CN103122068A - Polyimide acrylic ester oligomer for UV (ultraviolet) paint - Google Patents
Polyimide acrylic ester oligomer for UV (ultraviolet) paint Download PDFInfo
- Publication number
- CN103122068A CN103122068A CN2012105695826A CN201210569582A CN103122068A CN 103122068 A CN103122068 A CN 103122068A CN 2012105695826 A CN2012105695826 A CN 2012105695826A CN 201210569582 A CN201210569582 A CN 201210569582A CN 103122068 A CN103122068 A CN 103122068A
- Authority
- CN
- China
- Prior art keywords
- polyimide
- acrylate
- tetracarboxylic dianhydride
- origoester acrylate
- amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 68
- 239000004642 Polyimide Substances 0.000 title claims abstract description 60
- -1 acrylic ester Chemical class 0.000 title claims abstract description 21
- 239000003973 paint Substances 0.000 title abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 13
- 238000006297 dehydration reaction Methods 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000004985 diamines Chemical class 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000006136 alcoholysis reaction Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 239000003456 ion exchange resin Substances 0.000 claims description 7
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 5
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 5
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical class C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 5
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- SHALVKVVWYJLCA-UHFFFAOYSA-N propane-1,1,1,2-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)(C(O)=O)C(O)=O SHALVKVVWYJLCA-UHFFFAOYSA-N 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011521 glass Substances 0.000 abstract description 15
- 239000009719 polyimide resin Substances 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 125000003368 amide group Chemical group 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 238000009775 high-speed stirring Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical class C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 125000004386 diacrylate group Chemical group 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 229910005965 SO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001030 cadmium pigment Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- WAAJSDWCENLNRJ-UHFFFAOYSA-N propanedioic acid prop-2-enoic acid Chemical class C(CC(=O)O)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O WAAJSDWCENLNRJ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a preparation method and application of polyimide acrylic ester oligomer for a UV (ultraviolet) paint. The photo-curable polyimide acrylic ester oligomer is synthetized by leading an acrylate monomer with a double-bond reaction group at the tail end of polyimide, and corresponding UV paint is prepared. Thus, the excellent performance of the polyimide resin is applied to the UV paint; defects of the UV paint on a special base material (especially glass) are solved; the polyimide acrylic ester oligomer provides the performances, such as excellent high temperature resistance, water resistance and high hardness, to the prepared UV paint, and has good adhesion force on the base materials such as glass, metal, ceramics and plastic; and the blank of the polyimide resin in the field of the UV paint is filled.
Description
Technical field
The present invention relates to a kind of photocurable oligopolymer, be specifically related to the application of the polyimide origoester acrylate that a kind of UV coating produces with the preparation method of polyimide origoester acrylate with the method.
Technical background
Polyimide is one of organic polymer material of over-all properties the best.Polyimide is to contain the macromolecular material of imide ring on a class main chain.Owing to containing aromatic nucleus on main chain, it has outstanding heat resistance and excellent mechanical property as the advanced composite material matrix, is one of material that in present polymer matrix composites, temperature tolerance is the highest.As electronic information material, polyimide also has outstanding dielectric properties and radiation resistance except having outstanding resistance to elevated temperatures, is one of encapsulation best in current microelectronics message area and coating material.In addition, polyimide resin also shows the characteristics of excellent combination property as aspects such as tackiness agent, fiber, plastics and photoresist materials.
Polyimide has been widely used in the fields such as Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, separatory membrane, laser as a kind of special engineered material.Recently, one of in most promising engineering plastics of 21 century are all being listed research, exploitation and the utilization of polyimide by each state.Polyimide, because of its performance and synthetic aspect outstanding feature, no matter be as structured material or as functional material, its huge application prospect is familiar with fully.
Since polyimide (PI) moulding compound (Vespei SP) in 1964 appearance, experienced the development of forties years: the 60's～70, goods mainly supplied war industry take the development high-temperature polymer as main, and especially aerospace industry is used; The new variety of PI processing characteristics have appearred improving the eighties, for example poly-(amide-imide) (PAI), polyetherimide (PEI); The nineties, the kinds such as transparent PI, photosensitivity PI continue to bring out; Up to the present, that PI has developed into is covering extensive fields, goods are various, and main goods comprise: moulding resin/part, insulated wire, film, fiber, preimpregnation material/matrix material, coating, tackiness agent and foam etc.
Polyimide also can be applied to paint field, mainly contains following aspect: CN1197925C and has prepared a kind of polyimide based high-temp-resistant radiation hardness slip coating; CN100492173C has prepared a kind of coating composition of polyimide of the positive light sensitivity that can be used for the indicating meter insulation layer; CN102516868A has prepared a kind of polyimide material surface protection coating that space environment uses that is suitable for; It is corrosionproof lubricant coating based that CN1450139A has prepared a kind of high temperature resistant thixotropic polyimide; CN101139501B has prepared a kind of polyimide thermostable aqueous dispersion coating material; CN102492320A has prepared a kind of Quick-curing polyimide coating for high-temperature-resistant optical fiber; CN102516867A has prepared a kind of polyimide paint for optical fiber; CN102220085A has prepared a kind of polyimide coating with high-temperature resistance.But also there is no polyimide resin in the related application of UV paint field at present.
The UV photo-cured coating be a kind ofly have that set time is short, solidification value is low, volatile matter is low, economize the energy, the coating new variety of the advantages such as resource-saving, nuisanceless, high-level efficiency, have very vast potential for future development.But there are the defectives such as poor adhesive force, temperature tolerance is poor, water boiling resistance is poor, hardness is low in UV coating on some special base materials (glass, metal, pottery, plastic cement) at present, particularly on glass.
The present invention is applied to UV coating with the excellent properties of polyimide resin innovatively, has solved some defectives that UV coating exists at non-absorbability base material (particularly glass).
Summary of the invention
The object of the invention is to fill up the blank that polyimide resin is used in the UV paint field, a kind of polyimide origoester acrylate for UV coating is provided.This oligopolymer is given the performances such as high temperature resistant, the water boiling resistance, high rigidity of UV coating excellence prepared therefrom and good sticking power on the base materials such as glass, metal, pottery, plastic cement.
The present invention discloses and has protected this application of polyimide origoester acrylate in UV coating simultaneously.
For achieving the above object, now provide a kind of UV coating polyimide origoester acrylate, it is characterized in that being obtained by following methods:
S1. with tetracarboxylic dianhydride, diamine with contain amino organic silicon acrylic ester and add in polar solvent, reaction generates intermediate;
S2. add dewatering agent (also having dehydration catalyst) and polar solvent in intermediate, carry out the chemical imidization reaction and make.
After described S2 reaction finishes, reaction solution is poured in dehydrated alcohol, be precipitated thing; Throw out obtains photocurable polyimide origoester acrylate through washing, drying.
At the described tetracarboxylic dianhydride of step S1, diamine with contain amino organic silicon acrylic ester and be calculated in molar ratio as n+1:n:2, described n is 1＜=n＜=20.
Described tetracarboxylic dianhydride is 1,2,4,5-pyromellitic acid anhydride, 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 2,2 '-two [4-(3,4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride, 2, one or more in 2 '-two (3,4-, two carboxyphenyls) HFC-236fa tetracarboxylic dianhydride, preferred 1,2,4,5-pyromellitic acid anhydride, 4,4 '-BPDA or 4, one or more in 4 '-phenyl ether tetracarboxylic dianhydride; Structural formula is as follows.
described diamine is 1, the 6-hexanediamine, 1, two (the 3-aminopropan alkyl) tetramethyl disiloxanes of 3-, 1, two (the 4-amino-benzene oxygen methane)-1 of 3-, 1, 3, the 3-tetramethyl disiloxane, 3, 4 '-diaminodiphenyl oxide, 4, 4 '-diaminodiphenyl oxide, 4, 4 '-diaminodiphenylsulfone(DDS), 1, two (4-amino-benzene oxygen) benzene of 4-, 2, two [(4-amino-benzene oxygen) phenyl] propane of 2-, one or more in two [4-(4-phenoxy group) phenyl] sulfone, preferred 1, two (the 3-aminopropan alkyl) tetramethyl disiloxanes of 3-, 4, 4 '-diaminodiphenyl oxide or 4, one or more in 4 '-diaminodiphenylsulfone(DDS), structural formula is as follows,
Described polar solvent is METHYLPYRROLIDONE, N, N '-dimethyl formamide, N, the mixing of one or more in N '-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO).
In described S1, after adding polar solvent, solids content is 25 grams per milliliter solvents; In S2, the described material that adds also comprises dehydration catalyst; After adding dewatering agent, dehydration catalyst and polar solvent in S2, solids content is 15 grams per milliliter solvents.
Described dewatering agent is diacetyl oxide, and dehydration catalyst is pyridine.Described dewatering agent consumption is 2～4 times of diamine amount of substance; Described dehydration catalyst consumption is 0.2～1 times of dewatering agent amount of substance.
Described S1 is under protection of inert gas, reacts under 20 ~ 30 ℃ 8 ~ 24 hours; S2 reacted under 30 ~ 90 ℃ 4 ~ 16 hours.
Described throw out absolute ethanol washing, then wash with anhydrous diethyl ether.
The described organic silicon acrylic ester that contains amino makes by containing amino organoalkoxysilane and the acrylate reactions of hydroxyl; The described organoalkoxysilane that contains amino is 3-TSL 8330 or APTES; The acrylate of described hydroxyl is for through one or more in the Hydroxyethyl acrylate of processed, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410.
The described preparation method who contains amino organic silicon acrylic ester is: will contain amino organoalkoxysilane and the acrylate of hydroxyl and add in reactor; add again the strong basic ion exchange resin that accounts for above-mentioned two material total masses 5%～15%; under protection of inert gas; be preferably nitrogen; stir under 70 ℃～150 ℃, allow this alcoholysis reaction carry out 6～18 hours, then carry out underpressure distillation under 130 ℃～180 ℃; filter, and get final product.
In order to understand better the present invention, below the present invention program's association reaction formula is done further explaination, listed reaction formula is only theoretical derivation gained, it can not be as the restriction of protection domain of the present invention.
preparation process of the present invention is: with tetracarboxylic dianhydride, diamine is calculated in molar ratio as (n+1): n:2 with the organic silicon acrylic ester that contains amino and successively joins in polar solvent, making its solids content is 25 grams per milliliter solvents, under nitrogen protection, after stirring 8～24 hours under 20 ~ 30 ℃, generate the intermediate polyamic acid, add immediately dewatering agent diacetyl oxide and dehydration catalyst pyridine and polar solvent, make its solids content reduce to 15 grams per milliliter solvents, again in 30 ℃～90 ℃ lower chemical imidization reactions 4～16 hours, reaction solution is poured in the dehydrated alcohol of high-speed stirring, be precipitated thing, after the gained throw out successively fully washs with dehydrated alcohol and anhydrous diethyl ether, vacuum-drying namely gets photocurable polyimide origoester acrylate, reaction process is (take the monobasic amido organosilicon acrylate that contains as example) as the formula (1),
In formula, n is the resin polymerization degree, 1≤n≤20.
Selected tetracarboxylic dianhydride monomer O (CO) in formula (1) reaction
2R
2(CO)
2O, wherein applicable R
2As the formula (2).Wherein X is O, S, SO
2, CO, CH
2, C (CH
3)
3, CF
2, C (CF
3)
2Perhaps do not exist.Wherein preferred tetracarboxylic dianhydride is 1,2,4,5-pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-BPDA (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 2,2 '-two [4-(3,4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride (BPADA), 2, the mixing of one or more in 2 '-two (3,4-, two carboxyphenyls) HFC-236fa tetracarboxylic dianhydride (6FDA).
Selected diamine H in formula (1) reaction
2N-R
3-NH
2, the R that wherein is suitable for
3As the formula (3).Wherein Z is O, S, SO
2, CO, CH
2, C (CH
3)
3, CF
2, C (CF
3)
2Perhaps there is not R
4Be C
1～C
12Alkyl or-oxyl.wherein preferred diamine is 1, the 6-hexanediamine, 1, two (the 3-aminopropan alkyl) tetramethyl disiloxanes of 3-, 1, two (the 4-amino-benzene oxygen methane)-1 of 3-, 1,3, the 3-tetramethyl disiloxane, 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 4,4 '-diaminodiphenylsulfone(DDS) (4,4 '-DDS), 1, two (4-amino-benzene oxygen) benzene (1 of 4-, 4-BAB), 2, two [(4-amino-benzene oxygen) phenyl] propane (4-BAPP) of 2-, the mixing of one or more in two [4-(4-phenoxy group) phenyl] sulfone (BAPS).
the preparation process that contains the amido organosilicon acrylate that is used as end-capping reagent in formula (1) reaction is: the acrylate that will contain amino organoalkoxysilane and hydroxyl is calculated in molar ratio as 1:3 and adds in reactor with water trap and condenser, add again the strong basic ion exchange resin that accounts for above-mentioned two material total masses 10%, under nitrogen protection, stir under 70 ℃～150 ℃ and react, the small molecules methyl alcohol or the ethanol that generate are constantly told by water trap, allow this alcoholysis reaction carry out 6～18 hours, carry out underpressure distillation again under 130 ℃～180 ℃, remove the acrylate of unreacted hydroxyl, filter, obtain monobasic amido organosilicon acrylate and the dibasic mix products that contains the amido organosilicon acrylate of containing, reaction process as the formula (4),
In formula, R
1Be CH
3Or C
2H
5
In formula (4) reaction, the organoalkoxysilane that contains amino used is 3-TSL 8330 (silane coupling agent KH-540) or APTES (silane resin acceptor kh-550); The acrylate of hydroxyl used is for through one or more the mixing in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate and the Rocryl 410 of processed.
UV coating polyimide origoester acrylate of the present invention can be used for preparing the UV coating that uses on the base materials such as glass, metal, pottery, plastic cement; As a kind of preferred version, described base material is preferably glass baseplate.
Oligopolymer used is the photocurable polyimide origoester acrylate that the present invention synthesizes;
Light trigger is 2, the mixing of one or more in 4,6-trimethylbenzoyl-diphenyl phosphine oxide, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl-2-hydroxyl-1-phenyl-1-acetone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone, 2-isopropyl thioxanthone;
Auxiliary agent is one or more the mixing in defoamer, flow agent, mould inhibitor, dispersion moisture agent;
Diluting monomer is NVP, vinylbenzene, butyl acrylate, tri (propylene glycol) diacrylate, 1, the mixing of one or more in 3-butylene glycol diacrylate, Viscoat 295, pentaerythritol triacrylate, PDDA, 1,4 butanediol diacrylate, phthalic acid three propanedioic acid diacrylates.
This UV coating can prepare as follows: first oligopolymer, dispersion agent, part reactive thinner, color stuffing and other part of auxiliary are joined in high speed dispersor by certain proportioning, allow it disperse 0.5～1 hour, after reaching required fineness, add light trigger and remaining reactive thinner and auxiliary agent, continue to mix until evenly, namely make UV coating.
The UV coating of the polyimide origoester acrylate preparation that described use the present invention synthesizes comprises following component: color stuffing, polyimide origoester acrylate, reactive thinner, light trigger, auxiliary agent etc.
Pigment used is one or more the mixing in the blue or green pigment of titanium dioxide, carbon black, iron oxide pigment, cadmium pigment, chromate pigments, pearly pigment, phthalein, azo pigment, heterocycle pigment; Filler is one or more the mixing in calcium carbonate, talcum powder, kaolin, calcium sulfate, barium sulfate, silicon-dioxide, mica, Calucium Silicate powder.
Major advantage of the present invention is:
1. by introduce the acrylate monomer with two key reactive groups at the polyimide end, synthesized a kind of photo curable polyimide origoester acrylate, and prepared corresponding UV coating.Therefore, the excellent properties of polyimide resin is applied to UV coating, has solved UV coating some defectives that (particularly glass) exists on special base material.
2. this polyimide origoester acrylate is given the performance such as high temperature resistant, water boiling resistance, high rigidity of UV coating excellence prepared therefrom and good sticking power on the base materials such as glass, metal, pottery, plastic cement.
3. filled up the blank that polyimide resin is used in the UV paint field.
Embodiment:
The invention will be further described below in conjunction with specific embodiment, but specific embodiment is not done any restriction to the present invention.
Embodiment 1
Propylene glycol monoacrylate 19.52 grams (0.15 mole) of 3-TSL 8330 8.96 grams (0.05 mole) and process processed are added in the reactor with water trap and condenser, add again strong basic ion exchange resin 2.85 grams, under nitrogen protection, stir under 130 ℃ and react, the small molecules methyl alcohol that generates is constantly told by water trap, allow this alcoholysis reaction carry out 14 hours, carry out again underpressure distillation under 150 ℃, remove unreacted Propylene glycol monoacrylate, filter, obtain monobasic amido organosilicon acrylate and the dibasic mix products that contains the amido organosilicon acrylate of containing.
with 1, 2, 4, 5-pyromellitic acid anhydride 47.98 grams (0.22 mole), 4, 4 '-diaminodiphenyl oxide, 40.04 grams (0.20 mole) and above-mentioned organic silicon acrylic ester 13.06 grams (0.04 mole) that contain amino successively join in 404 milliliters of DMF, under nitrogen protection, stir after 12 hours under 20 ℃～30 ℃, add dewatering agent diacetyl oxide 40.84 grams (0.40 mole), dehydration catalyst pyridine 31.64 grams (0.40 mole) and 270 milliliters of DMF, in 90 ℃ of lower chemical imidization reactions 10 hours, reaction solution is poured in the dehydrated alcohol of high-speed stirring, be precipitated thing, after the gained throw out successively fully washs with dehydrated alcohol and anhydrous diethyl ether, vacuum-drying namely gets photocurable polyimide origoester acrylate,
Take above-mentioned polyimide origoester acrylate 25 grams, with 12.5 gram NVPs (NVP) and the dissolving of 10 gram tri (propylene glycol) diacrylates (TPGDA), add again 2.5 gram light trigger 1-hydroxy-cyclohexyl phenyl ketones (184), be uniformly dispersed on high speed dispersor.This UV coating is coated on glass and stainless steel plate, then carries out photocuring under UV-irradiation, then carry out performance characterization and test, result is as shown in table 1.
Embodiment 2
Rocryl 410 21.63 grams (0.15 mole) of 3-TSL 8330 8.96 grams (0.05 mole) and process processed are added in the reactor with water trap and condenser, add again strong basic ion exchange resin 3.06 grams, under nitrogen protection, stir under 120 ℃ and react, the small molecules methyl alcohol that generates is constantly told by water trap, allow this alcoholysis reaction carry out 14 hours, carry out again underpressure distillation under 150 ℃, remove unreacted Rocryl 410, filter, obtain monobasic amido organosilicon acrylate and the dibasic mix products that contains the amido organosilicon acrylate of containing.
with 3, 3 ', 4, 4 '-BPDA, 52.96 grams (0.18 mole), 1, two (3-aminopropan alkyl) tetramethyl disiloxane 39.76 grams (0.16 mole) of 3-and above-mentioned organic silicon acrylic ester 13.90 grams (0.04 mole) that contain amino successively join in 426 milliliters of NMP, under nitrogen protection, stir after 12 hours under 20 ℃～30 ℃, add dewatering agent diacetyl oxide 32.67 grams (0.32 mole), dehydration catalyst pyridine 25.31 grams (0.32 mole) and 284 milliliters of NMP, in 80 ℃ of lower chemical imidization reactions 8 hours, reaction solution is poured in the dehydrated alcohol of high-speed stirring, be precipitated thing, after the gained throw out successively fully washs with dehydrated alcohol and anhydrous diethyl ether, vacuum-drying namely gets photocurable polyimide origoester acrylate,
Take above-mentioned polyimide origoester acrylate 25 grams, with 12.5 gram NVPs (NVP) and the dissolving of 10 gram tri (propylene glycol) diacrylates (TPGDA), add again 2.5 gram light trigger 1-hydroxy-cyclohexyl phenyl ketones (184), be uniformly dispersed on high speed dispersor.This UV coating is coated on glass and stainless steel plate, then carries out photocuring under UV-irradiation, then carry out performance characterization and test, result is as shown in table 1.
Embodiment 3
Hydroxyethyl acrylate 17.42 grams (0.15 mole) of APTES 11.07 grams (0.05 mole) and process processed are added in the reactor with water trap and condenser, add again strong basic ion exchange resin 2.85 grams, under nitrogen protection, stir under 140 ℃ and react, the small molecules ethanol that generates is constantly told by water trap, allow this alcoholysis reaction carry out 14 hours, carry out again underpressure distillation under 150 ℃, remove unreacted Hydroxyethyl acrylate, filter, obtain monobasic amido organosilicon acrylate and the dibasic mix products that contains the amido organosilicon acrylate of containing.
with 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, 45.11 grams (0.14 mole), 1, 6-hexanediamine 13.94 grams (0.12 mole) and above-mentioned organic silicon acrylic ester 13.06 grams (0.04 mole) that contain amino successively join in 288 milliliters of DMAc, under nitrogen protection, stir after 12 hours under 20 ℃～30 ℃, add dewatering agent diacetyl oxide 24.50 grams (0.24 mole), dehydration catalyst pyridine 19.98 grams (0.24 mole) and 192 milliliters of DMAc, in 70 ℃ of lower chemical imidization reactions 9 hours, reaction solution is poured in the dehydrated alcohol of high-speed stirring, be precipitated thing, after the gained throw out successively fully washs with dehydrated alcohol and anhydrous diethyl ether, vacuum-drying namely gets photocurable polyimide origoester acrylate,
Take above-mentioned polyimide origoester acrylate 25 grams, with 12.5 gram NVPs (NVP) and the dissolving of 10 gram tri (propylene glycol) diacrylates (TPGDA), add again 2.5 gram light trigger 1-hydroxy-cyclohexyl phenyl ketones (184), be uniformly dispersed on high speed dispersor.This UV coating is coated on glass and stainless steel plate, then carries out photocuring under UV-irradiation, then carry out performance characterization and test, result is as shown in table 1.
Embodiment 4
hydroxyethyl methylacrylate 19.53 grams (0.15 mole) of APTES 11.07 grams (0.05 mole) and process processed are added in the reactor with water trap and condenser, add again strong basic ion exchange resin 3.06 grams, under nitrogen protection, stir under 150 ℃ and react, the small molecules ethanol that generates is constantly told by water trap, allow this alcoholysis reaction carry out 14 hours, carry out again underpressure distillation under 150 ℃, remove unreacted hydroxyethyl methylacrylate, filter, obtain monobasic amido organosilicon acrylate and the dibasic mix products that contains the amido organosilicon acrylate of containing.
with 3, 3 ', 4, 4 '-phenyl ether tetracarboxylic dianhydride, 31.02 grams (0.10 mole), 4, 4 '-diaminodiphenylsulfone(DDS), 18.58 grams (0.08 mole) and above-mentioned organic silicon acrylic ester 13.90 grams (0.04 mole) that contain amino successively join in 254 milliliters of DMSO, under nitrogen protection, stir after 12 hours under 20 ℃～30 ℃, add dewatering agent diacetyl oxide 16.34 grams (0.16 mole), dehydration catalyst pyridine 12.66 grams (0.16 mole) and 169 milliliters of DMSO, in 80 ℃ of lower chemical imidization reactions 11 hours, reaction solution is poured in the dehydrated alcohol of high-speed stirring, be precipitated thing, after the gained throw out successively fully washs with dehydrated alcohol and anhydrous diethyl ether, vacuum-drying namely gets photocurable polyimide origoester acrylate,
Take above-mentioned polyimide origoester acrylate 25 grams, with 12.5 gram NVPs (NVP) and the dissolving of 10 gram tri (propylene glycol) diacrylates (TPGDA), add again 2.5 gram light trigger 1-hydroxy-cyclohexyl phenyl ketones (184), be uniformly dispersed on high speed dispersor.This UV coating is coated on glass and stainless steel plate, then carries out photocuring under UV-irradiation, then carry out performance characterization and test, result is as shown in table 1.
Table 1
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Testing method |
| Paint film appearance | Light yellow transparent | Light yellow transparent | Light yellow transparent | Light yellow transparent | Range estimation |
| Weightless 5% temperature/℃ | 372 | 365 | 360 | 353 | TG |
| Second-order transition temperature/℃ | 238 | 246 | 225 | 221 | DSC |
| Hardness/H | 5 | 4 | 4 | 4 | GB/T 6739-1996 |
| Attachment fastness on glass/level | 0 | 0 | 0 | 0 | GB/T 9286-1998 |
| Attachment fastness/level on stainless steel plate | 0 | 0 | 0 | 0 | GB/T 9286-1998 |
| Soak 1h(25 ℃ in water) | Do not come off, do not whiten | Do not come off, do not whiten | Do not come off, do not whiten | Do not come off, do not whiten | GB/T 1733-1993 |
| Soak 1h(100 ℃ in water) | Do not come off, do not whiten | Do not come off, do not whiten | Do not come off, do not whiten | Do not come off, do not whiten | GB/T 1733-1993 |
| Water-intake rate/% | <1.0 | <1.0 | <1.0 | <1.0 | HG/T 3344-1985 |
Claims (10)
1. UV coating polyimide origoester acrylate is characterized in that being obtained by following methods:
S1. with tetracarboxylic dianhydride, diamine with contain amino organic silicon acrylic ester and add in polar solvent, reaction generates intermediate;
S2. add dewatering agent and polar solvent in intermediate, carry out the chemical imidization reaction and make.
2. UV coating polyimide origoester acrylate according to claim 1, is characterized in that, after the S2 reaction finishes, reaction solution poured in dehydrated alcohol, is precipitated thing; Throw out obtains photocurable polyimide origoester acrylate through washing, drying.
3. UV coating polyimide origoester acrylate according to claim 1, is characterized in that, the described tetracarboxylic dianhydride of S1, diamine and contain amino organic silicon acrylic ester and be calculated in molar ratio as n+1:n:2, and described n is 1＜=n＜=20.
4. UV coating polyimide origoester acrylate according to claim 1 is characterized in that:
Described tetracarboxylic dianhydride is 1,2,4,5-pyromellitic acid anhydride, 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 2,2 '-two [4-(3,4-dicarboxyl phenoxy group) phenyl] propane tetracarboxylic dianhydride, 2, one or more in 2 '-two (3,4-, two carboxyphenyls) HFC-236fa tetracarboxylic dianhydride;
Described diamine is 1,6-hexanediamine, 1, two (the 3-aminopropan alkyl) tetramethyl disiloxanes, 1 of 3-, two (the 4-amino-benzene oxygen methane)-1 of 3-, 1,3,3-tetramethyl disiloxane, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenylsulfone(DDS), Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene, 2, one or more in two [(4-amino-benzene oxygen) phenyl] propane of 2-, two [4-(4-phenoxy group) phenyl] sulfone;
Described polar solvent is METHYLPYRROLIDONE, N, N '-dimethyl formamide, N, one or more in N '-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO);
Described dewatering agent is diacetyl oxide.
5. UV coating polyimide origoester acrylate according to claim 1, is characterized in that, in S2, the described material that adds also comprises dehydration catalyst, and described dehydration catalyst is pyridine.
6. UV coating polyimide origoester acrylate according to claim 5, is characterized in that, in S1, after adding polar solvent, solids content is 25 grams per milliliter solvents; After adding dewatering agent, dehydration catalyst and polar solvent in S2, solids content is 15 grams per milliliter solvents.
7. UV coating polyimide origoester acrylate according to claim 1, is characterized in that, S1 is under protection of inert gas, reacted under 20 ~ 30 ℃ 8 ~ 24 hours; S2 reacted under 30 ~ 90 ℃ 4 ~ 16 hours.
8. UV coating polyimide origoester acrylate according to claim 2, is characterized in that, described throw out absolute ethanol washing, then wash with anhydrous diethyl ether.
9. UV coating polyimide origoester acrylate as claimed in claim 1, is characterized in that, the described organic silicon acrylic ester that contains amino makes by containing amino organoalkoxysilane and the acrylate reactions of hydroxyl; The described organoalkoxysilane that contains amino is 3-TSL 8330 or APTES; The acrylate of described hydroxyl is for through one or more in the Hydroxyethyl acrylate of processed, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410.
10. UV coating polyimide origoester acrylate as claimed in claim 9; it is characterized in that; the described preparation method who contains amino organic silicon acrylic ester is: will contain amino organoalkoxysilane and the acrylate of hydroxyl and add in reactor; add again the strong basic ion exchange resin that accounts for above-mentioned two material total masses 5%～15%; under protection of inert gas; stir under 70 ℃～150 ℃; allow this alcoholysis reaction carry out 6～18 hours; carry out underpressure distillation again under 130 ℃～180 ℃; filter, and get final product.
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| TWI666670B (en) * | 2018-05-18 | 2019-07-21 | 致伸科技股份有限公司 | Keycap structure and manufacturing method thereof |
| CN108795315A (en) * | 2018-05-30 | 2018-11-13 | 宁波科莱恩新材料科技有限公司 | A kind of anti-sticking antiacid protective films of UV based on active fluorinated polyimide |
| CN108795315B (en) * | 2018-05-30 | 2021-02-12 | 宁波科莱恩新材料科技有限公司 | UV anti-adhesion acid-resistant protective film based on active fluorine-containing polyimide |
| CN115197399A (en) * | 2022-07-12 | 2022-10-18 | 中山大学 | Preparation method and application of alicyclic epoxy polyimide |
| CN115197399B (en) * | 2022-07-12 | 2023-06-16 | 中山大学 | Preparation method and application of alicyclic epoxy polyimide |
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