KR100513604B1 - Novel Gemini Surfactants and Method for Preparing Mesoporous Materials Using the Same - Google Patents
Novel Gemini Surfactants and Method for Preparing Mesoporous Materials Using the Same Download PDFInfo
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- KR100513604B1 KR100513604B1 KR10-2002-0071571A KR20020071571A KR100513604B1 KR 100513604 B1 KR100513604 B1 KR 100513604B1 KR 20020071571 A KR20020071571 A KR 20020071571A KR 100513604 B1 KR100513604 B1 KR 100513604B1
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 56
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920000469 amphiphilic block copolymer Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000011514 reflex Effects 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WDVUXWDZTPZIIE-UHFFFAOYSA-N trichloro(2-trichlorosilylethyl)silane Chemical compound Cl[Si](Cl)(Cl)CC[Si](Cl)(Cl)Cl WDVUXWDZTPZIIE-UHFFFAOYSA-N 0.000 description 2
- ABDDAHLAEXNYRC-UHFFFAOYSA-N trichloro(trichlorosilylmethyl)silane Chemical compound Cl[Si](Cl)(Cl)C[Si](Cl)(Cl)Cl ABDDAHLAEXNYRC-UHFFFAOYSA-N 0.000 description 2
- FOQJQXVUMYLJSU-UHFFFAOYSA-N triethoxy(1-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)[Si](OCC)(OCC)OCC FOQJQXVUMYLJSU-UHFFFAOYSA-N 0.000 description 2
- DJYGUVIGOGFJOF-UHFFFAOYSA-N trimethoxy(trimethoxysilylmethyl)silane Chemical compound CO[Si](OC)(OC)C[Si](OC)(OC)OC DJYGUVIGOGFJOF-UHFFFAOYSA-N 0.000 description 2
- MAFQBSQRZKWGGE-UHFFFAOYSA-N trimethoxy-[2-[4-(2-trimethoxysilylethyl)phenyl]ethyl]silane Chemical compound CO[Si](OC)(OC)CCC1=CC=C(CC[Si](OC)(OC)OC)C=C1 MAFQBSQRZKWGGE-UHFFFAOYSA-N 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- ZXFNVHQEUQDKSZ-UHFFFAOYSA-N dimethyl(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[SiH](C)C ZXFNVHQEUQDKSZ-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- KNYWDHFOQZZIDQ-UHFFFAOYSA-N trimethoxy-(2-trimethoxysilylphenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1[Si](OC)(OC)OC KNYWDHFOQZZIDQ-UHFFFAOYSA-N 0.000 description 1
- YIRZROVNUPFFNZ-UHFFFAOYSA-N trimethoxy-(4-trimethoxysilylphenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=C([Si](OC)(OC)OC)C=C1 YIRZROVNUPFFNZ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
본 발명은 새로운 제미니형 계면활성제 및 이를 이용한 메조포러스 물질의 제조방법에 관한 것으로, 보다 상세하게는 하기 화학식 1로 표시되는 제미니형 계면활성제 및 이를 구조 유도체로 이용한 메조포러스 물질의 제조방법에 관한 것이며, 본 발명에 의하여 10 nm 이하의 기공들이 균일하게 분포된 메조포러스 물질을 제공할 수 있다.The present invention relates to a new gemini-type surfactant and a method for producing a mesoporous material using the same, and more particularly, to a method for producing a mesoporous material using the Gemini-type surfactant represented by the following formula (1) and a structural derivative thereof According to the present invention, it is possible to provide a mesoporous material in which pores of 10 nm or less are uniformly distributed.
[화학식 1] [Formula 1]
상기 식에서 R1 및 R2는 각각 독립적으로 메틸 또는 에틸기이고, R3는 탄소수 5∼40의 알킬기이며, X는 할로겐 원자이고, r은 각각 독립적으로 수소원자, 메틸기 또는 탄소수 1∼10의 알콕시이며, n은 1∼12의 정수이고, m은 0∼10의 정수이다.Wherein R 1 and R 2 are each independently a methyl or ethyl group, R 3 is an alkyl group having 5 to 40 carbon atoms, X is a halogen atom, and r is each independently a hydrogen atom, a methyl group or alkoxy having 1 to 10 carbon atoms and n is an integer of 1-12, m is an integer of 0-10.
Description
본 발명은 새로운 계면활성제 및 이를 이용한 메조포러스 물질의 제조방법에 관한 것으로, 보다 상세하게는 실록산기가 포함된 새로운 제미니형 계면활성제 (gemini surfactant) 및 이를 구조 유도체(structure-directing agent)로 이용하여 10 nm 이하의 기공이 규칙적으로 배열된 메조포러스(mesoporous) 물질을 제조하는 방법에 관한 것이다.The present invention relates to a new surfactant and a method for producing a mesoporous material using the same, and more particularly, to a novel gemini surfactant containing a siloxane group and a structure-directing agent. It relates to a method for producing mesoporous (mesoporous) material in which sub-nm pores are regularly arranged.
1991년도에 모빌(Mobil)사의 연구진에 의하여 구조유도체로 이온성 계면활성제(ionic surfactants)를 이용하여 제조된 M41S 군(M41S family)이라고 명명된 새로운 형태의 메조포러스 분자체(mesoporous molecular sieve) 물질들이 미합중국 특허 제5,057,296호 및 제5,102,643호 등에 발표된 이래로, 이러한 메조포러스 분자체 물질에 대한 연구가 현재 전세계적으로 활발히 진행되고 있다. 메조포러스 물질은 기존의 제올라이트나 AlPO 계통의 물질과 같이 기공의 크기가 1.5 nm 이하인 미세기공성(microporous) 물질과는 달리 그 기공의 크기를 중형기공(mesopore)의 범위(2∼50 nm)로 확장시킴으로써 그 동안 분자체 물질의 응용에 있어서 제한이 되어왔던, 예를 들면 미세기공성 물질의 기공 크기보다 큰 크기를 갖는 분자들의 흡착 및 분리, 촉매전환 반응 등에 대한 분자체 물질의 응용이 가능하게 되었다. 모빌사에서 발표한 M41S 군에는, 일차원의 메조포러스 기공이 벌집과 같은 육방 배열(hexagonal array)을 이루고 있는 MCM-41 물질과 메조포러스 기공이 1a3d의 입방구조(cubic structure)의 배열로 연결되어 있는 MCM-48 물질이 있다. 미합중국 특허 제6,027,706호, 제6,054,111호 및 1998년 Science지, volume 279, page 548에서는 중성계열의 계면활성제(nonionic surfactants)인 양친성 블럭 공중합체In 1991, a new form of mesoporous molecular sieve material, named M41S family, was produced by Mobil's team using ionic surfactants as structural derivatives. Since the publication of US Pat. Nos. 5,057,296 and 5,102,643, and the like, research on such mesoporous molecular sieve materials is now actively conducted worldwide. Mesoporous materials, unlike microporous materials whose pore size is 1.5 nm or less, like those of conventional zeolite or AlPO-based materials, extend the pore size to the mesopore range (2-50 nm). This enables the application of molecular sieve materials to adsorption and separation of molecules having a size larger than the pore size of microporous materials, catalytic conversion reactions, and the like, which have been limited in the application of molecular sieve materials. In the M41S family announced by Mobil, one-dimensional mesoporous pores are composed of a hexagonal array of MCM-41 and mesoporous pores connected in a cubic structure of 1a3d. There is an MCM-48 material. U.S. Pat.Nos. 6,027,706, 6,054,111 and 1998, Science Volume 279, page 548 describe amphiphilic block copolymers that are nonionic surfactants.
(amphiphilic block copolymers)를 이용하여 제조된 메조포러스 물질이 개시되어 있다. 1995년 Science지, volume 8, page 1324 및 1996년 Chemistry of Materials지, volume 8, page 1147에서는 제미니형 계면활성제(gemini surfactants)를 사용한 메조포러스 물질의 제조가 발표되었다. 이러한 규칙적인 기공을 가지는 메조포러스 물질은 표면적이 매우 커서 원자나 분자의 흡착특성이 우수하고, 기공의 크기가 일정함으로써 분자를 거르는 체, 즉 분자체(molecular sieve) 등으로 응용할 수 있을 뿐 아니라 전도성 재료, 광 디스플레이 재료, 화학센서, 정밀화학 및 생체 촉매(bio-catalysis), 새로운 기계적, 열적 성질의 절연체 및 패키징 재료로의 응용 등 많은 응용분야가 기대된다.A mesoporous material prepared using amphiphilic block copolymers is disclosed. The production of mesoporous materials using gemini surfactants was published in the 1995 Science, volume 8, page 1324 and 1996 Chemistry of Materials, volume 8, page 1147. The mesoporous material having such regular pores has a very large surface area, which is excellent in adsorption characteristics of atoms or molecules, and the size of the pores is constant, so that the mesoporous material can be applied as a sieve for filtering molecules, that is, as a molecular sieve. Many applications are expected, including materials, optical display materials, chemical sensors, fine chemicals and bio-catalysis, and new mechanical and thermal insulators and packaging materials.
메조포러스 물질의 설계 및 합성에 있어서 가장 중요한 요인 중의 하나는 구조유도체이다. 기존에 메조포러스 물질을 제조하는데 구조유도체로서 주로 사용된 계면활성제는 하나의 소수성기와 친수성기를 갖는 일반적인 형태의 계면활성제였는데 비해, 본 발명에서 추구하고자 하는 계면활성제는 친수성 부분에 두 개 또는 세 개의 이온성 부분을 갖고 여러 개의 소수성 알킬 사슬을 갖는 제미니형 계면활성제로 특히 이온성 부분 중간에 실록산기를 함유시킨 형태이다.One of the most important factors in the design and synthesis of mesoporous materials is the structural derivatives. Conventionally, the surfactant mainly used as a structural derivative for preparing mesoporous material was a general type of surfactant having one hydrophobic group and a hydrophilic group, whereas the surfactant to be pursued in the present invention has two or three ions in the hydrophilic part. Gemini-type surfactants having an acidic moiety and several hydrophobic alkyl chains, particularly those containing siloxane groups in the middle of the ionic moiety.
제미니형 계면활성제는 그 구조적인 특성으로 인해 매우 낮은 임계미셀농도Gemini surfactants have very low critical micelle concentrations due to their structural properties.
(critical micellar concentration)와 높은 표면장력 저하능, 우수한 기포력 및 유화력, 물에 대한 양호한 용해성과 내경수성 등 우수한 계면 물성을 나타내기 때문에 차세대 계면활성제로 인식되고 있는 물질로, 분자의 특성상 분자내 소수작용에 의하여 미셀 형성에 있어서 기존의 계면활성제보다 획기적인 특성을 갖는다. 전술한 바와 같이 제미니형 계면활성제는 1995년에 처음 메조포러스 물질의 제조에 구조유도체로 사용되어 다양한 구조의 메조포러스 물질들을 제조할 수 있다고 보고되었다. 그러나 그 이후에는 이에 대한 연구가 활발히 진행되지 못하고 있는데 이는 제미니형 계면활성제는 그 제조가 기존의 계면활성제에 비하여 용이하지 못한데 비해, 이를 구조 유도체로 사용하였을 때 얻어지는 메조포러스 물질의 물리적 특성이 기존의 메조포러스 물질과 유사한 정도이기 때문이다. 따라서 원하는 메조포러스 물질의 물리적 특성(특히 소수성 표면 특성 및 기공크기)을 부여하기 위해서는 제미니형 계면활성제의 설계 및 제조가 필요하다.It is recognized as a next-generation surfactant because it shows excellent interfacial properties such as critical micellar concentration, high surface tension lowering ability, excellent foaming and emulsifying ability, good solubility in water and water resistance. By action, the micelle formation has more innovative properties than conventional surfactants. As mentioned above, Gemini-type surfactants were first reported in 1995 to be used as structural derivatives in the preparation of mesoporous materials to produce mesoporous materials of various structures. However, since then, research on this has not been actively carried out, because the preparation of Gemini surfactants is not easy compared to conventional surfactants, whereas the physical properties of mesoporous materials obtained when using them as structural derivatives are This is because the degree is similar to mesoporous material. Therefore, in order to impart the desired physical properties (especially hydrophobic surface properties and pore size) of the mesoporous material, it is necessary to design and manufacture the Gemini type surfactant.
본 발명은 상기와 같은 종래기술의 문제점을 해결하기 위한 것으로 실록산 부분(siloxane mioety)이 포함된 새로운 구조의 제미니형 계면활성제를 제공하는 것을 목적으로 한다.The present invention is to solve the problems of the prior art as described above, and an object of the present invention is to provide a Gemini-type surfactant having a new structure including a siloxane mioety.
본 발명의 다른 목적은 상기 새로운 제미니형 계면활성제를 구조유도체로 이용하여 10 nm 이하의 기공이 균일하게 분포된 메조포러스(mesoporous) 물질을 제조하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing a mesoporous (mesoporous) material with uniformly distributed pores of 10 nm or less by using the new gemini-type surfactant as a structural derivative.
상기 목적을 달성하기 위한 본 발명의 하나의 측면은 하기 화학식 1로 표시되는 제미니형 계면활성제에 관한 것이다.One aspect of the present invention for achieving the above object relates to a Gemini type surfactant represented by the following formula (1).
[화학식 1] [Formula 1]
상기 식에서 R1 및 R2는 각각 독립적으로 메틸 또는 에틸기이고, R3는 탄소수 5∼40의 알킬기이며, X는 할로겐 원자이고, r은 각각 독립적으로 수소원자, 메틸기 또는 탄소수 1∼10의 알콕시이며, n은 1∼12의 정수이고, m은 0∼10의 정수이다.Wherein R 1 and R 2 are each independently a methyl or ethyl group, R 3 is an alkyl group having 5 to 40 carbon atoms, X is a halogen atom, and r is each independently a hydrogen atom, a methyl group or alkoxy having 1 to 10 carbon atoms and n is an integer of 1-12, m is an integer of 0-10.
본 발명의 다른 측면은 하기 화학식 2로 표시되는 물질 및 하기 화학식 3으로 표시되는 물질을 몰비 1:2∼1:3으로 혼합한 후, 용매로서 에탄올, 아세토니트릴 또는 톨루엔을 사용하여 반응온도 30~120℃에서 1~100시간 반응시켜 제미니형 계면활성제를 제조하는 방법에 관한 것이다.Another aspect of the present invention is a mixture of the material represented by the following formula (2) and the material represented by the following formula (3) in a molar ratio 1: 2 to 1: 3, using a reaction temperature of 30 ~ ethanol, acetonitrile or toluene as a solvent It is related with the method of manufacturing a gemini type surfactant by making it react at 120 degreeC for 1 to 100 hours.
[화학식 2] [Formula 2]
상기 식에서 X는 할로겐 원자이고, r은 각각 독립적으로 수소 원자, 메틸기 또는 탄소수 1∼10의 알킬기이며, n은 1∼12의 정수이고, m은 0∼10의 정수이다. In said formula, X is a halogen atom, r is respectively independently a hydrogen atom, a methyl group, or a C1-C10 alkyl group, n is an integer of 1-12, m is an integer of 0-10.
[화학식 3][Formula 3]
R3R2R1NR 3 R 2 R 1 N
상기 식에서 R1 및 R2는 각각 독립적으로 메틸기 또는 에틸기이고, R3는 탄소수 5∼40의 알킬기이다.In the above formula, R 1 and R 2 are each independently a methyl group or an ethyl group, and R 3 is an alkyl group having 5 to 40 carbon atoms.
본 발명의 또 다른 측면은 상기 제미니형 계면활성제를 구조유도체Another aspect of the invention the structure of the Gemini-type surfactant
(structure-directing agent)로 사용하여 메조포러스 물질을 제조하는 방법에 관한 것이다. It relates to a method for producing mesoporous material using as a (structure-directing agent).
이하에서 본 발명을 하기 첨부된 실시예를 참조하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to the following examples.
본 발명에서는 메조포러스 물질을 제조하기 위해서 구조유도체로서 실록산 부분(siloxane mioety)이 포함된, 하기의 화학식 1로 표시되는 제미니형 계면활성제를 제공한다. The present invention provides a gemini-type surfactant represented by the following Chemical Formula 1 including a siloxane mioety as a structural derivative to prepare a mesoporous material.
상기 식에서 R1 및 R2는 각각 독립적으로 메틸 또는 에틸기이고, R3는 탄소수 5∼40의 알킬기이며, X는 할로겐 원자이고, r은 각각 독립적으로 수소원자, 메틸기 또는 탄소수 1∼10의 알콕시이며, n은 1∼12의 정수이고, m은 0∼10의 정수이다.Wherein R 1 and R 2 are each independently a methyl or ethyl group, R 3 is an alkyl group having 5 to 40 carbon atoms, X is a halogen atom, and r is each independently a hydrogen atom, a methyl group or alkoxy having 1 to 10 carbon atoms and n is an integer of 1-12, m is an integer of 0-10.
상기 계면활성제는 하기 화학식 2과 화학식 3으로 표시되는 물질을 에탄올, 아세토니트릴, 톨루엔 등의 용매를 사용하여 반응온도는 30∼120 ℃, 바람직하기로는 60∼90 ℃에서 1∼100 시간, 바람직하기로는 24∼72시간 동안 반응시켜 제조된다. 이때 화학식 3으로 표시되는 물질과 화학식 4로 표시되는 물질의 반응 몰비는 1:2∼1:3이다.The surfactant is a reaction temperature of 30 to 120 ℃, preferably 60 to 90 ℃ 1 to 100 hours, preferably using a solvent such as ethanol, acetonitrile, toluene and the like represented by the formula (2) and (3) Is prepared by reacting for 24 to 72 hours. In this case, the reaction mole ratio of the material represented by Chemical Formula 3 and the material represented by Chemical Formula 4 is 1: 2 to 1: 3.
상기 식에서 X는 할로겐 원자이고, r은 각각 독립적으로 수소 원자, 메틸기 또는 탄소수 1∼10의 알킬기이며, n은 1∼12의 정수이고, m은 0∼10의 정수이다.In said formula, X is a halogen atom, r is respectively independently a hydrogen atom, a methyl group, or a C1-C10 alkyl group, n is an integer of 1-12, m is an integer of 0-10.
상기 식에서 R1 및 R2는 각각 독립적으로 메틸기 또는 에틸기이고, R3는 탄소수 5∼40의 알킬기이다.In the above formula, R 1 and R 2 are each independently a methyl group or an ethyl group, and R 3 is an alkyl group having 5 to 40 carbon atoms.
본원 발명에서는 상기 제미니형 계면활성제를 구조유도체(structure-In the present invention, the gemini-type surfactant is a structure derivative (structure-
directing agent)로 사용하여 메조포러스 물질을 제조하는 방법을 제공한다.It provides a method for producing mesoporous material using a directing agent).
상기 메조포러스 물질을 제조하는 방법은 바람직하게는 다음의 단계를 통하여 이루어진다:The method for producing the mesoporous material is preferably carried out through the following steps:
(A) 상기 화학식 1로 표현되는 제미니형 계면활성제의 수용액을 전구체와 혼합하는 단계;(A) mixing an aqueous solution of the gemini surfactant represented by Formula 1 with a precursor;
(B) 상기 산 또는 염기를 이용하여 (A) 단계의 혼합물의 pH를 조절하는 단계;(B) adjusting the pH of the mixture of step (A) using the acid or base;
(C) 상기 (B)단계의 혼합물을 수열반응시키는 단계;(C) hydrothermally reacting the mixture of step (B);
(D) 상기 (C)단계에서 얻어진 물질을 여과, 세척 및 건조시키는 단계; 및(D) filtering, washing and drying the material obtained in step (C); And
(E) 상기 (D)단계에서 얻어진 물질을 소성(calcination)시키는 단계.(E) calcining the material obtained in step (D).
이하에서 각 단계를 보다 상세하게 설명하면 다음과 같다.Hereinafter, the steps will be described in more detail.
(A) 단계에서, 제미니형 계면활성제 수용액은 염기성 또는 산성으로 제조될 수 있다. 염기성 수용액은 제미니형 계면활성제 0.1∼5.0 중량%, 바람직하기로는 0.5∼3.0 중량%와, 강염기, 예를 들어 수산화나트륨 0.5∼2.0 중량%, 바람직하기로는 0.7∼1.0 중량%가 포함되어 제조된다. 산성 수용액은 제미니형 계면활성제 0.1∼5.0 중량%, 바람직하기로는 0.5∼3.0 중량%와, 강산, 예를 들어 염산 또는 황산 0.5∼10 중량%, 바람직하기로는 1.0∼5.0 중량%가 포함되어 제조된다.In step (A), the aqueous solution of gemini surfactant may be prepared either basic or acidic. The basic aqueous solution is prepared by containing 0.1 to 5.0% by weight of Gemini-type surfactant, preferably 0.5 to 3.0% by weight, and 0.5 to 2.0% by weight of a strong base such as sodium hydroxide, preferably 0.7 to 1.0% by weight. The acidic aqueous solution is prepared by containing 0.1 to 5.0% by weight of Gemini-type surfactant, preferably 0.5 to 3.0% by weight, and 0.5 to 10% by weight of strong acid, such as hydrochloric acid or sulfuric acid, preferably 1.0 to 5.0% by weight. .
상기 (A)단계에서 전구체로는 하기 화학식 4 내지 6로 표시되는 물질로 이루어진 군에서 선택된 물질을 단독으로 또는 2종 이상을 혼합하여 사용한다.As the precursor in step (A), a material selected from the group consisting of substances represented by the following Chemical Formulas 4 to 6 is used alone or in combination of two or more.
상기 식에서 R4 및 R5는 각각 독립적으로 탄소수 1~10의 알킬기이며, Y는 탄소수 1~5의 알콕시기이고, M은 Si 또는 Ti 원자이며, M'은 Al 원자이고, Q는 탄소수 1~15의 알킬렌기, 탄소수 6~40의 아릴렌기, 알킬아릴렌기, 또는 아릴알킬렌기이며, j 및 k는 각각 독립적으로 0≤j+k≤3를 만족시키는, 0 내지 3의 정수이고, h 및 p는 각각 독립적으로 0≤h+p≤2를 만족시키는, 0 내지 2의 정수이다.In the above formula, R 4 and R 5 are each independently an alkyl group having 1 to 10 carbon atoms, Y is an alkoxy group having 1 to 5 carbon atoms, M is a Si or Ti atom, M 'is an Al atom, and Q is 1 to C An alkylene group of 15, an arylene group of 6 to 40 carbon atoms, an alkylarylene group, or an arylalkylene group, j and k each independently represent an integer of 0 to 3 satisfying 0 ≦ j + k ≦ 3, h and p is an integer of 0 to 2, each independently satisfying 0 ≦ h + p ≦ 2.
상기 전구체의 바람직한 예로서 테트라에틸오르토실리케이트Tetraethylorthosilicate as a preferred example of the precursor
(tetraethylorthosilicate: TEOS), 테트라메틸오르토실리케이트 (tetramethylorthosilicate: TMOS), 메틸트리메톡시실란(methyltrimethoxysilane), 디메틸디메톡시실란(Dimethyldimethoxysilane), 트리메틸메톡시실란(tetraethylorthosilicate (TEOS), tetramethylorthosilicate (TMOS), methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane
(Trimethylmethoxysilane), 메틸트리에톡시실란(methyltriethoxysilane), 디메틸디에톡시실란(Dimethyldiethoxysilane), 트리메틸에톡시실란(Trimethylmethoxysilane), methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane
(Trimethylethoxysilane), 메틸트리크로로실란(methyltrichlorosilane), 디메틸디크로로실란(Dimethyldichlorosilane), 트리메틸크로로실란(Trimethylethoxysilane), methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane
(Trimethylchlorosilane), 비스(트리크로로실릴)메탄(Trimethylchlorosilane), Bis (trichlorosilyl) methane
(Bis(trichlorosilyl)methane), 1,2-비스(트리크로로실릴)에탄(Bis (trichlorosilyl) methane), 1,2-bis (trichlorosilyl) ethane
(1,2-Bis(trichlorosilyl)ethane), 비스(트리메톡시실릴)메탄(1,2-Bis (trichlorosilyl) ethane), bis (trimethoxysilyl) methane
(Bis(trimethoxysilyl)methane), 1,2-비스(트리에톡시실릴)에탄(1,2-(Bis (trimethoxysilyl) methane), 1,2-bis (triethoxysilyl) ethane (1,2-
Bis(triethoxysilyl)ethane), 1,4-비스(트리메톡시실릴)벤젠(1,4-Bis (triethoxysilyl) ethane), 1,4-bis (trimethoxysilyl) benzene (1,4-
Bis(trimethoxysilyl)benzene), 1,4-비스(트리메톡시실릴에틸)벤젠(1,4-Bis (trimethoxysilyl) benzene), 1,4-bis (trimethoxysilylethyl) benzene (1,4-
Bis(trimethoxysilylethyl)benzene)등을 들 수 있으며, 보다 바람직하게는 테트Bis (trimethoxysilylethyl) benzene) etc. are mentioned, More preferably, tet
라에틸오르토실리케이트(tetraethylorthosilicate: TEOS), 테트라메틸오르토실리케Tetraethylorthosilicate (TEOS), tetramethylorthosilicate
이트(tetramethylorthosilicate: TMOS)를 사용한다.Tetramethylorthosilicate (TMOS).
전구체는 교반 장치를 이용하여 계면활성제 수용액을 상온에서 격렬히 교반하면서 천천히 첨가하는 것이 좋다. 이때 첨가되는 전구체의 양은 제미니형 계면활성제 1몰을 기준으로 하여 1 내지 100 몰이 되게 하는 것이 적당하고, 바람직하기로는 10 내지 50 몰이 적당하다. 전구체를 계면활성제 수용액에 첨가한 후에 반응 혼합물을 상온에서 1 내지 2시간 동안 교반시키는 것이 좋다.Precursor is preferably added slowly while stirring vigorously at room temperature using a stirring apparatus. At this time, the amount of the added precursor is suitably 1 to 100 moles based on 1 mole of the gemini-type surfactant, and preferably 10 to 50 moles. After the precursor is added to the aqueous surfactant solution, the reaction mixture is preferably stirred at room temperature for 1 to 2 hours.
(B) 단계에서는, 상기 (A)단계에서 제조된 수용액의 pH를 산 또는 염기를 이용하여 9 내지 13, 바람직하기로는 11 내지 12로 조절한다.In step (B), the pH of the aqueous solution prepared in step (A) is adjusted to 9 to 13, preferably 11 to 12, using an acid or a base.
(C) 단계에서는 수열반응을 통하여 메조포러스 물질을 제조한다. 이때, 수열반응 온도는 60∼150℃가 적당하며, 반응 시간은 1시간 내지 144 시간, 바람직하게는 12시간 내지 48 시간이 적당하다.In step (C), a mesoporous material is prepared through hydrothermal reaction. At this time, the hydrothermal reaction temperature is suitable 60 to 150 ℃, the reaction time is 1 hour to 144 hours, preferably 12 hours to 48 hours.
(D) 단계에서는, 제조된 침전물을 여과 장치를 통하여 여과한 후 증류수를 사용하여 2 내지 5 차례 세척하고 50∼200℃에서 3 내지 30 시간 동안 건조시킨다.In step (D), the prepared precipitate is filtered through a filtration apparatus, washed 2 to 5 times with distilled water, and dried at 50 to 200 ° C. for 3 to 30 hours.
(E) 단계에서, 공기 또는 질소 분위기 하에서 400 내지 600℃로 0.3∼30 시간 소성 처리하여 포함되어 있는 계면활성제를 제거한다.In step (E), the contained surfactant is removed by baking at 400 to 600 ° C. for 0.3 to 30 hours in an air or nitrogen atmosphere.
상기와 같은 본 발명의 방법을 통하여 10 nm이하의 기공이 균일하게 분포된 메조포러스(mesoporous) 물질의 분말을 제조할 수 있다.Through the method of the present invention as described above it is possible to prepare a powder of mesoporous (mesoporous) material with pores of less than 10 nm uniformly distributed.
상기 방법 이외에도 본 발명의 목적을 해하지 않는 범위에서 종래에 주지된 방법에 의해 메조포러스 물질을 제조하는 것이 가능하다. 예를 들어, 아니졸In addition to the above method, it is possible to produce a mesoporous material by a method known in the art within a range that does not impair the object of the present invention. For example, anisole
(anisole), 크실렌(xylene)등의 방향족계 탄화수소, 메틸이소부틸케톤(anisole), aromatic hydrocarbons such as xylene, methyl isobutyl ketone
(methyl isobutyl ketone), 아세톤(acetone)등의 케톤계 용매, 테트라히드로퓨란Ketone solvents such as (methyl isobutyl ketone) and acetone (acetone), tetrahydrofuran
(tetrahydrofuran), 이소프로필에테르(isopropyl ether)등의 에테르계 용매, 에탄올(ethanol), 이소프로필 알콜(isopropylalcohol), 부탄올(butanol)등의 알코올류, 또는 이들의 혼합물 등의 용매에 제미니형 계면활성제를 용해시키고, 여기에 전구체 수용액을 혼합한 후, 이를 코팅, 건조, 소성하는 단계를 거쳐 메조포러스 박막을 형성하는 것도 가능하다.Gemini-type surfactant in a solvent such as ether solvents such as (tetrahydrofuran) and isopropyl ether, alcohols such as ethanol, isopropylalcohol, butanol, or mixtures thereof It is also possible to form a mesoporous thin film by dissolving and mixing the precursor aqueous solution therein, followed by coating, drying and firing it.
다음으로 실시예를 통하여 본 발명을 보다 상세하게 설명하고자 하나, 하기의 실시예는 설명의 목적을 위한 것으로 본 발명은 제한하고자 하는 것은 아니다.Next, the present invention will be described in more detail with reference to Examples, but the following Examples are provided for the purpose of explanation and are not intended to limit the present invention.
실시예 1 : 계면활성제 합성Example 1 Surfactant Synthesis
(CnH2n+1N(CH3)2BrCH2CH2CH2OSi(CH3)2OSi(CH3)2OSi(CH3)2OCH2CH2CH2BrN(CH3)2CnH2n+1, n=6,8,10,12,16,18,22)(C n H 2n + 1 N (CH 3 ) 2 BrCH 2 CH 2 CH 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 OCH 2 CH 2 CH 2 BrN (CH 3 ) 2 C n H 2n + 1 , n = 6,8,10,12,16,18,22)
200 ml의 에탄올과 7.24 g의200 ml of ethanol and 7.24 g
BrCH2CH2CH2OSi(CH3)2OSi(CH3)2 OSi(CH3)2OCH2CH2CH2Br (A)을 혼합하여 용액을 제조한 후 9.15 g의 옥타데실디메틸아민(octadecyldimethlyamine, n = 18, B)을 이 용액에 첨가하였다. 반응물내의 A와 B의 몰비는 1 : 2.05 이었다. 준비된 용액을 환류 (reflex) 조건 하에서 48 시간 동안 가열하였다. 용액을 회전증발기 (rotary evaporator)를 이용하여 용매인 에탄올을 제거하여 고체형태의 생성물을 얻었다. 이 고체 생성물에 2 ml의 클로로포름을 첨가하여 용해시킨 후 500 ml의 에틸아세테이트를 첨가한 후 0 ℃에서 12 시간 방치하여 재결정하였다. 재결정된 물질을 여과하고 에틸아세테이트로 세 차례 세척한 후 재결정 및 여과, 세척 과정을 두 번 더 반복하였다. 얻어진 물질은 진공 오븐을 이용하여 50 ℃에서 12 시간 동안 건조시켜 용매를 완전히 제거하여 상기 화합물을 40%의 수율로 제조하였다. 다음으로, 알킬 사슬 길이가 다른 알킬디메틸아민(CnH2n+1N(CH3)2, n = 6, 8, 10, 12, 16, 22)을 사용하는 것을 제외하고는 동일하게 실시하여 n의 크기가 6, 8, 10, 12, 16, 22로 조절된 제미니형 계면활성제를 제조하였다.BrCH 2 CH 2 CH 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 OCH 2 CH 2 CH 2 Br ( A ) to prepare a solution, and then 9.15 g of octadecyldimethylamine ( octadecyldimethlyamine, n = 18, B ) was added to this solution. The molar ratio of A and B in the reaction was 1: 2.05. The prepared solution was heated for 48 hours under reflex conditions. The solution was removed using a rotary evaporator to remove the solvent ethanol to obtain a solid product. 2 ml of chloroform was added to the solid product to dissolve it, and 500 ml of ethyl acetate was added thereto, followed by standing at 0 ° C. for 12 hours for recrystallization. The recrystallized material was filtered, washed three times with ethyl acetate, and then recrystallized, filtered and washed twice more. The obtained material was dried at 50 ° C. for 12 hours using a vacuum oven to completely remove the solvent to prepare the compound in 40% yield. Next, except that alkyldimethylamine (C n H 2n + 1 N (CH 3 ) 2 , n = 6, 8, 10, 12, 16, 22) having different alkyl chain lengths was used, Gemini-type surfactants with sizes n adjusted to 6, 8, 10, 12, 16, 22 were prepared.
실시예 2 : 계면활성제 합성Example 2 Surfactant Synthesis
(CnH2n+1N(CH3)2BrCH2CH2OSi(CH3)2OSi(CH3)2OSi(CH3)2OCH2CH2BrN(CH3)2CnH2n+1, n=6,8,10,12,16,18,22)(C n H 2n + 1 N (CH 3 ) 2 BrCH 2 CH 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 OCH 2 CH 2 BrN (CH 3 ) 2 C n H 2n + 1 , n = 6,8,10,12,16,18,22)
200 ml의 에탄올과 7.01 g의 BrCH2CH2OSi(CH3)2OSi(CH3 )2OSi(CH3)2OCH2CH2Br (A)을 혼합하여 용액을 제조한 후 9.15 g의 옥타데실디메틸실란(n = 18, B)을 이 용액에 첨가하였다. 반응물내의 A와 B의 몰비는 1 : 2.05 이었다. 준비된 용액을 환류(reflex) 조건 하에서 48 시간 동안 가열하였다. 용액을 회전증발기(rotary evaporator)를 이용하여 용매인 에탄올을 제거하여 고체형태의 생성물을 얻었다.200 ml of ethanol and 7.01 g of BrCH 2 CH 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 OCH 2 CH 2 Br ( A ) to prepare a solution, followed by 9.15 g of octa Decyldimethylsilane (n = 18, B ) was added to this solution. The molar ratio of A and B in the reaction was 1: 2.05. The prepared solution was heated for 48 hours under reflex conditions. The solution was removed using a rotary evaporator to remove the solvent ethanol to obtain a solid product.
이 고체 생성물에 2 ml의 클로로포름을 첨가하여 용해시킨 후 500 ml의 에틸아세테이트를 첨가한 후 0 ℃에서 12 시간 방치하여 재결정하였다. 재결정된 물질을 여과하고 에틸아세테이트로 세 차례 세척한 후 재결정 및 여과, 세척 과정을 두 번 더 반복하였다. 얻어진 물질은 진공 오븐을 이용하여 50 ℃에서 12 시간 동안 건조시켜 용매를 완전히 제거하여, 상기 화합물을 35%의 수율로 제조하였다. 다음으로, 알킬 사슬 길이가 다른 알킬디메틸아민(CnH2n+1N(CH3)2, n = 6, 8, 10, 12, 16, 22)을 사용하는 것을 제외하고는 동일하게 실시하여 n의 크기가 6, 8, 10, 12, 16, 22로 조절된 제미니형 계면활성제를 제조하였다.2 ml of chloroform was added to the solid product to dissolve it, and 500 ml of ethyl acetate was added thereto, followed by standing at 0 ° C. for 12 hours for recrystallization. The recrystallized material was filtered, washed three times with ethyl acetate, and then recrystallized, filtered and washed twice more. The obtained material was dried at 50 ° C. for 12 hours using a vacuum oven to completely remove the solvent, thereby preparing the compound in 35% yield. Next, except that alkyldimethylamine (C n H 2n + 1 N (CH 3 ) 2 , n = 6, 8, 10, 12, 16, 22) having different alkyl chain lengths was used, Gemini-type surfactants with sizes n adjusted to 6, 8, 10, 12, 16, 22 were prepared.
실시예 3 : 메조포러스 물질 합성Example 3 Synthesis of Mesoporous Material
상기 실시예 1에서 제조된 제미니형 계면활성제 중 알킬 사슬의 길이가 18인 C18H37N(CH3)2BrCH2CH2CH2OSi(CH3)2OSi(CH3)2OSi(CH3)2OCH2CH2CH2BrN(CH3)2C18H37 0.42 g과 0.202 g의 수산화나트륨을 26.5 g의 이차 증류수에 용해시켜 수용액을 제조하였다. 이 수용액을 자력 교반장치를 이용하여 강력하게 저어주면서 2.0 g의 TEOS를 첨가하였다. 반응 혼합물 내의 반응물들의 몰비는 0.04 계면활성제 : 1 TEOS : 0.5 NaOH : 150 H2O 였다. 반응 혼합물을 상온에서 1시간 동안 교반한 후 100 ℃ 오븐에서 24시간동안 반응시켰다. 이후 침전물을 여과하고 이차 증류수로 깨끗하게 세척하여 100 ℃에서 건조시켰다. 건조된 시료 내에 들어 있는 계면활성제를 제거하기 위해 공기 중에서 550℃로 10시간 동안 소성 처리하였다. 도 1은 제조한 메조포러스 물질에 대한 X-선 회절 그래프로서 A는 소정처리 전, B는 소성처리 후의 결과이다. 도 1에서 보면 소성처리 전후에 따라 약 10% 정도의 구조 수축만 있을 뿐 소성 처리 전후에 관계 없이 X선 회절형태는 2차원 육방배열로 표시될 수 있는 (100), (110) 및 (200)의 피크를 낮은 각도 영역에서 보여준다. 따라서 도 1에 의해 제조된 나노포러스 실리카 물질이 뛰어난 구조적 균일성을 가짐을 확인할 수 있다.C 18 H 37 N (CH 3 ) 2 BrCH 2 CH 2 CH 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH) having an alkyl chain length of 18 in the gemini-type surfactant prepared in Example 1 3 ) 2 OCH 2 CH 2 CH 2 BrN (CH 3 ) 2 C 18 H 37 0.42 g and 0.202 g of sodium hydroxide were dissolved in 26.5 g of distilled water to prepare an aqueous solution. 2.0 g of TEOS was added while stirring this solution strongly using a magnetic stirrer. The molar ratio of reactants in the reaction mixture was 0.04 surfactant: 1 TEOS: 0.5 NaOH: 150 H 2 O. The reaction mixture was stirred at room temperature for 1 hour and then reacted in an oven at 100 ° C. for 24 hours. The precipitate was then filtered, washed clean with secondary distilled water and dried at 100 ° C. It was calcined at 550 ° C. for 10 hours in air to remove the surfactant contained in the dried sample. 1 is an X-ray diffraction graph of the prepared mesoporous material, where A is a result before a predetermined treatment and B is a result of a calcination treatment. In FIG. 1, only about 10% of the structure shrinkage occurs before and after the firing treatment, regardless of the before and after firing treatment, the X-ray diffraction pattern may be represented by two-dimensional hexagonal arrangements (100), (110), and (200). The peak of is shown in the low angle region. Therefore, it can be seen that the nanoporous silica material prepared by FIG. 1 has excellent structural uniformity.
도 2는 소성 처리한 시료에 대한 질소 흡착-탈착 등온선이며, 도 3은 도 2의 질소 흡착 등온선으로부터 BJH(Barett-Joyner-Halenda)방법으로 구한 기공크기 분포곡선이다. 도 2의 질소 흡착 등온선으로부터 구한 BET 표면적은 1g 당 1336 m2이었으며, 도 3의 기공크기는 2.30 nm이었다.FIG. 2 is a nitrogen adsorption-desorption isotherm of a fired sample, and FIG. 3 is a pore size distribution curve obtained by the Barett-Joyner-Halenda (BJH) method from the nitrogen adsorption isotherm of FIG. 2. The BET surface area determined from the nitrogen adsorption isotherm of FIG. 2 was 1336 m 2 per g, and the pore size of FIG. 3 was 2.30 nm.
실시예 4 : 메조포러스 물질 합성Example 4 Synthesis of Mesoporous Material
상기 실시예 2에서 제조된 제미니형 계면활성제 중 알킬 사슬의 길이가 다른 세중류의 계면활성제를 사용하여 메조포러스 물질을 합성하였다. 알킬 사슬의 길이가 각각 12, 14, 18인 제미니형 계면활성제를 각각 0.86 g, 0.92 g, 1.03 g을 66.1 g의 이차 증류수에 용해시킨 후 0.51 g의 수산화나트륨을 첨가하여 수용액을 제조하였다. 이 수용액을 자력교반장치를 이용하여 강력하게 저어주면서 5.0 g의 TEOS를 첨가하였다. 반응 혼합물 내의 반응물들의 몰비는 0.04 계면활성제 : 1 TEOS : 0.5 NaOH : 150 H2O 였다. 반응 혼합물을 상온에서 1시간 동안 교반한 후 100 ℃ 오븐에서 24시간 동안 반응시켰다. 이후 침전물을 여과하고 이차 증류수로 깨끗하게 세척하여 100 ℃에서 건조시켰다. 제조한 메조포러스 물질에 대한 X-선 회절 그래프는 도 4와 같고 각각의 X-선 회절 형태로부터 얻은 격자 상수 값은 3.97 nm, 4.25 nm 및 5.26 nm로 도 5에서 볼 수 있듯이 격자 상수 값은 알킬 사슬의 탄소 수에 비례하여 증가하였다.Mesoporous material was synthesized using a triclass surfactant having a different alkyl chain length among the Gemini type surfactants prepared in Example 2. An aqueous solution was prepared by dissolving Gemini surfactants having alkyl chain lengths of 12, 14, and 18, respectively, in 0.86 g, 0.92 g, and 1.03 g in 66.1 g of secondary distilled water, and then adding 0.51 g of sodium hydroxide. 5.0 g of TEOS was added while stirring this solution strongly using a magnetic stirrer. The molar ratio of reactants in the reaction mixture was 0.04 surfactant: 1 TEOS: 0.5 NaOH: 150 H 2 O. The reaction mixture was stirred at room temperature for 1 hour and then reacted in an oven at 100 ° C. for 24 hours. The precipitate was then filtered, washed clean with secondary distilled water and dried at 100 ° C. The X-ray diffraction graph of the prepared mesoporous material is shown in FIG. 4, and the lattice constant values obtained from the respective X-ray diffraction patterns are 3.97 nm, 4.25 nm and 5.26 nm. As shown in FIG. 5, the lattice constant values are alkyl. It increased in proportion to the number of carbons in the chain.
실시예 5 : 메조포러스 물질 합성 Example 5 Mesoporous Material Synthesis
상기 실시예 1에서 제조된 제미니형 계면활성제 중 알킬 사슬의 길이가 18인 C18H37N(CH3)2BrCH2CH2CH2OSi(CH3)2OSi(CH3)2OSi(CH3)2OCH2CH2CH2BrN(CH3)2C18H37 0.69 g과 0.21 g의 수산화나트륨을 12.0 g의 이차 증류수에 용해시켜 수용액을 제조하였다. 이 수용액을 자력교반장치를 이용하여 강력하게 저어주면서 0.70 g의 비스(트리에톡시실릴)에탄(BTME)을 첨가하였다. 반응 혼합물 내의 반응물들의 몰비는 0.04 계면활성제 : 1 BTME : 2.62 NaOH : 356 H2O 였다. 반응 혼합물을 상온에서 20시간 동안 교반한 후 100 ℃ 오븐에서 20시간 동안 반응시켰다. 이후 침전물을 여과하고 이차 증류수로 깨끗하게 세척하여 100 ℃에서 건조시켰다. 건조된 시료 내에 들어 있는 계면활성제를 제거하기 위해 시료 1.0 g을 100 g의 에탄올과 5 g의 35% HCl이 혼합된 용액으로 두차례 세척하였다. 제조한 메조포러스 물질에 대한 X-선 회절 그래프는 도 6에 나타내었으며, 이때 A는 세척 전의 결과, B는 세척 후의 결과를 나타낸다.C 18 H 37 N (CH 3 ) 2 BrCH 2 CH 2 CH 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH) having an alkyl chain length of 18 in the gemini-type surfactant prepared in Example 1 3) 2 with sodium hydroxide of OCH 2 CH 2 CH 2 BrN ( CH 3) 2 C 18 H 37 0.69 g and 0.21 g of an aqueous solution was prepared by dissolving in distilled water of 12.0 g. 0.70 g of bis (triethoxysilyl) ethane (BTME) was added to this aqueous solution with vigorous stirring using a magnetic stirrer. The molar ratio of reactants in the reaction mixture was 0.04 Surfactant: 1 BTME: 2.62 NaOH: 356 H 2 O. The reaction mixture was stirred at room temperature for 20 hours and then reacted in an oven at 100 ° C. for 20 hours. The precipitate was then filtered, washed clean with secondary distilled water and dried at 100 ° C. To remove the surfactant contained in the dried sample, 1.0 g of the sample was washed twice with a solution of 100 g of ethanol and 5 g of 35% HCl. An X-ray diffraction graph of the prepared mesoporous material is shown in FIG. 6, where A is the result before washing and B is the result after washing.
본 발명에 의해 크기가 10nm 이하인 기공이 규칙적으로 배열된 메조포러스 물질을 제공할 수 있다.The present invention can provide a mesoporous material in which pores having a size of 10 nm or less are regularly arranged.
도 1은 실시예 3에서 제조된 메조포러스 실리카 물질에 대한 X-선 회절 그래프;1 is an X-ray diffraction graph of the mesoporous silica material prepared in Example 3;
도 2는 실시예 3에서 제조된 메조포러스 물질에 대하여 액체 질소 온도에서 구한 질소의 흡착-탈착 등온선(adsorption-desorption isotherm);2 is an adsorption-desorption isotherm of nitrogen obtained at liquid nitrogen temperature for the mesoporous material prepared in Example 3;
도 3은 도 2에서 나타난 질소의 흡착 등온선으로부터 BJH(Barrett-Joyner-Halenda) 방법으로 구한 기공크기 분포곡선(pore size distribution curve);Figure 3 is a pore size distribution curve (pore size distribution curve) obtained by the Barrett-Joyner-Halenda (BJH) method from the adsorption isotherm of nitrogen shown in Figure 2;
도 4는 실시예 4에서 제조된 메조포러스 물질에 대한 X-선 회절 그래프;4 is an X-ray diffraction graph of the mesoporous material prepared in Example 4;
도 5는 도 4의 X-선 회절 그래프로부터 구한 각각의 메조포러스 실리카 물질들에 대한 격자상수 a의 값을 계면활성제의 알킬사슬의 탄소수 n으로 표시한 그래프; 및FIG. 5 is a graph showing the value of lattice constant a for each mesoporous silica material obtained from the X-ray diffraction graph of FIG. 4 as the carbon number n of the alkyl chain of the surfactant; FIG. And
도 6은 실시예 5에서 제조된 유기-무기 복합 골격을 갖는 메조포러스 물질에 대한 X-선 회절 그래프이다.6 is an X-ray diffraction graph of a mesoporous material having an organic-inorganic composite backbone prepared in Example 5. FIG.
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| DE60301928T DE60301928T2 (en) | 2002-08-28 | 2003-08-21 | Gemini surfactants and process for producing mesoporous material |
| EP03255188A EP1394165B1 (en) | 2002-08-28 | 2003-08-21 | Gemini surfactants and method for preparing mesoporous materials |
| JP2003302316A JP4482298B2 (en) | 2002-08-28 | 2003-08-27 | Gemini type surfactant and method for producing mesoporous material using the same |
| CNB031553338A CN100488614C (en) | 2002-08-28 | 2003-08-27 | Noval double-structure surfactant and method for producing mesoporous materials with the same |
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| US4005030A (en) * | 1975-04-22 | 1977-01-25 | The Procter & Gamble Company | Organosilane-containing anionic detergent composition |
| US4005028A (en) * | 1975-04-22 | 1977-01-25 | The Procter & Gamble Company | Organosilane-containing detergent composition |
| KR19990018318A (en) * | 1997-08-27 | 1999-03-15 | 남창우 | Method for producing a medium-porous molecular sieve material in which a metal element is substituted in a skeletal structure using a metal adhesion method and the molecular sieve material |
| KR19990025016A (en) * | 1997-09-09 | 1999-04-06 | 박원훈 | Process for the preparation of mesoporous macromolecule silica material and mesoporous mesoporous silica material prepared |
| KR20000066438A (en) * | 1999-04-16 | 2000-11-15 | 남창우 | Synthesis of Cubic Mesoporous Molecular Sieve |
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| US4005030A (en) * | 1975-04-22 | 1977-01-25 | The Procter & Gamble Company | Organosilane-containing anionic detergent composition |
| US4005028A (en) * | 1975-04-22 | 1977-01-25 | The Procter & Gamble Company | Organosilane-containing detergent composition |
| KR19990018318A (en) * | 1997-08-27 | 1999-03-15 | 남창우 | Method for producing a medium-porous molecular sieve material in which a metal element is substituted in a skeletal structure using a metal adhesion method and the molecular sieve material |
| KR19990025016A (en) * | 1997-09-09 | 1999-04-06 | 박원훈 | Process for the preparation of mesoporous macromolecule silica material and mesoporous mesoporous silica material prepared |
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