CN1319617A - Reversible light-sensitive resin containing heteroaryl ethylene lateral chain and preparation process thereof - Google Patents
Reversible light-sensitive resin containing heteroaryl ethylene lateral chain and preparation process thereof Download PDFInfo
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- CN1319617A CN1319617A CN 00135773 CN00135773A CN1319617A CN 1319617 A CN1319617 A CN 1319617A CN 00135773 CN00135773 CN 00135773 CN 00135773 A CN00135773 A CN 00135773A CN 1319617 A CN1319617 A CN 1319617A
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Abstract
Under the irradiation of UV light wight longer wave length said invented resin can be cross-linked to form non-meltable insoluble three-dimensional polymer, and can be film-formed or imaged, also under the irrdiation of UV light weigh shorter wave length the cross-linked three-dimensional polymer can be depolymerized and again made into linear polymer with the features of resisting oxidation, resisting dampness and stable storage. It is made up by grafting the heteroaryl ethylene photofunctional group capable of implementing reversible photochemical addition reaction on the molecular chain of polymer of polystyrene, etc. Its preparation process is simple.
Description
The present invention relates to a kind of reversible light-sensitive resin that contains heteroaryl ethylene lateral chain and preparation method thereof, belong to the technology of preparing of reversible light-sensitive resin.
Photosensitive resin is the simple linear polymer that a class can issue biochemical reaction (normally crosslinking reaction) in rayed, and they obtain widespread use in industries such as opticfiber communication, decorating film material, laser plate-making and printed ICs.More typically have in these photosensitive resins:
1, with the free radical be the acrylate type photosensitive resin of initiator, the crosslinking polymerization of this type of photosensitive resin belongs to radical chain reaction, and is very responsive to oxygen in the air, often needs protection of inert gas during use, and often causes surface aggregate incomplete.
2, with diaryl group iodized salt and uncle's sulfonium salt be the Resins, epoxy type photosensitive resin of photosensitive dose of positively charged ion, this type of photosensitive resin is very responsive to water in air vapour, needs the exsiccant workshop during curing, uses summer solidification effect bad.
The shelf lives of above photosensitive resin is shorter, the condition of cure harshness.And in case through the illumination crosslinking curing, depolymerization reaction can not take place again generate original oligopolymer.
The object of the present invention is to provide a class to contain reversible light-sensitive resin of heteroaryl ethylene lateral chain and preparation method thereof.This photosensitive resin has the high advantage of oxytolerant, moisture-proof, stable storing, luminous sensitivity and resolving power.Its preparation method is simpler.
For achieving the above object, the present invention is realized by following technical proposals.The invention provides two class reversible light-sensitive resins, it is characterized in that: a class formation formula is shown in 1～3 formula, another kind of structural formula is shown in 4～7 formulas, this two class contains the reversible light-sensitive resin of heteroaryl ethylene lateral chain, at wavelength is the insoluble three-dimensional polymeric molecule of crosslinking polymerization formation not melting under 300～450nm ultraviolet, one radiation of visible light, but and film forming or imaging, be that three-dimensional polymer generation photodepolymerization crosslinked under 250～350nm UV-irradiation regenerates simple linear polymer at wavelength.
Formula 1 formula 2 formulas 3
Y=O,S,NH,NR,NRCH
2
X=O,S,NH
R
1=H,F,Cl,Br,CN,R,RO,R
2N,RCONH,SO
3H
R=alkyl (C
1～C
12), cyclopentyl, cyclohexyl, vinyl, allyl group, phenyl, benzyl
Formula 4 formulas 5
Formula 6 formulas 7
Y=O,S,NH,NCH
3,OCH
2,NRCH
2,X(CH
2)
nX；n=1～12
X=O,S,NH
X′=CH,N
R
1=H,F,Cl,Br,CN,R,RO,R
2N,RCONH
R
2=H,F,Cl,Br,CN,R,RO,R
2N,RCONH
R=alkyl (C
1～C
12), cyclopentyl, cyclohexyl, vinyl, allyl group, phenyl, benzyl
Prepare method that the above-mentioned first kind contains the reversible light-sensitive resin of heteroaryl ethylene lateral chain and be that to adopt methylate polystyrene or polyene propyl chloride (bromine) or poly-epoxy chlorine (bromine) propane of chlorine (bromine) be polymer backbone, be solvent then with the dimethyl formamide, with salt of wormwood is acid binding agent, to contain phenolic hydroxyl group or thiol or amino substituted benzaldehyde is grafted on the above-mentioned polymer backbone through nucleophilic substitution reaction, last polymkeric substance and the heteroaromatic compounds that contains labile methyl group that again will the above-mentioned substituted benzaldehyde of grafting carry out the condensation reaction of class aldol condensation or carry out condensation reaction with Wittig (Witting) reagent of the heteroaromatic compounds that contains monochloromethyl forming.
Prepare method that above-mentioned second class contains the reversible light-sensitive resin of heteroaryl ethylene lateral chain and be that to adopt methylate polystyrene or polyene propyl chloride (bromine) or poly-epoxy chlorine (bromine) propane or resol of chlorine (bromine) be polymer backbone, be solvent then with the dimethyl formamide, with salt of wormwood is acid binding agent, to contain phenolic hydroxyl group or thiol or heteroaromatic compounds amino and that contain labile methyl group is grafted on the skeleton of above-mentioned polymkeric substance through nucleophilic substitution reaction, and carry out the condensation reaction of class aldol condensation with aromatic aldehyde more at last and form.
The electron-microscope scanning picture of accompanying drawing for obtaining after adopting photosensitive resin of the present invention illumination under 2000 purpose copper mesh cover crosslinked.
Resin of the present invention, because the polymer that has good reversable light sensitive characteristics and be cross-linked into build is easy to the film forming imaging, Therefore oxytolerant, moisture-proof can replace existing acrylic ester type and cationic photosensitive resin, are widely used in fiber optic communication, swash In the industries such as light plate-making, integrated circuit. In the manufacturing process, environmentally safe, process is simple.
With embodiment the present invention is further specified below.
Embodiment one:
Grafting 4-[2-[2-(5-Jia base benzoxazolyl)] vinyl] chloromethylated polystyrene (CPS-p-P) synthetic of phenoxy group
Get the adding of 3g chloromethylated polystyrene and be equipped with in the 50mL flask of 25mL DMF, add 2.4g4-hydroxy benzaldehyde and 2.7g Anhydrous potassium carbonate again, on constant temperature blender with magnetic force, be heated to 130 ℃, constant temperature stirring reaction 5 hours.While hot the reaction product impouring is contained in the beaker of 100mL distilled water, separate out the khaki color precipitation, standing over night, suction filtration gets the khaki color powder.Handle the molten small molecules product that goes with 30mL methyl alcohol, suction filtration again, the chloromethylated polystyrene 4.25g of dry the Powdered grafting 4-of khaki color formyl phenoxy group, 115 ℃～125 ℃ of softening temperatures.
The chloromethylated polystyrene of getting the above-mentioned grafting 4-of 2.38g formyl phenoxy group adds and to be equipped with in the 50mL flask of 15mLDMF, adds 3gKOH and 1.35mL (0.01mol) 2 again, and the 5-benzoxazole dimethyl was in stirring at room 2 hours.The reactant impouring is contained in the large beaker of 200mL distilled water, generate precipitation in a large number, standing over night, the dry light-yellow precipitate that gets of suction filtration.This precipitation adding is contained in the 50mL flask of 20mL methyl alcohol, stirred 30 minutes, get 3.42g yellow powder powder product (CPS-p-PEBOMe) after the suction filtration drying, softening temperature is 140 ℃～150 ℃.
Embodiment two:
In being housed, the 100mL round-bottomed flask of reflux condensing tube adds 4g2-methyl-6-Qiang base benzoxazole, 5g chloromethylated polystyrene, 4.5g salt of wormwood and 50mL DMF.Magnetic agitation, hot water bath after 4 hours, in reaction solution impouring 200mL water, form precipitation in 80 ℃ of heating, leave standstill, suction filtration, drying, light grey powdery product 8.66g, 100 ℃～110 ℃ of product softening temperatures.
In the 100mL there-necked flask of reflux condensing tube, micro-dropping funnel is housed, add the above-mentioned grafting 2-methyl of the 1.33g-chloromethylated polystyrene of 6-benzoxazole oxygen base, the hydrochlorinate potassium 2g of grinding, excessive phenyl aldehyde and 15mL DMF.In room temperature magnetic agitation reaction 2 hours.In reaction solution impouring 100mL water, standing over night, suction filtration, washing, methyl alcohol drip washing make the light salmon target product at last, 160 ℃～170 ℃ of softening temperatures.
Embodiment three:
Reversible light-sensitive resin among the embodiment one 1 gram is dissolved in the tetrahydrofuran (THF) of 40mL, coats on the copper coin, cover 2000 order copper mesh after the seasoning, lamp and high pressure mercury 30 minutes, tetrahydrofuran (THF) flushing.Scanning electron microscope analysis imaging situation as shown in drawings.
Claims (2)
1, a kind of reversible light-sensitive resin that contains heteroaryl ethylene lateral chain, it has two types, it is characterized in that: a class formation formula is shown in 1～3 formula, another kind of structural formula is shown in 4～7 formulas, this two class contains the reversible light-sensitive resin of heteroaryl ethylene lateral chain, at wavelength is that crosslinking polymerization is shaped as and does not melt insoluble three-dimensional polymeric molecule under 300～450nm ultraviolet-visible rayed, but and film forming or imaging, be that three-dimensional polymer generation photodepolymerization crosslinked under 250～350nm UV-irradiation regenerates simple linear polymer at wavelength.
Formula 1 formula 2 formulas 3
Y=O,S,NH,NR,NRCH
2
X=O,S,NH
R
1=H,F,Cl,Br,CN,R,RO,R
2N,RCONH,SO
3H
R=alkyl (C
1～C
12), cyclopentyl, cyclohexyl, vinyl, allyl group, phenyl, benzyl
Formula 4 formulas 5
Formula 6 formulas 7
Y=O,S,NH,NCH
3,OCH
2,NRCH
2,X(CH
2)
nX；n=1～12
X=O,S,NH
X′=CH,N
R
1=H,F,Cl,Br,CN,R,RO,R
2N,RCONH
R
2=H,F,Cl,Br,CN,R,RO,R
2N,RCONH
R=alkyl (C
1～C
12), cyclopentyl, cyclohexyl, vinyl, allyl group, phenyl, benzyl
2, a kind of preparation is by the said method that contains the reversible light-sensitive resin of heteroaryl ethylene lateral chain of claim 1, it is characterized in that: it is polymer backbone that above-mentioned first kind resin adopts methylate polystyrene or polyene propyl chloride (bromine) or poly-epoxy chlorine (bromine) propane of chlorine (bromine), be solvent then with the dimethyl formamide, with salt of wormwood is acid binding agent, to contain phenolic hydroxyl group or thiol or amino substituted benzaldehyde is grafted on the above-mentioned polymer backbone through nucleophilic substitution reaction, last polymkeric substance and the heteroaromatic compounds that contains labile methyl group that again will the above-mentioned substituted benzaldehyde of grafting carry out the condensation reaction of class aldol condensation or carry out condensation reaction with Wittig (Witting) reagent of the heteroaromatic compounds that contains monochloromethyl forming; It is polymer backbone that above-mentioned second resinoid adopts methylate polystyrene or polyene propyl chloride (bromine) or poly-epoxy chlorine (bromine) propane or resol of chlorine (bromine), be solvent then with the dimethyl formamide, with salt of wormwood is acid binding agent, to contain phenolic hydroxyl group or thiol or heteroaromatic compounds amino and that contain labile methyl group is grafted on the above-mentioned polymer backbone through nucleophilic substitution reaction, and carry out the condensation reaction of class aldol condensation with aromatic aldehyde more at last and form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001357735A CN1137160C (en) | 2000-12-20 | 2000-12-20 | Reversible light-sensitive resin containing heteroaryl ethylene lateral chain and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001357735A CN1137160C (en) | 2000-12-20 | 2000-12-20 | Reversible light-sensitive resin containing heteroaryl ethylene lateral chain and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1319617A true CN1319617A (en) | 2001-10-31 |
| CN1137160C CN1137160C (en) | 2004-02-04 |
Family
ID=4596862
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001357735A Expired - Fee Related CN1137160C (en) | 2000-12-20 | 2000-12-20 | Reversible light-sensitive resin containing heteroaryl ethylene lateral chain and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101490099B (en) * | 2006-07-12 | 2013-03-27 | 诺瓦提斯公司 | Actinically crosslinkable copolymers for manufacturing contact lenses |
-
2000
- 2000-12-20 CN CNB001357735A patent/CN1137160C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101490099B (en) * | 2006-07-12 | 2013-03-27 | 诺瓦提斯公司 | Actinically crosslinkable copolymers for manufacturing contact lenses |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1137160C (en) | 2004-02-04 |
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