JP2019507191A - Method for acidifying terephthalylidene dicamphorsulfonate - Google Patents
Method for acidifying terephthalylidene dicamphorsulfonate Download PDFInfo
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- terephthalylidene
- acid
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- 238000000034 method Methods 0.000 title claims abstract description 48
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 18
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229920001890 Novodur Polymers 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 33
- 238000006243 chemical reaction Methods 0.000 abstract description 32
- HEAHZSUCFKFERC-UHFFFAOYSA-N ecamsule Chemical compound CC1(C)C2CCC1(CS(O)(=O)=O)C(=O)C2=CC(C=C1)=CC=C1C=C1C(=O)C2(CS(O)(=O)=O)CCC1C2(C)C HEAHZSUCFKFERC-UHFFFAOYSA-N 0.000 abstract description 18
- 150000003839 salts Chemical class 0.000 abstract description 14
- 239000007787 solid Substances 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 230000020477 pH reduction Effects 0.000 description 10
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- -1 Ca 2+ Chemical class 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
Abstract
本発明は、テレフタリリデンジカンフルスルホン酸塩を酸性化してテレフタリリデンジカンフルスルホン酸に転換する方法を提供し、具体的には、陽イオン交換樹脂の存在下でテレフタリリデンジカンフルスルホン酸塩をテレフタリリデンジカンフルスルホン酸に転換する方法に関するものであって、本発明の転換方法は、簡単な工程による転換率が高く且つ非常に効果的な方法である。【選択図】なしThe present invention provides a method for acidifying a terephthalylidene dicamphorsulfonate salt to convert it to terephthalylidene dicamphorsulfonic acid, specifically, terephthalylidene dicanfursulfone in the presence of a cation exchange resin. The present invention relates to a method for converting an acid salt to terephthalylidene dicamphorsulfonic acid, and the conversion method of the present invention is a highly effective method with a high conversion rate by a simple process. [Selection figure] None
Description
本発明は、テレフタリリデンジカンフルスルホン酸塩の酸性化方法に関し、より詳細には、陽イオン交換樹脂の存在下でテレフタリリデンジカンフルスルホン酸塩をテレフタリリデンジカンフルスルホン酸に転換する方法に関する。 The present invention relates to a method for acidifying terephthalylidene dican full sulfonate, and more particularly, converting terephthalylidene dican full sulfonate to terephthalylidene dican full sulfonic acid in the presence of a cation exchange resin. Regarding the method.
紫外線には、紫外線Ａ（３２０−４００ｎｍ）と紫外線Ｂ（２９０−３２０ｎｍ）があり、紫外線の９０％以上を紫外線Ａが占める。日光に頻繁に曝される夏季において、紫外線Ｂは、紅斑、軽症のやけどなどを引き起こす主要因として知られているのに対し、紫外線Ａは、皮膚中まで侵透して細胞に影響を与え、光老化、皮膚アレルギー、ひどい場合には皮膚癌などを引き起こす紫外線であると知られている。したがって、紫外線Ａは、季節を問わずに皮膚に影響を与えるため、さらに格別の管理が必要である。 The ultraviolet rays include ultraviolet rays A (320 to 400 nm) and ultraviolet rays B (290 to 320 nm), and the ultraviolet rays A occupy 90% or more of the ultraviolet rays. In the summer, which is frequently exposed to sunlight, ultraviolet B is known as the main cause of erythema and mild burns, whereas ultraviolet A penetrates into the skin and affects cells. It is known to be UV light that causes photoaging, skin allergies, and severe cases of skin cancer. Therefore, since ultraviolet rays A affect the skin regardless of the season, further special management is required.
現在流通されている有機紫外線遮断剤用素材は、殆どが脂溶性であって、水に対する溶解度を有しない。したがって、現在流通されている有機紫外線遮断剤用素材を用いて製造された化粧品は、殆どの場合、皮膚に塗布した時の使用感が良くないという欠点を有する。また、無機紫外線遮断剤は、のびがさらに良くなく、塗布時に皮膚が厚くなることが感じられるほど使用感が悪い。 Most materials for organic ultraviolet light blocking agents currently distributed are fat-soluble and have no solubility in water. Therefore, cosmetics manufactured using organic UV blocker materials that are currently distributed have the disadvantage that the feeling of use when applied to the skin is not good in most cases. In addition, the inorganic ultraviolet blocking agent does not spread much more, and the usability is so bad that it can be felt that the skin becomes thicker during application.
一方、特許文献１と特許文献２に開示のテレフタリリデンジカンフルスルホン酸は、紫外線Ａから皮膚を保護して皮膚老化を防止することができ、水に対する溶解度が高いため、これを含む化粧品ののびが良く、使用感の良い製品を製造することができ、洗浄が容易であって純粋な皮膚を維持するのに寄与する。 On the other hand, the terephthalylidene dicanfursulfonic acid disclosed in Patent Document 1 and Patent Document 2 can protect the skin from ultraviolet rays A and prevent skin aging, and has high solubility in water. A product that is easy to spread and easy to use can be manufactured, and is easy to clean and contributes to maintaining pure skin.
さらに、テレフタリリデンジカンフルスルホン酸は、種々の剤型で製造が可能な水溶性有機紫外線遮断剤用素材であって、３３％水溶液で流通されており、食品医薬品安全処にも３３％水溶液と登録されている。 Furthermore, terephthalylidene dicamphorsulfonic acid is a water-soluble organic UV-blocking material that can be produced in various dosage forms, and is distributed in 33% aqueous solution. It is registered with.
テレフタリリデンジカンフルスルホン酸の製造方法は、、特許文献１と特許文献３に開示されているが、下記反応式１のように、塩基の存在下で２モルの１０−ｄｌ−カンフルスルホン酸と１モルのテレフタルアルデヒドを縮合反応させることでテレフタリリデンジカンフルスルホン酸塩を得て、それを塩酸を用いて酸性化することによりテレフタリリデンジカンフルスルホン酸を得ると知られている。 The method for producing terephthalylidene dicamphulsulfonic acid is disclosed in Patent Document 1 and Patent Document 3, but 2 mol of 10-dl-camphorsulfonic acid in the presence of a base as shown in Reaction Scheme 1 below. It is known that terephthalylidene dicanfulsulfonic acid salt is obtained by a condensation reaction of 1 mol of terephthalaldehyde with 1 mol of terephthalaldehyde and then acidified with hydrochloric acid to obtain terephthalylidenedicanfulsulfonic acid.
［反応式１］
しかし、かかる酸性化反応は、下記反応式２のような平衡反応に相当する。 However, this acidification reaction corresponds to an equilibrium reaction as shown in the following reaction formula 2.
［反応式２］
したがって、テレフタリリデンジカンフルスルホン酸塩の酸性化がなされるためには、過量の酸を用いなければならず、これは、製造コストの上昇の要因となり、過量で用いた酸を除去するための別の工程が必要となる。また、水によく溶けるテレフタリリデンジカンフルスルホン酸から副産物として生成されるＮａＣｌのように、水によく溶ける塩を除去するためのさらに別の工程が必要となる。 Therefore, in order to acidify the terephthalylidene dicamphorsulfonate, an excessive amount of acid must be used, which causes an increase in manufacturing cost and removes the acid used in an excessive amount. Another process is required. In addition, another step is required to remove a salt that is well soluble in water, such as NaCl produced as a by-product from terephthalylidene dicanfursulfonic acid that is well soluble in water.
さらに、実質的に過量の酸を用いても、テレフタリリデンジカンフルスルホン酸への酸性化反応が完結されなかった。換言すれば、一般の無機酸や有機酸を用いる従来の方法は、酸性化反応の工程も複雑であり、経済的に非効率的であるだけでなく、テレフタリリデンジカンフルスルホン酸の収率も非常に低かった。 Furthermore, even when a substantially excessive amount of acid was used, the acidification reaction to terephthalylidene dicamphorsulfonic acid was not completed. In other words, the conventional method using a general inorganic acid or organic acid is not only economically inefficient but also has a complicated acidification reaction process, and also yields of terephthalylidene dicanfursulfonic acid. Was also very low.
したがって、反応工程が簡単で且つ効率的なテレフタリリデンジカンフルスルホン酸塩の酸性化方法に関する研究が求められている。 Accordingly, there is a need for research on acidification methods for terephthalylidene dican full sulfonates that have a simple reaction process and are efficient.
そこで、本発明者らは、上記のような問題を解決するために、テレフタリリデンジカンフルスルホン酸塩の酸性化反応を研究して本発明を完成した。 Accordingly, the present inventors have completed the present invention by studying the acidification reaction of terephthalylidene dican full sulfonate in order to solve the above problems.
したがって、本発明は、簡単な工程により、収率及び純度が高く且つ非常に経済的な、テレフタリリデンジカンフルスルホン酸塩（terephthalylidene dicamphor sulfonic acid salt）をテレフタリリデンジカンフルスルホン酸（terephthalylidene dicamphor sulfonic acid）に転換する方法を提供する。 Accordingly, the present invention provides terephthalylidene dicamphor sulfonic acid salt to terephthalylidene dicamphor sulfonic acid salt with high yield and purity through a simple process. A method for converting to sulfonic acid is provided.
本発明は、従来と異なって、簡単な工程により収率及び純度を高めた、テレフタリリデンジカンフルスルホン酸塩をテレフタリリデンジカンフルスルホン酸に転換する方法を提供する。本発明の転換方法は、陽イオン交換樹脂の存在下で、下記化学式２で表されるテレフタリリデンジカンフルスルホン酸塩を、下記化学式１で表されるテレフタリリデンジカンフルスルホン酸に転換するステップを含むことを特徴とする。 The present invention provides a method for converting terephthalylidene dican full sulfonic acid salt to terephthalylidene dican full sulfonic acid, which is different from conventional ones, and has improved yield and purity by a simple process. In the conversion method of the present invention, in the presence of a cation exchange resin, terephthalylidene dican full sulfonate represented by the following chemical formula 2 is converted to terephthalylidene dican full sulfonic acid represented by the following chemical formula 1. Including steps.
［化学式１］
［化学式２］
（前記化学式１および２中、
Ｍは、アルカリ金属またはＮ（Ｒ１）（Ｒ２）（Ｒ３）（Ｒ４）であり、Ｒ１〜Ｒ４は、互いに独立して、水素または（Ｃ１−Ｃ７）アルキルであり；
Ｒは、（Ｃ１−Ｃ７）アルキルまたは（Ｃ１−Ｃ７）アルコキシであり；
ｎは、０または１〜４の整数であって、ｎが２以上である場合、Ｒは互いに異なっても同一でもよい。）
[Chemical formula 2]
(In the chemical formulas 1 and 2,
M is an alkali metal or N (R 1 ) (R 2 ) (R 3 ) (R 4 ), and R 1 to R 4 are independently of each other hydrogen or (C1-C7) alkyl;
R is (C1-C7) alkyl or (C1-C7) alkoxy;
n is 0 or an integer of 1 to 4, and when n is 2 or more, R may be different or the same. )
本発明の一実施形態による前記化学式２中、ＭはＮａであり、ｎは０であってもよい。 In Formula 2, according to an embodiment of the present invention, M may be Na and n may be 0.
本発明の一実施形態による陽イオン交換樹脂は、Ｈ型陽イオン交換樹脂であり、ジビニルベンゼンで架橋結合されたスルホン化スチレン系樹脂であってもよく、イオン交換容量が１〜３ｍｅｑ／ｍｌであってもよい。 The cation exchange resin according to an embodiment of the present invention is an H-type cation exchange resin, and may be a sulfonated styrene resin cross-linked with divinylbenzene, and has an ion exchange capacity of 1 to 3 meq / ml. There may be.
本発明の一実施形態による転換方法は、前記化学式２で表されるテレフタリリデンジカンフルスルホン酸塩を水に溶かしたテレフタリリデンジカンフルスルホン酸塩の水溶液を用いてもよく、テレフタリリデンジカンフルスルホン酸塩の水溶液は、テレフタリリデンジカンフルスルホン酸塩１００重量部に対して、５００〜１０００重量部の水を用いて製造されてもよい。 The conversion method according to an embodiment of the present invention may use an aqueous solution of terephthalylidene dican full sulfonate obtained by dissolving terephthalylidene dican full sulfonate represented by Formula 2 in water. The aqueous solution of dendicanful sulfonate may be produced using 500 to 1000 parts by weight of water with respect to 100 parts by weight of terephthalylidene dicanfulsulfonate.
本発明の転換方法は、陽イオン交換樹脂の存在下で、テレフタリリデンジカンフルスルホン酸塩をテレフタリリデンジカンフルスルホン酸に転換することで、少量の陽イオン交換樹脂の存在下でも転換率が非常に高いため、略全量が酸性化され、生成された塩の除去が非常に容易である。 The conversion method of the present invention converts the terephthalylidene dican full sulfonic acid salt to terephthalylidene dican full sulfonic acid in the presence of a cation exchange resin, thereby converting the conversion rate even in the presence of a small amount of cation exchange resin. Is so high that almost the whole amount is acidified and the salt formed is very easy to remove.
また、本発明の転換方法は、テレフタリリデンジカンフルスルホン酸が水溶液状態で得られるため、３３％のテレフタリリデンジカンフルスルホン酸水溶液を容易に得ることができ、別の工程なしに直ちに流通可能な製品として製造することができる。 Moreover, since the terephthalylidene dican full sulfonic acid is obtained in an aqueous solution state, the conversion method of the present invention can easily obtain a 33% aqueous solution of terephthalylidene dican full sulfonic acid, and can be immediately distributed without a separate step. It can be manufactured as a possible product.
また、本発明の転換方法は、略全量がテレフタリリデンジカンフルスルホン酸に転換されるだけでなく、用いられた陽イオン交換樹脂も回収して再使用が可能であるため、非常に経済的で且つ効率的な方法である。 In addition, the conversion method of the present invention is not only converted into terephthalylidene dican full sulfonic acid, but also recovers the used cation exchange resin and can be reused. And an efficient method.
本発明は、陽イオン交換樹脂の存在下で、下記化学式２で表されるテレフタリリデンジカンフルスルホン酸塩を、下記化学式１で表されるテレフタリリデンジカンフルスルホン酸に転換するステップを含む転換方法を提供する。 The present invention includes a step of converting a terephthalylidene dican full sulfonate represented by the following chemical formula 2 into a terephthalylidene dican full sulfonic acid represented by the following chemical formula 1 in the presence of a cation exchange resin. Provide a conversion method.
［化学式１］
［化学式２］
（前記化学式１および２中、
Ｍは、アルカリ金属またはＮ（Ｒ１）（Ｒ２）（Ｒ３）（Ｒ４）であり、Ｒ１〜Ｒ４は、互いに独立して、水素または（Ｃ１−Ｃ７）アルキルであり；
Ｒは、（Ｃ１−Ｃ７）アルキルまたは（Ｃ１−Ｃ７）アルコキシであり；
ｎは、０または１〜４の整数であって、ｎが２以上である場合、Ｒは互いに異なっても同一でもよい。）
[Chemical formula 2]
(In the chemical formulas 1 and 2,
M is an alkali metal or N (R 1 ) (R 2 ) (R 3 ) (R 4 ), and R 1 to R 4 are independently of each other hydrogen or (C1-C7) alkyl;
R is (C1-C7) alkyl or (C1-C7) alkoxy;
n is 0 or an integer of 1 to 4, and when n is 2 or more, R may be different or the same. )
本発明の転換方法は、従来の方法である無機酸または有機酸を用いず、陽イオン交換樹脂を用いることで、略全量を転換することができ、従来の方法である無機酸または有機酸を用いる方法に比べて少量の陽イオン交換樹脂を用いても転換率が高いため、非常に経済的な方法である。 The conversion method of the present invention can convert almost the whole amount by using a cation exchange resin without using an inorganic acid or organic acid which is a conventional method. Even if a small amount of cation exchange resin is used as compared with the method used, the conversion rate is high, so that it is a very economical method.
また、副産物として生成される塩を容易に除去でき、塩を除去するための別の工程が不要である。 Moreover, the salt produced | generated as a by-product can be removed easily, and another process for removing a salt is unnecessary.
従来に公知の無機酸や有機酸を用いて転換する方法は、共通的に、過量の酸を除去しなければならないという問題と、副産物として生成されるそれぞれの酸に対応する塩を除去しなければならないという問題があった。また、この時に用いられる酸の種類によって酸性化の程度が変わり得るため、一般の酸を用いる従来の方法では、テレフタリリデンジカンフルスルホン酸の含量が著しく減少する。 Conventional conversion methods using inorganic or organic acids commonly require the removal of excess acid and the removal of salts corresponding to each acid produced as a by-product. There was a problem that had to be done. In addition, since the degree of acidification can vary depending on the type of acid used at this time, the content of terephthalylidene dicamphsulfonic acid is significantly reduced in the conventional method using a general acid.
これに対し、本発明によるテレフタリリデンジカンフルスルホン酸塩を酸性化してテレフタリリデンジカンフルスルホン酸に転換する転換方法は、陽イオン交換樹脂を用いることで、過量の酸を用いなくてもよく、塩を除去するための別の工程が不要であって、テレフタリリデンジカンフルスルホン酸が水溶液状態で得られるため、３３％の濃度を合わせるだけで直ちに流通可能な製品として製造されることができる。 On the other hand, the conversion method of acidifying the terephthalylidene dicamphorsulfonic acid salt according to the present invention to convert it to terephthalylidene dicamphulsulfonic acid uses a cation exchange resin without using an excessive amount of acid. Well, there is no need for a separate step to remove the salt, and terephthalylidene dican full sulfonic acid is obtained in an aqueous solution, so it can be manufactured as a product that can be immediately distributed just by adjusting the concentration of 33%. Can do.
具体的な一実施形態を挙げて説明すると、先ず、陽イオン交換樹脂をカラムに満たした後、水に溶かしたテレフタリリデンジカンフルスルホン酸塩を通過させると、一般の無機酸や有機酸の使容量よりも著しく少ない当量比にあたる陽イオン交換樹脂のみを用いても、略全量が酸性化される。また、副産物として生成される塩が容易に除去され、テレフタリリデンジカンフルスルホン酸が水溶液状態で得られるため、３３％の濃度を合わせるだけで直ちに流通可能な製品が製造される。 A specific embodiment will be described. First, after filling a column with a cation exchange resin, and passing a terephthalylidene dican full sulfonate dissolved in water, a general inorganic acid or organic acid Even if only a cation exchange resin having an equivalent ratio significantly smaller than the capacity used is used, almost the entire amount is acidified. In addition, since the salt produced as a by-product is easily removed and terephthalylidene dican full sulfonic acid is obtained in an aqueous solution state, a product that can be immediately distributed is produced only by adjusting the concentration of 33%.
したがって、本発明のテレフタリリデンジカンフルスルホン酸塩をテレフタリリデンジカンフルスルホン酸に転換する方法は、工程が非常に簡単であるとともに、転換率と純度が高く、非常に効率的な方法である。 Therefore, the method of converting the terephthalylidene dicamphorsulfonic acid salt of the present invention to terephthalylidene dican full sulfonic acid is a very efficient method with a very simple process and high conversion and purity. is there.
本発明の一実施形態による陽イオン交換樹脂を用いてテレフタリリデンジカンフルスルホン酸塩をテレフタリリデンジカンフルスルホン酸に転換する方法は、テレフタリリデンジカンフルスルホン酸塩の水溶液に陽イオン交換樹脂を添加して酸性化させることができる。この際、高い収率、工程の単純化と経済性の点から、陽イオン交換樹脂をカラムに満たした後、テレフタリリデンジカンフルスルホン酸塩の水溶液を通過させる方法により酸性化させることが好ましい。 A method of converting terephthalylidene dicamphsulfonic acid salt to terephthalylidene dicamphulsulfonic acid using a cation exchange resin according to an embodiment of the present invention includes cation exchange in an aqueous solution of terephthalylidene dicamphsulfonic acid salt. Resin can be added and acidified. At this time, from the viewpoint of high yield, simplification of the process and economy, it is preferable to acidify by filling the column with a cation exchange resin and then passing an aqueous solution of terephthalylidene dicanfursulfonate. .
本発明に記載の前記化学式１および化学式２で表される化合物は、それぞれの二重結合に対してシス−トランス（cis−trans）形態の異性体などを全て含むことはいうまでもなく、本発明に記載の「アルキル」および「アルコキシ」は、直鎖状または分岐状の両方を含み、１〜７個の炭素原子、好ましくは１〜５、より好ましくは１〜３の炭素原子を有する。 Needless to say, the compounds represented by Chemical Formula 1 and Chemical Formula 2 described in the present invention include all cis-trans isomers and the like for each double bond. “Alkyl” and “alkoxy” according to the invention include both straight-chain or branched and have 1 to 7 carbon atoms, preferably 1 to 5, more preferably 1 to 3 carbon atoms.
本発明の一実施形態によるＭのアルカリ金属は、当業者が認識する範囲のアルカリ金属であれば何れも可能であって、一例として、Ｌｉ、Ｎａ、Ｋなどが挙げられ、反応効率の点から、Ｎａであることが好ましい。 The alkali metal of M according to an embodiment of the present invention can be any alkali metal within the range recognized by those skilled in the art. Examples thereof include Li, Na, K, and the like, from the viewpoint of reaction efficiency. Na is preferable.
本発明の一実施形態によるＲは、（Ｃ１−Ｃ５）アルキルまたは（Ｃ１−Ｃ５）アルコキシであり、好ましくは（Ｃ１−Ｃ５）アルキルであってもよく、フェニレンに置換基が存在しない場合に、ｎは０であってもよい。 R according to one embodiment of the present invention is (C1-C5) alkyl or (C1-C5) alkoxy, preferably (C1-C5) alkyl, and when no substituent is present in phenylene, n may be 0.
本発明の一実施形態による陽イオン交換樹脂は、網状構造の基礎高分子母体に交換基としてスルホン酸基（−ＳＯ３Ｈ）またはカルボキシル基（−ＣＯＯＨ）などを結合させたものであって、Ｃａ２＋、Ｎａ＋、Ｈ＋などのような陽イオンを交換するものであり、強酸性陽イオン交換樹脂または弱酸性陽イオン交換樹脂であってもよく、好ましくは、Ｈ＋の陽イオンを交換できるＨ型陽イオン交換樹脂であってもよい。 A cation exchange resin according to an embodiment of the present invention is obtained by bonding a sulfonic acid group (—SO 3 H) or a carboxyl group (—COOH) as an exchange group to a basic polymer matrix having a network structure, It exchanges cations such as Ca 2+ , Na + , H +, etc., and may be a strong acid cation exchange resin or a weak acid cation exchange resin, preferably exchanging cations of H + It may be an H-type cation exchange resin.
具体的に、本発明の一実施形態による陽イオン交換樹脂は、母体として、ジビニルベンゼンとスチレンまたはジビニルベンゼンとアクリレートの共重合体、またはテトラフルオロエチレン高分子を含んでもよく、交換基として、スルホン酸やカルボン酸、好ましくはスルホン酸を含んでもよい。また、前記陽イオン交換樹脂は、反応効率の点から、ジビニルベンゼンで架橋結合されたスルホン化スチレン系樹脂であることがより好ましい。 Specifically, the cation exchange resin according to an embodiment of the present invention may include a copolymer of divinylbenzene and styrene or divinylbenzene and acrylate, or a tetrafluoroethylene polymer as a base, and a sulfone as an exchange group. Acids or carboxylic acids, preferably sulfonic acids may be included. The cation exchange resin is more preferably a sulfonated styrene resin crosslinked with divinylbenzene from the viewpoint of reaction efficiency.
好ましくは、本発明の一実施形態による陽イオン交換樹脂はＨ型陽イオン交換樹脂であって、ジビニルベンゼンで架橋結合されたスルホン化スチレン系樹脂であり、イオン交換容量が１ｍｅｑ／ｍｌ以上、好ましくは１〜３ｍｅｑ／ｍｌ、より好ましくは１．５〜３ｍｅｑ／ｍｌであってもよい。 Preferably, the cation exchange resin according to an embodiment of the present invention is an H-type cation exchange resin, which is a sulfonated styrene resin crosslinked with divinylbenzene, and has an ion exchange capacity of 1 meq / ml or more, preferably May be 1 to 3 meq / ml, more preferably 1.5 to 3 meq / ml.
本発明に記載のイオン交換容量は、交換され得るイオンの数当量として測定され、重合体体積（体積当たりのイオン交換容量（Volume Capacity））で表現されることができ、好ましくは、濡れたベッド（wetted bed、wetted polymer）の膨潤体積当たりの交換容量のミリ当量を意味する。 The ion exchange capacity according to the present invention is measured as a few equivalents of ions that can be exchanged and can be expressed in polymer volume (Volume Capacity per volume), preferably a wet bed. It means milliequivalents of exchange capacity per swollen volume of (wetted bed, wetted polymer).
具体的に、陽イオン交換樹脂をカラムに満たして用いる場合、陽イオン交換樹脂は、テレフタリリデンジカンフルスルホン酸塩の重量に対して２〜６倍の体積比、もしくは１〜３倍の当量にあたる量を満たして用いてもよく、薄い塩酸を用いて再生して繰り返して用いることができる。カラムの溶出速度については、カラムに満たされた陽イオン交換樹脂の体積に対して時間当り０．２〜２倍の反応液を通過させることができる。 Specifically, when the column is filled with a cation exchange resin, the cation exchange resin is used in a volume ratio of 2 to 6 times, or an equivalent of 1 to 3 times the weight of terephthalylidene dican full sulfonate It may be used by satisfying the corresponding amount, and it can be regenerated and reused with thin hydrochloric acid. About the elution rate of a column, the reaction liquid of 0.2-2 times per time can be passed with respect to the volume of the cation exchange resin with which the column was filled.
カラムから溶出されるテレフタリリデンジカンフルスルホン酸水溶液を全て濃縮することで、目的化合物であるテレフタリリデンジカンフルスルホン酸を褐色の固体形態で得ることができる。また、溶出されるテレフタリリデンジカンフルスルホン酸水溶液中の一部の水を蒸留除去し、０．１モルの水酸化カリウムで定量して３３％の水溶液を製造することで、直ちに市販可能な製品として製造することができる。 By concentrating all of the aqueous terephthalylidene dicanfulsulfonic acid eluted from the column, the target compound, terephthalylidenedicanfulsulfonic acid, can be obtained in the form of a brown solid. In addition, some water in the aqueous solution of terephthalylidene dicamphulsulfonic acid that is eluted is distilled off, and quantitatively determined with 0.1 mol of potassium hydroxide to produce a 33% aqueous solution, which is immediately commercially available. Can be manufactured as a product.
好ましくは、本発明の転換方法は、前記化学式２で表されるテレフタリリデンジカンフルスルホン酸塩を水に溶かしたテレフタリリデンジカンフルスルホン酸塩の水溶液を用いてもよく、前記水溶液は、テレフタリリデンジカンフルスルホン酸塩１００重量部に対して、５００〜１０００重量部、好ましくは７００〜１０００重量部の水を用いて製造されたものであってもよい。 Preferably, the conversion method of the present invention may use an aqueous solution of terephthalylidene dican full sulfonate obtained by dissolving the terephthalylidene dican full sulfonate represented by the chemical formula 2 in water. It may be produced using 500 to 1000 parts by weight, preferably 700 to 1000 parts by weight of water with respect to 100 parts by weight of terephthalylidene dican full sulfonate.
以下、次の実施例によって本発明をより詳細に説明するが、本発明が次の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples.
［実施例１］テレフタリリデンジカンフルスルホン酸の製造
１２ｇ（２０ｍｍｏｌ）のジソジウムテレフタリリデンジカンフルスルホネートを１００ｍｌの水に溶かした後、２００ｍｌ（１．８ｍｅｑ／ｍｌ）の陽イオン交換樹脂であるトリライトＳＣＲ−ＢＨ型（ＴＲＩＬＩＴＥ ＳＣＲ−ＢＨ；Samyang Corporation製）を添加し、室温で５時間撹拌した。ろ過して樹脂を除去し、５０ｍｌの水で洗浄した。水を減圧蒸留して除去し、生成された固体を減圧して乾燥することで、目的化合物である褐色固体のテレフタリリデンジカンフルスルホン酸１０．４ｇ（収率＝９３．４％）を得た。
[Example 1] Production of terephthalylidene dicanfursulfonic acid 12 g (20 mmol) of disodium terephthalylidene dican full sulfonate was dissolved in 100 ml of water, and then 200 ml (1.8 meq / ml) of cation exchange resin was used. A certain trilite SCR-BH type (TRILITE SCR-BH; manufactured by Samyang Corporation) was added and stirred at room temperature for 5 hours. The resin was removed by filtration and washed with 50 ml of water. The water was removed by distillation under reduced pressure, and the resulting solid was dried under reduced pressure to obtain 10.4 g (yield = 93.4%) of the target compound, a brown solid, terephthalylidene dicanfulsulfonic acid. It was.
この固体１ｇを精秤して水５０ｍｌに入れて溶かし、０．１モルの水酸化カリウム液で滴定した（指示薬：フェノールフタレイン試液１ｍｌ）。同様の方法により空試験して補正すると、酸性化された固体のテレフタリリデンジカンフルスルホン酸の含量は８９．７％であった。 1 g of this solid was precisely weighed and dissolved in 50 ml of water, and titrated with 0.1 molar potassium hydroxide solution (indicator: 1 ml of phenolphthalein test solution). Corrected by a blank test by the same method, the content of acidified solid terephthalylidene dicanfulsulfonic acid was 89.7%.
［実施例２］テレフタリリデンジカンフルスルホン酸の製造
１２．７ｇのジポタシウムテレフタリリデンジカンフルスルホネートを使用したことを除き、実施例１と同様に行うことで、目的化合物である褐色固体のテレフタリリデンジカンフルスルホン酸１０．５ｇを得た。この固体のテレフタリリデンジカンフルスルホン酸の含量は８９．６％であった。
[Example 2] Production of terephthalylidene dicanful sulfonic acid The same procedure as in Example 1 was carried out except that 12.7 g of dipotassium terephthalylidene dican full sulfonate was used. 10.5 g of terephthalylidene dicamphorsulfonic acid was obtained. The content of this solid terephthalylidene dicamphorsulfonic acid was 89.6%.
［実施例３］テレフタリリデンジカンフルスルホン酸の製造
１１．９ｇのジアンモニウムテレフタリリデンジカンフルスルホネートを使用したことを除き、実施例１と同様に行うことで、目的化合物である褐色固体のテレフタリリデンジカンフルスルホン酸１０．４ｇを得た。この固体のテレフタリリデンジカンフルスルホン酸の含量は８９．５％であった。
[Example 3] Production of terephthalylidene dicamphulsulfonic acid The same procedure as in Example 1 was carried out except that 11.9 g of diammonium terephthalylidene dikanfursulphonate was used. 10.4 g of terephthalylidene dicamphorsulfonic acid was obtained. The content of the solid terephthalylidene dicamphorsulfonic acid was 89.5%.
［実施例４］テレフタリリデンジカンフルスルホン酸の製造
２０Ｌ（１．８ｍｅｑ／ｍｌ）の陽イオン交換樹脂であるトリライトＳＣＲ−ＢＨ型（ＴＲＩＬＩＴＥ ＳＣＲ−ＢＨ；Samyang Corporation製）をカラムに満たした。４ｋｇ（６．６ｍｏｌ）のジソジウムテレフタリリデンジカンフルスルホネートを２８Ｌの水に溶かしたものを、９Ｌ／ｈｒの速度で溶出させた。１６Ｌの水で洗浄した後に得た反応液から水を減圧蒸留除去し、生成された固体を減圧して乾燥することで、目的化合物である褐色固体のテレフタリリデンジカンフルスルホン酸３．６ｋｇ（収率＝９７％）を得た。
[Example 4] Production of terephthalylidene dicamphorsulfonic acid 20 L (1.8 meq / ml) cation exchange resin, Trilite SCR-BH type (TRILITE SCR-BH; manufactured by Samyang Corporation) was filled in a column. A solution prepared by dissolving 4 kg (6.6 mol) of disodium terephthalylidene dicanfulsulfonate in 28 L of water was eluted at a rate of 9 L / hr. Water was distilled off under reduced pressure from the reaction liquid obtained after washing with 16 L of water, and the resulting solid was dried under reduced pressure to obtain 3.6 kg of terephthalylidene dicamphulsulfonic acid as a brown solid as the target compound ( Yield = 97%).
この固体１ｇを精秤して水５０ｍｌに入れて溶かし、０．１モルの水酸化カリウム液で滴定した（指示薬：フェノールフタレイン試液１ｍｌ）。同様の方法により空試験して補正すると、テレフタリリデンジカンフルスルホン酸の含量は９９．９％であった。 1 g of this solid was precisely weighed and dissolved in 50 ml of water, and titrated with 0.1 molar potassium hydroxide solution (indicator: 1 ml of phenolphthalein test solution). When a blank test was performed and corrected by the same method, the content of terephthalylidene dicanfulsulfonic acid was 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) 1 H-NMR (CD 3 OD) 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)
［実施例５］テレフタリリデンジカンフルスルホン酸の３３％水溶液の製造
実施例４と同様に行った後に得られた生成液から、水を３分の２のみ除去して、１０．７ｋｇの褐色の水溶液を得た。実施例４と同様に定量して含量を確認し、テレフタリリデンジカンフルスルホン酸の３３％水溶液を得た。
[Example 5] Preparation of 33% aqueous solution of terephthalylidene dicamphorsulfonic acid After removing the water from the product obtained in the same manner as in Example 4, 20.7 kg of brown An aqueous solution of was obtained. The content was confirmed by quantification in the same manner as in Example 4 to obtain a 33% aqueous solution of terephthalylidene dicamphorsulfonic acid.
［比較例１］塩酸を用いた酸性化
１２ｇ（２０ｍｍｏｌ）のジソジウムテレフタリリデンジカンフルスルホネートを３０ｍｌの水および３０ｍｌの濃い塩酸（３６０ｍｍｏｌ）に溶かした。１時間還流した後、濃縮および冷却して生成された固体をろ過した。６Ｎ−塩酸で洗浄し、８０℃で減圧して乾燥し、１００℃で減圧乾燥することで、７．０２ｇの固体を得た。
[Comparative Example 1] Acidification with hydrochloric acid 12 g (20 mmol) of disodium terephthalylidene dicanfulsulfonate was dissolved in 30 ml of water and 30 ml of concentrated hydrochloric acid (360 mmol). After refluxing for 1 hour, the solid produced after concentration and cooling was filtered. The solid was washed with 6N-hydrochloric acid, dried at 80 ° C. under reduced pressure, and dried at 100 ° C. under reduced pressure to obtain 7.02 g of a solid.
この固体１ｇを精秤して水５０ｍｌに入れて溶かし、０．１モルの水酸化カリウム液で滴定した（指示薬：フェノールフタレイン試液１ｍｌ）。同様の方法により空試験して補正すると、塩酸で酸性化した固体のテレフタリリデンジカンフルスルホン酸の含量は３３．６％であった。 1 g of this solid was precisely weighed and dissolved in 50 ml of water, and titrated with 0.1 molar potassium hydroxide solution (indicator: 1 ml of phenolphthalein test solution). When corrected by a blank test according to the same method, the content of solid terephthalylidene dicamphorsulfonic acid acidified with hydrochloric acid was 33.6%.
［比較例２］メタンスルホン酸を用いた酸性化
６．０６ｇ（１０ｍｍｏｌ）のジソジウムテレフタリリデンジカンフルスルホネートを５０ｍｌの水に溶かした後、１７．２９ｇ（１８０ｍｍｏｌ）のメタンスルホン酸を添加して室温で２時間撹拌した。反応液を濃縮し、トルエン１００ｍｌを用いてディーン・スターク装置により水分を完全に除去した。冷却して生成された固体をろ過し、トルエンで洗浄し、８０℃で減圧して乾燥し、１００℃で減圧乾燥することで、７．６８ｇの固体を得た。
[Comparative Example 2] Acidification with methanesulfonic acid After dissolving 6.06 g (10 mmol) of disodium terephthalylidene dicanfulsulfonate in 50 ml of water, 17.29 g (180 mmol) of methanesulfonic acid was added. And stirred at room temperature for 2 hours. The reaction solution was concentrated, and water was completely removed by using a Dean-Stark apparatus using 100 ml of toluene. The solid produced upon cooling was filtered, washed with toluene, dried under reduced pressure at 80 ° C., and dried under reduced pressure at 100 ° C. to obtain 7.68 g of a solid.
ソジウムメタンスルホネートが含まれていることを考慮して、比較例１のように定量すると、メタンスルホン酸で酸性化した固体のテレフタリリデンジカンフルスルホン酸の含量は約２２．５％であった。 Considering the presence of sodium methanesulfonate, the amount of solid terephthalylidene dicamphorsulfonic acid acidified with methanesulfonic acid was about 22.5% when quantified as in Comparative Example 1. It was.
［比較例３］トリフルオロ酢酸を用いた酸性化
６．０６ｇ（１０ｍｍｏｌ）のジソジウムテレフタリリデンジカンフルスルホネートを５０ｍｌの水に溶かした後、２０．５２ｇ（１８０ｍｍｏｌ）のトリフルオロ酢酸を添加したことを除き、比較例２と同様に行うことで、５．９１ｇの固体を得た。
[Comparative Example 3] Acidification with trifluoroacetic acid 6.06 g (10 mmol) of disodium terephthalylidene dicanfulsulfonate was dissolved in 50 ml of water, and then 20.52 g (180 mmol) of trifluoroacetic acid was added. Except that, 5.91 g of solid was obtained in the same manner as in Comparative Example 2.
ソジウムトリフルオロアセテートが含まれていることを考慮して、比較例１のように定量すると、トリフルオロ酢酸で酸性化した固体のテレフタリリデンジカンフルスルホン酸の含量は約７．５％であった。 Considering the presence of sodium trifluoroacetate, the amount of solid terephthalylidene dicamphsulfonic acid acidified with trifluoroacetic acid was about 7.5% when quantified as in Comparative Example 1. there were.
［比較例４］硫酸を用いた酸性化
６．０６ｇ（１０ｍｍｏｌ）のジソジウムテレフタリリデンジカンフルスルホネートを５０ｍｌの水に溶かした後、８．８２ｇ（９０ｍｍｏｌ）の硫酸を添加したことを除き、比較例２と同様に行うことで、６．４４ｇの固体を得た。
[Comparative Example 4] Acidification with sulfuric acid Except that 6.06 g (10 mmol) of disodium terephthalylidene dicanful sulfonate was dissolved in 50 ml of water, and then 8.82 g (90 mmol) of sulfuric acid was added. By carrying out similarly to the comparative example 2, 6.44 g of solid was obtained.
ソジウムサルフェートが含まれていることを考慮して、比較例１のように定量すると、硫酸で酸性化した固体のテレフタリリデンジカンフルスルホン酸の含量は約１９．７％であった。 In consideration of the presence of sodium sulfate, the content of solid terephthalylidene dicamphorsulfonic acid acidified with sulfuric acid was about 19.7% when quantified as in Comparative Example 1.
前記実施例１〜４より製造されたテレフタリリデンジカンフルスルホン酸の転換率が、比較例１に比べて非常に高いことが分かる。さらに、実施例１〜４は、別の塩を除去する工程が不要であるため、工程がより簡単であり、純度も高い。 It can be seen that the conversion rate of terephthalylidene dican full sulfonic acid produced from Examples 1 to 4 is very high compared to Comparative Example 1. Furthermore, since Examples 1-4 do not require a step of removing another salt, the steps are simpler and the purity is high.
また、比較例２〜４は、転換率も低いだけでなく、それぞれの有機酸と無機酸に相当する塩が含まれたテレフタリリデンジカンフルスルホン酸が得られ、純度が低く、それを除去するための別の工程が必要であることが分かる。 In addition, Comparative Examples 2 to 4 not only have a low conversion rate, but also obtained terephthalylidene dican full sulfonic acid containing salts corresponding to the respective organic and inorganic acids, and the purity is low, thus removing it. It can be seen that another process is necessary to do this.
結論として、本発明の陽イオン交換樹脂の存在下でテレフタリリデンジカンフルスルホン酸塩をテレフタリリデンジカンフルスルホン酸に転換する方法は、従来の方法に比べて高い転換率および純度を有する方法であるだけでなく、転換工程が簡単であって、経済的で且つ効率的な方法であることが分かる。 In conclusion, the method for converting terephthalylidene dican full sulfonic acid salt to terephthalylidene dican full sulfonic acid in the presence of the cation exchange resin of the present invention is a method having higher conversion and purity than the conventional method. It can be seen that the conversion process is simple, economical and efficient.
Claims (6)
［化学式１］
［化学式２］
（前記化学式１および２中、
Ｍは、アルカリ金属またはＮ（Ｒ１）（Ｒ２）（Ｒ３）（Ｒ４）であり、Ｒ１〜Ｒ４は、互いに独立して、水素または（Ｃ１−Ｃ７）アルキルであり；
Ｒは、（Ｃ１−Ｃ７）アルキルまたは（Ｃ１−Ｃ７）アルコキシであり；
ｎは０または１〜４の整数であって、ｎが２以上である場合、Ｒは互いに異なっても同一でもよい。） A method comprising a step of converting a terephthalylidene dican full sulfonic acid salt represented by the following chemical formula 2 into a terephthalylidene dican full 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 formulas 1 and 2,
M is an alkali metal or N (R 1 ) (R 2 ) (R 3 ) (R 4 ), and R 1 to R 4 are independently of each other hydrogen or (C1-C7) alkyl;
R is (C1-C7) alkyl or (C1-C7) alkoxy;
n is 0 or an integer of 1 to 4, and when n is 2 or more, R may be different or the same. )
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| PCT/KR2017/001584 WO2017155217A1 (en) | 2016-03-11 | 2017-02-14 | Method for acidifying terephthalylidene dicamphor sulfonic acid salt |
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| JP2023041625A (en) * | 2021-09-13 | 2023-03-24 | セラ・スー・カンパニー・リミテッド | Method for acidifying terephthalylidene dicamphor sulfonate using cation exchange fibers |
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| 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 |
| KR20240051688A (en) * | 2022-10-13 | 2024-04-22 | 신성소재 주식회사 | Manufacturing method of terephthalylidene dicamphor sulfonic acid using electrodialysis |
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