CN114805642A - Polymerizable benzophenone photoinitiator and preparation method thereof - Google Patents
Polymerizable benzophenone photoinitiator and preparation method thereof Download PDFInfo
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- CN114805642A CN114805642A CN202210239175.2A CN202210239175A CN114805642A CN 114805642 A CN114805642 A CN 114805642A CN 202210239175 A CN202210239175 A CN 202210239175A CN 114805642 A CN114805642 A CN 114805642A
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- benzophenone
- polymerizable
- photoinitiator
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- 239000012965 benzophenone Substances 0.000 title claims abstract description 38
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004593 Epoxy Substances 0.000 claims abstract description 15
- -1 acrylate compound Chemical class 0.000 claims abstract description 11
- 150000008366 benzophenones Chemical class 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 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 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 3
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical compound ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 3
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000000016 photochemical curing Methods 0.000 abstract 2
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PNTLMFABGCHLMN-UHFFFAOYSA-N [4-(2-hydroxyethoxy)phenyl]-phenylmethanone Chemical compound C1=CC(OCCO)=CC=C1C(=O)C1=CC=CC=C1 PNTLMFABGCHLMN-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
- C08F222/205—Esters containing oxygen in addition to the carboxy oxygen the ester chains containing seven or more carbon atoms
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing and preparing a polymerizable benzophenone photoinitiator, which comprises the step of initiating an epoxy ring-opening reaction between a benzophenone derivative containing hydroxyl and an acrylate compound with epoxy groups under the action of a catalyst to ensure that the benzophenone compound has polymerizable unsaturated bonds. In the application of the photocuring coating, the mobility of the photoinitiator is reduced, the odor is reduced, the preparation method is simple, no aftertreatment and no micromolecule removal are performed, and the atom utilization rate is high, so that the method has wide application prospect in the field of photocuring.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a polymerizable benzophenone photoinitiator and a preparation method thereof.
Background
The photopolymerization coating has high efficiency in industrial flow line production, and is widely applied to various aspects of life. Such as wood furniture, packaging materials, dental filling materials, 3D printing materials, and the like.
The photo-polymerization coating mainly comprises a photoinitiator, an oligomer, a monomer and an auxiliary agent. The photoinitiators therein play a crucial role in the polymerization rate and degree of polymerization.
The common benzophenone photoinitiator has obvious defects and shortcomings, mainly has larger smell, and certain toxicity is caused by the migration of residual photoinitiator in materials.
Currently, many people have studied in this field. Neiji et al designed and synthesized a macromolecular benzophenone photoinitiator (Neiji et al, synthesis and performance research of macromolecular benzophenone photoinitiators) and proved that the benzophenone photoinitiator is a high-activity and low-migration photoinitiator. Nee Jun et al synthesized polymerizable photoinitiators by bromination followed by esterification (Polymer Chemistry, 55(2), 313-320), and by reacting epoxidized benzophenone with acrylic acid (CN 102863323A). Wearmy et al synthesized a polymerizable benzophenone photoinitiator (CN 102212151B) containing co-initiator amine, which was capable of initiating polymerization with high activity without the need for additional reactive amine.
However, the existing methods for synthesizing polymerizable photoinitiators are relatively complex, have long routes and high cost, and are disadvantageous to application and popularization of polymerizable photoinitiators.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polymerizable benzophenone photoinitiator and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a polymerizable benzophenone photoinitiator, which has the following chemical structural formula: mono-epoxy reaction product (I) and poly-epoxy reaction product (II):
wherein R1 represents oxygen, ethoxy of O (CH2)2O, propoxy of O (CH2) 3O;
the substitution of R1 in benzophenone is mono-substituted or multi-substituted, and the position of R1 comprises ortho-position, para-position and meta-position relative to the carbonyl position of benzophenone;
said R2 represents hydrogen or methyl;
n is not less than 1 and not more than 9.
The invention also provides a preparation method of the polymerizable benzophenone photoinitiator, which comprises the following steps:
heating and stirring benzophenone derivative A and epoxy acrylate compound B in the presence of a catalyst and a polymerization inhibitor to obtain target products (I) and (II), wherein the reaction formula is as follows:
a is benzophenone derivative, B is epoxy acrylate compound;
(I) is a mono-epoxy reaction product, (II) is a poly-epoxy reaction product;
wherein R1 represents oxygen, ethoxy of O (CH2)2O, propoxy of O (CH2) 3O.
Preferably, the substitution of R1 in benzophenone is mono-or poly-substituted, and the position of R1 comprises ortho, para and meta relative to the carbonyl position of benzophenone;
said R2 represents hydrogen or methyl;
n is not less than 1 and not more than 9.
Preferably, the molar ratio of the benzophenone derivative to the epoxy acrylate compound is 1: 1-1: 10.
preferably, the catalyst is any one or a mixture of more than two of the following;
triphenylphosphine, triphenyl antimony, triethylamine, N-dimethyl benzyl amine, benzyl trimethyl ammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide and chromium acetylacetonate.
Preferably, the dosage of the catalyst is 0.1-5% of the total mass of the reactants.
Preferably, the polymerization inhibitor is any one or a mixture of two or more of the following: p-hydroxyanisole, hydroquinone, tert-butyl hydroquinone, cuprous chloride, phenothiazine and nitroxide radical piperidinol.
Preferably, the dosage of the polymerization inhibitor is 0.01-1% of the total mass of the reactants.
Preferably, the reaction temperature is 50-130 ℃.
Preferably, the reaction time is 2-12 h.
Compared with the prior art, the invention has the following beneficial effects:
1. the polymerizable benzophenone photoinitiator synthesized by the invention can effectively reduce the surface migration and toxicity of the photoinitiator.
2. The photoinitiator synthesis method is simple, few in steps and free of post-treatment.
3. The method has mild reaction conditions and low requirements on reaction equipment.
Drawings
FIG. 1 is a nuclear magnetic H spectrum of a monoepoxy reaction product obtained in example 1;
FIG. 2 is a nuclear magnetic C spectrum of the monoepoxy reaction product obtained in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The polymerizable benzophenone photoinitiator of the embodiment has the following chemical structural formula: mono-epoxy reaction product (I) and poly-epoxy reaction product (II):
wherein R1 represents oxygen, ethoxy of O (CH2)2O, propoxy of O (CH2) 3O;
the substitution of R1 in benzophenone is mono-substituted or multi-substituted, and the position of R1 comprises ortho-position, para-position and meta-position relative to the carbonyl position of benzophenone;
said R2 represents hydrogen or methyl;
n is not less than 1 and not more than 9.
The invention also provides a preparation method of the polymerizable benzophenone photoinitiator, which comprises the following steps:
heating and stirring benzophenone derivative A and epoxy acrylate compound B in the presence of a catalyst and a polymerization inhibitor to obtain target products (I) and (II), wherein the reaction formula is as follows:
a is benzophenone derivative, B is epoxy acrylate compound;
(I) is a mono-epoxy reaction product, (II) is a poly-epoxy reaction product;
wherein R1 represents oxygen, ethoxy group of O (CH2)2O, propoxy group of O (CH2) 3O.
The substitution of R1 in benzophenone is mono-or poly-substituted, and the position of R1 relative to the carbonyl position of benzophenone comprises ortho, para and meta;
said R2 represents hydrogen or methyl;
n is not less than 1 and not more than 9.
The molar ratio of the benzophenone derivative to the epoxy acrylate compound in this example is 1: 1-1: 10.
the catalyst of the embodiment is any one or a mixture of more than two of the following;
triphenylphosphine, triphenyl antimony, triethylamine, N-dimethyl benzyl amine, benzyl trimethyl ammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide and chromium acetylacetonate.
The dosage of the catalyst in the embodiment is 0.1-5% of the total mass of reactants.
The polymerization inhibitor in this embodiment is any one or a mixture of two or more of the following: p-hydroxyanisole, hydroquinone, tert-butyl hydroquinone, cuprous chloride, phenothiazine and nitroxide radical piperidinol.
The dosage of the polymerization inhibitor in the embodiment is 0.01-1% of the total mass of reactants.
The reaction temperature in this example is 50-130 ℃.
The reaction time of the embodiment is 2-12 h.
Example 1
100mL of 0.1mol (19.82 g) of 4-hydroxybenzophenone, 0.2mol (28.43 g) of glycidyl methacrylate, 24mg of p-hydroxyanisole and 480mg of triphenylphosphine were stirred at 100 ℃ for 6 hours, and the reaction was monitored by thin layer chromatography until the starting material reaction was complete. The product was obtained as a yellow oily liquid comprising a mixture of mono-epoxy reaction products and poly-epoxy reaction products. And (3) carrying out column chromatography treatment on the reaction product to obtain a monoepoxy reaction product. FIGS. 1 and 2 are nuclear magnetic H spectrum and nuclear magnetic C spectrum, respectively, of the monoepoxy reaction product obtained in this example. Chemical shifts 1H NMR (400 MHz, CDCl3) of peaks in the hydrogen spectrum of fig. 1 are δ 7.81 (d, J = 8.8 Hz, 2H), 7.74 (d, J = 7.1 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.5 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H), 6.15 (s, 1H), 5.62 (s, 1H), 4.43-4.36 (m, 2H), 4.32 (dt, J = 9.7, 3.9 Hz, 1H), 4.14 (H, J = 4.3 Hz, 2H), 2.93 (s, 1H), 1.96 (s, 3H); chemical shifts 13C NMR (100MHz, CDCl3) of peaks in the carbon spectrum of fig. 2 were δ 195.54, 167.46, 161.85, 137.99, 135.71, 132.53, 131.99, 130.61, 129.70, 128.17, 126.41, 114.02, 68.86, 68.42, 65.48, 18.28, confirming that the obtained substance was the target compound.
Example 2
100mL of 0.1mol (19.82 g) of 4-hydroxybenzophenone, 0.2mol (28.43 g) of glycidyl methacrylate, 24mg of p-hydroxyanisole and 480mg of benzyltrimethylammonium chloride were stirred at 100 ℃ for 6 hours, and the reaction was monitored by thin layer chromatography until the starting material reaction was completed. The product was obtained as a yellow oily liquid.
Example 3
100mL of 4-hydroxybenzophenone 0.1mol (19.82 g), glycidyl methacrylate 0.3mol (42.6 g), p-hydroxyanisole 30mg and triphenylphosphine 500mg were stirred at 110 ℃ for 6 hours, and the reaction was monitored by thin layer chromatography until the starting material reaction was complete. The product was obtained as a yellow oily liquid.
Example 4
100mL of 0.1mol (24.2 g) of 4- (2-hydroxyethoxy) benzophenone, 0.2mol (28.43 g) of glycidyl methacrylate, 30mg of p-hydroxyanisole and 500mg of benzyltrimethylammonium chloride were taken, stirred at 100 ℃ for 6 hours, and the reaction was monitored by thin layer chromatography until the starting material reaction was complete. The product was obtained as a yellow oily liquid.
Example 5
Taking 0.4g of the yellow oily product obtained in the example 1, uniformly mixing the polyurethane acrylate W2524B 10g produced by the company, taking 0.4g of the yellow oily product, coating the mixture by using a film coater to form a film with the thickness of 50 mu m, irradiating and curing the film by using a UV machine, and testing the surface dryness by using a drying method to be good, which shows that the photoinitiator synthesized by the invention still keeps good initiation performance after polymerizable double bonds are introduced.
Comparative example 1
Commercial products: benzophenone, BP for short
Comparative example 2
Commercial products: 4-methylbenzophenone, CBP for short
Comparative example 3
Commercial products: 4-phenyl benzophenone PBZ for short
Performance testing
The formulation was designed and the same molar amount of initiator was added, the specific formulation is shown in table 1. The gel fraction was measured as follows: the formula is uniformly coated on the surface of glass with the area of 16cm 2 Thickness of 45 μm, curing under 500W Hg lamp for 15 s, wrapping with metal screen, placing into Soxhlet extractor, and dissolving with butanoneAnd (4) refluxing and extracting for 8 hours, and testing the gel rate. Comparison of odor: is judged by human olfaction after solidification.
TABLE 1
Unit: g
The performance data for the products of examples 1, 4 and comparative examples 1-3 were tested, and Table 2 is as follows
As can be seen from examples 1 and 4 and comparative examples 1 to 3, when the initiator with the same molar weight is added, the gel rate of the product is high, and the performance of the initiator of the product is good and is superior to that of the product in the market.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A polymerizable benzophenone photoinitiator is characterized by having the following chemical structural formula: mono-epoxy reaction product (I) and poly-epoxy reaction product (II):
wherein R1 represents oxygen, ethoxy of O (CH2)2O, propoxy of O (CH2) 3O;
the substitution of R1 in benzophenone is mono-substituted or multi-substituted, and the position of R1 comprises ortho-position, para-position and meta-position relative to the carbonyl position of benzophenone;
said R2 represents hydrogen or methyl;
n is not less than 1 and not more than 9.
2. The preparation method of the polymerizable benzophenone photoinitiator is characterized by comprising the following steps:
heating and stirring benzophenone derivative A and epoxy acrylate compound B in the presence of a catalyst and a polymerization inhibitor to obtain target products (I) and (II), wherein the reaction formula is as follows:
a is benzophenone derivative, B is epoxy acrylate compound;
(I) is a mono-epoxy reaction product, (II) is a poly-epoxy reaction product;
wherein R1 represents oxygen, ethoxy of O (CH2)2O, propoxy of O (CH2) 3O.
3. A polymerizable benzophenone-type photoinitiator according to claim 2 wherein the substitution of R1 in benzophenone is mono-or poly-substituted and the position of R1 comprises ortho, para, meta with respect to the carbonyl position of benzophenone;
said R2 represents hydrogen or methyl;
n is not less than 1 and not more than 9.
4. The polymerizable benzophenone-based photoinitiator according to claim 1, wherein the molar ratio of the benzophenone derivative to the epoxy acrylate compound is 1: 1-1: 10.
5. the polymerizable benzophenone-based photoinitiator according to claim 1, wherein the catalyst is any one or a mixture of two or more of the following;
triphenylphosphine, triphenyl antimony, triethylamine, N-dimethyl benzyl amine, benzyl trimethyl ammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide and chromium acetylacetonate.
6. The polymerizable benzophenone photoinitiator according to claim 5, wherein the amount of the catalyst is 0.1-5% of the total mass of the reactants.
7. The polymerizable benzophenone-based photoinitiator according to claim 1, wherein the polymerization inhibitor is any one or a mixture of two or more of the following: p-hydroxyanisole, hydroquinone, tert-butyl hydroquinone, cuprous chloride, phenothiazine and nitroxide radical piperidinol.
8. The polymerizable benzophenone photoinitiator as claimed in claim 7, wherein the polymerization inhibitor is used in an amount of 0.01-1% of the total mass of the reactants.
9. A polymerizable benzophenone-type photoinitiator according to claim 1, wherein the reaction temperature is 50 to 130 ℃.
10. The polymerizable benzophenone-based photoinitiator according to claim 9, wherein the reaction time is 2-12 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115572229A (en) * | 2022-11-10 | 2023-01-06 | 江苏三木化工股份有限公司 | Preparation method of polymerizable photoinitiator based on alpha-hydroxyketone |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3173893A (en) * | 1962-06-18 | 1965-03-16 | Nat Starch Chem Corp | Polymeric compositions resistant to ultra-violet light containing benzophenone derivatives |
| US3429852A (en) * | 1967-03-30 | 1969-02-25 | Nat Starch Chem Corp | Ethylenically unsaturated derivatives of benzophenone and crosslinkable polymers thereof |
| US4177122A (en) * | 1978-01-13 | 1979-12-04 | Toyo Ink Manufacturing Co., Ltd. | Photopolymerizable hydroxy-benzophenone derivative compounds and photocurable compositions |
| CN1727320A (en) * | 2005-02-03 | 2006-02-01 | 常州华钛化学有限公司 | reactive benzophenone photoinitiator and preparation method thereof |
| CN101333278A (en) * | 2008-08-07 | 2008-12-31 | 北京化工大学 | Method for preparing water-soluble polymerisable macromolecule photoinitiator |
| 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 |
-
2022
- 2022-03-11 CN CN202210239175.2A patent/CN114805642A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3173893A (en) * | 1962-06-18 | 1965-03-16 | Nat Starch Chem Corp | Polymeric compositions resistant to ultra-violet light containing benzophenone derivatives |
| US3429852A (en) * | 1967-03-30 | 1969-02-25 | Nat Starch Chem Corp | Ethylenically unsaturated derivatives of benzophenone and crosslinkable polymers thereof |
| US4177122A (en) * | 1978-01-13 | 1979-12-04 | Toyo Ink Manufacturing Co., Ltd. | Photopolymerizable hydroxy-benzophenone derivative compounds and photocurable compositions |
| CN1727320A (en) * | 2005-02-03 | 2006-02-01 | 常州华钛化学有限公司 | reactive benzophenone photoinitiator and preparation method thereof |
| CN101333278A (en) * | 2008-08-07 | 2008-12-31 | 北京化工大学 | Method for preparing water-soluble polymerisable macromolecule photoinitiator |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| LIN ET AL: "Photoreactive Polymers Bearing a Zwitterionic Phosphorylcholine Group for Surface Modification of Biomaterials", 《APPLIED MATERIALS & INTERFACES》, no. 7, pages 17489 - 17498 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115572229A (en) * | 2022-11-10 | 2023-01-06 | 江苏三木化工股份有限公司 | Preparation method of polymerizable photoinitiator based on alpha-hydroxyketone |
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