CN108698986A - Method for keeping Terephthalidene Dicamphor Sulfonic Acid acidified - Google Patents
Method for keeping Terephthalidene Dicamphor Sulfonic Acid acidified Download PDFInfo
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- CN108698986A CN108698986A CN201780015581.8A CN201780015581A CN108698986A CN 108698986 A CN108698986 A CN 108698986A CN 201780015581 A CN201780015581 A CN 201780015581A CN 108698986 A CN108698986 A CN 108698986A
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- sulfonic acid
- dicamphor sulfonic
- terephthalidene dicamphor
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- 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
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Abstract
It provides a kind of for keeping Terephthalidene Dicamphor Sulfonic Acid acidified so that the method that Terephthalidene Dicamphor Sulfonic Acid's salt is converted into Terephthalidene Dicamphor Sulfonic Acid, and specifically, a kind of method for making Terephthalidene Dicamphor Sulfonic Acid's salt be converted into Terephthalidene Dicamphor Sulfonic Acid in the presence of cation exchange resin is provided, wherein the method for transformation of the present invention is the notable effective method with high conversion by simple procedure.
Description
Technical field
The present invention relates to a kind of methods for keeping Terephthalidene Dicamphor Sulfonic Acid acidified, and more specifically,
It is related to a kind of sub- to benzene two for being converted into Terephthalidene Dicamphor Sulfonic Acid's salt in the presence of cation exchange resin
The method of two camphorsulfonic acid of methyl.
Background technology
Ultraviolet light includes ultraviolet light,long wave (320nm to 400nm) and Ultraviolet B (290nm to 320nm), and wherein ultraviolet light,long wave accounts for
90% or more of ultraviolet light.In general, ultraviolet light is more frequently exposed to during summer, for example it is known that ultraviolet
The main reason for line B is erythema, mild burn etc., and known ultraviolet light,long wave penetrates skin and influences cell, and cause light old
Change, skin allergy even cutaneum carcinoma etc..Therefore, regardless of season, ultraviolet light,long wave all influences skin, and therefore need it is more special
Nursing.
Nearly all material for Orangic sunscreen is all fat-soluble, and not soluble in water currently on the market.Therefore,
Using currently on the market be used for Orangic sunscreen material manufacture cosmetics the shortcomings that be:When by cosmetic application in skin
When, use feeling is bad.In addition, the spreadability of inorganic sunscreen is bad, and make skin when sun-screening agent is applied to skin
Feel thick and heavy, use feeling is poor.
On the other hand, it is known that terephthalylidene two from U.S. Patent Publication the 4th, 585,597 and 5,698,595
Camphorsulfonic acid can protect the skin from the influence of ultraviolet light,long wave to prevent skin aging, and have high dissolubility to water.Cause
This, including the cosmetics of Terephthalidene Dicamphor Sulfonic Acid sprawl characteristic to produce with good use feeling with good
Product, and it is easy washing, this is conducive to keep clean skin.
In addition, Terephthalidene Dicamphor Sulfonic Acid is assigned to 33% aqueous solution as the water-soluble of Orangic sunscreen
Property material, can be produced, and be also registered as 33% aqueous solution with multiple formulations.
For producing the method for Terephthalidene Dicamphor Sulfonic Acid in U.S. Patent Publication the 4,585,597th and 4,588,
It is known in No. 839.As shown in following reaction scheme 1, it is known that make 2 moles of 10-dl- camphorsulfonic acids and 1 in the presence of base
Mole terephthalaldehyde carries out condensation reaction to obtain Terephthalidene Dicamphor Sulfonic Acid's salt, and is made to benzene by using hydrochloric acid
Two camphorsulfonic acid of dimethylene is acidified to obtain Terephthalidene Dicamphor Sulfonic Acid:
[Reaction scheme 1]
However, the acidification reaction corresponds to the balanced reaction as shown in following reaction scheme 2:
[Reaction scheme 2]
Therefore, should be using excessive acid to realize the acidification of Terephthalidene Dicamphor Sulfonic Acid's salt, this to be produced into
This increase and need for remove be excessively used acid separate processes.In addition it is also necessary to for removing water soluble salt for example
Another process of NaCl (its by-product as water-soluble Terephthalidene Dicamphor Sulfonic Acid and generate).
In addition, even if using acidification reaction from significant excess of acid to Terephthalidene Dicamphor Sulfonic Acid if it is incomplete.
In other words, according to the existing method for using general inorganic acid or general organic acid, acidification reaction process be also it is complicated and
Economically efficiency is low, and the yield of Terephthalidene Dicamphor Sulfonic Acid is also very low.
Therefore, it is necessary to study to be used to make Terephthalidene Dicamphor Sulfonic Acid's salt including simple and effective reaction process
The method of acidification.
Invention content
Technical problem
Present inventors studied the acidification reactions of Terephthalidene Dicamphor Sulfonic Acid's salt to solve the above problems, and completes
The present invention.
The object of the present invention is to provide one kind to be made by simple procedure with high yield and high-purity in a highly economical manner
The method that Terephthalidene Dicamphor Sulfonic Acid's salt is converted into Terephthalidene Dicamphor Sulfonic Acid.
Technical solution
In a general aspect, providing is made by simple procedure with high yield and high-purity different from the relevant technologies
The method that Terephthalidene Dicamphor Sulfonic Acid's salt is converted into Terephthalidene Dicamphor Sulfonic Acid.The method for transformation packet of the present invention
Terephthalidene Dicamphor Sulfonic Acid's salt that including makes to be indicated by following formula 2 in the presence of cation exchange resin is converted into
The Terephthalidene Dicamphor Sulfonic Acid indicated by following formula 1:
[Chemical formula 1]
[Chemical formula 2]
In chemical formula 1 and 2,
M is alkali metal or N (R1)(R2)(R3)(R4) and R1To R4It is each independently hydrogen or (C1 to C7) alkyl;
R is (C1 to C7) alkyl or (C1 to C7) alkoxy;And
The integer that n is 0 or 1 to 4, and when n is two or more, R can be the same or different from each other.
In the chemical formula 2 of property embodiment according to an example of the present invention, M can be that Na and n can be 0.
The cation exchange resin of property embodiment can be H-type cation exchange resin according to an example of the present invention
With the sulfonated resin with the styrene-based of divinyl benzene crosslinked, and can have 1meq/ml to 3meq/ml from
Sub- exchange capacity.
The method for transformation of property embodiment can use pair wherein indicated by chemical formula 2 according to an example of the present invention
The aqueous solution for Terephthalidene Dicamphor Sulfonic Acid's salt that two camsilate of phenylenedimethylidyne is dissolved in the water, and relative to
Terephthalidene Dicamphor Sulfonic Acid's salt of 100 parts by weight, can be by using the water next life of 500 parts by weight to 1000 parts by weight
Produce the aqueous solution of Terephthalidene Dicamphor Sulfonic Acid's salt.
Advantageous effect
Method for transformation according to the present invention, Terephthalidene Dicamphor Sulfonic Acid's salt is in the presence of cation exchange resin
It is converted into Terephthalidene Dicamphor Sulfonic Acid.Therefore, though in the presence of a small amount of cation exchange resin conversion ratio
It is very high, therefore Terephthalidene Dicamphor Sulfonic Acid's salt of almost all amount is acidified, and the salt produced holds very much
It changes places and is removed.
In addition, the method for transformation of the present invention can obtain Terephthalidene Dicamphor Sulfonic Acid under aqueous solution state, because
This, is easily obtained 33% aqueous solution of Terephthalidene Dicamphor Sulfonic Acid, can be manufactured to directly to distribute without
Carry out the product of separate processes.
In addition, the method for transformation of the present invention is method significantly economically and efficiently, because almost all amount is sub- to benzene two
Two camsilate of methyl is converted into Terephthalidene Dicamphor Sulfonic Acid, and used cation exchange resin energy
Enough it is recycled and reused.
Specific implementation mode
The present invention provides it is a kind of for make in the presence of cation exchange resin by following formula 2 indicate to benzene
The method that two camsilate of dimethylene is converted into the Terephthalidene Dicamphor Sulfonic Acid indicated by following formula 1:
[Chemical formula 1]
[Chemical formula 2]
In chemical formula 1 and 2,
M is alkali metal or N (R1)(R2)(R3)(R4) and R1To R4It is each independently hydrogen or (C1 to C7) alkyl;
R is (C1 to C7) alkyl or (C1 to C7) alkoxy;And
The integer that n is 0 or 1 to 4, and when n is two or more, R can be the same or different from each other.
Method for transformation according to the present invention, by using cation exchange resin without the use of the inorganic acid of conventional method or
Terephthalidene Dicamphor Sulfonic Acid's salt of organic acid, almost all amount can be converted, and with use inorganic acid or organic
The conventional method of acid is compared, even if using a small amount of cation exchange resin, due to high conversion rate, which is also very
Economic method.
In addition, can be readily removed as the salt that by-product generates, therefore, there is no need to for except the independent mistake to desalt
Journey.
Usually there is following problem using the method for transformation of inorganic acid known in the art or organic acid:It needs to remove excessive
Acid, and need to remove the corresponding salt of each acid that generates as by-product.In addition, the possible basis of acidizing degree uses at this time
Acid type and change, therefore, the content of Terephthalidene Dicamphor Sulfonic Acid due to the use of general acid conventional method and
It deteriorates significantly.
On the other hand, according to the present invention for keeping Terephthalidene Dicamphor Sulfonic Acid acidified so as to two methylene of benzene
The method for transformation that two camsilate of base is converted into Terephthalidene Dicamphor Sulfonic Acid uses cation exchange resin, therefore,
Excessive acid need not be used, need not be used for except the separate processes to desalt, and obtained to benzene two under aqueous solution state
Two camphorsulfonic acid of methylene, to only manufacture the product that can directly distribute when its concentration is set as 33%.
In a specific embodiment, first, with cation exchange resin packed column, then, make to be dissolved in water
Terephthalidene Dicamphor Sulfonic Acid's salt is by the column, even if being much smaller than general inorganic acid or general organic acid using only equivalent proportion
Usage amount cation exchange resin, Terephthalidene Dicamphor Sulfonic Acid's salt of almost all amount is also acidified.In addition,
The salt generated as by-product is dispensed, and obtains the Terephthalidene Dicamphor Sulfonic Acid under aqueous solution state,
Therefore, the product that can directly distribute only has been manufactured when its concentration is set as 33%.
Therefore, Terephthalidene Dicamphor Sulfonic Acid's salt of the invention is to the conversion side of Terephthalidene Dicamphor Sulfonic Acid
Method is notable effective method, the reason is that the process is very simple and conversion ratio and purity are high.
Two camphor tree of terephthalylidene using cation exchange resin of property embodiment according to an example of the present invention
The method for transformation of brain sulfonate to Terephthalidene Dicamphor Sulfonic Acid can be by Terephthalidene Dicamphor Sulfonic Acid's salt
Aqueous solution in addition cation exchange resin keep Terephthalidene Dicamphor Sulfonic Acid acidified.It is preferable, however, that considering
The increase of yield, the simplification of process and business efficiency, can be sub- to benzene two by then being made with cation exchange resin packed column
The aqueous solution of two camsilate of methyl is by keeping Terephthalidene Dicamphor Sulfonic Acid acidified.
For each double bond, the compound described in the present invention indicated by chemical formula 1 and 2 includes cis-trans form
Deng all isomers." alkyl " and " alkoxy " used in the present invention includes both linear and branched chains, and has 1
To 7 carbon atoms, preferably 1 to 5 carbon atom, and more preferable 1 to 3 carbon atom.
Alkali metal as the M of property embodiment according to an example of the present invention can be by those skilled in the art's public affairs
Any alkali metal in the range of recognizing.The example of alkali metal may include Li, Na, K etc., and consider reaction efficiency, preferably
Na。
According to an example of the present invention the R of property embodiment can be (C1 to C5) alkyl or (C1 to C5) alkoxy,
And it is preferred that (C1 to C5) alkyl, and when phenylene does not have substituent group, n can be zero.
The cation exchange resin of property embodiment will be by that will be used as the sulphur of cation exchange groups according to an example of the present invention
Acidic group (- SO3H), carboxyl (- COOH) etc. is bound to the base polymer matrices with network structure to obtain, and exchanges sun
Ion such as Ca2+,Na+,H+Deng.Cation exchange resin can be that storng-acid cation exchange resin or Subacidity cation exchange
Resin, and be preferably able to exchange H+The H-type cation exchange resin of cation.
Specifically, the cation exchange resin of property embodiment can include divinyl according to an example of the present invention
The copolymer or divinylbenzene of benzene and styrene and the copolymer or tetrafluoro ethylene polymer of acrylate as matrix, and
And can include sulfonic acid or carboxylic acid, and preferably sulfonic acid is as cation exchange groups.More preferably, it is contemplated that reaction efficiency, cation
Exchanger resin can be the sulfonated resin with the styrene-based of divinyl benzene crosslinked.
Preferably, the cation exchange resin of property embodiment can be H-type cation according to an example of the present invention
Exchanger resin and the sulfonated resin with the styrene-based of divinyl benzene crosslinked, and can have 1meq/ml or more
Greatly, preferably 1meq/ml is to 3meq/ml, and the ion exchange capacity of more preferably 1.5meq/ml to 3meq/ml.
Ion exchange capacity described in the present invention is measured as the quantity equivalent for the ion that can be swapped, and can be with
It is expressed as polymer volume (ion exchange capacity per volume, i.e. volume capacity), and preferably means that soaking bed (soaks poly-
Close object) every swelling volume exchange capacity milliequivalent.
Specifically, when the filling male ion-exchange resin in column and in use, relative to constant weight to two methylene of benzene
Two camsilate of base, cation exchange resin can have 2 times to 6 times of the amount corresponding to volume ratio, and can make
Make its regeneration and Reusability with diluted hydrochloric acid.For the elution rate of column, relative to the certain volume being filled in column
Cation exchange resin can be such that the reaction solution of 0.2 times to 2 times of amount per hour passes through.
The aqueous solution of all Terephthalidene Dicamphor Sulfonic Acids eluted from column can be made to concentrate to obtain targeted
Close object, the i.e. Terephthalidene Dicamphor Sulfonic Acid of brown solid form.Furthermore, it is possible to distill out eluted from column to benzene two
Some water in the aqueous solution of two camphorsulfonic acid of methylene are used in combination the potassium hydroxide of 0.1mol is quantitative can be manufactured to production
It is prepared to enter into 33% aqueous solution of the product in market.
Preferably, method for transformation of the invention can use two camphor of terephthalylidene wherein indicated by chemical formula 2
The aqueous solution for Terephthalidene Dicamphor Sulfonic Acid's salt that sulfonate is dissolved in the water, and relative to 100 parts by weight to benzene
Two camsilate of dimethylene, can be by using 500 parts by weight to 1000 parts by weight, and preferably 700 parts by weight are extremely
The water of 1000 parts by weight produces the aqueous solution.
Hereinafter, the present invention will be more fully described with reference to following embodiment, but the present invention is not limited by following embodiment
System.
[Embodiment 1]The production of Terephthalidene Dicamphor Sulfonic Acid
12g (20mmol) Terephthalidene Dicamphor Sulfonic Acid's disodium is dissolved in 100ml water, 200ml is then added
(1.8meq/ml) cation exchange resin, i.e. TRILITE SCR-BH (Samyang Corp.), and it is small to be stirred at room temperature 5
When.Resin is removed by filtration, 50ml water washing products are used in combination.Exist by the way that water is distilled off under reduced pressure, and by obtained solid
Decompression is lower dry to obtain 10.4g (yields:93.4%) Terephthalidene Dicamphor Sulfonic Acid of brown solid form is as mesh
Mark compound.
Solid described in 1g by accurate weighing is dissolved in 50ml water, and 0.1mol potassium hydroxide solution (indicator is used in combination:
1ml phenolphthalein solutions) titration.After being calibrated with blank test by using identical method, acidified solid form to benzene
The content of two camphorsulfonic acid of dimethylene is 89.7%.
[Embodiment 2]The production of Terephthalidene Dicamphor Sulfonic Acid
Embodiment 2 is carried out in the same manner as in example 1, the difference is that using 12.7g terephthalylidenes
Two camphorsulfonic acid dipotassiums, thus to obtain 10.5g brown solid forms Terephthalidene Dicamphor Sulfonic Acid as target chemical combination
Object.The content of the Terephthalidene Dicamphor Sulfonic Acid of solid form is 89.6%.
[Embodiment 3]The production of Terephthalidene Dicamphor Sulfonic Acid
Embodiment 3 is carried out in the same manner as in example 1, the difference is that using 11.9g terephthalylidenes
Two camphorsulfonic acid diammoniums, thus to obtain 10.4g brown solid forms Terephthalidene Dicamphor Sulfonic Acid as target chemical combination
Object.The content of the Terephthalidene Dicamphor Sulfonic Acid of solid form is 89.5%.
[Embodiment 4]The production of Terephthalidene Dicamphor Sulfonic Acid
20L (1.8meq/ml) cation exchange resin, i.e. TRILITE SCR-BH (Samyang are filled in column
Corp.).It is dissolved in 4kg (6.6mol) Terephthalidene Dicamphor Sulfonic Acid two in 28L water with rate elution in 9L/ hours
Sodium.By the product through elution with 16L water washings to obtain reaction solution, and removed from reaction solution by distilling under reduced pressure
Water, and generated solid is dried under reduced pressure to obtain 3.6kg (yields:97%) terephthalylidene of brown solid form
Two camphorsulfonic acids are as target compound.
Solid described in 1g by accurate weighing is dissolved in 50ml water, and 0.1mol potassium hydroxide solution (indicator is used in combination:
1ml phenolphthalein solutions) titration.After being calibrated with blank test by using identical method, Terephthalidene Dicamphor Sulfonic Acid
Content be 99.9%.
1H-NMR(CD3OD)δ(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)
[Embodiment 5]The production of 33% aqueous solution of Terephthalidene Dicamphor Sulfonic Acid
Only removed from the gained liquid obtained after implementing such as identical method in embodiment 4 2/3rds water with
Obtain 10.7kg brown aqueous solutions.It is quantified as in Example 4 to determine content, thus to obtain terephthalylidene two
33% aqueous solution of camphorsulfonic acid.
[Comparative example 1]The acidification carried out using hydrochloric acid
12g (20mmol) Terephthalidene Dicamphor Sulfonic Acid's disodium is dissolved in 30ml water and 30ml concentrated hydrochloric acids
In (360mmol).After reflux 1 hour, product is set to concentrate and cool down, and filter obtained solid.Filtered solid is used
6N salt acid elutions, are dried under reduced pressure under 80, and are dried under reduced pressure at 100 to obtain 7.02g solids.
Solid described in 1g by accurate weighing is dissolved in 50ml water, and 0.1mol potassium hydroxide solution (indicator is used in combination:
1ml phenolphthalein solutions) titration.It is sub- to benzene two in the solid through hydrochloric acid acidification after being calibrated with blank test using identical method
The content of two camphorsulfonic acid of methyl is 33.6%.
[Comparative example 2]The acidification carried out using methanesulfonic acid
6.06g (10mmol) Terephthalidene Dicamphor Sulfonic Acid's disodium is dissolved in 50ml water, 17.29g is added
(180mmol) methanesulfonic acid, and be stirred at room temperature 2 hours.So that reaction solution is concentrated, and is used using Dean-Stark devices
100ml toluene removes water completely.It will be filtered by the cooling solid generated, be used in combination toluene to wash filtered solid, under 80
It is dried under reduced pressure, and is dried under reduced pressure at 100 to obtain 7.68g solids.
When carrying out quantitative in such as comparative example 1, it is contemplated that comprising methanesulfonic sodium, to benzene two in the solid through methanesulfonic acid acidification
The content of two camphorsulfonic acid of methylene is about 22.5%.
[Comparative example 3]The acidification carried out using trifluoroacetic acid
Be compared example 3 in a manner of identical with comparative example 2, the difference is that by 6.06g (10mmol) to benzene
Two camphorsulfonic acid disodium of dimethylene adds 20.52g (180mmol) trifluoroacetic acid after being dissolved in 50ml water, thus to obtain
5.91g solid.
When carrying out quantitative in such as comparative example 1, it is contemplated that right in the solid through trifluoroacetic acid acidification comprising sodium trifluoroacetate
The content of two camphorsulfonic acid of phenylenedimethylidyne is about 7.5%.
[Comparative example 4]The acidification carried out using sulfuric acid
Be compared example 4 in a manner of identical with comparative example 2, the difference is that by 6.06g (10mmol) to benzene
Two camphorsulfonic acid disodium of dimethylene adds 8.82g (90mmol) sulfuric acid after being dissolved in 50ml water, solid thus to obtain 6.44g
Body.
When carrying out quantitative in such as comparative example 1, it is contemplated that comprising sodium sulphate, to two methylene of benzene in the solid through sulfuric acid acidification
The content of two camphorsulfonic acid of base is about 19.7%.
It is appreciated that the conversion ratio of the Terephthalidene Dicamphor Sulfonic Acid produced in embodiment 1 to 4 is than in comparative example 1
It is much higher.In addition, embodiment 1 to 4 need not be used for except the separate processes to desalt, therefore, the process is simpler, and purity is high
In the purity of comparative example 1.
Furthermore, it is to be understood that in comparative example 2 to 4, conversion ratio is low, and obtains comprising corresponding to each organic acid and nothing
The Terephthalidene Dicamphor Sulfonic Acid of the salt of machine acid, therefore purity is low and needs for except the separate processes to desalt.
In a word, it is possible to understand that in the presence of the cation exchange resin of the present invention, Terephthalidene Dicamphor Sulfonic Acid
The method for transformation of salt to Terephthalidene Dicamphor Sulfonic Acid not only have higher conversion ratio and higher purity, but also have
There is simpler transfer process, is method economically and efficiently compared with conventional method.
Claims (6)
1. a kind of method for keeping Terephthalidene Dicamphor Sulfonic Acid acidified, including:
Make the Terephthalidene Dicamphor Sulfonic Acid's salt conversion indicated by following formula 2 in the presence of cation exchange resin
For the Terephthalidene Dicamphor Sulfonic Acid indicated by following formula 1:
[Chemical formula 1]
[Chemical formula 2]
In chemical formula 1 and 2,
M is alkali metal or N (R1)(R2)(R3)(R4) and R1To R4It is each independently hydrogen or (C1 to C7) alkyl;
R is (C1 to C7) alkyl or (C1 to C7) alkoxy;And
The integer that n is 0 or 1 to 4, and when n is two or more, R can be the same or different from each other.
2. according to the method described in claim 1, it is 0 that wherein M, which is Na and n,.
3. according to the method described in claim 1, the wherein described cation exchange resin is H-type cation exchange resin.
4. according to the method described in claim 3, the wherein described cation exchange resin is handed over to be sulfonated with divinylbenzene
The resin of the styrene-based of connection.
5. according to the method described in claim 4, the ion exchange capacity of the wherein described cation exchange resin be 1meq/ml extremely
3meq/ml。
6. according to the method described in claim 1, wherein the method uses the terephthalylidene wherein indicated by chemical formula 2
The aqueous solution for Terephthalidene Dicamphor Sulfonic Acid's salt that two camsilates are dissolved in the water.
Applications Claiming Priority (3)
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| 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 |
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| CN108698986A true CN108698986A (en) | 2018-10-23 |
| CN108698986B CN108698986B (en) | 2020-12-15 |
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| JP (1) | JP6659876B2 (en) |
| KR (1) | KR102066003B1 (en) |
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| WO (1) | WO2017155217A1 (en) |
Cited By (2)
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| 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 |
| CN115784942A (en) * | 2021-09-13 | 2023-03-14 | 株式会社世来秀 | Method for acidifying p-xylylene dicamphor sulfonate using cation exchange fibers |
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 |
| KR102099831B1 (en) * | 2020-01-29 | 2020-04-10 | 주식회사 세라수 | a method for acidifying terephthalylidene dicamphor sulfonate |
| KR20240051688A (en) | 2022-10-13 | 2024-04-22 | 신성소재 주식회사 | Manufacturing method of terephthalylidene dicamphor sulfonic acid using electrodialysis |
| KR20240122081A (en) * | 2023-02-03 | 2024-08-12 | 신성소재 주식회사 | Maufacturing method of concentrated terephthalylidene dicamphor sulfonic acid aqueous solution using nanofiltration membrane |
| WO2024205310A1 (en) * | 2023-03-31 | 2024-10-03 | (주)에이에스텍 | Novel method for producing terephthalylidene dicamphor sulfonic acid |
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| CN115784942A (en) * | 2021-09-13 | 2023-03-14 | 株式会社世来秀 | Method for acidifying p-xylylene dicamphor sulfonate using cation exchange fibers |
| TWI824501B (en) * | 2021-09-13 | 2023-12-01 | 南韓商世來秀股份有限公司 | A method for acidifying terephthalylidene dicamphor sulfonate using cation exchange fiber |
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| JP2019507191A (en) | 2019-03-14 |
| KR102066003B1 (en) | 2020-01-15 |
| WO2017155217A1 (en) | 2017-09-14 |
| CN108698986B (en) | 2020-12-15 |
| JP6659876B2 (en) | 2020-03-04 |
| DE112017001272T5 (en) | 2019-02-14 |
| DE112017001272B4 (en) | 2023-01-19 |
| KR20170105939A (en) | 2017-09-20 |
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