KR20130008431A - The methode silver antibacteries polymerization - Google Patents

The methode silver antibacteries polymerization Download PDF

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KR20130008431A
KR20130008431A KR1020110069436A KR20110069436A KR20130008431A KR 20130008431 A KR20130008431 A KR 20130008431A KR 1020110069436 A KR1020110069436 A KR 1020110069436A KR 20110069436 A KR20110069436 A KR 20110069436A KR 20130008431 A KR20130008431 A KR 20130008431A
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silver
polyester
ethylene glycol
solution
antibacterial
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KR1020110069436A
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Korean (ko)
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최명부
박근식
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최명부
박근식
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings

Abstract

PURPOSE: A polymerization method of silver-antibacterial polyester is provided to enhance antibacterial activity and to prevent discoloration. CONSTITUTION: A polymerization method of silver-antibacterial polyester comprises the following stages: stirring water, hydrogen peroxide, and chlorine as electrolyte, and benzoyl peroxide in an electrolyzer; manufacturing a silver solution through electrolysis after adding silver rods in the electrolyzer; adding terephthalic acid and silver antimicrobial composition into a reactor after manufacturing ethylene glycol; and manufacturing polyester by cooling after reaction.

Description

은항균 폴리에스테르 중합방법{The methode silver antibacteries polymerization}The methode silver antibacteries polymerization

본 발명은 은항균 폴리레스테르 중합 방법에관한 것으로 현제 기존 폴리에스테르글리콜의 에스테르화 반응 후에 이를 다시 촉매로 산화디알킬주석 등 여러 가지 촉매제를 선택하여 촉매제를 사용하여 폴리에스테르를 중합 하고 있는데The present invention relates to a silver antibacterial polyster polymerization method, and currently, after esterification of existing polyester glycol, various catalysts such as dialkyl tin oxide are selected as a catalyst and polymerized polyester using a catalyst.

본 발명은 은항균 폴리에스테르를 제조하기 위하여 상기 공정에서 사용되는 에칠렌 글리콜에 일정한 비율로 은 용액을 이온화시켜 은나노 에칠렌 글리콜을 제조하여 기존 폴리에스테르 제조 시 사용하는 테레 플탈산과 은나노 에칠렌글리콜을 일정한 비율로 혼합하여 기존 사용하는 촉매제를 이용하여 은항균 폴리에스테르를 제조 하는 방법이다.The present invention is to produce a silver nano ethylene glycol by ionizing the silver solution in a certain ratio in the ethylene glycol used in the above process to produce a silver antibacterial polyester to a constant ratio of terephthalic acid and silver nano ethylene glycol used in the production of conventional polyester It is a method for producing silver antibacterial polyester by using a conventional catalyst used by mixing.

본 발명에서 사용되는 은나노 이온수는 황변이 되지 않고 PH7 정도의 중성으로 에칠렌글리콜 혼합 했을 때 은나노 입자가 에치렌 글리콜 분자에 이온화 형태로 결합하여 항균력이 우수한 은 항균 에치렌 글리콜이 제조된 본 발명에서 제조된 은(Ag)입도는 약 4나노 정돌로 분자정도의 작은 입자로 침투력과 분산력이 우수하고 분자 표면에 이온화 형태 물성에 아루런 변화를 주지 않고 전자 현미경으로도 식별 이 어려울 정도로 무전극 도금이 되어 있다고 볼수 있다.본 발명의 기술 핵심은 현재 까지 은나노 용액은 열고 햇볕 각종 유기,무기 화합물과또는 할로rps화합물과 결합할 때 황변이 생겨 항균력은 우수하다.The silver nano-ionized water used in the present invention is not yellowed, but when the ethylene glycol is mixed with neutral pH of about PH7, the silver nanoparticles are bound to the ethylene glycol molecules in an ionized form, thus preparing silver antibacterial ethylene glycol having excellent antibacterial activity. The silver (Ag) particle size is about 4 nanocrystals, and it is a small particle of molecular size, and has excellent penetration and dispersing power, and it is electrodeless plated so that it is difficult to identify even by electron microscope without changing the ionization form property on the surface The technical core of the present invention is that until now silver nano solution is open and combined with sunlight and various organic and inorganic compounds, or halorps compound, yellowing occurs and the antibacterial activity is excellent.

황변이 되는 것이 문제가 되고 있다.Yellowing is a problem.

본 발명은 황변이 되지 않는 새로운 은(Ag)이온수로 제조하여 폴리에스테르 중합 원료인 에치렌글리콜에 이온화시켜 은항균 에치렌글리콜 을 제조하여 폴리에스테르 중합원료인 테레프탈산과 합성하여 은항균 폴리에스테르 를 중합하는것이 본 발명의 기술 핵심이다.The present invention is prepared by using a new silver (Ag) ionized water that does not turn yellow and ionized to ethylene glycol, a raw material for polyester polymerization, to prepare silver antibacterial ethylene glycol and to synthesize silver antibacterial polyester by synthesizing with terephthalic acid, a polyester polymerization raw material. It is the technical core of the present invention.

현재까지 보고에 의하면 은(Ag)은 인체에 아무런 해를 주지 않고, 모든 병균을 살균 하는 무기 항균제로 높이 평가 하고 있다.To date, silver (Ag) is highly regarded as an inorganic antibacterial agent that kills all germs without harming the human body.

현재까지 폴리에스테르는 널리 알려진 열가소성 중합체로서 글리콜과 디카르복실산의 잔기가 교대로 연결되어 구성된 사슬을 가지고 있다.To date, polyesters are well known thermoplastic polymers and have chains composed of alternating residues of glycols and dicarboxylic acids.

원사, 필름 등 기타 산업제품으로 널리 사용 되고 있는데 상기 제품에서 항균을 요구하는 상품개발을 필요로 하고 있다. 따라서 폴리에스테르 제조방법에 않은 연구가 있어 왔다.It is widely used as yarn, film, and other industrial products, and it requires the development of products that require antibacterial properties. Therefore, research has not been made in the polyester manufacturing method.

선 기술 들을 찾아보면 대한민국 특허공보 번호 특1983-886 호에는 페놀과 선구물질이 제조된 물질을 폴리에스테르 중합 하는 방법 대한민국 특허 공보 1999-6540호 에틸렌글리콜 과 에스테르 반응을 위하여 반응장치를 조작하여 액상 투입하여 제조되는 폴리에스터를 조중합 방법들이 있다.In terms of prior arts, Korean Patent Publication No. 1983-886 discloses a method of polyester polymerization of a phenol and a precursor material. Korean Patent Publication No. 1999-6540. There are methods for co-polymerizing the polyester produced.

특히 본 발명자들이 대한민국 특허 등록을 받은 특허발명의 명칭 폴리에스테 르의 중합방법이 있는데 상기 발명에서는 은항균 폴리에스테르를 중합하기 위하여 폴리에스테르 중합시 촉매제로 사용되는 촉매제중 어느한것을 선택하여 은항균제로 촉매제와 합성하여 폴리에스테르 중합방법인데 본 발명은 폴리에스테르 중합시 에치렌글리콜에 황변이 되지 않은 새로운 은나노 용객을 제조하여 은항균 에치렌글리콜 조성물을 제조하여 은항균 폴리에스테르 를 제조 한 것이 특징이다. 특히 은항균 콜로이드는 에칠렌글리콜에 이온화가 잘되기 때문에 상기와 같은 방법으로 은항균 폴리에스테르 를제조한 것이 특징이다.Particularly, the present inventors have a method of polymerization of polyester, which is the name of the patent invention, which has been registered in the Republic of Korea patent. Synthesis with a catalyst is a polyester polymerization method. The present invention is characterized in that a silver antibacterial ethylene glycol composition is prepared by preparing a new silver nano-solvent which does not yellow in ethylene glycol during polyester polymerization. In particular, the silver antibacterial colloid is well ionized to the ethylene glycol is characterized by the production of silver antibacterial polyester in the same way as described above.

본 발명에서 새로운 은항균제 제조방법에 있어서 통상 기존 상용하고 있는 전기 분해기의 전해도에 물을 사용 하는것을 물 1500ml 비울에 과산화수소 500g 을 혼합한휴 과산화벤조오일 4g을 용해한 다음 전해질로 염소 50g을 넣고 교반한 다음 전기 분해기기의 +,- 극에 은봉 직경 1cm, 길이 20m, 무개 100g을 각각 연결시켜 3볼트의 전류기의 전기를 13암페어로 하여 5시간 동안 전기 분해하여 은봉을 용출시켜 은나노 항균제를 제조하여 은항균 제50000PPM 을 제조 한 다음 상기와 같이 은항균제를 폴리에스테르 를 중합하기 위하여 테레플탈산과 에틸엔글리콜에 은 물 합성한 에틸렌글리콜 조성물의 에스테르화 반응 후에 이를 다시 중축 합시켜 폴리에스테르를 제조하기 위하여 촉매로 산화 디알킬주석, 이산화티타늄, 알콜시티타늄, 실리케이트티타늄 및 알코올레이트, 카르복실산의 알카리금속 및 알카리토금속염 및 루이스산등에서 선택된 어느 하나의 화합물과 촉매로 사용하여 제조하는 폴리에스테르 중합방법을 제공 하는것이 본 발명이 이루고자 하는 기술적 과제인것이다.In the present invention, in the preparation method of the new silver antimicrobial agent, water is generally used for the electrolytic degree of an existing electrolyzer, and 4 g of benzoyl peroxide mixed with 500 g of hydrogen peroxide in 1500 ml of water is dissolved. Then, connect silver rod diameter 1cm, length 20m, and 100g to the + and-poles of the electrolysis equipment, respectively, and electrolytically dissolve the silver rod for 5 hours using 13 amp electric current of 3 volts to manufacture silver nano antibacterial. To prepare a silver antibacterial 50000PPM, and then to the polymerization of the silver antibacterial agent polyester as described above, after the esterification reaction of the ethylene glycol composition synthesized by silver water to terephthalic acid and ethylen glycol polycondensation of the silver antibacterial agent to prepare a polyester Dialkyltin oxide, titanium dioxide, alcoholititanium, silicatetitanium and alcohol It is a technical object of the present invention to provide a polyester polymerization method prepared by using any one compound selected from the group consisting of alkali metal and alkali metal salt of carboxylic acid and salt and Lewis acid and catalyst.

본 발명에서 언급되는 물성중 일반적으로 보틀은 유연하고 연신율이 우수한 특성은 물론 항균 폴리에스터 원사 및 필름은 중간 정도의 적당한 연신성과 스프트감이 우수한 물성의 폴리에스테르 를 제조하기 위한 중합방법에 관한것이다.Among the properties mentioned in the present invention, in general, the bottle is flexible and has excellent elongation, as well as antimicrobial polyester yarns and films, and relates to a polymerization method for producing a polyester having a moderate moderate elongation and a good sense of swelling.

본 발명에서는 사용되는 디카르복실산 성분의 함량을 지군으로 디올 성분을 1.1-1.3 몰비로 에스테르화 반응기에 투입하고 240°c～250°c 의 온도에서 폴리에스테르 를 제조하는 것이다.In the present invention, the dicarboxylic acid component is used as a group, and the diol component is introduced into the esterification reactor at a molar ratio of 1.1-1.3 to prepare a polyester at a temperature of 240 ° C to 250 ° C.

이하 실시 예를 들어 본 발명을 설명한다.Hereinafter, the present invention will be described with reference to Examples.

[실시예][Example]

제 1공정(은 나노제조)First Process (Silver Nano Manufacturing)

전기 분해기기 전류를 3V 를 13A 로 고정시켜 놓고 전기 분해기기의 +,-극에 은봉 직경1cm, 길이 20m, 무개 각각 100g 이되는 은봉을 연결 신킨 다음 전해조에 물 1500ml 과산화수소 500g 을 혼합한후 과산화벤조일 4g을 용해한다음 전해질조 염소 50g 을 넣고 교반한후 전기분해기기의 +,-극에 연결된 은봉을 5cm 간격이 되도록 전해조에 넣고 5시간 동안 전기 분해 하여 은(Ag)을 석출시켜 약 100,000ppm 의 은(Ag)나노 용액을 제좋 하여 여과조에 여과 하여 은나노 용액 100,000g을 제조한다음Set the current of electrolysis equipment to 3A at 13A, connect silver rods of 1cm diameter, 20m length, and 100g each to the + and-poles of the electrolysis equipment, and mix 1500ml of water 500g of hydrogen peroxide in the electrolytic cell, and then add benzoyl peroxide. After dissolving 4g, 50g of electrolytic chlorine is added and stirred.The silver bar connected to the + and-poles of the electrolytic device is placed in the electrolytic cell at 5cm intervals and electrolyzed for 5 hours to precipitate silver (Ag). (Ag) Nano solution was prepared and filtered through a filtration tank to prepare 100,000 g of silver nano solution.

제 2공정(폴리에스테르 제조)2nd process (polyester manufacture)

에치렌글리콜 1,000g 비율로 제 1공정에 은(Ag)용액 100g을 혼합믹스한다음 테레프탈산과 상기 은(Ag)이 합성된 에치렌그리콜 각각 1, 2몰을 반응기에 주입하고 질소기류 하에 처음 에는 200°c 의 온도 하에서 진행 시킨후에 300°c에서 약 15분 간 진공 도 를 점차 올리고 반응 혼합물을 0.1몰로드에서 25분간 유지 시키면 서 촉매로 산화 디알킬주석 을 주입 하여 반응 시킨후 냉각시켜 은 항균 폴리에스테를 중합체를 제조하였다.100 g of silver (Ag) solution was mixed and mixed in the first step at a ratio of 1,000 g of ethylene glycol, and then 1 and 2 moles of ethylene glycol, in which terephthalic acid and silver (Ag) were synthesized, were introduced into the reactor. After proceeding under the temperature of 200 ° C, the degree of vacuum was gradually increased at 300 ° C for about 15 minutes, and the reaction mixture was kept in 0.1 mol rod for 25 minutes while injecting dialkyltin oxide into the catalyst, followed by cooling. Polyester polymers were prepared.

이때 제조된 중합체를 원하는 크기로 분쇄 하여 130°c에서 1시간건조시켜 포장 하여 사용하였다.)At this time, the prepared polymer was ground to a desired size, dried at 130 ° C. for 1 hour, and used for packaging.)

상기와 같은 본 발명은 항균력이 우수한 폴리에스테르 를 제조 할 수 있는 장점이 있다.The present invention as described above has the advantage of producing a polyester having excellent antibacterial activity.

상기와 같이 제조된 폴리에스테르 수지는 항균력이 우수하고 색상이 변하지 않고 점도 및 방사성도 기존 폴리에스테르 와 하등의 차이가 없는 것이 장점이 되고 있다.The polyester resin prepared as described above has an advantage that it is excellent in antimicrobial activity, color does not change, and viscosity and radioactivity do not differ from conventional polyester.

..

..

본 발명에서 폴리에스테르 를 중합할 때 에치렌클리코올 에 항변이 되지 않는 은 항균제로 합성하여 기곤 폴리에스테르 중합에서 사용되는 원료와 온도 및 방법을 그대로 하여 은 항균 폴리에스테르 를 중합화는 것이 특징이다.In the present invention, it is characterized by polymerizing silver antimicrobial polyester by synthesizing it with a silver antimicrobial agent which is not resistant to ethylene glycol when polymerizing polyester, and using the raw material, temperature and method used in the conventional polyester polymerization.

Claims (1)

제 1공정(은나노 용액제조)First process (silver nano solution production) 전기 분해기기의 전류를 3V 13A 로 고정시켜 놓고 전기 분해기기의 +,-극에 은봉 직경 1cm, 길이20cm, 무개 각각 100g 이되는 은봉을 연결 시킨다음 전해조에 물 1500ml 넣고 과산화수소 500g 혼합한 후 과산화벤조일 4g 용해한다음 전해질로 염소 50g을 넣고 교반한 후 전기분해기기의 +,-극에 연결된 은봉을 5cm, 간격이 되도록 전해조에 넣고 5시간 또는 일정한 시간동안 전기 분해 하여 은(Ag)을 석출시켜 은나노 용액 100,000pmm 또 는 일정한 함량의 은 용액1,000g을 제조한 후에Fix the current of electrolysis equipment to 3V 13A and connect silver rods of 1cm in diameter, 20cm in length and 100g each to the + and-poles of the electrolysis equipment, add 1500ml of water to the electrolytic cell, mix 500g of hydrogen peroxide, and then add benzoyl peroxide. After dissolving 4g, 50g of chlorine is added to the electrolyte and stirred.The silver bar connected to the + and -poles of the electrolytic device is placed in an electrolytic cell at an interval of 5cm, and then electrolyzed for 5 hours or a predetermined time to precipitate silver (Ag) to deposit silver nano solution. After preparing 100,000g of silver solution or 1,000g of silver content 제 2공정(폴리애스테르 제조) 에치렌클리콜 1,000g 비율로 제 1공정의 은 용액 100g을 넣고 혼합믹스 하여 에치렌글리콜 은항균 조성물을 제조한 다음 테레프탈산과 에치렌글리콜 은항균조성 물 각각 1,2 몰을 반응기에 주입하고 질소기류 하에 처음에는 260°c 의 온도에서 진행 시킨 후에 300°c에서 약 15분 간 진공도를 점차 올리고 반응 혼합물 0.1로드에서 25분간 유지시키면서 촉매로 산화 디알킬주석을 주입하여 반응 후에 냉각시켜 제조함을 특징으로 하는 폴리에스테르 중합방법Second process (polyester production) Ethyren glycol silver antibacterial composition was prepared by mixing 100 g of the silver solution of the first process at a ratio of 1,000 g of ethylene glycol and preparing an ethylene glycol antibacterial composition, and then terephthalic acid and ethylene glycol antimicrobial composition 1, 2 moles were introduced into the reactor and initially run at a temperature of 260 ° C. under a nitrogen stream, then gradually increasing the vacuum at 300 ° C. for about 15 minutes and injecting dialkyltin oxide into the catalyst while maintaining the reaction mixture at 0.1 rod for 25 minutes. Polyester polymerization method characterized by cooling after the reaction
KR1020110069436A 2011-07-12 2011-07-12 The methode silver antibacteries polymerization KR20130008431A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108912696A (en) * 2018-04-11 2018-11-30 杭州牛墨科技有限公司 A kind of graphene/nanometer composite fiber membrane and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108912696A (en) * 2018-04-11 2018-11-30 杭州牛墨科技有限公司 A kind of graphene/nanometer composite fiber membrane and preparation method thereof

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