CN111269336A - Polymerizable photoinitiator and preparation method thereof - Google Patents
Polymerizable photoinitiator and preparation method thereof Download PDFInfo
- Publication number
- CN111269336A CN111269336A CN202010204680.4A CN202010204680A CN111269336A CN 111269336 A CN111269336 A CN 111269336A CN 202010204680 A CN202010204680 A CN 202010204680A CN 111269336 A CN111269336 A CN 111269336A
- Authority
- CN
- China
- Prior art keywords
- stirring
- organic solvent
- photoinitiator
- parts
- 30min
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- KZNIFHPLKGYRTM-UHFFFAOYSA-N apigenin Chemical compound C1=CC(O)=CC=C1C1=CC(=O)C2=C(O)C=C(O)C=C2O1 KZNIFHPLKGYRTM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940117893 apigenin Drugs 0.000 claims abstract description 10
- XADJWCRESPGUTB-UHFFFAOYSA-N apigenin Natural products C1=CC(O)=CC=C1C1=CC(=O)C2=CC(O)=C(O)C=C2O1 XADJWCRESPGUTB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000008714 apigenin Nutrition 0.000 claims abstract description 10
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical class C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 39
- 239000003960 organic solvent Substances 0.000 claims description 26
- 239000002966 varnish Substances 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000013067 intermediate product Substances 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 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 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- DEDZSLCZHWTGOR-UHFFFAOYSA-N propylcyclohexane Chemical group CCCC1CCCCC1 DEDZSLCZHWTGOR-UHFFFAOYSA-N 0.000 claims description 6
- 125000004386 diacrylate group Chemical group 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 claims description 2
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- AXTLFVLHXSDZOW-UHFFFAOYSA-N n-ethyl-2-methylprop-2-en-1-amine Chemical compound CCNCC(C)=C AXTLFVLHXSDZOW-UHFFFAOYSA-N 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 10
- 230000005012 migration Effects 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 230000005764 inhibitory process Effects 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 239000003999 initiator Substances 0.000 abstract description 7
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 238000000016 photochemical curing Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 150000003512 tertiary amines Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 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
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- SMBYUOXUISCLCF-UHFFFAOYSA-N n-ethyl-n-methylpropan-1-amine Chemical compound CCCN(C)CC SMBYUOXUISCLCF-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- ZZIZZTHXZRDOFM-XFULWGLBSA-N tamsulosin hydrochloride Chemical compound [H+].[Cl-].CCOC1=CC=CC=C1OCCN[C@H](C)CC1=CC=C(OC)C(S(N)(=O)=O)=C1 ZZIZZTHXZRDOFM-XFULWGLBSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to the field of new materials. The invention relates to a polymerizable photoinitiator and a preparation method thereof, and the polymerizable photoinitiator material is obtained by taking apigenin, bromohydrocarbon, a secondary amino structure, a 4-hydroxybenzophenone derivative and acryloyl chloride as raw materials through multi-step coupling reaction. The novel polymerizable photoinitiator not only effectively solves the problems of oxygen inhibition, addition of a co-initiator, easy migration, environmental pollution and the like existing in the conventional micromolecular photoinitiator, but also has high-efficiency antibacterial performance, can be expected to have wide market prospect in the field of photocuring, and is particularly suitable for the fields of food packaging, medical treatment and the like.
Description
Technical Field
The invention relates to a polymerizable photoinitiator and a preparation method thereof. The invention belongs to the field of new materials.
Background
Since the concept of photoinitiators was first proposed in environmentally friendly and energy saving UV curable coatings developed by Bayer corporation in germany in 1968, photoinitiators were successively applied to the development of a variety of UV curable products in countries around the world. In recent years, with the increasing perfection of energy-saving and environment-friendly regulations, new requirements are put on UV curing products, and thus higher requirements are put on photoinitiators. The traditional photoinitiator is a micromolecular photoinitiator which has the defects of easy volatilization, easy migration, low initiation efficiency, high viscosity, easy yellowing, odor and the like, so that the development requirement of rapidness and environmental protection in the industrial production process is difficult to meet.
While macromolecular photoinitiators can effectively solve the above problems. The macromolecular photoinitiator contains a plurality of photoactive groups on a molecular chain, and can generate free radicals under the illumination condition; the free radicals further initiate the functional group monomer to polymerize, so that the polymer has excellent properties of high activity, low volatility, low toxicity, environmental protection, miscibility, low mobility and the like. However, the macro-photoinitiators also have some disadvantages, such as general initiation efficiency, excessive cost, etc.
Therefore, new macromolecular photoinitiators are gradually receiving a great deal of attention. It is an urgent task to develop a small molecule photoinitiator which can be self-initiated to become a macroinitiator and can also be cross-linked to polymerize, thus avoiding the disadvantages of the traditional photoinitiator such as easy volatilization, easy migration, low initiation efficiency and pungent odor.
Disclosure of Invention
The invention aims to solve the problems of oxygen inhibition, addition of an auxiliary initiator, easy migration and environmental pollution caused by the existence of a small molecular photoinitiator in the prior art, and the like, and provides a polymerizable photoinitiator and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a polymerizable photoinitiator having the formula:
wherein x is 2-4; -R1、-R2、-R3is-OCH3、-Cl、-CH3、-C6H6Any one of-H, -R1、-R2、-R3Are independent substituents.
A method for preparing a polymerizable photoinitiator is characterized by comprising the following steps: comprises the following steps:
step (1): coupling reaction to obtain an apigenin modified intermediate product I;
step (2): coupling reaction to obtain an intermediate product II;
and (3): coupling reaction to obtain an intermediate product III;
and (4): coupling reaction to obtain an intermediate product IV;
and (5): coupling reaction to obtain polymerizable photoinitiator, namely the target product V.
Preferably, the step (1) is specifically:
adding 1mol of apigenin (A), 1-1.2mol of bromoalkane (B) and 1-1.2mol of potassium carbonate into 80mol of organic solvent a, heating to 110-; slowly adding 90mol of water, stirring for 30min, adding 100mol of organic solvent b, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product I.
Preferably, the step (2) is specifically:
adding 1mol of I and 1-1.2mol of secondary amino structural derivative (C) into 50mol of anhydrous organic solvent a, heating to 75-85 ℃, strongly stirring for 2-5h, cooling, standing, and vacuum concentrating; slowly adding 70mol of water, stirring for 30min, adding 100mol of organic solvent b, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product II.
Preferably, the step (3) is specifically:
adding 1mol of II, 1-1.2mol of bromoalkane (B) and 1-1.2mol of potassium carbonate into 80mol of organic solvent a, heating to 110-; slowly adding 90mol of water, stirring for 30min, adding 100mol of organic solvent b, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product III.
Preferably, the step (4) is specifically:
adding 1mol of III, 1-1.2mol of 4-hydroxybenzophenone derivative (D) and 1-1.2mol of potassium carbonate into 50mol of organic solvent a, heating to 120-130 ℃, strongly stirring for 3-6h, cooling, standing, and then carrying out vacuum concentration on the solution, wherein the residual components are enriched; slowly adding 90mol of water, stirring for 30min, adding 100mol of organic solvent b, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV.
Preferably, the step (5) is specifically:
adding 1mol of III, 1-1.5mol of triethylamine and 0.5mol of 4-dimethylaminopyridine into 50mol of organic solvent c, carrying out ice-water bath, stirring, slowly dripping 1-1.5mol of acryloyl chloride (E) into the solution, and stirring for 6-12 h; standing, distilling under reduced pressure, adding residual components into 100mol of organic solvent b, washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated saline solution respectively, separating liquid, drying an organic phase with anhydrous sodium sulfate, filtering, drying in vacuum, and recrystallizing the obtained solid with ethanol to obtain the polymerizable photoinitiator, namely the target product V.
Preferably, the organic solvent a is N, N-dimethylformamide or dimethyl sulfoxide.
Preferably, the organic solvent c is N, N-dimethylformamide, tetrahydrofuran or dimethylsulfoxide.
Preferably, the organic solvent b is ethyl acetate, dichloromethane or dimethyl sulfoxide.
Preferably, the secondary amino structure derivative is N-propylcyclohexane, dihexylamine, diisopropylamine, 3-methylpiperidine, N-ethylmethylpropylamine or N-ethylisopropylamine.
The light-cured varnish is prepared from the following raw materials in parts by weight: the adhesive comprises the following components, by weight, SM620563-67 parts of aliphatic polyurethane diacrylate, 10 parts of TMPTA, 10 parts of TPGDA, 12 parts of butyl acrylate and 5-78 parts of a target product V1.
Preferably, the preparation method of the light-cured varnish is as follows: the raw materials were mixed in parts by weight in a dark room, coated on primed PET and then irradiated under UV light for 10-180s to give a dry film 2 μm thick clear coat.
The preparation process of the novel polymerizable photoinitiator provided by the invention comprises the following steps:
the invention has the beneficial effects that:
(1) the invention provides a preparation method of a polymerizable photoinitiator, which adopts apigenin, bromohydrocarbon, a secondary amino structure, a 4-hydroxybenzophenone derivative and acryloyl chloride as raw materials to prepare a novel polymerizable photoinitiator, solves the defects of environmental protection caused by oxygen inhibition or easy migration due to the need of adding an auxiliary initiator in the traditional small-molecule photoinitiator, and has the advantages of wide raw material source, simple reaction steps and easy operation.
(2) The invention provides a polymerizable photoinitiator, wherein a tertiary amine structure is introduced into a target product. On one hand, the tertiary amine as the co-initiator directly exists in a molecular structure and can be directly used; on the other hand, the benzophenone and tertiary amine structures exist in the same molecule at the same time, so that energy transfer is facilitated, and the initiation efficiency is higher.
(3) The invention provides a polymerizable photoinitiator, and a target product contains a benzophenone structure. Because the benzophenone is a common hydrogen abstraction type photoinitiator, the defect of oxygen inhibition is avoided.
(4) The invention provides a polymerizable photoinitiator, and a target product contains an apigenin structure. Firstly, apigenin is a naturally-occurring substance, and has wide source and good biocompatibility; secondly, apigenin can be used as an active point of reaction for chemical modification; finally, apigenin has excellent antibacterial and bactericidal effects.
(5) The invention provides a polymerizable photoinitiator which can be used as a photoinitiator and can also be used as a UV light curing monomer, namely, the polymerizable photoinitiator has the effect of self-initiating self-crosslinking.
(6) The invention provides a polymerizable photoinitiator, which solves the problems of environmental pollution and the like caused by oxygen inhibition or addition of an auxiliary initiator, easy migration and the like of the existing small-molecule photoinitiator by molecular design and chemical modification means, and has the functions of antibiosis and sterilization while the material has high-efficiency photoinitiation efficiency. It is expected that the material will meet wide market prospects.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.
Example 1
Adding 1mol of apigenin (A), 1.2mol of 1, 2-dibromoethane (B) and 1.2mol of potassium carbonate into 80mol of N, N-dimethylformamide, heating to 120 ℃, stirring strongly for 2h, cooling, standing, and then carrying out vacuum concentration on the solution, wherein residual components are enriched; slowly adding 90mol water, stirring for 30min, adding 100mol dichloromethane, stirring for 30min, standing for layering, drying organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain intermediate I (IR: 1638 cm)-1: -C ═ C-is present; 1581cm-1、1473cm-1、1444cm-1: a benzene ring is present; 3512cm-1: the phenol-OH is weakened; 640cm-1: -C-Br generation).
Step (2) adding 1mol of I and 1.1mol of N-propylcyclohexane (C) into 50mol of anhydrous N, N-dimethylformamide, heating to 85 ℃, stirring strongly for 2h, cooling, standing, and concentrating in vacuum; slowly adding 70mol water, stirring for 30min, adding 100mol dichloromethane, stirring for 30min, standing for layering, drying organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain intermediate product II (IR: 1635 cm)-1: -C ═ C-is present; 1580cm-1、1472cm-1、1440cm-1: a benzene ring is present; 3509cm-1: phenol-OH is present; 1050cm-1: tertiary amine-C-N-formation; 640cm-1: disappearance of-C-Br).
Step (3) adding 1mol of II, 1.2mol of 1, 2-dibromoethane (B) and 1.2mol of potassium carbonate into 80mol of N, N-dimethylformamide, heating to 120 ℃, stirring strongly for 2h, cooling,after standing, carrying out vacuum concentration on the solution, and enriching residual components; slowly adding 90mol water, stirring for 30min, adding 100mol dichloromethane, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain intermediate product III (IR: 1637 cm)-1: -C ═ C-is present; 1580cm-1、1470cm-1、1439cm-1: a benzene ring is present; 3511cm-1: phenol-OH is present; 1050cm-1: tertiary amine-C-N-is present; 646cm-1: -C-Br generation).
Step (4) adding 1mol of III, 1.1mol of 4-hydroxybenzophenone (D) and 1.1mol of potassium carbonate into 50mol of N, N-dimethylformamide, heating to 120 ℃, stirring strongly for 6h, cooling, standing, concentrating the solution in vacuum, and enriching residual components; slowly adding 90mol water, stirring for 30min, adding 100mol dichloromethane, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain intermediate product IV (IR: 1637 cm)-1: -C ═ C-is present; 1580cm-1、1470cm-1、1440cm-1: a benzene ring is present; 3511cm-1: phenol-OH is present; 1050cm-1: tertiary amine-C-N-is present; 1690cm-1: (ii) an aryl ketone-C ═ O is present; 647cm-1: disappearance of-C-Br).
Step (5), adding 1mol of III, 1.2mol of triethylamine and 0.5mol of 4-dimethylaminopyridine into 50mol of anhydrous tetrahydrofuran, carrying out ice-water bath, stirring, slowly dripping 1.2mol of acryloyl chloride (E) into the solution, and stirring for 10 hours; standing, distilling under reduced pressure, adding residual components into 100mol of dichloromethane, washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated sodium chloride solution, separating, drying organic phase with anhydrous sodium sulfate, filtering, vacuum drying, recrystallizing the obtained solid with ethanol to obtain polymerizable photoinitiator, namely the target product V (IR: 1637 cm)-1、811cm-1: -C ═ C-is present; 1580cm-1、1470cm-1、1440cm-1: a benzene ring is present; 1050cm-1: tertiary amine-C-N-is present; 3511cm-1: disappearance of phenol-OH, 1690cm-1、1710cm-1: -C ═ O)。
Examples 2-6, otherwise identical to example 1, differ as set forth in the following table:
the polymerizable photoinitiator obtained in specific example 1 was used as a base material of application examples, and was prepared into a photocurable varnish.
Application example 1
The preparation method of the light-cured varnish comprises the following formula and steps:
the light-cured varnish is prepared from the following raw materials in parts by weight: aliphatic polyurethane diacrylate SM 620566 parts, TMPTA 10 parts, TPGDA 10 parts, butyl acrylate 12 parts and target product V2 parts.
The preparation method of the light-cured varnish comprises the following steps: the raw materials are mixed according to the weight part, coated on PET with a base coat, and irradiated for 180s under UV light to obtain a varnish coating with the thickness of 2 mu m of a dry film.
Application examples 2 to 5 were conducted in the same manner as in application example 1 except for the differences shown in the following Table
Practical example comparative example 1
The preparation method of the light-cured varnish comprises the following formula and steps:
the light-cured varnish is prepared from the following raw materials in parts by weight: aliphatic urethane diacrylate SM 620566 parts, TMPTA 10 parts, TPGDA 10 parts, butyl acrylate 12 parts, 1842 parts.
The preparation method of the light-cured varnish comprises the following steps: the raw materials are mixed according to the weight part, coated on PET with a base coat, and irradiated for 180s under UV light to obtain a varnish coating with the thickness of 2 mu m of a dry film.
Practical example comparative example 2
The preparation method of the light-cured varnish comprises the following formula and steps:
the light-cured varnish is prepared from the following raw materials in parts by weight: aliphatic urethane diacrylate SM 620566 parts, TMPTA 10 parts, TPGDA 10 parts, butyl acrylate 12 parts, 11732 parts.
The preparation method of the light-cured varnish comprises the following steps: the raw materials are mixed according to the weight part, coated on PET with a base coat, and irradiated for 180s under UV light to obtain a varnish coating with the thickness of 2 mu m of a dry film.
Practical example comparative example 3
The preparation method of the light-cured varnish comprises the following formula and steps:
the light-cured varnish is prepared from the following raw materials in parts by weight: aliphatic polyurethane diacrylate SM 620566 parts, TMPTA 10 parts, TPGDA 10 parts, butyl acrylate 12 parts and TPO 2 parts.
The preparation method of the light-cured varnish comprises the following steps: the raw materials are mixed according to the weight part, coated on PET with a base coat, and irradiated for 180s under UV light to obtain a varnish coating with the thickness of 2 mu m of a dry film.
Practical example comparative example 4
The preparation method of the light-cured varnish comprises the following formula and steps:
the light-cured varnish is prepared from the following raw materials in parts by weight: aliphatic polyurethane diacrylate SM 620566 parts, TMPTA 10 parts, TPGDA 10 parts, butyl acrylate 12 parts, BP 2 parts and EDAB 2 parts.
The preparation method of the light-cured varnish comprises the following steps: the raw materials are mixed according to the weight part, coated on PET with a base coat, and irradiated for 180s under UV light to obtain a varnish coating with the thickness of 2 mu m of a dry film.
Physical properties including migration, initiation efficiency, antibacterial property, and the like of the polymerizable photoinitiators prepared in practical examples 1 to 5 of the present invention and practical examples 1 to 4 were measured, respectively, and the results are shown in table 1.
Table 1 physical test properties of the examples
Firstly, as can be seen from table 1, compared with the conventional common small molecule photoinitiator, the polymerizable photoinitiator of the present invention has a molecular structure containing a UV-polymerizable structure, and can react with UV resin or a monomer, so that the polymerizable photoinitiator is bonded in a main resin in a form of a chemical bond and can form a macromolecular photoinitiator through self-crosslinking, and therefore, the polymerizable photoinitiator is difficult to migrate, has no odor and no yellowing, and is more environment-friendly;
secondly, compared with the conventional hydrogen abstraction photoinitiator BP, the polymerizable photoinitiator simultaneously contains benzophenone and tertiary amine structures in a molecular structure, does not need to be added with an auxiliary initiator, and has more efficient energy transfer;
thirdly, compared with the conventional common cracking photoinitiator, the polymerizable photoinitiator has the initiating efficiency equivalent to that of TPO and does not have the problem of oxygen inhibition;
fourth, compared with the conventional common photoinitiator, the polymerizable photoinitiator has the antibacterial property which is not possessed by other photoinitiators because the apigenin in the structure has natural antibacterial property.
In sum, compared with the existing photoinitiator, the polymerizable photoinitiator disclosed by the invention not only overcomes the defects of oxygen inhibition or need of an auxiliary initiator and easiness in migration and precipitation of the traditional micromolecular photoinitiator, but also has high-efficiency antibacterial property. Has wide market prospect, and is particularly suitable for the fields of food packaging, medical treatment and the like.
The test method comprises the following steps:
(1) odor: the lower the odor, the less migration is indicated, as evaluated by the direct fan-smelling method.
(2) Mobility: and (3) soaking the sample to be tested in acetonitrile for 24h in a 40 ℃ oven, preparing the same concentration, and testing the molar absorption coefficient of the sample under the corresponding photoinitiator by using an ultraviolet-visible spectrometer. Migration representation method: 5 is optimal and 1 is worst.
(3) Film color: the darker the film color, the darker the yellowing, as observed directly with the naked eye.
(4) Oxygen inhibition and initiation efficiency test of double bond:
the test method comprises the following steps: the polymerization kinetics of the photocurable resin was monitored by a series of real-time infrared spectroscopy. Coating a sample containing photoinitiator on a KBr salt sheet, then putting into RTIR, irradiating with an ultraviolet point source for 120s for curing, wherein the light intensity is measured by a UV-A ultraviolet radiometer and is set to 80mW/cm2. By monitoring the near infrared region C-H at 776-828 cm--1The change in the absorption peak area of (2) intuitively reflects the degree of progress of polymerization. The double bond conversion rate (DC) of the polymerization system can be calculated by combining OMNIC 8.2 infrared software and Excel data processing software with a formula, each sample is tested and repeated for 3 times, and an average value is taken.
Wherein DC represents the conversion rate of carbon-carbon double bonds when the illumination time is t, A0Represents the initial area of the double bond absorption peak before illumination, AtRepresents the double bond absorption peak area at the time of illumination t.
(5) Refer to GB4789.2-2010 food safety national standard food microbiology test colony total determination.
Stirring the above composition under yellow light, taking out, coating on PET template, drying at 90 deg.C for 2min to obtain coating film with dry film thickness of 2 μm, cooling to room temperature, and using high-pressure mercury lamp (exposure of 150m J/cm)2) The coating film is exposed to light and cured to form a film.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. A polymerizable photoinitiator, characterized by the following structural formula:
wherein x is 2-3; -R1、-R2、-R3is-OCH3、-Cl、-CH3、-C6H6Any one of-H, -R1、-R2、-R3Are independent substituents.
2. A method for preparing a polymerizable photoinitiator is characterized by comprising the following steps: comprises the following steps:
step (1): adding 1mol of apigenin (A), 1-1.2mol of bromoalkane (B) and 1-1.2mol of potassium carbonate into 80mol of organic solvent a, heating to 110-; slowly adding 90mol of water, stirring for 30min, adding 100mol of organic solvent b, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product I;
step (2): adding 1mol of I and 1-1.2mol of secondary amino structural derivative (C) into 50mol of anhydrous organic solvent a, heating to 75-85 ℃, strongly stirring for 2-5h, cooling, standing, and vacuum concentrating; slowly adding 70mol of water, stirring for 30min, adding 100mol of organic solvent b, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product II;
and (3): adding 1mol of II, 1-1.2mol of bromoalkane (B) and 1-1.2mol of potassium carbonate into 80mol of organic solvent a, heating to 110-; slowly adding 90mol of water, stirring for 30min, adding 100mol of organic solvent b, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product III;
and (4): adding 1mol of III, 1-1.2mol of 4-hydroxybenzophenone derivative (D) and 1-1.2mol of potassium carbonate into 50mol of organic solvent a, heating to 120-130 ℃, strongly stirring for 3-6h, cooling, standing, and then carrying out vacuum concentration on the solution, wherein the residual components are enriched; slowly adding 90mol of water, stirring for 30min, adding 100mol of organic solvent b, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain an intermediate product IV;
and (5): adding 1mol of III, 1-1.5mol of triethylamine and 0.5mol of 4-dimethylaminopyridine into 50mol of organic solvent c, carrying out ice-water bath, stirring, slowly dripping 1-1.5mol of acryloyl chloride (E) into the solution, and stirring for 6-12 h; standing, distilling under reduced pressure, adding residual components into 100mol of organic solvent b, washing with 1M dilute hydrochloric acid solution, deionized water, saturated sodium bicarbonate solution and saturated saline solution respectively, separating liquid, drying an organic phase with anhydrous sodium sulfate, filtering, drying in vacuum, and recrystallizing the obtained solid with ethanol to obtain the polymerizable photoinitiator, namely the target product V.
3. The method of claim 2, wherein the photoinitiator is selected from the group consisting of: the organic solvent a is N, N-dimethylformamide or dimethyl sulfoxide.
4. The method of claim 2, wherein the photoinitiator is selected from the group consisting of: the organic solvent c is N, N-dimethylformamide, tetrahydrofuran or dimethyl sulfoxide.
5. The method of claim 2, wherein the photoinitiator is selected from the group consisting of: the organic solvent b is ethyl acetate, dichloromethane or dimethyl sulfoxide.
6. The method of claim 2, wherein the photoinitiator is selected from the group consisting of: the secondary amino structure derivative is N-propylcyclohexane, dihexylamine, diisopropylamine, 3-methylpiperidine, N-ethyl methyl allylamine and N-ethyl isopropylamine.
7. The light-cured varnish is prepared from the following raw materials in parts by weight: aliphatic polyurethane diacrylate SM620563-67 parts, TMPTA 10 parts, TPGDA 10 parts, butyl acrylate 12 parts and a target product V1-5 parts.
8. A photocurable varnish according to claim 7 prepared by a process comprising: the raw materials were mixed in parts by weight in a dark room, coated on primed PET and then irradiated under UV light for 10-180s to give a dry film 2 μm thick clear coat.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010204680.4A CN111269336A (en) | 2020-03-22 | 2020-03-22 | Polymerizable photoinitiator and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010204680.4A CN111269336A (en) | 2020-03-22 | 2020-03-22 | Polymerizable photoinitiator and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111269336A true CN111269336A (en) | 2020-06-12 |
Family
ID=71002590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010204680.4A Pending CN111269336A (en) | 2020-03-22 | 2020-03-22 | Polymerizable photoinitiator and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111269336A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894202A (en) * | 2022-12-06 | 2023-04-04 | 常州久日化学有限公司 | Method for treating distillation still residue of photoinitiator 1173 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212150A (en) * | 2011-04-26 | 2011-10-12 | 盐城工学院 | Polymerizable thioxanthone photoinitiator containing auxiliary initiator amine and preparation method thereof |
| CN102863323A (en) * | 2012-08-03 | 2013-01-09 | 北京化工大学常州先进材料研究院 | Method for preparing polymeric benzophenone derivative photoinitiator |
| CN103113498A (en) * | 2013-01-31 | 2013-05-22 | 北京化工大学常州先进材料研究院 | Polymeric photoinitiator and preparation method thereof |
| CN103497263A (en) * | 2013-09-17 | 2014-01-08 | 常州大学 | Benzophenone-containing macromolecular photoinitiator and preparation method thereof |
| CN109265345A (en) * | 2017-07-18 | 2019-01-25 | 北京化工大学常州先进材料研究院 | A kind of fluorine-containing polymerizable photoinitiator and preparation method thereof |
| CN110615861A (en) * | 2019-08-28 | 2019-12-27 | 苏州欧纳克纳米科技有限公司 | Chloroacetate resin-based benzophenone macromolecular photoinitiator and preparation method thereof |
-
2020
- 2020-03-22 CN CN202010204680.4A patent/CN111269336A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212150A (en) * | 2011-04-26 | 2011-10-12 | 盐城工学院 | Polymerizable thioxanthone photoinitiator containing auxiliary initiator amine and preparation method thereof |
| CN102863323A (en) * | 2012-08-03 | 2013-01-09 | 北京化工大学常州先进材料研究院 | Method for preparing polymeric benzophenone derivative photoinitiator |
| CN103113498A (en) * | 2013-01-31 | 2013-05-22 | 北京化工大学常州先进材料研究院 | Polymeric photoinitiator and preparation method thereof |
| CN103497263A (en) * | 2013-09-17 | 2014-01-08 | 常州大学 | Benzophenone-containing macromolecular photoinitiator and preparation method thereof |
| CN109265345A (en) * | 2017-07-18 | 2019-01-25 | 北京化工大学常州先进材料研究院 | A kind of fluorine-containing polymerizable photoinitiator and preparation method thereof |
| CN110615861A (en) * | 2019-08-28 | 2019-12-27 | 苏州欧纳克纳米科技有限公司 | Chloroacetate resin-based benzophenone macromolecular photoinitiator and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894202A (en) * | 2022-12-06 | 2023-04-04 | 常州久日化学有限公司 | Method for treating distillation still residue of photoinitiator 1173 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112358592B (en) | Polyurethane structure photoinitiator and preparation method thereof | |
| CN105037587B (en) | Sensitizer applicable to UV-LED photocuring system | |
| CN112321812A (en) | Polyester type composite photoinitiator and preparation method thereof | |
| CN114478436B (en) | Alpha-aminoketone photoinitiator modified by containing polymerizable itaconic acid group, and preparation method and application thereof | |
| CN110606902B (en) | Novel macromolecular photoinitiator and synthesis method thereof | |
| CN111138290B (en) | Aromatic ring-containing benzophenone derivative and preparation method and application thereof | |
| CN107987244B (en) | Water-based photosensitive supramolecular polyurethane resin and preparation method and application thereof | |
| CN109280002A (en) | A kind of benzophenone analog derivative photoinitiator and preparation method thereof | |
| DE112018007592T5 (en) | MACROMOLECULAR POLYACRYLATE PHOTOINITIATOR, SYNTHESIS METHOD FOR IT, AND USES THEREOF | |
| CN111269336A (en) | Polymerizable photoinitiator and preparation method thereof | |
| CN111218193A (en) | Antibacterial UV varnish and preparation method and application thereof | |
| CN111440082A (en) | Plant oil-based UV resin and pressure-sensitive adhesive | |
| CN110615861B (en) | Chloroacetate resin-based benzophenone macromolecular photoinitiator and preparation method thereof | |
| CN109053934B (en) | Rare earth modified photoinitiator and preparation method thereof | |
| CN102031055A (en) | Volatile organic solvent-free UV spraying finish coat | |
| CN113651904B (en) | Photopolymerizable single-component thioxanthone photoinitiator | |
| CN110776587B (en) | Polymerizable photoinitiator based on benzophenone and preparation method thereof | |
| CN110305086B (en) | Benzophenone derivative containing five-membered heterocycle and preparation method and application thereof | |
| TW201533177A (en) | Photocuring paint and preparation method thereof | |
| CN114751861B (en) | Intramolecular sensitized macromolecular photoinitiator containing pyrazoline and N, N-dialkyl benzoate and preparation method and application thereof | |
| CN110857336B (en) | Polymerizable lignin-based macromolecular photoinitiator and preparation method and application thereof | |
| CN114605572B (en) | Vinyl modified alpha-aminoketone photoinitiator containing polymerizable group and preparation method and application thereof | |
| CN114591452B (en) | Multifunctional macromolecular photoinitiator containing alpha-amino ketone and preparation method and application thereof | |
| Xiao et al. | Synthesis and characterization of copolymerizable one‐component type II photoinitiator | |
| Wang et al. | Benzophenone-1, 3-dioxane as a free radial initiator for photopolymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200612 |