CN114057918B - Amine modified resin and preparation method and application thereof - Google Patents
Amine modified resin and preparation method and application thereof Download PDFInfo
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- CN114057918B CN114057918B CN202111474514.7A CN202111474514A CN114057918B CN 114057918 B CN114057918 B CN 114057918B CN 202111474514 A CN202111474514 A CN 202111474514A CN 114057918 B CN114057918 B CN 114057918B
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- 239000011347 resin Substances 0.000 title claims abstract description 106
- 229920005989 resin Polymers 0.000 title claims abstract description 106
- 150000001412 amines Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 acrylate compound Chemical class 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 40
- 238000006116 polymerization reaction Methods 0.000 claims description 35
- 229920002367 Polyisobutene Polymers 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 16
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 10
- 229940014800 succinic anhydride Drugs 0.000 claims description 10
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 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 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 2
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 claims description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- CFXXUPHGWZCTNG-UHFFFAOYSA-N propane-1,2-diol prop-2-enoic acid Chemical compound CC(O)CO.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C CFXXUPHGWZCTNG-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 abstract description 45
- 239000001301 oxygen Substances 0.000 abstract description 45
- 230000005764 inhibitory process Effects 0.000 abstract description 28
- 238000006243 chemical reaction Methods 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000001723 curing Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 18
- 229940126062 Compound A Drugs 0.000 description 12
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 12
- 230000002401 inhibitory effect Effects 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000000016 photochemical curing Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 125000001302 tertiary amino group Chemical group 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 6
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 229940124530 sulfonamide Drugs 0.000 description 5
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- DFTLCMTWNXAGSL-UHFFFAOYSA-N 2-methylprop-1-ene;oxolane-2,5-dione Chemical compound CC(C)=C.O=C1CCC(=O)O1 DFTLCMTWNXAGSL-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical class N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DFPGBRPWDZFIPP-UHFFFAOYSA-N n'-butylethane-1,2-diamine Chemical compound CCCCNCCN DFPGBRPWDZFIPP-UHFFFAOYSA-N 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002023 wood 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to an amine modified resin, a preparation method and application thereof. The amine-modified resin has a structure as shown in formula (I):wherein n is an integer of 7 to 30; r is a residue after Michael addition of one carbon-carbon double bond and a secondary amino group of the multifunctional acrylate compound; r is R 1 Is C 1～4 Straight or branched alkylene of (a); r is R 2 Is C 1～4 Straight or branched alkyl of (a); or R is 2 And R is as follows 2 Attached N atom and R 1 Is combined intoThe amine modified resin has excellent oxygen inhibition property, especially surface oxygen inhibition property. In addition, the amine-modified resin of the present invention is inexpensive compared to other resin materials that also have oxygen inhibition properties.
Description
Technical Field
The invention relates to the field of photocuring of high polymer materials, in particular to an amine modified resin and a preparation method and application thereof.
Background
The photocuring technology is widely applied to the fields of wood lacquer, paper gloss oil, nail polish glue, ink-jet printing, 3D printing, PCB circuit protection ink and the like due to the advantages of environment friendliness, high curing efficiency, convenience in operation and the like. Free radical photo-curing is the most commonly used curing mode in the photo-curing field, and has the advantages of high curing speed, convenient operation, mature technology and the like. However, since oxygen exists in air in a steady state of triplet state, oxygen can react with active radicals generated during curing to inactivate the active radicals, thereby reducing or even quenching polymerization, and causing incomplete curing or even stickiness of the material. The incomplete curing of the material can seriously affect the performance of the material, so that the inhibition of oxygen inhibition is one of the important problems to be solved in the technical field of photo-curing, especially the thin coating in the photo-curing of an LED, and the inhibition of oxygen inhibition is the first problem to be solved to inhibit the surface oxygen inhibition.
The prior oxygen inhibition polymerization mainly comprises a physical method and a chemical method, wherein the physical method is generally to cure in an inert atmosphere; the most common chemical methods are to increase the photoinitiator content, add oxygen scavengers, add hydrogen donors or peroxide reducing agents, and the like. The photoinitiator content is increased, so that the coating cost is increased, and excessive residual of small molecules is possibly caused, so that the material does not meet the relevant standards in the aspect of environmental protection; the addition auxiliary agent is usually a micromolecular compound with high irritation and high smell, which is not beneficial to the health of constructors.
There is also a method of modifying a resin material to thereby provide itself with a property of suppressing oxygen inhibition. The silicone oil compound modified resin material has good low surface tension, can enrich the material on the surface of a coating layer, and inhibit surface oxygen polymerization inhibition, but the silicone oil modified resin material has great defects because the silicone chain structure is easily influenced by catalysts, such as common catalysts of alkali, organic tin and the like, and the silicone oil chain is broken or crosslinked, so that the synthesized material is unstable. Patent with publication number of CN108409688A, named as perfluoroalkyl sulfonamide active amine acrylate compound and preparation method, discloses a perfluoroalkyl sulfonamide active amine acrylate compound which has good low surface tension, can be enriched on the surface of a coating, and inhibits surface oxygen polymerization inhibition. However, the synthesis of the compound requires a fluorocarbon long-chain compound, which has high cost and price of more than 200 yuan/kg, thereby limiting the use of downstream factories.
Based on the above problems, it is important to develop a resin material which has oxygen inhibition properties and is inexpensive.
Disclosure of Invention
The invention aims to solve the problems of oxygen polymerization inhibition phenomenon of an LED thin coating curing material in the prior art or high price of the existing oxygen polymerization inhibition resin, and provides an amine modified resin. The amine modified grease has excellent characteristic of inhibiting oxygen polymerization, especially in the aspect of inhibiting surface oxygen polymerization, as the tertiary amino group contained in the amine modified grease can release active free radicals, the polymerization of the resin is continuously initiated, thereby improving the surface layer curing speed and inhibiting the surface oxygen polymerization. In addition, the amine-modified resin of the present invention is inexpensive compared to other resin materials that also have oxygen inhibition properties.
Another object of the present invention is to provide a method for producing the above amine-modified resin.
It is another object of the present invention to provide the use of the amine-modified resins described above for the preparation of LED cured thin coating materials.
In order to achieve the above object, the present invention provides the following technical solutions.
An amine-modified resin having a structure according to formula (i):
wherein n is an integer of 7 to 30;
r is a residue after Michael addition of one carbon-carbon double bond and a secondary amino group of the multifunctional acrylate compound;
R 1 is C 1～4 Straight or branched alkylene of (a);
R 2 is C 1～4 Straight or branched alkyl of (a); or R is 2 And R is as follows 2 Attached N atom and R 1 Is combined into
The amine-modified resin of the present invention has a structure comprising a polyisobutenyl segment having a specific polymerization degree, a tertiary amino group and a plurality of acrylate groups. Wherein the polyisobutenyl segment is linked to a tertiary amino group through a specific structure, and the tertiary amino group is also linked to a structure containing multiple acrylate groups.
In the structure of the amine modified resin, on one hand, the polyisobutenyl chain segment can endow the amine modified resin with low enough surface tension, so that the amine modified resin is enriched on the surface of the coating to form a compact protective layer, and oxygen is prevented from entering a coating system, so that the oxygen content is reduced, and the occurrence of oxygen polymerization inhibition is inhibited; on the other hand, the activity of the tertiary amino group in the structure is not affected, and the tertiary amino group can be combined with oxygen or react with peroxide to release active free radicals, so that the polymerization of acrylate groups is continuously initiated, the surface layer curing speed is improved, and the surface oxygen polymerization inhibition is inhibited. Therefore, the amine-modified resin has excellent oxygen inhibition properties, particularly surface oxygen inhibition.
In addition, the amine-modified resin of the present invention can be produced from inexpensive raw materials and is inexpensive compared with other resin materials having oxygen inhibition properties as well.
Preferably, n is an integer from 8 to 21.
Preferably, R 1 is-CH 2 CH 2 -、R 2 is-CH 3 The method comprises the steps of carrying out a first treatment on the surface of the Or R is 1 is-CH 2 CH 2 -、R 2 is-CH 2 CH 3 The method comprises the steps of carrying out a first treatment on the surface of the Or R is 1 is-CH 2 CH 2 -、R 2 is-CH 2 CH 2 CH 2 CH 3 。
Preferably, the multifunctional acrylate compound comprises an acrylate compound having 2 to 6 acrylate groups.
More preferably, the multifunctional acrylate compound is one or more of dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, or ditrimethylolpropane tetraacrylate.
Preferably, the amine-modified resin has a molecular weight M n 600 to 2400。
More preferably, the amine-modified resin has a molecular weight M n 900-2000.
The preparation method of the amine modified resin is characterized by comprising the following steps:
s1: mixing polyisobutylene succinic anhydride of the formula (II), a compound of the formula (III) and a catalyst, and reacting to obtain a compound of the formula (IV);
s2: and (3) mixing the compound shown in the formula (IV) with the multifunctional acrylate compound in the presence of a polymerization inhibitor, and performing Michael addition reaction to obtain the amine modified resin.
The price of the raw material of the isobutene succinic anhydride is 10-15 yuan/kg, and the amine modified resin prepared by taking the isobutene succinic anhydride as the raw material has lower price than other resin materials with the same oxygen polymerization inhibition characteristic.
Preferably, the molecular weight M of the polyisobutene succinic anhydride of the formula (II) described in step S1 n 500 to 1400.
More preferably, the molecular weight M of the polyisobutene succinic anhydride of the formula (II) in step S1 n 800-1000.
Preferably, the compound of formula (III) in step S1 is one or more of N-aminoethylpiperazine, N-methylethylenediamine, N-ethylethylenediamine or N-N-butylethylenediamine.
Preferably, the ratio of the amounts of the substances of the formula (II) polyisobutene succinic anhydride and the formula (III) in step S1 is from 1 (1.1 to 1.5).
Preferably, the ratio of the amounts of the substances of the compound of formula (III) in step S1 to the polyfunctional acrylate compound in step S2 is 1 (1.5-2).
Preferably, the catalyst in step S1 is one or more of Lewis base triphenylphosphine, potassium hydroxide, sodium hydroxide, trifluoroacetic acid, p-toluenesulfonic acid or boron trifluoride diethyl ether of Lewis acid.
More preferably, the amount of catalyst in step S1 is from 100 to 2000ppm of the sum of the amounts of the polyisobutene succinic anhydride of formula (II), the compound of formula (III) and the polyfunctional acrylate compound in step S2.
Preferably, the polymerization inhibitor in the step S2 is one or two of para-hydroxyanisole or phenothiazine.
More preferably, the polymerization inhibitor in step S2 is 500 to 2000ppm of the sum of the masses of the polyisobutylene succinic anhydride of formula (II), the compound of formula (III) and the multifunctional acrylate compound in step S2.
Preferably, the temperature of the reaction in the step S1 is 100-120 ℃, and the reaction time is 3-8 h.
Preferably, the temperature of the reaction in the step S2 is 50-100 ℃, and the reaction time is 3-8 h.
The application of the amine modified resin in preparing the LED curing thin coating material is also within the protection scope of the invention.
The amine modified resin has excellent characteristic of inhibiting oxygen polymerization, especially inhibiting surface oxygen polymerization, so that the amine modified resin can be used as a main resin in the preparation of LED curing thin coating materials, so that the coating can be completely cured, and the serious influence of oxygen polymerization on the performance of the coating can be avoided.
Compared with the prior art, the invention has the following beneficial effects:
(1) The amine modified resin has excellent characteristic of inhibiting oxygen polymerization, especially in the aspect of inhibiting surface oxygen polymerization, as the tertiary amino group contained in the amine modified resin can release active free radicals, the polymerization of the resin is continuously initiated, thereby improving the surface layer curing speed and inhibiting the surface oxygen polymerization.
(2) The amine-modified resin of the present invention is less expensive than other resin materials that also have oxygen inhibition properties.
(3) The amine modified resin has excellent characteristic of inhibiting oxygen polymerization, especially inhibiting surface oxygen polymerization, so that the amine modified resin can be used as a main resin in LED curing thin coating to enable the coating to be completely cured, and the condition that the oxygen polymerization seriously affects the performance of the coating is avoided.
Drawings
FIG. 1 is a schematic illustration of the reaction process of example 1.
FIG. 2 is a schematic illustration of the reaction process of example 2.
FIG. 3 is a schematic illustration of the reaction process of example 3.
FIG. 4 is resin M of comparative example 1 4 Is a structural formula of (a).
FIG. 5 is resin M of comparative example 2 5 Is a structural formula of (a).
FIG. 6 is compound A of example 1 1 Compound a of example 2 2 And an infrared spectrum of polyisobutylene succinic anhydride.
FIG. 7 is an amine-modified resin M of example 1 1 Is an infrared spectrum of (c).
FIG. 8 is an amine-modified resin M of example 2 2 Is an infrared spectrum of (c).
FIG. 9 is an amine-modified resin M of example 3 3 Is an infrared spectrum of (c).
Detailed Description
The present invention is further described below with reference to examples and comparative examples. These examples are merely typical descriptions of the present invention, but the present invention is not limited thereto. The test methods used in the following examples and comparative examples are, unless otherwise specified, conventional methods, and the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional commercial sources and the like.
Example 1
This example provides an amine-modified resin M 1 The preparation method comprises the following steps:
into a 250ml four-necked flask apparatus with reflux condenser, a molecular weight M was added n 1000 polyisobutene succinic anhydride (100 g), N-aminoethylpiperazine (14.21 g), dried toluene solution (50 g), catalyst triphenylphosphine (0.11 g), and the mixture was reacted at 100℃for 3 hours, and the solvent was distilled off by rotary evaporation to give Compound A 1 . Taking compound A 1 (100g) Adding 1, 6-hexanediol diacrylate (35 g), p-hydroxyanisole (0.11 g), reacting at constant temperature of 60 ℃ for 4h, discharging to obtain amine modified resin M 1 The isocyanate compound for sampling is reacted with the isocyanate compound, a proper amount of anhydrous toluene solution is added, and the mixture is placed at 60 ℃ for dryingAfter 0.5h of reaction in the box, the NCO conversion rate is measured, and the NCO conversion rate is 0, which indicates that the amine-double bond Michael addition reaction is completed (the reaction of isocyanate groups and-NH-groups is very rapid, and the conversion rate can reach 100% in a very short time), and the amine modified resin M is successfully synthesized 1 。
The reaction process of this example is schematically shown in FIG. 1.
Compound A in this example 1 The infrared spectrum of (2) is shown in FIG. 6, wherein A in the spectrum 1 At 1865cm -1 The anhydride absorption peak completely disappeared, indicating successful bonding of primary amine to the polyisobutylene succinic anhydride.
The amine-modified resin M 1 The infrared spectrum of (2) is shown in FIG. 7, the infrared shift: 2951.52cm -1 (C-H stretching vibration in acrylate double bond, and methyl methylene stretching vibration peak on polyisobutene group), 1727.53cm -1 (carbon oxygen stretching vibration in ester group), 1191.82cm -1 (C-O-C stretching vibration peak) 810.33cm -1 (C-H out-of-plane bending vibration in acrylate double bond), 1471.76cm -1 (C-O stretching vibration peak), 1407.82cm -1 (C-O stretching vibration peak), 1636.12cm -1 (acrylate double bond stretching vibration peaks) which illustrate the structural presence of an acrylate double bond and a carbon-oxygen directly attached group; and 1061.98cm -1 (C-N stretching vibration peak), 2951.52cm -1 (C-H stretching vibration in acrylate double bond, and methyl methylene stretching vibration peak on polyisobutene group), 1619.79cm -1 (end group C=C double bond stretching vibration peak), 1389.49cm -1 (peak of shear vibration with dimethyl and tert-butyl) 984.52cm -1 (methylene and methyl C-H out-of-plane bending vibrations), indicating the inclusion of a polyisobutylene structure. The infrared spectrogram proves that the clear and transparent amine modified resin M is successfully synthesized 1 。
Example 2
This example provides an amine-modified resin M 2 The preparation method comprises the following steps:
into a 250ml four-necked flask apparatus with reflux condenser, a molecular weight M was added n 800 polyisobutene succinic anhydride (80 g), N-ethyl ethylenediamine (9.70 g), dried toluene solution (50 g),triphenylphosphine (0.10 g) as catalyst, reacting at 100deg.C for 3h, and removing solvent by rotary evaporation to obtain compound A 2 . Taking compound A 2 (100g) Adding trimethylolpropane triacrylate (58.20 g), para-hydroxyanisole (0.10 g), reacting at 60deg.C for 4 hr, discharging to obtain amine modified resin M 2 The isocyanate compound for sampling reacts with the isocyanate compound, a proper amount of anhydrous toluene solution is added, the mixture is placed in a baking oven at 60 ℃ for reaction for 0.5h, the NCO conversion rate is measured, the NCO conversion rate is 0, the completion of the Michael addition reaction of amine-double bonds (the reaction of isocyanate groups and-NH-groups is very rapid, the conversion rate can reach 100% in a very short time) is indicated, and the amine modified resin M is successfully synthesized 2 。
The reaction process of this example is schematically shown in FIG. 2.
Compound A in this example 2 The infrared spectrum of (2) is shown in FIG. 5, wherein A in the spectrum 2 At 1865cm -1 The anhydride absorption peak completely disappeared, indicating successful bonding of primary amine to the polyisobutylene succinic anhydride.
The amine-modified resin M 2 The infrared spectrum of (2) is shown in FIG. 8, the infrared shift: 2952.74cm -1 (C-H stretching vibration in acrylate double bond, and methyl methylene stretching vibration peak on polyisobutene group), 1732.90cm -1 (carbon oxygen stretching vibration in ester group), 1184.22cm -1 (C-O-C stretching vibration peak) 808.45cm -1 (C-H out-of-plane bending vibration in acrylate double bond), 1471.22cm -1 (C-O stretching vibration peak), 1407.45cm -1 (C-O stretching vibration peak), 1634.58cm -1 (acrylate double bond stretching vibration peaks) which illustrate the structural presence of an acrylate double bond and a carbon-oxygen directly attached group; and 1061.14cm -1 (C-N stretching vibration peak), 2952.74cm -1 (C-H stretching vibration in acrylate double bond, and methyl methylene stretching vibration peak on polyisobutene group), 1615.94cm -1 (end group C=C double bond stretching vibration peak), 1390.08cm -1 (peak of shear vibration with dimethyl and tert-butyl) 984.36cm -1 (methylene and methyl C-H out-of-plane flexural vibration), indicating polyisobutene containing results. The infrared spectrogram proves that the clear and transparent amine is successfully synthesizedModified resin M 2 。
Example 3
This example provides an amine-modified resin M 3 The preparation method comprises the following steps:
taking the compound A obtained in example 1 1 (100g) Adding tripropylene glycol diacrylate (47 g), para-hydroxyanisole (0.11 g), reacting to release heat, reacting at constant temperature 60 ℃ for 5h, discharging to obtain amine modified resin M 3 The isocyanate compound for sampling reacts with the isocyanate compound, a proper amount of anhydrous toluene solution is added, the mixture is placed in a baking oven at 60 ℃ for reaction for 0.5h, the NCO conversion rate is measured, the NCO conversion rate is 0, the completion of the Michael addition reaction of amine-double bonds (the reaction of isocyanate groups and-NH-groups is very rapid, the conversion rate can reach 100% in a very short time) is indicated, and the amine modified resin M is successfully synthesized 3 。
The reaction process of this example is schematically shown in FIG. 3.
The amine-modified resin M 3 As shown in fig. 9, infrared shift: 2951.49cm -1 (C-H stretching vibration in acrylate double bond, and methyl methylene stretching vibration peak on polyisobutene group), 1725.47cm -1 (carbon oxygen stretching vibration in ester group), 1189.49cm -1 (C-O-C stretching vibration peak) 810.44cm -1 (C-H out-of-plane bending vibration in acrylate double bond), 1467.13cm -1 (C-O stretching vibration peak), 1407.48cm -1 (C-O stretching vibration peak), 1633.72cm -1 (acrylate double bond stretching vibration peaks) which illustrate the structural presence of an acrylate double bond and a carbon-oxygen directly attached group; and 1063.94cm -1 (C-N stretching vibration peak), 2951.49cm -1 (C-H stretching vibration in acrylate double bond, and methyl methylene stretching vibration peak on polyisobutene group), 1616.82cm -1 (end group C=C double bond stretching vibration peak), 1366.38cm -1 (peak of shear vibration with dimethyl and tert-butyl) 979.44cm -1 (methylene and methyl C-H out-of-plane bending vibrations), indicating the inclusion of a polyisobutylene structure. The infrared spectrogram proves that the clear and transparent amine modified resin M is successfully synthesized 3 。
Comparative example 1
Comparative exampleProviding a molecular weight M n Amine modified resin M for 1500 polyisobutylene succinic anhydride 4 The preparation method comprises the following steps:
into a 250ml four-necked flask apparatus with reflux condenser, a molecular weight M was added n 1500 polyisobutene succinic anhydride (150 g), N-ethyl ethylenediamine (9.70 g), dried toluene solution (50 g), catalyst triphenylphosphine (0.10 g), reaction at 100deg.C for 3h, and rotary evaporation to remove solvent, to give compound A 4 . Taking compound A 4 (120g) Adding trimethylolpropane triacrylate (58.20 g), para-hydroxyanisole (0.10 g), reacting at 60deg.C for 4 hr, discharging to obtain amine modified resin M 4 The isocyanate compound for sampling reacts with the isocyanate compound, a proper amount of anhydrous toluene solution is added, the mixture is placed in a baking oven at 60 ℃ for reaction for 0.5h, the NCO conversion rate is measured, the NCO conversion rate is 0, the completion of the Michael addition reaction of amine-double bonds (the reaction of isocyanate groups and-NH-groups is very rapid, the conversion rate can reach 100% in a very short time) is indicated, and the amine modified resin M is successfully synthesized 4 . Synthesized amine-modified resin M 4 Cloudy, opaque and transparent, and mixed with conventional epoxy acrylate resin or polyurethane acrylate resin in a mass fraction of 1:1, the mixed solution is cloudy, opaque and transparent, and the molecular weight M of the polyisobutene succinic anhydride is shown n The compatibility of the amine modified resin synthesized for 1500 and the conventional light-cured acrylic resin is poor, and the compatibility of the formula system and further the performance are affected, so that the resin cannot be used in the light-cured formula system. The amine-modified resin M of this comparative example 4 No performance comparisons were made.
The amine-modified resin M obtained in this comparative example 4 The structural formula of (2) is shown in figure 4.
Comparative example 2
This comparative example provides a molecular weight M n Modified amine resin M of 400 polyisobutene succinic anhydride 5 The preparation method comprises the following steps:
into a 250ml four-necked flask apparatus with reflux condenser, a molecular weight M was added n 400 (40 g), N-ethylethylenediamine (9.70 g), a toluene solution after drying (50 g),triphenylphosphine (0.10 g) as catalyst, reacting at 100deg.C for 3h, and removing solvent by rotary evaporation to obtain compound A 5 . Taking compound A 5 (120g) Adding trimethylolpropane triacrylate (58.20 g), para-hydroxyanisole (0.10 g), reacting at 60deg.C for 4 hr, discharging to obtain amine modified resin M 5 The isocyanate compound for sampling reacts with the isocyanate compound, a proper amount of anhydrous toluene solution is added, the mixture is placed in a baking oven at 60 ℃ for reaction for 0.5h, the NCO conversion rate is measured, the NCO conversion rate is 0, the completion of the Michael addition reaction of amine-double bonds (the reaction of isocyanate groups and-NH-groups is very rapid, the conversion rate can reach 100% in a very short time) is indicated, and the amine modified resin M is successfully synthesized 5 。
The amine-modified resin M obtained in this comparative example 5 The structural formula of (2) is shown in figure 5.
The resins of examples 1, 2, 3 and comparative example 2 were prepared as LED cured coatings.
1. LED curing paint formula
TABLE 1 formulation of LED curing coatings
In Table 1, component 1 is propylene glycol diacrylate (TPGDA); the method comprises the steps of carrying out a first treatment on the surface of the The component 2 is polyethylene glycol diacrylate-200 (PEGDA-200); the component 3 is epoxy acrylate resin (B-100, guangdong Boxing New Material science and technology Co., ltd.); component 4 is the photoinitiator Isopropylthioxanthone (ITX) (1 wt%); component 5 is auxiliary BDMA (1 wt%) and is only added into coating 5 #; component 6 is a resin added in examples, comparative examples, or a resin not added in examples and comparative examples, respectively, wherein component 6 of coating 1#, coating 2# and coating 3# is added with M of examples 1, 2 and 3, respectively 1 、M 2 And M 3 Component 6 of coating 4# adds M of comparative example 2 5 Component 6 of coating 5# and coating 6# are both added with conventional resin B-296 (a difunctional urethane acrylate resin from Boxing New Material science Co., ltd., guangdong) and component 6 of coating 7# is comparative resin M 0 From publication number CN108409688The patent specification of A the perfluoroalkyl sulfonamide active amine acrylate compound of example 1.
The components of the formula are all from Guangdong Boxing New Material technology Co. After the components are prepared according to the formula, the components are uniformly stirred to obtain the LED curing coating No. 1-No. 7.
2. Testing
The prepared LED curing paint is respectively coated on a glass plate by a wire rod, and the film thickness is controlled to be about 3 mu m. Respectively using different light sources to irradiate and solidify, and using 1000W medium-pressure mercury lamp to irradiate light with 24.9mW/cm 2 Light intensity of 375UV LED irradiation is 260mW/cm 2 Irradiation time 10sec;385nm UV LED irradiation light intensity 400mW/cm 2 Irradiation time 10sec;395nm UV LED irradiation light intensity 260mW/cm 2 Irradiation time 10sec;385nm UV LED irradiation light intensity 500mW/cm 2 The irradiation time was 10sec. Detecting the surface solidification condition by a finger touch method, wherein fingerprint indentation appears on the surface of the coating, and the fingerprint indentation is expressed by x, which indicates that obvious surface oxygen polymerization inhibition exists; fingerprint indentation does not appear on the surface of the coating, which is indicated by the fact that the oxygen inhibition of the photocuring surface is overcome, and the fact that the surface layer is better in photocrosslinking is indicated.
The adopted photoinitiator is isopropyl thioxanthone ITX (component 4), and the photoinitiator is Type II photoinitiator, and can rapidly and effectively generate active free radicals to initiate double bond polymerization by being matched with hydrogen donor auxiliary agents such as tertiary amines. The test results are shown in table 2:
TABLE 2
As is clear from Table 2, the amine-modified resin resins (M) of examples 1 to 3 were added 1 、M 2 、M 3 ) The thin coating of the LED cured coating No. 1-3 can be dried under the irradiation of a medium-pressure mercury lamp and a 375/385/395nm UV LED light source; comparative example 2 resin M was added 5 LED cured coating of (C)No. 4 can be surface dried under the curing of a mercury lamp and 375nm LED, and can not be surface dried under the curing of 385/395nm LED; the LED curing coating 5# added with the active amine auxiliary BDMA can be dried under the irradiation of a medium-pressure mercury lamp and a 375nm UV LED light source, and can not be dried under the irradiation of a 385/395nm UV LED light source; the LED curing coating 6# without any auxiliary agent is not dry under the curing of a mercury lamp and the irradiation of an LED light source, and has the phenomenon of stickiness on the surface; the LED cured coating 7# added with the perfluoroalkyl sulfonamide active amine acrylate compound can be dried by irradiation of a 375/385/395nm UV LED light source in a medium-pressure mercury lamp.
By adding the amine-modified resin resins of examples 1 to 3 (M 1 、M 2 、M 3 ) The comparison of the surface dry results of the LED cured coatings 1# to 3# and the LED cured coating 5# with the active amine auxiliary BDMA added and the LED cured coating 6# without any auxiliary added shows that the resins (M 1 、M 2 、M 3 ) The epoxy resin plays a better role in inhibiting oxygen polymerization in the formula of the LED curing coating, can play a better role with ITX, and can inhibit oxygen polymerization, so that a good curing effect is achieved, namely, the epoxy resin is suitable for being applied to a formula system of the LED curing coating.
By adding the amine-modified resin resins of examples 1 to 3 (M 1 、M 2 、M 3 ) The comparison of the surface dry results of the LED cured coatings 1# to 3# and the LED cured coating 7# containing the perfluoroalkyl sulfonamide-active amine acrylate compound shows that the amine modified resin resins (M 1 、M 2 、M 3 ) As good as the oxygen inhibition effect, particularly the surface oxygen inhibition effect, of the perfluoroalkyl sulfonamide-active amine acrylate compound, the amine-modified resins (M 1 、M 2 、M 3 ) The cost is far lower than that of perfluoroalkyl sulfonamide active amine acrylate compounds.
By adding the amine-modified resin resins of examples 1 to 3 (M 1 、M 2 、M 3 ) LED cured coatings 1# to 3# of (C) and addition of comparative example 2 resin M 5 The comparison of the surface dry results of LED cured coating # 4, demonstrates the molecular weight M of the polyisobutylene succinic anhydride used to synthesize the amine modified resins herein n In the case of the value of 400, the number of the components is,the synthesized amine modified resin cannot be enriched on the surface of the coating, is not distributed in a gradient manner in a formula system, greatly reduces the effect of inhibiting surface oxygen polymerization inhibition, and cannot be applied to LED curing thin coating.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (8)
1. An amine-modified resin characterized by having a structure of formula (i):
wherein n is an integer of 8 to 21;
r is a residue after Michael addition of one carbon-carbon double bond and a secondary amino group of the multifunctional acrylate compound; the multifunctional acrylate compound is an acrylate compound containing 2-6 acrylate groups;
R 1 is C 1～4 Straight or branched alkylene of (a);
R 2 is C 1～4 Straight or branched alkyl of (a); or R is 2 And R is as follows 2 Attached N atom and R 1 Is combined into
2. The amine-modified resin of claim 1, wherein R 1 is-CH 2 CH 2 -、R 2 is-CH 3 The method comprises the steps of carrying out a first treatment on the surface of the Or R is 1 is-CH 2 CH 2 -、R 2 is-CH 2 CH 3 The method comprises the steps of carrying out a first treatment on the surface of the Or R is 1 is-CH 2 CH 2 -、R 2 is-CH 2 CH 2 CH 2 CH 3 。
3. The amine-modified resin of claim 1, wherein the multifunctional acrylate compound is one or more of propylene glycol diacrylate, 1, 6-hexanediol diacrylate, propylene glycol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, or ditrimethylolpropane tetraacrylate.
4. The amine-modified resin of claim 1, wherein the amine-modified resin has a molecular weight M n 600-2400.
5. The process for producing an amine-modified resin according to any one of claims 1 to 4, comprising the steps of:
s1: mixing polyisobutylene succinic anhydride of the formula (II), a compound of the formula (III) and a catalyst, and reacting to obtain a compound of the formula (IV);
s2: and (3) mixing the compound shown in the formula (IV) with the multifunctional acrylate compound in the presence of a polymerization inhibitor, and performing Michael addition reaction to obtain the amine modified resin.
6. The process according to claim 5, wherein the ratio of the amounts of the substances of the polyisobutene succinic anhydride of formula (II) in step S1 and the compound of formula (III) in step S1 is 1 (1.1 to 1.5); the ratio of the amounts of the compound of formula (III) in step S1 to the polyfunctional acrylate compound in step S2 is 1 (1.5-2).
7. The preparation method according to claim 5, wherein the catalyst in the step S1 is one or more of Lewis base triphenylphosphine, potassium hydroxide, sodium hydroxide, trifluoroacetic acid, p-toluenesulfonic acid or Lewis acid boron trifluoride diethyl ether; and the polymerization inhibitor in the step S2 is one or two of para-hydroxyanisole or phenothiazine.
8. Use of an amine-modified resin according to any one of claims 1 to 4 for the preparation of a cured thin coating material for LEDs.
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| CN109651296A (en) * | 2019-01-23 | 2019-04-19 | 安庆北化大科技园有限公司 | A kind of Water-soluble methyl acrylate monomer and preparation method thereof |
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| CN104254552B (en) * | 2012-04-27 | 2018-12-11 | 汉高知识产权控股有限责任公司 | The distant pawl polyisobutene of grafting, preparation method and the curable compositions comprising it with reactive functional groups |
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| CN108409688A (en) * | 2018-02-12 | 2018-08-17 | 中山大学 | A kind of perfluorinated alkyl sulfonamide reactive amines acrylate compounds and preparation method |
| CN109651296A (en) * | 2019-01-23 | 2019-04-19 | 安庆北化大科技园有限公司 | A kind of Water-soluble methyl acrylate monomer and preparation method thereof |
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