CN110922346A - Tris (4-acetyldiphenyl sulfide) thioylium hexafluorophosphate and synthesis method thereof - Google Patents
Tris (4-acetyldiphenyl sulfide) thioylium hexafluorophosphate and synthesis method thereof Download PDFInfo
- Publication number
- CN110922346A CN110922346A CN201911100517.7A CN201911100517A CN110922346A CN 110922346 A CN110922346 A CN 110922346A CN 201911100517 A CN201911100517 A CN 201911100517A CN 110922346 A CN110922346 A CN 110922346A
- Authority
- CN
- China
- Prior art keywords
- hexafluorophosphate
- tris
- sulfide
- acetyldiphenyl
- acetyldiphenylsulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XUDYHODVSUXRPW-UHFFFAOYSA-N 1-(4-phenylsulfanylphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1SC1=CC=CC=C1 XUDYHODVSUXRPW-UHFFFAOYSA-N 0.000 title claims abstract description 76
- -1 hexafluorophosphate Chemical compound 0.000 title claims abstract description 75
- 239000007983 Tris buffer Substances 0.000 title claims abstract description 50
- 238000001308 synthesis method Methods 0.000 title claims abstract description 22
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 title description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- MWDNZMWVENFVHT-UHFFFAOYSA-L (2-decoxy-2-oxoethyl)-[2-[2-[(2-decoxy-2-oxoethyl)-dimethylazaniumyl]ethylsulfanyl]ethyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCOC(=O)C[N+](C)(C)CCSCC[N+](C)(C)CC(=O)OCCCCCCCCCC MWDNZMWVENFVHT-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims abstract description 11
- 230000001070 adhesive effect Effects 0.000 claims abstract description 11
- 239000000976 ink Substances 0.000 claims abstract description 11
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 11
- 150000003839 salts Chemical group 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 93
- 238000000034 method Methods 0.000 claims description 26
- 238000005191 phase separation Methods 0.000 claims description 13
- 239000005457 ice water Substances 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000005022 packaging material Substances 0.000 abstract description 7
- 230000000171 quenching effect Effects 0.000 abstract description 6
- 239000012071 phase Substances 0.000 description 18
- 238000001723 curing Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000005409 triarylsulfonium group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000012952 cationic photoinitiator Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000005917 acylation reaction Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004807 desolvation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- OLPZCIDHOZATMA-UHFFFAOYSA-N 2,2-dioxooxathiiran-3-one Chemical class O=C1OS1(=O)=O OLPZCIDHOZATMA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000012803 optimization experiment Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate and a synthesis method thereof, comprising the following steps of reacting 4-acetyldiphenyl sulfide and aluminum trichloride serving as raw materials with thionyl chloride until the 4-acetyldiphenyl sulfide is completely reacted; and step two, adding water into the reaction liquid obtained in the step one for quenching, adding a potassium hexafluorophosphate aqueous solution for carrying out a salt exchange reaction, and removing the solvent after the reaction is finished to obtain white solid tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate. The tris (4-acetyldiphenyl sulfide) thioylium hexafluorophosphate is a novel cationic curing agent and can be used in the fields of coatings, printing ink, adhesives, packaging materials of the electronic industry, photoresists, printing materials and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate and a synthesis method thereof.
Background
Cationic photoinitiators are important photo-initiation reagents, including diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxy ethers; its basic action features that the light activation makes the molecule to excited state, and the molecule takes part in serial decomposition reaction to generate super-strong protonic acid as cationic polymerization activity to initiate the polymerization of epoxy compound, vinyl ether, lactone, acetal, cyclic ether, etc.
Compared with a free radical type photocuring system, the cationic photocuring system has the advantages of (1) small curing shrinkage; (2) is not blocked by oxygen; (3) curing the thick film; (4) low toxicity. The important component of the system is the wide variety of cationic photoinitiators, among which triarylsulfonium salts have the unique advantage that they are soluble in most cationically polymerized monomers. Although the initiation speed is not as fast as that of other cationic photoinitiators, the stability is far superior to them. The existing preparation method of triarylsulfonium salt has the influence on the wide application of triarylsulfonium salt due to more synthesis steps and expensive raw material price.
Therefore, there is a need to provide an improved technical solution to overcome the technical problems in the prior art.
Disclosure of Invention
In order to solve the problems, the invention provides a novel cationic light curing agent tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate and a synthesis method thereof; the synthesis of the novel cationic light curing agent comprises the following steps: taking 4-acetylbiphenyl thioether and aluminum trichloride as raw materials, and reacting with thionyl chloride until the 4-acetylbiphenyl thioether is completely reacted; and step two, adding water into the reaction liquid obtained in the step one for quenching, adding a potassium hexafluorophosphate aqueous solution for carrying out a salt exchange reaction, and removing the solvent after the reaction is finished to obtain white solid tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate. The tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate is a novel cationic photocuring agent and can be used in the fields of coatings, printing ink, adhesives, packaging materials of the electronic industry, photoresists, printing materials and the like.
The invention provides a novel cationic light curing agent tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate, which has the structure as follows:
（I）；
wherein the chemical formula of (I) is C42H33F6O3PS4Molecular weight (Exact Mass): 858.10, molar atomic weight (mol. wt.) 858.93.
The invention provides a synthesis method of novel cationic light curing agent tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate, which comprises the following steps:
step one, mixing and stirring dichloromethane, aluminum trichloride and 4-acetyldiphenyl sulfide, cooling in an ice water bath, then dropwise adding thionyl chloride, controlling the dropwise adding temperature to be 0-5 ℃, reacting at 30-40 ℃ until the end after the dropwise adding is finished, and finishing the HPLC central control detection reaction;
step two, after the 4-acetyldiphenyl sulfide completely reacts, cooling the reaction liquid in an ice-water bath, dropwise adding water to quench, standing for phase separation, extracting the water phase once with dichloromethane, and combining dichloromethane phases; adding the prepared potassium hexafluorophosphate aqueous solution into a dichloromethane phase, stirring for 1.5-3 hours at the temperature of 30-40 ℃, completing salt exchange, carrying out phase separation, and removing a solvent to obtain white solid tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate.
Preferably, in the synthesis method, in the first step, 4-acetylbiphenyl sulfide and aluminum trichloride are used as raw materials, and the molar ratio of 4-acetylbiphenyl sulfide to aluminum trichloride is 1: 1 to 6.
Preferably, in the synthesis method as described above, the molar ratio of the thionyl chloride to the 4-acetylbiphenyl sulfide in the first step is 1: 1 to 5.
Preferably, in the synthesis method as described above, the molar ratio of the 4-acetyldiphenyl sulfide to potassium hexafluorophosphate used in the first step is 1: 1 to 2.5.
Preferably, in the synthesis method as described above, the molar ratio of dichloromethane to aluminum trichloride in the first step is 116: 1 to 3.
The invention also provides a product containing the tri (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate.
The invention also provides a product prepared by using the synthesis method.
The invention also provides the application of the tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate in coating, printing ink, adhesive, packaging material of the electronic industry, photoresist or printing material.
The invention also provides the use of a product according to the preceding description in coatings, inks, adhesives, encapsulating materials for the electronics industry, photoresists or printing materials.
The tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate is a novel cationic curing agent; the (4-acetyldiphenyl sulfide) thioether onium hexafluorophosphate is prepared by taking 4-acetyldiphenyl sulfide and thionyl chloride as starting materials and carrying out acylation reaction under the condition of aluminum trichloride, and the reaction process is as follows:
（II） （III）；
wherein the chemical formula of (II) is C14H12OS, molecular weight (Exact Mass): 228.06, molar atomic weight (mol. wt.) 228.31. (III) has the chemical formula C42H33F6O3PS4Molecular weight (Exact Mass): 858.10, molar atomic weight (mol. wt.) 858.93.
The beneficial effects created by the invention are as follows:
the invention provides a novel cationic light curing agent tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate and a preparation method thereof; the cationic light curing agent can be used in the fields of coating, printing ink, adhesive, packaging material of electronic industry, photoresist, printing material and the like.
Detailed Description
In order to solve the problems of multiple steps, high production cost, high price of raw materials and the like of the existing cationic light curing agent in the prior art, the inventor develops a novel method for synthesizing the tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate serving as the cationic light curing agent; the method comprises the following steps: taking 4-acetylbiphenyl thioether and aluminum trichloride as raw materials, and reacting with thionyl chloride until the 4-acetylbiphenyl thioether is completely reacted; and step two, adding water into the reaction liquid obtained in the step one for quenching, adding a potassium hexafluorophosphate aqueous solution for carrying out a salt exchange reaction, and removing the solvent after the reaction is finished to obtain white solid tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate. The tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate synthesized by the invention is a novel cationic photocuring agent, and can be used in the fields of coatings, printing ink, adhesives, packaging materials of the electronic industry, photoresists, printing materials and the like.
The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer.
As used herein, "comprising," having, "or" including "includes" comprising, "" consisting essentially of … …, "" consisting essentially of … …, "and" consisting of … …; "consisting essentially of … …", "consisting essentially of … …", and "consisting of … …" are subordinate concepts of "comprising", "having", or "including".
The features mentioned with reference to the invention or the features mentioned with reference to the embodiments can be combined. All the features disclosed in this specification may be combined in any combination, and each feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
The "ranges" disclosed herein are in the form of lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this manner are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, the ranges of 2000-. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
In the present invention, all "parts" and percentages (%) refer to weight percentages unless otherwise indicated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers.
The term "a" or "an" as used herein means "at least one" if not otherwise specified.
All percentages (including weight percentages) stated herein are based on the total weight of the composition, unless otherwise specified.
In the present invention, all embodiments and preferred embodiments mentioned herein may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the steps mentioned herein may be performed sequentially or randomly, if not specifically stated, but preferably sequentially. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
In the present invention, specific numerical values and specific substances in the examples herein may be combined with other features of the parts described herein, if not specifically stated. For example, where the temperature of the reaction is mentioned in the description section as being 45-105 ℃ and the temperature of the reaction is mentioned in the examples as being 60 ℃, it is to be understood that the range of 45-60 ℃ or the range of 60-105 ℃ has been specifically disclosed herein and that the other features of the description section can be combined to form new embodiments.
In the present invention, all embodiments and preferred embodiments mentioned herein may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, unless otherwise specified, "salt exchange" as used herein means that the product is a hydrochloride in the reaction solution and that the product forms a hexafluorophosphate after potassium hexafluorophosphate is added.
In the present invention, unless otherwise specified, reference herein to "phase separation" means that the organic and aqueous phases are brought together with a distinct separating interface separating the organic and aqueous phases.
In the present invention, the term "desolvation" or "desolvation" as used herein means that the organic phase is evaporated to dryness under reduced pressure, unless otherwise specified.
The invention provides a novel cationic light curing agent tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate, which has the structure as follows:
（I）；
wherein the chemical formula of (I) is C42H33F6O3PS4Molecular weight (Exact Mass): 858.10, molar atomic weight (mol. wt.) 858.93.
The invention provides a synthesis method of novel cationic light curing agent tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate, which comprises the following steps:
step one, mixing and stirring dichloromethane, aluminum trichloride and 4-acetyldiphenyl sulfide, cooling in an ice water bath, then dropwise adding thionyl chloride, controlling the dropwise adding temperature to be 0-5 ℃, reacting at 30-40 ℃ until the end after the dropwise adding is finished, and finishing the HPLC central control detection reaction;
step two, after the 4-acetyldiphenyl sulfide completely reacts, cooling the reaction liquid in an ice-water bath, dropwise adding water to quench, standing for phase separation, extracting the water phase once with dichloromethane, and combining dichloromethane phases; adding the prepared potassium hexafluorophosphate aqueous solution into a dichloromethane phase, stirring for 1.5-3 hours at the temperature of 30-40 ℃, completing salt exchange, carrying out phase separation, and removing a solvent to obtain white solid tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate.
In some preferred embodiments, for the synthesis method as described above, the raw materials in step one are 4-acetylbiphenyl sulfide and aluminum trichloride, and the molar ratio of 4-acetylbiphenyl sulfide to aluminum trichloride includes but is not limited to 1: 1 to 6.
In some preferred embodiments, for the synthesis method as described above, the raw materials in step one are 4-acetylbiphenyl sulfide and aluminum trichloride, and the molar ratio of 4-acetylbiphenyl sulfide to aluminum trichloride includes but is not limited to 1: 1. 1: 2. 1: 3. 1: 4. 1: 5 or 1: 6.
in some preferred embodiments, for the synthesis methods as described above, the molar ratio of thionyl chloride to 4-acetyldiphenyl sulfide used in step one includes, but is not limited to, 1: 1 to 5.
In some preferred embodiments, for the synthesis methods as described above, the molar ratio of thionyl chloride to 4-acetyldiphenyl sulfide used in step one includes, but is not limited to, 1: 1. 1: 2. 1: 3. 1: 4 or 1: 5.
in some preferred embodiments, for the synthesis methods as described above, the molar ratio of 4-acetyldiphenyl sulfide and potassium hexafluorophosphate used in step one includes, but is not limited to, 1: 1 to 2.5.
In some preferred embodiments, for the synthesis methods as described above, the molar ratio of 4-acetyldiphenyl sulfide and potassium hexafluorophosphate used in step one includes, but is not limited to, 1: 1. 1: 1.1, 1: 1.2, 1: 1.3, 1: 1.4, 1: 1.5, 1: 1.6, 1: 1.7, 1: 1.8, 1: 1.9, 1: 2. 1: 2.1, 1: 2.2, 1: 2.3, 1: 2.4, 1: 2.5.
in some preferred embodiments, for the synthesis methods described above, the molar ratio of dichloromethane to aluminum trichloride in step one includes, but is not limited to, 116: 1 to 3.
The invention also provides a product containing the tri (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate.
The invention also provides a product prepared by using the synthesis method.
The invention also provides application of the tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate in the fields of coatings, printing ink, adhesives, packaging materials of the electronic industry, photoresists or printing materials and the like.
The invention also provides the application of the product in the fields of paint, ink, adhesive, packaging material of electronic industry, photoresist or printing material and the like.
The tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate is a novel cationic curing agent; the (4-acetyldiphenyl sulfide) thioether onium hexafluorophosphate is prepared by taking 4-acetyldiphenyl sulfide and thionyl chloride as starting materials and carrying out acylation reaction under the condition of aluminum trichloride, and the reaction process is as follows:
（II） （III）；
wherein the chemical formula of (II) is C14H12OS, molecular weight (Exact Mass): 228.06, molar atomic weight (mol. wt.) 228.31. (III) has the chemical formula C42H33F6O3PS4Molecular weight (Exact Mass): 858.10, molar atomic weight (mol.wt.): 858.93.
in order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments, but the invention includes but is not limited to the embodiment.
Example 1 Synthesis of tris (4-acetyldiphenylsulfide) thioylium hexafluorophosphate
This example describes a method for synthesizing tris (4-acetyldiphenylsulfide) sulfonium hexafluorophosphate, which comprises the following steps:
the first step of reaction operation process: 500ml of dichloromethane, 87g of aluminum trichloride and 50g of 4-acetylbiphenyl thioether are sequentially added into a three-necked bottle, mixed and stirred, and cooled in an ice-water bath. And (3) dropwise adding 13.1g of thionyl chloride into the reaction bottle, controlling the dropwise adding temperature to be 0-5 ℃, reacting at 35 ℃ after the dropwise adding is finished, and performing HPLC (high performance liquid chromatography) central control detection.
The second step of reaction operation process: after the 4-acetyldiphenyl sulfide completely reacts, cooling the reaction solution in an ice-water bath, dropwise adding 500ml of water for quenching, standing for phase separation, extracting the water phase once with 400ml of dichloromethane, and combining the dichloromethane phases; the prepared potassium hexafluorophosphate aqueous solution (44 g KPF)6+320g H2O) adding the mixture into a dichloromethane phase, stirring for 2 hours at 35 ℃, completing salt exchange, phase separation, drying the dichloromethane phase, removing the solvent to obtain 55g of white solid, detecting the white solid by conventional methods such as nuclear magnetism and mass spectrum characterization and the like, and identifying the white solid as tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate with the chemical formula of C42H33F6O3PS4Molecular weight (Exact Mass): 858.10, molar atomic weight (mol.Wt.) 858.93, structure shown as (IV); the yield is 90.7%, the melting point is 192 ℃, and the product meets the standard of the literature.
（IV）。
Example 2 Synthesis of tris (4-acetyldiphenylsulfide) thioylium hexafluorophosphate
This example describes a tris (4-acetyldiphenylsulfide) thionium hexafluorophosphate structure and a method for synthesizing the same, and the specific preparation process is as follows:
the first step of reaction operation process: 500ml of dichloromethane, 29g of aluminum trichloride and 50g of 4-acetylbiphenyl thioether are sequentially added into a three-necked bottle, mixed and stirred, and cooled in an ice-water bath. And (3) dropwise adding 26.2g of thionyl chloride into the reaction bottle, controlling the dropwise adding temperature to be 0-5 ℃, reacting at 30 ℃ until the reaction is finished after the dropwise adding is finished, and finishing the HPLC (high performance liquid chromatography) central control detection reaction.
The second step of reaction operation process: after the 4-acetyldiphenyl sulfide completely reacts, cooling the reaction solution in an ice-water bath, dropwise adding 500ml of water for quenching, standing for phase separation, extracting the water phase once with 400ml of dichloromethane, and combining the dichloromethane phases; the prepared potassium hexafluorophosphate aqueous solution (50 g KPF)6+320g H2O) adding the mixture into a dichloromethane phase, stirring for 3 hours at the temperature of 30 ℃, completing salt exchange, phase separation, drying the dichloromethane phase, removing the solvent to obtain 25g of white solid, detecting the white solid by conventional methods such as nuclear magnetism and mass spectrum characterization and the like, and identifying the white solid as tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate with the chemical formula of C42H33F6O3PS4Molecular weight (Exact Mass): 858.10, molar atomic weight (mol.Wt.) 858.93, structure shown as (IV); the yield thereof is 41.2%; the white solid was again determined to be tris (4-acetyldiphenylsulfide) thionium hexafluorophosphate by the melting point method or the like.
Example 3 Synthesis of tris (4-acetyldiphenylsulfide) thioylium hexafluorophosphate
This example describes a tris (4-acetyldiphenylsulfide) thionium hexafluorophosphate structure and a method for synthesizing the same, and the specific preparation process is as follows:
the first step of reaction operation process: 500ml of dichloromethane, 174g of aluminum trichloride and 50g of 4-acetylbiphenyl sulfide are sequentially added into a three-necked bottle, mixed and stirred, and cooled in an ice-water bath. And (3) dropwise adding 5.2g of thionyl chloride into the reaction bottle, controlling the dropwise adding temperature to be 0-5 ℃, reacting at 40 ℃ after the dropwise adding is finished, and performing HPLC (high performance liquid chromatography) central control detection.
The second step of reaction operation process: after the 4-acetyldiphenyl sulfide completely reacts, cooling the reaction solution in an ice-water bath, dropwise adding 500ml of water for quenching, standing for phase separation, extracting the water phase once with 400ml of dichloromethane, and combining the dichloromethane phases; the prepared potassium hexafluorophosphate aqueous solution (44 g KPF)6+160g H2O) is added into a dichloromethane phase, stirred for 1.5 hours at 40 ℃, salt exchange is completed, phase separation is carried out, the dichloromethane phase is dried, solvent is removed to obtain 20g of white solid, and the white solid is subjected to conventional methods such as nuclear magnetism and mass spectrum characterizationDetecting to identify the tri (4-acetyldiphenyl sulfide) thionium hexafluorophosphate with the chemical formula C42H33F6O3PS4Molecular weight (Exact Mass): 858.10, molar atomic weight (mol.Wt.) 858.93, structure shown as (IV); the yield thereof is 33%; the white solid was again determined to be tris (4-acetyldiphenylsulfide) thionium hexafluorophosphate by the melting point method or the like.
For examples 1-3, the inventors conducted the following optimization experiments through continuous exploration and extensive demonstration:
examples 4 to 6: when the synthesis method of tris (4-acetylbiphenyl sulfide) sulfonium hexafluorophosphate is otherwise the same as that in any one of examples 1 to 3, in the first step, 4-acetylbiphenyl sulfide and aluminum trichloride are used as raw materials, and the molar ratio of 4-acetylbiphenyl sulfide to aluminum trichloride is adjusted to 1: 1-6, and compared with other proportioning ranges, the proportioning range can improve the yield of tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate by at least 49.5% and the purity by at least 10%.
Examples 7 to 9: a method for synthesizing tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate under the same conditions as any one of examples 1 to 3, wherein the molar ratio of thionyl chloride to 4-acetyldiphenyl sulfide in the first step is adjusted to 1: 1-5, and compared with other proportioning ranges, the proportioning range can improve the yield of tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate by at least 57.1% and the purity by at least 20%.
Examples 10 to 12: a method for synthesizing tris (4-acetyldiphenyl sulfide) thioylium hexafluorophosphate under otherwise the same conditions as in any one of examples 1 to 3, wherein the molar ratio of dichloromethane to aluminum trichloride in the first step is adjusted to 116: 1-3, and compared with other proportioning ranges, the proportioning range can improve the yield of tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate by at least 49.5% and the purity by at least 10%.
Examples 13 to 15: a method for synthesizing tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate under the same conditions as in any one of examples 1 to 3, wherein the amount of potassium hexafluorophosphate used in step two is: adjusting the molar use ratio of potassium hexafluorophosphate to 4-acetyldiphenyl sulfide to be 1-2.5: 1, compared with other proportioning ranges, the proportioning range can improve the yield of the tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate by at least 49.5 percent and the purity by at least 10 percent.
The inventors have found that tris (4-acetyldiphenyl sulfide) sulfonium hexafluorophosphate prepared in examples 1 to 15 can be applied to coating materials, inks, adhesives, encapsulating materials for the electronics industry, photoresists or printing materials.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A tris (4-acetyldiphenylsulfide) thioylium hexafluorophosphate having the structure:
2. a method for synthesizing tri (4-acetyl diphenyl sulfide) sulfur onium hexafluorophosphate is characterized in that,
step one, mixing and stirring dichloromethane, aluminum trichloride and 4-acetyldiphenyl sulfide, cooling in an ice water bath, then dropwise adding thionyl chloride, controlling the dropwise adding temperature to be 0-5 ℃, reacting at 30-40 ℃ until the end after the dropwise adding is finished, and finishing the HPLC central control detection reaction;
step two, after the 4-acetyldiphenyl sulfide completely reacts, cooling the reaction liquid in an ice-water bath, dropwise adding water to quench, standing for phase separation, extracting the water phase once with dichloromethane, and combining dichloromethane phases; adding the prepared potassium hexafluorophosphate aqueous solution into a dichloromethane phase, stirring for 1.5-3 hours at the temperature of 30-40 ℃, completing salt exchange, carrying out phase separation, and removing a solvent to obtain white solid tris (4-acetyldiphenyl sulfide) thionium hexafluorophosphate.
3. The method for synthesizing tris (4-acetyldiphenylsulfide) ylium hexafluorophosphate according to claim 2, wherein the molar ratio of 4-acetyldiphenylsulfide to aluminum trichloride in the first step is 1: 1 to 6.
4. The method for synthesizing tris (4-acetylbiphenyl sulfide) sulfonium hexafluorophosphate according to claim 2, wherein the molar ratio of the thionyl chloride to the 4-acetylbiphenyl sulfide in the first step is 1: 1 to 5.
5. The method for synthesizing tris (4-acetyldiphenylsulfide) sulfonium hexafluorophosphate according to claim 2, wherein the amount of potassium hexafluorophosphate used in step two is: the molar ratio of the potassium hexafluorophosphate to the 4-acetyldiphenyl sulfide is 1-2.5: 1.
6. the method for synthesizing tris (4-acetyldiphenylsulfide) ylium hexafluorophosphate according to claim 2, wherein the molar ratio of dichloromethane to aluminum trichloride in the step one is 116: 1 to 3.
7. A product comprising tris (4-acetyldiphenylsulfide) sulfonium hexafluorophosphate of claim 1.
8. A product prepared using the synthesis method of any one of claims 2 to 6.
9. Use of the tris (4-acetyldiphenylsulfide) ylium hexafluorophosphate of claim 1 in coating, ink, adhesive, encapsulating material for electronics industry, photoresist or printing material.
10. Use of the product according to claim 8 in coatings, inks, adhesives, encapsulating materials for the electronics industry, photoresists or printing materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911100517.7A CN110922346A (en) | 2019-11-12 | 2019-11-12 | Tris (4-acetyldiphenyl sulfide) thioylium hexafluorophosphate and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911100517.7A CN110922346A (en) | 2019-11-12 | 2019-11-12 | Tris (4-acetyldiphenyl sulfide) thioylium hexafluorophosphate and synthesis method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110922346A true CN110922346A (en) | 2020-03-27 |
Family
ID=69853815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911100517.7A Pending CN110922346A (en) | 2019-11-12 | 2019-11-12 | Tris (4-acetyldiphenyl sulfide) thioylium hexafluorophosphate and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110922346A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101466804A (en) * | 2006-04-13 | 2009-06-24 | 西巴控股有限公司 | Sulphonium salt initiators |
| CN101952248A (en) * | 2007-10-10 | 2011-01-19 | 巴斯夫欧洲公司 | Sulphonium salt initiators |
| CN109134711A (en) * | 2017-06-15 | 2019-01-04 | 常州强力电子新材料股份有限公司 | A kind of sulfosalt photoinitiator and its preparation and application |
| CN111825781A (en) * | 2019-04-16 | 2020-10-27 | 北京英力科技发展有限公司 | Photoinitiator composition containing sensitizer and sulfonium salt and application of photoinitiator composition in LED cation photocuring composition |
-
2019
- 2019-11-12 CN CN201911100517.7A patent/CN110922346A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101466804A (en) * | 2006-04-13 | 2009-06-24 | 西巴控股有限公司 | Sulphonium salt initiators |
| CN101952248A (en) * | 2007-10-10 | 2011-01-19 | 巴斯夫欧洲公司 | Sulphonium salt initiators |
| CN109134711A (en) * | 2017-06-15 | 2019-01-04 | 常州强力电子新材料股份有限公司 | A kind of sulfosalt photoinitiator and its preparation and application |
| CN111825781A (en) * | 2019-04-16 | 2020-10-27 | 北京英力科技发展有限公司 | Photoinitiator composition containing sensitizer and sulfonium salt and application of photoinitiator composition in LED cation photocuring composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3680234B1 (en) | Sulfonium salt photoinitiator, preparation method therefor, photocurable composition containing sulfonium salt photoinitiator, and use thereof | |
| CN110845704A (en) | Preparation process of high-temperature-resistant glycidylamine epoxy resin | |
| CN110760068A (en) | Modified MQ resin, synthesis method and application in pressure-sensitive adhesive | |
| CN110922346A (en) | Tris (4-acetyldiphenyl sulfide) thioylium hexafluorophosphate and synthesis method thereof | |
| EP0286454B1 (en) | Polymerised vinyl resins | |
| CN109679581B (en) | Composition containing 3- (N-vinylbenzyl-2-aminoethyl) aminopropyltrimethoxysilane hydrochloride and methanol | |
| CN104513138A (en) | Styrenated phenol compound and method of preparing same | |
| US9499498B2 (en) | Process for the preparation of triazine carbamates | |
| DE10333571A1 (en) | New aryl-substituted adamantane derivatives, useful in preparation of insulating resins, particularly for miniaturized semiconductor devices | |
| JPH08188569A (en) | Production of sulfonium compound | |
| CN114181110A (en) | Bisphenol fluorene oxime ester photoinitiator and preparation method and application thereof | |
| US2472310A (en) | Process for preparing the ethynyl carbinol of beta-ionone | |
| KR20120097458A (en) | Novel episulfide compounds curable resin compositions containing the episulfide compounds and cured products thereof | |
| CN112390718A (en) | Degradable photoresist resin monomer synthesized from trimethylbicyclo [2.2.2] octane dione and synthesis method thereof | |
| CN111138280A (en) | Photoresist resin monomer synthesized from 3-ethylbicyclo [3.3.1] nonane-2, 4-diketone and synthesis method thereof | |
| JPH01168722A (en) | Preparation of polyfunctional epoxy resin | |
| US2844632A (en) | New composition of matter | |
| MX2013005763A (en) | Epoxy resin comprising an adduct of dvbdo as toughener. | |
| CN101153016A (en) | Method for producing 3-(substituted phenyl) sulfur onium chloride salt | |
| TWI789520B (en) | Composition and manufacturing method thereof | |
| CN111057028B (en) | Fluorine-containing cationic polymerization monomer and synthesis and application thereof | |
| CN102177184B (en) | Modified triaroylbenzene-based polymer | |
| JP4190367B2 (en) | Process for producing B, B ', B "-trichloro-N, N', N" -trialkylborazine and hexaalkylborazine | |
| JP2018095591A (en) | Sulphonium compound and thermal polymerization initiator | |
| Kim et al. | Phosphonic acid esters as thermally latent initiatiors: Initiation process in the polymerization of glycidyl phenyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200327 |
|
| RJ01 | Rejection of invention patent application after publication |