CN115010614B - Alpha-amino ketone difunctional compound, preparation method thereof and photopolymerization initiator thereof - Google Patents

Alpha-amino ketone difunctional compound, preparation method thereof and photopolymerization initiator thereof Download PDF

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CN115010614B
CN115010614B CN202210804454.9A CN202210804454A CN115010614B CN 115010614 B CN115010614 B CN 115010614B CN 202210804454 A CN202210804454 A CN 202210804454A CN 115010614 B CN115010614 B CN 115010614B
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photoinitiator
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amino ketone
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CN115010614A (en
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王桂选
张翠娥
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Hunan Qinrun New Materials Co ltd
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/108—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/14—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated
    • C07C225/16—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
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    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • G03F7/004—Photosensitive materials
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Abstract

The invention provides an alpha-aminoketone difunctional compound, which has a structural general formula shown in (I):

Description

Alpha-amino ketone difunctional compound, preparation method thereof and photopolymerization initiator thereof
Technical Field
The invention belongs to the field of materialogy, relates to a new radiation curing material, and in particular relates to an alpha-amino ketone difunctional compound, a preparation method thereof and a photopolymerization initiator thereof.
Background
In the field of Ultraviolet (UV) radiation curing new materials, photoinitiators (Photo-initiators) are key materials that absorb the energy of UV radiation sources to generate active substances such as free radicals, cations or anions to initiate polymerization of ethylenically unsaturated double bonds or epoxy compounds, vinyl ethers, lactones, acetals, cyclic ethers and the like. The aminoketone compound is a high-activity free radical photopolymerization initiator used for an olefinically unsaturated compound system, and commercial trade mark products include Irgacure 907, irgacure 369, irgacure 379, APi-307 and the like.
However, most photoinitiators generally produce a series of volatile toxic organic compounds (Volatile Organic Compounds, VOCs for short) such as benzaldehyde, acetone, cyclohexanone, thioether, etc., which are not friendly to the environment and even seriously injure the health of human bodies when polymerization occurs. Thus, environmental and health pollution has become an increasing concern in the field of radiation curing, while promoting the continued development of new environmentally friendly photoinitiators, especially in an effort to alleviate and eliminate the above-mentioned drawbacks of conventional commercially available photoinitiators in polymerization applications, including cracking or residual carcinogenicity, contamination of the reproductive toxic compounds benzene/thioether/aromatic hydrocarbons due to compound migration, release of VOCs, and residual unpleasant odors after packaging of finished products (especially some sulfur-containing photoinitiators), limited use range and dosage due to poor solubility properties, etc. However, from the viewpoint of civil environmental protection application, the development of a novel photoinitiator is not only aimed at solving the above-mentioned challenging problems, but also needed to provide green and environmental-friendly novel compounds, and at the same time, the novel compounds are as good as possible to have the characteristics of economical cost competitiveness and comprehensive performance competitiveness.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides an alpha-amino ketone difunctional compound, a preparation method thereof and a photopolymerization initiator thereof, and the alpha-amino ketone difunctional compound, the preparation method thereof and the photopolymerization initiator thereof aim to solve the technical problems that the existing photocuring industry application scene is unfriendly to the environment and human health due to the toxicity or migration of the photoinitiator and the like.
The invention aims to solve the technical problem of providing a novel alpha-amino ketone difunctional compound and a derivative thereof.
The invention aims to provide a preparation method of the alpha-amino ketone difunctional compound.
The invention aims to provide an application of the alpha-amino ketone difunctional compound, in particular to a free radical photopolymerization initiator of an olefinically unsaturated photopolymerizable compound system taking the alpha-amino ketone difunctional compound as an active ingredient.
The invention provides an alpha-aminoketone difunctional compound and a derivative thereof, and the structural formula of the compound is shown as a general formula (I):
wherein,
M is oxygen (O), sulfur (S), silicon (Si), phosphorus (P), nitrogen (N), C 1-C6 straight or branched alkyl; any one of ethylene glycol (-OCH 2CH2 O-), propylene glycol (-OCH 2CH2CH2 O-), carbonyl (-CO-), oxime (-CNOH-) or oxime ester;
R 1 is any one of branched or branched alkyl of C 1-C20, cycloalkyl of C 3-C20, cycloalkylalkyl of C 4-C20, aryl of C 6-C20, alkylaryl of C 6-C20;
R 2 is any one of branched or branched alkyl of C 1-C20, cycloalkyl of C 3-C20, cycloalkylalkyl of C 4-C20, aryl of C 6-C20, alkylaryl of C 6-C20;
r 3 represents any one of N-morpholinyl, N-piperidinyl, N-pyrrolyl, N-piperazinyl or N-dialkyl.
Further, one or more hydrogens in the groups of R 1 or R 2 may be substituted independently of each other with alkyl, halogen, hydroxy, nitro.
Further, the-CH 2-group in the group of R 1 or R 2 is substituted or interrupted by 1 to 4 oxygen atoms, silicon atoms, sulfur atoms, nitrogen atoms, carbonyl groups, or the R1 and R2 groups may form a cyclic structure.
Further, wherein one or more hydrogens of these groups may be substituted with alkyl, halogen, hydroxy, nitro, independently of each other, and optionally, -CH 2-in R1 and R2 is substituted or interrupted with 1-4 oxygen atoms, silicon atoms, sulfur atoms, nitrogen atoms, carbonyl groups, or the R1 and R2 groups may form a cyclic structure.
Further, one or more hydrogen atoms in the R3 group may be replaced by halogen or hydroxy.
Further, the structure of the multifunctional aromatic ketone compound is selected from, but not limited to, the following structures:
On the other hand, the invention also provides a preparation method of the alpha-amino ketone difunctional compound, and the alpha-amino ketone difunctional compound is obtained by modifying groups such as diphenylmethane and homologues thereof or diphenyl ether.
The invention also provides a preparation method of the alpha-amino ketone difunctional compound, which utilizes the Friedel-Crafts acylation reaction of the diphenylmethane homolog structure X and the acyl donor Y under the action of Lewis acid to obtain the corresponding acylated product aromatic ketone, and the acylated aromatic ketone is subjected to halogenation (chlorination or bromination) reaction and substitution of ammonia substituent to obtain the corresponding target product alpha-amino ketone difunctional compound.
Wherein:
n is any integer between 1 and 6;
The invention also provides a preparation method of the alpha-amino ketone difunctional compound, which comprises the steps of carrying out Friedel-Crafts acylation reaction on diphenyl ether structure X 1 and acyl donor Y under the action of Lewis acid to obtain corresponding acylated product aromatic ketone, and carrying out halogenation (chlorination or bromination) reaction and substitution of ammonia substituent on the acylated aromatic ketone to obtain a corresponding target product namely the alpha-amino ketone difunctional compound;
Wherein:
M is a linear or branched alkyl group of oxygen (O), sulfur (S), silicon (Si), phosphorus (P), nitrogen (N), C 1-C6; ethylene glycol (-OCH 2CH2 O-), propylene glycol (-OCH 2CH2CH2 O-), carbonyl (-CO-), oxime (-CNOH-) or oxime ester;
r 1 and R 2 independently represent a branched or branched alkyl group of C 1-C20, a cycloalkyl group of C 3-C20, a cycloalkylalkyl group of C 4-C20, an aryl group of C 6-C20, an alkylaryl group of C 6-C20, wherein one or more hydrogens of these groups may be substituted independently of each other by an alkyl group, a halogen group, a hydroxyl group, a nitro group, and optionally-CH 2 -in R 1 and R 2 is substituted or interrupted by 1 to 4 oxygen atoms, silicon atoms, sulfur atoms, nitrogen atoms, carbonyl groups, or R 1 and R 2 groups may form a cyclic structure;
r 3 represents N-morpholinyl, N-piperidinyl, N-pyrrolyl, N-piperazinyl or N-dialkyl, wherein one or more hydrogen atoms of these groups may be substituted by halogen, hydroxy.
The alpha-amino ketone difunctional compound can be used for preparing a photocuring mixed system or a photocuring radiation material formula system, and can also be used for preparing a free radical photopolymerization initiator compound.
The invention also provides a photocuring mixed system, which comprises at least one ethylenically unsaturated photopolymerizable compound system and a photopolymerization system of an alpha-amino ketone difunctional compound with a general formula (I).
Preferably, the photoinitiator of the α -aminoketone difunctional class of compounds defined by the general formula (I) is used in an amount ranging from 0.01 to 20 parts per 100 parts by weight of total ethylenically unsaturated containing material. More preferably, the aromatic ketone type photoinitiator defined by the general formula (I) is used in an amount of 0.5 to 10 parts, for example, the α -aminoketone difunctional type photoinitiator is used in an amount of 0.8, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0 parts, etc. (mass ratio).
The invention also provides a formula system of the photo-curing radiation material, which at least meets any one of the following conditions:
(1) Comprises at least one photoinitiator defined by the general formula (I) or a mixture thereof;
(2) Containing at least one photoinitiator defined by the general formula (I) or a mixture with other conventional commercially available photoinitiators;
(3) The system of at least one ethylenically unsaturated photopolymerizable compound, including compounds having free radically polymerizable ethylenically unsaturated bonds, may be reactive diluents (low molecular weight) or oligomers (higher molecular weight).
(4) Containing or containing functional additives and/or coagents, etc. required for part of the properties. Including, but not limited to, inhibitors, leveling agents, defoamers, anti-sagging agents, thickeners, tackifiers, dispersants, solubilizing agents, diluents, antistatic agents, water or organic solvents, antimicrobial agents, flame retardants, active amine co-initiators, inorganic or organic fillers (e.g., carbonates, sulfates, titanium white, etc.) and/or organic, inorganic colorants (e.g., pigments or dyes, etc.), ultraviolet absorbers or/and light stabilizers to enhance weatherability of the coating ink, and suitable aqueous dispersions or water-soluble products of the foregoing components, and the like.
The formula system of the photo-curing radiation material provided by the invention is suitable for coating materials of all base materials, such as timber, fabrics, paper, glass, plastic products (polyester, polyolefin, polyethylene terephthalate, polyacetate cellulose and the like), glass, metal (iron, aluminum, copper, nickel, zinc, cobalt, alloy and silicon or silicon oxide) and the like, particularly in the form of films, and can be used as protective coatings, decorative coatings or etched images through imaging exposure and the like on the base materials.
Further, in the photocurable radiation material formulation system, the ethylenically unsaturated photopolymerizable compound is a monomer compound or oligomer, preferably: a compound containing one carbon-carbon double bond, preferably an acrylate compound or a methacrylate compound; or ethylenically unsaturated photopolymerizable compounds are compounds containing two or more carbon-carbon double bonds, preferably alkyl diols, acrylic or methacrylic esters of polyols or unsaturated polyesters of polyester polyols, polyether polyols, epoxy polyols, acrylic esters of polyurethane polyols, vinyl ethers and unsaturated dicarboxylic acid polyols.
Furthermore, the invention also provides application of the light-cured radiation material formula system, and application of the novel light-cured radiation material formula system in wood furniture paint, plastic product paint, printing packaging ink, ink-jet printing, electronic consumer goods, automotive vehicle interior and exterior trim, pipeline section bar, industrial floor paint, building curtain wall paint, 3D printing additive manufacturing, industrial paint of ships or container bodies and the like. Further, when the photocurable radiation material formulation system is applied to the applications such as a photocurable radiation resist ink, a photocurable radiation solder resist ink and a photoresist, at least one of the ethylenically unsaturated photopolymerizable compounds used contains an alkali-soluble group, preferably a carboxyl group-containing resin.
Furthermore, the novel UV radiation curing material formula system comprises a photo-curing coating or ink material, is matched with various construction modes (such as spraying, rolling coating, curtain coating, wiping coating, dip coating and the like) and/or construction procedures (such as putty, base coating, coloring, middle coating, top coating and the like), and has extremely wide application value in downstream markets of wood furniture, plastic products, printing and packaging, ink-jet printing, electronic consumer products, motor vehicle interior and exterior trim, pipeline profiles, industrial floors, building curtain walls, 3D printing additive manufacturing, ships or container bodies and the like.
The invention also provides a free radical photopolymerization initiator of an ethylenically unsaturated system which takes the alpha-amino ketone difunctional compound as an active ingredient. The ethylenically unsaturated system composition has the function of being used as a negative resist film, can be diffused into an alkaline water system without swelling and can be developed through an alkaline water system medium, has very high sensitivity, and is very suitable for being used as an electronic photoetching material (photoresist, corrosion resistance and welding resistance), printing plate production (offset plate or silk screen plate) and the like. Preferred embodiments include those coatings or inks for the preparation of pigmented and unpigmented paints and varnishes, powder coatings, printing inks, printing plates, adhesives, pressure sensitive adhesives, dental compositions, gel coats, photoresists for electronic devices, electro-forge resists, etch resists, both liquid and dry films, solder resists, resists for the manufacture of color filters for various display applications, resists for the manufacture of plasma display panels, structures in the manufacture of electroluminescent displays and LCDs, for LCD, holographic data storage, compositions for encapsulating electronic components, for the manufacture of magnetic recording materials, micromechanical parts, waveguides, optical switches, forge masks, etch masks, color proofing systems, fiberglass cable coatings, screen printing stencils, for the production of three-dimensional objects by means of stereolithography, as image recording materials, for holographic recording, microelectronic circuits, decolorizing materials for image recording materials, image recording materials using microcapsules, as photoresist materials for UV and visible laser direct imaging systems, as photoresist materials for the formation of dielectric layers in sequential build-up layers of printed circuit boards; in particular, the photopolymerizable compositions described above are used for the preparation of pigmented and unpigmented paints and varnishes, powder coatings, printing inks (e.g. screen printing inks, inks for offset, flexo or inkjet printing), printing plates, adhesives, seals, potting components, dental compositions, foams, molding compounds, composite compositions, glass fiber cable coatings, screen printing stencils, for the production of three-dimensional objects by means of stereolithography, and as image recording materials, photoresist compositions, decolorizing materials for image recording materials, for image recording materials using microcapsules.
Compared with the prior art, the invention has the technical effects of being positive and obvious. The alpha-amino ketone difunctional compound provided by the invention is aromatic ketone which takes derivatives such as diphenylmethane or diphenyl ether as key groups and can contain or not contain hetero atoms (oxygen, nitrogen, phosphorus, silicon and other elements) for substitution. The compound does not contain any sulfur element, is an environment-friendly, nontoxic and efficient photoinitiator, and avoids the problems of escape of volatile toxic micromolecular organic compounds, or generation of pungent smell, or physiological toxicity caused by compound migration in the reaction. Compared with the existing products, the invention uses the cheap and easily available industrial raw materials as starting points for breaking, and applies the compound to the application of the photoinitiator in radiation curing, so as to solve the problems of the toxicity of the photoinitiator and the pollution of VOCs, and simultaneously strive for the economic competitiveness of the photoinitiator, thereby reducing the overall cost and improving the photoinitiation efficiency. The invention applies the alpha-amino ketone difunctional compound to the photoinitiator in radiation curing, can solve the problems of toxicity and VOCs pollution of the photoinitiator, and simultaneously strives for economic competitiveness of the photoinitiator so as to reduce the overall cost and improve the photoinitiation efficiency.
Detailed Description
The invention provides a preparation method of an alpha-aminoketone difunctional compound and a derivative thereof, which are represented by a general formula (I):
example 1 preparation example 1
170 Kg of diphenyl ether and 500 l of dichloroethane are put into a reaction kettle under the protection of nitrogen, stirring is started, cooling is carried out, 280 kg of aluminum trichloride is put into the reaction kettle, stirring and cooling are kept for 1 hour, 215 kg of isobutyryl chloride is then dropwise added into the reaction kettle for 2 hours, the kettle temperature is kept below 5 ℃, and after the dropwise addition is finished, stirring is continued for 6 hours, and the Friedel-crafts acylated intermediate is obtained through purification. Then 300 kg of Friedel-crafts acylation intermediate is put into a chlorination kettle, 500L of dichloroethane is added, the mixture is mixed and stirred, 160 kg of chlorine is introduced after the catalyst is added, the introduction of chlorine is stopped, and the chlorinated intermediate is obtained by purification. 355 kg of chlorinated intermediate is put into a substitution kettle, 700 liters of dichloroethane and 540 kg of aluminum trichloride are added, stirring and cooling are carried out to 5-10 ℃, 180 kg of morpholine is added dropwise, after the dropwise addition is finished, the temperature is raised to 60 ℃ for reaction for 6 hours, the reaction solution is cooled to 5 ℃, 500 liters of 1N hydrochloric acid is slowly added into the reaction solution, stirring is carried out for 3 hours, the organic phase is collected by separating liquid, 300 kg of 10% sodium bicarbonate aqueous solution is added for washing, the organic phase is collected by separating liquid, the solvent is removed from the organic phase, and 420 kg of white-like powder is obtained by recrystallization by cyclohexane. The total yield was 87%.
1H NMR(300MHz,CDCl3),δ:8.14(4H,d),7.12(4H,d),3.57(8H，t),2.50(8H,t),1.65(12H,s)。
Example 2 preparation example 2
The specific operation steps are as follows:
Under the protection of nitrogen, 450 liters of dichloroethane and 150 kg of diphenylmethane are added into a reaction kettle, stirring and cooling are started, 500 kg of aluminum trichloride is added into the reaction kettle, stirring and cooling are kept for 1 hour, then 200 kg of isobutyryl chloride is dropwise added into the reaction kettle for 2 hours, the kettle temperature is kept below 5 ℃, and stirring is continued for 6 hours after the dropwise addition is finished, so that 262 kg of Friedel-crafts acylated intermediate is obtained, and the yield is 96%. And then, through the alternative two-stage serial arrangement of the primary and secondary chlorination kettles, firstly, respectively putting 100 kg of Friedel-crafts acylation intermediate into the primary kettle, introducing chlorine into the primary kettle, introducing tail gas containing the chlorine after the chlorine is absorbed by the primary kettle into the secondary kettle for environmental protection and absorption again, stopping introducing the chlorine after the chlorine is introduced into 100 kg, introducing nitrogen into the primary kettle for 20 minutes for replacing excessive chlorine, collecting the chlorination intermediate of the primary kettle, and simultaneously putting 100 kg of Friedel-crafts acylation intermediate into the primary kettle again, and changing the primary kettle into the secondary kettle for repeated operation. Adding the chlorinated intermediate into a substitution kettle, adding 200 liters of dichloroethane and 210 kg of aluminum trichloride, stirring and cooling to 5-10 ℃, then dropwise adding 75 kg of morpholine, heating to 60 ℃ after dropwise adding, reacting for 6 hours, cooling the reaction liquid to 5 ℃, slowly adding 200 liters of 1N hydrochloric acid into the reaction liquid, stirring for 2 hours, collecting an organic phase by separating liquid, adding 200 kg of 10% sodium bicarbonate aqueous solution for washing, collecting the organic phase by separating liquid, removing the solvent from the organic phase, and recrystallizing with cyclohexane to obtain 289 kg of off-white powder as a target product. The total yield was 93%.
1H NMR(300MHz,CDCl3),δ:7.36(4H,d),6.85(4H,d),4.08(2H,s),3.59(8H，t),2.51(8H,t),1.47(12H,s)。
Example 3 preparation example 3
Under the protection of nitrogen, 171 kg of diphenylmethane and 500L of dichloroethane are added into a reaction kettle, stirring is started, cooling is carried out, 280 kg of aluminum trichloride is added into the reaction kettle, stirring and cooling are kept for 1 hour, 215 kg of isobutyryl chloride is then dropwise added into the reaction kettle for 2 hours, the kettle temperature is kept below 5 ℃, and after the dropwise addition is finished, stirring is continued for 6 hours, and the Friedel-crafts acylated intermediate is obtained through purification. Then, putting 301 kg of Friedel-crafts acylation intermediate into a chlorination kettle, adding 500L of dichloroethane, mixing and stirring, adding 160 kg of chlorine after adding a catalyst, stopping chlorine introduction, and purifying to obtain a chlorinated intermediate. 361 kg of chlorinated intermediate is put into a substitution kettle, 700 liters of dichloroethane and 540 kg of aluminum trichloride are added, stirring and cooling are carried out, 175 kg of piperidine is added dropwise after 5-10 ℃, after the dropwise addition is finished, the temperature is raised to 60 ℃ for reaction for 6 hours, the reaction solution is cooled to 5 ℃, 1N hydrochloric acid is slowly added into the reaction solution for 500 liters, stirring is carried out for 3 hours, the organic phase is collected by separating liquid, 300 kg of 10% sodium bicarbonate aqueous solution is added for washing, the organic phase is collected by separating liquid, the solvent is removed from the organic phase, and 409 kg of white powder is obtained by recrystallization by cyclohexane. The total yield was 86%.
1H NMR(300MHz,CDCl3),δ:7.34(4H,d),6.82(4H,d),4.11(2H,s),2.59(8H,m),1.51(8H,m),1.52(12H,s),1.45(4H,m).
Example 4 preparation example 4
Under the protection of nitrogen, 168 kg of diphenyl ether and 500 l of dichloroethane are put into a reaction kettle, stirring is started, cooling is carried out, 280 kg of aluminum trichloride is put into the reaction kettle, stirring and cooling are kept for 1 hour, 215 kg of isobutyryl chloride is then dropwise added into the reaction kettle for 2 hours, the kettle temperature is kept below 5 ℃, and after the dropwise addition is finished, stirring is continued for 6 hours, and the Friedel-crafts acylated intermediate is obtained through purification. Then 300 kg of Friedel-crafts acylation intermediate is put into a chlorination kettle, 500L of dichloroethane is added, the mixture is mixed and stirred, 160 kg of chlorine is introduced after the catalyst is added, the introduction of chlorine is stopped, and the chlorinated intermediate is obtained by purification. 358 kg of chlorinated intermediate is put into a substitution kettle, 700 liters of dichloroethane and 540 kg of aluminum trichloride are added, the mixture is stirred and cooled to 5-10 ℃, 150 kg of diethylamine is added dropwise, after the dropwise addition is finished, the mixture is heated to 60 ℃ for reaction for 6 hours, the reaction solution is cooled to 5 ℃, 1N hydrochloric acid is slowly added into the reaction solution for 500 liters, the mixture is stirred for 3 hours, the organic phase is collected by separating liquid, 300 kg of 10% sodium bicarbonate aqueous solution is added for washing, the organic phase is collected by separating liquid, the solvent is removed from the organic phase, and 382 kg of light yellow powder is obtained by recrystallization by cyclohexane. The total yield was 84.6%.
1H NMR(300MHz,CDCl3),δ:8.04(4H,d),7.19(4H,d),2.57(8H，q),1.55(12H,s),1.09(12H,t),
Example 5 preparation example 5
Under the protection of nitrogen, 171 kg of diphenylmethane and 500L of dichloroethane are added into a reaction kettle, stirring is started, cooling is carried out, 280 kg of aluminum trichloride is added into the reaction kettle, stirring and cooling are kept for 1 hour, 215 kg of isobutyryl chloride is then dropwise added into the reaction kettle for 2 hours, the kettle temperature is kept below 5 ℃, and after the dropwise addition is finished, stirring is continued for 6 hours, and the Friedel-crafts acylated intermediate is obtained through purification. Then, putting 301 kg of Friedel-crafts acylation intermediate into a chlorination kettle, adding 500L of dichloroethane, mixing and stirring, adding 160 kg of chlorine after adding a catalyst, stopping chlorine introduction, and purifying to obtain a chlorinated intermediate. 361 kg of chlorinated intermediate is put into a substitution kettle, 700 liters of dichloroethane and 540 kg of aluminum trichloride are added, the mixture is stirred and cooled to 5-10 ℃, 150 kg of diethylamine is added dropwise, after the dropwise addition is finished, the mixture is heated to 60 ℃ for reaction for 6 hours, the reaction solution is cooled to 5 ℃, 1N hydrochloric acid is slowly added into the reaction solution for 500 liters, the mixture is stirred for 3 hours, the organic phase is collected by separating liquid, 300 kg of 10% sodium bicarbonate aqueous solution is added for washing, the organic phase is collected by separating liquid, the solvent is removed from the organic phase, and 373 kg of light yellow crystals are obtained by recrystallization by cyclohexane. The total yield thereof was found to be 83%.
1H NMR(300MHz,CDCl3),δ:7.24(4H,d),6.77(4H,d),4.10(2H,s),2.61(8H，q),1.52(12H,s),1.45(12H，t)。
Example 6: evaluation of Performance
By formulating the exemplary photocurable compositions, the photoinitiators of the present invention of formula I are evaluated for their various application properties, including storage cure rate, odor, solubility, and the like.
1. Preparation of photocurable composition
Application examples:
TABLE 1
In the composition, the photoinitiator is an alpha-amino ketone difunctional photoinitiator shown in the general formula I disclosed by the invention or a photoinitiator known in the prior art for comparison, and the components are all in parts by mass.
The addition amount of the photoinitiator in the photo-curing composition system is the addition amount of the known formula experience, and the addition amount in different composition systems needs to be adjusted according to the overall performance activity of the composition system and the requirement of the composition system, and can be determined according to actual requirements. For example, the aromatic ketone photoinitiator of the formula (I) may be used in an amount ranging from 0.01 to 20 parts by weight, more preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the total ethylenically unsaturated-containing material.
2. Cure rate
The above composition was coated on white cardboard using a 25 μm bar coater to compare the properties of the photoinitiators Irgacure 907, irgacure 369, APi-307 and the inventive example compounds as photoinitiators. The coated sample was mounted on a belt and transported under a medium pressure mercury lamp. The tape speed of the fully cured samples was determined with the nail repeated embossing scratch producing no marks as a fully cured standard.
3. Odor rating
The photocurable composition was completely cured according to the above-mentioned curing method and curing speed. The residual odor test uses 5 persons to evaluate the odor grades independently, and uses the odor grade evaluation of more than or equal to 3 persons as a standard.
The criteria for evaluation are numerically indicated as follows:
Class a: no smell was felt;
b level: very slight smell;
C level: a slight smell;
d stage: a noticeable smell;
e level: a strong odor;
grade F: very strong smell
4. Adhesion test
The adhesiveness is tested by adopting a hundred-grid method according to the GB/T9286-1998 test standard, and is evaluated according to the 0-5 grade standard;
the evaluation results are shown in table 2:
TABLE 2
Photoinitiator Curing speed Odor rating Yellowing (delta E) Adhesion and transmittance
Example 1 92 B-C 0.13 1/Film clarity, no turbidity
Example 2 95 B-C 0.14 1/Film clarity, no turbidity
Example 3 98 B-C 0.13 1/Film clarity, no turbidity
Example 4 92 B-C 0.15 0/Film clarity, no turbidity
Example 5 94 B-C 0.15 0/Film clarity, no turbidity
Irgacure 907 92 D-E 0.25 1/Slightly cloudy and dull film
Irgacure 369 99 B-C 0.31 2/Cloudiness and darkness of the paint film, no clarity
APi 307 82 B-C 0.14 1/Film clarity, no turbidity
As can be seen from the results in Table 2, the photo-curing composition containing the novel alpha-aminoketone difunctional photoinitiator shown in the general formula (I) has good photo-initiation activity, and the photo-initiation activity is obviously higher than that of the commercially available photoinitiators Irgacure 907, irgacure 369 and APi 307, is not lower than that of the Irgacure 907 and is slightly lower than that of the Irgacure 369; the yellowing resistance has competitive advantages compared with Irgacure 907, irgacure 369 and APi 307, and also shows low-odor environment-friendly performance; under the requirement of fixed activity, the photoinitiator shown in the general formula (I) has lower addition, can effectively reduce cost, improves yellowing resistance and has low-odor environment-friendly performance, and the application range of the initiator structure shown in the general formula (I) is expanded.
5. Solubility and dissolution rate test
Solubility test the solubility of the photoinitiators according to the invention and of the commercially available photoinitiators Irgacure 907, irgacure 369, APi 307 were tested against the more widely known reactive diluents HDDA (1, 6-hexanediol diacrylate) in the art and acetone as solvents, and the maximum weight of 100g of solvent in solution at 25℃was used as evaluation criterion. The dissolution rate was measured at 50℃at a stirring speed of 120 rpm for a period of time required for complete dissolution of the test photoinitiator at a mass ratio of 5% to HDDA (1, 6-hexanediol diacrylate) and the results are shown in Table 3.
TABLE 3 Table 3
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As can be seen from Table 3, the novel alpha-amino ketone difunctional photoinitiator has a competitive advantage in solubility compared with the commercial photoinitiators Irgacure 907, irgacure 369 and APi-307, and can greatly reduce the use of small molecular reactive diluents and solvents during use.
In conclusion, compared with the prior art, the novel alpha-amino ketone difunctional photoinitiator shown in the general formula (I) has more excellent application performance, and can greatly improve the performance of the prior art photo-curing products or develop new application in the field.
It is emphasized that the above listed compounds are only some of the preferred exemplary structures and should not be considered limiting structures. Any reaction conditions or parameter adjustment variations that may be generally changed or optimized by one skilled in the art of radiation photocuring based on the disclosure herein are intended to be within the scope of the present invention without departing from the gist of the present invention.

Claims (2)

1. An alpha-amino ketone difunctional compound is characterized in that the structural formula is any one structure shown as the following,
Or alternatively
2. A radiation-curable mixture comprising at least one polymerizable ethylenically unsaturated photopolymerizable compound and the α -aminoketone difunctional compound according to claim 1, the α -aminoketone difunctional compound according to claim 1 being used as photoinitiator in an amount of between 0.01 and 20 parts by weight per 100 parts by weight of the total amount of ethylenically unsaturated photopolymerizable compounds.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
US4496447A (en) * 1980-03-05 1985-01-29 Merck Patent Gesellschaft Mit Beschraenkter Haftung Aromatic-aliphatic ketones useful as photoinitiators
CN103664827A (en) * 2013-12-18 2014-03-26 浙江扬帆新材料股份有限公司 Method for compounding photo-initiator
CN106947057A (en) * 2016-01-07 2017-07-14 北京英力科技发展有限公司 A kind of Photocurable composition and its purposes as varnish and colored paint

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4496447A (en) * 1980-03-05 1985-01-29 Merck Patent Gesellschaft Mit Beschraenkter Haftung Aromatic-aliphatic ketones useful as photoinitiators
CN103664827A (en) * 2013-12-18 2014-03-26 浙江扬帆新材料股份有限公司 Method for compounding photo-initiator
CN106947057A (en) * 2016-01-07 2017-07-14 北京英力科技发展有限公司 A kind of Photocurable composition and its purposes as varnish and colored paint

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