CN115141162B - Preparation method of photoinitiator and product thereof - Google Patents
Preparation method of photoinitiator and product thereof Download PDFInfo
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- CN115141162B CN115141162B CN202211075491.7A CN202211075491A CN115141162B CN 115141162 B CN115141162 B CN 115141162B CN 202211075491 A CN202211075491 A CN 202211075491A CN 115141162 B CN115141162 B CN 115141162B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000007787 solid Substances 0.000 claims abstract description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims description 83
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 30
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000012074 organic phase Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000003495 polar organic solvent Substances 0.000 claims description 12
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004817 gas chromatography Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 36
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000004949 mass spectrometry Methods 0.000 description 8
- 238000010998 test method Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000005805 hydroxylation reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- -1 4-methylthiophenyl Chemical group 0.000 description 1
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a photoinitiator and a product thereof, wherein the photoinitiator is obtained by an ether forming reaction, so that a higher target product yield can be obtained, the yield of the target photoinitiator in the ether forming reaction can reach more than 80%, and the purity of the obtained product is higher; the photoinitiator prepared by the method is a solid powdery photoinitiator, the purity can reach more than 98%, the photoinitiator has good solubility in a base material, has higher initiation activity when being applied to a photocuring system, and has lower mobility in a photocuring coating.
Description
Technical Field
The invention belongs to the field of photocuring, and relates to a preparation method of a photoinitiator and a product thereof.
Background
2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone (photoinitiator 907) is widely applied by virtue of high initiating efficiency, low price advantage and deep curing capability suitable for a colored system; however, reproductive toxicity is becoming an increasing concern to the industry; especially after appearing in the 22 nd batch hazardous substance control list of the European Union, the search for a new substitute of the photoinitiator 907 becomes a problem which needs to be solved at present.
CN1347432A discloses a resin composition and a cured product made of the same, wherein a series of N-morpholino group-containing aromatic ketones are contained as a polymerization initiator, but the appearance, the use properties, the preparation method, and the like are not specifically disclosed.
Therefore, it is still of great importance to develop a substitute for the photoinitiator 907 which has excellent solubility in the binder and has low migration and higher photocuring activity, and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a preparation method of a photoinitiator and a product thereof, wherein the photoinitiator is obtained through an ether forming reaction, so that a higher target product yield can be obtained, the yield of the target photoinitiator in the ether forming reaction can reach more than 80%, and the purity of the obtained product is higher; the photoinitiator prepared by the method is a solid powdery photoinitiator, the purity can reach more than 98%, the photoinitiator has good solubility in a base material, has higher initiation activity when being applied to a photocuring system, and has lower mobility in a photocuring coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a photoinitiator, wherein the formula of the photoinitiator is represented by formula a below;
the preparation method comprises the following steps: mixing the compound of the formula a, alkali and a polar organic solvent, then adding the compound of the formula b, and heating for reaction to obtain the photoinitiator;
wherein n is selected from 1 to 8, such as 1, 2, 3, 4, 5, 6, 7 or 8.
The photoinitiator adopts the compounds of the formula a and the formula b as raw materials, and is obtained through one-step ether forming reaction, and the obtained photoinitiator is solid powder; the obtained photoinitiator is easy to purify, has high purity which can reach more than 98 percent and high yield which can reach more than 80 percent.
The photoinitiator obtained by the preparation method is solid powder, is applied to a photocuring system, has good solubility in a base material, has high photocuring activity, and has low mobility in a cured coating and good application performance.
Preferably n is selected from 4 to 6, for example 4, 5 or 6.
Preferably, the base is selected from potassium carbonate and/or sodium carbonate.
Preferably, the polar organic solvent is selected from DMF and/or DMSO.
According to the preparation method, DMF and/or DMSO is/are used as a solvent, so that the reaction rate is favorably improved, the reaction time is shortened, side reactions in the reaction process are fewer, and the yield and the purity of the product are favorably improved.
Preferably, the molar weight ratio of the compound of formula a to the compound of formula b is 1.2 to 1.8, such as 1.
The temperature at which the reaction is carried out under elevated temperature is preferably 85 to 115 ℃ such as 90 ℃, 95 ℃, 100 ℃, 105 ℃ or 110 ℃, and more preferably 95 to 105 ℃.
The preparation method provided by the invention adopts the raw material proportion and the reaction temperature, and is beneficial to improving the purity and yield of the target product.
Preferably, the method further comprises the following steps after the reaction is finished: desolventizing the reaction solution, adding water and a non-polar organic solvent, separating liquid to obtain an organic phase, washing with water, and desolventizing to obtain the photoinitiator;
the preparation method provided by the invention is simple in purification operation, and is beneficial to obtaining a target product with higher purity and yield.
Preferably, the non-polar organic solvent is selected from dichloroethane and/or dichloromethane.
Preferably, the compound of formula a is prepared by a process comprising the steps of:
(1) Cyclization reaction: mixing the compound of the formula c, methanol and sodium methoxide in an inert atmosphere, and reacting to obtain a compound of a formula d;
wherein X is selected from Br or Cl;
(2) Morpholine substitution reaction: mixing the compound of the formula d obtained in the step (1), morpholine and water, and heating for reaction to obtain a compound of a formula e;
(3) Hydroxyl substitution reaction: mixing the compound of the formula e obtained in the step (2), an organic solvent and water, then adding an alkali metal hydroxide, heating for reaction, and adding acid to adjust the pH value to obtain a compound of a formula a;
the preparation method of the compound of the formula a sequentially comprises cyclization reaction, morpholine substitution reaction and hydroxylation reaction, the preparation process is simple to operate, and the compound of the formula a with higher purity and yield can be obtained.
Preferably, the inert atmosphere in step (1) comprises any one of nitrogen, helium or argon or a mixture of at least two of them.
Preferably, the reaction in step (1) is carried out at a temperature of 23 to 27 ℃, for example, 24 ℃, 25 ℃, or 26 ℃.
Preferably, the method of mixing the compound of formula c, methanol and sodium methoxide in step (1) comprises: and (3) mixing the compound of the formula c and anhydrous methanol, controlling the temperature to 23-27 ℃, such as 24 ℃, 25 ℃ or 26 ℃, and the like, then dropwise adding a methanol solution of sodium methoxide, and continuing controlling the temperature to react until the reaction is complete.
Preferably, the concentration of the sodium methoxide in methanol is 20-40 wt.%, such as 22 wt.%, 25 wt.%, 28 wt.%, 30 wt.%, 32 wt.%, 35 wt.%, or 38 wt.%, etc., preferably 25-35 wt.%.
Preferably, the molar ratio of the compound of formula c to sodium methoxide is 1 (1.05 to 1.2), such as 1.
Preferably, the reaction in step (1) is carried out with stirring.
Preferably, the reaction in step (1) is further performed after the completion of desolvation to obtain the compound of formula d.
Preferably, the molar ratio of the compound of formula d to morpholine in step (2) is 1 (5-6), such as 1.
Preferably, the molar ratio of the compound of formula d to water in step (2) is 1.
In the invention, the addition amount of morpholine and water is controlled within the range, which is beneficial to the full progress of ring-opening morpholine substitution reaction, and further improves the yield and product purity of the target product.
Preferably, the heating in step (2) is carried out at a temperature of 80 to 90 deg.C, such as 82 deg.C, 85 deg.C or 88 deg.C.
The temperature of the morpholine substitution reaction is controlled within the range, so that the reaction can be fully performed, and the yield and the purity of a target product are improved.
Preferably, the reaction in step (2) is further followed by a post-treatment, wherein the post-treatment comprises desolventizing to obtain a desolventized product, then adding a non-polar organic solvent and water, separating to obtain an organic phase, desolventizing, and washing with the organic solvent to obtain the compound of formula e.
Preferably, the non-polar organic solvent is selected from toluene; preferably the volume ratio of non-polar organic solvent to water is 1.
Preferably, the organic solvent used for the organic solvent washing comprises petroleum ether.
After the morpholine substitution reaction is finished, firstly removing excessive morpholine by desolventizing, then adding an organic solvent and water for washing, separating liquid, desolventizing an organic phase, and washing with petroleum ether to realize the purification of the compound of the formula e. The invention combines the preparation method and the purification operation, the yield of the compound shown in the formula e can reach more than 82%, and the purity can reach more than 95%.
Preferably, the organic solvent in step (3) is selected from dimethyl sulfoxide and/or sulfolane.
Preferably, the alkali metal hydroxide of step (3) is selected from sodium hydroxide.
In the hydroxylation reaction in the step (3), dimethyl sulfoxide and/or sulfolane are/is used as a solvent, so that the reaction rate is improved, the side reactions are reduced, and the yield and the purity of the target product are improved.
Preferably, the molar amount ratio of the compound of formula e to the alkali metal hydroxide in step (3) is 1. The proportion is controlled within the above range, which is favorable for achieving sufficient reaction; when the amount of the alkali metal hydroxide added is small, the raw material consumption is incomplete, and when the amount of the alkali metal hydroxide added is excessive, the difficulty of the post-reaction treatment increases.
Preferably, the mixture of the compound of formula e, the organic solvent and water is temperature controlled to 10-40 ℃, e.g. 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃ etc., before the addition of the alkali metal hydroxide in step (3).
Preferably, the temperature for raising the temperature in step (3) to carry out the reaction is 120 to 130 ℃, such as 123 ℃, 125 ℃, or 128 ℃ and the like.
The hydroxylation reaction needs to be carried out at the temperature in the process, so that high yield and purity of a target product can be obtained, and when the temperature is too low, the reaction is slow; when the temperature is too high, the reaction system is liable to be contaminated.
Preferably, after the reaction in step (3) is completed, the reaction solution is cooled, water is added, and then an organic solvent is added for washing and liquid separation to obtain an aqueous phase, followed by filtration, acid addition to adjust the pH to 6 to 6.5, for example, 6.1, 6.2, 6.3 or 6.4, etc., to precipitate a solid, and solid-liquid separation to obtain the compound of formula a.
In the preparation method, after the alkali metal hydroxide and the compound shown in the formula e completely react, the reaction liquid is cooled to room temperature, water is added, then an organic solvent is added for washing and liquid separation to obtain a water phase, an intermediate product obtained in the reaction is dissolved in the water phase, then acid is added to adjust the pH value to be within the range, the compound shown in the formula a is separated out in a solid form, and the solid compound shown in the formula a is obtained through solid-liquid separation.
Preferably, the filtration medium comprises diatomaceous earth and/or clay.
Preferably, the organic solvent added for washing is selected from toluene and/or dichloromethane.
Preferably, the acid is selected from hydrochloric acid.
As a preferable technical scheme of the invention, the preparation method of the photoinitiator comprises the following steps:
(1) Adding the compound of the formula c and absolute methanol into a reactor under the stirring condition with the protection of nitrogen atmosphere, controlling the temperature to be 23-27 ℃, dropwise adding a methanol solution of 25-35wt% of sodium methoxide into the reactor, after dropwise adding, continuously controlling the temperature to react until the gas chromatography detection raw materials completely react, and then desolventizing to obtain a compound of the formula d;
wherein X is selected from Br or Cl;
(2) Adding morpholine and water into the compound of the formula d obtained in the step (1), heating to 80-90 ℃ for reaction, detecting by gas chromatography until the reaction is complete, desolventizing, adding toluene and water, separating liquid to obtain an organic phase, desolventizing, then adding petroleum ether for washing, and performing solid-liquid separation to obtain a compound of the formula e;
(3) Adding the compound of the formula e obtained in the step (2), dimethyl sulfoxide and water into a reactor, controlling the temperature to 10-40 ℃, adding sodium hydroxide in batches, after the addition is finished, heating to 120-130 ℃ to react completely, then cooling, adding water into a reaction solution, adding toluene to wash, separating liquid to obtain a water phase, filtering, adding hydrochloric acid into the water phase to adjust the pH value to 6-6.5, separating out a solid, and carrying out solid-liquid separation to obtain a compound of the formula a;
(4) Adding the compound of the formula a obtained in the step (3), potassium carbonate and DMF (dimethyl formamide) into a reactor, then adding the compound of the formula b, heating to 95-105 ℃, reacting completely, desolventizing, adding water and dichloroethane, separating to obtain an organic phase, washing the organic phase with water, and desolventizing to obtain the photoinitiator;
wherein n is selected from 1-8.
In a second aspect, the present invention provides a photoinitiator prepared according to the method of the first aspect, wherein the formula of the photoinitiator is represented by formula a below;
wherein n is selected from 1-8, such as 2, 3, 4, 5, 6 or 7, and the like.
Preferably, the photoinitiator is a solid powdered photoinitiator.
The photoinitiator is a solid powdery photoinitiator, has good solubility in a base material, and has the characteristics of high photocuring activity and low migration.
Preferably, n is selected from 4 to 6, such as 4, 5 or 6.
When n is selected from the above range, the photoinitiator has high yield and purity using the above preparation method, and the resulting photoinitiator has lower mobility and odor and more excellent solubility in the binder while having high curing activity.
Preferably, the photoinitiator is a pale yellow solid powdered photoinitiator.
Preferably, the melting point of the photoinitiator is 68 ℃ to 75 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the photoinitiator is obtained by taking a compound shown in a formula a and a compound shown in a formula b as raw materials and carrying out an ether forming reaction; by adopting the preparation method, the target photoinitiator has higher yield and purity;
(2) The photoinitiator prepared by the preparation method of the photoinitiator is solid powder, has good solubility in a base material, has higher photocuring activity, and has low mobility in a cured coating.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The embodiment provides a preparation method of a photoinitiator and a product thereof, wherein the method comprises the following steps:
(1) Adding a compound (2.492 mol) of the formula c and absolute methanol (1000 mL) into a reaction bottle under the protection of nitrogen, controlling the temperature to 25 ℃, dropwise adding a 30% sodium methoxide methanol solution (the molar weight of the sodium methoxide is 2.741 mol), after dropwise adding, converting the system from brown yellow to milky white, continuing stirring for reaction for 1h, detecting the reaction of the raw materials in a gas phase, and then concentrating and desolventizing until no distillation is produced to obtain a compound of the formula d;
the molecular formula of the compound of the formula c is shown as follows;
(2) Adding morpholine (13.457 mol) and water (7.476 mol) into the product (the compound of the formula d) obtained in the step (1), heating to 85 ℃ after the addition is finished, reacting, and detecting that the raw materials are basically completely reacted by gas chromatography; concentrating and desolventizing at 60 ℃ to obtain a brown yellow oily substance, adding toluene (1000 mL) and water (1500 mL), separating, desolventizing an organic phase to obtain a light yellow solid, adding petroleum ether (1500 mL), stirring at room temperature for 1h, performing suction filtration and desolventizing to obtain a compound of a formula e, wherein the yield of the obtained product is 83.3%, and the purity of the obtained product is 95.6%;
the molecular formulas of the compound of the formula d and the compound of the formula e are respectively shown as follows;
(3) Adding the compound (0.159 mol) of the formula e obtained in the step (2), DMSO (120 mL) and water (40 mL) into a reaction bottle, controlling the temperature to 30 ℃, adding sodium hydroxide (0.478 mol in three batches), heating to 125 ℃, stirring for reaction for 24h after the addition is finished, cooling the reaction liquid to room temperature after TLC detection raw materials disappear, adding water (200 mL) into the reaction liquid, washing with toluene (80 mL each time), separating to obtain a lower-layer water phase, filtering through diatomite, adding concentrated hydrochloric acid to adjust the pH to 6.5, precipitating a large amount of solid, filtering, and drying at 50 ℃ to obtain the compound of the formula a; the yield of the compound of formula a is 77.1% and the purity is 96.7%;
the molecular formula of the compound of the formula a is shown as follows;
(4) Adding the compound (0.08022 mol) of the formula a obtained in the step (3), potassium carbonate (0.12033 mol) and DMF (80 mL) into a reaction bottle, then adding 2-bromoethanol (0.12033 mol), heating to 100 ℃, reacting for 12h, detecting that raw materials are basically completely reacted by TLC, removing DMF by desolventizing, adding water (60 mL) and dichloroethane (60 mL), separating to obtain an organic phase, washing three times by water (60 mL each time), and concentrating to obtain a light yellow solid powdery photoinitiator with a molecular formula shown below; the product yield was 82.26% with a purity of 98.1%.
The results of H-NMR and mass spectrometry tests on the photoinitiator prepared above are shown below:
the mass spectrometry method and test results are as follows:
MS: m/z = [M+1] + = 294.16 (MW = 293.36)；
the H-NMR test methods and results are shown below:
1 H-NMR (400MHz, CDCl 3 ): δ 7.91~7.89 (m, 2H), 6.91~6.88 (m, 2H), 4.46~4.44 (t, 2H), 3.76~3.72 (m, 2H), 3.66~3.64 (m, 4H), 2.50~2.48 (t, 4H), 1.95~1.93 (m, 1H), 1.55 (s, 6H)。
example 2
This example differs from example 1 only in that an equimolar amount of 2-bromoethanol in step (4) is replaced by a compound of the following formula b;
other parameters and conditions were exactly the same as in example 1;
the photoinitiator obtained in the embodiment is light yellow solid powder, and the molecular formula is shown as follows;
in the embodiment, the yield of the product in the step (4) is 81.1%, and the purity of the product is 98.3%;
the results of H-NMR and mass spectrometry tests on the photoinitiator prepared above are shown below:
the mass spectrometry method and test results are as follows:
MS: m/z = [M+1] + = 322.19 (MW = 321.42)；
the H-NMR test methods and results are shown below:
1 H-NMR (400MHz, CDCl 3 ): δ 7.92~7.89 (m, 2H), 6.90~6.88 (m, 2H), 4.12~4.09 (t, 2H), 3.66~3.61 (m, 6H), 1.92~1.85 (m, 2H), 1.72~1.66 (m, 2H), 1.55 (s, 6H), 1.31~1.28 (t, 1H)。
example 3
This example differs from example 1 only in that an equimolar amount of 2-bromoethanol in step (4) is replaced by a compound of formula b below;
other parameters and conditions were exactly the same as in example 1;
the photoinitiator obtained in the embodiment is light yellow solid powder, and the molecular formula is shown as follows;
in the embodiment, the yield of the product in the step (4) is 84.3%, and the purity of the product is 98.5%;
the results of H-NMR and mass spectrometry tests on the photoinitiator prepared above are shown below:
the mass spectrometry method and test results are as follows:
MS: m/z = [M+1] + = 350.23 (MW = 349.47)；
the H-NMR test methods and results are shown below:
1 H-NMR (400MHz, CDCl 3 ): δ 7.93~7.90 (m, 2H), 6.91~6.88 (m, 2H), 4.12~4.10 (t, 2H), 3.66~3.64 (m, 4H), 3.35~3.31 (m, 2H), 2.50~2.48 (t, 4H), 1.80~1.74 (m, 2H), 1.55 (s, 6H), 1.54~1.44 (m, 4H), 1.36~1.25 (m, 3H)。
example 4
This example differs from example 1 only in that an equimolar amount of 2-bromoethanol in step (4) is replaced by a compound of formula b below;
other parameters and conditions were exactly the same as in example 1;
the photoinitiator obtained in the embodiment is light yellow solid powder, and the molecular formula is shown as follows;
in the embodiment, the yield of the product in the step (4) is 86.3%, and the purity of the product is 98.3%;
the results of H-NMR and mass spectrometry tests on the photoinitiator prepared above are shown below:
the mass spectrometry method and test results are as follows:
MS: m/z = [M+1] + = 378.26 (MW = 377.53)；
the H-NMR test methods and results are shown below:
1 H-NMR (400MHz, CDCl 3 ): δ 7.92~7.88 (m, 2H), 6.90~6.88 (m, 2H), 4.12~4.10 (t, 2H), 3.66~3.63 (m, 4H), 3.35~3.30 (m, 2H), 2.50~2.48 (t, 4H), 1.77~1.71 (m, 2H), 1.55 (s, 6H), 1.50~1.41 (m, 4H), 1.36~1.24 (m, 7H)。
example 5
This example differs from example 1 in that the same volume of DMF in step (4) was replaced with acetone, and other parameters and conditions were exactly the same as in example 1.
The product yield in step (4) of this example was 82.2%, the product purity was 95.5%, and the appearance of the obtained product was light brown solid.
Example 6
This example differs from example 2 only in that the reaction temperature in step (4) was replaced with 115 ℃ and the other parameters and conditions were exactly the same as in example 2.
In this example, the product yield in step (4) was 85.2%, the product purity was 94.1%, and the appearance of the obtained product was a light brown solid.
Example 7
This example differs from example 2 only in that the reaction temperature in step (4) was replaced by 130 ℃ and the other parameters and conditions were exactly the same as in example 2.
The product yield in step (4) in this example was 82.7%, the product purity was 94.8%, and the appearance of the resulting product was a brown solid.
Comparative example 1
This comparative example employed photoinitiator 907 as a control; from Tianjin Jieshi New materials, inc.; the molecular formula is shown as follows; the product appearance is white powder;
and (3) performance testing:
the photoinitiators of examples 1 to 4 and comparative example 1 were tested for their photocuring activity, solubility in the binder and migration in the coating, the test methods and results being shown below;
photocuring activity test method and conditions:
weighing resin, monomer and photoinitiator according to the proportion of 30.5%, 23%, 43.5% and 3% of trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA), polyurethane acrylate and photoinitiator respectively to prepare a photoinitiation system, mixing the photoinitiation system by ultrasonic stirring, coating the mixed coating on a glass slide by a wire bar coater with the thickness of 10 mu m, placing the glass slide under a mercury lamp light source for irradiating once to form a film, repeatedly drawing A4 paper by a weight of 1kg without generating scratches as a complete curing standard, and recording the energy required by curing by a UV energy meter.
Solubility test methods and conditions:
respectively dissolving the photoinitiators obtained in the examples and the comparative examples in trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA) or 1, 6-hexanediol diacrylate (HDDA), preparing samples with the concentration increment of 5%, standing in the dark at 25 ℃ for 72h, and determining the solubility of the initiator by taking no obvious precipitation as a standard;
migration test methods and conditions:
taking down the film obtained after complete curing, soaking in 100mL of ethanol, and standing for 8h; the concentration of the initiator contained in the ethanol solution was measured to obtain the migration amount.
The above test results are shown in table 1;
TABLE 1
| Photoinitiator | Photocuring energy, mJ/cm 2 | Solubility in TMPTA | Solubility in TPGDA | Solubility in HDDA | Transport amount, ppm |
| Example 1 | 43.1 | 20% | 25% | 30% | 65 |
| Example 2 | 49.8 | 20% | 25% | 30% | 51 |
| Example 3 | 52.3 | 25% | 30% | 35% | 43 |
| Example 4 | 56.7 | 25% | 30% | 35% | 35 |
| Comparative example 1 | 38.3 | 15% | 20% | 25% | 150 |
As can be seen from the test results, the photoinitiator has the photocuring activity close to that of the photoinitiator 907, and the low mobility of the photoinitiator is obviously better than that of the photoinitiator 907; and has better solubility in resin monomers.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein fall within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a solid powdery photoinitiator is characterized in that the molecular formula of the photoinitiator is shown as the following formula A;
the preparation method comprises the following steps: mixing a compound shown in the formula a, alkali and a polar organic solvent, adding a compound shown in the formula b, and heating for reaction to obtain the photoinitiator;
wherein n is selected from 3-8;
the alkali is selected from potassium carbonate and/or sodium carbonate;
the polar organic solvent is selected from DMF and/or DMSO;
the molar weight ratio of the compound of formula a to the compound of formula b is 1.2 to 1.8;
the temperature for heating to carry out reaction is 95 to 105 ℃;
after the reaction is finished, the method also comprises the following steps: desolventizing the reaction solution, adding water and a non-polar organic solvent, separating liquid to obtain an organic phase, washing with water, and desolventizing to obtain the photoinitiator;
the non-polar organic solvent is selected from dichloroethane and/or dichloromethane.
2. The process of claim 1, wherein the compound of formula a is prepared by a process comprising the steps of:
(1) Cyclization reaction: mixing the compound of the formula c, methanol and sodium methoxide in an inert atmosphere, and reacting to obtain a compound of a formula d;
wherein X is selected from Br or Cl;
(2) Morpholine substitution reaction: mixing the compound of the formula d obtained in the step (1), morpholine and water, and heating for reaction to obtain a compound of a formula e;
(3) Hydroxyl substitution reaction: mixing the compound of the formula e obtained in the step (2), an organic solvent and water, then adding an alkali metal hydroxide, heating for reaction, and adding acid to adjust the pH value to obtain a compound of a formula a;
3. the method according to claim 2, wherein the inert atmosphere of step (1) comprises any one of nitrogen, helium or argon or a mixture of at least two thereof;
the temperature for the reaction in the step (1) is 23 to 27 ℃;
the method for mixing the compound of formula c, methanol and sodium methoxide in the step (1) comprises the following steps: mixing the compound of the formula c and absolute methanol, controlling the temperature to 23-27 ℃, then dropwise adding a methanol solution of sodium methoxide, and continuing controlling the temperature to react until the reaction is complete;
the concentration of the methanol solution of sodium methoxide is 20-40wt%;
the molar ratio of the compound of the formula c to sodium methoxide is 1 (1.05 to 1.2);
stirring is carried out along with the reaction process in the step (1);
and (2) desolventizing after the reaction in the step (1) is finished to obtain the compound shown in the formula d.
4. The process according to claim 3, wherein the concentration of the sodium methoxide in methanol is 25 to 35 wt.%.
5. The preparation method according to claim 2, wherein the molar weight ratio of the compound of formula d to morpholine in step (2) is 1 (5-6);
the molar weight ratio of the compound of the formula d to water in the step (2) is 1;
the temperature for heating and reacting in the step (2) is 80-90 ℃;
after the reaction in the step (2) is finished, post-treatment is further included, the post-treatment includes desolventizing to obtain a desolventized product, then adding a nonpolar organic solvent and water, separating liquid to obtain an organic phase, desolventizing, and washing with the organic solvent to obtain the compound of the formula e;
the non-polar organic solvent is selected from toluene; the volume ratio of the nonpolar organic solvent to the water is 1-2;
the organic solvent adopted for washing comprises petroleum ether.
6. The method according to claim 2, wherein the organic solvent in the step (3) is selected from dimethyl sulfoxide and/or sulfolane;
the alkali metal hydroxide of step (3) is selected from sodium hydroxide;
the molar weight ratio of the compound of formula e to the alkali metal hydroxide in step (3) is 1.
7. The method according to claim 2, wherein the mixture of the compound of formula e, the organic solvent and water is controlled to 10-40 ℃ before the alkali metal hydroxide is added in step (3);
the temperature for raising the temperature to carry out the reaction in the step (3) is 120-130 ℃.
8. The preparation method according to claim 2, wherein after the reaction in step (3) is finished, the reaction solution is cooled, water is added, then an organic solvent is added for washing, liquid separation is carried out to obtain an aqueous phase, filtration is carried out, acid is added to adjust the pH to 6-6.5, a solid is separated out, and solid-liquid separation is carried out to obtain the compound of formula a;
the organic solvent added for washing is selected from toluene and/or dichloromethane;
the acid is selected from hydrochloric acid.
9. The method for preparing according to claim 1, characterized in that it comprises the following steps:
(1) Adding the compound of the formula c and absolute methanol into a reactor under the stirring condition with the protection of nitrogen atmosphere, controlling the temperature to be 23-27 ℃, dropwise adding a methanol solution of 25-35wt% of sodium methoxide into the reactor, after dropwise adding, continuously controlling the temperature to react until the gas chromatography detection raw materials completely react, and then desolventizing to obtain a compound of the formula d;
wherein X is selected from Br or Cl;
(2) Adding morpholine and water into the compound of the formula d obtained in the step (1), heating to 80-90 ℃ for reaction, detecting by gas chromatography until the reaction is complete, desolventizing, adding toluene and water, separating liquid to obtain an organic phase, desolventizing, then adding petroleum ether for washing, and performing solid-liquid separation to obtain a compound of the formula e;
(3) Adding the compound of the formula e obtained in the step (2), dimethyl sulfoxide and water into a reactor, controlling the temperature to 10-40 ℃, adding sodium hydroxide in batches, after the addition is finished, heating to 120-130 ℃ to react completely, then cooling, adding water into a reaction solution, adding toluene to wash, separating liquid to obtain a water phase, filtering, adding hydrochloric acid into the water phase to adjust the pH value to 6-6.5, separating out a solid, and carrying out solid-liquid separation to obtain a compound of the formula a;
(4) Adding the compound of the formula a obtained in the step (3), potassium carbonate and DMF (dimethyl formamide) into a reactor, then adding the compound of the formula b, heating to 95-105 ℃, reacting completely, desolventizing, adding water and dichloroethane, separating to obtain an organic phase, washing the organic phase with water, and desolventizing to obtain the photoinitiator;
wherein n is selected from 3-8.
10. The solid, powdered photoinitiator according to any one of claims 1 to 9, characterised in that it has the formula a;
wherein n is selected from 3 to 8.
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