grafted on fluorocarbon resin molecular skeleton by the present invention by chemical bond, in ultraviolet light
Under irradiation, the photochromic group in photochromic fluorocarbon resin structure can occur photoisomerization, thus changing the color of resin；
And photochromic fluorocarbon resin of the present invention not only can occur in liquid photochromic, with cured with isocyanates film forming it
Photochromic reactions also can occur afterwards.
(2) diarylethene with photochromic function is smoothly incorporated on fluorocarbon resin by the present invention, and achieves
The photochromic properties of photochromic fluorocarbon resin film.
(3) photochromic fluorocarbon resin film of the present invention can carry out the write of word by ultraviolet light；And due to
Fluorocarbon resin resistance to overwhelming majority solvent wiping, so can also be using oil pen in described photochromic fluorocarbon resin film coated surface
Write, and easily wiped, left no trace.Photochromic fluorocarbon resin film of the present invention is particularly useful for making needs
The coating material of photochromic characteristic, the field such as leakage for information write and real-time monitoring ultraviolet light it can also be used to other
Need the place of multiple wiring method demands.
Brief description
Fig. 1 is the absorption under ultraviolet-visible of fluorocarbon resin film and photochromic fluorocarbon resin film of the present invention
Spectrogram.
Fig. 2 is purple after the ultraviolet light different time of 365nm for the photochromic fluorocarbon resin film of the present invention
Outer visible absorption spectra figure.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
Embodiment 1
A kind of photochromic fluorocarbon resin, by diaryl ethylene photochromic material 9,10- bis- (2,5- dimethyl thiophenes
Fen) phenanthrene -2,7- dimethyl chloride carries out graft modification to fluorocarbon resin and is prepared, and preparation process includes the following raw material：100g
Fluorocarbon resin (solid content 50%), the photochromic carboxylic acid material of 0.243g 9,10- bis- (2,5- thioxene) phenanthrene -2,7- diformazan
Acid, 500mL dichloromethane, 0.5mL oxalyl chloride, catalytic amount DMF.
Preparation method comprises the following steps that：
(1) prepare the solution of acid chloride of variable color functional group：Reference literature (Junjie He et al, J.Mater.Chem.C,
2014,2,7531-7540), by photochromic for 0.243g carboxylic acid material 9,10- bis- (2,5- thioxene) phenanthrene -2,7- diformazan
Acid adds in single-necked flask, adds 50mL dichloromethane, with syringe Deca 0.5mL oxalyl chloride and catalytic amount N, N- dimethyl methyl
Amide, room temperature reaction 3～5 hours；Then evaporated under reduced pressure solvent, repeatedly adds 100mL dichloromethane, is evaporated after dissolving acyl chlorides,
Remove unreacted oxalyl chloride, be finally dissolved in 100mL dichloromethane solution, acquisition 9,10- bis- (2,5- thioxene) phenanthrene-
2,7- dimethyl chloride solution；
(2) fluorocarbon resin graft modification：By gained 9,10- bis- (2,5- thioxene) phenanthrene -2,7- dimethyl chloride solution
It is slowly dropped in the middle of the glue of 100g fluorocarbon resin, reaction 12 hour is stirred at room temperature；
(3) purification is dried：Step (2) is reacted resulting material pressurization and steams the hydrogen chloride that solvent and reaction produce, then weigh
Multiple three addition dichloromethane, are evaporated off solvent and eliminate hydrogen chloride, and being subsequently adding toluene solvant and adjusting solid content is 40～60%,
Obtain described photochromic fluorocarbon resin.
Embodiment 2
A kind of photochromic fluorocarbon resin, by diaryl ethylene photochromic material 9,10- bis- (2,5- dimethyl thiophenes
Fen) phenanthrene -2,7- dimethyl chloride carries out graft modification to fluorocarbon resin and is prepared, and preparation process includes the following raw material：10g fluorine
Carbon resin (solid content 50%), the photochromic carboxylic acid material of 0.243g 9,10- bis- (2,5- thioxene) phenanthrene -2,7- diformazan
Acid, 50mL dichloromethane, 0.5mL thionyl chloride, catalytic amount DMF.
Preparation method comprises the following steps that：
(1) prepare the solution of acid chloride of variable color functional group：Reference literature (Junjie He et al, J.Mater.Chem.C,
2014,2,7531-7540), by photochromic for 0.243g carboxylic acid material 9,10- bis- (2,5- thioxene) phenanthrene -2,7- diformazan
Acid adds in single-necked flask, adds 10mL dichloromethane, with syringe Deca 0.5mL thionyl chloride and catalytic amount N, N- dimethyl
Methanamide, room temperature reaction 3～5 hours；Then evaporated under reduced pressure solvent, repeatedly adds 10mL dichloromethane, is evaporated after dissolving acyl chlorides,
Remove unreacted thionyl chloride, be finally dissolved in 10mL dichloromethane solution, obtain 9,10- bis- (2,5- thioxene)
Phenanthrene -2,7- dimethyl chloride solution；
(2) fluorocarbon resin graft modification：By gained 9,10- bis- (2,5- thioxene) phenanthrene -2,7- dimethyl chloride solution
It is slowly dropped in the middle of the glue of 10g fluorocarbon resin, reaction 12 hour is stirred at room temperature；
(3) purification is dried：Step (2) is reacted resulting material pressurization and steams the hydrogen chloride that solvent and reaction produce, then weigh
Multiple three addition dichloromethane, are evaporated off solvent and eliminate hydrogen chloride, and being subsequently adding toluene solvant and adjusting solid content is 40～60%,
Obtain described photochromic fluorocarbon resin.
Embodiment 3
A kind of photochromic fluorocarbon resin film, using toluene di-isocyanate(TDI) to described in the embodiment of the present invention 1 preparation
Photochromic fluorocarbon resin carries out solidification and is obtained, and raw material includes：Photochromic fluorocarbon resin 10g, toluene di-isocyanate(TDI)
0.38g.Its preparation method specifically includes following steps：
1st, 0.38g toluene di-isocyanate(TDI) is added in photochromic fluorocarbon resin described in 10g, is uniformly mixing to obtain mixed
Compound material；
2nd, by gained mixed material evacuation, until removing bubble completely；
3rd, on the sheet glass of step 2 resulting material smooth and clean or iron plate, thin film, horizontal positioned, stream are formed by blade coating
Heisei film；
4th, step 3 gained film aeration-drying is solidified 7 days, obtain described photochromic fluorocarbon resin film.
Comparative example 1
A kind of fluorocarbon resin film, carries out solidification by toluene di-isocyanate(TDI) and is obtained, raw material includes to fluorocarbon resin：Fluorine carbon
Resin 10g, toluene di-isocyanate(TDI) 0.38g.Its preparation method specifically includes following steps：
1st, 0.38g toluene di-isocyanate(TDI) is added in fluorocarbon resin described in 10g, is uniformly mixing to obtain mixed material；
2nd, by gained mixed material evacuation, until removing bubble completely；
3rd, on the sheet glass of step 2 resulting material smooth and clean or iron plate, thin film, horizontal positioned, stream are formed by blade coating
Heisei film；
4th, step 3 gained film aeration-drying is solidified 7 days, obtain described fluorocarbon resin film.
Embodiment 4
A kind of photochromic fluorocarbon resin film, using toluene di-isocyanate(TDI) to light-induced variable described in the embodiment of the present invention 1
Color fluorocarbon resin carries out solidification and is obtained, and raw material includes：Photochromic fluorocarbon resin 10g, toluene di-isocyanate(TDI) 0.38g, zinc barium
White 2g.Its preparation method specifically includes following steps：
1st, 0.38g toluene di-isocyanate(TDI) and 2g Griffith's zinc white. are added in photochromic fluorocarbon resin described in 10g, stirring
Uniformly obtain mixed material；
2nd, by gained mixed material evacuation, until removing bubble completely；
3rd, on the sheet glass of step 2 resulting material smooth and clean or iron plate, thin film, horizontal positioned, stream are formed by blade coating
Heisei film；
4th, step 3 gained film aeration-drying is solidified 7 days, obtain described photochromic fluorocarbon resin film.
Embodiment 5
A kind of photochromic fluorocarbon resin film, is prepared to the embodiment of the present invention 1 using hexamethylene diisocyanate
Described photochromic fluorocarbon resin carries out solidification and is obtained, and raw material includes：Photochromic fluorocarbon resin 10g, hexa-methylene two isocyanide
Acid esters 0.37g.Its preparation method specifically includes following steps：
1st, 0.37g hexamethylene diisocyanate is added in photochromic fluorocarbon resin described in 10g, stirs
To mixed material；
2nd, by gained mixed material evacuation, until removing bubble completely；
3rd, on the sheet glass of step 2 resulting material smooth and clean or iron plate, thin film, horizontal positioned, stream are formed by blade coating
Heisei film；
4th, step 3 gained film aeration-drying is solidified 7 days, obtain described photochromic fluorocarbon resin film.
Embodiment 6
A kind of photochromic fluorocarbon resin film, is prepared to the embodiment of the present invention 2 using isophorone diisocyanate
Described photochromic fluorocarbon resin carries out solidification and is obtained, and raw material includes：Photochromic fluorocarbon resin 10g, isophorone two isocyanide
Acid esters 0.49g.Its preparation method specifically includes following steps：
1st, 0.49g isophorone diisocyanate is added in photochromic fluorocarbon resin described in 10g, stirs
To mixed material；
2nd, by gained mixed material evacuation, until removing bubble completely；
3rd, on the sheet glass of step 2 resulting material smooth and clean or iron plate, thin film, horizontal positioned, stream are formed by blade coating
Heisei film；
4th, step 3 gained film aeration-drying is solidified 7 days, obtain described photochromic fluorocarbon resin film.
Performance detection：
1st, the photochromic fluorocarbon resin film of embodiment 3 gained and comparative example 1 gained fluorocarbon resin film are measured in ultraviolet
Absorbance under visible ray, gained abosrption spectrogram is as shown in Figure 1.
It will be seen from figure 1 that the photochromic fluorocarbon resin of the cured gained of photochromic fluorocarbon resin of the present invention
(in Fig. 1, curve is labeled as fluorocarbon resin film after film (in Fig. 1, curve is labeled as P-FEVE) and conventional fluorocarbon resin solidification
FEVE) extremely close on absorption spectrum, absorb weaker in visible region, photochromic fluorocarbon resin film shows slightly faint yellow；
2nd, measure the photochromic fluorocarbon resin film of embodiment 3 gained under 365nm ultraviolet light through 0s, 5s, 10s, 20s,
The change of the ultraviolet-visible absorption spectroscopy after the different irradiation times of 40s, 70s or 130s, ultraviolet-visible absorption spectroscopy figure such as Fig. 2
Shown.
Figure it is seen that when not being subject to ultraviolet light, photochromic fluorocarbon resin film is to 500nm band above
Light there is no any absorption, and after 365nm ultraviolet light 5s, at 550nm, just have an obvious absworption peak to occur, with
, to before 130s, this absworption peak is all in enhancing, and just no longer changes after 130s, illustrates photic for ultraviolet light time lengthening
Metachromasia terminates.
3rd, color change before and after ultraviolet light for the photochromic fluorocarbon resin film that detection embodiment 3 is obtained.Institute
Obtaining photochromic fluorocarbon resin film is in light yellow before through ultraviolet light, assumes bronzing, explanation after ultraviolet light
Photochromic fluorocarbon resin of the present invention, after film-forming, still has photochromic properties.
4th, photochromic fluorocarbon resin film of the present invention is photic with making after ultraviolet light local irradiation locally to occur
Variable color and take on a red color, and be not subject to ultraviolet light part keep faint yellow, such that it is able to smoothly realize the ablation process of word.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any spirit without departing from the present invention and the change made under principle, modification, replacement, combine, simplify,
All should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (9)
1. a kind of photochromic fluorocarbon resin is it is characterised in that described photochromic fluorocarbon resin is photic by diarylethene
Off-color material carries out graft modification to fluorocarbon resin and is prepared；Wherein, each raw material is in parts by weight：Fluorocarbon resin is 10～20
Weight portion, diaryl ethylene photochromic material is 0.001～0.01 weight portion；Described diaryl ethylene photochromic material
Expect for 9,10- bis- (2,5- thioxene) phenanthrene photochromic material.
2. a kind of photochromic fluorocarbon resin according to claim 1 it is characterised in that：Described diarylethene is photic
Off-color material is 9,10- bis- (2,5- thioxene) phenanthrene -2,7- dimethyl chloride.
3. the photochromic fluorocarbon resin described in a kind of any one according to claim 1～2 preparation method it is characterised in that
Comprise the steps：
(1) dichloromethane solution of diaryl ethylene photochromic material is added drop-wise in the toluene solution of fluorocarbon resin, room
The lower stirring reaction of temperature；
(2) step (1) is reacted resulting material decompression and steam the hydrogen chloride that solvent and reaction produce, repeat addition dichloromethane
So that solvent and hydrogen chloride are evaporated off, it is subsequently adding toluene solvant and adjusts solid content, obtain described photochromic fluorocarbon resin.
4. photochromic fluorocarbon resin according to claim 3 preparation method it is characterised in that：The described room of step (1)
The response time of the lower stirring reaction of temperature is 12～24 hours；The described solid content of step (2) is 40%～60%.
5. the photochromic fluorocarbon resin according to any one of claim 1～2 writes or ultraviolet light for information in preparation
Reveal the application in the photochromic characteristic coating material in monitoring technology field.
6. the photochromic fluorocarbon resin according to any one of claim 1～2 is preparing photochromic fluorocarbon resin film
In application.
7. application in preparing photochromic fluorocarbon resin film for the photochromic fluorocarbon resin according to claim 6,
It is characterized in that, the method that described photochromic fluorocarbon resin prepares photochromic fluorocarbon resin film, comprise the steps：
A () adds isocyanates in photochromic fluorocarbon resin and stirs；
B () is by step (a) resulting material evacuation until removing bubble completely；
C () step (b) resulting material is scraped in clean substrate surface and is painted thin film, horizontal positioned levelling film forming；
D step (c) gained film aeration-drying is solidified by (), obtain described photochromic fluorocarbon resin film.
8. application in preparing photochromic fluorocarbon resin film for the photochromic fluorocarbon resin according to claim 7,
It is characterized in that：The addition of the described isocyanates of step (a) is the 1.1～1.2 of photochromic fluorocarbon resin middle hydroxyl value content
Times amount；The described isocyanates of step (a) are toluene di-isocyanate(TDI), hexamethylene diisocyanate or isophorone two isocyanide
Acid esters.
9. application in preparing photochromic fluorocarbon resin film for the photochromic fluorocarbon resin according to claim 7,
It is characterized in that：Step (a) adds reinforcer in photochromic fluorocarbon resin again and is stirred；Described reinforcer
For triple superphosphate or Griffith's zinc white..
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