CN115010614A - Alpha-aminoketone bifunctional compound, preparation method thereof and photopolymerization initiator thereof - Google Patents
Alpha-aminoketone bifunctional compound, preparation method thereof and photopolymerization initiator thereof Download PDFInfo
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- CN115010614A CN115010614A CN202210804454.9A CN202210804454A CN115010614A CN 115010614 A CN115010614 A CN 115010614A CN 202210804454 A CN202210804454 A CN 202210804454A CN 115010614 A CN115010614 A CN 115010614A
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- Prior art keywords
- aminoketone
- compound
- alpha
- bifunctional compound
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
-
- 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
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Abstract
The invention provides an alpha-aminoketone bifunctional compound, which has a structural general formula shown as (I):
Description
Technical Field
The invention belongs to the field of materials science, relates to a novel radiation curing material, and particularly relates to an alpha-aminoketone bifunctional 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 energy of UV radiation light sources to generate active substances such as free radicals, cations or anions and the like to initiate polymerization reactions of ethylenically unsaturated double bonds or epoxy compounds, vinyl ethers, lactones, acetals, cyclic ethers and the like. Aminoketones are a class of highly active free radical photopolymerization initiators useful in ethylenically unsaturated compound systems, commercially available products are Irgacure 907, Irgacure 369, Irgacure 379, APi-307, and the like.
However, most photoinitiators generally produce a series of Volatile Organic Compounds (VOCs) which are not friendly to the environment and even seriously harmful to human health, such as benzaldehyde, acetone, cyclohexanone, thioether and the like. Therefore, the environmental and health pollution has become a problem of increasing concern in the field of radiation curing, and the development of new environmentally friendly photoinitiators is being promoted, and in particular, efforts are being made to alleviate and eliminate the above-mentioned disadvantages of conventional commercially available photoinitiators in polymerization applications, including carcinogenicity due to cracking or residue, contamination of procreation toxic compounds (benzene/thioether/aromatic hydrocarbons) due to compound migration, release of VOCs and unpleasant odor (especially some sulfur-containing photoinitiators) remaining after packaging of the final product, limited application range and dosage due to poor solubility, and the like. However, from the viewpoint of civil environmental protection, the development of new photoinitiators is not only aimed at solving the above-mentioned challenging problems and providing new green and environmental-friendly compounds, but also at providing new compounds having characteristics of economic cost competitiveness and comprehensive performance competitiveness as much as possible.
Disclosure of Invention
The invention provides an alpha-aminoketone bifunctional compound, a preparation method thereof and a photopolymerization initiator thereof, aiming at solving the technical problem that the existing photocuring industrial application scene is not friendly to the environment and human health due to the toxicity or mobility of the photoinitiator.
The invention aims to solve the technical problem of providing a novel alpha-aminoketone bifunctional compound and a derivative thereof.
The invention also provides a preparation method of the alpha-aminoketone bifunctional compound.
The invention also aims to provide application of the alpha-aminoketone bifunctional compound, in particular to a free radical photopolymerization initiator of an ethylenically unsaturated photopolymerizable compound system taking the alpha-aminoketone bifunctional compound as an effective component.
The invention provides an alpha-aminoketone bifunctional compound and a derivative thereof, wherein the structural formula of the compound is shown as the general formula (I):
wherein the content of the first and second substances,
m is oxygen (O), sulfur (S), silicon (Si), phosphorus (P), nitrogen (N), C 1 -C 6 Linear or branched alkyl of (a); ethylene glycol group (-OCH) 2 CH 2 O-), propylene glycol group (-OCH) 2 CH 2 CH 2 O-), carbonyl (-CO-), oximino (-CNOH-) or oximino ester;
R 1 is C 1 -C 20 Branched or branched alkyl of C 3 -C 20 Cycloalkyl of, C 4 -C 20 Cycloalkylalkyl of (C) 6 -C 20 Aryl of (C) 6 -C 20 Any one of the alkylaryl groups of (a);
R 2 is C 1 -C 20 Branched or branched alkyl of C 3 -C 20 Cycloalkyl of, C 4 -C 20 Cycloalkyl ofAlkyl radical, C 6 -C 20 Aryl of (C) 6 -C 20 Any one of the alkylaryl groups of (a);
R 3 represents any one of N-morpholinyl, N-piperidyl, N-pyrrolyl, N-piperazinyl or N-dialkyl.
Further, R 1 Or R 2 One or more hydrogens of the group (b) may be independently substituted with alkyl, halogen, hydroxy, nitro.
Further, R 1 Or R 2 The group of (A) wherein-CH 2-is substituted or interrupted by 1 to 4 oxygen atoms, silicon atoms, sulfur atoms, nitrogen atoms, carbonyl groups, or the groups R1 and R2 may form a cyclic structure.
Further, wherein one or more hydrogens in these groups may be substituted independently of each other by alkyl, halogen, hydroxy, nitro, and optionally, -CH 2-in R1 and R2 may be substituted or interrupted by 1 to 4 oxygen atoms, silicon atoms, sulfur atoms, nitrogen atoms, carbonyl groups, or R1 and R2 groups may form a cyclic structure.
Further, one or more hydrogen atoms in the R3-substituted group may be substituted by halogen, 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-aminoketone bifunctional compound, which obtains the general formula (I) of the alpha-aminoketone bifunctional compound by modifying diphenylmethane and homologues thereof or diphenyl ether and other groups.
The invention also provides a preparation method of the alpha-aminoketone bifunctional compound, which comprises the steps of carrying out Friedel-Crafts acylation reaction on a diphenylmethane homologue structure X and an acyl donor Y under the action of Lewis acid to obtain a corresponding acylated product aromatic ketone, and carrying out halogenation (chlorination or bromination) reaction and amino substituent substitution on the acylated aromatic ketone to obtain a corresponding target product, namely the alpha-aminoketone bifunctional compound.
Wherein:
n is an integer between 1 and 6;
the invention also provides a preparation method of the alpha-aminoketone bifunctional compound, which utilizes diphenyl ether structure X 1 Carrying out Friedel-Crafts acylation reaction on the acyl donor Y under the action of Lewis acid to obtain corresponding acylated aromatic ketone, and carrying out halogenation (chlorination or bromination) reaction and amino substituent substitution on the acylated aromatic ketone to obtain a corresponding target product, namely an alpha-aminoketone bifunctional compound;
wherein:
m is oxygen (O), sulfur (S), silicon (Si), phosphorus (P), nitrogen (N), C 1 -C 6 Linear or branched alkyl of (a); ethylene glycol group (-OCH) 2 CH 2 O-), propylene glycol group (-OCH) 2 CH 2 CH 2 O-), carbonyl (-CO-), oximino (-CNOH-) or oximino ester;
R 1 and R 2 Each independently represents C 1 -C 20 Branched or branched alkyl of C 3 -C 20 Cycloalkyl of, C 4 -C 20 Cycloalkylalkyl of (C) 6 -C 20 Aryl of (C) 6 -C 20 Wherein one or more hydrogens in these groups may be substituted independently of each other by alkyl, halogen, hydroxy, nitro, and optionally, R 1 And R 2 In (C-CH) 2 Substituted or interrupted by 1 to 4 oxygen atoms, silicon atoms, sulfur atoms, nitrogen atoms, carbonyl groups, or R 1 And R 2 The groups may form a cyclic structure;
R 3 represents N-morpholinyl, N-Piperidinyl, N-pyrrolyl, N-piperazinyl or N-dialkyl, wherein one or more of the hydrogen atoms of these groups may be substituted by halogen, hydroxy.
The alpha-aminoketone bifunctional 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-aminoketone bifunctional compound with the general formula (I).
Preferably, the photoinitiator of the alpha-aminoketone bifunctional class of compounds defined by general formula (I) is used in an amount varying from 0.01 to 20 parts per 100 parts by weight of the total amount of ethylenically unsaturated substances. More preferably, the amount of the aromatic ketone photoinitiator defined by the formula (I) is 0.5 to 10 parts, for example, the amount of the α -aminoketone bifunctional photoinitiator used is 0.8, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0 parts, etc. (by mass ratio).
The invention also provides a photocuring radiation material formula system, which at least meets any one of the following conditions:
(1) containing at least one photoinitiator as defined by the general formula (I) or mixtures thereof;
(2) containing at least one photoinitiator as defined by the general formula (I) or in a mixture with other customary commercial photoinitiators;
(3) the system containing at least one ethylenically unsaturated photopolymerizable compound, including compounds having free-radically polymerizable ethylenic unsaturation, may be a reactive diluent (low molecular weight) or an oligomer (higher molecular weight).
(4) Contains or contains functional additives or/and active auxiliary agents and the like required by partial performance. Including but not limited to polymerization inhibitors, leveling agents, defoamers, anti-sagging agents, thickeners, tackifiers, dispersants, solubilizers, diluents, antistatic agents, water or organic solvents, antimicrobials, flame retardants, reactive amine co-initiators, inorganic or organic fillers (e.g., carbonates, sulfates, titanium dioxide, etc.) and/or organic, inorganic colorants (e.g., pigments or dyes, etc.), ultraviolet absorbers or/and light stabilizers to enhance the weatherability of the coating ink, and suitable aqueous dispersions or water-soluble products of the above components, and the like.
The photocurable radiation material formulation system provided by the present invention is suitable for coating substances of all substrates, such as wood, textiles, paper, glass, plastic articles (polyester, polyolefin, polyethylene terephthalate, cellulose acetate, etc.), glass, metals (iron, aluminum, copper, nickel, zinc, cobalt, alloys, and silicon or silicon oxide), etc., especially in the form of films, and can be used as protective coatings, finish coatings, or etched images by imagewise exposure, etc., on the above-mentioned substrates.
Further, in the photocurable radiation material formulation system, the ethylenically unsaturated photopolymerizable compound is a monomer compound or an oligomer, and preferably: a compound containing one carbon-carbon double bond, preferably an acrylate compound or a methacrylate compound; or the ethylenically unsaturated photopolymerizable compound is a compound containing two or more carbon-carbon double bonds, and is preferably an alkyl diol, an acrylate or methacrylate of a polyol, or an unsaturated polyester of a polyester polyol, a polyether polyol, an epoxy polyol, an acrylate of a polyurethane polyol, a vinyl ether, and an unsaturated dicarboxylic acid polyol.
Furthermore, the invention also provides application of the light-cured radiation material formula system, and the novel light-cured radiation material formula system is applied to wood furniture paint, plastic product coating, printing and packaging ink, ink-jet printing, electronic consumer goods, automotive interior and exterior trim, pipeline section bar, industrial floor paint, building curtain wall paint, 3D printing additive manufacturing, industrial paint for ships or container bodies and the like. Further, when the photocurable radiation material formulation system is applied to photocurable radiation resist ink, photoresist and the like, at least one of the ethylenically unsaturated photopolymerizable compounds used contains an alkali-soluble group, preferably a carboxyl-containing resin.
Furthermore, the novel UV radiation curing material formula system comprises a photo-curing coating or an ink material, and has very wide application value in downstream markets such as wood furniture, plastic products, printing and packaging, ink-jet printing, electronic consumer goods, automotive interior and exterior decorations, pipeline profiles, industrial terraces, building curtain walls, 3D printing additive manufacturing, ships or container bodies and the like by matching with various construction modes (such as spraying, rolling, curtain coating, wiping, dip coating and the like) and/or construction processes (such as putty, base coating, coloring, middle coating, surface coating and the like).
The invention also provides a free radical photopolymerization initiator containing an ethylenic unsaturated system, which takes the alpha-aminoketone bifunctional compound as an effective component. The composition containing ethylenic unsaturated system has the function as a negative film resist film, does not swell because it can diffuse into an alkaline water system and is developed by an alkaline water system medium, and has very high sensitivity, thus being very suitable for electronic photoetching materials (electroetching, corrosion and soldering resistance), printing plate production (offset printing plates or silk screens) and the like. Preferred embodiments include the use of such 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 electronics, electrographic 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 structures in the manufacturing process for plasma display panels, electroluminescent displays and LCDs, for LCDs, holographic data storage, compositions for encapsulating electronic components, for the preparation of magnetic recording materials, micromechanical components, waveguides, optical switches, stencils, etch masks, color proofing systems, glass fiber cable coatings, screen printing stencils, for the production of three-dimensional objects by means of stereolithography, as image recording materials, a decolorizing material for holographic recording, microelectronic circuits, decolorizing materials, for image recording materials using microcapsules, as photoresist material for UV and visible laser direct imaging systems, as photoresist material for forming 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, moulding compounds, composite compositions, glass fibre 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, image recording materials using microcapsules.
Compared with the prior art, the invention has the advantages of positive and obvious technical effect. The alpha-aminoketone bifunctional compound provided by the invention takes derivatives such as diphenylmethane or diphenyl ether and the like as key groups, and aromatic ketone substituted by heteroatom (elements such as oxygen, nitrogen, phosphorus, silicon and the like) can be contained or not contained. 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 small-molecular organic compounds in the reaction, generation of pungent odor, physiological toxicity caused by compound migration and the like. Compared with the existing products, the invention uses cheap and easily available industrial raw materials as a starting point breakthrough, applies the compound to the application of the photoinitiator in radiation curing, aims at solving the problems of toxicity and VOCs pollution of the photoinitiator and simultaneously strives for economic competitiveness so as to reduce the overall cost and improve the photoinitiation efficiency. The invention applies the alpha-aminoketone bifunctional 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 so as to reduce the overall cost and improve the photoinitiation efficiency.
Detailed Description
The invention provides a preparation method of alpha-aminoketone bifunctional compounds and derivatives thereof, which have a general formula (I):
example 1 preparation example 1
Under the protection of nitrogen, 170 kg of diphenyl ether and 500L of dichloroethane are put into a reaction kettle, stirring is started and the temperature is reduced, 280 kg of aluminum trichloride is put into the reaction kettle, stirring and the temperature is reduced for 1 hour, 215 kg of isobutyryl chloride is then added into the reaction kettle dropwise, the dropwise adding time is 2 hours, the temperature of the reaction kettle is kept lower than 5 ℃, and after the dropwise adding is finished, stirring is continued for 6 hours for purification to obtain a Friedel-crafts acylation intermediate. Then putting 300 kg of Friedel-crafts acylated 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. 355 kg of chlorinated intermediate is put into a substitution kettle, 700 l 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, heating is carried out to 60 ℃ after dropwise addition is finished, reaction is carried out for 6 hours, the temperature of reaction liquid is reduced to 5 ℃, 500 l of 1N hydrochloric acid is slowly added into the reaction liquid, stirring is carried out for 3 hours, liquid separation is carried out, an organic phase is collected, 300 kg of 10% sodium bicarbonate aqueous solution is added for washing, liquid separation is carried out, the organic phase is collected, solvent is removed from the organic phase, and 420 kg of similar white powder is obtained by recrystallization of cyclohexane as a target product. The total yield was 87%.
1 H 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, 450L of dichloroethane and 150 kg of diphenylmethane are added into a reaction kettle, stirring is started and the temperature is reduced, 500 kg of aluminum trichloride is added into the reaction kettle, stirring and temperature reduction are kept for 1 hour, then 200 kg of isobutyryl chloride is added into the reaction kettle in a dropwise manner, the dropwise addition time is 2 hours, the temperature of the reaction kettle is kept lower than 5 ℃, after the dropwise addition is finished, stirring is continued for 6 hours, 262 kg of Friedel-crafts acylation intermediate is obtained, and the yield is 96%. Then through the alternative two-stage series arrangement of the primary and secondary chlorinated kettles, firstly, respectively putting 100 kg of Friedel-crafts acylation intermediate into the primary kettle, introducing chlorine into the primary kettle, introducing the chlorine into the secondary kettle after the chlorine is absorbed by the primary kettle for environment-friendly absorption again, stopping introducing the chlorine after 100 kg of chlorine is introduced, introducing nitrogen into the primary kettle for 20 min to replace excessive chlorine, then collecting the chlorinated intermediate in the primary kettle, 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. And (2) putting the chloro intermediate into a substitution kettle, adding 200L of dichloroethane and 210 kg of aluminum trichloride, stirring, cooling to 5-10 ℃, dropwise adding 75 kg of morpholine, heating to 60 ℃ after dropwise adding, reacting for 6 hours, cooling the reaction liquid to 5 ℃, slowly adding 200L of 1N hydrochloric acid into the reaction liquid, stirring for 2 hours, separating and collecting an organic phase, adding 200 kg of 10% sodium bicarbonate aqueous solution, washing, separating and collecting the organic phase, removing a solvent from the organic phase, and recrystallizing with cyclohexane to obtain 289 kg of similar white powder serving as a target product. The total yield thereof was found to be 93%.
1 H 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 and the temperature is reduced, 280 kg of aluminum trichloride is added into the reaction kettle, stirring and temperature reduction are kept for 1 hour, 215 kg of isobutyryl chloride is then added into the reaction kettle dropwise, the dropwise adding time is 2 hours, the temperature of the reaction kettle is kept lower than 5 ℃, and after the dropwise adding is finished, stirring is continued for 6 hours for purification to obtain a Friedel-crafts acylation intermediate. Then putting 301 kg of Friedel-crafts acylated intermediate into a chlorination kettle, adding 500L of dichloroethane for 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 chloro intermediate is put into a substitution kettle, 700 l of dichloroethane and 540 kg of aluminum trichloride are added, stirring and cooling are carried out to 5-10 ℃, 175 kg of piperidine is added dropwise, heating is carried out to 60 ℃ after dropwise addition is finished, reaction is carried out for 6 hours, the temperature of reaction liquid is reduced to 5 ℃, 500 l of 1N hydrochloric acid is slowly added into the reaction liquid, stirring is carried out for 3 hours, liquid separation is carried out, an organic phase is collected, 300 kg of 10% sodium bicarbonate water solution is added for washing, liquid separation is carried out, the organic phase is collected, solvent is removed from the organic phase, and cyclohexane is used for recrystallization, thus 409 kg of similar white powder is obtained as a target product. The total yield thereof was found to be 86%.
1 H 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 500L of dichloroethane are put into a reaction kettle, stirring is started and the temperature is reduced, 280 kg of aluminum trichloride is put into the reaction kettle, stirring and the temperature is reduced for 1 hour, 215 kg of isobutyryl chloride is then dripped into the reaction kettle, the dripping time is 2 hours, the temperature of the reaction kettle is kept lower than 5 ℃, and after the dripping is finished, stirring is continued for 6 hours for purification to obtain a Friedel-crafts acylation intermediate. And then putting 300 kg of Friedel-crafts acylated intermediate into a chlorination kettle, adding 500L of dichloroethane, mixing and stirring, adding 160 kg of chlorine after adding a catalyst, stopping introducing chlorine, and purifying to obtain a chlorinated intermediate. 358 kg of chlorinated intermediate is put into a substitution kettle, 700 l of dichloroethane and 540 kg of aluminum trichloride are added, stirring and cooling are carried out to 5-10 ℃, 150 kg of diethylamine is added dropwise, after the dropwise addition is finished, the temperature is raised to 60 ℃ for reaction for 6 hours, the reaction liquid is cooled to 5 ℃, 500 l of 1N hydrochloric acid is slowly added into the reaction liquid, stirring is carried out for 3 hours, an organic phase is collected by liquid separation, 300 kg of 10% sodium bicarbonate aqueous solution is added for washing, the organic phase is collected by liquid separation, the solvent is removed from the organic phase, and 382 kg of light yellow powder is obtained by recrystallization of cyclohexane. The total yield is 84.6%.
1 H 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 and the temperature is reduced, 280 kg of aluminum trichloride is added into the reaction kettle, stirring and temperature reduction are kept for 1 hour, 215 kg of isobutyryl chloride is then added into the reaction kettle dropwise, the dropwise adding time is 2 hours, the temperature of the reaction kettle is kept lower than 5 ℃, and after the dropwise adding is finished, stirring is continued for 6 hours for purification to obtain a Friedel-crafts acylation intermediate. And then putting 301 kg of Friedel-crafts acylated intermediate into a chlorination kettle, adding 500L of dichloroethane, mixing and stirring, adding 160 kg of chlorine after adding a catalyst, stopping introducing chlorine, and purifying to obtain a chlorinated intermediate. 361 kg of chloro intermediate is put into a substitution kettle, 700 l of dichloroethane and 540 kg of aluminum trichloride are added, stirring and cooling are carried out to 5-10 ℃, 150 kg of diethylamine is added dropwise, heating is carried out to 60 ℃ after dropwise addition is finished, reaction is carried out for 6 hours, the temperature of reaction liquid is reduced to 5 ℃, 500 l of 1N hydrochloric acid is slowly added into the reaction liquid, stirring is carried out for 3 hours, organic phase is collected by liquid separation, 300 kg of 10% sodium bicarbonate aqueous solution is added for washing, organic phase is collected by liquid separation, solvent is removed from the organic phase, and 373 kg of light yellow crystal is obtained by recrystallization of cyclohexane as a target product. The total yield thereof was found to be 83%.
1 H 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 Properties
By formulating the exemplary photocurable compositions, the photoinitiators of formula I of the present invention were evaluated for various applications, including storage cure rate, odor, solubility, etc.
1. Preparation of Photocurable compositions
The application example is as follows:
TABLE 1
In the composition, the photoinitiator is an alpha-aminoketone bifunctional photoinitiator shown as a general formula I disclosed by the invention or a comparative photoinitiator known in the prior art, and all the components are in parts by mass.
The addition amount of the photoinitiator in the photocuring composition system is known formula experience addition amount, and the dosage of the photoinitiator in different composition systems needs to be adjusted according to the overall activity of the composition system and the requirements of the composition system, and can be determined according to actual requirements. For example, the amount of the aromatic ketone photoinitiator defined by the general formula (I) may vary from 0.01 to 20 parts by weight, and more preferably, the amount of the aromatic ketone photoinitiator defined by the general formula (I) may be 0.5 to 10 parts by weight, per 100 parts by weight of the total amount of the ethylenically unsaturated materials.
2. Rate of cure
The above composition was coated on white cardboard using a 25 μm wire bar coater to compare the performance of the photoinitiators Irgacure 907, Irgacure 369, APi-307 and the compounds of the examples of the invention as photoinitiators. The coated sample was mounted on a belt and transported under a medium pressure mercury lamp. Repeated indentation and scratching with fingernails did not produce prints as a complete cure standard, determining the belt speed for a fully cured sample.
3. Odor grade
The photocurable composition was completely cured according to the above-mentioned curing method and curing speed. The residual odor test takes 5 persons as independent evaluation odor grades, and takes more than or equal to 3 persons as a standard for similar or uniform evaluation of odor grades.
The criteria for evaluation are numerically expressed as follows:
a level: no smell can be felt;
b stage: very mild odor;
c level: a slight odor;
d stage: a noticeable odor;
e, grade: a strong odor;
f grade: very strong odor
4. Adhesion test
The adhesiveness is tested by adopting a grid marking method according to the test standard GB/T9286-1998 and is evaluated according to the 0-5 level standard;
the evaluation results are shown in table 2:
TABLE 2
| Photoinitiator | Speed of curing | Odor grade | Yellowing (Delta E) | Adhesion and light transmittance |
| Example 1 | 92 | B-C | 0.13 | 1/clear and no turbidity of the paint film |
| Example 2 | 95 | B-C | 0.14 | 1/clear and no turbidity of the paint film |
| Example 3 | 98 | B-C | 0.13 | 1/clear and no turbidity of the paint film |
| Example 4 | 92 | B-C | 0.15 | 0/paint film is clear and not turbid |
| Example 5 | 94 | B-C | 0.15 | 0/paint film is clear and not turbid |
| Irgacure 907 | 92 | D-E | 0.25 | 1/paint film slightly cloudy and dull |
| Irgacure 369 | 99 | B-C | 0.31 | 2/cloudy, dull and cloudy film |
| APi 307 | 82 | B-C | 0.14 | 1/clear and no turbidity of the paint film |
As can be seen from the results in Table 2, the photo-curing composition containing the novel alpha-aminoketone bifunctional photoinitiator represented by the general formula (I) has very good photo-initiation activity, and compared with the commercial photoinitiators Irgacure 907, Irgacure 369 and APi 307, the photo-initiation activity is obviously higher than that of APi 307, not lower than that of Irgacure 907 and slightly lower than that of Irgacure 369; compared with Irgacure 907, Irgacure 369 and APi 307, the yellowing resistance has competitive advantages and also shows low-odor environment-friendly performance; under the requirement of fixed activity, the photoinitiator shown in the general formula (I) has low addition amount, can effectively reduce the cost, improve the yellowing resistance and have low-odor environmental protection performance, and expands the application range of the initiator structure shown in the general formula (I).
5. Solubility and dissolution Rate test
Solubility test compares the solubility of HDDA (1, 6-hexanediol diacrylate) which is a widely used active diluent in the field and acetone as solvents, and the solubility of Irgacure 907, Irgacure 369 and APi 307 which are photoinitiators of the invention and commercially available photoinitiators is compared, and the maximum weight of 100g of solvent which can be dissolved at 25 ℃ is used as an evaluation standard. The dissolution rate test conditions were the time required for complete dissolution of the photoinitiator in HDDA (1, 6-hexanediol diacrylate) at 50 ℃ with a stirring speed of 120 rpm and a mass ratio of 5%, and the test results are shown in Table 3.
TABLE 3
As can be seen from Table 3, compared with the commercially available photoinitiators Irgacure 907, Irgacure 369 and APi-307, the novel alpha-aminoketone bifunctional photoinitiator has competitive solubility, and can greatly reduce the use of small-molecule active diluents and solvents when in use.
In conclusion, compared with the known commercially available aminoketone photoinitiator, the novel α -aminoketone bifunctional photoinitiator represented by the general formula (I) disclosed by the invention has more excellent application performance, and can greatly improve the performance of the known photocuring product or develop new applications in the field.
It is emphasized that the above-listed compounds are merely some preferred exemplary structures and should not be considered limiting structures. Any variation in the reaction conditions or parameter adjustments that may be routinely altered or optimized by those skilled in the art of radiation photocuring based on the disclosure of this application is within the scope of the present invention.
Claims (14)
1. An alpha-aminoketone bifunctional compound is characterized in that the structural general formula is shown as (I):
wherein the content of the first and second substances,
m is oxygen, sulfur, silicon, phosphorus, nitrogen, C 1 -C 6 Any one of a linear or branched alkyl group of (a), an ethylene glycol group, a propylene glycol group, a carbonyl group, an oxime group, or an oxime ester;
R 1 is C 1 -C 20 Branched or branched alkyl of C 3 -C 20 Cycloalkyl of, C 4 -C 20 Cycloalkylalkyl of (C) 6 -C 20 Aryl of (C) 6 -C 20 Any one of the alkylaryl groups of (a);
R 2 is C 1 -C 20 Branched or branched alkyl of C 3 -C 20 Cycloalkyl of, C 4 -C 20 Cycloalkylalkyl of (C) 6 -C 20 Aryl of (C) 6 -C 20 Any one of the alkylaryl groups of (a);
R 3 is N-morpholinyl, N-piperidinylAny one of N-pyrrolyl, N-piperazinyl and N-dialkyl.
2. The alpha-aminoketone bifunctional compound of claim 1, wherein R is 1 、R 2 One or more hydrogens in the group may be substituted independently of each other by alkyl, halogen, hydroxy, nitro.
3. The alpha-aminoketone bifunctional compound of claim 1, wherein R is 1 Or R 2 Of the group-CH 2 -substituted or interrupted by 1 to 4 oxygen atoms, silicon atoms, sulfur atoms, nitrogen atoms or carbonyl groups, or the R1 and R2 groups may form a cyclic structure.
4. The α -aminoketone bifunctional compound of claim 1, wherein one or more hydrogen atoms in the R3-substituted group can be replaced by halogen or hydroxyl.
5. The alpha-aminoketone bifunctional compound of claim 1, wherein the structural formula of the compound is any one of the structures shown in the following,
6. the method for preparing the alpha-aminoketone bifunctional compound as claimed in any one of claims 1 to 5, characterized in that a diphenylmethane homolog structure X and an acyl donor Y are used for carrying out Friedel-Crafts acylation reaction under the action of a catalyst Lewis acid to obtain a corresponding acylated product aromatic ketone, and the acylated aromatic ketone is subjected to chlorination or bromination reaction and amino substituent substitution to obtain a corresponding target product, namely the alpha-aminoketone bifunctional compound;
wherein n is an integer between 1 and 6;
R 1 is C 1 -C 20 Branched or branched alkyl of C 3 -C 20 Cycloalkyl of, C 4 -C 20 Cycloalkylalkyl of (C) 6 -C 20 Aryl of (C) 6 -C 20 Any one of the alkylaryl groups of (a);
R 2 is C 1 -C 20 Branched or branched alkyl of (C) 3 -C 20 Cycloalkyl of (C) 4 -C 20 Cycloalkylalkyl of (C) 6 -C 20 Aryl of (C) 6 -C 20 Any one of the alkylaryl groups of (a);
R 3 represents any one of N-morpholinyl, N-piperidyl, N-pyrrolyl, N-piperazinyl or N-dialkyl.
7. The method for preparing alpha-aminoketone bifunctional compounds as claimed in any of claims 1 to 5, characterized in that diphenyl ether structure X is used 1 Carrying out Friedel-Crafts acylation reaction on the acyl donor Y under the action of Lewis acid to obtain corresponding acylated aromatic ketone, and carrying out chlorination or bromination reaction and amino substituent substitution on the acylated aromatic ketone to obtain a corresponding target product, namely an alpha-aminoketone bifunctional compound;
wherein:
m is oxygen, sulfur, silicon, phosphorus, nitrogen, C 1 -C 6 Any one of a linear or branched alkyl group of (a), an ethylene glycol group, a propylene glycol group, a carbonyl group, an oxime group, or an oxime ester;
R 1 is C 1 -C 20 Branched or branched alkyl of C 3 -C 20 Cycloalkyl of, C 4 -C 20 Cycloalkylalkyl of (C) 6 -C 20 Aryl of (C) 6 -C 20 Any one of the alkylaryl groups of (a);
R 2 is C 1 -C 20 Branched or branched alkyl of C 3 -C 20 Cycloalkyl of, C 4 -C 20 Cycloalkylalkyl of (C) 6 -C 20 Aryl of, C 6 -C 20 Any one of the alkylaryl groups of (a);
R 3 represents any one of N-morpholinyl, N-piperidyl, N-pyrrolyl, N-piperazinyl or N-dialkyl.
8. A hybrid system curable by actinic radiation, comprising at least one polymerizable ethylenically unsaturated photopolymerizable compound and an α -aminoketone bifunctional compound corresponding to the general formula (I) in any one of claims 1 to 5.
9. The hybrid system according to claim 8, wherein the α -aminoketone bifunctional compound defined by the general formula (I) is used as the photoinitiator in an amount varying from 0.01 to 20 parts by weight, and further preferably from 0.5 to 10 parts by weight, per 100 parts by weight of the total ethylenically unsaturated photopolymerizable compound.
10. A photocuring radiation material formula system is characterized in that: at least one of the following conditions is satisfied:
(1) contains at least one photoinitiator conforming to the structural definition of the general formula (I) or a derivative compound thereof, and is mixed into a mixture of two or more compounds;
(2) containing at least one photoinitiator corresponding to the structural definition of the general formula (I) or mixtures with other customary commercial photoinitiators;
(3) containing at least one ethylenically unsaturated photopolymerizable monomer compound or photopolymerizable oligomer.
(4) Contains additives or/and active auxiliary agents, which are any one or combination of more than two of polymerization inhibitor, flatting agent, defoaming agent, anti-sagging agent, thickening agent, tackifier, dispersant, solubilizer, diluent, antistatic agent, water or organic solvent, antibacterial agent, flame retardant, active amine auxiliary initiator, inorganic or organic filler and/or organic and inorganic colorant, ultraviolet absorbent or/and light stabilizer for enhancing the weather resistance of coating ink, and proper aqueous dispersion or water-soluble product of the components.
11. The photocurable radiation material formulation system of claim 10, wherein: the ethylenically unsaturated photopolymerizable compound is a monomer compound or an oligomer or the ethylenically unsaturated photopolymerizable compound is a compound containing two or more carbon-carbon double bonds.
12. Use of the photocurable radiation material formulation system according to claim 10, characterized in that: the novel photocuring radiation curing material formula system is applied to wood furniture paint, plastic product paint, printing and packaging ink, inkjet printing, electronic consumer goods, automotive interior and exterior decoration, pipeline section bar, industrial floor paint, building curtain wall paint, 3D printing additive manufacturing or industrial paint for ships or container bodies.
13. Use according to claim 12, characterized in that: when the light-cured radiation material formula system is applied to light-cured radiation resist ink, light-cured radiation resist ink or photoresist and the like, at least one compound in the used ethylenically unsaturated photopolymerizable compounds contains an alkali soluble group.
14. Use according to claim 12, characterized in that: the light-cured radiation material formula system comprises dilution, a dissolving-assistant solvent and inorganic compounds.
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| CN116003273A (en) * | 2023-02-09 | 2023-04-25 | 深圳市大衍创新材料科技有限公司 | Alpha-aminoketone compound, preparation method thereof and application thereof in field of photo-radiation curing |
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| 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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| CN116003273B (en) * | 2023-02-09 | 2023-11-07 | 湖南勤润新材料有限公司 | Alpha-aminoketone compound, preparation method thereof and application thereof in field of photo-radiation curing |
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