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.

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• Chemical & Material Sciences (AREA)
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• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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• 2020
  • 2020-01-29 KR KR1020200010594A patent/KR102099831B1/ko active IP Right Grant
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