CN115925564A - Alpha-aminoketone compound, preparation method thereof and photopolymerization initiator - Google Patents
Alpha-aminoketone compound, preparation method thereof and photopolymerization initiator Download PDFInfo
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- CN115925564A CN115925564A CN202211073970.5A CN202211073970A CN115925564A CN 115925564 A CN115925564 A CN 115925564A CN 202211073970 A CN202211073970 A CN 202211073970A CN 115925564 A CN115925564 A CN 115925564A
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- aminoketone
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- 239000003999 initiator Substances 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 238000003847 radiation curing Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 230000005855 radiation Effects 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000003973 paint Substances 0.000 claims description 18
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000000016 photochemical curing Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- -1 N-morpholinyl Chemical group 0.000 claims description 12
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 238000005660 chlorination reaction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 150000008365 aromatic ketones Chemical class 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000009472 formulation Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 229920002120 photoresistant polymer Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 125000004193 piperazinyl group Chemical group 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
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- 125000002252 acyl group Chemical group 0.000 claims description 2
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- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
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- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 9
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- 238000012360 testing method Methods 0.000 description 7
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- 238000011156 evaluation Methods 0.000 description 6
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- 238000010438 heat treatment Methods 0.000 description 6
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- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
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- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
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- KXFSUVJPEQYUGN-UHFFFAOYSA-N trimethyl(phenyl)silane Chemical compound C[Si](C)(C)C1=CC=CC=C1 KXFSUVJPEQYUGN-UHFFFAOYSA-N 0.000 description 3
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- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention providesProvides an alpha-aminoketone compound, which has a structural general formula shown as (I):
Description
Technical Field
The invention belongs to the field of new photocuring materials, and relates to a new radiation curing material, in particular to a novel environment-friendly and nontoxic alpha-aminoketone 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. The alpha-aminoketones are a high-activity free radical photopolymerization initiator used in ethylenically unsaturated compound systems, and commercially available commercial 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 when polymerization occurs, such as benzaldehyde, acetone, cyclohexanone, etc. Therefore, the environmental and health pollution has become a problem of increasing concern in the field of radiation curing, and meanwhile, the continuous development of novel environmentally-friendly photoinitiators is promoted, and especially, the shortcomings of the traditional commercially-available photoinitiators, including carcinogenicity caused by cracking or residue, benzene/aromatic hydrocarbon pollution caused by compound migration, release of VOCs and unpleasant odor caused by residue after packaging of finished products, limited application range and dosage caused by poor solubility, and the like, are alleviated and eliminated. 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. For example: the KIP150 product overcomes the difficulty of VOCs, and simultaneously has the new problems of greatly reduced photopolymerization activity (the photopolymerization activity is only 1/4 of Darocure 1173) and greatly increased cost.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a novel environment-friendly nontoxic alpha-aminoketone compound, a preparation method thereof and a photopolymerization initiator thereof, and the novel environment-friendly nontoxic alpha-aminoketone compound, the preparation method thereof and the photopolymerization initiator thereof aim to solve the technical problems of environmental and human health unfriendliness caused by the toxicity or mobility and the like of a photoinitiator in the existing photocuring industrial application scene, the industrial application scene limitation caused by poor solubility, poor formula stability and the like.
The invention aims to solve the technical problem of providing a novel environment-friendly and nontoxic alpha-aminoketone compound and a derivative thereof.
The invention also aims to provide a preparation method of the novel environment-friendly and nontoxic alpha-aminoketone compound.
The invention aims to solve the technical problem of providing the application of the environment-friendly and nontoxic alpha-aminoketones, in particular to a free radical photopolymerization initiator of an ethylenically unsaturated photopolymerizable compound system taking the alpha-aminoketones as an effective component.
The invention provides an environment-friendly and nontoxic alpha-aminoketone 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,
a is any one of silane group, nitrogen alkyl group, nitrogen heterocycle, aromatic ring group, substituted aromatic ring group and aromatic ring containing hetero atom;
R 1 is any one of morpholine, piperidine, pyrrolidine, piperazinyl or N-dialkyl, wherein the N-dialkyl is preferably dimethylamine, diethylamine, N-methylbutylamine, diethanolamine, and the like.
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 compound, which comprises the steps of carrying out Friedel-Crafts acylation reaction on an aromatic compound and an acyl donor isobutyryl chloride under the action of a catalyst Lewis acid to obtain a corresponding acylation product aromatic ketone, and carrying out halogenation (chlorination or bromination) reaction and amino substituent substitution on the acylation aromatic ketone to obtain a corresponding target product, namely the alpha-amino ketone compound.
Wherein the content of the first and second substances,
a is any one of silane group, nitrogen alkyl, nitrogen heterocycle, aromatic ring group, substituted aromatic ring group and aromatic ring containing hetero atom;
R 1 is any one of morpholine, piperidine, pyrrolidine, piperazinyl or N-dialkyl, wherein the N-dialkyl is preferably dimethylamine, diethylamine, N-methylbutylamine, diethanolamine, and the like.
The alpha-amino ketone 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 contains at least one ethylenically unsaturated photopolymerizable compound system and a novel environment-friendly and nontoxic alpha-aminoketone compound photopolymerization system with the general formula (I).
Preferably, the photoinitiator of the α -aminoketone compound defined by the general formula (I) is used in an amount varying from 0.01 to 20 parts by weight per 100 parts by weight of the total amount of the ethylenically unsaturated-containing substance. More preferably, the aromatic ketone photoinitiator defined by the general formula (I) is used in an amount of 0.5 to 10 parts by weight, for example, the α -aminoketone 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 by weight, etc. (mass ratio).
The invention also provides a photocuring radiation material formula system, which at least meets any one of the following conditions:
(1) Contains any one or a mixture of more than two of at least one photoinitiator which conforms to the structural definition of the general formula (I);
(2) Containing at least one photoinitiator as defined by the general formula (I) or in a mixture with other customary commercial photoinitiators;
further, the photo-curing radiation material formula system at least meets any one of the following conditions:
(1) 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).
(2) 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 the use of photocurable radiation resist ink, photoresist and the like, at least one compound 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 and taking the alpha-aminoketone 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, has very high sensitivity, and is very suitable for electronic lithography materials (electroerosion resistance, erosion resistance and solder resistance), printing plate production (offset printing plates or silk screen plates) 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, electroformed resists, etch resists, both liquid and dry films, solder resists, resists for the manufacture of color filters for various display applications, resists for the preparation of structures in the manufacturing process of plasma display panels, electroluminescent displays and LCDs, resists for LCDs, holographic data storage, compositions for encapsulating electronic components, compositions for the preparation of magnetic recording materials, micromechanical parts, waveguides, optical switches, forge masks, 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, for holographic recording, microelectronic circuits, decolorizing materials, for image recording materials using microcapsules, as image decolorizing materials for UV and visible laser direct imaging systems, as photoresist materials for the formation of dielectric layers in the resist building layers of printed circuit boards, in sequence; 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, sealings, potting components, dental compositions, foams, moulding compounds, composite material 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 compound provided by the invention is aromatic ketone which takes diphenylmethane or diphenyl ether derivatives as a key group and can contain or not contain heteroatoms (oxygen, nitrogen, phosphorus, silicon and other elements). The compound 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 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 alpha-aminoketone compounds and derivatives thereof with a general formula (I):
example 1
Under the protection of nitrogen, 154 kg of biphenyl and 300L of dichloroethane are put into a reaction kettle, stirring is started, the temperature is reduced, 140 kg of aluminum trichloride is put into the reaction kettle, stirring and temperature reduction are kept for 1 hour, then 112 kg of isobutyryl chloride is 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, and purification is carried out, so as to obtain a Friedel-crafts acylated intermediate. Then 230 kg of Friedel-crafts acylated intermediate is put into a chlorination kettle, 400L of dichloroethane is added for mixing and stirring, 80 kg of chlorine is introduced after the catalyst is added, the chlorine introduction is stopped, and the chlorinated intermediate is obtained through purification. Putting 265 kg of chloro intermediate into a substitution kettle, adding 20 kg of catalyst, 500L of dichloroethane and 270 kg of aluminum trichloride, stirring, cooling to 5-10 ℃, introducing 95 kg of dimethylamine gas, heating to 35 ℃ after dropwise addition, reacting for 8 hours, cooling the reaction solution to 5 ℃, slowly adding 250L of 1N hydrochloric acid into the reaction solution, stirring for 3 hours, separating and collecting an organic phase, adding 200 kg of 10% sodium bicarbonate water solution for washing, separating and collecting the organic phase, removing the solvent from the organic phase, and recrystallizing with methanol to obtain 246 kg of white-like crystals as a target product. The total yield was 92%. Melting point: 93-97 ℃.
1 H NMR(300MHz,CDCl3),δ:8.04(2H,d),7.75(2H,d),7.73(2H,d)，7.45(2H,t)，7.40(1H,t)2.36(6H，s),1.55(6H,s)。
Example 2
The specific operation steps are as follows:
under the protection of nitrogen, 300 liters of dichloroethane and 112 kilograms of chlorobenzene are added into a reaction kettle, stirring is started and the temperature is reduced, 144 kilograms of aluminum trichloride are added into the reaction kettle, stirring and temperature reduction are kept for 1 hour, then 110 kilograms of isobutyryl chloride are dropwise added into the reaction kettle for 2 hours, the temperature of the reaction kettle is kept lower than 5 ℃, and after dropwise addition is finished, stirring is continued for 6 hours to obtain 175 kilograms of Friedel-crafts acylation intermediates, wherein the yield is 96%. Then, two chlorinated kettles are alternately and secondarily connected in series, 87.5 kilograms of Friedel-crafts acylated intermediates are respectively put into the two chlorinated kettles, chlorine is introduced into the chlorinated kettles, tail gas containing the chlorine is introduced into the secondary kettle after the chlorine is absorbed by the chlorinated kettles for environment-friendly absorption again, after the chlorine is introduced into 37 kilograms of chlorine, the chlorine introduction is stopped, nitrogen is introduced into the chlorinated kettles for 20 minutes to replace excessive chlorine, then the chlorinated intermediates in the chlorinated kettles are collected, and 87.5 kilograms of Friedel-crafts acylated intermediates are put into the chlorinated kettles again, and the chlorinated kettles are changed into the secondary kettle for repeated operation. And (2) putting the chloro intermediate into a substitution kettle, adding 300L of dichloroethane, 21 kg of composite catalyst and 60 kg of sodium methoxide, stirring, cooling to 10 ℃, introducing 130 kg of dimethylamine gas, heating to 40 ℃ after dropwise addition, reacting for 6 hours, cooling the reaction liquid to 5 ℃, slowly adding 100L of 1N hydrochloric acid into the reaction liquid, stirring for 2 hours, separating and collecting an organic phase, adding 100 kg of 10% sodium bicarbonate water solution, washing, separating and collecting the organic phase, removing the solvent from the organic phase, and recrystallizing with cyclohexane to obtain 210 kg of similar white powder as a target product. The total yield is 89.7%.
1 H NMR(300MHz,CDCl3),δ:7.85(2H,d),6.71(2H,d),3.08(6H,s),2.29(6H，s),1.57(6H,s)。
Example 3
Under the protection of nitrogen, 151 kg of trimethylphenylsilane and 300 l of dichloroethane are added into a reaction kettle, stirring is started and the temperature is reduced, 142 kg of aluminum trichloride is added into the reaction kettle, stirring and the temperature is reduced for 1 hour, then 112 kg of isobutyryl chloride is 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 219 kg of Friedel-crafts acylated intermediate is put into a chlorination kettle, 400L of dichloroethane is added for mixing and stirring, 75 kg of chlorine is introduced after the catalyst is added, the chlorine introduction is stopped, and the chlorinated intermediate is obtained through purification. Adding 250 kg of chlorinated intermediate into a substitution kettle, adding 400L of dichloroethane and 270 kg of aluminum trichloride, stirring, cooling to 5-10 ℃, dropwise adding 179 kg of anhydrous 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 3 hours, separating liquid, collecting an organic phase, adding 200 kg of 10% sodium bicarbonate water solution, washing, separating liquid, collecting the organic phase, removing a solvent from the organic phase, and recrystallizing with cyclohexane to obtain 262 kg of white-like powder as a target product. The total yield thereof was found to be 86%.
1 H NMR(300MHz,CDCl3),δ:7.94(2H,d),7.52(2H,d),3.58(2H,t),2.49(2H，t),1.56(6H,s),0.22(9H,s)。
Example 4
Under the protection of nitrogen, 151 kg of trimethylphenylsilane and 300 l of dichloroethane are added into a reaction kettle, stirring is started and the temperature is reduced, 143 kg of aluminum trichloride is added into the reaction kettle, stirring and the temperature is reduced for 1 hour, then 110 kg of isobutyryl chloride is dropwise added into the reaction kettle, 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 218 kg of Friedel-crafts acylated intermediate into a chlorination kettle, adding 400L of dichloroethane, mixing and stirring, adding 75 kg of chlorine after adding a catalyst, stopping introducing chlorine, and purifying to obtain a chlorinated intermediate. 357 kg of chlorinated intermediate is put into a substitution kettle, 700 l of dichloroethane, 20 kg of catalyst and 62 kg of sodium methoxide are added, stirring and cooling are carried out to 5-10 ℃,60 kg of dimethylamine gas is introduced, after dropwise addition, the temperature is raised to 60 ℃ for reaction for 6 hours, the temperature of reaction liquid is reduced to 5 ℃, 200 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, 200 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 223 kg of light yellow powder is obtained by recrystallization of cyclohexane as a target product. The total yield is 84.6%.
1 H NMR(300MHz,CDCl3),7.91(2H,d),7.52(2H,d),2.28(6H,s),1.59(6H，s),0.23(9H,s)。
Example 5
Under the protection of nitrogen, 154 kg of biphenyl and 250L of dichloroethane are put into a reaction kettle, stirring is started, the temperature is reduced, 143 kg of aluminum trichloride is put into the reaction kettle, stirring and temperature reduction are kept for 1 hour, then 110 kg of isobutyryl chloride is 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, and purification is carried out, so as to obtain a Friedel-crafts acylated intermediate. And then putting 220 kg of Friedel-crafts acylated intermediate into a chlorination kettle, adding 400L of dichloroethane, mixing and stirring, adding 75 kg of chlorine after adding a catalyst, stopping introducing chlorine, and purifying to obtain a chlorinated intermediate. Adding 250 kg of chloro intermediate into a substitution kettle, adding 400L of dichloroethane and 270 kg of aluminum trichloride, stirring, cooling to 5-10 ℃, dropwise adding 175 kg of anhydrous N-methylbutylamine, heating to 60 ℃ after dropwise adding, reacting for 6 hours, cooling the reaction solution to 5 ℃, slowly adding 200L of 1N hydrochloric acid into the reaction solution, stirring for 3 hours, separating and collecting an organic phase, adding 200 kg of 10% sodium bicarbonate aqueous solution for washing, separating and collecting the organic phase, removing a solvent from the organic phase, and recrystallizing by cyclohexane to obtain 281 kg of white-like powder serving as a target product. The total yield thereof was found to be 91%.
1 H NMR(300MHz,CDCl3),8.05(2H,d),7.74(2H,d),7.71(2H,d)，7.47(2H,t)，7.40(1H,t)，2.49(2H，t),2.36(3H，s),1.41(2H,m),1.28(2H,m),1.56(6H,s),0.95(3H,t)。
Example 6
Under the protection of nitrogen, 154 kg of biphenyl and 300L of dichloroethane are put into a reaction kettle, stirring is started, the temperature is reduced, 143 kg of aluminum trichloride is put into the reaction kettle, stirring and temperature reduction are kept for 1 hour, then 110 kg of isobutyryl chloride is 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, and purification is carried out, so as to obtain a Friedel-crafts acylated intermediate. And then putting 220 kg of Friedel-crafts acylated intermediate into a chlorination kettle, adding 400L of dichloroethane, mixing and stirring, adding 75 kg of chlorine after adding a catalyst, stopping introducing chlorine, and purifying to obtain a chlorinated intermediate. Adding 250 kg of chlorinated intermediate into a substitution kettle, adding 400L of dichloroethane and 270 kg of aluminum trichloride, stirring, cooling to 5-10 ℃, dropwise adding 145 kg of anhydrous pyrrolidine, heating to 60 ℃ after dropwise adding, reacting for 6 hours, cooling the reaction solution to 5 ℃, slowly adding 200L of 1N hydrochloric acid into the reaction solution, stirring for 3 hours, separating liquid, collecting an organic phase, adding 200 kg of 10% sodium bicarbonate water solution, washing, separating liquid, collecting the organic phase, removing a solvent from the organic phase, and recrystallizing with cyclohexane to obtain 264 kg of similar white powder as a target product. The total yield is 90%.
1 H NMR(300MHz,CDCl3),8.04(2H,d),7.73(2H,d),7.70(2H,d)，7.46(2H,t)，7.39(1H,t)，2.51(4H，t),1.69(4H，t),1.55(6H,s)
Example 7
Under the protection of nitrogen, 278 kg of trimethylphenylsilane and 400L of dichloroethane are added into a reaction kettle, stirring is started and the temperature is reduced, 143 kg of aluminum trichloride is added into the reaction kettle, stirring and the temperature is reduced for 1 hour, then 110 kg of isobutyryl chloride is dropwise added into the reaction kettle, 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 348 kg of Friedel-crafts acylation intermediate into a chlorination kettle, adding 500L of dichloroethane for mixing and stirring, adding 80 kg of chlorine after adding a catalyst, stopping chlorine introduction, and purifying to obtain a chlorinated intermediate. 375 kg of chloro intermediate is put into a substitution kettle, 700L of dichloroethane, 20 kg of catalyst and 60 kg of sodium methoxide are added, 96 kg of dimethylamine gas is introduced after stirring and cooling to 5-10 ℃, the temperature is raised to 60 ℃ after dropwise addition, reaction is carried out for 6 hours, the reaction liquid is cooled to 5 ℃, 200L 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, 200 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 320 kg of white powder is obtained by recrystallization of cyclohexane as a target product. The total yield thereof was found to be 82%.
1 H NMR(300MHz,CDCl3),8.20(1H,s),8.02(1H,d),7.98(1H,d),7.90(1H,d),7.58(1H,d),7.38(1H,t),7.27(1H,t),2.30(6H，s),1.85(4H,t),1.33(8H,m)0.85(6H,t)。
Example 8
Under the protection of nitrogen, 112 kg of chlorobenzene and 200L of dichloroethane are added into a reaction kettle, stirring is started and the temperature is reduced, 143 kg of aluminum trichloride is added into the reaction kettle, stirring and temperature reduction are kept for 1 hour, then 110 kg of isobutyryl chloride is dropwise added into the reaction kettle, 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, sequentially adding 182 kg of Friedel-crafts acylated intermediate, 20 kg of tetrabutyl ammonium bromide, 400 kg of prepared 20% sodium methanethiolate aqueous solution and 100 kg of water mixed toluene into a reaction kettle, keeping the temperature at 95 ℃, stirring for 10 hours, and purifying to obtain 193 kg of methylthio crude product. Putting the obtained methylthio crude product into a chlorination kettle, adding 300L of dichloroethane, mixing and stirring, adding catalyst, introducing 80 kg of chlorine, stopping introducing chlorine, purifying to obtain a chlorinated intermediate, putting 215 kg of chlorinated intermediate into a substitution kettle, adding 400L of dichloroethane, 20 kg of a composite catalyst and 60 kg of sodium methoxide, stirring, cooling to 5-10 ℃, introducing 59 kg of dimethylamine gas, heating to 60 ℃ after dropwise adding, reacting for 6 hours, cooling the reaction liquid to 5 ℃, slowly adding 100L of 1N hydrochloric acid into the reaction liquid, stirring for 3 hours, separating, collecting an organic phase, adding 100 kg of 10% sodium bicarbonate water solution, washing, separating, collecting the organic phase, removing the solvent from the organic phase, and recrystallizing with cyclohexane to obtain 196 kg of similar white powder as a target product. The total yield is 87.3%.
1 H NMR(300MHz,CDCl3),7.88(2H,d),7.50(2H,d),2.38(3H,s),2.28(6H，s)，1.53(6H，s)。
Example 9: 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
| Components | Formulation (%) |
| Epoxy acrylic resin B-100 | 35 |
| Polyurethane acrylic resin B-520 | 30 |
| Tripropylene glycol diacrylate | 30 |
| Defoaming agent BYK-057 | 1 |
| Wetting agent BYK-34 | 1 |
| Photoinitiator(s) | 3 |
In the composition, the photoinitiator is an alpha-aminoketone photoinitiator shown in 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 material.
2. Rate of cure
The above compositions were coated on white cardboard using a 10 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 was 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 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 | Speed of curing | Odor grade | Yellowing (Delta E) | Adhesion and light transmittance |
| Example one | 85 | B-C | 0.11 | 1/clear and no turbidity of the paint film |
| Example two | 85 | B-C | 0.18 | 1/clear and no turbidity of the paint film |
| EXAMPLE III | 98 | B-C | 0.10 | 1/the varnish film is clear and not turbid |
| Example four | 92 | B-C | 0.12 | 1/clear and no turbidity of the paint film |
| EXAMPLE five | 85 | B-C | 0.13 | 1/clear and no turbidity of the paint film |
| Example six | 86 | B-C | 0.12 | 1/the varnish film is clear and not turbid |
| EXAMPLE seven | 83 | B-C | 0.12 | 1/clear and no turbidity of the paint film |
| Example eight | 93 | D-E | 0.20 | 1/clear and no turbidity of the paint film |
| Irgacure 907 | 92 | D-E | 0.25 | 1/paint film slightly cloudy and dull |
| Irgacure 369 | 99 | B-C | 0.31 | 2/film turbidity, dullness and cloudiness |
| APi 307 | 82 | B-C | 0.14 | 1/film clearWithout turbidity |
As can be seen from the results shown in Table 2, the photocurable composition containing the novel alpha-aminoketone photoinitiator represented by the general formula (I) of the invention has very good photoinitiation activity, and the photoinitiation activity is slightly higher than that of the commercial photoinitiators Irgacure 907, irgacure 369 and APi 307 than that of the commercial photoinitiators Irgacure 907, irgacure 369 and is 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).
Particularly, the photoinitiators containing silicon modified structures in the third and fourth embodiments are particularly suitable for the compatibility of the silicon modified resin system, and the phenomena of formula atomization and the like are avoided.
In particular, the properties of example seven are similar to those of Irgacure 907, and the problem of large odor after curing cannot be avoided.
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 369 and APi-307, the novel alpha-aminoketone photoinitiator has competitive solubility, is basically equivalent to Irgacure 907, 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 photoinitiators, the novel alpha-aminoketone 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 products or develop new application 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 compound is characterized in that the structural general formula is shown as (I):
wherein the content of the first and second substances,
a is any one of silane group, nitrogen alkyl, nitrogen heterocycle, aromatic ring group, substituted aromatic ring group and aromatic ring containing hetero atom;
R 1 is any one of N-morpholinyl, N-piperidyl, N-pyrrolyl, N-piperazinyl or N-dialkyl.
2. The α -aminoketones according to claim 1, wherein one or more hydrogen atoms in the R1-generation group are substituted by hydroxyl groups.
3. The α -aminoketone compound according to claim 1, wherein the N-dialkyl group is any one selected from dimethylamine, diethylamine, N-methylbutylamine, and diethanolamine.
4. The α -aminoketone compound according to claim 1, characterized in that it has any one of the structures represented by the following structural formulae,
5. the method for preparing alpha-aminoketone compounds according to any one of claims 1 to 4, characterized in that an aromatic compound structure and an acyl donor isobutyryl chloride are used to perform Friedel-Crafts acylation reaction under the action of a catalyst Lewis acid to obtain 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 alpha-aminoketone compounds;
wherein, the first and the second end of the pipe are connected with each other,
a is any one of silane group, nitrogen alkyl, nitrogen heterocycle, aromatic ring group, substituted aromatic ring group and aromatic ring containing hetero atom;
R 1 is any one of morpholine, piperidine, pyrrolidine, piperazinyl or N-dialkyl.
6. A hybrid system curable by actinic radiation, comprising at least one polymerizable ethylenically unsaturated photopolymerizable compound and an α -aminoketone compound corresponding to formula (I) in any one of claims 1 to 4.
7. The mixing system as claimed in claim 6, wherein the α -aminoketones as defined by the general formula (I) are used as photoinitiators in amounts of from 0.01 to 20 parts by weight per 100 parts by weight of the total polymerizable ethylenically unsaturated photopolymerizable compounds.
8. The mixing system as claimed in claim 7, wherein the α -aminoketones as defined by the general formula (I) are used as photoinitiators in amounts of from 0.5 to 10 parts by weight per 100 parts by weight of the total polymerizable ethylenically unsaturated photopolymerizable compound.
9. A photocuring radiation material formula system is characterized by at least meeting any one of the following conditions:
(1) Comprises any one or a mixture of more than two of at least one photoinitiator which accords with the structural definition of the general formula (I);
(2) Containing at least one photoinitiator corresponding to the structural definition of the general formula (I) or in a mixture with other customary commercial photoinitiators.
10. The photocurable radiation material formulation system according to claim 9, further satisfying at least one of the following conditions:
(1) Containing at least one ethylenically unsaturated photopolymerizable monomer compound or photopolymerizable oligomer;
(2) 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 9, wherein: the olefinic unsaturated photopolymerisable compound is a monomer compound or an oligomer or the olefinic unsaturated photopolymerisable compound is a compound containing two or more carbon-carbon double bonds.
12. Use of the photocurable radiation material formulation system of claim 9, wherein: 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 photocurable radiation material formulation system is applied to the use of a photocurable radiation resist ink, a photoresist or the like, at least one compound of the ethylenically unsaturated photopolymerizable compounds used contains an alkali-soluble group.
14. Use according to claim 12, characterized in that: the formula system of the photo-curing radiation material contains a diluting solvent, a cosolvent and an inorganic compound.
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