CN115612103B - Preparation method of efficient co-initiator for ultraviolet light curing - Google Patents
Preparation method of efficient co-initiator for ultraviolet light curing Download PDFInfo
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- CN115612103B CN115612103B CN202211301575.8A CN202211301575A CN115612103B CN 115612103 B CN115612103 B CN 115612103B CN 202211301575 A CN202211301575 A CN 202211301575A CN 115612103 B CN115612103 B CN 115612103B
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- ester
- initiator
- diacrylate
- prepolymer
- ultraviolet light
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- 239000003999 initiator Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 150000003568 thioethers Chemical class 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 125000004386 diacrylate group Chemical group 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004662 dithiols Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 30
- -1 ethylene glycol di (3-mercaptopropionic acid) ester Chemical class 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 150000003335 secondary amines Chemical class 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 5
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-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 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 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 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 claims description 3
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 3
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 3
- LBDSQNRQXIKAGX-UHFFFAOYSA-N (2-methyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(C)COC(=O)C=C LBDSQNRQXIKAGX-UHFFFAOYSA-N 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
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 24
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of an efficient co-initiator for ultraviolet light curing, which comprises the steps of firstly reacting dithiol with a diacrylate monomer to synthesize a thioether prepolymer, then reacting with a polyfunctional acrylic monomer to obtain a hyperbranched prepolymer, and finally reacting with secondary amine to obtain a target product. The invention uses a one-pot method for continuous feeding, and the operation is simple and easy to implement. The high-efficiency co-initiator for ultraviolet light curing prepared by the method has the advantages of high polymerization rate, low mobility and low odor, and good technical effect is achieved.
Description
Technical Field
The invention belongs to the technical field of ultraviolet light curing, and particularly relates to a preparation method of an efficient co-initiator for ultraviolet light curing.
Background
The Ultraviolet (UV) curing technology is a novel technology, has the advantages of high production efficiency, low VOC emission, low energy consumption, good performance of a cured film and the like, and is widely applied to the fields of wood lacquer coating, photo-curing ink and the like. The light-cured material formulation mainly comprises an oligomer (also called light-cured resin), a reactive diluent (also called light-cured monomer), a photoinitiator and the like. Wherein the photoinitiator is a substance capable of generating active species to initiate chemical crosslinking of the oligomer and the reactive diluent under ultraviolet light irradiation. Hydrogen abstraction type radical photoinitiators (including benzophenone, thioxanthone, camphorquinone, coumarone, anthraquinone, etc.) are among the most commonly used photoinitiators currently, and require co-initiator use. The co-initiator generally acts as a hydrogen donor and does not itself absorb ultraviolet light. The hydrogen abstraction initiator absorbs light energy and reaches an excited state, and the hydrogen abstraction initiator has a double molecular effect with the auxiliary initiator, and abstracts hydrogen atoms on the auxiliary initiator to generate active free radicals so as to initiate polymerization. The co-initiator is typically a tertiary amine compound including aliphatic tertiary amines, ethanolamines tertiary amines, benzoate tertiary amines, and the like.
Chinese patent application No. 201710695551.8 discloses a synthesis and preparation method of a modified active amine co-initiator, and the main idea is to increase the molecular weight of the co-initiator so as to reduce the odor and migration of the traditional co-initiator, specifically, 4' -diamino dicyclohexylmethane is used for reacting with different mono-functional acrylate monomers, so as to obtain the aliphatic tertiary amine compound with dicyclohexylmethane as a core. The method effectively solves the problems of smell and mobility, but obviously reduces the initiation efficiency, cannot achieve the effect of the conventional co-initiator in actual use, and in addition, methanol is used as a solvent in the preparation process, and the solvent is removed after the reaction is finished, so that the method is relatively complicated in operation and not environment-friendly.
Chinese patent application No. 202011620363.7 discloses a tertiary amine containing an amine group and a triazine ring structure as a co-initiator, reacting dimethylaminoalkylamine or diethylaminoalkylamine with formaldehyde solution, then adding potassium hydroxide, separating the organic phase, and finally vacuum distilling to obtain a compound containing a tertiary amine and a triazine ring structure. The compound has better initiation efficiency as a co-initiator, but formaldehyde solution used in the preparation process can cause residual formaldehyde as a product, so that the compound has great harm to human bodies, and more chemical wastewater can be generated by repeated water washing.
Disclosure of Invention
The invention aims to: the invention aims to overcome the defects in the prior art and provide a simple preparation method for preparing a photo-curing auxiliary initiator with high polymerization efficiency, low mobility and low smell.
The technical scheme is as follows: in order to achieve the above object, the present invention adopts the following technical scheme:
the preparation method of the efficient co-initiator for ultraviolet light curing comprises the following steps:
(1) Reacting dithiol with a diacrylate monomer to synthesize a thioether prepolymer;
(2) Reacting a thioether prepolymer with a polyfunctional acrylic monomer to obtain a hyperbranched prepolymer;
(3) Secondary amine is used to react with hyperbranched prepolymer, and then the efficient auxiliary initiator is obtained.
As a preferred scheme, the preparation method of the high-efficiency co-initiator for ultraviolet light curing comprises the following steps of: the dithiol, the diacrylate monomer and the catalyst with certain mass are placed in a reaction flask, and the temperature is slowly raised to 45-50 ℃ for reaction until the infrared spectrogram of the reactant is positioned at 810cm -1 The double bond characteristic peak of (2) disappears.
As a preferred scheme, the preparation method of the efficient co-initiator for ultraviolet light curing comprises the following steps of: putting a certain mass of thioether prepolymer, a polyfunctional acrylic monomer, a catalyst and a polymerization inhibitor into a reaction flask, slowly heating to 50-55 ℃ for reaction until the infrared spectrogram of the reactant is located at 2568cm -1 The thiol characteristic peak of (2) disappeared.
As a preferred scheme, the preparation method of the efficient co-initiator for ultraviolet light curing comprises the following steps of: firstly placing a certain mass of hyperbranched prepolymer and polymerization inhibitor into a reaction flask, then dropwise adding secondary amine into the flask, slowly heating to 60 ℃, and reacting for 8 hours at 60 ℃.
As a preferred scheme, the catalyst in the step (1) is one or more selected from triethylamine, pyridine, N-methylpiperidine, tri-N-butylamine and triethanolamine, and the addition amount is 0.1% -1.0% of the total mass of the reaction solution.
As a preferred scheme, the preparation method of the efficient co-initiator for ultraviolet light curing is characterized in that the polymerization inhibitor is one or more selected from the group consisting of p-hydroxyanisole, hydroquinone and p-tert-butyl catechol, and the addition amount is 0.05% -0.15% of the total mass of the reaction solution.
As a preferred scheme, in the preparation method of the high-efficiency co-initiator for ultraviolet light curing, in the step (1), the molar ratio of dithiol to diacrylate monomers is controlled to be between 1.5 and 2;
in the step (2), controlling the molar ratio of the double bond in the multifunctional acrylic monomer to the mercapto group in the thioether prepolymer to be 2-8;
in the step (3), the molar ratio of the double bond to the secondary amine in the hyperbranched prepolymer is controlled to be 1-3.
As a preferred scheme, the preparation method of the efficient initiator for ultraviolet light curing is characterized in that dithiol is selected from one or more of ethylene glycol di (3-mercaptopropionic acid) ester, ethylene glycol di (2-mercaptoacetic acid) ester, 1, 4-butanediol di (3-mercaptopropionic acid) ester, 1, 4-butanediol di (2-mercaptoacetic acid) ester, neopentyl glycol di (3-mercaptopropionic acid) ester, neopentyl glycol di (2-mercaptoacetic acid) ester, 1, 6-hexanediol di (3-mercaptopropionic acid) ester, 1, 6-hexanediol di (2-mercaptoacetic acid) ester, polyethylene glycol di (3-mercaptopropionic acid) ester, polyethylene glycol di (2-mercaptoacetic acid) ester, polypropylene glycol di (3-mercaptopropionic acid) ester and polypropylene glycol di (2-mercaptoacetic acid) ester.
As a preferred scheme, the preparation method of the efficient co-initiator for ultraviolet light curing is characterized in that the diacrylate monomer is selected from one or more of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate and 2-methyl-1, 3-propanediol diacrylate.
In a preferred scheme, the preparation method of the high-efficiency co-initiator for ultraviolet light curing is characterized in that the multifunctional acrylic monomer is one or more selected from ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate and ditrimethylolpropane tetraacrylate.
In the preferred scheme, the catalyst in the step (2) is one or more selected from triethylamine, pyridine, N-methylpiperidine, tri-N-butylamine, N-dimethylbenzylamine and pentamethyldiethylenetriamine.
In a preferred scheme, the preparation method of the efficient co-initiator for ultraviolet light curing is characterized in that the secondary amine is one or more selected from diethylamine, di-n-propylamine, di-n-butylamine, diethanolamine, morpholine and piperidine.
The beneficial effects of the invention are as follows:
the invention uses dithiol to react with diacrylate monomer, synthesizes thioether prepolymer, then reacts with polyfunctional acrylic monomer to obtain hyperbranched prepolymer, and finally reacts with secondary amine to obtain efficient initiator. The method uses a one-pot method for continuous feeding to synthesize the high-efficiency auxiliary initiator for ultraviolet light curing, and the method is simple and easy to implement and does not generate three wastes.
Oxygen inhibition is a common phenomenon in free radical photo-curing reaction, the combination rate of oxygen and free radicals is far greater than the initiation or chain growth rate of free radical chains, peroxy free radicals without initiation activity are more easily generated, the polymerization reaction is forced to stop, the curing of a paint film is insufficient, and the performance is reduced. However, the methylene hydrogen atom of the thioether has higher activity and can be combined with peroxy radicals to form methylene radicals, and polymerization is initiated again. That is, the thioether can effectively overcome the polymerization inhibition effect of oxygen and improve the double bond conversion rate.
Compared with the prior art, the synthesis route of the invention is unique and novel, and the prepared high-efficiency co-initiator for ultraviolet light curing contains tertiary amine, thioether and acrylate groups, wherein the tertiary amine can provide hydrogen atoms for the hydrogen abstraction photoinitiator, so as to provide a large number of active free radicals; the thioether can effectively overcome the polymerization inhibition effect of oxygen and improve the double bond conversion rate; the acrylate groups may participate in the photo-curing reaction, reducing overall mobility and odor. The high-efficiency co-initiator for ultraviolet light curing has the advantages of high polymerization rate, low mobility and low odor, and good technical effect is achieved.
Detailed Description
Example 1
The preparation method of the efficient co-initiator for ultraviolet light curing comprises the following steps:
(1) 532 g of 1, 6-hexanediol di (2-thioglycollic acid) ester, 198 g of 1, 4-butanediol diacrylate and 0.73 g of tri-n-butylamine are sequentially fed into a reaction flask, uniformly stirred, slowly heated to 45 ℃, reacted for 5 hours, sampled and tested for infrared absorption spectrum every 1 hour until the infrared spectrum is positioned at 810cm -1 The double bond characteristic peak of (2) disappeared to obtain thioether prepolymer 1.
(2) 1112.8 g of ethoxylated trimethylolpropane triacrylate, 1.66 g of para-hydroxyanisole and 2.21 g of triethylamine are mixed with the thioether prepolymer 1 in the step (1), stirring is kept, and the temperature is slowly increased to 50 ℃ for reaction until the infrared spectrum of the reactant is located at 2568cm -1 The mercapto characteristic peak of (2) disappeared to obtain hyperbranched prepolymer 1.
(3) 1.03 g of hydroquinone is added into the hyperbranched prepolymer 1 in the step (2), stirring is kept, 219 g of diethylamine is added dropwise, then the temperature is slowly increased to 60 ℃ and the reaction is continued for 8 hours, thus obtaining the efficient co-initiator 1.
Example 2
The preparation method of the efficient co-initiator for ultraviolet light curing comprises the following steps:
(1) 428.4 g of ethylene glycol di (3-mercaptopropionic acid) ester, 300 g of tripropylene glycol diacrylate and 1.1 g of pyridine are sequentially fed into a reaction flask, uniformly stirred, slowly heated to 50 ℃, reacted for 5 hours, sampled and tested for infrared absorption spectrum every 1 hour until the infrared spectrum is positioned at 810cm -1 The double bond characteristic peak of (2) disappeared to obtain thioether prepolymer (2).
(2) 774.8 g of pentaerythritol triacrylate, 1.2 g of p-tert-butylcatechol and 1.81 g of N-methylpiperidine are mixed with the thioether prepolymer 2 in the step (1), the mixture is stirred and slowly heated to 55 ℃ for reaction until the infrared spectrum of the reactant is located at 2568cm -1 The mercapto characteristic peak of (2) disappeared to obtain hyperbranched prepolymer (2).
(3) Adding 1.86 g of p-hydroxyanisole into the hyperbranched prepolymer 2 in the step (2), keeping stirring, dripping 348.4 g of morpholine, slowly heating to 60 ℃, and continuously reacting for 8 hours to obtain the efficient co-initiator 2.
Example 3
The preparation method of the efficient co-initiator for ultraviolet light curing comprises the following steps:
(1) 392.7 g of 1, 4-butanediol di (2-thioglycollic acid) ester, 212 g of neopentyl glycol diacrylate and 0.73 g of triethanolamine are sequentially fed into a reaction flask, uniformly stirred, slowly heated to 50 ℃, reacted for 4 hours, and then sampled and tested for infrared absorption spectrum every 1 hour until the infrared spectrum is positioned at 810cm -1 The double bond characteristic peak of (2) disappeared to obtain thioether prepolymer 3.
(2) 563.2 g of pentaerythritol tetraacrylate, 0.7 g of hydroquinone and 1.75 g of tri-n-butylamine are mixed with the thioether prepolymer 3 in the step (1), stirring is kept, and the temperature is slowly increased to 55 ℃ for reaction until the infrared spectrum of the reactant is located at 2568cm -1 The mercapto characteristic peak of (2) disappeared to obtain hyperbranched prepolymer 3.
(3) 1.62 g of p-hydroxyanisole is added into the hyperbranched prepolymer 3 in the step (2), stirring is kept, 451.5 g of di-n-butylamine is dropwise added, then the temperature is slowly increased to 60 ℃ and the reaction is continued for 8 hours, so that the efficient auxiliary initiator 3 is obtained.
Example 4
The preparation method of the efficient co-initiator for ultraviolet light curing comprises the following steps:
(1) 476 g of neopentyl glycol di (3-mercaptopropionic acid) ester, 242 g of dipropylene glycol diacrylate and 0.86 g of N-methylpiperidine are sequentially fed into a reaction flask, uniformly stirred, slowly heated to 48 ℃, reacted for 4 hours, and then sampled and tested for infrared absorption spectrum every 1 hour until the infrared spectrum is positioned at 810cm -1 The double bond characteristic peak of (2) disappeared to obtain thioether prepolymer 4.
(2) 727.6 g of propoxylated glycerol triacrylate, 1.45 g of p-hydroxyanisole and 1.88 g of triethylamine are mixed with the thioether prepolymer 4 in the step (1), stirring is kept, and the temperature is slowly increased to 52 ℃ for reaction until the infrared spectrum of the reactant is located at 2568cm -1 The mercapto characteristic peak of (2) disappeared to obtain hyperbranched prepolymer 4.
(3) Adding 1.1 g of hydroquinone into the hyperbranched prepolymer 4 in the step (2), keeping stirring, dripping 262.7 g of diethanolamine, slowly heating to 60 ℃, and continuously reacting for 8 hours to obtain the efficient auxiliary initiator 4.
Example 5 Performance test example
Polyurethane acrylic acid ester 6201 (produced by Jiangsu Sanmu chemical Co., ltd.) and 1, 6-hexanediol diacrylate (HDDA, produced by Jiangsu Sanmu chemical Co., ltd.) were uniformly mixed in a mass ratio of 7:3 to obtain a matrix resin.
The following formulations of the high-efficiency co-initiators 1 to 4 prepared in examples 1 to 4, the commercial product co-initiator 6338 (manufactured by Jiangsu Sanmu chemical Co., ltd.), the co-initiator P115 (manufactured by Belgium Zhangxin) and the matrix resin, and the photo-initiator benzophenone (manufactured by Jiangsu Sanmu chemical Co., ltd.) were prepared to obtain photo-curing varnishes according to the following formulation of Table 1.
TABLE 1 photo-curable varnish formulations
| 1# | 2# | 3# | 4# | 5# | 6# | |
| Matrix resin | 92 | 92 | 92 | 92 | 92 | 92 |
| Photoinitiator diphenyl ketone | 2 | 2 | 2 | 2 | 2 | 2 |
| High efficiency co-initiator 1 | 6 | |||||
| High efficiency co-initiator 2 | 6 | |||||
| High-efficiency auxiliary initiator3 | 6 | |||||
| High efficiency co-initiator 4 | 6 | |||||
| Auxiliary initiator 6338 (three-wood) | 6 | |||||
| Co-initiator P115 (Zhan Xin) | 6 |
Taking a varnish sample prepared in Table 1, coating a film on a glass plate by using a wire rod to obtain a coating film with the thickness of about 25 micrometers, and then irradiating by using a mercury lamp light source to respectively determine the energy required for surface drying and the gel content of a cured film; the corresponding co-initiators in the 1# to 6# formulations were used to determine their own odor and the results are shown in Table 2.
TABLE 2 comparative results of the film properties of photo-curable varnishes
Gel content test:
taking a certain mass of solidified film (mass is m 1 ) Wrapping with filter paper, refluxing with acetone in Soxhlet extractor for 48 hr, taking out, drying to constant weight, and weighing the dried solidified film with mass of m 2 The calculation formula is as follows:
gel content= (m 1 -m 2 )/m 1 *100％
The lower the gel content means that the less material participates in the crosslinking reaction, whereas the higher the gel content, the more material participates in the crosslinking reaction.
Odor test:
the corresponding co-initiators in the 1# to 6# formulations were placed in weighing bottles of the same size with samples of the same mass, sealed for 24 hours, removed and evaluated for odor, and scored according to the criteria of table 3 below.
TABLE 3 Table 3
Compared with the current commercial auxiliary initiator, the ultraviolet curing auxiliary initiator has the advantages that various reaction raw material compositions are screened through a large number of experiments, and the high-efficiency auxiliary initiator for ultraviolet curing has the advantages of high polymerization rate, low mobility and low odor, and good technical effect.
Claims (2)
1. The preparation method of the efficient co-initiator for ultraviolet light curing is characterized by comprising the following steps of:
(1) Reacting dithiol with a diacrylate monomer to synthesize a thioether prepolymer;
(2) Reacting a thioether prepolymer with a polyfunctional acrylic monomer to obtain a hyperbranched prepolymer;
(3) Secondary amine is used for reacting with hyperbranched prepolymer, so that a high-efficiency auxiliary initiator is obtained;
the method for synthesizing the thioether prepolymer in the step (1) comprises the following steps: placing dithiol, diacrylate monomer and catalyst with certain mass into a reaction flask, slowly heating to 45-50 ℃ for reaction until the infrared spectrogram of the reactant is positioned at 810cm -1 The double bond characteristic peak of (2) disappears;
the synthetic method of the hyperbranched prepolymer in the step (2) comprises the following steps: putting a certain mass of thioether prepolymer, a polyfunctional acrylic monomer, a catalyst and a polymerization inhibitor into a reaction flask, slowly heating to 50-55 ℃ for reaction until the infrared spectrogram of the reactant is positioned at 2568cm -1 The thiol characteristic peak of (2) disappears;
the synthesis method of the efficient auxiliary initiator in the step (3) comprises the following steps: firstly, placing a certain mass of hyperbranched prepolymer and a polymerization inhibitor into a reaction flask, then dripping secondary amine into the flask, slowly heating to 60 ℃, and reacting for 8 hours at 60 ℃;
the dithiol is selected from one or more of ethylene glycol di (3-mercaptopropionic acid) ester, ethylene glycol di (2-mercaptoacetic acid) ester, 1, 4-butanediol di (3-mercaptopropionic acid) ester, 1, 4-butanediol di (2-mercaptoacetic acid) ester, neopentyl glycol di (3-mercaptopropionic acid) ester, neopentyl glycol di (2-mercaptoacetic acid) ester, 1, 6-hexanediol di (3-mercaptopropionic acid) ester, 1, 6-hexanediol di (2-mercaptoacetic acid) ester, polyethylene glycol di (3-mercaptopropionic acid) ester, polyethylene glycol di (2-mercaptoacetic acid) ester, polypropylene glycol di (3-mercaptopropionic acid) ester and polypropylene glycol di (2-mercaptoacetic acid) ester;
the diacrylate monomer is selected from one or more of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate and 2-methyl-1, 3-propanediol diacrylate;
the multifunctional acrylic monomer is one or more selected from ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate and ditrimethylolpropane tetraacrylate;
the secondary amine is selected from one or more of diethylamine, di-n-propylamine, di-n-butylamine, diethanolamine, morpholine and piperidine;
the catalyst in the step (1) is one or more selected from triethylamine, pyridine, N-methylpiperidine, tri-N-butylamine and triethanolamine, and the addition amount is 0.1% -1.0% of the total mass of the reaction liquid.
2. The method for preparing a high-efficiency co-initiator for ultraviolet light curing according to claim 1, wherein in the step (1), the molar ratio of dithiol to diacrylate monomer is controlled to be 1.5-2.0;
in the step (2), controlling the molar ratio of the double bond in the multifunctional acrylic monomer to the mercapto group in the thioether prepolymer to be 2.0-5.0;
in the step (3), the molar ratio of the double bond to the secondary amine in the hyperbranched prepolymer is controlled to be 1.0-3.0.
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| US4110184A (en) * | 1973-04-24 | 1978-08-29 | Imperial Chemical Industries Limited | Photocurable dental filling compositions |
| CN1526740A (en) * | 2003-03-03 | 2004-09-08 | 珠海东诚化工有限公司 | Photoinitiator composition capable of initiating via visible light and its use |
| CN108329453A (en) * | 2018-03-07 | 2018-07-27 | 长兴（广州）精细涂料有限公司 | A kind of preparation method of novel aqueous light-cured resin |
| CN112250866A (en) * | 2019-07-22 | 2021-01-22 | 江汉大学 | Preparation method of free radical type photocuring resin with thioether as main chain |
| CN114262395A (en) * | 2022-01-05 | 2022-04-01 | 江南大学 | Photocuring system containing sulfonium salt hybrid photoinitiator and application |
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| KR20160150248A (en) * | 2015-06-19 | 2016-12-29 | 주식회사 케이오씨솔루션 | Preparation method of 3-mercaptopropionic acid and preparation method of carbonic acid ester compounds bearing mercapto group and thioepoxy based optical material using it |
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| US4110184A (en) * | 1973-04-24 | 1978-08-29 | Imperial Chemical Industries Limited | Photocurable dental filling compositions |
| CN1526740A (en) * | 2003-03-03 | 2004-09-08 | 珠海东诚化工有限公司 | Photoinitiator composition capable of initiating via visible light and its use |
| CN108329453A (en) * | 2018-03-07 | 2018-07-27 | 长兴（广州）精细涂料有限公司 | A kind of preparation method of novel aqueous light-cured resin |
| CN112250866A (en) * | 2019-07-22 | 2021-01-22 | 江汉大学 | Preparation method of free radical type photocuring resin with thioether as main chain |
| CN114262395A (en) * | 2022-01-05 | 2022-04-01 | 江南大学 | Photocuring system containing sulfonium salt hybrid photoinitiator and application |
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