CN1137160C - Reversible photosensitive resin containing heteroaryl vinyl side chain and preparation method thereof - Google Patents
Reversible photosensitive resin containing heteroaryl vinyl side chain and preparation method thereof Download PDFInfo
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- CN1137160C CN1137160C CNB001357735A CN00135773A CN1137160C CN 1137160 C CN1137160 C CN 1137160C CN B001357735 A CNB001357735 A CN B001357735A CN 00135773 A CN00135773 A CN 00135773A CN 1137160 C CN1137160 C CN 1137160C
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- sensitive resin
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- lateral chain
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- reversible light
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- 229920005989 resin Polymers 0.000 title claims abstract description 30
- 239000011347 resin Substances 0.000 title claims abstract description 30
- 230000002441 reversible effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 heteroaryl ethylene Chemical compound 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000004793 Polystyrene Substances 0.000 claims abstract description 16
- 229920002223 polystyrene Polymers 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 238000003384 imaging method Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000005575 aldol reaction Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 2
- 150000003935 benzaldehydes Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 150000002390 heteroarenes Chemical class 0.000 claims description 2
- 229920003987 resole Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 abstract 2
- 230000005855 radiation Effects 0.000 abstract 2
- 238000007259 addition reaction Methods 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- ITHWNFOIKVZJFS-UHFFFAOYSA-N [O].C1=CC=C2OC=NC2=C1 Chemical compound [O].C1=CC=C2OC=NC2=C1 ITHWNFOIKVZJFS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
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Abstract
The present invention discloses a reversible light-sensitive resin containing a heteroaryl ethylene lateral chain and a preparation method thereof. The resin can form non-meltable insoluble three-dimensional macromolecules for forming films or images in a crosslinking mode under the condition of the radiation of long-wavelength ultraviolet light; crosslinked three-dimensional macromolecules are depolymerized for a new forming linear polymer under the condition of the radiation of short-wavelength ultraviolet light; the present invention has the characteristics of oxidation resistance, moisture resistance and stable storage. The present invention has the preparation method that the present invention can graft a heteroaryl ethylene light functional group which can carry out reversible light loop addition reaction on a polymer molecule chain of polystyrene, etc. The 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 cationic photosensitizers, 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-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.
Prepare method that the above-mentioned first kind contains the reversible light-sensitive resin of heteroaryl ethylene lateral chain and be that to adopt chloromethylated polystyrene or bromomethylation polystyrene or polyene propyl chloride or the bright basic bromine of polyene or Hydrin 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 again will the above-mentioned substituted benzaldehyde of grafting polymkeric substance and the heteroaromatic ring compounds that contains labile methyl group carry out the class aldol reaction or with the heteroaromatic compounds that contains monochloromethyl Wittig (Wittig) reagent carry out condensation reaction and form.
Formula 1 formula 2 formulas 3
Y=O, S, NH, NR, NRCH
2X=O, S, NHR
1=H, F, Cl, Br, CN, R, RO, R
2N, RCONH, SO
3HR=is no more than the alkyl of 12 carbon atoms, cyclopentyl, cyclohexyl, vinyl, allyl group, phenyl, benzyl
Prepare method that above-mentioned second class contains the reversible light-sensitive resin of heteroaryl ethylene lateral chain and be that to adopt chloromethylated polystyrene or bromomethylation polystyrene or polyene propyl chloride or the bright basic bromine of polyene or Hydrin or resol 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 ring compounds amino and that contain labile methyl group is grafted on the above-mentioned polymer backbone through nucleophilic substitution reaction, and carry out the class aldol reaction with aromatic aldehyde more at last and form.
Formula 4 formulas 5
Formula 6 formulas 7
Y=O, S, NH, NCH
3, OC; H
2, NRCH
2, X (CH
2) n ' X; N '=1～12X=O, S, NHX '=CH, NR
1=H, F, Cl, Br, CN, R, RO, R
2N, RCONHR
2=H, F, Cl, Br, CN, R, RO, R
2N, RCONHR=are no more than the alkyl of 12 carbon atoms, cyclopentyl, cyclohexyl, vinyl, allyl group, phenyl, benzyl
The electron-microscope scanning picture of accompanying drawing for obtaining after adopting photosensitive resin of the present invention illumination under 2000 order 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-methylbenzoxazole base)] 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 2.4g 4-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 a large amount of khaki color precipitations, 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 benzyloxy, 115 ℃-125 ℃ of softening temperatures.
The chloromethylated polystyrene of getting the above-mentioned grafting 4-of 2.38g formyl benzyloxy adds and to be equipped with in the 50mL flask of 15mL DMF, 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:
Grafting 6-(synthesizing of the chloromethylated polystyrene of 2-styryl) benzoxazole oxygen base
In being housed, the 100mL round-bottomed flask of reflux condensing tube adds 4g 2-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 a large number in 80 ℃ of heating, leave standstill, and suction filtration, drying gets 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 potassium hydroxide 2g of grinding, excessive phenyl aldehyde and 15mLDMF.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 (4)
1. the reversible light-sensitive resin that contains heteroaryl ethylene lateral chain, its structural formula is shown in 1～3 formula, this 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-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
2X=O, S, NHR
1=H, F, Cl, Br, CN, R, RO, R
2N, RCONH, SO
3HR=is no more than the alkyl of 12 carbon atoms, cyclopentyl, cyclohexyl, vinyl, allyl group, phenyl, benzyl.
2, the reversible light-sensitive resin that contains heteroaryl ethylene lateral chain, its structural formula is shown in 4～7 formulas, this 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-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 4 formulas 5
Formula 6 formulas 7
Y=O, S, NH, NCH
3, OCH
2, NRCH
2, X (CH
2) n ' X; N '=1～12X=O, S, NHX '=CH, NR
1=H, F, Cl, Br, CN, R, RO, R
2N, RCONHR
2=H, F, Cl, Br, CN, R, RO, R
2N, RCONHR=are no more than the alkyl of 12 carbon atoms, cyclopentyl, cyclohexyl, vinyl, allyl group, phenyl, benzyl.
3, the said method that contains the reversible light-sensitive resin of heteroaryl ethylene lateral chain of preparation claim 1, it is characterized in that: adopting chloromethylated polystyrene or bromomethylation polystyrene or polyene propyl chloride or polyene propyl bromide or Hydrin is 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 again will the above-mentioned substituted benzaldehyde of grafting polymkeric substance and the heteroaromatic ring compounds that contains labile methyl group carry out the class aldol reaction or with the heteroaromatic compounds that contains monochloromethyl Wittig (Wittig) reagent carry out condensation reaction and form.
4, the said method that contains the reversible light-sensitive resin of heteroaryl ethylene lateral chain of preparation claim 2, it is characterized in that: adopting chloromethylated polystyrene or bromomethylation polystyrene or polyene propyl chloride or polyene propyl bromide or Hydrin or resol is 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 ring compounds amino and that contain labile methyl group is grafted on the above-mentioned polymer backbone through nucleophilic substitution reaction, and carry out the class aldol reaction 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 photosensitive resin containing heteroaryl vinyl side chain and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001357735A CN1137160C (en) | 2000-12-20 | 2000-12-20 | Reversible photosensitive resin containing heteroaryl vinyl side chain and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1319617A CN1319617A (en) | 2001-10-31 |
| CN1137160C true CN1137160C (en) | 2004-02-04 |
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|---|---|---|---|
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| ES2346812T3 (en) * | 2006-07-12 | 2010-10-20 | Novartis Ag | CURRENTLY CRUSHABLE COPOLYMERS FOR THE MANUFACTURE OF CONTACT LENSES. |
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