CN105585653A - Reversible CO2-cured photosensitive oligomer and application thereof - Google Patents
Reversible CO2-cured photosensitive oligomer and application thereof Download PDFInfo
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- CN105585653A CN105585653A CN201610110094.7A CN201610110094A CN105585653A CN 105585653 A CN105585653 A CN 105585653A CN 201610110094 A CN201610110094 A CN 201610110094A CN 105585653 A CN105585653 A CN 105585653A
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- 230000002441 reversible effect Effects 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract 5
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 39
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 15
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 15
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 15
- -1 aliphatic acyclic hydrocarbon Chemical class 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 8
- 235000009508 confectionery Nutrition 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 150000002334 glycols Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 238000000016 photochemical curing Methods 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 230000004936 stimulating effect Effects 0.000 abstract description 4
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006845 Michael addition reaction Methods 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 238000001723 curing Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000005395 methacrylic acid group Chemical group 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 abstract 2
- 238000012660 binary copolymerization Methods 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000000638 stimulation Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 32
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 238000013019 agitation Methods 0.000 description 15
- 150000003335 secondary amines Chemical class 0.000 description 15
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000005554 pickling Methods 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000010382 chemical cross-linking Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000004494 ethyl ester group Chemical group 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HEKCXLNLIMLZJU-UHFFFAOYSA-N C(C(=C)C)(=O)[N+]#[C-] Chemical compound C(C(=C)C)(=O)[N+]#[C-] HEKCXLNLIMLZJU-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GELMBWBSDUPRQJ-UHFFFAOYSA-N 9-methyldecan-2-yl prop-2-enoate Chemical compound C(C=C)(=O)OC(C)CCCCCCC(C)C GELMBWBSDUPRQJ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical class [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000012046 mixed solvent Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a reversible CO2-cured photosensitive oligomer and an application thereof and belongs to the field of synthesis of photo-cured oligomers. According to the invention, a photo-cured oligomer carrying a secondary amine group is synthesized, CO2 stimulative response is given to the photo-cured oligomer, and photo-cured oligomer carrying the secondary amine group has better stability, hardly causes autopolymerization and is easy to store compared with an existing CO2 stimulation response oligomer; and meanwhile, the photo-cured oligomer is good in photocuring property, has certain mechanical strength after being photo-cured, has good adhesion and can serve as photocuring matrix resin. The reversible CO2-cured photosensitive oligomer provided by the invention is synthesized by adopting a three-step process, firstly binary copolymerization is carried out on 2-ethylhexyl acrylate (EHA) and p-chloromethyl styrene, so as to form a long-chain oligomer; secondly, a secondary amine group with CO2 stimulative response is introduced; and thirdly, a methacrylic acid group with the photocuring property is introduced by utilizing Michael addition between the secondary amine group and isocyanatoethyl methacrylate. The reversible CO2-cured photosensitive oligomer provided by the invention has the advantages that viscosity of a system is regulated by controlling content of amino groups on an oligomer main chain and molecular weight of the oligomer, different levels of CO2 stimulative response are realized, and CO2 response curing effect is achieved.
Description
Technical field
This product is the oligomer of stimulating responsive, specifically in oligomeric segment with CO2Stimuli responsiveSecondary amine group, it can and CO2React and form intermolecular crosslinked generation carbamic acid amine salt. CauseThis passes into CO in oligomer2Can there is the violent increase of the order of magnitude in rear its viscosity, this oligomer is in processCO2After stimuli responsive, there is photopolymerisable ability simultaneously. Therefore this be belong to a kind of eco-friendly based onCO2The synthetic field of the photocuring oligomer of stimuli responsive.
Background technology
Photocuring technology is an energy-conservation and clean and environment-friendly technology, and it saves the energy---energy consumption is only for passingSystem mercury lamp 1/10th, and containing solvent, ecological environment is had to protective effect, can be to airborne releasePoison gas and carbon dioxide, therefore be described as " green technology ". Photocuring technology (UV-cure) is by a standing waveLong UV-irradiation, makes oligomer or the methyl methacrylates etc. such as liquid epoxy acrylic resin singleThe height speed solid-state a kind of light processing technology that is polymerized, photocuring reaction be in essence light-initiated polymerization,Cross-linking reaction. Photocureable coating, light-curable ink and curable adhesive are that photocuring technology is industrialThe example the earliest of extensive successful Application, is also the product of current photocuring industrial field volume of production and marketing maximum,And the compound of Epoxy Acrylates is main photocureable coating. Compared with other curing technologies, lightCuring technology has following advantage: 1, speed is fast: the soonest can be in 0.05s～0.1s completion of cure; 2,Expense is low: the radiant energy that only needs exciting light initator (or sensitizer); 3, pollute little: non-volatility is organicThing. The character of oligomer has decisive role to the character of film after solidifying. Polyacrylate acrylic acidEster as the novel esters of acrylic acid photocuring oligomer of a class because its structure is various, excellent performance andCoating, ink, the fields such as adhesive have wide practical use.
The present burning along with fossil fuel, the CO in atmosphere2Isothermal chamber gas content is more and more higher, leadsCaused the environmental problems such as greenhouse effects, people day by day exigence exploitation one can be used for CO2AbsorbMaterial. Research shows that material with amine is as amidino groups, primary amine, secondary amine, tertiary amine etc. can and CO2OccurThe reversible crosslinked reaction of crosslinked solution, this reaction can be for the synthesis of CO2Absorbing material, also can use simultaneouslyIn synthetic CO2The material of stimuli responsive. Based on this, we have synthesized a kind of CO2The light of stimuli responsive is poly-Close oligomer, CO2Absorb stimuli responsive characteristic and combine with photopolymerization, formed a kind of viscosity along withCO2The Photopolymer System that passes into and get rid of reversible variation. It has photopolymerisable plurality of advantages, simultaneously energyAbsorb CO2There is CO2The character of stimuli responsive, the character of its reversible Liquid-solid conversion can be used for impression,For photocuring patterning.
Summary of the invention
The present invention has synthesized a kind of CO based on secondary amine group2The photopolymerization oligomer of stimuli responsive, itsPass into CO2Secondary amine group on rear molecular side chain and CO2After reaction, the violent increase of viscosity generation forms liquid-solidChange, form reversible solidifying, (methyl) acrylic double bond on molecular side chain is light-initiated simultaneouslyAfter agent UV Light, cause irreversible double-bond polymerization reaction, thoroughly crosslinking curing. Its feature is gramTake the system that the Michael addition side reaction that causes due to the existence of primary amine group in conventional method causesUnstable, perishable shortcoming has ensured that good stimuli responsive solid-liquid turns when guarantee has storedBecome characteristic and its molecular structure of photocuring ability as follows:
Wherein o, p, the unit that q is corresponding is monomeric repeating unit, monomeric repeating unit adds up to 20-100, oCorresponding content of monomer amount of substance accounts for the 20%-60% of total monomer content, and the corresponding monomer of p containsAmount accounts for 20% of total monomer content, and the content of monomer that q is corresponding accounts for the 60%-20% of total monomer content; R1Represent that carbon number is 2 to 6 alkyl or benzyl or aliphatic acyclic hydrocarbon, R2Represent that carbon number isThe alkane of 2-18, R3Represent hydrogen or methyl;
The monomeric unit that wherein o is corresponding is the styrene of contraposition with alkyl secondary amine base, the monomer list that p is correspondingUnit is specially the product after secondary amine and the esterification of (methyl) acrylic acid isocyano group Arrcostab ammonia in o monomer,The monomeric unit that q is corresponding is (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl)Acrylic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl)Isodecyl acrylate, (methyl) dodecyl acrylate, (methyl) tetradecyl acrylate, (methyl)Process Conditions of Cetane Acrylate or (methyl) octadecyl acrylate.
The present invention also provides a kind of synthetic synthetic method containing secondary amine oligomer, is divided into three steps, concreteStep is as follows:
The first step is for to mix comonomer according to different proportion, the corresponding content of monomer amount of substance of o accounts forThe 40%-80% of total monomer content, the content of monomer that q is corresponding accounts for the 60%-20% of total monomer content; AddEnter the radical initiator of the 0.5mol%-2.5mol% content of monomer total content, comprise azo two isobutylsNitrile (AIBN), dibenzoyl peroxide (BPO), add monomer total amount 1mol%-5mol% to rubThe chain-transferring agent of your content, or do not add chain-transferring agent, comprise positive lauryl mercaptan and n-octyl mercaptan, willMonomer, chain-transferring agent and solvent, that solvent is that organic solvent comprises is aromatic hydrocarbon based, epoxies, esterOne or more mixed solvents of class, ketone. Initator is dissolved in a certain amount of solvent, then willIt dropwise adds in solvent monomer mixed system. Reaction temperature is controlled at 60-100 DEG C, and the reaction time exists6-10 hour.
Second step building-up process is that high molecular modification introducing can CO2The secondary amine group of stimuli responsive is logicalThe one of crossing in n-hexylamine, benzylamine, cyclohexylamine, n-propylamine is reacted with first step product, for introducing toolThere is CO2The secondary amine group of stimuli responsive activity. Concrete steps are that the oligomer synthetic first step is dissolved in to secondIn the organic solvents such as acetoacetic ester, dioxane, toluene, DMF (DMF), then willA kind of and benzyl chlorine unit mole 1-3 three second doubly in benzyl chlorine unit mole 1-5 primary amine doublyAmine mixes, and triethylamine, as acid binding agent, dropwise adds primary amine and triethylamine by oligomer organic solvent solutionMixed system in, stirring at normal temperature, the reaction time is 3-10 hour. Benzyl chlorine unit is that the first step is syntheticOligomer in benzyl chlorine unit.
The 3rd step building-up process is to introduce the two keys of methacrylate of photopolymerization, passes through methacrylic acidThe Michael addition of the secondary amine group of isocyano group ethyl ester and second step product is introduced the metering system of photopolymerizationThe two keys of acid esters. Concrete steps are that the synthetic amino modified oligomer of second step is dissolved in the acetic acid dewatering in advanceIn the organic solvents such as ethyl ester, carrene, chloroform or Isosorbide-5-Nitrae-dioxane, more dropwise add methyl-propOlefin(e) acid isocyano group ethyl ester, addition is all monomeric repeating units on strand in amino modified oligomer20% of molar content, stirring at normal temperature, the reaction time is 4-8 hour.
Reversible CO2Stimuli responsive oligomer, its using method is: by synthetic reversible CO2Response light is poly-Close oligomer: by synthetic reversible CO2Response light polymerization oligomer and glycols (methyl) acrylate,Propandiols (methyl) acrylate, ethoxy base class (methyl) acrylate, alkyls (methyl) acrylateOne or more of monomer diluent are mixed, and addition is the 5wt%～30wt% of oligomer; Add again bagDraw together 1173,184,2959 one or more light triggers, addition is photocuring system gross massAfter 0.5wt%～5wt% mixes by Photopolymer System on base material after film again by surface withThe PDMS template of 10～50 μ m candy strips impresses in oligomer film surface, passes into CO2, pressure is10kPa～5MPa, with CO2Gas reaction 0.5h～12h. With CO2Fully, after response, throw off PDMSMask obtains being with streaky pattern, under UV illumination, solidifies, and sizing obtains imprinted pattern.
Brief description of the drawings
Fig. 1: propylamine modification is containing the infrared spectrum of secondary amine photocuring oligomer
678cm in the first step corresponding to A curve-1S is the absworption peak of C-Cl, and this absworption peak is at BIn second step corresponding to curve, disappear, the C-N peak 1122cm of corresponding secondary amine in second step-1Occur, whereinWeak 3322cm-1The N-H peak of the corresponding secondary amine generating. The 3rd step that C curve is corresponding connects after two keysThere is 1637cm-1、815cm-1The two keys of methacrylate peak, stronger 3352cm-1GenerationThe N-H peak of acid amides. Successfully synthesize with the two keys of secondary amine and photopolymerization by infrared spectrum explanationOligomer.
Fig. 2: propylamine modification is containing the nuclear magnetic spectrogram of secondary amine photocuring oligomer
The corresponding first step product of A curve: 1HNMR (400MHz, Acetone-d6, δ): 6.34-7.54 (4H,ArH)，4.38-4.85(2H,Ar-CH2)，3.40-4.17(2H,COO-CH2)。Ar-CH2WithCOO-CH2The ratio of the peak area of hydrogen is 1.75, can calculate in oligomer molecules p-chloromethyl styrene andThe amount of substance ratio of Isooctyl acrylate monomer, in strand, poly-p-chloromethyl styrene accounts for 64%, polyacrylic acidDifferent monooctyl ester accounts for 36%.
Corresponding the 3rd step product: 1HNMR (400MHz, Acetone-d6, δ): the 6.43-7.74 of B curve (4H,ArH), 6.11 (s, 1H, CH2=), 5.61 (s, 1H, CH2=). The ratio of two keys and the hydrogen peak area of phenyl ringBe 0.19, obtain amount of substance account for 40% of strand than secondary amine by conversion, two keys account for 24% of strand,Isooctyl acrylate monomer accounts for 36% of strand.
Fig. 3: propylamine modification is containing the thermogravimetric curve of secondary amine photocuring oligomer
A, B are respectively oligomer CO2Thermogravimetric curve before and after response. In figure B, can see30 DEG C to 88 DEG C have one section of weightlessness is 4.488%, and maximum weightless peak position is in 57 DEG C, however in figure A CO2Before response, do not occur this section of weightless peak, this is that system is due to the CO that is heated2The process being excluded, knownCO2Uptake be 4.488%. Then oligomer starts thermal decomposition, and maximum heat is decomposed weightless peak for the first timeBeing positioned at 200 DEG C, is the decomposition of oligomer side chain; Maximum weightless peak position, in 389 DEG C, is oligomer for the second timeThe decomposition of main chain, during to 500 DEG C, polymer unwinds is complete, remaining 5% carbide.
Fig. 4: propylamine modification is containing the viscosity variation diagram of secondary amine photocuring oligomer
As can be seen from the figure at CO2Before response, oligomer is the flowable state that viscosity is less, and at CO2RingShould after become very thickness, gelatinous solid-state, viscosity from initial 11.87Pas to response1267.65Pa·s。
Detailed description of the invention
Below with reference to specific embodiment, the present invention is described in further detail, but should not be understood asLimiting the scope of the invention.
The gel permeation chromatograph that molecular weight and molecular weight distribution are produced by Waters company records, and weight average dividesThen son amount is converted and obtains by bioassay standard polystyrene, and the concentration of GPC test sample is4mg/ml, Sample introduction amount is 50 μ L, 30 DEG C of temperature, under the condition of flow velocity 1ml/min by oxolaneDissolve and measure.
Oligomer CO2Viscosity before and after stimuli responsive changes to be surveyed by Anton Paar MCR301 rotational rheometerFixed. Use parallel disk (diameter 25mm measures gap 0.5mm) to measure. Before test, sample is 25At DEG C, keep stablizing 5min to reduce mechanical hysteresis effect. The viscoelastic property of each sample is by dynamicallyStress scans is measured.
On following molecular backbone, all monomeric units refer to the reversible CO of one of generation2Solidify photosensitive oligomerAll monomeric units on molecular backbone, are specifically o, p, the monomeric unit that q is corresponding. All lists on molecular backboneBody unit integral molar quantity is o, p, the monomeric unit integral molar quantity that q is corresponding. And all monomer lists on molecular backboneUnit's gross mass is o, p, the monomeric unit gross mass that q is corresponding.
Example 1
The first step, solution copolymerization reaction:
Measure 40ml toluene and pour 100ml there-necked flask into, be warming up to 80 DEG C. Take 0.03mol to chlorineMethyl styrene, 0.02mol Isooctyl acrylate monomer, is all monomeric unit gross masses 1.5 on molecular backboneThe positive lauryl mercaptan 0.12g of wt% mixes, and adds there-necked flask magnetic agitation, constantly passes into nitrogen. ClaimGet is that on molecular backbone, all monomeric unit integral molar quantity 1.3mol% azodiisobutyronitrile 0.1066g are dissolved in10ml toluene, adds constant pressure funnel to be added dropwise in reaction system, keeps claiming after 80 DEG C of reaction 3hGet is that on molecular backbone, all monomeric unit integral molar quantity 1.3mol% azodiisobutyronitrile 0.1066g are dissolved in10ml toluene adds constant pressure funnel to be added dropwise in reaction system, keeps 80 DEG C to continue reaction 3h. Reaction knotBundle, 50 DEG C revolve to steam after a large amount of toluene and go out product, 40 DEG C of vacuum drying 24h of product with petroleum ether precipitationStand-by, product is faint yellow sticky shape resin.
Second step, propylamine modified-reaction:
First step product is dissolved in 50mlDMF, takes 0.15mol propylamine, 0.03mol tri-secondAmine mixes and adds 100ml there-necked flask, then adds constant pressure funnel to drip oligomer DMF solutionIn there-necked flask, magnetic agitation normal-temperature reaction 8h stops reaction. Pour reactant liquor into separatory funnel, thenAdd 50ml carrene, with the 1mol/L salt pickling of 20ml, after layering, upper strata is water and DMFMixed solution layer, lower floor is the mixed solution layer of carrene and DMF, the solution that separates lower floor continues to useThe pickling of 20ml1mol/L salt, until the pH on upper strata is neutral. Lower floor's modification oligomer dichloromethane solutionSpend the night with anhydrous sodium sulfate drying, then 40 DEG C revolve and steam the resin of removing carrene and obtain yellow thickness.By stand-by its 40 DEG C of vacuum drying 24h.
The 3rd step, the two keys of methacrylate of grafting photopolymerization
The product 6.12g of second step is dissolved in to the ethyl acetate that 30ml dewaters in advance, adds there-necked flask,Magnetic agitation. Adding is the first of the total amount of substance 20mol% of all monomeric units molar fraction on molecular backboneBase acrylic acid isocyano group ethyl ester 1.13g, continues to stir 2h. 40 DEG C revolve steam remove ethyl acetate, normal temperature is trueEmpty dry 24h.
GPC test number-average molecular weight Mn=3200, Polydispersity PDI=1.82.
Rotation viscometer records CO2Before response, viscosity is 11.87Pas, and after response, viscosity is 1267.65Pa·s。
Be that 40mg mixes by adding 2wt% light trigger 1173 in 2g oligomer, then by oligomericThing blade coating, on glass baseplate, passes into after using the PDMS template impression of the candy strip wide with 10 μ mCO2, pressure is that 2MPa keeps 30min, gets rid of CO2After throw off PDMS mask develop, be placed in normal temperatureLower its accuracy of shape can keep three days indeformable. After three days, cured pattern is placed under UV illumination to lightStrong is 30mW/cm-1, light application time is 1min, and there are two key chemical crosslinkings and solidify in oligomer, and pattern is foreverMoulding for a long time, has good heat endurance, corrosion-resistant.
Example 2
The first step, solution copolymerization reaction:
Measure 40ml toluene and pour 100ml there-necked flask into, be warming up to 80 DEG C. Take 0.035mol to chlorineMethyl styrene, 0.015mol Isooctyl acrylate monomer, is all monomeric unit gross masses on molecular backboneThe positive lauryl mercaptan 0.12g of 1.5wt% mixes, and adds there-necked flask magnetic agitation, constantly passes into nitrogen.Take is that on molecular backbone, all monomeric unit integral molar quantity 1.3mol% azodiisobutyronitrile 0.1066g are moltenIn 10ml toluene, add constant pressure funnel to be added dropwise in reaction system, keep 80 DEG C of reaction 3hAfter to take be the azodiisobutyronitrile 0.1066 of all monomeric unit integral molar quantity 1.3mol% on molecular backboneG is dissolved in 10ml toluene and adds constant pressure funnel to be added dropwise in reaction system, keeps 80 DEG C to continue reaction 3h.Reaction finishes, and 50 DEG C revolve to steam after a large amount of toluene and go out product with petroleum ether precipitation, and 40 DEG C of vacuum of product are dryDry 24h is stand-by, and product is faint yellow sticky shape resin.
Second step, propylamine modified-reaction:
First step product is dissolved in 50mlDMF, takes 0.175mol propylamine, 0.035mol tri-Ethamine mixes and adds 100ml there-necked flask, then adds constant pressure funnel to drip oligomer DMF solutionBe added in there-necked flask, magnetic agitation normal-temperature reaction 8h stops reaction. Pour reactant liquor into separatory funnel,Add 50ml carrene, with the 1mol/L salt pickling of 20ml, after layering, upper strata is water and DMF againMixed solution layer, lower floor is the mixed solution layer of carrene and DMF, separate lower floor solution continueWith the pickling of 20ml1mol/L salt, until the pH on upper strata is neutral. Lower floor's modification oligomer carrene is moltenLiquid spends the night with anhydrous sodium sulfate drying, and then 40 DEG C revolve and steam the resin of removing carrene and obtain yellow thickness.By stand-by its 40 DEG C of vacuum drying 24h.
The 3rd step, the two keys of methacrylate of grafting photopolymerization
The product 6.35g of second step is dissolved in to the carrene that 30ml dewaters in advance, adds there-necked flask,Magnetic agitation. Adding is the methacrylic acid isocyanide of all monomeric unit amount of substances 20% on molecular backboneBase ethyl ester 1.22g, continues to stir 2h. 40 DEG C revolve steam remove carrene, normal-temperature vacuum is dried 24h.
GPC test number-average molecular weight Mn=2400, Polydispersity PDI=2.15
Rotation viscometer records CO2Before response, viscosity is 20.01Pas, and after response, viscosity is 5834.12Pa·s。
In 2g oligomer, adding 2wt% light trigger 1173 is that 40mg mixes, then by oligomericThing blade coating, on glass baseplate, passes into after using the PDMS template impression of the candy strip wide with 10 μ m2MPa keeps 1h, gets rid of CO2After throw off PDMS mask develop, be placed in its accuracy of shape under normal temperatureCan keep one week indeformable. After one week, cured pattern is placed under UV illumination, light intensity is 30mW/cm-1，Light application time is 1min, and oligomer two key chemical crosslinkings occurs and solidifies, and pattern permanent shaped, has fineHeat endurance, corrosion-resistant.
Example 3
The first step, solution copolymerization reaction:
Measure 40ml toluene and pour 100ml there-necked flask into, be warming up to 80 DEG C. Take 0.04mol to chlorineMethyl styrene, 0.01mol Isooctyl acrylate monomer, is all monomeric unit gross masses 1.5 on molecular backboneThe positive lauryl mercaptan 0.12g of wt% mixes, and adds there-necked flask magnetic agitation, constantly passes into nitrogen. ClaimGet is that on molecular backbone, all monomeric unit integral molar quantity 1.3mol% azodiisobutyronitrile 0.1066g are dissolved in10ml toluene, adds constant pressure funnel to be added dropwise in reaction system, keeps claiming after 80 DEG C of reaction 3hGet is that on molecular backbone, all monomeric unit integral molar quantity 1.3mol% azodiisobutyronitrile 0.1066g are dissolved in10ml toluene adds constant pressure funnel to be added dropwise in reaction system, keeps 80 DEG C to continue reaction 3h. Reaction knotBundle, 50 DEG C revolve to steam after a large amount of toluene and go out product, 40 DEG C of vacuum drying 24h of product with petroleum ether precipitationStand-by, product is faint yellow sticky shape resin.
Second step, propylamine modified-reaction:
First step product is dissolved in 50mlDMF, takes 0.2mol propylamine, 0.04mol triethylamineMix and add 100ml there-necked flask, then add constant pressure funnel to be added drop-wise to oligomer DMF solutionIn there-necked flask, magnetic agitation normal-temperature reaction 8h stops reaction. Pour reactant liquor into separatory funnel, then addEnter 50ml carrene, with the 1mol/L salt pickling of 20ml, after layering, upper strata is the mixed of water and DMFClose solution layer, lower floor is the mixed solution layer of carrene and DMF, and the solution that separates lower floor continues to useThe pickling of 20ml1mol/L salt, until the pH on upper strata is neutral. Lower floor's modification oligomer dichloromethane solutionSpend the night with anhydrous sodium sulfate drying, then 40 DEG C revolve and steam the resin of removing carrene and obtain yellow thickness.By stand-by its 40 DEG C of vacuum drying 24h.
The 3rd step, the two keys of methacrylate of grafting photopolymerization
The product 6.52g of second step is dissolved in to the carrene that 30ml dewaters in advance, adds there-necked flask,Magnetic agitation. Adding is the methacrylic acid isocyanide of all monomeric unit amount of substances 20% on molecular backboneBase ethyl ester 1.27g, continues to stir 2h. 40 DEG C revolve steam remove carrene, normal-temperature vacuum is dried 24h.
GPC test number-average molecular weight Mn=2900, Polydispersity PDI=1.73
Rotation viscometer records CO2Before response, viscosity is 99.00Pas, and after response, viscosity is 36306.25Pa·s。
Be that 40mg mixes by adding 2wt% light trigger 1173 in 2g oligomer, then by oligomericThing blade coating, on glass baseplate, passes into after using the PDMS template impression of the candy strip wide with 10 μ m2MPa keeps 2h, gets rid of CO2After throw off PDMS mask develop, its accuracy of shape can keep oneThe moon is indeformable. After one month, cured pattern is placed under UV illumination, light intensity is 30mW/cm-1, illuminationTime is 1min, and oligomer two key chemical crosslinkings occurs and solidifies, and pattern permanent shaped, has good heatStability, corrosion-resistant.
Example 4
The first step, solution copolymerization reaction:
The unmodified oligomer presoma that can obtain the first step with embodiment 1, outward appearance is faint yellow transparenceMobile thick liquid.
Second step, benzylamine modified-reaction:
First step product is dissolved in 50mlDMF, takes 0.15mol benzylamine, 0.03mol triethylamineMix and add 100ml there-necked flask, then add constant pressure funnel to be added drop-wise to oligomer DMF solutionIn there-necked flask, magnetic agitation normal-temperature reaction 8h stops reaction. Pour reactant liquor into separatory funnel, then addEnter 50ml carrene, with the 1mol/L salt pickling of 20ml, after layering, upper strata is the mixed of water and DMFClose solution layer, lower floor is the mixed solution layer of carrene and DMF, and the solution that separates lower floor continues to useThe pickling of 20ml1mol/L salt, until the pH on upper strata is neutral. Lower floor's modification oligomer dichloromethane solutionSpend the night with anhydrous sodium sulfate drying, then 40 DEG C revolve and steam the resin of removing carrene and obtain yellow thickness.By stand-by its 40 DEG C of vacuum drying 24h.
The 3rd step, the two keys of methacrylate of grafting photopolymerization
The product 6.68g of second step is dissolved in to the carrene that 30ml dewaters in advance, adds there-necked flask,Magnetic agitation. Adding is the methacrylic acid isocyanide of all monomeric unit amount of substances 20% on molecular backboneBase ethyl ester 1.25g, continues to stir 2h. 40 DEG C revolve steam remove carrene, normal-temperature vacuum is dried 24h.
GPC test number-average molecular weight Mn=3200, Polydispersity PDI=1.82.
Rotation viscometer records CO2Before response, viscosity is 16.06Pas, and after response, viscosity is 7351Pas.
Be that 40mg mixes by adding 2wt% light trigger 1173 in 2g oligomer, then by oligomericThing blade coating, on glass baseplate, passes into after using the PDMS template impression of the candy strip wide with 10 μ m2MPa keeps 5h, gets rid of CO2After throw off PDMS mask develop, be placed in its accuracy of shape under normal temperatureCan keep one week indeformable. After one week, cured pattern is placed under UV illumination, light intensity is 30mW/cm-1，Light application time is 1min, and oligomer two key chemical crosslinkings occurs and solidifies, and pattern permanent shaped, has fineHeat endurance, corrosion-resistant.
Example 5
The first step, solution copolymerization reaction:
The unmodified oligomer presoma that can obtain the first step with embodiment 2, outward appearance is faint yellow transparenceMobile thick liquid.
Second step, benzylamine modified-reaction:
First step product is dissolved in 50mlDMF, takes 0.175mol benzylamine, 0.035mol tri-Ethamine mixes and adds 100ml there-necked flask, then adds constant pressure funnel to drip oligomer DMF solutionBe added in there-necked flask, magnetic agitation normal-temperature reaction 8h stops reaction. Pour reactant liquor into separatory funnel,Add 50ml carrene, with the 1mol/L salt pickling of 20ml, after layering, upper strata is water and DMF againMixed solution layer, lower floor is the mixed solution layer of carrene and DMF, separate lower floor solution continueWith the pickling of 20ml1mol/L salt, until the pH on upper strata is neutral. Lower floor's modification oligomer carrene is moltenLiquid spends the night with anhydrous sodium sulfate drying, and then 40 DEG C revolve and steam the resin of removing carrene and obtain yellow thickness.By stand-by its 40 DEG C of vacuum drying 24h.
The 3rd step, the two keys of methacrylate of grafting photopolymerization
The product 6.52g of second step is dissolved in to the carrene that 30ml dewaters in advance, adds there-necked flask,Magnetic agitation. Adding is the methacrylic acid isocyanide of all monomeric unit amount of substances 20% on molecular backboneBase ethyl ester 1.25g, continues to stir 2h. 40 DEG C revolve steam remove carrene, normal-temperature vacuum is dried 24h.
GPC test number-average molecular weight Mn=2400, Polydispersity PDI=2.15.
Rotation viscometer records CO2Before response, viscosity is 22.37Pas, and after response, viscosity is 35780Pas.
Be that 40mg mixes by adding 2wt% light trigger 1173 in 2g oligomer, then by oligomericThing blade coating, on glass baseplate, passes into after using the PDMS template impression of the candy strip wide with 10 μ m2MPa keeps 10h, gets rid of CO2After throw off PDMS mask and develop, be placed under normal temperature its shape accurateDegree can keep one month indeformable. After one month, cured pattern is placed under UV illumination, light intensity is 30mW/cm-1, light application time is 1min, there are two key chemical crosslinkings and solidify in oligomer, and pattern permanent shaped,There is good heat endurance, corrosion-resistant.
Example 6
The first step, solution copolymerization reaction:
The unmodified oligomer presoma that can obtain the first step with embodiment 3, outward appearance is faint yellow transparenceMobile thick liquid.
Second step, benzylamine modified-reaction:
First step product is dissolved in 50mlDMF, takes 0.2mol benzylamine, 0.04mol triethylamineMix and add 100ml there-necked flask, then add constant pressure funnel to be added drop-wise to oligomer DMF solutionIn there-necked flask, magnetic agitation normal-temperature reaction 8h stops reaction. Pour reactant liquor into separatory funnel, then addEnter 50ml carrene, with the 1mol/L salt pickling of 20ml, after layering, upper strata is the mixed of water and DMFClose solution layer, lower floor is the mixed solution layer of carrene and DMF, and the solution that separates lower floor continues to useThe pickling of 20ml1mol/L salt, until the pH on upper strata is neutral. Lower floor's modification oligomer dichloromethane solutionSpend the night with anhydrous sodium sulfate drying, then 40 DEG C revolve and steam the resin of removing carrene and obtain yellow thickness.By stand-by its 40 DEG C of vacuum drying 24h.
The 3rd step, the two keys of methacrylate of grafting photopolymerization
The product 6.92g of second step is dissolved in to the carrene that 30ml dewaters in advance, adds there-necked flask,Magnetic agitation. Adding is the methacrylic acid isocyanide of all monomeric unit amount of substances 20% on molecular backboneBase ethyl ester 1.34g, continues to stir 2h. 40 DEG C revolve steam remove carrene, normal-temperature vacuum is dried 24h.
GPC test number-average molecular weight Mn=2900, Polydispersity PDI=1.73.
Rotation viscometer records CO2Before response, viscosity is 30.56Pas, and after response, viscosity is 74350Pas.
Be that 40mg mixes by adding 2wt% light trigger 1173 in 2g oligomer, then by oligomericThing blade coating, on glass baseplate, passes into after using the PDMS template impression of the candy strip wide with 10 μ m2MPa keeps 12h, gets rid of CO2After throw off PDMS mask and develop, be placed under normal temperature its shape accurateDegree can keep two months indeformable. After two months cured pattern is placed under UV illumination, light intensity is 30mW/cqm-1, light application time is 1min, there are two key chemical crosslinkings and solidify in oligomer, and pattern permanent shaped,There is good heat endurance, corrosion-resistant.
Claims (3)
1. a reversible CO2Stimuli responsive photopolymerization oligomer, its structure is suc as formula shown in (Ι):
Wherein o, p, the unit that q is corresponding is that monomeric repeating unit adds up to 20-100, o is correspondingContent of monomer amount of substance accounts for the 20%-60% of total monomer content, and the corresponding content of monomer of p accounts for always20% of content of monomer, the content of monomer that q is corresponding accounts for the 60%-20% of total monomer content; R1RepresentativeCarbon number is 2 to 6 alkyl or benzyl or aliphatic acyclic hydrocarbon, R2Represent that carbon number is 2-18Alkane, R3Represent hydrogen or methyl;
The monomeric unit that wherein o is corresponding is the styrene of contraposition with alkyl secondary amine base, the list that p is correspondingBody unit is specially after the secondary amine and the esterification of (methyl) acrylic acid isocyano group Arrcostab ammonia in o monomerProduct, the monomeric unit that q is corresponding is (methyl) ethyl acrylate, the positive fourth of (methyl) acrylic acidEster, (methyl) acrylic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid is justThe last of the ten Heavenly stems ester, (methyl) isodecyl acrylate, (methyl) dodecyl acrylate, (methyl) acrylic acid14 esters, (methyl) Process Conditions of Cetane Acrylate or (methyl) octadecyl acrylate.
2. the synthetic reversible CO of one as claimed in claim 12Stimuli responsive photopolymerization oligomerMethod, is characterized in that concrete steps are:
The first step is mixed comonomer according to different proportion
The corresponding content of monomer amount of substance of o accounts for the 20%-60% of total monomer content, and p institute is correspondingContent of monomer account for 20% of total monomer content, content of monomer that q is corresponding accounts for total monomer content60%-20%; Add the free radical of the 0.5mol%-2.5mol% molar content of monomer total content to drawSend out agent, add the chain-transferring agent of monomer total amount 1mol%-5mol% molar content, or do not addChain-transferring agent, is mixed to get solvent monomer mixed system by monomer, chain-transferring agent and organic solvent, willInitator is dissolved in organic solvent and obtains initiator solution, then initiator solution is dropwise added moltenIn agent monomer mixed system; Reaction temperature is controlled at 60-100 DEG C, and the reaction time is at 6-10 hour;
Second step building-up process be by the oligomer synthetic first step be dissolved in organic solvent, obtain oligomericThing organic solvent solution, then by one and benzyl chlorine in benzyl chlorine unit mole 1-5 primary amine doublyMole 1-3 triethylamine doubly in unit mixes, and oligomer organic solvent solution is dropwise added to primary amineIn the mixed system of triethylamine, stir, the reaction time be within 3-10 hour, obtain amino modified lowPolymers; Benzyl chlorine unit is the benzyl chlorine unit in the synthetic oligomer of the first step;
The 3rd step building-up process is that the synthetic amino modified oligomer of second step is dissolved in advance and is dewateredOrganic solvent in, more dropwise add methacrylic acid isocyano group ethyl ester, addition is amino modifiedIn oligomer, on strand 20% of all monomeric repeating unit molar content, stirring at normal temperature, when reactionBetween be 4-8 hour.
3. reversible CO according to claim 12The application of stimuli responsive oligomer, its featureBe: by synthetic reversible CO2Response light polymerization oligomer mixes with monomer diluent, and monomer is rareReleasing agent is glycols (methyl) acrylate, propandiols (methyl) acrylate, ethoxy base class (firstBase) one or more of acrylate, alkyls (methyl) acrylate monomer diluent mix, addEntering amount is the 5wt%～30wt% of oligomer; Add again and comprise 1173,184,2,959 one kindsOr several light triggers, addition is the 0.5wt%～5wt% of monomer diluent and oligomer gross mass,The Photopolymer System after mixing, monomer diluent, oligomer, light trigger being formed is on base materialAfter being coated with one deck 10～30 μ m films, again surface is impressed with the PDMS template of 10～50 μ m candy stripsIn oligomer film surface, pass into CO2, pressure is 10kPa～5MPa, with CO2Gas reaction 0.5h～12h; With CO2After reaction, throw off PDMS mask and obtain being with streaky pattern, then will be tentatively fixedThe pattern of type is crosslinking curing under UV illumination, and sizing obtains imprinted pattern.
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