KR100295583B1 - Method of producing organic gel microsphere - Google Patents
Method of producing organic gel microsphere Download PDFInfo
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- KR100295583B1 KR100295583B1 KR1019990015373A KR19990015373A KR100295583B1 KR 100295583 B1 KR100295583 B1 KR 100295583B1 KR 1019990015373 A KR1019990015373 A KR 1019990015373A KR 19990015373 A KR19990015373 A KR 19990015373A KR 100295583 B1 KR100295583 B1 KR 100295583B1
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- particles
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000004005 microsphere Substances 0.000 title 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 53
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 12
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002612 dispersion medium Substances 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims abstract description 8
- GGUPMVXPXHZNKF-UHFFFAOYSA-N benzene-1,2-diol;formaldehyde Chemical compound O=C.OC1=CC=CC=C1O GGUPMVXPXHZNKF-UHFFFAOYSA-N 0.000 claims abstract description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000012530 fluid Substances 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920003986 novolac Polymers 0.000 claims description 7
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- -1 polydimethylsiloxanes Polymers 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000012674 dispersion polymerization Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000012774 insulation material Substances 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 51
- 239000002904 solvent Substances 0.000 description 20
- 239000007863 gel particle Substances 0.000 description 19
- 239000004964 aerogel Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical compound CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- BTQAJGSMXCDDAJ-UHFFFAOYSA-N 2,4,6-trihydroxybenzaldehyde Chemical compound OC1=CC(O)=C(C=O)C(O)=C1 BTQAJGSMXCDDAJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
본 발명은 입자형태의 유기 겔의 제조방법에 관한 것으로서, 페놀릭-퍼퍼랄, 레소시놀-포름알데히드, 멜라민-포름알데히드, 카테콜-포름알데히드, 페놀-레소시놀-포름알데히드, 플로로글루시놀-포름알데히드, 페놀-포름알데히드 등과 같은 다기능성 단량체를 사용하여 초임계 이산화탄소를 분산매질로 하여 졸-분산-겔(sol-dispersion-gel) 방법을 통해 단일 공정으로 초단열용 재료로 유용한 입자형태의 유기 겔을 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing an organic gel in the form of particles, which includes phenolic-peralal, resorcinol-formaldehyde, melamine-formaldehyde, catechol-formaldehyde, phenol-resosocinol-formaldehyde, fluoro Supercritical carbon dioxide as a dispersion medium using multifunctional monomers such as glutinol-formaldehyde, phenol-formaldehyde, etc., which is useful as a super insulation material in a single process through a sol-dispersion-gel method It relates to a method for preparing an organic gel in the form of particles.
Description
본 발명은 입자형태의 유기 겔의 제조방법에 관한 것으로서, 더욱 상세하게는 페놀릭-퍼퍼랄 겔과 같은 유기 겔을 초임계 이산화탄소를 분산매질로 하여 단일공정으로 입자형태로 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing an organic gel in the form of particles, and more particularly, to a method for preparing an organic gel such as a phenolic-perperal gel in the form of particles in a single process using a supercritical carbon dioxide as a dispersion medium. .
겔은 졸 상태에서 확장되는 3차원 연속상 구조를 가지는 고체 물질로서 공유 결합, 이온 결합 및 사슬 얽힘에 의한 수소 결합 등의 복합 결합에 의해 형성되어진다. 겔은 넓은 응용범위를 갖는 물질로서, 예를 들면, 단백질 혼합물의 전기 영동 분야, 크로마토그래피 패킹분야, 소프트 렌즈 분야 및 에어로겔의 중간체로 사용된다.Gel is a solid material having a three-dimensional continuous phase structure extending in the sol state is formed by complex bonds such as covalent bonds, ionic bonds and hydrogen bonds by chain entanglement. Gels are materials with a wide range of applications, for example as electrophoretic fields of protein mixtures, chromatography packing fields, soft lens fields and intermediates of aerogels.
에어로겔은 저밀도이면서 높은 다공성으로 인해 매우 큰 내부 표면적으로 가지고 있는 물질로서, 1931년 Kisler에 의해 처음으로 만들어졌다. 이러한 에어로겔은 단열재로 사용되고 있는 기존의 CFC 블로운(blown) 폴리우레탄 폼 또는 무기계 단열재 등의 대체 재료로 사용될 수 있고, 화학 촉매, 이온교환수지, 입자 가속기, 소음제거, 압전소자, 단열유리 및 방출조절 약품 소재 등 다양한 응용 범위를 가지고 있다.Aerogels are materials made by Kisler in 1931 that have a very large inner surface area due to their low density and high porosity. These aerogels can be used as alternative materials, such as conventional CFC blown polyurethane foams or inorganic insulations, which are used as insulation, and can be used as chemical catalysts, ion exchange resins, particle accelerators, noise reduction, piezoelectric elements, insulating glass and release It has a wide range of applications, including controlled pharmaceutical materials.
기존의 폼 단열재는 비교적 밀도가 크기 때문에 100kg/㎡ 이하의 저밀도용으로는 사용될 수 없고, 기공 크기가 커서 열전도도를 낮추는데 한계가 있으므로, 초단열용 재료로는 사용이 어려웠다. 이를 위해 단열용 재료로서 무기 및 유기 에어로겔의 연구가 진행되고 있다. 무기 에어로겔 중 실리카계 에어로겔은 산 또는 염기 촉매 하에서 테트라메톡시실란(tetramethoxy silane, TMOS) 또는 테트라에톡시실란(tetraethoxy silane, TEOS)의 가수분해와 축중합 반응을 거쳐 초임계 건조에 의해 제조된다. 산촉매를 사용하는 경우 선형 또는 약간의 가교된 고분자가 형성되고 이들의 얽힘에 의해 겔이 형성되며, 염기 촉매의 경우 가교된 고분자에 의한 콜로이드 형태의 겔을 형성한다. 이러한 실리카계 에어로겔은 높은 기공도와 매우 작은 기공 크기(100nm 이하)를 가지고 있어 열전도도를 낮추는 효과가 있다.Existing foam insulation can not be used for low density of less than 100kg / ㎡ because of the relatively high density, and because the pore size is limited to lower the thermal conductivity, it was difficult to use as a super insulation material. To this end, research into inorganic and organic aerogels is being conducted as a heat insulating material. Silica-based airgels in inorganic airgels are prepared by supercritical drying through hydrolysis and polycondensation of tetramethoxy silane (TMOS) or tetraethoxy silane (TEOS) under acid or base catalysts. In the case of using an acid catalyst, linear or slight crosslinked polymers are formed and gels are formed by entanglement thereof, and in the case of a base catalyst, a colloidal gel is formed by the crosslinked polymer. Such silica-based airgel has high porosity and very small pore size (100 nm or less), thereby lowering thermal conductivity.
지금까지의 무기 에어로겔 중에서 단열효과가 가장 우수한 실리카 에어로겔은 상온, 공기 중에서 밀도가 120kg/㎥일 때 총괄 열전도도가 0.013W/m·K로서 기존의 섬유나 폼 형태의 단열재보다 약 2배 이상의 단열 효과를 보이고 있다. 하지만 유기 에어로겔에 비해서는 일반적으로 단열 성능이 떨어지며 구조면에서도 깨지기 쉬운 취약한 점을 보이고 있다. 또한, 저밀도용 응용을 위해서는 원자번호가 8이하인 원자이어야 하는데, 실리카계 에어로겔은 규소(Si)의 원자번호가 14로서,유기 에어로겔에 비해 고밀도와 높은 열전도도를 가지게 된다. 반면, 에어로겔의 경우 구조의 대부분을 구성하고 있는 탄소의 원자번호가 6이며, 나머지 원소인 수소, 산소도 1과 8로, 작은 셀 및 기공 크기를 갖기에 적합하고, 무기 에어로겔에 비해 낮은 열전도도를 가지므로 초단열 재료로의 응용에 더욱 적합하다.Among the inorganic airgels, silica airgels with the highest thermal insulation effect have a total thermal conductivity of 0.013 W / m · K at a density of 120 kg / m3 at room temperature and in air. It is showing effect. However, compared with organic aerogels, the thermal insulation performance is generally poor and fragile in terms of structure. In addition, for low-density applications, atoms having atomic numbers of 8 or less should be used. Silica-based airgels have an atomic number of silicon (Si) of 14, which has higher density and higher thermal conductivity than organic airgels. On the other hand, in the case of an airgel, the atomic number of carbon constituting most of the structure is 6, and the remaining elements hydrogen and oxygen are 1 and 8, which are suitable for small cell and pore size, and have lower thermal conductivity than that of inorganic airgel. It is more suitable for application to ultra-insulating materials.
이러한 유기 에어로겔은 최근에 와서야 개발되기 시작했으며, 1984년 미국의 L.L.N.L(Lawrence Livermore National Laboratory)에서 시작되었다. 이중 레소시놀-포름알데히드계(resorcinol-formaldehyde) 에어로겔은 무기 에어로겔과 가장 유사한 구조를 가지며 이산화탄소를 초임계 유체로 사용하여 저온에서 용매를 추출하여 구조의 변형없이 에어로겔을 만들게 된다.This organic airgel was only recently developed and started in 1984 at the Lawrence Livermore National Laboratory (L.L.N.L) in the United States. Dual resorcinol-formaldehyde aerogels have the structure most similar to inorganic aerogels and use carbon dioxide as a supercritical fluid to extract solvents at low temperature to form aerogels without modification of the structure.
레소시놀-포름알데히드계 유기 에어로겔은 미국 특허 제4,873,218호, 및 미국특허 제4,997,804호에 개시된 바와 같이 R.W. Pekala에 의해 발명되었고, 멜라민-포름알데히드(melamine-formaldehyde) 유기 에어로겔도 미국 특허 제5,081,163호, 제5,086,085호에 개시된 바와 같이 R.W. Pekala에 의해 발명되었다.Resorcinol-formaldehyde-based organic aerogels are described in R.W. No. 4,873,218 and US Pat. No. 4,997,804. Invented by Pekala, melamine-formaldehyde organic aerogels are also described in R.W. No. 5,081,163, 5,086,085. Invented by Pekala.
페놀릭-퍼퍼랄-알코올(phenolic-furfural-alcohol) 용액으로부터 졸-겔 방법에 의해 제조된 모노리드 형태의 유기 겔은 미국특허 제5,476,878호 및 제5,556,892호에서 R.W. Pekala에 의해 발명되었다.Organic gels in monolithic form prepared by sol-gel methods from phenolic-furfural-alcohol solutions are described in US Pat. Nos. 5,476,878 and 5,556,892. Invented by Pekala.
페놀릭-퍼퍼랄 에어로겔은 이산화탄소와 친한 알코올에서 반응이 일어나기 때문에 레소시놀-포름알데히드나 멜라민-포름알데히드 반응에서 필요한 용매 치환공정을 생략하므로 공정의 단순화를 이룩할 수 있다.Since phenolic-perforated aerogels react with carbon dioxide and friendly alcohols, simplification of the process can be achieved by eliminating the solvent substitution process required in the resorcinol-formaldehyde or melamine-formaldehyde reactions.
그런데, 페놀릭 퍼퍼랄 에어로겔을 모노리드 형태보다 입자형태로 제조하는 것이 많은 장점을 가지는 바, 예를 들면 에너지 저장 응용분야에서 입자형태로 제조하므로 복합체 전극의 기계적 탄성을 증가시킬 수 있으며, 적절한 바인더를 사용하므로 기존의 'AA', 'C', 'D'셀들과 유사한 '젤리 롤(jelly roll)' 셀과 같은 저전압, 단일 셀로도 응용될 수 있다. 또한, 공기 여과 및 의료용 응용분야에서 이용될 수 있다. 공정 측면을 살펴보면, 회분식(batch) 공정에서 제조되는 모노리드 형태와 달리 입자 형태는 회분식 및 반연속식(semicontinuous) 공정을 통해 제조할 수 있어 실제 공정 적용에 유리하며, 흐름성이 우수하여 이송이 용이하다.However, the manufacturing of phenolic perforated aerogels in the form of particles rather than monolithic has a number of advantages, for example, in the form of particles in energy storage applications can increase the mechanical elasticity of the composite electrode, suitable binder As a result, it can be applied to a low voltage, single cell such as a 'jelly roll' cell similar to the existing 'AA', 'C' and 'D' cells. It can also be used in air filtration and medical applications. In terms of the process aspect, unlike the monolithic form produced in the batch process, the particle form can be produced through the batch and semicontinuous processes, which is advantageous for the actual process application, and the flowability is excellent due to the excellent flowability. It is easy.
졸-겔 공정을 이용한 겔 입자의 합성은 크게 4가지 방법으로 분류되어지고 있다. 첫째로는 모노리드 형태의 겔을 합성하여 밀링을 통하여 제조하는 방법과 가수분해시 화학적인 방법으로 입자의 응집을 이용한 방법이 있으며, 에어로졸이나 유화법 또는 역상유화를 이용하여 입자를 생성하는 방법 등이 있다. 이러한 방법을 통하여 나노미터 크기에서 마이크로미터 크기의 입자가 합성된다.Synthesis of gel particles using the sol-gel process has been largely classified into four methods. The first method is to synthesize a monolithic gel by milling and to use agglomeration of particles as a chemical method during hydrolysis, and to generate particles using aerosol, emulsification method or reverse phase emulsification. There is this. In this way, nanometer-sized particles are synthesized.
기존의 졸-에멀젼-겔 방법을 통한 레소시놀-포름알데히드 겔의 제조 방법을 설명하면 다음과 같다.Hereinafter, a method of preparing a resorcinol-formaldehyde gel using a conventional sol-emulsion-gel method will be described.
레소시놀-포름알데히드 용액을 부유시킨 후 적절한 계면활성제를 사용하여 유기 무극성 용매에서 안정화시킨다. 이때, 계면활성제의 선택은 에멀젼에서 사용되는 계면활성제의 친수성-소수성 평형(Hydrophilic Lipophilic Balance, HLB)수의 적합성과 부유 조성에 의해 결정된다. 이때, 에멀젼 액적은 겔화 단계 동안 미니 반응기로서의 역할을 수행한다.The resorcinol-formaldehyde solution is suspended and stabilized in an organic nonpolar solvent with the appropriate surfactant. At this time, the choice of surfactant is determined by the suitability and suspension composition of the hydrophilic lipophilic balance (HLB) water of the surfactant used in the emulsion. The emulsion droplets then serve as mini reactors during the gelling step.
그런데, 이와 같은 졸-에멀젼 겔 방법을 통해 유기 겔을 제조하는 경우 환경에 유해한 용매를 사용하는 문제가 있을뿐더러 최종 제품인 에어로겔을 단일 공정으로 제조할 수 없어 생산성을 떨어뜨리는 문제점 등이 있다.However, when the organic gel is manufactured through the sol-emulsion gel method, there is a problem of using a solvent harmful to the environment, and there is a problem in that the final product of the airgel cannot be manufactured in a single process, thereby reducing productivity.
본 발명의 목적은 상기와 같이 환경에 유해한 용매를 사용하는 졸-에멀젼-겔 방법에서와는 달리 친환경 용매인 초임계 이산화탄소를 용매로 하여 졸-분산-겔 방법을 통해 모노리드 형태가 아닌 입자형태로 유기 겔을 제조하는 방법을 제공하는 데 있다.Unlike the sol-emulsion-gel method using a solvent that is harmful to the environment as described above, an object of the present invention is to form organic particles in the form of particles rather than monoliths through the sol-dispersion-gel method using supercritical carbon dioxide as a solvent. It is to provide a method for preparing a gel.
도 1은 본 발명 실시예 1에 따라 제조된 유기 겔 입자의 주사전자현미경 사진(×5000)이다.1 is a scanning electron micrograph (× 5000) of organic gel particles prepared according to Example 1 of the present invention.
이와 같은 목적을 달성하기 위한 본 발명의 입자형태의 유기 겔의 제조방법은 다기능성 단량체를 고압 반응기에서 산촉매 및 안정제를 첨가한 다음, 40∼120℃, 1200∼4000psi 압력하에서 초임계 이산화탄소를 분산매질로 하여 4∼24시간 동안 분산중합한 후, 10∼72시간 동안 경화시킨 후, 초임계 이산화탄소를 배출하는 것을 그 특징으로 한다.In order to achieve the above object, the method for preparing an organic gel in the form of particles of the present invention is to add an acid catalyst and a stabilizer to a multifunctional monomer in a high pressure reactor, and then disperse the supercritical carbon dioxide under a pressure of 40 to 120 ° C. and 1200 to 4000 psi. After the dispersion polymerization for 4 to 24 hours, after curing for 10 to 72 hours, the supercritical carbon dioxide is discharged.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명에서는 초임계 유체를 반응용매로 사용하는 것을 그 특징으로 한다. 일반적으로 초임계 유체는 임계온도(Tc)와 임계압력(Pc) 이상의 물질로 정의된다. 연속상으로 초임계 유체를 사용하는 중요한 장점 중의 하나는 단순히 계의 온도나 압력을 변화시킴으로써 유전상수와 같은 용매의 성질을 조절할 수 있다는 점이다. 게다가 초임계 유체는 액체와 기체 중간의 성질을 갖는다. 초임계 유체는 특히, 액체와 같은 밀도와 기체와 같은 점도를 갖고 있다. 초임계 유체 중에서도 CO2는 많은 장점으로 여러 분야에서 매우 효과적인 연속상으로 사용되었다.In the present invention, it is characterized by using a supercritical fluid as a reaction solvent. In general, supercritical fluid is defined as a material above the critical temperature (Tc) and the critical pressure (Pc). One important advantage of using supercritical fluids in a continuous phase is the ability to control the properties of solvents such as dielectric constants simply by changing the temperature or pressure of the system. In addition, supercritical fluids have properties between liquid and gas. Supercritical fluids, in particular, have the same density as the liquid and the same viscosity as the gas. Among supercritical fluids, CO 2 has been used as a highly effective continuous phase for many applications.
우선, CO2의 공급원은 풍부하게 존재하는 자연상태의 CO2와 에탄올, 암모니아, 수소, 에틸렌 옥사이드를 생산하는 공장이나 발전소의 배출흐름에서 회수된 재활용 CO2이다. 또한, CO2는 31.1℃의 Tc와 73.8bar의 Pc와 같이 접근하기 쉬운 임계점을 가진다.First, the sources of CO 2 are abundant natural CO 2 and recycled CO 2 recovered from the emission streams of plants and power plants producing ethanol, ammonia, hydrogen and ethylene oxide. CO 2 also has easy-to-access critical points such as Tc at 31.1 ° C. and Pc at 73.8 bar.
용매로 CO2를 사용하는 다른 장점은 값이 싸고, 불연성이면서, 무독성이며, 쉽게 재활용할 수 있다는 점이다. 게다가, 초임계 CO2는 고분자로부터 잔류 단량체, 용매, 촉매를 효과적으로 추출하는 데 사용될 수 있다. 게다가 초임계 유체를 이용한 중합은 단순히 압력을 변화시킴으로 밀도를 변화시킬 수 있기 때문에 분자량이 다른 고분자 혼합물을 효과적으로 분리할 수 있다. 초임계 CO2가 고분자에 흡착될 때 용융 점도나, 용액 점도를 줄일 수 있기 때문에 고분자의 형태를 초임계 건조나 발포에 의해 조절할 수 있다.Another advantage of using CO 2 as a solvent is that it is inexpensive, nonflammable, nontoxic and easily recyclable. In addition, supercritical CO 2 can be used to effectively extract residual monomers, solvents, and catalysts from polymers. In addition, polymerization with supercritical fluids can change the density simply by changing the pressure, effectively separating polymer mixtures of different molecular weights. When the supercritical CO 2 is adsorbed onto the polymer, the melt viscosity and the solution viscosity can be reduced, so that the form of the polymer can be controlled by supercritical drying or foaming.
본 발명에서 사용한 반응 장치에서는 이산화탄소를 초임계 용매로 사용하기 때문에 이산화탄소 용기에 사이펀 튜브를 장착하여 액체 이산화탄소가 분출되게 하였으며, 이를 냉각기에 통과시켜 완전히 액화시켜서 고압용 액체 펌프를 이용하여 가압하여 고압 반응기에 액체 이산화탄소가 들어가도록 한다. 고압 반응기는 압력이 4000psi까지 밀봉되는 재킷 부분과 -20℃ 내지 200℃까지 온도를 제어할 수 있는 비례 적분 미분 제어기, 온도계, 가열기, 압력계, 안전 밸브 및 반응물을 교반할 수 있는 교반기와 이에 따르는 속도조절기와 속도를 측정하기 위한 회전 속도계가 부착되어 있다.In the reaction apparatus used in the present invention, since carbon dioxide is used as a supercritical solvent, a siphon tube is mounted in a carbon dioxide container to eject liquid carbon dioxide, and the liquid carbon dioxide is completely liquefied by passing it through a cooler to pressurize using a high pressure liquid pump. Allow liquid carbon dioxide to enter. The high pressure reactor is equipped with a jacketed portion of which pressure is sealed up to 4000 psi and a proportional integral derivative controller capable of temperature control from -20 ° C to 200 ° C, a stirrer capable of stirring the thermometer, heater, pressure gauge, safety valves and reactants and the following speeds. A tachometer is attached to the controller and to measure the speed.
본 발명에서는 반응 조건을 설정하기 위해서 우선 모노리드 형태의 겔을 합성한다. 적량의 단량체와 촉매를 알코올에 용해시켜 앰플(ampule)에 넣고 공기와 접촉하지 못하도록 토치로 가열하여 밀봉하였다. 이때, 촉매의 함량 및 고형분의 농도비를 변화시켜 이에 따른 물성을 보고자 하였다.In the present invention, in order to set the reaction conditions, a monolithic gel is first synthesized. The appropriate amount of monomer and catalyst was dissolved in alcohol and placed in an ampule and sealed by heating with a torch to prevent contact with air. At this time, by changing the content ratio of the content of the catalyst and the solid content it was intended to see the properties accordingly.
밀봉된 앰플을 80℃ 내지 85℃ 오븐에 넣어서 7일간 겔화시킨다. 반응이 끝나면 어두운 갈색의 겔을 형성한다.The sealed ampoules are placed in an 80 ° C. to 85 ° C. oven to gel for 7 days. At the end of the reaction, a dark brown gel is formed.
본 발명에서는 환경에 유해한 용매를 사용하는 졸-에멀젼-겔 기술과는 달리 친환경 용매인 초임계 이산화탄소를 용매로 하여 졸-분산-겔(sol-dispersion-gel) 기술을 통한 입자 형태의 페놀릭-퍼퍼랄 겔 입자를 합성한다.In the present invention, unlike the sol-emulsion-gel technology using a solvent that is harmful to the environment, phenolic- in the form of particles through a sol-dispersion-gel technology using supercritical carbon dioxide, which is an environmentally friendly solvent, as a solvent. Synthetic gel particles.
보다 상세하게는 우선 다기능성 단량체를 고압 반응기에 넣고, 여기에 산촉매 및 안정제를 첨가한다.More specifically, first, the multifunctional monomer is placed in a high pressure reactor, and an acid catalyst and a stabilizer are added thereto.
다기능성 단량체로는 페놀릭-퍼퍼랄, 레소시놀-포름알데히드, 멜라민-포름알데히드, 카테콜-포름알데히드(Catechol-formaldehyde), 페놀-레소시놀-포름알데히드, 플로로글루시놀-포름알데히드(Phloroglucinol-formaldehyde), 페놀-포름알데히드 중에서 1종 선택하여 사용한다.Multifunctional monomers include phenolic-peralal, resorcinol-formaldehyde, melamine-formaldehyde, catechol-formaldehyde, phenol-resosocinol-formaldehyde, fluoroglucinol-formaldehyde (Phloroglucinol-formaldehyde) or phenol-formaldehyde is used to select one.
안정제로는 폴리디메틸실록산류, 폴리디하이드로퍼플루오로옥틸 아크릴레이트류 중에서 선택하여 사용할 수 있으며, 그 함량은 초임계 유체에 대해 2∼20%인것이 바람직하다.The stabilizer may be selected from polydimethylsiloxanes and polydihydroperfluorooctyl acrylates, and the content thereof is preferably 2 to 20% based on the supercritical fluid.
그리고, 산촉매를 사용하는 바, 산촉매로는 파라톨루엔 술폰산, 인산(phosphoric acid) 중에서 1종을 선택하여 사용한다. 산촉매의 함량은 페놀릭 노볼락에 대하여 5∼40%인 것이 바람직하다.As the acid catalyst is used, one of the acid catalyst is selected from paratoluene sulfonic acid and phosphoric acid. The content of the acid catalyst is preferably 5 to 40% with respect to the phenolic novolac.
그 다음, 초임계 이산화탄소를 분산매질로 하여 40∼120℃에서 1200∼4000psi 압력하에서 4∼24시간 동안 분산 중합을 수행한다.Then, dispersion polymerization is performed for 4 to 24 hours at a pressure of 1200 to 4000 psi at 40 to 120 ° C. using supercritical carbon dioxide as a dispersion medium.
만일, 반응온도가 알코올의 비점보다 높으면 반응물질이 끓는 문제가 발생할 수 있다. 반응압력이 낮고 반응온도가 높아야 초임계 이산화탄소에 대한 페놀릭 노볼락의 용해도가 나빠져 분산이 용이하다. 반면 반응온도가 너무 낮으면 겔화 시간이 오래 걸리는 단점이 있다. 또한 반응시간이 반응물질의 겔화 시간보다 짧으면 졸-겔 반응이 완전히 진행될 수 없다는 문제가 발생할 수 있다.If the reaction temperature is higher than the boiling point of the alcohol, a problem of boiling the reactant may occur. When the reaction pressure is low and the reaction temperature is high, the solubility of phenolic novolac in supercritical carbon dioxide deteriorates, which facilitates dispersion. On the other hand, if the reaction temperature is too low, there is a disadvantage in that it takes a long time to gel. In addition, if the reaction time is shorter than the gelling time of the reactant may cause a problem that the sol-gel reaction cannot proceed completely.
이와 같이 다기능성 단량체를 초임계 이산화탄소에 부유시키고 안정제를 사용하여 분산시키는 경우 종래 졸-에멀젼-겔 방법과는 달리 결과물을 세척할 필요가 없다.As such, when the multifunctional monomer is suspended in supercritical carbon dioxide and dispersed using a stabilizer, the resultant does not need to be washed, unlike the conventional sol-emulsion-gel method.
상기와 같이 분산중합을 수행한 다음, 10∼72시간 동안 경화시키고, 초임계 이산화탄소를 서서히 배출한다.After the dispersion polymerization is carried out as described above, the mixture is cured for 10 to 72 hours, and the supercritical carbon dioxide is gradually discharged.
초임계 이산화탄소를 반응 종결 후 배출하는 것은 제조된 유기 겔이 깨지지 않도록 하기 위한 것으로서, 초임계 유체의 배출시간은 스테인레스 스틸 반응기 크기에 따라 0.5∼5시간으로 하는 것이 바람직하다.The discharge of the supercritical carbon dioxide after completion of the reaction is to prevent the prepared organic gel from breaking, and the discharge time of the supercritical fluid is preferably 0.5 to 5 hours depending on the size of the stainless steel reactor.
본 발명은 페놀릭-퍼퍼랄 겔을 입자 형태로는 최초로 합성하였으며, 반응용매로 초임계 이산화탄소를 이용한 겔의 합성으로는 최초이다. 또한, 이 발명은 유기 겔의 합성으로만 그치는 것이 아니라 페놀릭-퍼퍼랄 에어로겔을 단일공정으로 제조할 수 있는 중간체의 합성이라는 점에서 중요하다.The present invention first synthesized phenolic-peralal gel in the form of particles, and is the first to synthesize a gel using supercritical carbon dioxide as a reaction solvent. In addition, this invention is important not only in the synthesis of organic gels but also in the synthesis of intermediates capable of producing phenolic-perforated aerogels in a single process.
본 발명은 다기능성 단량체를 초임계 유체 용매 상에서 졸-분산-겔 방법의 형태로 목적하는 유기 겔 입자를 합성하고 열처리하는 고체 입자의 제조방법로서, 유기 겔 입자는 입경 500nm∼100㎛이고, 입경분포는 1∼10㎛인 입자가 90%이상인 것을 그 특징으로 한다. 그리고, 유기 겔 입자는 밀도가 0.03∼1.0g/cc이다.The present invention provides a method for preparing solid particles for synthesizing and heat treating the desired organic gel particles in the form of a sol-dispersion-gel method in a supercritical fluid solvent, wherein the organic gel particles have a particle diameter of 500 nm to 100 μm, The distribution is characterized by having 90% or more of particles having a size of 1 to 10 µm. The organic gel particles have a density of 0.03 to 1.0 g / cc.
본 발명에 따른 유기 겔의 제조방법 중 페놀릭-퍼퍼랄 겔의 제조방법을 구체적으로 살펴보면, 우선 고압 반응기에서 페놀릭 노볼락, 퍼퍼랄, 알코올, 산촉매 및 안정제를 혼합하여 혼합용액을 만든다.Looking specifically at the method for producing a phenolic-perforated gel of the organic gel according to the present invention, first, phenolic novolac, peroxide, alcohol, acid catalyst and stabilizer are mixed in the high pressure reactor to make a mixed solution.
이때, 알코올로는 헵틸 알코올, 옥틸 알코올, 노말프로판올, 이소프로판올, 에탄올, 메탄올 중에서 1종을 선택하여 사용한다. 이때, 혼합용매의 고형분 함량비는 10∼70중량% 되도록 하는 것이 바람직하다.In this case, one alcohol is selected from heptyl alcohol, octyl alcohol, normal propanol, isopropanol, ethanol and methanol. At this time, the solid content ratio of the mixed solvent is preferably 10 to 70% by weight.
그 다음, 반응물을 교반하는 바, 교반속도는 100∼500rpm인 것이 바람직하고, 교반기의 종류에 따라 평균입경, 입경분포, 입자형태가 달라지므로 선택적으로 사용한다.Then, the reaction mixture is stirred, it is preferable that the stirring speed is 100 to 500rpm, and the average particle size, particle size distribution, and particle shape vary depending on the type of the stirrer.
교반 후 초임계 이산화탄소를 분산매질로 하고 가압, 가열하여 졸-겔 반응을 수행하는 바, 반응온도는 40∼120℃이며, 반응압력은 1200∼4000psi로 하는 것이 바람직하고, 반응시간은 4∼24시간으로 하여 결과적으로 전화율이 70% 이상 되도록 하여야 한다.After stirring, supercritical carbon dioxide was used as a dispersion medium, and the sol-gel reaction was carried out by pressing and heating. The reaction temperature was 40 to 120 ° C, the reaction pressure was preferably 1200 to 4000 psi, and the reaction time was 4 to 24. As a result, the conversion rate should be 70% or more as a result.
그 다음, 이를 10∼72시간 동안 경화시키고, 초임계 이산화탄소를 서서히 배출하면 본 발명에 따른 페놀릭-퍼퍼랄 겔을 얻을 수 있다.Then, it is cured for 10 to 72 hours, and the supercritical carbon dioxide is slowly discharged to obtain a phenolic-perforated gel according to the present invention.
한편, 페놀릭노볼락과 퍼퍼랄의 개략적 반응단계는 다음과 같다.On the other hand, the schematic reaction step of phenolic novolac and perperal is as follows.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.
[실시예 1]Example 1
헵틸 알코올 용매 70g에 13.6g의 페놀수지와 13,6g의 퍼퍼랄을 녹인 후 고압 반응기에 넣었다. 여기에 염화수소를 생성시키는 촉매(파라톨루엔술폰산, 일본 Junsei사 제품) 2.8g과 안정제인 폴리디메틸실록산 20g을 넣고 80℃의 초임계 이산화탄소를 분산 매질로 하여 12시간 동안 졸-겔 반응한 후, 하루 동안 경화시킨다(압력 1200psi). 그 다음, 초임계 이산화탄소를 대기중으로 1시간에 걸쳐 서서히 배출하였다.After dissolving 13.6 g of phenol resin and 13,6 g of perol in 70 g of heptyl alcohol solvent, the mixture was put in a high pressure reactor. 2.8 g of a catalyst for producing hydrogen chloride (paratoluene sulfonic acid, manufactured by Junsei Japan) and 20 g of polydimethylsiloxane as a stabilizer were added thereto, followed by sol-gel reaction for 12 hours using supercritical carbon dioxide at 80 ° C. as a dispersion medium. Harden (pressure 1200psi) Then, supercritical carbon dioxide was slowly discharged into the atmosphere over 1 hour.
제조된 페놀릭-퍼퍼랄 겔은 어두운 갈색을 띄고, 0.03∼1.0g/cc의 밀도를 갖는다. 다른 종류의 용매로 이소프로판올, 노말 프로판올, 에탄올, 메탄올, 옥탄올을 사용할 수 있다. 그러나, 위와 같이 용매를 달리 할 때는 경화온도를 다르게 하여 주어야 한다.The phenolic-perforated gel produced had a dark brown color and had a density of 0.03 to 1.0 g / cc. Other solvents may be used isopropanol, normal propanol, ethanol, methanol, octanol. However, when the solvent is different as above, the curing temperature should be different.
제조된 페놀릭-퍼퍼랄 겔에 대하여 전자현미경(SEM, S4200, 일본 Hitachi사)으로 평균입경 및 입경 분포를 측정하였다. 측정결과는 평균입경이 3.5㎛이고, 입경 분포는 3∼5㎛인 입자분포가 90%이었다.The average particle diameter and particle size distribution of the prepared phenolic-peral gel were measured by an electron microscope (SEM, S4200, Hitachi, Japan). The measurement result was 90% of the particle distribution with an average particle diameter of 3.5 micrometers and a particle size distribution of 3-5 micrometers.
페놀릭-퍼퍼랄-알코올 용액의 겔화 시간은 5시간이었다.The gelling time of the phenolic-peralal-alcohol solution was 5 hours.
[실시예 2]Example 2
80g의 옥틸 알코올 용매에 9.09g의 페놀수지와 9.09g의 퍼퍼랄을 녹인 후 고압 반응기에 넣었다. 여기에 염화수소를 생성시키는 촉매(인산, 일본 Junsei사 제품) 1.82g과 안정제인 폴리디메틸실록산 10g을 넣고 80℃의 초임계 이산화탄소를 분산 매질로 하여 18시간 동안 졸-겔반응하여 유기 겔 입자를 제조하였다(압력 1200psi). 이때 공정은 상기 실시예 1과 동일하다.After dissolving 9.09 g of phenol resin and 9.09 g of perol in 80 g of octyl alcohol solvent, the mixture was placed in a high pressure reactor. 1.82 g of a catalyst for producing hydrogen chloride (phosphate, manufactured by Junsei, Japan) and 10 g of polydimethylsiloxane as a stabilizer were added thereto, and an organic gel particle was prepared by sol-gel reaction for 18 hours using a supercritical carbon dioxide at 80 ° C. as a dispersion medium. (Pressure 1200 psi). At this time, the process is the same as in Example 1.
다른 종류의 용매로 이소프로판올, 노말 프로판올, 에탄올, 메탄올, 옥탄올을 사용할 수 있다. 그러나, 위와 같이 용매를 달리 할 때는 경화온도를 다르게 한다.Other solvents may be used isopropanol, normal propanol, ethanol, methanol, octanol. However, when the solvent is different as above, the curing temperature is different.
제조된 유기 겔 입자의 입경 및 입경 분포를 주사전자현미경으로 측정하였다.The particle diameter and particle size distribution of the prepared organic gel particles were measured by scanning electron microscope.
[실시예 3] Example 3
상기 실시예 1과 동일한 공정을 이용하여 안정제의 함량을 초임계 유체에 대해 20%로 변경하여 유기 겔 입자를 제조하였다.Organic gel particles were prepared by changing the content of the stabilizer to 20% with respect to the supercritical fluid using the same process as in Example 1.
제조된 페놀릭-퍼퍼랄 겔 입경 및 입경분포를 주사전자현미경으로 측정하였다. 이때 페놀릭 퍼퍼랄 겔의 입자색이 어두워서 광산란법을 이용하여 페놀릭 퍼퍼랄 겔 입경을 측정할 수 없다.The prepared phenolic-perforated gel particle diameter and particle size distribution were measured by scanning electron microscopy. At this time, since the particle color of the phenolic peripheral gel is dark, the particle size of the phenolic peripheral gel cannot be measured using the light scattering method.
[실시예 4] Example 4
상기 실시예 1과 동일한 공정을 이용하여 산촉매의 함량을 페놀릭 노볼락에 대하여 30%로 변경하여 유기 겔 입자를 제조하였다.Organic gel particles were prepared by changing the content of the acid catalyst to 30% with respect to the phenolic novolac using the same process as in Example 1.
제조된 페놀릭 퍼퍼랄 겔 입경 및 입경분포를 전자현미경으로 측정하였다.The prepared phenolic peripheral gel particle diameter and particle size distribution were measured by an electron microscope.
[실시예 5] Example 5
상기 실시예 1과 같은 공정을 이용하여 반응온도를 40℃로, 반응압력을 2500psi로 변화시켜 12시간동안 졸-겔 반응한 후, 하루 동안 경화시킨다. 제조된 페놀릭-퍼퍼랄 겔 입경 및 입경 분포를 전자현미경으로 측정하였다.Using the same process as in Example 1, the reaction temperature was changed to 40 ° C., the reaction pressure was changed to 2500 psi, and the sol-gel reaction was carried out for 12 hours, followed by curing for one day. The prepared phenolic-perforated gel particle diameter and particle size distribution were measured by an electron microscope.
[실시예 6] Example 6
상기 실시예 1과 같은 공정을 이용하여 223g의 프로판올에 8g의 레소시놀과 12g의 포름알데히드를 녹인 후 고압 반응기에 넣었다. 여기에 염화수소를 생성시키는 촉매(파라톨루엔술폰산, 일본 Junsei사 제품) 1.6g과 안정제인 폴리디메틸실록산 20g을 넣고 80℃, 1200psi에서 24시간동안 졸-겔 반응시킨 후 하루 동안 경화시켜 레소시놀-포름알데히드 겔 입자를 제조하였다. 이때 제조된 에소시놀-포름알데히드 겔 입자는 적갈색을 나타낸다.Using the same process as in Example 1, 8g of resorcinol and 12g of formaldehyde were dissolved in 223g of propanol and then placed in a high pressure reactor. Here, 1.6 g of a catalyst for producing hydrogen chloride (paratoluene sulfonic acid, manufactured by Junsei, Japan) and 20 g of polydimethylsiloxane as a stabilizer were added thereto, followed by a sol-gel reaction at 80 ° C. and 1200 psi for 24 hours, followed by curing for one day. Formaldehyde gel particles were prepared. At this time, the prepared isosinol-formaldehyde gel particles are reddish brown.
[실시예 7] Example 7
상기 실시예 1과 같은 공정을 이용하여 156.64g의 에탄올에 21.44g의 멜라인 단량체와18.86g의 포름알데히드를 녹인 후 고압 반응기에 넣었다. 여기에 염화수소를 생성시키는 촉매(파라톨루엔술폰산, 일본 Junsei사 제품) 9.5g과 안정제인 폴리디메틸실록산 20g을 넣고 80℃, 1200psi에서 24시간 동안 졸-겔 반응시킨 후 이틀 동안 경화시켜 멜라민-포름알데히드 겔 입자를 제조하였다. 제조된 멜라민-포름알데히드 겔 입자는 흰색을 나타낸다.Using the same process as in Example 1, 21.44 g of melanin monomer and 18.86 g of formaldehyde were dissolved in 156.64 g of ethanol and then placed in a high pressure reactor. Here, 9.5 g of a catalyst for producing hydrogen chloride (paratoluenesulfonic acid, manufactured by Junsei Co., Ltd.) and 20 g of polydimethylsiloxane as a stabilizer were added thereto, followed by sol-gel reaction at 80 ° C. and 1200 psi for 24 hours, followed by curing for 2 days, followed by melamine-formaldehyde. Gel particles were prepared. The melamine-formaldehyde gel particles produced are white.
상기 실시예 1∼7에 따라 제조된 페놀릭-퍼퍼랄 겔의 평균입경 및 입경분포는 다음 표 1에 나타낸 바와 같다.The average particle diameter and particle size distribution of the phenolic-peral gel prepared according to Examples 1 to 7 are as shown in Table 1 below.
한편, 상기 실시예 1에 따라 제조된 페놀릭-퍼퍼랄 겔 입자의 전자현미경 사진(×5000)을 도 1에 나타내었다.Meanwhile, an electron micrograph (× 5000) of phenolic-perforated gel particles prepared according to Example 1 is shown in FIG. 1.
상기 표 1 및 첨부된 도 1의 결과로부터 본 발명에 따라 초임계 이산화탄소를 분산매질로 하여 졸-분산-겔 방법을 통해 제조된 유기 겔은 입자 형태로서 초임계 유체에 대한 안정체의 함량이 증가할수록 평균 입경은 줄어들었고, 페놀릭 노볼락에 대한 산촉매의 함량을 변화시키거나 반응압력 및 온도를 변화시켜도 겔의 평균 입경은 거의 비슷하게 나타났다. 또한 다기능성 단량체로 레소시놀 포름알데히드나 멜라민-포름알데히드를 사용한 경우 평균 입경이 페놀릭-퍼퍼랄을 사용한 경우보다 크게 나타났다.The organic gel prepared by the sol-dispersion-gel method using supercritical carbon dioxide as a dispersion medium according to the present invention from the results of Table 1 and the attached FIG. 1 has a particle content in the form of a stabilizer for the supercritical fluid. As the mean particle size decreased, the average particle diameter of the gel was almost the same even if the acid catalyst content of phenolic novolac was changed or the reaction pressure and temperature were changed. In addition, the use of resorcinol formaldehyde or melamine-formaldehyde as the multifunctional monomer showed a larger average particle diameter than that of phenolic-peral.
이상에서 상세히 설명한 바와 같이, 본 발명에 따라 초임계 이산화탄소를 분산매질로 하여 졸-분산-겔 방법을 통해 페놀릭-퍼퍼랄 겔 등과 같은 유기 겔 입자를 제조하는 경우 그 형태는 입자형태로서 단일공정으로 유기 겔을 제조할 수 있으며 졸-에멀젼-겔 방법에서와 같이 유해한 용매를 사용할 필요가 없으며, 결과물의 세척 등이 필요없는 효과 등이 있다.As described in detail above, in the case of preparing organic gel particles such as phenolic-peripheral gel, etc. by the sol-dispersion-gel method using supercritical carbon dioxide as a dispersion medium according to the present invention, the form is in the form of a single process. It is possible to prepare an organic gel, there is no need to use a harmful solvent as in the sol-emulsion-gel method, there is an effect that does not need to wash the resultant.
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US5260855A (en) * | 1992-01-17 | 1993-11-09 | Kaschmitter James L | Supercapacitors based on carbon foams |
US5376744A (en) * | 1993-11-10 | 1994-12-27 | The University Of Akron | Carbocationic polymerizations in supercritical CO2 |
US5420168A (en) * | 1993-04-01 | 1995-05-30 | The Regents Of The University Of California | Method of low pressure and/or evaporative drying of aerogel |
US5508341A (en) * | 1993-07-08 | 1996-04-16 | Regents Of The University Of California | Organic aerogel microspheres and fabrication method therefor |
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US5420168A (en) * | 1993-04-01 | 1995-05-30 | The Regents Of The University Of California | Method of low pressure and/or evaporative drying of aerogel |
US5508341A (en) * | 1993-07-08 | 1996-04-16 | Regents Of The University Of California | Organic aerogel microspheres and fabrication method therefor |
US5376744A (en) * | 1993-11-10 | 1994-12-27 | The University Of Akron | Carbocationic polymerizations in supercritical CO2 |
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