CN108698986B - Process for acidifying p-xylylene dicamphor sulfonate - Google Patents
Process for acidifying p-xylylene dicamphor sulfonate Download PDFInfo
- Publication number
- CN108698986B CN108698986B CN201780015581.8A CN201780015581A CN108698986B CN 108698986 B CN108698986 B CN 108698986B CN 201780015581 A CN201780015581 A CN 201780015581A CN 108698986 B CN108698986 B CN 108698986B
- Authority
- CN
- China
- Prior art keywords
- xylylene dicamphor
- xylylene
- sulfonic acid
- sulfonate
- cation exchange
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Provided is a process for acidifying p-xylylene dicamphor sulfonate to convert the same into p-xylylene dicamphor sulfonic acid, and in particular, a process for converting the same into p-xylylene dicamphor sulfonic acid in the presence of a cation exchange resin, wherein the conversion process of the present invention is a remarkably efficient process with high conversion through a simple process.
Description
Technical Field
The present invention relates to a process for acidifying p-xylylene dicamphor sulfonate, and more particularly, to a process for converting p-xylylene dicamphor sulfonate into p-xylylene dicamphor sulfonic acid in the presence of a cation exchange resin.
Background
The ultraviolet rays include ultraviolet rays A (320nm to 400nm) and ultraviolet rays B (290nm to 320nm), wherein the ultraviolet rays A account for 90% or more of the ultraviolet rays. Generally, exposure to ultraviolet rays occurs more frequently during summer, for example, it is well known that ultraviolet rays B are a main cause of erythema, mild burns, and the like, while ultraviolet rays a are known to penetrate the skin and affect cells, and cause photoaging, skin allergy, even skin cancer, and the like. Therefore, ultraviolet rays a affect the skin regardless of seasons, and thus more special care is required.
Almost all materials currently on the market for organic sunscreens are lipid soluble and insoluble in water. Therefore, the cosmetic manufactured using the materials currently on the market for organic sunscreens has disadvantages in that: when the cosmetic is applied to the skin, the feeling of use is not good. In addition, inorganic sunscreens are poor in spreadability and give the skin a heavy feel when applied to the skin, giving a poor feel in use.
On the other hand, it is known from U.S. patent publication nos. 4,585,597 and 5,698,595 that terephthalylidene dicamphor sulfonic acid can protect skin from ultraviolet rays a to prevent skin aging, and has high solubility in water. Therefore, the cosmetics comprising p-xylylene dicamphor sulfonic acid have good spreading characteristics to produce products with good feeling in use, and are easy to wash, which is advantageous for maintaining clean skin.
Furthermore, p-xylylene dicamphor sulfonic acid is distributed as a 33% aqueous solution as a water-soluble material for an organic sunscreen agent, which can be produced in various formulations, and is also registered as a 33% aqueous solution.
Processes for producing p-xylylene dicamphor sulfonic acid are known in U.S. patent publication nos. 4,585,597 and 4,588,839. As shown in the following reaction scheme 1, it is known that 2 moles of 10-dl-camphorsulfonic acid and 1 mole of terephthalaldehyde are subjected to a condensation reaction in the presence of a base to obtain terephthalylidene dicamphor sulfonate, and that p-xylylene dicamphor sulfonate is acidified by using hydrochloric acid to obtain terephthalylidene dicamphor sulfonic acid:
[ reaction scheme 1]
However, this acidification reaction corresponds to an equilibrium reaction as shown in reaction scheme 2 below:
[ reaction scheme 2]
Therefore, an excess of acid should be used to achieve acidification of p-xylylene dicamphor sulfonate, which increases production costs and requires a separate process for removing the excess acid. In addition, another process for removing water-soluble salts such as NaCl, which is produced as a by-product of water-soluble p-xylylene dicamphor sulfonic acid, is also required.
Furthermore, even with a significant excess of acid, the acidification reaction to terephthalylidene dicamphor sulfonic acid is not complete. In other words, according to the existing methods using general inorganic acids or general organic acids, the acidification reaction process is also complicated and economically inefficient, and the yield of terephthalylidene dicamphor sulfonic acid is also very low.
Therefore, there is a need to develop a method for acidifying terephthalylidene dicamphor sulfonate, which includes a simple and efficient reaction process.
Disclosure of Invention
Technical problem
The present inventors have studied the acidification reaction of p-xylylenedicamphor sulfonate to solve the above problems, and have completed the present invention.
It is an object of the present invention to provide a process for converting p-xylylene dicamphor sulfonate into p-xylylene dicamphor sulfonic acid in a very economical manner in high yield and high purity by a simple process.
Technical scheme
In one general aspect, there is provided a process for converting p-xylylene dicamphor sulfonate to p-xylylene dicamphor sulfonic acid in high yield and high purity by a simple process, unlike the related art. The conversion process of the present invention comprises converting p-xylylene dicamphor sulfonate represented by the following chemical formula 2 into p-xylylene dicamphor sulfonic acid represented by the following chemical formula 1 in the presence of a cation exchange resin:
[ chemical formula 1]
[ chemical formula 2]
In the chemical formulae 1 and 2,
m is an alkali metal or N (R)1)(R2)(R3)(R4) And R1To R4Each independently hydrogen or (C1 to C7) alkyl;
r is (C1 to C7) alkyl or (C1 to C7) alkoxy; and
n is 0 or an integer of 1 to 4, and when n is 2 or more, R may be the same as or different from each other.
In chemical formula 2 according to an exemplary embodiment of the present invention, M may be Na, and n may be 0.
The cation exchange resin according to an exemplary embodiment of the present invention may be an H-type cation exchange resin and a sulfonated styrene-based resin crosslinked with divinylbenzene, and may have an ion exchange capacity of 1meq/ml to 3 meq/ml.
The conversion method according to an exemplary embodiment of the present invention may use an aqueous solution of p-xylylene dicamphor sulfonate in which p-xylylene dicamphor sulfonate represented by chemical formula 2 is dissolved in water, and the aqueous solution of p-xylylene dicamphor sulfonate may be produced by using 500 parts by weight to 1000 parts by weight of water with respect to 100 parts by weight of p-xylylene dicamphor sulfonate.
Advantageous effects
According to the conversion process of the present invention, p-xylylene dicamphor sulfonate is converted into p-xylylene dicamphor sulfonic acid in the presence of a cation exchange resin. Therefore, even in the presence of a small amount of cation exchange resin, the conversion is very high, so that almost the whole amount of p-xylylene dicamphor sulfonate is acidified and the produced salt is very easily removed.
Further, the conversion process of the present invention can obtain p-xylylene dicamphor sulfonic acid in an aqueous solution state, and thus, a 33% aqueous solution of p-xylylene dicamphor sulfonic acid is easily obtained, which can be manufactured as a product that can be directly distributed without a separate process.
Furthermore, the conversion process of the present invention is a remarkably economical and efficient process because almost the entire amount of the p-xylylene dicamphor sulfonate is converted into p-xylylene dicamphor sulfonic acid, and the cation exchange resin used can be recovered and reused.
Detailed Description
The present invention provides a process for converting p-xylylene dicamphor sulfonate represented by the following chemical formula 2 into p-xylylene dicamphor sulfonic acid represented by the following chemical formula 1 in the presence of a cation exchange resin:
[ chemical formula 1]
[ chemical formula 2]
In the chemical formulae 1 and 2,
m is an alkali metal or N (R)1)(R2)(R3)(R4) And R1To R4Each independently hydrogen or (C1 to C7) alkyl;
r is (C1 to C7) alkyl or (C1 to C7) alkoxy; and
n is 0 or an integer of 1 to 4, and when n is 2 or more, R may be the same as or different from each other.
According to the conversion method of the present invention, almost the entire amount of the terephthalylidene dicamphor sulfonate can be converted by using the cation exchange resin without using the inorganic acid or organic acid of the conventional method, and the conversion method is very economical process due to high conversion rate even with a small amount of the cation exchange resin as compared with the conventional method using the inorganic acid or organic acid.
In addition, salts generated as by-products can be easily removed, and thus, a separate process for removing salts is not required.
The conversion processes using inorganic or organic acids known in the art generally have the following problems: it is necessary to remove the excess acid and to remove the corresponding salt of each acid produced as a by-product. Further, the degree of acidification may vary depending on the kind of acid used at this time, and therefore, the content of terephthalylidene dicamphor sulfonic acid is greatly deteriorated due to the conventional method using a general acid.
On the other hand, the conversion method for acidifying p-xylylene dicamphor sulfonate according to the present invention to convert p-xylylene dicamphor sulfonate into p-xylylene dicamphor sulfonic acid uses a cation exchange resin, and therefore, it is not necessary to use an excessive amount of acid, a separate process for removing salts is not required, and p-xylylene dicamphor sulfonic acid is obtained in an aqueous solution state, thereby producing a product capable of being directly distributed only when the concentration thereof is set to 33%.
In a specific embodiment, first, a column is packed with a cation exchange resin, and then, the p-xylylene dicamphor sulfonate dissolved in water is passed through the column, and even if only a cation exchange resin having an equivalent ratio much smaller than the amount used of a general inorganic acid or a general organic acid is used, almost the entire amount of the p-xylylene dicamphor sulfonate is acidified. Further, salts generated as by-products are easily removed and p-xylylene dicamphor sulfonic acid in an aqueous solution state is obtained, and therefore, a product capable of being directly distributed is produced only when the concentration thereof is set to 33%.
Thus, the process for the conversion of p-xylylene dicamphor sulfonate to p-xylylene dicamphor sulfonic acid of the present invention is a remarkably effective process because the process is very simple and the conversion rate and purity are high.
The method for converting p-xylylene dicamphor sulfonate into p-xylylene dicamphor sulfonic acid using a cation exchange resin according to an exemplary embodiment of the present invention may acidify the p-xylylene dicamphor sulfonate by adding the cation exchange resin to an aqueous solution of the p-xylylene dicamphor sulfonate. However, preferably, the terephthalylidene dicamphor sulfonate can be acidified by packing the column with a cation exchange resin and then passing an aqueous solution of the same, in view of an increase in yield, simplification of the process, and economic efficiency.
The compounds represented by chemical formulas 1 and 2 described in the present invention include all isomers of cis-trans form and the like for each double bond. The "alkyl" and "alkoxy" groups used in the present invention include both linear and branched forms, and have 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.
The alkali metal of M according to an exemplary embodiment of the present invention may be any alkali metal within a range recognized by those skilled in the art. Examples of the alkali metal may include Li, Na, K, etc., and Na is preferable in view of reaction efficiency.
R according to an exemplary embodiment of the present invention may be a (C1 to C5) alkyl group or a (C1 to C5) alkoxy group, and preferably a (C1 to C5) alkyl group, and when the phenylene group has no substituent, n may be zero.
The cation exchange resin according to an exemplary embodiment of the present invention is prepared by reacting sulfonic acid groups (-SO) as exchange groups3H) Carboxyl group (-COOH), etc. are bonded to a base polymer matrix having a network structure, and exchange cations such as Ca2+、Na+、H+And the like. The cation exchange resin may be a strongly acidic cation exchange resin or a weakly acidic cation exchange resin, and is preferably capable of exchanging H+Cationic polymerA daughter type H cation exchange resin.
Specifically, the cation exchange resin according to an exemplary embodiment of the present invention may include a copolymer of divinylbenzene with styrene, or a copolymer of divinylbenzene with acrylate, or a tetrafluoroethylene polymer as a matrix, and may include sulfonic acid or carboxylic acid, and preferably sulfonic acid as an exchange group. More preferably, the cation exchange resin may be a sulfonated styrene-based resin crosslinked with divinylbenzene in consideration of reaction efficiency.
Preferably, the cation exchange resin according to an exemplary embodiment of the present invention may be an H-type cation exchange resin and a sulfonated styrene-based resin crosslinked with divinylbenzene, and may have an ion exchange capacity of 1meq/ml or more, preferably 1meq/ml to 3meq/ml, and more preferably 1.5meq/ml to 3 meq/ml.
The ion exchange capacity described in the present invention is measured as the number equivalent of ions that can be exchanged and can be expressed as the polymer volume (ion exchange capacity per volume, i.e. volume capacity) and preferably means the milliequivalent of the exchange capacity per swollen volume of the wet bed (wet polymer).
Specifically, when the cation exchange resin is packed in a column and used, the cation exchange resin may have an amount corresponding to 2 times to 6 times of a volume ratio with respect to a certain weight of the terephthalylidene dicamphor sulfonate, and may be regenerated using diluted hydrochloric acid and reused. As for the elution rate of the column, the reaction solution may be passed in an amount of 0.2 to 2 times per hour with respect to a certain volume of the cation exchange resin packed in the column.
The aqueous solution of all the p-xylylene dicamphor sulfonic acid eluted from the column may be concentrated to obtain the target compound, i.e., p-xylylene dicamphor sulfonic acid in the form of brown solid. In addition, some of the water in the aqueous solution of terephthalylidene dicamphor sulfonic acid eluting from the column may be distilled off and quantified with 0.1 moles of potassium hydroxide to produce a 33% aqueous solution that can be made into a product ready for market.
Preferably, the conversion process of the present invention may use an aqueous solution of p-xylylene dicamphor sulfonate in which the p-xylylene dicamphor sulfonate represented by chemical formula 2 is dissolved in water, and the aqueous solution may be produced by using 500 parts by weight to 1000 parts by weight, and preferably 700 parts by weight to 1000 parts by weight of water, relative to 100 parts by weight of the p-xylylene dicamphor sulfonate.
Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited by the following examples.
EXAMPLE 1 production of p-xylylene dicamphor sulfonic acid
12g (20mmol) of disodium p-xylylene dicamphor sulfonate was dissolved in 100ml of water, and then 200ml (1.8meq/ml) of a cation exchange resin, TRILITE SCR-BH (Samyang Corp.), was added and stirred at room temperature for 5 hours. The resin was removed by filtration and the product was washed with 50ml of water. Water was removed by distillation under reduced pressure, and the resulting solid was dried under reduced pressure to obtain 10.4g (yield: 93.4%) of p-xylylene dicamphor sulfonic acid as an aimed compound in the form of a brown solid.
An accurately weighed amount of 1g of the solid was dissolved in 50ml of water and titrated with 0.1mol of potassium hydroxide solution (indicator: 1ml of phenolphthalein solution). The content of p-xylylene dicamphor sulfonic acid in the acidified solid form after calibration in a blank test by using the same method was 89.7%.
EXAMPLE 2 production of p-xylylene dicamphor sulfonic acid
Example 2 was conducted in the same manner as in example 1 except that 12.7g of dipotassium p-xylylene dicamphor sulfonate was used, thereby obtaining 10.5g of p-xylylene dicamphor sulfonate as a brown solid as a target compound. The content of p-xylylene dicamphor sulfonic acid in the solid form was 89.6%.
EXAMPLE 3 production of p-xylylene dicamphor sulfonic acid
Example 3 was conducted in the same manner as in example 1 except that 11.9g of diammonium p-xylylenedicamphor sulfonate was used, thereby obtaining 10.4g of p-xylylenedicamphor sulfonic acid as a brown solid as a target compound. The content of p-xylylene dicamphor sulfonic acid in the solid form was 89.5%.
EXAMPLE 4 production of p-xylylene dicamphor sulfonic acid
The column was packed with 20L (1.8meq/ml) of a cation exchange resin, TRILITE SCR-BH (Samyang Corp.). 4kg (6.6mol) of disodium p-xylylenedicamphor sulfonate dissolved in 28L of water was eluted at a rate of 9L/hr. The eluted product was washed with 16L of water to obtain a reaction solution, and water was removed from the reaction solution by distillation under reduced pressure, and the resulting solid was dried under reduced pressure to obtain 3.6kg (yield: 97%) of p-xylylene dicamphor sulfonic acid as a brown solid as an aimed compound.
An accurately weighed amount of 1g of the solid was dissolved in 50ml of water and titrated with 0.1mol of potassium hydroxide solution (indicator: 1ml of phenolphthalein solution). The content of p-xylylene dicamphor sulfonic acid after calibration in a blank test by using the same method was 99.9%.
1H-NMR(CD3OD)(ppm)：0.83(s，6H)，1.18(s，6H)，1.61(m，2H)，1.71(m，2H)，2.32(m，2H)，2.73(m，2H)，2.98(d，2H)，3.18(m，2H)，3.48(d，2H)，7.22(s，2H)，7.59(s，4H)
EXAMPLE 5 production of a 33% aqueous solution of p-xylylene dicamphor sulfonic acid
Only two thirds of water were removed from the obtained liquid after the same method as in example 4 was performed to obtain 10.7kg of a brown aqueous solution. The quantification was performed as in example 4 to determine the content, thereby obtaining a 33% aqueous solution of terephthalylidene dicamphor sulfonic acid.
Comparative example 1 acidification with hydrochloric acid
12g (20mmol) of disodium p-xylylene dicamphor sulfonate were dissolved in 30ml of water and 30ml of concentrated hydrochloric acid (360 mmol). After 1 hour of reflux, the product was concentrated and cooled, and the resulting solid was filtered. The filtered solid was washed with 6N hydrochloric acid, dried under reduced pressure at 80, and dried under reduced pressure at 100 to obtain 7.02g of a solid.
An accurately weighed amount of 1g of the solid was dissolved in 50ml of water and titrated with 0.1mol of potassium hydroxide solution (indicator: 1ml of phenolphthalein solution). The content of terephthalylidene dicamphor sulfonic acid in the solid acidified with hydrochloric acid, after calibration with a blank test using the same method, was 33.6%.
Comparative example 2 acidification with methanesulfonic acid
6.06g (10mmol) of disodium p-xylylene dicamphor sulfonate was dissolved in 50ml of water, and 17.29g (180mmol) of methanesulfonic acid was added thereto, and the mixture was stirred at room temperature for 2 hours. The reaction solution was concentrated and water was completely removed with 100ml of toluene using a Dean-Stark apparatus. The solid produced by cooling was filtered, and the filtered solid was washed with toluene, dried under reduced pressure at 80, and dried under reduced pressure at 100 to obtain 7.68g of a solid.
When quantified as in comparative example 1, the content of terephthalylidenedicamphor sulfonic acid in the methanesulfonic acid acidified solid was about 22.5% taking into account the inclusion of sodium methanesulfonate.
Comparative example 3 acidification with trifluoroacetic acid
Comparative example 3 was conducted in the same manner as in comparative example 2 except that 20.52g (180mmol) of trifluoroacetic acid was added after 6.06g (10mmol) of disodium p-xylylene dicamphor sulfonate was dissolved in 50ml of water, thereby obtaining 5.91g of a solid.
In the quantification as in comparative example 1, the content of terephthalylidenedicamphor sulfonic acid in the trifluoroacetic acid-acidified solid was about 7.5%, taking into account the presence of sodium trifluoroacetate.
Comparative example 4 acidification with sulfuric acid
Comparative example 4 was conducted in the same manner as in comparative example 2 except that 8.82g (90mmol) of sulfuric acid was added after 6.06g (10mmol) of disodium p-xylylene dicamphor sulfonate was dissolved in 50ml of water, whereby 6.44g of a solid was obtained.
When quantified as in comparative example 1, the content of terephthalylidenedicamphor sulfonic acid in the sulfuric acid-acidified solid was about 19.7% in view of the inclusion of sodium sulfate.
It can be understood that the conversion of p-xylylene dicamphor sulfonic acid produced in examples 1 to 4 is much higher than that in comparative example 1. In addition, examples 1 to 4 did not require a separate process for removing salts, and thus, the process was simpler and the purity was higher than that of comparative example 1.
Further, it is understood that in comparative examples 2 to 4, the conversion rate was low, and terephthalylidene dicamphor sulfonic acid containing salts corresponding to the respective organic and inorganic acids was obtained, and thus the purity was low and a separate process for removing the salts was required.
In conclusion, it can be understood that the process for the conversion of p-xylylene dicamphor sulfonate to p-xylylene dicamphor sulfonic acid in the presence of the cation exchange resin of the present invention has not only higher conversion and higher purity, but also a simpler conversion process, which is an economical and efficient process compared to the conventional process.
Claims (4)
1. A process for acidifying p-xylylene dicamphor sulfonate comprising:
converting a p-xylylene dicamphor sulfonate represented by the following chemical formula 2 into a p-xylylene dicamphor sulfonic acid represented by the following chemical formula 1 in the presence of a sulfonated styrene-based cation exchange resin crosslinked with divinylbenzene:
[ chemical formula 1]
[ chemical formula 2]
In the chemical formulae 1 and 2,
m is an alkali metal or N (R)1)(R2)(R3)(R4) And R1To R4Each independently of the others is hydrogen or(C1 to C7) alkyl;
r is (C1 to C7) alkyl or (C1 to C7) alkoxy; and
n is 0 or an integer of 1 to 4, and when n is 2 or more, R may be the same as or different from each other.
2. The method of claim 1, wherein M is Na and n is 0.
3. The method of claim 1, wherein the cation exchange resin has an ion exchange capacity of 1meq/ml to 3 meq/ml.
4. The method of claim 1, wherein the method uses an aqueous solution of p-xylylene dicamphor sulfonate represented by chemical formula 2 in which the p-xylylene dicamphor sulfonate is dissolved in water.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160029353A KR102066003B1 (en) | 2016-03-11 | 2016-03-11 | Process for the acidification of terephthalylidene dicamphor sulfonic acid salt |
| KR10-2016-0029353 | 2016-03-11 | ||
| PCT/KR2017/001584 WO2017155217A1 (en) | 2016-03-11 | 2017-02-14 | Method for acidifying terephthalylidene dicamphor sulfonic acid salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108698986A CN108698986A (en) | 2018-10-23 |
| CN108698986B true CN108698986B (en) | 2020-12-15 |
Family
ID=59790775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780015581.8A Active CN108698986B (en) | 2016-03-11 | 2017-02-14 | Process for acidifying p-xylylene dicamphor sulfonate |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6659876B2 (en) |
| KR (1) | KR102066003B1 (en) |
| CN (1) | CN108698986B (en) |
| DE (1) | DE112017001272B4 (en) |
| WO (1) | WO2017155217A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102066003B1 (en) * | 2016-03-11 | 2020-01-15 | 주식회사 카이로켐 | Process for the acidification of terephthalylidene dicamphor sulfonic acid salt |
| KR101937332B1 (en) | 2018-06-18 | 2019-01-11 | 신성소재 주식회사 | Purification method of terephthalylidene dicamphor sulfonic acid |
| CN110156642A (en) * | 2019-06-25 | 2019-08-23 | 陕西莱特光电材料股份有限公司 | A kind of synthetic method of sun-screening agent intermediate Terephthalidene Dicamphor Sulfonic Acid |
| KR102099831B1 (en) * | 2020-01-29 | 2020-04-10 | 주식회사 세라수 | a method for acidifying terephthalylidene dicamphor sulfonate |
| KR102341174B1 (en) * | 2021-09-13 | 2021-12-20 | 주식회사 세라수 | a method for acidifying terephthalylidene dicamphor sulfonate using cation exchange fiber |
| KR20240051688A (en) | 2022-10-13 | 2024-04-22 | 신성소재 주식회사 | Manufacturing method of terephthalylidene dicamphor sulfonic acid using electrodialysis |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3439026A (en) * | 1964-12-23 | 1969-04-15 | Marathon Oil Co | Manufacture of carboxylic acids from corresponding metallic salts |
| US4585597A (en) * | 1982-06-15 | 1986-04-29 | L'oreal | 3-benzylidene-camphors, process for their preparation and their use in protection against UV rays |
| US4588839A (en) * | 1982-07-08 | 1986-05-13 | L'oreal | Sulphonamides derived from 3-benzylidene-camphor and their application as UV filters |
| CN1116924A (en) * | 1994-03-08 | 1996-02-21 | 莱雅公司 | Utilisation des acides sulfoniques comme agents antivieillissement dans une composition cosmetiqueou dermatologique |
| CN101391949A (en) * | 2007-09-17 | 2009-03-25 | 罗门哈斯公司 | Process for converting a hydroxy carboxylic acid or salts thereof, to an unsaturated carboxylic acid and/or its esters |
| CN101573331A (en) * | 2006-12-27 | 2009-11-04 | 旭化成精细化工股份有限公司 | Process for producing vinylsulfonic acid |
| CN102633690A (en) * | 2012-04-11 | 2012-08-15 | 上海康福赛尔医药科技有限公司 | Method for preparing levo- and dextro-camphor sulfonic acid by induced crystallization and resolution of racemized camphor sulfonic acid |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60152425A (en) * | 1984-01-20 | 1985-08-10 | Oyo Seikagaku Kenkyusho:Kk | Novel optical resolution of racemic compound |
| JPH08325262A (en) * | 1995-05-30 | 1996-12-10 | Mitsui Toatsu Chem Inc | Production of (+)-3-phenyl-5-(2-(1-pyrrolidinylmethyl) butyryl) isoxazone and its salt |
| FR2911504B1 (en) * | 2007-01-19 | 2009-03-13 | Oreal | COSMETIC O / W EMULSION CONTAINING LIPOPHILIC UV FILTER, POLAR OIL AND COPOLYMER DIBLOC (POLYSTYRENE) -BLOCK-POLY (ACRYLIC ACID-STAT ACRYLATE, C1-C4 ALKYL) |
| US20120244202A1 (en) * | 2009-10-12 | 2012-09-27 | L'oreal | Methods of photoprotecting a material against solar uv radiation using photonic particles; compositions |
| WO2015030702A2 (en) * | 2013-08-26 | 2015-03-05 | Keith Desanto | High purity rhamnolipid cosmetic application |
| KR102066003B1 (en) * | 2016-03-11 | 2020-01-15 | 주식회사 카이로켐 | Process for the acidification of terephthalylidene dicamphor sulfonic acid salt |
| CN106831503A (en) * | 2016-12-28 | 2017-06-13 | 广州星业科技股份有限公司 | A kind of preparation method of Terephthalidene Dicamphor Sulfonic Acid's sun-screening agent |
-
2016
- 2016-03-11 KR KR1020160029353A patent/KR102066003B1/en active IP Right Grant
-
2017
- 2017-02-14 CN CN201780015581.8A patent/CN108698986B/en active Active
- 2017-02-14 JP JP2018566176A patent/JP6659876B2/en active Active
- 2017-02-14 DE DE112017001272.4T patent/DE112017001272B4/en active Active
- 2017-02-14 WO PCT/KR2017/001584 patent/WO2017155217A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3439026A (en) * | 1964-12-23 | 1969-04-15 | Marathon Oil Co | Manufacture of carboxylic acids from corresponding metallic salts |
| US4585597A (en) * | 1982-06-15 | 1986-04-29 | L'oreal | 3-benzylidene-camphors, process for their preparation and their use in protection against UV rays |
| US4588839A (en) * | 1982-07-08 | 1986-05-13 | L'oreal | Sulphonamides derived from 3-benzylidene-camphor and their application as UV filters |
| CN1116924A (en) * | 1994-03-08 | 1996-02-21 | 莱雅公司 | Utilisation des acides sulfoniques comme agents antivieillissement dans une composition cosmetiqueou dermatologique |
| CN101573331A (en) * | 2006-12-27 | 2009-11-04 | 旭化成精细化工股份有限公司 | Process for producing vinylsulfonic acid |
| CN101391949A (en) * | 2007-09-17 | 2009-03-25 | 罗门哈斯公司 | Process for converting a hydroxy carboxylic acid or salts thereof, to an unsaturated carboxylic acid and/or its esters |
| CN102633690A (en) * | 2012-04-11 | 2012-08-15 | 上海康福赛尔医药科技有限公司 | Method for preparing levo- and dextro-camphor sulfonic acid by induced crystallization and resolution of racemized camphor sulfonic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6659876B2 (en) | 2020-03-04 |
| WO2017155217A1 (en) | 2017-09-14 |
| KR20170105939A (en) | 2017-09-20 |
| DE112017001272B4 (en) | 2023-01-19 |
| KR102066003B1 (en) | 2020-01-15 |
| DE112017001272T5 (en) | 2019-02-14 |
| CN108698986A (en) | 2018-10-23 |
| JP2019507191A (en) | 2019-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108698986B (en) | Process for acidifying p-xylylene dicamphor sulfonate | |
| KR100684090B1 (en) | Organophosphorus compounds for dental polymerizable compositions | |
| JP2732921B2 (en) | Method for producing polyglycerin | |
| US11046798B2 (en) | Phosphono-phosphate containing compounds and polymers | |
| US11198763B2 (en) | Oral care compositions comprising phosphono-phosphate and anionic group containing polymers | |
| DK2917171T3 (en) | METHOD FOR PREPARING MK-7 TYPE OF K2 VITAMIN | |
| TWI303630B (en) | A method for inhibiting polymerization of (meth)acrylic acid and its esters using an inhibitor and a process for making a compound useful as such an inhibitor | |
| EP3063131B1 (en) | Methods of making polymerizable resins containing a 1,3,5-hexahydro-1,3,5-triazine moiety | |
| JP2022522252A (en) | Acidification method of terephthalylidene dicanfur sulfonate {amethod for acidifying terephthallylidene dicamphor sulphonate} | |
| JP3830723B2 (en) | (Poly) thiaalkyne (acid) type compounds and derivatives thereof, compositions containing them, and uses thereof | |
| IN2004KO00058A (en) | ||
| Bunnett et al. | Attempts to Resolve Racemic Amines by Means of Optically Active, Acidic Synthetic Polymers1a | |
| TWI239945B (en) | Arylbis(perfluoroalkylsulfonyl) methane and metallic salt thereof and methods for producing the same | |
| JP2859350B2 (en) | Phenylhydrazone | |
| TWI573782B (en) | Novel sulfonium salt, method for producing the same, and photoacid generator | |
| Khan et al. | Glyceride derivatives as potential prodrugs: synthesis, biological activity and kinetic studies of glyceride derivatives of mefenamic acid | |
| WO2007102501A1 (en) | Polymerizable spherical transition metal complexes, spherical transition metal complexes, and processes for the production of both | |
| TWI723967B (en) | Substituted aromatic compounds and pharmaceutical compositions for tissue self-repair and regeneration | |
| JP3780581B2 (en) | Organic compound conversion catalyst | |
| JP3147942B2 (en) | Crosslinked anion exchanger for water production for pharmaceuticals and cosmetics | |
| US2617832A (en) | Method for preparing diphenylol methane | |
| JP4304758B2 (en) | Method for producing para-acetoxystyrene | |
| AU598842B2 (en) | Preparation of 3-(alkylthio) aldehydes | |
| JPH07304708A (en) | Novel di(meth)acrylate and production thereof | |
| JPH1017541A (en) | Bis-perfluoroalkylsuleonylimide and its production |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |