CN116425795A - Acylphosphine oxide photoinitiator and preparation method and application thereof - Google Patents
Acylphosphine oxide photoinitiator and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 20
- 239000012074 organic phase Substances 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 8
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- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 241000209094 Oryza Species 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
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- 230000007935 neutral effect Effects 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 150000002978 peroxides Chemical group 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 4
- 229940037003 alum Drugs 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000010146 3D printing Methods 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
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- 230000035484 reaction time Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 231100000053 low toxicity Toxicity 0.000 abstract description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- -1 acyl phosphine oxide Chemical compound 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical group [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
Abstract
The invention relates to an acylphosphine oxide photoinitiator, a preparation method and application thereof, wherein the acylphosphine oxide photoinitiator comprises two or three acylphosphine oxide groups which are symmetrically distributed, and the acylphosphine oxide groups are connected through specific groups, so that the obtained photoinitiator has high photoinitiation activity, has the characteristics of low mobility, low odor and low toxicity compared with the photoinitiator TPO, and has wider application prospect compared with TPO; the preparation method has the advantages of short process flow, simple operation and convenient industrialized application.
Description
Technical Field
The invention belongs to the field of photo-curing materials, and relates to an acylphosphine oxide photoinitiator, a preparation method and application thereof.
Background
The acyl phosphine oxide photoinitiator is a photoinitiator with higher photoinitiation activity and better comprehensive performance, and belongs to a cleavable free radical photoinitiator; currently, the product that has been commercialized and widely used is 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide (TPO); wherein, the photo initiator TPO has enough solubility in the active diluent, the absorption wavelength can reach 430nm, and two free radicals with high initiator activity, namely, the mesityl free radical and the diphenyl phosphono free radical are generated after photolysis. In practical use, the photoinitiator TPO acts as a small molecule photoinitiator, which runs the risk of migration and toxicity.
In the prior art, based on a photoinitiator TPO and a TPO-L, the photoinitiator TPO or the TPO-L is used as a raw material, and polymerizable double bond functional groups are introduced through reaction to respectively obtain TPO-X and TPO-SJ, wherein the molecular formula is shown as follows; wherein, the polymerizable double bond participates in the polymerization reaction, thereby improving the mobility of the photoinitiator in the polymer and reducing the odor and toxicity caused by the migration of the low molecular photoinitiator; however, the implementation of the scheme needs to prepare TPO or TPO-L firstly, the process is complex, TPO or TPO-L is easy to deteriorate under the reaction condition of strong acid or strong alkali, and the yield and purity of the product are affected.
Therefore, development of an acylphosphine oxide photoinitiator with high photoinitiator activity, low mobility, low odor and low toxicity, and a preparation method thereof, is still of great significance.
Disclosure of Invention
The invention aims to provide an acylphosphine oxide photoinitiator, a preparation method and application thereof, wherein the acylphosphine oxide photoinitiator comprises two or three acylphosphine oxide groups which are symmetrically distributed, and the acylphosphine oxide groups are connected through specific groups, so that the obtained photoinitiator has high photoinitiation activity, has the characteristics of low mobility, low odor and low toxicity compared with a photoinitiator TPO, and has wider application prospect compared with the TPO; the preparation method has the advantages of short process flow, simple operation and convenient industrialized application.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an acylphosphine oxide photoinitiator having the formula shown below;
wherein X is selected from O, S, -NR, - (CH) 2 ) m -or any one of the groups of formula (b) below; r is selected from any one of C1-C12 linear or branched alkyl, a group shown in the following formula (C) or a group shown in the following formula (d);
m is selected from 1 to 4, n is selected from 1 to 4, R 1 Selected from C1-C12 straight or branched alkyl.
The acylphosphine oxide photoinitiator comprises two or three acylphosphine oxide groups which are symmetrically distributed, and the acylphosphine oxide groups are connected through a specific X group, so that the acylphosphine oxide photoinitiator has the characteristics of low mobility, low odor, low toxicity and high initiation activity.
The acylphosphine oxide photoinitiator has high photoinitiation activity, and has low molecular mobility and low odor and toxicity compared with a photoinitiator TPO.
Preferably, X is selected from O, -NR, - (CH) 2 ) m -or any one of the groups of formula (b).
Preferably, m is 1 or 2.
Preferably, n is 1 or 2.
In the acylphosphine oxide photoinitiator, the selection of X has a certain influence on the active agent of the photoinitiator, and the invention discovers that the photoinitiator has higher photoinitiation activity when X is selected from O, -NR or a group shown in a formula (b) through researches.
Preferably, R is selected from any one of a C1-C4 linear or branched alkyl group, a group represented by formula (C) or a group represented by formula (d).
Preferably, R 1 Selected from C1-C4 straightChain or branched alkyl groups.
Preferably, the acylphosphine oxide photoinitiator comprises any one of the following structures;
in a second aspect, the present invention provides a process for the preparation of an acylphosphine oxide photoinitiator according to the first aspect, the process comprising the steps of:
(1) Mixing phenyl phosphine dichloride, a compound shown in a formula (e) and a catalyst, and heating for reaction to obtain a mixture containing an intermediate product;
wherein Y is selected from O, S, -NR', - (CH) 2 ) m -or any one of the groups of formula (b); r' is selected from any one of C1-C12 straight-chain or branched alkyl, a group shown in a formula (C) or phenyl;
(2) Hydrolyzing the mixture obtained in the step (1), and separating the solution to obtain an organic phase;
(3) Adding rice aldehyde into the organic phase in the step (2) to react;
(4) And (3) oxidizing the reaction product in the step (3) to obtain the acylphosphine oxide photoinitiator.
In the preparation method of the acylphosphine oxide photoinitiator, when Y is selected from O, S, -NR', - (CH) 2 ) m -or any one of the groups of formula (b), R' being selected from the group consisting of C1-C12 linear or branched alkyl groups or any one of the groups of formula (C); the reaction equation is shown below; the preparation method takes phenyl phosphine dichloride and a compound shown in a formula (e) as raw materials, and obtains a photoinitiator containing two acyl phosphorus oxide symmetrical groups in a molecule through four-step reaction；
As can be seen from the above reaction equation, the four-step reactions are respectively shown below;
firstly, phenyl phosphine dichloride and a compound shown in a formula (e) react under the action of a catalyst to obtain the compound shown in the formula (f);
secondly, hydrolyzing the compound shown in the formula (f) to obtain a compound shown in the formula (g);
thirdly, carrying out mixed addition reaction on the compound shown in the formula (g) and mildly aldehyde to obtain a compound shown in the formula (h);
and fourthly, mixing the compound shown in the formula (h) with an oxidant under the action of a catalyst, and performing an oxidation reaction to obtain the compound shown in the formula (i), namely the acylphosphine oxide photoinitiator.
In the preparation method of the acylphosphine oxide photoinitiator, when Y is selected from-NR 'and R' is selected from phenyl, namely the compound shown in the formula (e) is triphenylamine; the photoinitiator containing three symmetrical acyl phosphine oxide groups in the molecule can be prepared; the reaction equation is shown below;
the reaction equation comprises four steps of reactions, respectively shown as follows;
firstly, reacting phenyl phosphine dichloride and triphenylamine under the action of a catalyst to obtain a compound shown in a formula (j);
secondly, hydrolyzing the compound shown in the formula (j) to obtain a compound shown in the formula (k);
thirdly, carrying out mixed addition reaction on the compound shown in the formula (k) and mildly aldehyde to obtain a compound shown in the formula (l);
and fourthly, mixing the compound shown in the formula (l) with an oxidant under the action of a catalyst, and performing an oxidation reaction to obtain the compound shown in the formula (m), namely the acylphosphine oxide photoinitiator.
The photoinitiator containing two or three acyl phosphine oxide symmetrical groups in the molecule is prepared by the method, and the technical process route is short and the cost is low.
Preferably, the catalyst in step (1) comprises aluminium trichloride.
Preferably, the temperature of the heating reaction in step (1) is from 100℃to 150℃such as 110℃120℃130℃or 140℃and the like, preferably from 110℃to 130 ℃.
The phenyl phosphine dichloride and the compound shown in the formula (e) react under the heating condition, and the reaction temperature is limited within the range, so that the reaction is facilitated, side reactions can be well avoided, and when the reaction temperature is too low, the reaction rate is slow and the reaction is incomplete; when the reaction temperature is too high, the selectivity of the reaction is lowered, side reactions are increased, and the side reactions are increased as follows: thereby reducing the reaction yield;
preferably, the molar ratio of phenyl phosphine dichloride, compound of formula (e) and catalyst in step (1) is from 2 to 3:1:2 to 4, e.g. 2:1:2.4 or 3:1:3.2, etc.
Preferably, the hydrolysis in step (2) further comprises mixing the mixture in step (1) with a nonpolar solvent for dilution.
Preferably, the dilution is preceded by a cooling.
Preferably, the nonpolar solvent includes at least one of toluene, xylene, ethylbenzene, and chlorobenzene.
After the first step reaction is finished, the mixture obtained in the first step reaction is diluted by adopting a nonpolar solvent before the hydrolysis reaction, so that the subsequent hydrolysis and liquid separation processes are convenient to carry out.
Preferably, the method of hydrolysis comprises adding the mixture obtained by diluting the mixture in step (1) to water in the form of droplets.
Preferably, the temperature during the hydrolysis is less than or equal to 20 ℃, for example 10 ℃, 12 ℃,15 ℃, 18 ℃, etc.
Preferably, the hydrolysis process is accompanied by agitation.
In the invention, the hydrolysis reaction adopts the mixing mode and the temperature condition, which is favorable for reducing the color of a reaction system, is easier to separate, is convenient for post-treatment, has obvious reaction heat release when the temperature is too high, is unfavorable for controlling the temperature, and can generate impurities to ensure that the water phase and the organic phase are unfavorable for separating, even are not separated, and the reaction system is a viscous liquid, so that the reaction is unfavorable for continuing.
Preferably, the ratio of the molar amount of mildly added in step (3) to the molar amount of phenyl phosphine dichloride in step (1) is 0.8 to 1.5:1, e.g. 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1 or 1.4:1, etc.
Preferably, the temperature at which the reaction of step (3) is carried out is from 15℃to 40℃such as 20℃25℃30℃or 35℃and the like, preferably from 20℃to 35 ℃.
Preferably, the reaction in step (3) is carried out for a period of time ranging from 2h to 12h, for example 3h, 5h, 7h, 9h or 11h, etc.
Preferably, the reaction in step (3) is completed by cooling to 10-15 ℃, such as 11 ℃, 12 ℃, 13 ℃ or 14 ℃ and the like.
In the invention, before the oxidation reaction starts, the temperature of the reaction solution is controlled within the range, and then the catalyst and the oxidant are added for the oxidation reaction, so that the reaction temperature is controlled to avoid the decomposition of Wen Dewu, the generation of side reaction is reduced, and the reaction is controlled to be carried out smoothly and safely.
Preferably, the method of the oxidation reaction in the step (4) comprises adding a catalyst and an oxidant into the reaction product in the step (3), and mixing to perform the oxidation reaction.
Preferably, the catalyst in the oxidation reaction is selected from at least one of a alum-containing catalyst, a heteropolyacid catalyst and a heteropolyacid salt catalyst, wherein the alum-containing catalyst is vanadyl acetylacetonate; heteropolyacid catalysts or heteropolyacid salt catalysts such as tungstic anhydride, tungstates, molybdic anhydride, molybdates, phosphomolybdates or mixtures thereof.
Preferably, the amount of catalyst used in the oxidation reaction is selected from 0.1% -10% by mass of phenylphosphine dichloride, for example 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9% etc.
Preferably, the oxidizing agent is selected from peroxides, preferably hydrogen peroxide and/or t-butyl peroxide;
preferably, the amount of oxidant used in the oxidation reaction is selected from 1 to 3 times the amount of phenylphosphine dichloride material; for example 1.5 times, 2 times or 2.5 times, etc.
Preferably, the oxidant is added dropwise.
Preferably, the oxidation reaction in the step (4) further comprises alkali washing, liquid separation, water washing and desolventizing.
Preferably, the alkaline solution used for alkaline washing comprises at least one of sodium hydroxide aqueous solution, sodium carbonate aqueous solution or sodium bicarbonate aqueous solution, preferably sodium hydroxide aqueous solution.
The alkaline washing method aims at removing organic acid impurities, improving layering effect of the water phase and the organic phase and avoiding long-time standing; meanwhile, in order to adjust the reaction liquid to be alkaline, the corrosion of an acidic system to subsequent reaction equipment is avoided.
Preferably, the alkaline washing is performed at a temperature of 20℃or less, for example, 10℃12℃14℃15℃16℃18℃or 19 ℃.
Preferably, the alkaline solution used for the alkaline washing is selected from aqueous sodium hydroxide solutions with a concentration of 15wt% to 25wt%, such as 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt% or 24wt%, etc.
In the invention, the alkaline washing temperature is controlled in the above range, and if the temperature is too high, the alkaline concentration is too high in an alkaline system, so that the decomposition of the product generated by the reaction can be accelerated.
Preferably, the alkaline washing process is accompanied by stirring.
Preferably, the organic phase obtained from the end point of the water washing to the separation is neutral.
As a preferable technical scheme of the invention, the preparation method of the acylphosphine oxide photoinitiator comprises the following steps:
mixing phenyl phosphine dichloride, a compound shown in a formula (e) and aluminum chloride in a reaction container, heating to 100-150 ℃ for heating reaction, and cooling to obtain a mixture containing an intermediate product;
wherein Y is selected from O, S, -NR', - (CH) 2 ) m -or any one of the groups of formula (b); r' is selected from any one of C1-C12 straight-chain or branched alkyl, a group shown in a formula (C) or phenyl;
adding a nonpolar solvent into the mixture in the step (I) for dilution to obtain a mixed solution, then adding the mixed solution into water for hydrolysis under the condition that the temperature is less than or equal to 20 ℃ and the stirring is carried out, and separating the solution to obtain an organic phase;
(III) adding rice aldehyde into the organic phase in the step (II), reacting for 2-12 h at 15-40 ℃, and then cooling to 10-15 ℃;
(IV) adding a catalyst into the reaction product in the step (III), and then dropwise adding peroxide to perform oxidation reaction;
(V) adding 15-25wt% sodium hydroxide aqueous solution into the reaction product in the step (IV) at the temperature of less than or equal to 20 ℃ with stirring, separating liquid, washing the organic phase to be neutral, and desolventizing to obtain the acylphosphine oxide photoinitiator.
In a third aspect, the present invention provides the use of an acylphosphine oxide photoinitiator according to the first aspect for use in a photocurable system having a wavelength in the range 300nm to 450 nm.
Preferably, the acylphosphine oxide photoinitiator is used in the fields of inks, coatings, dental restorations, 3D printing, and plumbing restorations.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with a photoinitiator TPO, the acylphosphine oxide photoinitiator has the characteristics of low mobility, low odor and low toxicity;
(2) The acylphosphine oxide photoinitiator comprises two or three acylphosphine oxide groups which are symmetrically distributed, and the groups are connected by adopting the specific groups defined by the invention, so that the obtained photoinitiator has high photoinitiation activity and photocuring efficiency.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The molecular formula of the acylphosphine oxide photoinitiator in this example is shown below;
the preparation method of the acylphosphine oxide photoinitiator in the embodiment comprises the following steps:
29.2g (0.22 mol) of aluminum trichloride, 36g (0.2 mol) of phenyl phosphine dichloride and 17g (0.1 mol) of diphenyl ether are sequentially added into a four-neck flask, mixed, heated to 120 ℃ for heating reaction until GC detects that the phenyl phosphine dichloride is completely reacted, and cooled to obtain a mixture containing an intermediate product;
adding toluene into the mixture in the step (I) for dilution to obtain a mixed solution, then dripping the mixed solution into 90g of water for hydrolysis for 30min at 15 ℃ under the condition of stirring, and separating the solution to obtain an organic phase;
(III) adding 29.7g (0.2 mol) of rice aldehyde into the organic phase in the step (II), reacting for 4 hours at room temperature (25 ℃), and then cooling to 15 ℃;
(IV) adding 0.5g of vanadyl acetylacetonate into the reaction product in the step (III), slowly dropwise adding 28g of 30% hydrogen peroxide, and carrying out oxidation reaction until the intermediate is completely reacted by HPLC;
(V) adding 50g of 20wt% sodium hydroxide aqueous solution into the reaction product in the step (IV) at 15 ℃ with stirring, stirring for 30min, separating liquid, washing the organic phase to be neutral, and desolventizing to obtain brown viscous liquid, namely the acylphosphine oxide photoinitiator; the yield of the acyl phosphine oxide photoinitiator is 78 percent and the purity is 98.5 percent through recrystallization and purification.
MS:m/z[M+1] + ＝711.24(Mw＝710.73)。
The results of H-NMR analysis of the photoinitiators in this example are shown below;
1 H-NMR(400MHz,CDCl3):δ7.30～7.1(m,14H),6.90-6.70(m,8H),2.40(s,12H),2.35(s,6H)。
example 2
The molecular formula of the acylphosphine oxide photoinitiator in this example is shown below;
the preparation of the acylphosphine oxide photoinitiator in this example differs from example 1 only in that the equimolar amount of diphenyl ether is replaced by diphenyl sulfide, and other parameters and conditions are exactly the same as in example 1. The yield of the acyl phosphine oxide photoinitiator is 70 percent and the purity is 98.3 percent through recrystallization and purification.
MS:m/z[M+1] + ＝727.21(Mw＝726.80)。
The results of H-NMR analysis of the photoinitiators in this example are shown below;
1 H-NMR(400MHz,CDCl3):δ7.40～7.15(m,14H),7.10～7.00(m,4H),6.86(s,4H),2.30(s,18H)。
example 3
The molecular formula of the acylphosphine oxide photoinitiator in this example is shown below;
the preparation of the acylphosphine oxide photoinitiator in this example differs from example 1 only in that the equimolar amount of diphenyl ether is replaced by N-methyldiphenylamine, and other parameters and conditions are exactly the same as in example 1.
MS:m/z[M+1] + ＝724.27(Mw＝723.77)。
The results of H-NMR analysis of the photoinitiators in this example are shown below;
1 H-NMR(400MHz,CDCl3):δ7.42～7.32(m,10H),7.20～7.12(m,4H),6.90-6.85(m,4H),6.50-6.38(m,4H),2.82(s,3H),2.40(s,12H),2.32(s,6H)。
example 4
The molecular formula of the acylphosphine oxide photoinitiator in this example is shown below;
the preparation of the acylphosphine oxide photoinitiator in this example differs from example 1 only in that the equimolar amount of diphenyl ether is replaced by 4-methyltrianiline, and other parameters and conditions are exactly the same as in example 1.
MS:m/z[M+1] + ＝800.30(Mw＝799.87)。
The results of H-NMR analysis of the photoinitiators in this example are shown below;
1 H-NMR(400MHz,CDCl3):δ7.50～7.41(m,10H),7.23～7.15(m,4H),7.08～6.90(m,6H),6.75-6.49(m,4H),6.39～6.30(m,2H),2.35(s,12H),2.28(s,6H),2.22(s,3H)。
example 5
The molecular formula of the acylphosphine oxide photoinitiator in this example is shown below;
the preparation method of the acylphosphine oxide photoinitiator in the embodiment comprises the following steps:
43.8g (0.33 mol) of aluminum trichloride, 54g (0.3 mol) of phenyl phosphine dichloride and 24.6g (0.1 mol) of triphenylamine are sequentially added into a four-neck flask, mixed, heated to 130 ℃ for heating reaction until the reaction of the phenyl phosphine dichloride is complete by GC, and cooled to obtain a mixture containing an intermediate product;
adding toluene into the mixture in the step (I) for dilution to obtain a mixed solution, then dropwise adding the mixed solution into 150g of water at 10 ℃ with stirring for hydrolysis for 45min, and separating the solution to obtain an organic phase;
(III) adding 44.4g (0.3 mol) of rice aldehyde into the organic phase in the step (II), reacting for 4 hours at 25 ℃, and then cooling to 15 ℃;
(IV) adding 0.75g of vanadyl acetylacetonate into the reaction product in the step (III), slowly dropwise adding 42g of 30% hydrogen peroxide, and carrying out oxidation reaction until the intermediate is completely reacted by HPLC;
(V) adding 75g of 20wt% sodium hydroxide aqueous solution into the reaction product in the step (IV) at 15 ℃ with stirring, stirring for 30min, separating liquid, washing the organic phase to be neutral, and desolventizing to obtain the acylphosphine oxide photoinitiator;
by HPLC, wherein the trifunctional groups: difunctional=8:2, ms: M/z [ m+1] + = 1056.36 (mw= 1056.11) (trifunctional), [ m+1 ]] + = 786.28 (mw= 785.84) (difunctional).
Example 6
The molecular formula of the acylphosphine oxide photoinitiator in this example is shown below;
the preparation method of the acylphosphine oxide photoinitiator in this example is different from that of example 1 only in that the equimolar amount of diphenyl ether is replaced by a compound represented by the following formula;
other parameters and conditions were exactly the same as in example 1.
MS:m/z[M+1] + ＝755.26(Mw＝754.79)。
The results of H-NMR analysis of the photoinitiators in this example are shown below;
1 H-NMR(400MHz,CDCl3):δ7.40～7.30(m,10H),7.29～7.20(m,4H),6.90～6.80(m,8H),4.4(s,4H),2.35(s,18H)。
example 7
The molecular formula of the acylphosphine oxide photoinitiator in this example is shown below;
the preparation of the acylphosphine oxide photoinitiator in this example differs from example 1 only in that the equimolar amount of diphenyl ether is replaced by diphenylmethane, and other parameters and conditions are exactly the same as in example 1.
MS:m/z[M+1] + ＝709.26(Mw＝708.76)。
The results of H-NMR analysis of the photoinitiators in this example are shown below;
1 H-NMR(400MHz,CDCl3):δ7.50～7.30(m,10H),7.29～7.20(m,4H),6.90～6.80(m,8H),4.4(s,4H),2.35(s,18H)。
comparative example 1
The comparative example uses photo initiator TPO as a control.
Comparative example 2
The molecular formula of the photoinitiator in this comparative example is shown below;
the preparation of the acylphosphine oxide photoinitiator in this example differs from example 1 only in that the equimolar amount of diphenyl ether is replaced by biphenyl, and other parameters and conditions are exactly the same as in example 1.
MS:m/z[M+1] + ＝695.24(Mw＝694.73)。
The results of H-NMR analysis of the photoinitiators in this comparative example are shown below;
1 H-NMR(400MHz,CDCl3):δ7.80～7.30(m,18H),6.92～6.85(m,4H),2.45(s,18H)。
performance test:
the photoinitiators obtained in examples and comparative examples were subjected to photoinitiation activity and mobility tests, and the test conditions are shown below, respectively;
test formulation and working conditions
The formula comprises the following components:
36wt% of epoxypropenecarboxylic acid resin (molecular weight 700-800)
Pentaerythritol triacrylate 60wt%
4.0wt% of the product of the example (or of the comparative example);
working conditions and evaluation
The above mixture was coated on a glass plate with a squeegee, and the film was cured by irradiation with a standard mercury vapor lamp or an LED lamp (360W, 390 nm light source exposure for 5 s). After passing the glass sheet through the lamp at a speed of 100 meters/minute, the film was found to wipe hard. The number of passes under the lamp required for complete curing of the surface was recorded. The results are shown in Table 1.
TABLE 1
Mobility test conditions:
the formula of the photo-curing composition for mobility test is the same as that of the photo-initiation activity test; the film was applied with a squeegee and cured by irradiation with a standard mercury vapor lamp. Take (15X 15 cm) 2 ) The cured coated samples were placed between two stainless steel plates with a 10cm diameter filter paper and held at five tons pressure for 72 hours, the filter paper was heated to reflux with THF extraction for three hours, and the content of the samples and comparative examples was determined by HPLC, the results are shown in table 2.
TABLE 2
As can be seen from the above data in tables 1 and 2, the acylphosphine oxide photoinitiators of the present invention have high photoinitiating activity and significantly reduced mobility compared to the photoinitiator TPO.
As can be seen from comparative examples 1-4 and 6-7, the photoinitiator molecules contain two symmetrically distributed acyl phosphine oxide groups, which have higher photoinitiator activity; furthermore, the invention adopts a specific group as a connecting group to connect two acyl phosphine oxide groups, and the synergistic effect between the two groups enhances the initiation activity of the photoinitiator; and wherein the linking group X is selected from O, -NR, -O (CH) 2 ) 2 At the time of O-, the photoinitiator activity is optimal; and is more preferably O or-O (CH) 2 ) 2 O-; in contrast, the photoinitiators TPO and comparative example 2 show that, although comparative example 2 also comprises two acylphosphine oxides, the photoinitiating activity is significantly reduced compared to TPO.
As can be seen from examples 3-4, when the linking group X is selected from the group consisting of-NR, R is further preferably alkyl, 4-substituted phenyl; and as can be seen from the photoinitiator in example 6, it contains three symmetrically distributed acylphosphine oxide groups, and the synergistic effect among the three results in higher photoinitiating activity and lower mobility than the photoinitiator TPO, but higher mobility than the photoinitiator with two symmetrically distributed acylphosphine oxide groups.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (8)
1. A method for preparing an acylphosphine oxide photoinitiator, which is characterized in that the molecular formula of the acylphosphine oxide photoinitiator is shown as follows;
wherein X is selected from O, S, - (CH) 2 ) m -or any one of the groups of formula (b) below;
m is selected from 1-4, n is selected from 1-4;
the preparation method comprises the following steps:
(1) Mixing phenyl phosphine dichloride, a compound shown in a formula (e) and a catalyst, and heating for reaction to obtain a mixture containing an intermediate product;
wherein Y is selected from O, S, - (CH) 2 ) m -or any one of the groups of formula (b);
(2) Hydrolyzing the mixture obtained in the step (1), and separating the solution to obtain an organic phase;
(3) Adding rice aldehyde into the organic phase in the step (2) to react;
(4) And (3) oxidizing the reaction product in the step (3) to obtain the acylphosphine oxide photoinitiator.
2. The process according to claim 1, wherein X is selected from the group consisting of O, - (CH) 2 ) m -or any one of the groups of formula (b);
preferably, m is 1 or 2;
preferably, n is 1 or 2.
3. The method of preparing as claimed in claim 1, wherein the acylphosphine oxide photoinitiator comprises any one of the following structures;
4. the process of claim 1 wherein the catalyst in step (1) comprises aluminum trichloride;
preferably, the temperature of the heating reaction in step (1) is 100 ℃ to 150 ℃, preferably 110 ℃ to 130 ℃;
preferably, the molar ratio of the phenyl phosphine dichloride, the compound shown in the formula (e) and the catalyst in the step (1) is 2-3:1:2-4;
preferably, the hydrolysis in the step (2) further comprises mixing the mixture in the step (1) with a nonpolar solvent for dilution;
preferably, the dilution is preceded by cooling;
preferably, the nonpolar solvent includes at least one of toluene, xylene, ethylbenzene, and chlorobenzene;
preferably, the method of hydrolysis comprises adding the mixture obtained by diluting the mixture in step (1) to water in a droplet manner;
preferably, the temperature in the hydrolysis process is less than or equal to 20 ℃;
preferably, the hydrolysis process is accompanied by agitation.
5. The process according to claim 1, wherein the molar amount of mildly added in step (3) to the molar amount of phenyl phosphine dichloride in step (1) is 0.8 to 1.5:1;
preferably, the temperature at which the reaction is carried out in the step (3) is 15-40 ℃; preferably 20-35 ℃;
preferably, the reaction time in the step (3) is 2-12 hours;
preferably, after the reaction in the step (3) is finished, the temperature is reduced to 10-15 ℃;
preferably, the method of the oxidation reaction in the step (4) comprises the steps of adding a catalyst and an oxidant into the reaction product in the step (3), mixing and carrying out the oxidation reaction;
preferably, the catalyst in the oxidation reaction is at least one selected from alum-containing catalyst, heteropolyacid catalyst and heteropolyacid salt catalyst;
preferably, the catalyst is used in the oxidation reaction in an amount selected from 0.1% -10% of the mass of phenyl phosphine dichloride;
preferably, the oxidizing agent is selected from peroxides, preferably hydrogen peroxide and/or t-butyl peroxide;
preferably, the amount of oxidant used in the oxidation reaction is selected from 1 to 3 times the amount of phenylphosphine dichloride material;
preferably, the oxidant is added dropwise.
6. The method of claim 1, wherein the oxidation reaction in step (4) is followed by alkaline washing, liquid separation, water washing, and desolventizing;
preferably, the alkali solution used for alkali washing comprises at least one of sodium hydroxide aqueous solution, sodium carbonate aqueous solution or sodium bicarbonate aqueous solution;
preferably, the temperature of the alkaline washing is less than or equal to 20 ℃;
preferably, the alkali liquor used for alkali washing is selected from sodium hydroxide aqueous solution with the concentration of 15-25 wt%;
preferably, the alkaline washing process is accompanied by stirring;
preferably, the organic phase obtained from the end point of the water washing to the separation is neutral.
7. The method of preparation according to claim 1, characterized in that the method comprises the steps of:
mixing phenyl phosphine dichloride, a compound shown in a formula (e) and aluminum chloride in a reaction container, heating to 100-150 ℃ for heating reaction, and cooling to obtain a mixture containing an intermediate product;
wherein Y is selected from O, S, - (CH) 2 ) m -or any one of the groups of formula (b);
adding a nonpolar solvent into the mixture in the step (I) for dilution to obtain a mixed solution, then adding the mixed solution into water for hydrolysis under the condition that the temperature is less than or equal to 20 ℃ and the stirring is carried out, and separating the solution to obtain an organic phase;
(III) adding rice aldehyde into the organic phase in the step (II), reacting for 2-12 h at 15-40 ℃, and then cooling to 10-15 ℃;
(IV) adding a catalyst into the reaction product in the step (III), and then dropwise adding peroxide to perform oxidation reaction;
(V) adding 15-25wt% sodium hydroxide aqueous solution into the reaction product in the step (IV) at the temperature of less than or equal to 20 ℃ with stirring, separating liquid, washing the organic phase to be neutral, and desolventizing to obtain the acylphosphine oxide photoinitiator.
8. Use of an acylphosphine oxide photoinitiator according to claim 1, wherein the acylphosphine oxide photoinitiator is used in a photocuring system having a wavelength of 300nm to 450 nm;
preferably, the acylphosphine oxide photoinitiator is used in the fields of inks, coatings, dental restorations, 3D printing, and plumbing restorations.
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