WO2022236524A1 - 光引发剂及其制备方法 - Google Patents
光引发剂及其制备方法 Download PDFInfo
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- WO2022236524A1 WO2022236524A1 PCT/CN2021/092574 CN2021092574W WO2022236524A1 WO 2022236524 A1 WO2022236524 A1 WO 2022236524A1 CN 2021092574 W CN2021092574 W CN 2021092574W WO 2022236524 A1 WO2022236524 A1 WO 2022236524A1
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 116
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- 239000001257 hydrogen Substances 0.000 claims description 49
- 229910052736 halogen Inorganic materials 0.000 claims description 45
- 150000002367 halogens Chemical class 0.000 claims description 45
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 23
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 4,4'-dihydroxyethoxybenzophenone methacrylate Chemical compound 0.000 description 5
- PNTLMFABGCHLMN-UHFFFAOYSA-N [4-(2-hydroxyethoxy)phenyl]-phenylmethanone Chemical compound C1=CC(OCCO)=CC=C1C(=O)C1=CC=CC=C1 PNTLMFABGCHLMN-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 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QMVCZBDMMOYLNI-UHFFFAOYSA-N (2-ethoxy-4-hydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound OC1=CC(=C(C(=O)C2=CC=C(C=C2)O)C=C1)OCC QMVCZBDMMOYLNI-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000012360 testing method Methods 0.000 description 3
- VKJFPNMKYBLWLN-UHFFFAOYSA-N (4-chlorophenyl)-[4-(2-hydroxyethoxy)phenyl]methanone Chemical compound C1=CC(OCCO)=CC=C1C(=O)C1=CC=C(Cl)C=C1 VKJFPNMKYBLWLN-UHFFFAOYSA-N 0.000 description 2
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- RUETVLNXAGWCDS-UHFFFAOYSA-N (4-chlorophenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(Cl)C=C1 RUETVLNXAGWCDS-UHFFFAOYSA-N 0.000 description 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical group [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 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
- 239000000178 monomer Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- 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
Definitions
- This application belongs to the field of materials chemistry.
- the application relates to processes for the preparation of compounds of formula I and their use as photoinitiators.
- Photointroducer is a kind of compound that absorbs energy of a certain wavelength in the ultraviolet region or visible region to generate free radicals, cations, etc., thereby initiating the polymerization, crosslinking and curing of monomers.
- the application provides a method for preparing a compound of formula I,
- each R1 and each R2 are each independently selected from hydrogen , alkyl, and halogen;
- R 3 and R 4 are each independently selected from hydrogen, halogen and
- R is selected from hydrogen and alkyl
- x and y are each independently selected from 0, 1, 2, 3 and 4 integers
- the methods include:
- R in formula a is selected from hydrogen, halogen and as well as
- R 1 , R 2 , x and y in formula a are as defined above.
- the application provides the use of a compound of formula I or a composition comprising it as a photoinitiator,
- each R1 and each R2 are each independently selected from hydrogen , alkyl, and halogen;
- R 3 and R 4 are each independently selected from hydrogen, halogen and
- R is selected from hydrogen and alkyl
- x and y are each independently selected from 0, 1, 2, 3 and 4 integers.
- the application provides a photoinitiator comprising a compound of formula I,
- each R 1 and each R 2 are each independently selected from hydrogen, alkyl and halogen;
- R 3 and R 4 are each independently selected from hydrogen, halogen and
- R is selected from hydrogen and alkyl
- x and y are each independently selected from 0, 1, 2, 3 and 4 integers.
- the application provides a method for preparing a compound of formula a,
- each R1 and each R2 are each independently selected from hydrogen , alkyl, and halogen;
- x and y are each independently an integer selected from 0, 1, 2, 3 and 4;
- R 0 is selected from hydrogen, halogen and
- the methods include:
- R 1 , R 2 , x and y in formula b are as defined above;
- R5 in formula b is selected from hydrogen, halogen and -OH.
- Figure 1 and Figure 2 are the ultraviolet absorption spectrum diagrams of exemplary compounds 2 and 3 of the present application, respectively.
- the term "optional” or “optionally” means that the subsequently described event or circumstance can, but need not occur, and that the description includes the circumstances under which said event or circumstance occurs as well as the circumstances under which they do not occur. happening.
- alkyl refers to a linear or branched saturated hydrocarbon group, such as C 1-8 alkyl, C 1-6 alkyl, C 1-4 alkyl .
- alkyl groups include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, s-butyl , t-butyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl), etc.; for example, the term "C 1-6 alkyl” refers to , 4, 5, 6) alkyl groups of carbon atoms (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1
- halogen denotes a fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) atom.
- C n means that the number of carbon atoms in a given molecule is n, where n is a positive integer, for example C 1-6 means that the number of carbon atoms in a given molecule can be 1, 2, 3, 4, 5 or 6. C 1-4 means that the number of carbon atoms in a given molecule can be 1, 2, 3 or 4.
- Structural units Indicates that the substituents R 1 and R 2 can be substituted at any one or more of the 4 substitution sites on the benzene ring.
- the step is carried out at a temperature of 120°C-170°C, which means that the reaction temperature can be 120°C, 121°C, 122°C, 123°C, 124°C, 125°C, 126°C, 127°C, 128°C, 129°C, 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C, 145°C , 146°C, 147°C, 148°C, 149°C, 150°C, 151°C, 152°C, 153°C, 154°C, 155°C, 156°C, 157°C, 158°C, 159°C, 160°C, 161°C, 162°C °C, 163°C, 164°C, 165°C
- the application provides a method for preparing a compound of formula I,
- each R1 and each R2 are each independently selected from hydrogen , alkyl, and halogen;
- R 3 and R 4 are each independently selected from hydrogen, halogen and
- R is selected from hydrogen and alkyl
- x and y are each independently selected from 0, 1, 2, 3 and 4 integers
- the methods include:
- R in formula a is selected from hydrogen, halogen and as well as
- R 1 , R 2 , x and y in formula a are as defined above.
- the esterification reaction is performed in the presence of methanesulfonic acid and hydroquinone.
- the esterification reaction is carried out in the presence of methanesulfonic acid, hydroquinone, and solvent A.
- the solvent A is selected from toluene or benzene.
- the esterification reaction is carried out under the condition of raising the temperature of the reaction to reflux state and separating water.
- the reaction time of the esterification reaction is 6h-12h (such as 6h, 7h, 8h, 9h, 10h, 11h, or 12h, etc.), 6h-12h, or 6h-8h.
- the compound of formula a is combined with The weight ratio is 1-3:1 or 1-2.5:1.
- the weight ratio of the methanesulfonic acid to the compound of formula a is 0.01-0.5:1 or 0.05-0.1:1.
- the weight ratio of the hydroquinone to the compound of formula a is 0.002-0.10:1 or 0.005-0.05:1.
- the solvent is removed followed by recrystallization.
- the recrystallization is performed in tert-butyl acetate, methanol, ethanol, or combinations thereof.
- the method also includes:
- R 1 , R 2 , x and y in formula b are as defined above;
- R in formula b is selected from hydrogen, halogen and -OH; wherein when R in said formula b is selected from -OH , R in the resulting formula a is When R 5 in the formula b is selected from hydrogen and halogen, the R 0 in the obtained formula a is the same as R 5 in the formula b.
- said halogen in the definition of R 3 , R 4 , R 5 and R 0 is selected from F, Cl, Br and I. In some embodiments, the halogen in the definitions of R 3 , R 4 , R 5 and R 0 is Cl.
- the reaction of the compound of formula b with the compound of formula c is carried out in the presence of a catalyst.
- the catalyst is selected from alkali metal halides.
- the catalyst is selected from KI and NaI.
- the catalyst is KI.
- the weight ratio of the catalyst to the compound of formula b is 0.01-0.1:1 or 0.01-0.05:1.
- the reaction between the compound of formula b and the compound of formula c is carried out at 120°C-170°C (for example, 120°C, 121°C, 122°C, 123°C, 124°C, 125°C, 126°C, 127°C, 128°C °C, 129°C, 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C, 150°C, 151°C, 152°C, 153°C, 154°C, 155°C, 156°C, 157°C, 158°C, 159°C, 160°C, 161°C , 162°C, 163°C,
- the reaction time of the compound of formula b and the compound of formula c is 4h-12h (such as 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h, etc.), or 6h-12h or 6h -8h.
- the weight ratio of the compound of formula b to the compound of formula c is 1-3:1 or 1-2.5:1.
- reaction of the compound of formula b with the compound of formula c is carried out with or without the presence of a solvent.
- the weight ratio of the catalyst to the compound of formula b is 0.01-0.1:1 or 0.01-0.05:1.
- R in formula b is -OH
- the reaction of the compound of formula b with the compound of formula c is carried out in the presence of a catalyst and solvent B.
- R 5 in formula b is hydrogen or halogen
- the reaction of the compound of formula b with the compound of formula c is carried out in the absence of solvent.
- the solvent B is selected from DMF and DMSO.
- the weight ratio of the solvent B to the compound of formula b is 0.1-0.5:1
- the resulting mixture is filtered or recrystallized.
- R5 in formula b is -OH
- the resulting mixture is cooled, optionally washed, and then filtered.
- the reaction between the compound of formula b and the compound of formula c is completed, the resulting mixture is cooled and water is added, and the solid is directly precipitated without separating the phases, and then filtered with suction to obtain the Formula a compound.
- R 5 in formula b is hydrogen or halogen
- solvent C is added for recrystallization.
- the solvent C is selected from toluene or benzene.
- the application provides the use of a compound of formula I or a composition comprising it as a photoinitiator,
- each R1 and each R2 are each independently selected from hydrogen , alkyl, and halogen;
- R 3 and R 4 are each independently selected from hydrogen, halogen and
- R is selected from hydrogen and alkyl
- x and y are each independently selected from 0, 1, 2, 3 and 4 integers.
- the application provides a photoinitiator comprising a compound of formula I,
- each R 1 and each R 2 are each independently selected from hydrogen, alkyl and halogen;
- R 3 and R 4 are each independently selected from hydrogen, halogen and
- R is selected from hydrogen and alkyl
- x and y are each independently selected from 0, 1, 2, 3 and 4 integers.
- R is selected from hydrogen and C 1-6 alkyl.
- R is selected from hydrogen and methyl.
- the compound of formula I is selected from the following compounds:
- the application provides a method for preparing a compound of formula a,
- each R1 and each R2 are each independently selected from hydrogen , alkyl, and halogen;
- x and y are each independently an integer selected from 0, 1, 2, 3 and 4;
- R 0 is selected from hydrogen, halogen and
- the methods include:
- R 1 , R 2 , x and y in formula b are as defined above;
- R5 in formula b is selected from hydrogen, halogen and -OH.
- said halogen in the definition of R and R is selected from F, Cl , Br and I. In some embodiments, the halogen in the definitions of R and R is Cl .
- the weight ratio of KI to the compound of formula b is 0.01-0.1:1 or 0.01-0.05:1.
- reaction of the compound of formula b with the compound of formula c is carried out at a temperature of 120°C-170°C, 120°C-150°C, or 135°C-140°C.
- reaction time between the compound of formula b and the compound of formula c is 4h-12h, or 6h-12h, or 6h-8h.
- the weight ratio of the compound of formula b to the compound of formula c is 1-3:1 or 1-2.5:1.
- reaction of the compound of formula b with the compound of formula c is carried out with or without the presence of a solvent.
- the preparation method of the light-initiating agent of the present application is simple, cost is low, and yield and productive rate are high (in a short time just can reach higher productive rate, for example can reach 90% under the reaction time of 6-8 hour. % more than the productive rate), suitable for industrial production.
- the free radicals generated by the photoinitiator of the present application under light can initiate self-polymerization, avoid the generation of small molecules after photoinitiation, and reduce molecular migration.
- the photointroducer of the present application has the advantages of low odor and little yellowing.
- Embodiment 11 performance test result:
- PETA refers to pentaerythritol triacrylate
- TMPTA (EO3) refers to (3) ethoxylated trimethylolpropane triacrylate
- EDB refers to ethyl 4-dimethylaminobenzoate.
- the curing energy of samples (such as No. 1 sample and No. 2 sample in the above table) prepared by the compound of the present application (such as compound 2 and compound 3) is between 40mj/cm 2 -330mj/cm between 2 .
- Compound 2 and Compound 3 have the characteristics of low odor and less yellowing.
- BP means benzophenone
- OmnipolBP refers to the following structure:
- Omnipol 2702 refers to polymerized benzophenone derivatives (brand: IGM, model: Omnipol 2702);
- OMBB refers to methyl 2-benzoylbenzoate
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Abstract
提供式Ⅰ化合物及其中间体式a化合物的制备方法,其中式Ⅰ化合物的制备方法包括:在甲基磺酸的存在下将式a 化合物与式(aa)进行酯化反应,得到式Ⅰ化合物。式Ⅰ化合物或包含其的组合物用作光引发剂的用途,以及包含式I 化合物的光引发剂,式Ⅰ化合物以及式a 化合物如下所示。
Description
本申请属于材料化学领域。具体而言,本申请涉及式I化合物的制备方法及其用作光引发剂的用途。
光引光剂是一类在紫外光区或可见光区吸收一定波长的能量,产生自由基、阳离子等,从而引发单体聚合交联固化的化合物。传统光引发剂的毒性、气味、固化速度和迁移以及产率低等方面的缺点限制了其发展,存在对开发改善的光引光剂的需求。同时为满足商业化的要求,亟需发展制备简单、低成本、且产率高的光引发剂的制备方法。
发明概述
第一方面,本申请提供了式I化合物的制备方法,
其中:
各个R
1和各个R
2各自独立地选自氢、烷基和卤素;
R选自氢和烷基;
x和y各自独立地选自0、1、2、3和4的整数,
所述方法包括:
式a中的R
1、R
2、x和y如上所定义。
第二方面,本申请提供了式I化合物或包含其的组合物用作光引发剂的用途,
其中:
各个R
1和各个R
2各自独立地选自氢、烷基和卤素;
R选自氢和烷基;
x和y各自独立地选自0、1、2、3和4的整数。
第三方面,本申请提供了光引发剂,其包含式I化合物,
其中:各个R
1和各个R
2各自独立地选自氢、烷基和卤素;
R选自氢和烷基;
x和y各自独立地选自0、1、2、3和4的整数。
第四方面,本申请提供了式a化合物的制备方法,
其中:
各个R
1和各个R
2各自独立地选自氢、烷基和卤素;
x和y各自独立地选自0、1、2、3和4的整数;以及
所述方法包括:
使式b化合物与式c化合物在KI的存在下反应得到所述式a化合物;
其中:
式b中的R
1、R
2、x和y如上所定义;以及
式b中的R
5选自氢、卤素和-OH。
图1和图2分别为本申请的示例性化合物2和3的紫外吸收光谱图。
发明详述
定义
提供以下定义和方法用以更好地界定本申请以及在本申请实践中指导本领域普通技术人员。除非另作说明,否则术语按照相关领域普通技术人员的常规用法理解。本文所引用的所有专利文献、学术论文及其他公开出版物,其中的全部内容整体并入本文作为参考。
本文所用术语“任选的”或“任选地”是指随后所描述的事件或情形可以、但不是必须发生,该描述包括所述事件或情形发生时的情况,也包括它们不发生时的情况。
术语“烷基”是指直链或支链的饱和烃基,例如C
1-8烷基、C
1-6烷基、C
1-
4烷基。烷基的例子包括甲基(Me),乙基(Et),丙基(如,n-丙基和异丙基),丁基(如,n-丁基,异丁基,s-丁基,t-丁基),戊基(如,n-戊基,异戊基,新戊基)等;例如,术语“C
1-6烷基”指含有1至6(例如1、2、3、4、5、6)个碳原子的烷基(例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、新戊基、己基、2-甲基戊基等)。
术语“卤素”表示氟(F)、氯(Cl)、溴(Br)或碘(I)原子。
本文所用术语“C
n”是指给定分子具有的碳原子数为n,其中n是正整数,例如C
1-6是指给定分子中碳原子数可以为1、2、3、4、5或6。C
1-4是指给定分子中碳原子数可以为1、2、3或4。
凡在本文中给出某一数值范围之处,所述范围包括其端点,以及位于所述范围内的所有单独整数和分数,并且还包括由其中那些端点和内部整数和分数的所有各种可能组合形成的每一个较窄范围,以在相同程度的所述范围内形成更大数值群的子群,如同每一个那些较窄范围被明确给出一样。例如,所述步骤在120℃-170℃的温度下进行是指所述反应温度可以为120℃、121℃、122℃、123℃、124℃、125℃、126℃、127℃、128℃、129℃、130℃、131℃、132℃、133℃、134℃、135℃、136℃、137℃、138℃、139℃、140℃、141℃、142℃、143℃、144℃、145℃、146℃、147℃、148℃、149℃、150℃、151℃、 152℃、153℃、154℃、155℃、156℃、157℃、158℃、159℃、160℃、161℃、162℃、163℃、164℃、165℃、166℃、167℃、168℃、169℃、或170℃等以及由它们所形成的范围等。
实施方案的详细描述
第一方面,本申请提供了式I化合物的制备方法,
其中:
各个R
1和各个R
2各自独立地选自氢、烷基和卤素;
R选自氢和烷基;
x和y各自独立地选自0、1、2、3和4的整数,
所述方法包括:
式a中的R
1、R
2、x和y如上所定义。
在一些实施方案中,所述酯化反应在甲基磺酸和对苯二酚的存在下进行。
在一些实施方案中,所述酯化反应在甲基磺酸、对苯二酚以及溶剂A的存 在下进行。在一些实施方案中,所述溶剂A选自甲苯或苯。
在一些实施方案中,所述酯化反应是在将反应升温至回流状态分水的条件下进行。
在一些实施方案中,所述酯化反应的反应时间为6h-12h(例如6h、7h、8h、9h、10h、11h、或12h等)、6h-12h、或6h-8h。
在一些实施方案中,所述甲基磺酸与式a化合物的重量比为0.01-0.5:1或0.05-0.1:1。
在一些实施方案中,所述对苯二酚与式a化合物的重量比为0.002-0.10:1或0.005-0.05:1。
在一些实施方案中,在酯化反应完成后,脱除溶剂,然后重结晶。
在一些实施方案中,所述重结晶在乙酸叔丁酯、甲醇、乙醇或其组合中进行。
在一些实施方案中,所述方法还包括:
使式b化合物与式c化合物反应得到所述式a化合物;
其中:
式b中的R
1、R
2、x和y如上所定义;
在一些实施方案中,R
3、R
4、R
5和R
0的定义中的所述卤素选自F、Cl、Br和I。在一些实施方案中,R
3、R
4、R
5和R
0的定义中的所述卤素为Cl。
在一些实施方案中,所述式b化合物与式c化合物的反应在催化剂的存在 下进行。在一些实施方案中,所述催化剂选自碱金属卤化物。在一些实施方案中,所述催化剂选自KI和NaI。在一些实施方案中,所述催化剂为KI。
在一些实施方案中,所述催化剂与式b化合物的重量比为0.01-0.1:1或0.01-0.05:1。
在一些实施方案中,所述式b化合物与式c化合物的反应在120℃-170℃(例如120℃、121℃、122℃、123℃、124℃、125℃、126℃、127℃、128℃、129℃、130℃、131℃、132℃、133℃、134℃、135℃、136℃、137℃、138℃、139℃、140℃、141℃、142℃、143℃、144℃、145℃、146℃、147℃、148℃、149℃、150℃、151℃、152℃、153℃、154℃、155℃、156℃、157℃、158℃、159℃、160℃、161℃、162℃、163℃、164℃、165℃、166℃、167℃、168℃、169℃、或170℃等),120℃-150℃,或135℃-140℃的温度下进行。
在一些实施方案中,所述式b化合物与式c化合物的反应时间为4h-12h(例如4h、5h、6h、7h、8h、9h、10h、11h或12h等)、或6h-12h或6h-8h。
在一些实施方案中,所述式b化合物与式c化合物的重量比为1-3:1或1-2.5:1。
在一些实施方案中,所述式b化合物与式c化合物的反应在有或没有溶剂的存在下进行。
在一些实施方案中,所述催化剂与式b化合物的重量比为0.01-0.1:1或0.01-0.05:1。
在一些实施方案中,当式b中的R
5为-OH时,所述式b化合物与式c化合物的反应在催化剂和溶剂B的存在下进行。
在一些实施方案中,当式b中的R
5为氢或卤素时,所述式b化合物与式c化合物的反应在没有溶剂的存在下进行。
在一些实施方案中,所述溶剂B选自DMF和DMSO。
在一些实施方案中,所述溶剂B与式b化合物的重量比为0.1-0.5:1
在一些实施方案中,在所述式b化合物与式c化合物的反应完成后,对所得混合物进行过滤或重结晶。
在一些实施方案中,当式b中的R
5为-OH时,在所述式b化合物与式c化合物的反应完成后,将所得混合物冷却、任选的洗涤、然后过滤。在一些更具体的实施方案中,在所述式b化合物与式c化合物的反应完成后,将所得混合物冷却后加入水,并且在无需分离各相的情况下直接析出固体,然后抽滤得到所述 式a化合物。
在一些实施方案中,当式b中的R
5为氢或卤素时,在所述式b化合物与式c化合物的反应完成后,加入溶剂C进行重结晶。
在一些实施方案中,所述溶剂C选自甲苯或苯。
第二方面,本申请提供了式I化合物或包含其的组合物用作光引发剂的用途,
其中:
各个R
1和各个R
2各自独立地选自氢、烷基和卤素;
R选自氢和烷基;
x和y各自独立地选自0、1、2、3和4的整数。
第三方面,本申请提供了光引发剂,其包含式I化合物,
其中:各个R
1和各个R
2各自独立地选自氢、烷基和卤素;
R选自氢和烷基;
x和y各自独立地选自0、1、2、3和4的整数。
在上述任一方面的一些实施方案中,R选自氢和C
1-6烷基。
在上述任一方面的一些实施方案中,R选自氢和甲基。
在上述任一方面的一些实施方案中,所述式I化合物选自以下化合物:
第四方面,本申请提供了式a化合物的制备方法,
其中:
各个R
1和各个R
2各自独立地选自氢、烷基和卤素;
x和y各自独立地选自0、1、2、3和4的整数;以及
所述方法包括:
使式b化合物与式c化合物在KI的存在下反应得到所述式a化合物;
其中:
式b中的R
1、R
2、x和y如上所定义;以及
式b中的R
5选自氢、卤素和-OH。
在一些实施方案中,R
5和R
0的定义中的所述卤素选自F、Cl、Br和I。在一些实施方案中,R
5和R
0的定义中的所述卤素为Cl。
在一些实施方案中,KI与式b化合物的重量比为0.01-0.1:1或0.01-0.05:1。
在一些实施方案中,所述式b化合物与式c化合物的反应在120℃-170℃、120℃-150℃、或135℃-140℃的温度下进行。
在一些实施方案中,所述式b化合物与式c化合物的反应时间为4h-12h、或6h-12h或6h-8h。
在一些实施方案中,所述式b化合物与式c化合物的重量比为1-3:1或1-2.5:1。
在一些实施方案中,所述式b化合物与式c化合物的反应在有或没有溶剂的存在下进行。
本申请的各项发明提供下述一种或多种优势:
本申请的光引光剂的制备方法简单、成本低、并且收率和产率高(在较短的时间内就能达到较高的产率,例如6-8小时的反应时间下能达到90%以上的产率),适于工业生产。
本申请的光引发剂光照下产生的自由基可以引发自身聚合反应,避免光引发后产生小分子,降低了分子迁移。
本申请的光引光剂具有气味低和黄变小的优点。
以下实施例仅用于说明而非限制本申请范围的目的。
实施例1
4,4’-二羟乙氧基二苯甲酮的制备
在500mL的四口瓶中,加入64.2g 4,4’-二羟基二苯甲酮,60g碳酸亚乙酯,3g碘化钾和20g DMF,升温至熔融状态,保持温度在130℃-135℃下,反应时间为8小时,停止反应,冷却,倒入100mL水里,抽滤,烘干得到产品82g,产率为90.5%。
1H-NMR:3.65-3.69(m,6H),4.33(t,4H,J=6.2Hz),7.09(m,4H),7.67(m,4H)。
实施例2
4,4’-二羟乙氧基二苯甲酮的制备
在500mL的四口瓶中,加入64.2g 4,4’-二羟基二苯甲酮,60g碳酸亚乙酯,3g碘化钾和30g二甲亚砜(DMSO),升温至130℃-140℃下,反应时间为8小时,停止反应,冷却,倒入100mL水,析出固体,抽滤,烘干,得到产品85g,产率为93.8%。
实施例3
4-羟乙氧基二苯甲酮的制备
将500g 4-羟基二苯甲酮,230g碳酸亚乙酯和15g碘化钾放入1000mL四口瓶中,加热升温,在130℃-140℃下反应,反应时间为8小时,停止反应,加入1000mL甲苯进行重结晶,得到白色产品为600g,熔点78℃-80℃,产率为98.2%。HPLC分析含量为99.52%。
1H-NMR:3.65(s,1H),3.69(t,3H,J=4.8Hz),4.35(t,2H,J=4.8Hz),7.09-7.78(m,9H)。
实施例4
4-羟乙氧基二苯甲酮的制备
将500g 4-羟基二苯甲酮,230g碳酸亚乙酯和15g碘化钠放入1000mL四口瓶中,加热升温,在140℃-150℃下反应,反应时间为8小时,停止反应,加入1000mL甲苯进行重结晶,得到白色产品为490g,熔点78℃-80℃,产率为80.4%。HPLC分析含量为98.35%。
实施例5
4-羟乙氧基二苯甲酮的制备
将500g 4-羟基二苯甲酮,250g碳酸亚乙酯和15g碘化钾放入1000mL四口瓶中,加热升温,在150℃-160℃下反应,反应时间为6小时,停止反应,加入1000mL甲苯进行重结晶,得到白色产品为540g,熔点78℃-80℃,产率为88.3%。HPLC分析含量为97.32%。
实施例6
4-羟乙氧基二苯甲酮的制备
将500g 4-羟基二苯甲酮,250g碳酸亚乙酯和15g碘化钾放入1000mL四口瓶中,加热升温,在160℃-176℃下反应,反应时间为8小时,停止反应,加入1000mL甲苯进行重结晶,得到白色产品为620g,产率为80.5%。HPLC分析含量为82.12%。
实施例7
4’-氯-4-羟乙氧基二苯甲酮的制备
将500g 4’-氯-4-羟基二苯甲酮,230g碳酸亚乙酯和15g碘化钾放入1000mL四口瓶中,加热升温,在140℃-150℃下反应,反应时间为8小时,停止反应,加入1000mL甲苯进行重结晶,得到白色产品为600g,熔点126-128℃,产率为95.2%。HPLC分析含量为99.52%。
1H-NMR:3.65-3.69(m,3H),4.35(t,2H,J=4.8Hz),7.099-7.83(m,8H)。
实施例8
4,4’-二羟乙氧基二苯甲酮甲基丙烯酸酯的制备
在500mL的四口瓶中,加入75g 4,4’-二羟乙氧基二苯甲酮,55g甲基丙烯酸,6g甲基磺酸,1.5g对苯二酚和150g甲苯,升温至回流状态分水,反应时间6小时,反应完成后,脱除甲苯,用乙酸叔丁酯进行重结晶,得到产品98g,熔点82℃-84℃,产率为90.1%。
1H-NMR:2.02(s,6H),4.42-4.53(m,8H),6.45(d,4H,J=12.8Hz),7.09-7.78(m,8H)。
实施例9
4-羟乙氧基二苯甲酮甲基丙烯酸酯的制备
在2000mL四口瓶中加入1200mL甲苯,600g 4-羟乙氧基二苯甲酮,240g甲基丙烯酸,然后加入40g甲基磺酸,5g对苯二酚,升温至回流状态下分水,反应时间为8小时,反应完成后,冷却,析出白色固体685g,熔点56℃-58℃,产率为97.3%,HPLC分析含量为99.38%。
1H-NMR:2.02(s,3H),4.42-4.53(m,4H),6.45(d,2H,J=12.8Hz),7.09-7.78(m,9H)。
实施例10
4’-氯-4-羟乙氧基二苯甲酮甲基丙烯酸酯的制备
在2000mL四口瓶中加入1200mL甲苯,600g 4’-氯-4-羟乙氧基二苯甲酮,260g甲基丙烯酸,然后加入40g甲基磺酸,5g对苯二酚,升温至回流状态下分水,反应完成后,冷却,析出白色固体680g,熔点80℃-81℃,产率为95.4%,HPLC分析含量为99.20%。
1H-NMR:2.02(s,3H),4.42-4.53(m,4H),6.45(d,2H,J=12.8Hz),7.09-7.67(m,8H)。
实施例11:性能测试结果:
1.固化速度测试
测试条件:
基料:环氧丙烯酸树脂:PETA:TMPTA(EO3)=5:3:2
基材:卡纸
光源:汞灯
涂层厚度:15微米
化合物2:4-羟乙氧基二苯甲酮甲基丙烯酸酯
化合物3:4,4’-二羟乙氧基二苯甲酮甲基丙烯酸酯
配比及结果
注:PETA是指季戊四醇三丙烯酸酯;
TMPTA(EO3)是指(3)乙氧基化三羟甲基丙烷三丙烯酸酯;
EDB是指4-二甲基氨基苯甲酸乙酯。
结论:根据上述固化速度测试测得,由本申请化合物(例如化合物2和化合物3)制备的样品(例如上述表中的①号样品和②号样品)的固化能量在40mj/cm
2-330mj/cm
2之间。
另外,与光引发剂MBZ、BP、OmnipolBP、Omnipol 2702和OMBB相比,化合物2和化合物3具有气味低和黄变小的特性。
注:MBZ:4-甲基二苯甲酮。
BP是指二苯甲酮;
OmnipolBP是指下述结构:
Omnipol 2702是指聚合二苯甲酮衍生物(品牌:IGM,型号:Omnipol 2702);
OMBB是指2-苯甲酰基苯甲酸甲酯;
2.化合物2和化合物3在不同的浓度下的紫外吸收光谱图分别如图1和图2所示。
上文中已经用一般性说明及具体实施方案对本申请作了详尽的描述,但在本申请基础上,可以对之作一些修改或改进,并根据需要进行任意组合,这对本 领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本申请要求保护的范围。
Claims (15)
- 如权利要求1所述的方法,其中,所述酯化反应在甲基磺酸和对苯二酚的存在下进行;和/或所述酯化反应的反应时间为6h-12h、或6h-8h。
- 如权利要求1至4中任一项所述的方法,其中:R 3、R 4、R 5和R 0的定义中的所述卤素选自F、Cl、Br和I,优选地,R 3、R 4、R 5和R 0的定义中的所述卤素为Cl。
- 如权利要求1至5中任一项所述的方法,其中:所述式b化合物与式c化合物的反应在催化剂的存在下进行,优选地所述催化剂选自碱金属卤化物,更优选地所述催化剂选自KI和NaI,还更优选地所述催化剂为KI。
- 如权利要求6中任一项所述的方法,其中所述催化剂与式b化合物的重 量比为0.01-0.1:1或0.01-0.05:1。
- 如权利要求4至7中任一项所述的方法,其中:所述式b化合物与式c化合物的反应在120℃-170℃、120℃-150℃、或135℃-140℃的温度下进行;和/或所述式b化合物与式c化合物的反应时间为4h-12h、或6h-12h或6h-8h;和/或所述式b化合物与式c化合物的重量比为1-3:1或1-2.5:1;和/或所述式b化合物与式c化合物的反应在有或没有溶剂的存在下进行。
- 如权利要求4至8中任一项所述的方法,还包括:当式b中的R 5为-OH时,在所述式b化合物与式c化合物的反应完成后,将所得混合物冷却、任选的洗涤、然后过滤;或者当式b中的R 5为氢或卤素时,在所述式b化合物与式c化合物的反应完成后,加入溶剂进行重结晶。
- 如权利要求13所述的方法,其中:R 5和R 0的定义中的所述卤素选自F、Cl、Br和I,优选地,R 5和R 0的定义中的所述卤素为Cl。
- 如权利要求13或14所述的方法,其中:KI与式b化合物的重量比为0.01-0.1:1或0.01-0.05:1;和/或所述式b化合物与式c化合物的反应在120℃-170℃、120℃-150℃、或135℃-140℃的温度下进行;和/或所述式b化合物与式c化合物的反应时间为4h-12h、或6h-12h或6h-8h;和/或所述式b化合物与式c化合物的重量比为1-3:1或1-2.5:1;和/或所述式b化合物与式c化合物的反应在有或没有溶剂的存在下进行。
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JPH08208776A (ja) * | 1995-02-07 | 1996-08-13 | Nippon Kayaku Co Ltd | 樹脂組成物、レンズ用組成物及びその硬化物 |
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CN110776587A (zh) * | 2019-10-24 | 2020-02-11 | 安庆飞凯新材料有限公司 | 一种基于二苯甲酮的可聚合型光引发剂及其制备方法 |
CN110818560A (zh) * | 2019-12-02 | 2020-02-21 | 怀化金鑫新材料有限公司 | 一种4-苄氧基苯基乙基正癸酸酯的制备方法 |
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JPH08208776A (ja) * | 1995-02-07 | 1996-08-13 | Nippon Kayaku Co Ltd | 樹脂組成物、レンズ用組成物及びその硬化物 |
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