KR101157527B1 - Photocatalytic thermo-responsive 3-dimensional copolymer and fabricating method of the same - Google Patents
Photocatalytic thermo-responsive 3-dimensional copolymer and fabricating method of the same Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 12
- 230000001699 photocatalysis Effects 0.000 title 1
- 239000011941 photocatalyst Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000011557 critical solution Substances 0.000 claims abstract description 18
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 10
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 10
- 150000004032 porphyrins Chemical class 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 6
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 claims description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 5
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 5
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 5
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 5
- 150000004056 anthraquinones Chemical class 0.000 claims description 5
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 5
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims description 5
- 229960002143 fluorescein Drugs 0.000 claims description 5
- 229940097275 indigo Drugs 0.000 claims description 5
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 5
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 claims description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 5
- 229940012189 methyl orange Drugs 0.000 claims description 5
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 5
- 229940043267 rhodamine b Drugs 0.000 claims description 5
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims description 5
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 5
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 claims description 3
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 3
- 239000012989 trithiocarbonate Substances 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000010865 sewage Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000011949 advanced processing technology Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
본 발명은 하폐수 내에 포함되어 있는 미량의 유해 화학물질을 효과적으로 분해, 제거할 수 있는 광촉매를 구비한 온도감응형 삼차원 공중합체 및 그 제조방법 에 관한 것으로서, 본 발명에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체는 코어 영역과 쉘 영역으로 이루어지며, 상기 코어 영역은 광촉매를 중심으로 소수성 고분자가 광촉매를 둘러싸고 있는 구조로 구성되고, 상기 쉘 영역은 양친성 고분자로 구성되며, 상기 양친성 고분자는 용액 내에서 상기 용액이 임계용액온도보다 낮으면 친수성을 띠고, 상기 용액이 임계용액온도보다 높으면 소수성을 띠며, 상기 광촉매는 광조사에 의해 활성산소를 생성하여 상기 코어 영역의 포집 영역에 포집된 유기성 유해물질을 분해하는 것을 특징으로 한다. The present invention relates to a temperature-sensitive three-dimensional copolymer having a photocatalyst capable of effectively decomposing and removing a small amount of harmful chemicals contained in sewage water, and a method of manufacturing the same. The three-dimensional copolymer is composed of a core region and a shell region, the core region is composed of a structure in which a hydrophobic polymer surrounds the photocatalyst around the photocatalyst, the shell region is composed of an amphiphilic polymer, the amphiphilic polymer is a solution The solution is hydrophilic when the solution temperature is lower than the critical solution temperature, hydrophobic when the solution is higher than the critical solution temperature, and the photocatalyst generates active oxygen by light irradiation to collect organic harmful substances in the trapping region of the core region. It is characterized by decomposing the substance.
Description
본 발명은 광촉매를 구비한 온도감응형 삼차원 공중합체 및 그 제조방법에 관한 것으로서, 보다 상세하게는 하폐수 내에 포함되어 있는 미량의 유해 화학물질을 효과적으로 분해, 제거할 수 있는 광촉매를 구비한 온도감응형 삼차원 공중합체 및 그 제조방법에 관한 것이다.
The present invention relates to a temperature-sensitive three-dimensional copolymer having a photocatalyst and a method of manufacturing the same, and more particularly, to a temperature-sensitive type having a photocatalyst capable of effectively decomposing and removing a small amount of harmful chemicals contained in sewage water. It relates to a three-dimensional copolymer and a method for producing the same.
하폐수 내에는 질소, 인 등의 생물학적 영양염류 외에도 벤젠(Benzene), 톨루엔(Toluene), 에틸벤젠(Etylbenzene), 크실렌(Xylene) 등의 미량의 유해 화학물질이 존재하는데, 이와 같은 미량의 유기성 유해물질은 질소, 인 제거를 위한 생물학적 하수처리공법을 통해서는 제거되지 않는 특성이 있다. 또한, 무기 산화물 광촉매를 이용하여 하폐수 내에 잔존하는 미량의 유기물을 분해, 정화하는 기술이 제시된 바 있으나 이 역시 벤젠, 톨루엔 등과 같은 발암성이 있는 물질은 제거되지 않는 단점이 있다. In addition to biological nutrients such as nitrogen and phosphorus, sewage wastes contain trace amounts of hazardous chemicals such as benzene, toluene, ethylbenzene, and xylene. Is characteristic that is not removed through biological sewage treatment method for nitrogen and phosphorus removal. In addition, there has been a technique for decomposing and purifying a small amount of organic matter remaining in the wastewater by using an inorganic oxide photocatalyst, but this also has a disadvantage in that carcinogenic substances such as benzene and toluene are not removed.
현재, 4만 여종의 화학물질이 국내에서 유통되고 있으며 매년 200여종의 신규 화학물질이 국내 시장에 진입하고 있다. 이에 따라, 하폐수에 유입되는 유해 화학물질의 종류뿐만 아니라 그 양도 증가하고 있다. 이러한 유해 화학물질을 제거하기 위해 오존산화공정 등과 같은 고도처리기술이 적용되고 있지만 분해된 후 부산물을 발생시켜 2차 오염을 일으키는 문제점이 있다. 따라서, 부산물 생성으로 인한 2차 오염을 일으키지 않으면서 유기성 유해물질을 효과적으로 분해, 제거할 수 있는 기술의 개발이 시급하다.
Currently, about 40,000 chemicals are distributed in Korea, and about 200 new chemicals enter the domestic market every year. As a result, not only the types of harmful chemicals flowing into sewage water, but also their amounts are increasing. In order to remove such harmful chemicals, advanced processing technologies such as ozone oxidation process are applied, but there is a problem of generating secondary by-products after decomposition. Therefore, it is urgent to develop a technology that can effectively decompose and remove organic harmful substances without causing secondary pollution due to the generation of by-products.
본 발명은 상기와 같은 문제점을 해결하기 위해 안출한 것으로서, 하폐수 내에 포함되어 있는 미량의 유해 화학물질을 효과적으로 분해, 제거할 수 있는 광촉매를 구비한 온도감응형 삼차원 공중합체 및 그 제조방법을 제공하는데 그 목적이 있다.
The present invention has been made to solve the above problems, to provide a temperature-sensitive three-dimensional copolymer having a photocatalyst capable of effectively decomposing and removing the trace amount of harmful chemicals contained in the sewage water and a method for producing the same. The purpose is.
상기의 목적을 달성하기 위한 본 발명에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체는 코어 영역과 쉘 영역으로 이루어지며, 상기 코어 영역은 광촉매를 중심으로 소수성 고분자가 광촉매를 둘러싸고 있는 구조로 구성되고, 상기 쉘 영역은 양친성 고분자로 구성되며, 상기 양친성 고분자는 용액 내에서 상기 용액이 임계용액온도보다 낮으면 친수성을 띠고, 상기 용액이 임계용액온도보다 높으면 소수성을 띠며, 상기 광촉매는 광조사에 의해 활성산소를 생성하여 상기 코어 영역의 포집 영역에 포집된 유기성 유해물질을 분해하는 것을 특징으로 한다. The temperature-sensitive three-dimensional copolymer with a photocatalyst according to the present invention for achieving the above object consists of a core region and a shell region, the core region is composed of a structure in which a hydrophobic polymer surrounds the photocatalyst around the photocatalyst The shell region is composed of an amphiphilic polymer, the amphiphilic polymer is hydrophilic when the solution is lower than the critical solution temperature in the solution, hydrophobic when the solution is higher than the critical solution temperature, the photocatalyst is light irradiation By generating active oxygen by decomposing the organic harmful substances collected in the capture region of the core region.
상기 광촉매는 포르피린 복합체(porphyrin complex), Xanthene, Thiazine, Anthraquinone, Triphenylmethane, Phthalocyanine, Indigo, Quinoline, Phenanthrene, Thionine, Eosin Y, Methyl Orange, Rhodamine B, Methylene Blue, Fluorescein 중 어느 하나가 사용될 수 있으며, 상기 소수성 고분자로는 폴리스티렌(polystyrene) 유도체, 폴리아크릴레이트(polyacrylates) 유도체, 폴리메타아크릴레이트(polymethacrylates) 유도체 중 어느 하나가 이용될 수 있다. 또한, 양친성 고분자는 N-Alkylacrylamide 유도체, Poly(vinyl ether), Poly(vinyl methyl ether) 중 어느 하나 형태의 폴리머로 구성될 수 있으며, 구체적으로 P(NIPAm)(Poly(N-isopropyl acrylamide))일 수 있다.The photocatalyst may be any one of porphyrin complex, Xanthene, Thiazine, Anthraquinone, Triphenylmethane, Phthalocyanine, Indigo, Quinoline, Phenanthrene, Thionine, Eosin Y, Methyl Orange, Rhodamine B, Methylene Blue, Fluorescein, As the hydrophobic polymer, any one of a polystyrene derivative, a polyacrylate derivative, and a polymethacrylate derivative may be used. In addition, the amphiphilic polymer may be composed of any one type of polymer of N-Alkylacrylamide derivative, Poly (vinyl ether), Poly (vinyl methyl ether), specifically P (NIPAm) (Poly (N-isopropyl acrylamide)) Can be.
본 발명에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체의 제조방법은 광촉매와 단분자를 분자량조절제와 반응시켜 광촉매를 소수성 고분자가 둘러쌓은 형태를 갖는 코어 영역을 형성하는 단계 및 상기 코어 영역의 둘레 양친성 고분자로 구성되는 쉘 영역을 형성하는 단계를 포함하여 이루어지며, 상기 양친성 고분자는 용액 내에서 상기 용액이 임계용액온도보다 낮으면 친수성을 띠고, 상기 용액이 임계용액온도보다 높으면 소수성을 띠는 것을 특징으로 한다. 상기 분자량조절제의 혼합량은 상기 포집 영역의 크기와 반비례하며, 상기 분자량조절제는 CTT(carboxyl terminated trithiocarbonates)일 수 있다.
Method for producing a temperature-sensitive three-dimensional copolymer with a photocatalyst according to the present invention is a step of forming a core region having a form in which the photocatalyst is surrounded by a hydrophobic polymer by reacting the photocatalyst and a single molecule with a molecular weight regulator and the circumference of the core region And forming a shell region composed of an amphiphilic polymer, wherein the amphiphilic polymer is hydrophilic when the solution is lower than the critical solution temperature in the solution, and hydrophobic when the solution is higher than the critical solution temperature. Characterized in that. The amount of the molecular weight modifier is inversely proportional to the size of the capture region, and the molecular weight modifier may be carboxyl terminated trithiocarbonates (CTT).
본 발명에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체 및 그 제조방법은 다음과 같은 효과가 있다. The temperature-sensitive three-dimensional copolymer with a photocatalyst according to the present invention and a method of manufacturing the same have the following effects.
임계용해온도에 따른 친수성 및 소수성 특성 및 광촉매에 의한 유해물질 분해 특성을 통해 유기성 유해물질의 포집 및 제거가 용이하다.
It is easy to collect and remove organic harmful substances through hydrophilicity and hydrophobicity according to critical melting temperature and decomposition of harmful substances by photocatalyst.
도 1은 본 발명의 일 실시예에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체를 나타낸 구성도.
도 2는 본 발명의 일 실시예에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체의 제조방법을 나타낸 모식도. 1 is a block diagram showing a temperature-sensitive three-dimensional copolymer having a photocatalyst according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing a method for producing a temperature-sensitive three-dimensional copolymer with a photocatalyst according to an embodiment of the present invention.
이하, 도면을 참조하여 본 발명의 일 실시예에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체 및 그 제조방법을 상세히 설명하기로 한다. Hereinafter, with reference to the drawings will be described in detail a temperature-sensitive three-dimensional copolymer with a photocatalyst according to an embodiment of the present invention and a method of manufacturing the same.
먼저, 본 발명의 일 실시예에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체를 설명하기로 한다. First, a temperature-sensitive three-dimensional copolymer having a photocatalyst according to an embodiment of the present invention will be described.
본 발명의 일 실시예에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체는 도 1에 도시한 바와 같이 코어(core) 영역과 쉘(shell) 영역으로 구성된다. 상기 코어 영역은 광촉매와 소수성 고분자로 이루어지고, 상기 쉘 영역은 양친성 고분자로 이루어진다. 이 때, 상기 코어 영역은 광촉매를 중심으로 소수성 고분자가 광촉매를 둘러쌓은 구조로 이룬다. 또한, 상기 코어 영역의 빈 공간은 포집 영역으로 정의된다. The temperature-sensitive three-dimensional copolymer with a photocatalyst according to an embodiment of the present invention is composed of a core region and a shell region as shown in FIG. 1. The core region consists of a photocatalyst and a hydrophobic polymer, and the shell region consists of an amphiphilic polymer. At this time, the core region has a structure in which a hydrophobic polymer surrounds the photocatalyst with respect to the photocatalyst. In addition, the empty space of the core region is defined as a collecting region.
상기 광촉매는 가시광선 또는 자외선이 조사되는 경우 활성산소(singlet oxygen)를 생성하여, 코어 영역의 포집 영역에 포집되는 유기성 유해물질을 이산화탄소(CO2), 물(H2O)로 분해하는 역할을 한다. The photocatalyst generates active oxygen when visible or ultraviolet rays are irradiated, and decomposes organic harmful substances collected in the capture region of the core region into carbon dioxide (CO 2 ) and water (H 2 O). do.
상기 광촉매는 포르피린 복합체(porphyrin complex), Xanthene, Thiazine, Anthraquinone, Triphenylmethane, Phthalocyanine, Indigo, Quinoline, Phenanthrene, Thionine, Eosin Y, Methyl Orange, Rhodamine B, Methylene Blue, Fluorescein 중 어느 하나가 사용될 수 있다. 또한, 상기 소수성 고분자는 폴리스티렌(polystyrene) 유도체, 폴리아크릴레이트(polyacrylates) 유도체, 폴리메타아크릴레이트(polymethacrylates) 유도체 중 어느 하나로 구성될 수 있다. The photocatalyst may be any one of porphyrin complex, Xanthene, Thiazine, Anthraquinone, Triphenylmethane, Phthalocyanine, Indigo, Quinoline, Phenanthrene, Thionine, Eosin Y, Methyl Orange, Rhodamine B, Methylene Blue, Fluorescein. In addition, the hydrophobic polymer may be composed of any one of a polystyrene derivative, a polyacrylate derivative, a polymethacrylate derivative.
한편, 상기 쉘 영역을 구성하는 양친성 고분자는 N-Alkylacrylamide 유도체, Poly(vinyl ether), Poly(vinyl methyl ether) 중 어느 하나 형태의 폴리머로 구성될 수 있으며, 구체적으로 P(NIPAm)(Poly(N-isopropyl acrylamide))일 수 있다. 상기 양친성 고분자라 함은 친수성과 소수성을 모두 띠는 고분자를 일컬으며, 본 발명에 있어서 상기 양친성 고분자는 온도에 따라 친수성 또는 소수성을 갖는다. 즉, 상기 양친성 고분자는 임계용액온도(lower critical solution temperature) 이상에서는 소수성을 띠고, 임계용액온도 이하에서는 친수성을 띤다. On the other hand, the amphiphilic polymer constituting the shell region may be composed of any one type of polymer of N-Alkylacrylamide derivative, Poly (vinyl ether), Poly (vinyl methyl ether), specifically P (NIPAm) (Poly ( N-isopropyl acrylamide)). The amphiphilic polymer refers to a polymer having both hydrophilicity and hydrophobicity. In the present invention, the amphiphilic polymer has hydrophilicity or hydrophobicity depending on temperature. In other words, the amphiphilic polymer has hydrophobicity above a critical solution temperature and hydrophilic below a critical solution temperature.
이와 같은 양친성 고분자의 임계용액온도에 따른 친수성, 소수성 특성은 유해물질의 포집 및 삼차원 공중합체의 회수에 이용된다. 구체적으로, 임계용액온도 이하의 용액에서 상기 양친성 고분자는 친수성을 띠게 되며 삼차원 공중합체는 코어 영역과 쉘 영역이 각각 소수성, 친수성을 이룬 상태에서 용액 내에서 부유하게 되며, 이와 같은 상태에서 소수성을 갖는 유해물질이 자유에너지를 낮추기 위해 소수성을 갖는 삼차원 공중합체의 코어 영역으로 이동되어 궁극적으로, 코어 영역의 빈 공간인 포집 영역에 포집된다. 유해물질이 포집 영역에 포집된 상태에서 전술한 바와 같은 광촉매에 의한 분해 반응을 진행할 수 있다. 또한, 임계용액온도 이상의 용액에서 상기 양친성 고분자는 소수성을 띠게 되며 이에 따라, 삼차원 공중합체는 용액 내에서 침전되고 침전된 삼차원 공중합체는 간단한 여과 등을 통해 회수할 수 있다. 참고로, 상기 임계용액온도는 양친성 고분자를 구성하는 물질에 따라 가변적이며, 본 발명에 있어서 임계용액온도는 폐수의 온도보다 높아야 하며 이를 만족하는 물질로 상기 양친성 고분자가 구성되어야 한다. 양친성 고분자가 P(NIPAm)로 구성되는 경우 임계용액온도는 32℃이다. Such hydrophilic and hydrophobic properties according to the critical solution temperature of the amphiphilic polymer is used for the collection of harmful substances and recovery of the three-dimensional copolymer. Specifically, the amphiphilic polymer is hydrophilic in a solution below the critical solution temperature, and the three-dimensional copolymer is suspended in the solution in a state where the core region and the shell region are hydrophobic and hydrophilic, respectively. In order to lower the free energy, the harmful substances are transferred to the core region of the hydrophobic three-dimensional copolymer and are ultimately collected in the empty region of the core region. The decomposition reaction by the photocatalyst as described above may be performed in the state in which the hazardous substances are collected in the collection region. In addition, the amphiphilic polymer becomes hydrophobic in a solution above the critical solution temperature, and thus, the three-dimensional copolymer is precipitated in the solution and the precipitated three-dimensional copolymer can be recovered through simple filtration. For reference, the critical solution temperature is variable according to the material constituting the amphiphilic polymer, in the present invention, the critical solution temperature should be higher than the temperature of the waste water and the amphiphilic polymer should be composed of a material satisfying this. If the amphiphilic polymer consists of P (NIPAm), the critical solution temperature is 32 ° C.
이상, 본 발명의 일 실시예에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체에 대해 설명하였다. 다음으로, 본 발명의 일 실시예에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체의 제조방법을 설명하기로 한다. 본 발명의 일 실시예에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체의 제조방법은 크게 코어 영역 형성단계 및 쉘 영역 형성단계의 순서로 진행된다. 도 2는 본 발명의 일 실시예에 따른 광촉매를 구비한 온도감응형 삼차원 공중합체의 제조방법을 나타낸 모식도이다. In the above, the temperature-sensitive three-dimensional copolymer with a photocatalyst according to an embodiment of the present invention has been described. Next, a method of manufacturing a temperature-sensitive three-dimensional copolymer having a photocatalyst according to an embodiment of the present invention will be described. Method for producing a temperature-sensitive three-dimensional copolymer with a photocatalyst according to an embodiment of the present invention proceeds in the order of the core region forming step and the shell region forming step. Figure 2 is a schematic diagram showing a method for producing a temperature-sensitive three-dimensional copolymer with a photocatalyst according to an embodiment of the present invention.
먼저, 코어 영역 형성단계는 광촉매와 단분자를 분자량조절제(chain transfer agent)를 반응시켜 광촉매의 둘레를 따라 소수성 고분자를 형성하는 단계이다. 상기 광촉매로는 포르피린 복합체(porphyrin complex), Xanthene, Thiazine, Anthraquinone, Triphenylmethane, Phthalocyanine, Indigo, Quinoline, Phenanthrene, Thionine, Eosin Y, Methyl Orange, Rhodamine B, Methylene Blue, Fluorescein 중 어느 하나가 사용될 수 있으며, 상기 소수성 고분자로는 폴리스티렌(polystyrene) 유도체, 폴리아크릴레이트(polyacrylates) 유도체, 폴리메타아크릴레이트(polymethacrylates) 유도체 중 어느 하나가 이용될 수 있다. 또한, 상기 분자량조절제로는 CTT(carboxyl terminated trithiocarbonates)가 이용될 수 있다. 단분자로 스티렌을 이용하는 경우 상기 코어 영역을 구성하는 소수성 고분자로 폴리스티렌(polystyrene)을 형성할 수 있다. 이 때, 상기 분자량조절제를 통해 코어 영역의 분자량을 조절할 수 있으며, 이를 통해 코어 영역 내 포집 영역의 크기를 조절할 수 있다. 참고로, 분자량조절제의 투입량과 포집 영역의 크기는 반비례 관계를 갖는다. First, the core region forming step is a step of forming a hydrophobic polymer along the circumference of the photocatalyst by reacting a photocatalyst and a single molecule with a chain transfer agent. The photocatalyst may be any one of porphyrin complex (porphyrin complex), Xanthene, Thiazine, Anthraquinone, Triphenylmethane, Phthalocyanine, Indigo, Quinoline, Phenanthrene, Thionine, Eosin Y, Methyl Orange, Rhodamine B, Methylene Blue, Fluorescein, As the hydrophobic polymer, any one of a polystyrene derivative, a polyacrylate derivative, and a polymethacrylate derivative may be used. In addition, carboxyl terminated trithiocarbonates (CTT) may be used as the molecular weight modifier. When styrene is used as a single molecule, polystyrene may be formed of a hydrophobic polymer constituting the core region. At this time, the molecular weight of the core region can be controlled through the molecular weight regulator, and through this, the size of the trapping region in the core region can be controlled. For reference, the dose of the molecular weight regulator and the size of the trapping region have an inverse relationship.
광촉매와 소수성 고분자로 구성된 코어 영역이 형성된 상태에서, 쉘 영역 형성단계를 진행한다. 구체적으로, 상기 코어 영역을 이루는 복합체 즉, 광촉매와 소수성 고분자의 복합체에 NIPAm(N-isopropyl acrylamide)을 혼합한 다음, RAFT(reversible addition-fragmentation chain-transfer) 반응을 통해 P(NIPAm)(poly-NIPAm)로 이루어지는 쉘 영역의 고분자를 형성한다. 이 때, 상기 NIPAm의 혼합량을 통해 P(NIPAm)의 분자량을 조절할 수 있으며, P(NIPAm)의 분자량이 커질수록 친수성시 용해도가 커진다. In the state where the core region composed of the photocatalyst and the hydrophobic polymer is formed, the shell region forming step is performed. Specifically, N-isopropyl acrylamide (NIPAm) is mixed in a complex constituting the core region, that is, a photocatalyst and a hydrophobic polymer complex, and then P (NIPAm) (poly-) through a reversible addition-fragmentation chain-transfer (RAFT) reaction. The polymer of the shell region which consists of NIPAm) is formed. At this time, the molecular weight of P (NIPAm) can be adjusted through the mixed amount of the NIPAm, the higher the molecular weight of P (NIPAm), the greater the solubility in hydrophilicity.
Claims (12)
상기 코어 영역은 광촉매를 중심으로 소수성 고분자가 광촉매를 둘러싸고 있는 구조로 구성되고, 상기 쉘 영역은 양친성 고분자로 구성되며,
상기 양친성 고분자는 용액 내에서 상기 용액이 임계용액온도보다 낮으면 친수성을 띠고, 상기 용액이 임계용액온도보다 높으면 소수성을 띠며,
상기 광촉매는 광조사에 의해 활성산소를 생성하여 상기 코어 영역의 포집 영역에 포집된 유기성 유해물질을 분해하는 것을 특징으로 하는 광촉매를 구비한 온도감응형 삼차원 공중합체.
It consists of a core region and a shell region,
The core region is composed of a structure in which a hydrophobic polymer surrounds the photocatalyst around the photocatalyst, and the shell region is composed of an amphiphilic polymer,
The amphiphilic polymer is hydrophilic when the solution is lower than the critical solution temperature in the solution, hydrophobic when the solution is higher than the critical solution temperature,
The photocatalyst is a temperature-sensitive three-dimensional copolymer with a photocatalyst, characterized in that to generate active oxygen by light irradiation to decompose organic harmful substances collected in the capture region of the core region.
According to claim 1, The photocatalyst is any one of porphyrin complex (porphyrin complex), Xanthene, Thiazine, Anthraquinone, Triphenylmethane, Phthalocyanine, Indigo, Quinoline, Phenanthrene, Thionine, Eosin Y, Methyl Orange, Rhodamine B, Methylene Blue, Fluorescein A temperature sensitive three-dimensional copolymer with a photocatalyst, characterized in that.
The method of claim 1, wherein the amphiphilic polymer of the shell region is a temperature-sensitive three-dimensional air with a photocatalyst, characterized in that the polymer of any one type of N-Alkylacrylamide, Poly (vinyl ether), Poly (vinyl methyl ether). coalescence.
The method of claim 1, wherein the amphiphilic polymer of the shell region is P (NIPAm) (Poly (N-isopropyl acrylamide)) temperature-sensitive three-dimensional copolymer with a photocatalyst, characterized in that.
상기 코어 영역의 둘레 양친성 고분자로 구성되는 쉘 영역을 형성하는 단계를 포함하여 이루어지며,
상기 양친성 고분자는 용액 내에서 상기 용액이 임계용액온도보다 낮으면 친수성을 띠고, 상기 용액이 임계용액온도보다 높으면 소수성을 띠는 것을 특징으로 하는 광촉매를 구비한 온도감응형 삼차원 공중합체의 제조방법.
Reacting the photocatalyst and a single molecule with a molecular weight modifier to form a core region having a form in which the photocatalyst is surrounded by a hydrophobic polymer; And
Forming a shell region composed of a circumferential amphiphilic polymer of the core region,
The amphiphilic polymer is hydrophilic when the solution is lower than the critical solution temperature in the solution, and hydrophobic when the solution is higher than the critical solution temperature, the method of producing a temperature-sensitive three-dimensional copolymer with a photocatalyst, characterized in that .
According to claim 6, The photocatalyst is any one of porphyrin complex (porphyrin complex), Xanthene, Thiazine, Anthraquinone, Triphenylmethane, Phthalocyanine, Indigo, Quinoline, Phenanthrene, Thionine, Eosin Y, Methyl Orange, Rhodamine B, Methylene Blue, Fluorescein Process for producing a temperature-sensitive three-dimensional copolymer with a photocatalyst, characterized in that.
The method of claim 6, wherein the amount of the molecular weight modifier is inversely proportional to the size of the trapping region in the core region.
The method of claim 6, wherein the molecular weight modifier is CTT (carboxyl terminated trithiocarbonates).
The method of claim 6, wherein the amphiphilic polymer is made of P (NIPAm).
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| US9447239B2 (en) | 2012-03-19 | 2016-09-20 | Samsung Electronics Co., Ltd. | Thermosensitive copolymers, forward osmosis water treatment devices including the same, and methods of producing and using the same |
| KR102132494B1 (en) | 2013-06-18 | 2020-07-09 | 충남대학교산학협력단 | Glycol chitin derivatives having temperature-sensitive sol-gel transition, a preparation method thereof and hydrogel prepared therefrom |
| CN104741048B (en) * | 2015-03-27 | 2017-05-03 | 东华大学 | Preparation method of N-isopropyl acrylamide red gel microspheres |
| KR102290665B1 (en) * | 2018-02-28 | 2021-08-19 | 단국대학교 산학협력단 | Water collecting sheet, method for producing the same, and water collecting apparatus including the same |
| CN109292953B (en) * | 2018-10-24 | 2020-07-10 | 湖南大学 | Method for treating antibiotics by using ferriporphyrin-flaky bismuth tungstate two-dimensional composite material |
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| JP2002265613A (en) | 2001-03-07 | 2002-09-18 | Kawamura Inst Of Chem Res | Star-shaped polymer micelle including porphyrin |
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| KR20110065291A (en) | 2011-06-15 |
| KR20110065290A (en) | 2011-06-15 |
| KR101109147B1 (en) | 2012-02-16 |
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