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Process for production of monosulfonium salts, cationic polymerization initiators, curable compositions, and products of curing

a monosulfonium salt and cationic polymerization technology, applied in the field of monosulfonium salt production, can solve the problems of reducing lowering the yield of sulfonium salts by several percent to about 10%, etc., and achieves excellent solubility in organic solvents, high purity and yield. , the effect of high yield

Inactive Publication Date: 2006-11-02
SAN APRO
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0014] Meanwhile, a product containing unreacted starting material can be refined by recrystallization and washing with a solvent such as ethanol, but a problem with performing this refining is that it lowers the yield of the sulfonium salt by several percent to about 10%.
[0015] It is an object of the present invention to provide a method for efficiently manufacturing a monosulfonium salt, by which a high-purity monosulfonium salt, that is, a product in which the residual content of unreacted material does not exceed 4%, can be obtained at a high yield without performing refining by washing and recrystallization, and furthermore can be obtained in the form of a monosulfonium salt solution in a high-boiling point solvent, and to provide a cationic polymerization initiator with excellent solubility in organic solvents, a curable composition with good storage stability, and a cured product.
[0018] More specifically, the method of the present invention for manufacturing a monosulfonium salt is a method for obtaining, at a high purity and yield, the desired monosulfonium salt by charging (a) an aryl compound, (b) a sulfoxide compound, (c) a dehydrating agent, and (d) a BF4, PF6, AsF6, or SbF6 salt of an alkali metal or an alkaline earth metal into a reaction system, then charging (e) an inorganic acid, so that (h) a strong acid, namely, HBF4, HPF6, HAsF6, or HSbF6, is produced by a reaction between (d) the BF4, PF6, AsF6, or SbF6 salt of an alkali metal or an alkaline earth metal and (e) the inorganic acid such as sulfuric acid, and the aryl compound (a) and the sulfoxide compound (b) undergo dehydration condensation at a high reactivity rate in the presence of this strong acid (h) and the dehydrating agent (c).
[0019] According to the manufacturing method of the present invention, a high-purity monosulfonium salt with a low unreacted starting material content can be obtained at a high yield. Also, a cationic polymerization initiator composed of a monosulfonium salt obtained by said manufacturing method exhibits excellent solubility in organic solvents in the course of blending in a cationic polymerizable monomer. The blended cationically polymerizable curable composition will have excellent storage stability and curability, and will cure into a material having a good hardness.
[0020] Therefore, a sulfonium salt obtained by the manufacturing method of the present invention is favorable as a cationic polymerization initiator for curing cationic polymerizable paints, coating agents, inks, resist films, liquid resists, adhesives, moldable materials, casting materials, putties, glass fiber impregnants, fillers, resins for rapid prototyping and the like with active energy rays such as light, electron beams, or X-rays.

Problems solved by technology

The product obtained by this method can be adequately used in an unmodified form as a polymerization initiator for a photo-cationic polymerization paint, for example, but surprisingly, when a photopolymerization composition containing said product was cured with ultraviolet rays or the like, the curing velocity was decreased by the unreacted starting material in said product, and as a result, the photopolymerization composition is not cured to a sufficient level, and furthermore it was found that this problem does not occur if the residual amount of unreacted starting material did not exceed 4%.
Meanwhile, a product containing unreacted starting material can be refined by recrystallization and washing with a solvent such as ethanol, but a problem with performing this refining is that it lowers the yield of the sulfonium salt by several percent to about 10%.

Method used

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  • Process for production of monosulfonium salts, cationic polymerization initiators, curable compositions, and products of curing
  • Process for production of monosulfonium salts, cationic polymerization initiators, curable compositions, and products of curing
  • Process for production of monosulfonium salts, cationic polymerization initiators, curable compositions, and products of curing

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0081] 4.28 g (23.3 mmol) of potassium hexafluorophosphate (KPF6), 10 ml of acetonitrile, 3.61 g (19.4 mmol) of diphenyl sulfide, 4.05 g (20.0 mmol) of diphenyl sulfoxide, and 5.94 g (58.2 mmol) of acetic anhydride were introduced into a 100 ml reaction vessel and uniformly mixed, and then 2.28 g (23.3 mmol) of concentrated sulfuric acid was added dropwise at room temperature over a period of 60 minutes. Heat was generated during this course to increase the temperature, but the system was cooled so that the temperature did not exceed 40° C. After 1 hour of stirring at 40° C., the system was cooled to room temperature, and 20 ml of water were added and stirred for 10 minutes, whereupon an oily substance became separated. 20 ml of ethyl acetate were added to this to dissolve the oily substance, and the organic layer was taken. This organic layer was washed with 10 ml of 20% caustic soda and washed three times with 10 ml of water, and then the acetonitrile and ethyl acetate were distil...

example 2

[0083] 3.91 g (23.3 mmol) of sodium hexafluorophosphate (NaPF6), 8 ml of acetonitrile, 3.61 g (19.4 mmol) of diphenyl sulfide, 4.05 g (20.0 mmol) of diphenyl sulfoxide, and 5.94 g (58.1 mmol) of acetic anhydride were introduced into a 100 ml reaction vessel and uniformly mixed, and then 2.28 g (23.3 mmol) of concentrated sulfuric acid were added dropwise at a temperature of 40° C. or lower over a period of 40 minutes. After 2 hours of stirring at 40° C., the system was cooled to room temperature, and 20 ml of water and 20 ml of ethyl acetate were added and stirred for 10 minutes, and the organic layer was taken. This organic layer was washed with 10 ml of water while the pH of the aqueous layer was adjusted to between 7 and 8 with 40% caustic soda, and then the organic layer was washed two more times with 10 ml of water. 10 g of propylene carbonate were added to this organic layer, and then the acetonitrile and ethyl acetate were distilled off under reduced pressure at 100° C. or lo...

example 3

[0085] 10.12 g (96% yield) of a slightly yellowish solid were obtained in the same manner as in Example 1, except that the diphenyl sulfoxide was replaced with 4.61 g (20.0 mmol) of 4,4′-dimethyldiphenyl sulfoxide.

[0086] This product was analyzed by 13C-NMR, IR, and HPLC, which revealed it to contain 99.1% (4-phenylthiophenyl)-4,4′-dimethyldiphenylsulfonium hexafluorophosphate, 0.4% thiodi-p-phenylenebis(4,4′-dimethyldiphenylsulfonium)bishexafluorophosphate, and 0.2% diphenyl sulfide and 0.3% 4,4′-dimethyldiphenyl sulfoxide as unreacted starting materials.

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Abstract

A monosulfonium salt in which very little unreacted raw material remains, which has a purity of at least 96%, and which has one sulfonio group in its molecule is manufactured without a refining step. After (a) an aryl compound, (b) a sulfoxide compound, (c) a dehydrating agent, and (d) a BF4, PF6, AsF6, or SbF6 salt of an alkali metal or an alkaline earth metal are introduced into a reaction system, (e) an inorganic acid is added, so that the aryl compound (a) and the sulfoxide compound (b) are subjected to dehydration condensation.

Description

TECHNICAL FIELD [0001] This invention relates to a method for manufacturing a monosulfonium salt that is useful as a cationic polymerization initiator, and more particularly to a high-purity monosulfonium salt (a sulfonium salt having one sulfonio group per molecule), having an aryl group (aromatic ring), to a cationic polymerization initiator, a curable composition, and a cured product. BACKGROUND ART [0002] BF4, PF6, AsF6 and SbF6 salts of triarylsulfonium are known and commonly used upto now as polymerization initiators of high cationic photopolymerization initiation performance. [0003] However, with methods proposed up to now for manufacturing a sulfonium salt, such as a method in which a sulfide and a sulfoxide are condensed in the presence of a strong organic acid such as methanesulfonic acid or an inorganic acid such as sulfuric acid, and then subjected to double decomposition in an aqueous solution of a BF4, PF6, AsF6 or SbF6 salt of an alkali metal or the like (see Japanese...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C08F4/06C07C321/24C07F9/90C07F9/66C07C381/12C08F2/50C08F4/00C08G59/68C08G65/10G03F7/004
CPCC07C381/12G03F7/0045C08G65/105C08G59/687
Inventor DATE, MASASHIKIMURA, HIDEKIYAMASHITA, SHINJIYAMAMOTO, JIRO
Owner SAN APRO
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