WO2021153847A1 - Procédé d'acidification d'un téréphtalylidène dicamphosulfonate - Google Patents

Procédé d'acidification d'un téréphtalylidène dicamphosulfonate Download PDF

Info

Publication number
WO2021153847A1
WO2021153847A1 PCT/KR2020/006134 KR2020006134W WO2021153847A1 WO 2021153847 A1 WO2021153847 A1 WO 2021153847A1 KR 2020006134 W KR2020006134 W KR 2020006134W WO 2021153847 A1 WO2021153847 A1 WO 2021153847A1
Authority
WO
WIPO (PCT)
Prior art keywords
terephthalylidene dicamphor
sulfonic acid
cation exchange
sulfonate
aqueous solution
Prior art date
Application number
PCT/KR2020/006134
Other languages
English (en)
Korean (ko)
Inventor
류동선
Original Assignee
주식회사 세라수
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 주식회사 세라수 filed Critical 주식회사 세라수
Priority to JP2021507518A priority Critical patent/JP7185017B2/ja
Publication of WO2021153847A1 publication Critical patent/WO2021153847A1/fr

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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/24—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
    • C07C309/32—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings containing at least two non-condensed six-membered aromatic rings in the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/44—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing doubly-bound oxygen atoms bound to the carbon skeleton

Definitions

  • the present invention relates to a method for acidifying terephthalylidene dicamphor sulfonate, and more particularly to a method for converting terephthalylidene dicamphor sulfonate to terephthalylidene dicamphor sulfonic acid using a cation exchange fiber.
  • the ultraviolet rays contained in sunlight When the ultraviolet rays contained in sunlight are excessively irradiated to the skin, it promotes the formation of erythema or the production of melanin in the skin cells, which can cause spots and blemishes. Not only does it cause trouble, but in severe cases, it can also cause skin cancer.
  • UV-A and UV-B Ultraviolet rays are divided into UV-A (320-400 nm), UV-B (280-320 nm), and UV-C (200-280 nm) depending on the wavelength. Since most of the short-wavelength ultraviolet rays are absorbed in the atmosphere, ultraviolet rays that directly affect the human body are known as UV-A and UV-B.
  • the sunscreens used for the purpose of preventing skin damage caused by ultraviolet rays are largely classified into chemical sunscreens and physical sunscreens.
  • Chemical sunscreens that have the mechanism of chemical absorption of ultraviolet rays include cinnamic acid, salicylic acid, and benzophenone, and physical sunscreens that physically scatter and shield ultraviolet rays are inorganic sunscreens such as titanium dioxide and zinc oxide. .
  • terephthalylidene dicamphor sulfonic acid is an organic sunscreen that can block UV-A and some UV-B.
  • terephthalylidene dicamphor sulfonic acid Various methods for preparing terephthalylidene dicamphor sulfonic acid are known, and a representative method among them is acidification of terephthalylidene dicamphor sulfonic acid salt with terephthalylidene dicamphor sulfonic acid using hydrochloric acid.
  • Patent Document 1 US Patent No. 4,585,597
  • An object of the present invention is to provide a method for acidifying terephthalylidene dicamphor sulfonate having a simple manufacturing process and high yield, purity and acid conversion rate to solve the problems of the prior art.
  • the present invention comprises the steps of (a) preparing an aqueous solution containing terephthalylidene dicamphor sulfonate;
  • the present invention comprises the steps of (a) preparing an aqueous solution containing terephthalylidene dicamphor sulfonate;
  • the cation exchange fiber is characterized in that it comprises at least one exchange group selected from a sulfonic acid group, a carboxyl group and a phosphoric acid group.
  • the cation exchange fiber is characterized in that it contains both a sulfonic acid group and a carboxyl group as an exchange group.
  • the cation exchange fiber is characterized by using a cation exchange fiber containing a sulfonic acid group and a cation exchange fiber containing a carboxyl group at the same time.
  • the weight ratio of the cation exchange fiber including the sulfonic acid group and the cation exchange fiber including the carboxyl group is 60-90:10-40.
  • the present invention can provide a method for acidifying terephthalylidene dicamphor sulfonate with a simple manufacturing process and high yield, purity, and acid conversion.
  • the present invention can convert terephthalylidene dicamphor sulfonic acid salt to terephthalylidene dicamphor sulfonic acid using a cation exchange fiber at a high conversion rate, and the salt formed during conversion is very easy to remove.
  • the present invention comprises the steps of (a) preparing an aqueous solution containing terephthalylidene dicamphor sulfonate;
  • the present invention comprises the steps of (a) preparing an aqueous solution containing terephthalylidene dicamphor sulfonate;
  • the step (a) is a step of preparing an aqueous solution containing terephthalylidene dicamphor sulfonate, and 300 to 1,500 parts by weight of water may be used based on 100 parts by weight of terephthalylidene dicamphor sulfonate.
  • the terephthalylidene dicamphor sulfonate is represented by the following formula (1).
  • M is an alkali metal or N(R 1 )(R 2 )(R 3 )(R 4 ), R 1 to R 4 are each independently hydrogen or (C1-C7)alkyl, and R is ( C1-C7)alkyl or (C1-C7)alkoxy, n is 0 or an integer from 1 to 4, and when n is 2 or more, R may be the same or different from each other.
  • the step (b) comprises the steps of preparing a mixed solution by mixing the aqueous solution and the cation exchange fiber; Alternatively, the aqueous solution is introduced into a column filled with cation exchange fibers and eluted.
  • polyolefin such as polyethylene and polypropylene, polyester, polyamide, polyurethane, polyacrylonitrile, acrylic resin, etc. may be used without limitation.
  • the cation exchange fiber includes an aggregate of fibers, that is, a nonwoven fabric, a mat, a web, a fabric, a filter, and the like.
  • the cation exchange fiber may include at least one exchange group selected from a sulfonic acid group, a carboxyl group and a phosphoric acid group on the surface.
  • the cation exchange fiber into which the sulfonic acid group is introduced can be prepared by the following method.
  • glycidyl acrylate or glycidyl methacrylate is treated with glycidyl acrylate or glycidyl methacrylate on the surface of the polypropylene fiber Rates can be grafted.
  • glycidyl acrylate or glycidyl methacrylate based on 100 parts by weight of the polypropylene fiber.
  • a sulfonation solution for example, NaHSO 3 solution, can be treated thereto to introduce sulfonic acid groups on the surface of the fibers.
  • the cation exchange fiber into which a carboxyl group is introduced can be prepared by the following method.
  • acrylic acid or methacrylic acid is grafted onto the surface of the polypropylene fiber by treatment with acrylic acid or methacrylic acid to introduce a carboxyl group on the surface of the fiber.
  • acrylic acid or methacrylic acid are used with respect to 100 parts by weight of the polypropylene fiber.
  • the cation exchange fiber of the present invention may include both a sulfonic acid group and a carboxyl group as an exchange group.
  • the polypropylene fiber is treated with plasma to form radicals on the polypropylene fiber, and then treated with glycidyl acrylate (or glycidyl methacrylate) and acrylic acid (or methacrylic acid) to form the polypropylene fiber.
  • Glycidyl acrylate and acrylic acid can be grafted onto the surface.
  • both sulfonic acid groups and carboxyl groups can be introduced on the surface of the fibers.
  • the weight ratio of glycidyl acrylate and acrylic acid is preferably 60 to 90:10 to 40, and when the weight ratio is less than 60:40, the cation exchange capacity is reduced, and when it exceeds 90:10, the durability and processability of the fiber is lowered
  • a cation exchange fiber containing a sulfonic acid group and a cation exchange fiber containing a carboxyl group may be used at the same time.
  • the weight ratio of the cation exchange fiber including the sulfonic acid group and the cation exchange fiber including the carboxyl group is preferably 60 to 90:10 to 40, and when the weight ratio is less than 60:40, the cation exchange capacity is reduced, and 90:10 is When it exceeds, the durability and workability of the fiber are reduced.
  • the present invention may use a cation exchange fiber and a cation exchange resin at the same time.
  • one or more exchange groups selected from a sulfonic acid group, a carboxyl group and a phosphoric acid group may be bonded to the polymer matrix.
  • the polymer matrix includes phenolformaldehyde condensate, phenol-benzaldehyde condensate, polystyrene, ethylstyrene polymer, divinylbenzene polymer, styrene-divinylbenzene copolymer, methacrylic acid-divinylbenzene copolymer, acrylic acid-divinyl benzene copolymer, methacrylate-divinylbenzene copolymer, acrylate-divinylbenzene copolymer, and the like.
  • the weight ratio of the cation exchange fiber and the cation exchange resin is 70 to 90:10 to 30, and when the weight ratio is less than 70:30, the cation exchange capacity is reduced, and when it exceeds 90:10, the processability and handleability are reduced do.
  • step (c) the obtained filtrate is dried to obtain terephthalylidene dicamphor sulfonic acid, and the obtained filtrate is distilled under reduced pressure, concentrated and dried to prepare solid terephthalylidene dicamphor sulfonic acid.
  • the terephthalylidene dicamphor sulfonic acid is represented by the following formula (2).
  • 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 the same or different from each other.
  • 100 parts by weight of polypropylene fibers were treated with argon plasma to form radicals on polypropylene fibers, and then treated with 5 parts by weight of glycidyl methacrylate to graft glycidyl methacrylate on the surface of polypropylene fibers.
  • NaHSO 3 solution was treated to introduce sulfonic acid groups on the surface of the fibers.
  • An aqueous solution was prepared by dissolving 10 g of disodium terephthalylidene dicamphor sulfonate in 100 ml of water.
  • 100 parts by weight of polypropylene fibers were treated with argon plasma to form radicals on polypropylene fibers, and then treated with 4 parts by weight of glycidyl methacrylate and 1 part by weight of methacrylic acid.
  • NaHSO 3 solution was treated to introduce a sulfonic acid group and a carboxyl group on the surface of the fiber.
  • An aqueous solution was prepared by dissolving 10 g of disodium terephthalylidene dicamphor sulfonate in 100 ml of water.
  • a solid terephthalylidene dicamphor sulfonic acid was obtained in the same manner as in Example 2, except that 2.5 parts by weight of glycidyl methacrylate and 2.5 parts by weight of methacrylic acid were used.
  • a solid terephthalylidene dicamphor sulfonic acid was obtained in the same manner as in Example 2, except that 6 parts by weight of glycidyl methacrylate and 0.5 parts by weight of methacrylic acid were used.
  • 100 parts by weight of polypropylene fibers were treated with argon plasma to form radicals on polypropylene fibers, and then treated with 5 parts by weight of glycidyl methacrylate to graft glycidyl methacrylate on the surface of polypropylene fibers.
  • NaHSO 3 solution was treated to introduce sulfonic acid groups on the surface of the fibers.
  • 100 parts by weight of the polypropylene fiber was treated with argon plasma to form radicals on the polypropylene fiber, and then treated with 5 parts by weight of methacrylic acid to prepare a polypropylene fiber having a carboxyl group introduced therein.
  • An aqueous solution was prepared by dissolving 10 g of disodium terephthalylidene dicamphor sulfonate in 100 ml of water.
  • 100 parts by weight of polypropylene fibers were treated with argon plasma to form radicals on polypropylene fibers, and then treated with 5 parts by weight of glycidyl methacrylate to graft glycidyl methacrylate on the surface of polypropylene fibers.
  • NaHSO 3 solution was treated to introduce sulfonic acid groups on the surface of the fibers.
  • An aqueous solution was prepared by dissolving 4 kg of disodium terephthalylidene dicamphor sulfonate in 24 kg of water.
  • the aqueous solution was put into a column filled with 5 kg of polypropylene fibers introduced with a sulfonic acid group and eluted.
  • An aqueous solution was prepared by dissolving 10 g of disodium terephthalylidene dicamphor sulfonate in 100 ml of water.
  • a cation exchange resin styrene-divinylbenzene copolymer introduced with a sulfonic acid group was added to the aqueous solution and stirred at room temperature for 5 hours to prepare a mixed solution.
  • the mixture was filtered to remove fibers, and the obtained filtrate was washed with 50 ml of water and then distilled under reduced pressure to obtain solid terephthalylidene dicamphor sulfonic acid.
  • Comparative Examples 1 and 2 are inferior in the above characteristics to those of Examples.
  • the present invention can provide a method for acidification of terephthalylidene dicamphor sulfonate with a simple manufacturing process and high yield, purity and acid conversion.
  • the present invention can convert terephthalylidene dicamphor sulfonic acid salt to terephthalylidene dicamphor sulfonic acid using a cation exchange fiber at a high conversion rate, and the salt formed during conversion is very easy to remove.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention concerne un procédé d'acidification d'un téréphtalylidène dicamphosulfonate, et plus précisément un procédé pour convertir un téréphtalylidène dicamphosulfonate en acide téréphtalylidène dicamphosulfonique à l'aide de fibres échangeuses de cations. La présente invention peut fournir un procédé d'acidification d'un téréphtalylidène dicamphosulfonate, le procédé de fabrication étant simple et conduisant à un rendement, une pureté et un taux de conversion en acide élevés. Dans la présente invention, le téréphtalylidène dicamphosulfonate peut être converti en acide téréphtalylidène dicamphosulfonique avec un taux de conversion élevé à l'aide de de fibres échangeuses de cations, et il est également très facile d'éliminer les sels formés pendant la conversion.
PCT/KR2020/006134 2020-01-29 2020-05-08 Procédé d'acidification d'un téréphtalylidène dicamphosulfonate WO2021153847A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021507518A JP7185017B2 (ja) 2020-01-29 2020-05-08 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｛ａ ｍｅｔｈｏｄ ｆｏｒ ａｃｉｄｉｆｙｉｎｇ ｔｅｒｅｐｈｔｈａｌｙｌｉｄｅｎｅ ｄｉｃａｍｐｈｏｒ ｓｕｌｆｏｎａｔｅ｝

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2020-0010594 2020-01-29
KR1020200010594A KR102099831B1 (ko) 2020-01-29 2020-01-29 테레프탈릴리덴 디캠퍼 설폰산염의 산성화 방법

Publications (1)

Publication Number Publication Date
WO2021153847A1 true WO2021153847A1 (fr) 2021-08-05

Family

ID=70292032

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2020/006134 WO2021153847A1 (fr) 2020-01-29 2020-05-08 Procédé d'acidification d'un téréphtalylidène dicamphosulfonate

Country Status (3)

Country Link
JP (1) JP7185017B2 (fr)
KR (1) KR102099831B1 (fr)
WO (1) WO2021153847A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115784942A (zh) * 2021-09-13 2023-03-14 株式会社世来秀 使用阳离子交换纤维酸化对苯二亚甲基二樟脑磺酸盐的方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102099831B1 (ko) * 2020-01-29 2020-04-10 주식회사 세라수 테레프탈릴리덴 디캠퍼 설폰산염의 산성화 방법
KR102212527B1 (ko) * 2020-08-12 2021-02-04 (주)삼양정밀화학 테레프탈릴리덴 디캠퍼 설폰산염을 포함하는 필름 제조용 수용성 자외선 흡수제
KR20240051688A (ko) 2022-10-13 2024-04-22 신성소재 주식회사 전기투석을 이용한 테레프탈릴리덴 디캠퍼 설폰산의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
KR20090032803A (ko) * 2007-09-28 2009-04-01 광주과학기술원 이온교환섬유, 이의 제조방법 및 이를 이용하는 전기탈이온장치
KR20170105939A (ko) * 2016-03-11 2017-09-20 주식회사 카이로켐 테레프탈릴리덴 디캠퍼 설폰산염의 산성화방법
KR101937332B1 (ko) * 2018-06-18 2019-01-11 신성소재 주식회사 테레프탈릴리덴 디캠퍼 설폰산의 정제방법
KR102099831B1 (ko) * 2020-01-29 2020-04-10 주식회사 세라수 테레프탈릴리덴 디캠퍼 설폰산염의 산성화 방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4878415B2 (ja) 2001-06-07 2012-02-15 新日鐵化学株式会社 ビスフェノールａの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
KR20090032803A (ko) * 2007-09-28 2009-04-01 광주과학기술원 이온교환섬유, 이의 제조방법 및 이를 이용하는 전기탈이온장치
KR20170105939A (ko) * 2016-03-11 2017-09-20 주식회사 카이로켐 테레프탈릴리덴 디캠퍼 설폰산염의 산성화방법
KR101937332B1 (ko) * 2018-06-18 2019-01-11 신성소재 주식회사 테레프탈릴리덴 디캠퍼 설폰산의 정제방법
KR102099831B1 (ko) * 2020-01-29 2020-04-10 주식회사 세라수 테레프탈릴리덴 디캠퍼 설폰산염의 산성화 방법

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115784942A (zh) * 2021-09-13 2023-03-14 株式会社世来秀 使用阳离子交换纤维酸化对苯二亚甲基二樟脑磺酸盐的方法
JP2023041625A (ja) * 2021-09-13 2023-03-24 セラ・スー・カンパニー・リミテッド カチオン交換繊維を用いた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
JP7349757B2 (ja) 2021-09-13 2023-09-25 セラ・スー・カンパニー・リミテッド カチオン交換繊維を用いた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
TWI824501B (zh) * 2021-09-13 2023-12-01 南韓商世來秀股份有限公司 使用陽離子交換纖維酸化對苯二亞甲基二樟腦磺酸鹽的方法

Also Published As

Publication number Publication date
JP7185017B2 (ja) 2022-12-06
JP2022522252A (ja) 2022-04-15
KR102099831B1 (ko) 2020-04-10

Similar Documents

Publication Publication Date Title
WO2021153847A1 (fr) Procédé d'acidification d'un téréphtalylidène dicamphosulfonate
EP0112120B1 (fr) Utilisation de 2(-2'hydroxyaryl)-2H-benzotriazol-sulphonates comme agents photostabilisants pour des fibres naturelles et synthétiques
KR100540720B1 (ko) 신규형의 ｓ-오메프라졸
EP0417603A3 (en) Process for the preparation of urethdione group-containing polyisocyanates
WO2019245133A1 (fr) Procédé de purification d'acide sulfonique de dicamphre téréphtalalylidène
WO2021071033A9 (fr) Procédé de préparation d'hexylbenzoate de diéthylaminohydroxybenzoyle
KR102341174B1 (ko) 양이온교환 섬유를 사용한 테레프탈릴리덴 디캠퍼 설폰산염의 산성화 방법
WO2021118124A1 (fr) Polyuréthane thermoplastique amphiphile non mélangé, son procédé de production, et dispositif médical implantable le comprenant
WO2021090997A1 (fr) Éponge d'acide hyaluronique photo-réticulé et son procédé de fabrication
KR100694946B1 (ko) 광중합반응에 적합한 이작용성 광개시제 및 이를 함유하는광중합성시스템
WO2019132470A1 (fr) Procédé de séparation d'un monomère n'ayant pas réagi à partir d'une solution mixte comprenant un monomère n'ayant pas réagi
WO2015034293A1 (fr) Procédé de préparation d'intermédiaire amélioré pour l'obtention de pémétrexed à haut degré de pureté et procédé d'obtention de pémétrexed à haut degré de pureté utilisant l'intermédiaire
WO2017116193A1 (fr) Formes cristallines d'un composé de thiénopyrimidine
WO2021015378A1 (fr) Méthode de production d'hydroxyde de lithium
WO2018190647A9 (fr) Composé à base de polyvinyle fonctionnel autocicatrisant et son procédé de préparation
WO2022131665A1 (fr) Nouveau copolymère réticulé à base de polyfluorène, son procédé de production, et membrane échangeuse d'anions pour une pile à combustible alcaline l'utilisant
WO2021251551A1 (fr) Nouveau composé et composition pharmaceutique le contenant pour traiter ou prévenir une lésion neuronale, une maladie neuronale ou un trouble du développement par activation de la prolifération, de la différenciation et/ou de la régénération de cellules neuronales
WO2019231166A1 (fr) Procédé de préparation de sel de sodium sugammadex
WO2020218776A1 (fr) Procédé de préparation d'eau avec ions hydronium dissous
WO2010050720A4 (fr) Absorbant de proche infrarouge constitué de complexe métallique de dithiol, procédé de préparation dudit complexe métallique de dithiol, et filtre optique et filtre de protection contre l'infrarouge thermique contenant un tel absorbant
WO2012091468A2 (fr) Fibre d'élasthanne à résistance améliorée au chlore et à une altération de la couleur et son procédé de préparation
WO2021071130A1 (fr) Procédé de préparation d'un cristal d'heptahydrate de 5'-guanylate disodique
WO2010107163A1 (fr) Pansement liquide pour protéger la peau et une lésion et procédé de fabrication de celui-ci
WO2019124674A1 (fr) Procédé de purification de maléimide n-substitué
WO2017209486A1 (fr) Polyéther autoréparant et son procédé de préparation

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021507518

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20917202

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20917202

Country of ref document: EP

Kind code of ref document: A1