CN104212334B - A kind of UV prepared based on advanced material with carbon element solidifies the antistatic hydrophobic coating of low refraction - Google Patents
A kind of UV prepared based on advanced material with carbon element solidifies the antistatic hydrophobic coating of low refraction Download PDFInfo
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Abstract
The invention discloses a kind of UV prepared based on advanced material with carbon element and solidify the antistatic hydrophobic coating of low refraction, described coating comprises component and each constituent mass mark is light-sensitive polyimide 45 55%, advanced material with carbon element 0 35%, light trigger 2 5%, diluent 10 16%, solvent 0 35%, each component is mixed in proportion and is spun on slide, through preliminary drying, photocuring, obtain UV and solidify the antistatic hydrophobic coating of low-refraction.Polymer used by coating of the present invention introduces photosensitive group, can be used for UV solidification；Introduce fluorine atom in reaction monomers used so that the coating of preparation has hydrophobicity, introduce material with carbon element, make coating have certain antistatic effect, fluorine atom and material with carbon element and simultaneously work as reducing the effect of the refractive index of material.
Description
Technical field
The present invention relates to ultraviolet light polymerization and field of nanocomposite materials, especially relate to a kind of photosensitive polyamides
UV solidification antistatic hydrophobic coating of low-refraction prepared by imines/material with carbon element and preparation method thereof.
Background technology
Organic-inorganic nanocomposite is owing to having the mechanics of excellence, calorifics, and the performance such as optics is by vast
The concern of researcher.In numerous organic materials, light-sensitive polyimide has the heat resistance of excellence, chemically-resistant
Property, low temperature resistivity and low dielectric constant, be excellent heat-resisting photosensitive multifunctional macromolecule material, extensively apply
In microelectronic industry, auto industry, aerospace industry etc..Rigidity benzene ring structure in polyimide molecule is formed
Conjugated system, causes polyimide material to have the highest glass transition temperature and fusing point, also causes gathering simultaneously
Acid imide is difficult to dissolve in organic solvent, and toughness is not enough, and mechanical property is not good enough.By montmorillonite, aluminium nitride,
Titanium dioxide, the heat resistance of composite organic-inorganic material of the preparation such as silica, mechanical strength, hydrophobicity etc.
Although increasing, but still can not meet the hot property of its application requirement, especially material, electrical property, power
Learn performance etc..
There is delocalizedπelectron in material with carbon element, the structure of this similar free electron can form conductor or semiconductor, tool
There is excellent electric property, therefore material with carbon element is disperseed in the polymer, antistatic and conduction height can be prepared
Molecular material.CNT and Graphene are two kinds of most advanced material with carbon elements of current most study, and they have very
Mechanical property well, optical property are with thermal property.Therefore, it can prepare heat by advanced material with carbon element modification
Performance, electrical property are with polyimides-CNT (Graphene) composite of good mechanical performance.
Summary of the invention
The problems referred to above existed for prior art, it is antistatic thin that the application provides a kind of UV to solidify low refraction
Water coating and preparation method thereof.Polymer used by coating of the present invention introduces photosensitive group, can be used for UV solid
Change；Introduce fluorine atom in reaction monomers used so that the coating of preparation has hydrophobicity, introduce material with carbon element,
Make coating have certain antistatic effect, fluorine atom and material with carbon element and simultaneously work as reducing the work of the refractive index of material
With.
Technical scheme is as follows:
A kind of UV prepared based on advanced material with carbon element solidifies the antistatic hydrophobic coating of low refraction, and contained material includes
Light-sensitive polyimide 45-55%, advanced material with carbon element 0-35%, light trigger 2-5%, diluent 10-16%,
Solvent 0-35%；
The preparation method of described light-sensitive polyimide is:
(1) with 4,4'-(hexafluoroisopropylidenyl) diphenylamines, hexafluorodianhydride (6FDA) are raw material, and 1-METHYLPYRROLIDONE is molten
Agent, reacts 8-10h at room temperature, obtains product A；
(2) in product A, the mixed of 1-METHYLPYRROLIDONE, PABA and m-dichlorobenzene is then dripped
Close liquid, at room temperature react 16-18h, be warming up to 180-200 DEG C, continue reaction 8-12h, be subsequently cooled to room
Temperature obtains end carboxylic product B；
(3) finally it is warming up to 90-120 DEG C, in product B, drips GMA, triphenylphosphine
With the mixed liquor of 4-methoxyl group phenol, react 6-8h, obtain light-sensitive polyimide C.
Described 4,4'-(hexafluoroisopropylidenyl) diphenylamines, hexafluorodianhydride (6FDA), PABA, methacrylic acid contract
The mol ratio of water glyceride is 1:2:2:0.5-1:2:2:1.5.
The 1-5% that consumption is GMA quality of described m-dichlorobenzene；Described triphenyl
The consumption of phosphine is the 1-3% of GMA quality；The consumption of described 4-methoxyl group phenol is methyl
The 1-3% of glycidyl acrylate quality.
Described advanced material with carbon element is one or more in CNT, Graphene.
Described light trigger is 1-hydroxy cyclohexyl phenylketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholine-1-third
One or more in ketone.
Described diluent is ethoxylated trimethylolpropane triacrylate EOTMPTA, tripropylene glycol dipropyl
One or more in olefin(e) acid ester TPGDA.
Described solvent is DMAC N,N' dimethyl acetamide DMAC, N,N-dimethylformamide DMF, N-methyl pyrrole
In pyrrolidone NMP one or more.
The preparation method that a kind of UV prepared based on advanced material with carbon element solidifies the antistatic hydrophobic coating of low refraction is:
Light-sensitive polyimide, advanced material with carbon element, light trigger, diluent, solvent are mixed in proportion and be spun on
On slide, 60-90 DEG C of preliminary drying 10-30min, 400-600mj/cm2Under the conditions of photocuring, obtain UV solidification
The antistatic hydrophobic coating of low-refraction.
Useful the having the technical effect that of the present invention
1, the conjugated body that the rigidity benzene ring structure in the polyimide molecule in coating material of the present invention is formed
System, causes polyimide material to have the highest glass transition temperature and fusing point, makes material have good resistance to
Hot.
2, the fluorine atom in the polyimide molecule in coating material of the present invention can reduce the surface energy of material,
Material tool is made to have certain effect；The refractive index of material can also be reduced.
3, the material with carbon element in coating material of the present invention (CNT and Graphene) has the electric conductivity of excellence, power
Learn performance and thermal property, make material possess antistatic or conductivity, simultaneously work as reinforcing material toughness and heat-resisting
Property, reduce material surface energy and the effect of refractive index.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrogram of light-sensitive polyimide；
Fig. 2 is the variations in refractive index curve of the UV solidification antistatic hydrophobic coating of low refraction in embodiment 1；
Fig. 3 is that in embodiment 1, UV solidifies low refraction antistatic hydrophobic coating surface resistance change curves；
Fig. 4 is that in embodiment 1, UV solidifies low refraction antistatic hydrophobic coating water contact angle change curve.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, the present invention is specifically described.
Embodiment 1
3.34g 4,4'-(hexafluoroisopropylidenyl) diphenylamines, 20ml N-first is added in 250ml three neck round bottom flask
Base pyrrolidones, drips 8.88g hexafluorodianhydride (6FDA) and 30ml N-methylpyrrole in the case of being stirred vigorously lentamente
The mixed liquor of alkanone, at room temperature after reaction 8h, products therefrom is designated as A；In flask, dropping 2.88g is to ammonia
The m-dichlorobenzene of yl benzoic acid, 15mg and the mixed liquor of 15mg 1-METHYLPYRROLIDONE, react at room temperature
16h, is then warming up to 200 DEG C, and continuation reaction obtains product for 12 hours and is designated as B；Dropping in flask
1.42g GMA, 0.043g catalyst triphenylphosphine and 0.043g hydroquinone of polymerization retarder
Mixed liquor, 120 DEG C reaction 6h, obtain product and be designated as C.Fig. 1 is the nuclear magnetic spectrogram of product C, from figure
Can be seen that δ=5.6 and δ=6.1 are the H in double bond, be the H on carboxyl at δ=13.2, δ=7.4 and δ
=8.3 is the H on phenyl ring, it was demonstrated that successfully synthesize light-sensitive polyimide.
Weighing the light-sensitive polyimide of certain mass, light trigger 1-hydroxy cyclohexyl phenylketone, activity is dilute
Releasing agent ethoxylated trimethylolpropane triacrylate, solvent DMF, CNT mixes
Uniformly it is spun on slide, 60 DEG C of preliminary drying 10min, 600mj/cm2Under the conditions of photocuring, obtain UV solidification
The antistatic hydrophobic coating of low refraction, each amounts of components is as shown in table 1 below.
Table 1
The refractive index of film that formed according to above-mentioned condition, resistivity, contact angle change see respectively Fig. 2,3,
4.As can be seen from Figure 2 along with the increase of CNT consumption, the refractive index of film is gradually lowered；From Fig. 3
Can be seen that, along with the increase of CNT consumption, the sheet resistance of film is gradually lowered；As can be seen from Figure 4
Along with the increase of CNT consumption, the contact angle of film is gradually increased.
Embodiment 2
3.34g 4,4'-(hexafluoroisopropylidenyl) diphenylamines, 20ml N-is added in 250ml three neck round bottom flask
Methyl pyrrolidone, drips 8.88g hexafluorodianhydride (6FDA) and 30ml N-methyl pyrrole in the case of being stirred vigorously lentamente
The mixed liquor of pyrrolidone, at room temperature after reaction 10h, products therefrom is designated as A；Dropping 2.88g in flask
The m-dichlorobenzene of p-aminobenzoic acid, 30mg and the mixed liquor of 30mg 1-METHYLPYRROLIDONE, at room temperature
Reaction 18h, is then warming up to 180 DEG C, and continuation reaction 12h obtains product and is designated as B；Dropping in flask
0.71g GMA, 0.043g catalyst triphenylphosphine and 0.043g hydroquinone of polymerization retarder
Mixed liquor, 100 DEG C reaction 7h, obtain product and be designated as C.
Weigh the light-sensitive polyimide of certain mass, light trigger 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-
Quinoline-1-acetone, reactive diluent ethoxylated trimethylolpropane triacrylate, solvent N, N-dimethyl second
Acid amides, Graphene mixes and is spun on slide, 75 DEG C of preliminary drying 20min, 500mj/cm2Under the conditions of light solid
Changing, obtain UV and solidify the antistatic hydrophobic coating of low refraction, each amounts of components is as shown in table 2 below.
Table 2
Embodiment 3
3.34g 4,4'-(hexafluoroisopropylidenyl) diphenylamines, 20ml N-is added in 250ml three neck round bottom flask
Methyl pyrrolidone, drips 8.88g hexafluorodianhydride (6FDA) and 30ml N-methyl pyrrole in the case of being stirred vigorously lentamente
The mixed liquor of pyrrolidone, at room temperature after reaction 9h, products therefrom is designated as A；Dropping 2.88g pair in flask
The m-dichlorobenzene of aminobenzoic acid, 15mg and the mixed liquor of 15mg 1-METHYLPYRROLIDONE, the most instead
Answering 17h, be then warming up to 190 DEG C, continuation reaction 10h obtains product and is designated as B；Dropping 2.13g in flask
GMA, 0.043g catalyst triphenylphosphine, 0.043g hydroquinone of polymerization retarder, 90 DEG C
Reaction 8h, obtains product and is designated as C.
Weigh the light-sensitive polyimide of certain mass, light trigger 1-hydroxy cyclohexyl phenylketone, reactive diluent
Tripropylene glycol diacrylate, solvent N-methyl pyrilidone, CNT mixes and is spun on slide
On, 60 DEG C of preliminary drying 10min, 400mj/cm2Under the conditions of photocuring, obtain UV solidify low refraction antistatic hydrophobic
Coating, each amounts of components is as shown in table 3 below.
Table 3
Claims (7)
1. the UV prepared based on advanced material with carbon element solidifies the antistatic hydrophobic coating of low refraction, it is characterised in that institute
State component contained by coating and each constituent mass mark be light-sensitive polyimide 45-55%, advanced material with carbon element 8.98-
35%, light trigger 2-5%, diluent 10-16%, solvent 0-35%；Each component proportion sum is
100%；
The preparation method of described light-sensitive polyimide is:
(1) with 4,4'-(hexafluoroisopropylidenyl) diphenylamines, hexafluorodianhydride (6FDA) are raw material, and 1-METHYLPYRROLIDONE is molten
Agent, reacts 8-10h at room temperature, obtains product A；
(2) in product A, the mixed of 1-METHYLPYRROLIDONE, PABA and m-dichlorobenzene is then dripped
Close liquid, at room temperature react 16-18h, be warming up to 180-200 DEG C, continue reaction 8-12h, be subsequently cooled to room
Temperature obtains end carboxylic product B；
(3) finally it is warming up to 90-120 DEG C, in product B, drips GMA, triphenylphosphine
With the mixed liquor of 4-methoxyl group phenol, react 6-8h, obtain light-sensitive polyimide C；
Described advanced material with carbon element is one or more in CNT, Graphene.
Coating the most according to claim 1, it is characterised in that described 4,4'-(hexafluoroisopropylidenyl) diphenylamines,
Hexafluorodianhydride (6FDA), PABA, the mol ratio of GMA are 1:2:2:0.5-
1:2:2:1.5。
Coating the most according to claim 1, it is characterised in that the consumption of described m-dichlorobenzene is methyl-prop
The 1-5% of olefin(e) acid ethylene oxidic ester quality；The consumption of described triphenylphosphine is GMA matter
The 1-3% of amount；The 1-3% that consumption is GMA quality of described 4-methoxyl group phenol.
Coating the most according to claim 1, it is characterised in that described light trigger is 1-hydroxy-cyclohexyl benzene
One or more in ketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholine-1-acetone.
Coating the most according to claim 1, it is characterised in that described diluent is ethoxylation trihydroxy methyl third
One or more in alkane triacrylate EOTMPTA, tripropylene glycol diacrylate TPGDA.
Coating the most according to claim 1, it is characterised in that described solvent is DMA
One or more in DMAC, N,N-dimethylformamide DMF, 1-METHYLPYRROLIDONE NMP.
7. the preparation method of coating described in an any one of claim 1～6, it is characterised in that described method is:
Light-sensitive polyimide, advanced material with carbon element, light trigger, diluent, solvent are mixed in proportion and be spun on
On slide, 60-90 DEG C of preliminary drying 10-30min, 400-600mj/cm2Under the conditions of photocuring, obtain UV solidification
The antistatic hydrophobic coating of low-refraction.
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| CN105273614B (en) * | 2015-10-12 | 2017-08-22 | 广东省宜华木业股份有限公司 | Prepared by room temperature reaction be used for the super-hydrophobic polyimide paints of wooden material surface UV |
| CN105353587B (en) * | 2015-12-15 | 2019-12-20 | 南方科技大学 | Nano-imprinting photoresist and preparation method thereof |
| CN105585671A (en) * | 2016-03-23 | 2016-05-18 | 江南大学 | Biologic photosensitive polyimide resin and coating prepared from same |
| CN113061392A (en) * | 2021-03-29 | 2021-07-02 | 东莞市鹏威能源科技有限公司 | Graphene PI composite material, and preparation method and application thereof |
| CN113388107A (en) * | 2021-06-09 | 2021-09-14 | 广东工业大学 | Photosensitive polyimide resin, polyimide photocuring coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492320A (en) * | 2011-12-05 | 2012-06-13 | 北方涂料工业研究设计院 | Quick-curing polyimide coating for high-temperature-resistant optical fiber |
| CN102712165A (en) * | 2009-10-13 | 2012-10-03 | 纳诺电子化学有限公司 | Antistatic sheet for stacking beverage and food containers and manufacturing method thereof |
| CN103236442A (en) * | 2013-04-23 | 2013-08-07 | 京东方科技集团股份有限公司 | Thin film transistor, manufacture method of thin film transistor, array base plate and electronic device |
-
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- 2014-09-12 CN CN201410464446.XA patent/CN104212334B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712165A (en) * | 2009-10-13 | 2012-10-03 | 纳诺电子化学有限公司 | Antistatic sheet for stacking beverage and food containers and manufacturing method thereof |
| CN102492320A (en) * | 2011-12-05 | 2012-06-13 | 北方涂料工业研究设计院 | Quick-curing polyimide coating for high-temperature-resistant optical fiber |
| CN103236442A (en) * | 2013-04-23 | 2013-08-07 | 京东方科技集团股份有限公司 | Thin film transistor, manufacture method of thin film transistor, array base plate and electronic device |
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