KR0142013B1 - Method of preparing synthetic adsorbent - Google Patents
Method of preparing synthetic adsorbentInfo
- Publication number
- KR0142013B1 KR0142013B1 KR1019940015906A KR19940015906A KR0142013B1 KR 0142013 B1 KR0142013 B1 KR 0142013B1 KR 1019940015906 A KR1019940015906 A KR 1019940015906A KR 19940015906 A KR19940015906 A KR 19940015906A KR 0142013 B1 KR0142013 B1 KR 0142013B1
- Authority
- KR
- South Korea
- Prior art keywords
- pore volume
- solvent
- surface area
- specific surface
- resin
- Prior art date
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Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 24
- -1 aliphatic vinyl compound Chemical class 0.000 claims abstract description 17
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 229920006216 polyvinyl aromatic Polymers 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 20
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002861 polymer material Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 claims description 2
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical group CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 claims description 2
- 150000007824 aliphatic compounds Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 78
- 239000004793 Polystyrene Substances 0.000 abstract description 31
- 229920002223 polystyrene Polymers 0.000 abstract description 31
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 10
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 description 33
- 229920005989 resin Polymers 0.000 description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012508 resin bead Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
본 발명은 합성 흡착제의 제조방법에 관한 것으로, 더욱 상세하게는 모노비닐방향족 화합물과 폴리비닐 방향족 화합물 및 지방족 비닐화합물을 함유하고 여기에 폴리스티렌 등의 선형 고분자물질과 양용매 및 불용매의 혼합물을 첨가하여 제조함으로써 비표적(specific surface area)이 크고 기공의 크기분포를 조절할 수 있는 다공성의 가교공중합체인 합성 흡착제를 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a synthetic adsorbent, and more particularly, to a monovinylaromatic compound, a polyvinyl aromatic compound and an aliphatic vinyl compound, and a mixture of a linear polymer such as polystyrene, a good solvent and a nonsolvent is added thereto. The present invention relates to a method for preparing a synthetic adsorbent, which is a porous crosslinked copolymer having a specific surface area and a pore size distribution.
Description
본 발명은 합성 흡착제의 제조방법에 관한 것으로, 더욱 상세하게는 모노 비닐 방향족 화합물과 폴리비닐 방향족 화합물 및 지방족 비닐화합물을 함유하고 여기에 폴리스티렌 등의 선형 고분자물질과 양용매 및 불용매의 혼합물을 첨가하여 제조함으로써 비표면적(specific surface area)이 크고 기공의 크기분포를 조절할 수 있는 다공성의 가교공중합체인 합성 흡착제를 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a synthetic adsorbent, and more particularly, to a monovinyl aromatic compound, a polyvinyl aromatic compound and an aliphatic vinyl compound, and a mixture of a linear polymer such as polystyrene, a good solvent and a nonsolvent is added thereto. The present invention relates to a method for producing a synthetic adsorbent, which is a porous crosslinked copolymer having a specific surface area and a pore size distribution.
일반적으로 흡착제라하면 혼합용액 중에서 어떤 특정한 화합물들에 대해서 선택성을 가지고 이들 물질을 분리해낼 수 있는 분말이나 과립상 또는 구형의 고체입자를 지칭한다. 그리고 이 선택성은 흡착제의 표면에서 발생하기 때문에 흡착 효율은 표면적의 크기와 매우 밀접한 관계가 있다. 과립 모양의 탄소나 실리카겔, 석면 등은 매우 잘 알려진 천연의 다공성 흡착제들이다.Generally, the adsorbent refers to a powder, granular or spherical solid particle capable of separating these substances with selectivity for certain compounds in the mixed solution. And since this selectivity takes place on the surface of the adsorbent, the adsorption efficiency is very closely related to the size of the surface area. Granular carbon, silica gel and asbestos are very well known natural porous adsorbents.
합성 흡착제라하면 비극성 또는 극성이 약한 가교결합된 구형의 다공성 물질로서 비표면적이 큰 합성고분자 물질로 주로 수용액중에 존재하는 유기물질을 분리하는데 이용된다. 따라서 의약 등과 같은 복잡한 화합물을 분리, 정제하는데 주로 사용되고있다.Synthetic adsorbent is a non-polar or weakly polarized crosslinked spherical porous material, a synthetic polymer material with a large specific surface area, and is mainly used to separate organic substances in an aqueous solution. Therefore, it is mainly used to separate and purify complex compounds such as medicine.
합성 흡착제에 사용되는 화합물은 모노비닐 화합물과 폴리비닐 화합물이 주원료로 사용되며 때때로 폴리스티렌 등과 같은 반응에 참여하지 않는 선형 중합체가 사용되기도 하고 용매 또는 용매 없이 현탁 중합된다. 반응에 참여하지 않는 선형 중합체는 수지제조 후 적당한 용매에 의해 추출된다.Compounds used in synthetic adsorbents are monovinyl compounds and polyvinyl compounds as main raw materials, and linear polymers that do not participate in the reaction, such as polystyrene, are sometimes used or are suspended or polymerized without solvent. Linear polymers that do not participate in the reaction are extracted with a suitable solvent after resin preparation.
지금까지 알려진 합성 흡착제 제조방법을 살펴보면, 스티렌 디비닐벤젠을 주원료로 하고 용매로서 톨루엔을 그리고 다공성을 증가시키기 위해 선형 폴리스티렌을 사용한 방법(일본특허공고 소46-40431호), 할로겐화 모노비닐 화합물과 소량의 폴리비닐 화합물을 사용하여 경가교된 중합체를 제조한 후 프리델-크래프트 반응(Friedel-Crafts reation)을 통해 후가교시키는 방법(미국특허 제4,191,813호, 제4,263,407호), 그리고 톨루엔 등과 같은 양용매 중에서 방향족 폴리비닐모노머를 40% 이상 사용하여 표면적을 증가시키는 방법(일본특허공고 소60-090040호)등이 있다. 그러나,이들 방법은 각각 어느정도 이상의 비표면적을 증가시킬 수 있다는 장점이 있지만 기공의 크기를 원하는 대로 조절하는데는 사실상 어려움이 있었다.Looking at the production method of synthetic adsorbents known to date, styrene divinylbenzene as the main raw material, toluene as a solvent and linear polystyrene to increase the porosity (Japanese Patent Publication No. 46-40431), a halogenated monovinyl compound and a small amount To prepare a light-crosslinked polymer using a polyvinyl compound, and then to post-crosslink through Friedel-Crafts reation (US Pat. Nos. 4,191,813, 4,263,407), and a good solvent such as toluene And a method of increasing the surface area by using at least 40% of an aromatic polyvinyl monomer (Japanese Patent Publication No. 60-090040). However, each of these methods has the advantage of increasing the specific surface area to some extent, but it is practically difficult to adjust the size of the pores as desired.
따라서, 본 발명자들은 상기 종래기술의 문제점을 극복하고자 노력한 결과 스티렌 등 공지의 모노비닐 방향족 화합물 1종 이상과 디비닐벤젠 등의 폴리비닐 방향족 화합물 1종 이상 및 메틸메타크릴레이트 등의 지방족 비닐화합물을 함유하고 여기에 선형 고분자물질인 폴리스티렌과, 벤젠 등의 양용매 및 n-헥산 등의 불용매를 적정비율로 혼합한 혼합물을 첨가함으로써 가교결합된 방향족 공중합체의 다공도를 증가시켜 비표면적을 크게하고 기공의 크기분포를 자유롭게 조절한 본발명의 합성 흡착제의 제조방법을 완성하였다.Accordingly, the present inventors have tried to overcome the problems of the prior art, and as a result, at least one known monovinyl aromatic compound such as styrene, at least one polyvinyl aromatic compound such as divinylbenzene, and an aliphatic vinyl compound such as methyl methacrylate And a mixture of polystyrene, a linear polymer material, a good solvent such as benzene, and an insoluble solvent such as n-hexane in an appropriate ratio, is added thereto to increase the porosity of the crosslinked aromatic copolymer to increase the specific surface area. A method for preparing a synthetic adsorbent of the present invention, in which the pore size distribution is freely controlled, was completed.
본 발명은 모노비닐 방향족 화합물 등으로 이루어지고 여기에 선형 고분자물질과 양용매 및 불용매의 혼합물을 첨가하여 이루어짐으로써 다공성이며 비표면적이 크고 기공의 크기분포를 자유롭게 조절할 수 있는 합성 흡착제의 제조방법을 제공하는데 그 목적이 있다.The present invention is made of a monovinyl aromatic compound and the like, and is made by adding a mixture of a linear polymer material, a good solvent and a non-solvent therein to a method of preparing a synthetic adsorbent that is porous and has a specific surface area and can freely control the size distribution of pores. The purpose is to provide.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 합성 흡착제를 제조하는데 있어서, 모노비닐 방향족 화합물, 폴리비닐 방향족 및 지방족 비닐화합물을 함유하고 여기에 선형 고분자물질과 양용매 및 불용매의 혼합물을 첨가하여 제조하는 것을 그 특징으로 한다.The present invention is characterized in that the synthetic adsorbent is prepared by containing a monovinyl aromatic compound, a polyvinyl aromatic and an aliphatic vinyl compound, and adding a mixture of a linear polymer material, a good solvent, and a nonsolvent thereto.
이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 비표면적이 크고 기공의 크기분포를 자유롭게 조절할 수 있는 합성 흡착제의 제조방법에 관한 것으로서, 본 발명에서 모노비닐 방향족 화합물로는 공지의 스티렌, 비닐톨루엔 및 에틸비닐벤젠 중에서 선택된 1종 이상의 것을 전체 비닐모노머중 85 ∼ 0.1 중량%의 범위로 사용한다.The present invention relates to a method for producing a synthetic adsorbent having a large specific surface area and capable of freely controlling the size distribution of pores. In the present invention, the monovinyl aromatic compound includes at least one selected from styrene, vinyltoluene and ethylvinylbenzene. It is used in the range of 85 to 0.1% by weight of all vinyl monomers.
또한, 폴리비닐 방향족 화합물로는 디비닐벤젠, 트리비닐벤젠, 디비닐톨루엔 및 디비닐크시렌 중에서 선택된 1종 이상의 것을 전체 비닐화합물중 15 ∼ 100 중량% 범위로 사용한다. 여기서 폴리비닐 방향족 화합물 사용량이 15 중량% 미만이면 합성흡착제로서 유용한 비표면적을 얻을 수 없다.As the polyvinyl aromatic compound, at least one selected from divinylbenzene, trivinylbenzene, divinyl toluene, and divinyl xylene is used in the range of 15 to 100% by weight in the total vinyl compound. If the amount of the polyvinyl aromatic compound used is less than 15% by weight, the specific surface area useful as a synthetic adsorbent cannot be obtained.
또한, 본 발명에서는 상기 방향족 비닐화합물 외에도 지방족 비닐화합물을 전체 비닐모노머중 0 ∼ 20 중량%의 범위로 사용할 수 있는데, 이중 지방족 모노비닐 화합물로는 메틸메타크릴레이트, 아크릴로니트릴, 2-히드록시에틸메타크릴레이트, 메타크릴산 또는 에틸아크릴레이트 등을 사용하고, 지방족 폴리비닐 화합물로는 에틸렌글리콜디메타크릴레이트 또는 트리메틸올프로판 트리메타크릴레이트 등의 사용이 가능하다. 상기 지방족 비닐화합물의 사용량이 전체 비닐모노머중 20 중량%를 초과하여 사용하면 내열성 및 색깔에 문제가 있어 바람직하지 않다.In addition, in the present invention, in addition to the aromatic vinyl compound, an aliphatic vinyl compound may be used in the range of 0 to 20% by weight of the total vinyl monomer, and as the aliphatic monovinyl compound, methyl methacrylate, acrylonitrile, and 2-hydroxy Ethyl methacrylate, methacrylic acid or ethyl acrylate is used, and as the aliphatic polyvinyl compound, ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate can be used. If the amount of the aliphatic vinyl compound to be used exceeds 20% by weight of the total vinyl monomer, it is not preferable because of problems in heat resistance and color.
또한, 본 발명에서는 다양한 평균 분자량을 가진 선형 고분자물질과 양용매 및 불용매를 적정비율로 혼합한 혼합물을 사용하는데, 특히 용매선정은 매우 중요하며 사용된 용매 또는 용매 혼합물에 따라서 기공의 분포, 기공의 구조 또는 비표면적이 크게 변할 수 있다.In addition, in the present invention, a mixture of linear polymers having various average molecular weights, a good solvent, and an insoluble solvent is used in an appropriate ratio. Particularly, the selection of a solvent is very important, and the distribution of pores and pores depending on the solvent or solvent mixture used. The structure or specific surface area of can vary significantly.
본 발명에서 기공의 분포를 비교적 정교하게 조절하기 위해서 선형 고분자물질로 선형 폴리스티렌을 사용하는데 분자량이 1,000 ∼ 50,000 인 것을 전체 비닐모노머중 25 중량% 이하로 사용한다. 이들 반응에 참여하지 않는 선형 고분자물질의 사용량이 25 중량%로 초과하게 되면 수지비드의 강도가 크게 저하되는 문제가 있다. 사용된 선형 고분자물질은 반응이 끝난 후 적당한 용매에 의해 용출되며, 이에 의해서 수지에 선형 고분자물질에 의한 기공이 형성된다. 이들 기공은 비닐화합물만을 사용해서 형성되는 기공과 형태가 다를 수도 있으며, 사용된 선형 고분자물질의 분자량에 따라 기공의 크기 또는 기공의 분포를 정교하게 조절할 수 있다는데 그 특징이 있다.In the present invention, in order to control the distribution of pores relatively precisely, linear polystyrene is used as a linear polymer material, and a molecular weight of 1,000 to 50,000 is used in 25% by weight or less of the vinyl monomers. When the amount of the linear polymer material that does not participate in these reactions exceeds 25% by weight, the strength of the resin beads is greatly reduced. The linear polymer used is eluted with a suitable solvent after the reaction, thereby forming pores by the linear polymer in the resin. These pores may be different from the pores formed by using only a vinyl compound, and the pore size or pore distribution can be precisely controlled according to the molecular weight of the linear polymer material used.
또한, 본 발명에서 양용매로는 벤제, 톨루엔, 크실렌 또는 에틸벤젠 등을 사용할 수 있고, 불용매로는 n-헥산 또는 n-헵탄의 사용이 가능한데, 이들 용매들의 혼합비는 필요에 따라 변할 수 있으나 불용매의 양이 20 부피% 이상이 되도록 하는 것이 다공도를 증가시키는 면에서 바람직하다.In addition, in the present invention, a good solvent may be Benze, toluene, xylene, ethylbenzene, and the like, and as an insolvent, n-hexane or n-heptane may be used, but the mixing ratio of these solvents may be changed as necessary. It is preferable to increase the porosity so that the amount of the non-solvent is 20% by volume or more.
특히, 본 발명에 따르면 용매의 선정은 매우 중요하며 사용된 용매 또는 용매혼합물에 따라서 기공의 분포, 기공의 구조 또는 비표면적이 크게 변할 수 있다.In particular, according to the present invention, the selection of the solvent is very important and depending on the solvent or solvent mixture used, the distribution of pores, the structure of the pores, or the specific surface area may vary greatly.
본 발명에서는 양용매로서 톨루엔을 사용하는 경우와 불용매로서 n-헵탄을 사용하는 것이 바람직하며, 그 사용비는 양용매 : 불용매가 1 : 3인 경우가 가장 유리한 결과를 나타낸다.In this invention, it is preferable to use toluene as a good solvent and to use n-heptane as an insoluble solvent, and the use ratio shows the most favorable result when a good solvent: non solvent is 1: 3.
만일, 불용매의 사용이 너무 적으면 다공도가 떨어지고 너무 많으면 상대적으로 양용매의 량이 낮아져서 합성반응이 잘 이루어지지 않게된다.If the amount of non-solvent is too small, the porosity is lowered. If the amount of the non-solvent is too high, the amount of the good solvent is relatively low, and thus the synthesis reaction is not easily performed.
또한, 본 발명에서 중합개시제로는 벤조일퍼옥사이드, 라우로일퍼옥사이드, t-부틸히드로퍼옥사이드 또는 아조비스이소부티로니트릴 등이 사용될 수 있으며, 그 양은 보통 전체 모노머에 대해서 0.1 ∼ 5 중량% 범위에서 사용된다. 그리고 현탁안정제로서 폴리비닐알코올을 사용할 수 있는데, 그 양은 전체 모노머에 대해서 0.1 ∼ 5 중량% 범위로 한다. 기타 NaNO₂등과 같은 수용성 무기염이 현탁안정 효과증진을 위해 사용될 수도 있다.In addition, as the polymerization initiator in the present invention, benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide or azobisisobutyronitrile may be used, the amount is usually 0.1 to 5% by weight relative to the total monomer Used in And polyvinyl alcohol can be used as a suspension stabilizer, the amount is in the range of 0.1 to 5% by weight based on the total monomers. Other water-soluble inorganic salts, such as NaNO₂, may also be used to enhance suspension stability.
또한, 중합온도는 중합개시제의 종류, 농도 등에 의해 영향을 받을 수 있으며, 보통 중합온도는 50 ∼ 90℃ 범위에서 선정된다. 반응속도를 높이고 반응시간을 단축 시키기 위해서는 100℃ 이상의 높은 온도에서 반응을 진행시킬 수도 있다. 또한 중합은 선정된 온도에서 5 ∼ 30시간 범위에서 실시된다.In addition, the polymerization temperature may be affected by the type, concentration, and the like of the polymerization initiator, and the polymerization temperature is usually selected in the range of 50 to 90 ° C. In order to increase the reaction rate and shorten the reaction time, the reaction may be performed at a high temperature of 100 ° C. or higher. In addition, polymerization is performed in the range of 5 to 30 hours at a selected temperature.
상기와 같이 본 발명의 방법에 의해서 제조된 흡착제는 비표면적이 크고 기공의 크기분포를 조절할 수 있으며, 본 발명에 의해 제조된 흡착제의 비표면적은 200 ∼ 1,000m2/g 이었으며, 기공의 부피는 0.2 ∼ 0.6 cc/cc 이었다.As described above, the adsorbent prepared by the method of the present invention has a large specific surface area and can control the size distribution of the pores. The specific surface area of the adsorbent prepared by the present invention is 200 to 1,000 m 2 / g, and the volume of the pores is It was 0.2-0.6 cc / cc.
이와같이 본 발명에 의해 제조된 합성 흡착제는 항생제정제 또는 식품정제 등에 아주 유용하게 사용될 수 있다.As described above, the synthetic adsorbent prepared according to the present invention can be very usefully used for antibiotic tablets or food tablets.
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 1Example 1
오일 욕조안에 교반기, 환류냉각기, 온도계, 질소주입구가 장비된 2L-4구 플라스크를 잠기게 하고, 탈이온수 700 mL, 폴리비닐알코올 1.4g NaNO20.003g을 플라스 크에 투입하고 40℃에서 2시간 정도 교반시켜 용질을 충분히 녹여 균일한 수용액상을 만든 후 교반을 중지시킨다.Locked with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet device is a 2L 4-neck flask in oil bath and added to 700 mL of deionized water, polyvinyl alcohol 1.4g NaNO 2 0.003g to a flask, and 2 hours at 40 ℃ Stir to about enough to dissolve the solute sufficiently to form a uniform aqueous phase and stop the stirring.
이와 별도로 300 mL-삼각플라스크에 디비닐벤젠(순도 56.7%) 70.2 mL, 스티렌 29.8 mL, 평균분자량이 5,000인 폴리스티렌 9.1g, 벤조일퍼옥사이드 0.5g, 톨루엔과 n-헵탄의 부피 혼합비가 1 : 3인 혼합용매 100mL를 넣고 균일하게 혼합된 유기상을 만 든 후 수용액상이 담겨 있는 반응 플라스크에 가한다.Separately, in a 300 mL triangle flask, 70.2 mL of divinylbenzene (purity 56.7%), 29.8 mL of styrene, 9.1 g of polystyrene having an average molecular weight of 5,000, 0.5 g of benzoyl peroxide, toluene and n-heptane were mixed in a volume ratio of 1: 3. 100 mL of a phosphorus mixed solvent was added to form a homogeneously mixed organic phase, and then added to a reaction flask containing an aqueous phase.
질소 유입구를 통해 질소를 서서히 유입시키면서 반응기 내부가 질소 분위기로 충분히 바뀐 다음 반응물의 온도를 80℃로 올린다. 80℃에 도달한 후 부터 8시간 중 합시킨 후 오일 욕조의 전원을 끄고 반응기를 담근채 자연 냉각시킨다.Slowly introducing nitrogen through the nitrogen inlet, allowing the inside of the reactor to sufficiently change to a nitrogen atmosphere, then raising the temperature of the reactants to 80 ° C. After reaching 80 ° C for 8 hours, the oil bath is turned off and the reactor is cooled down and cooled naturally.
냉각시킨 후 여과하고 탈이온수로 2 ∼ 3회 세척한 후 탈수기에 넣어서 3,700rpm으로 5분간 탈수시킨 후 60℃ 진공 오븐안에서 8시간 건조시킨다.After cooling, the mixture was filtered, washed 2-3 times with deionized water, put in a dehydrator, dehydrated at 3,700 rpm for 5 minutes, and dried in a vacuum oven at 60 ° C. for 8 hours.
수지의 모양은 거의 완전한 구형이었으며 수득량은 96g 이었다.The shape of the resin was almost completely spherical and the yield was 96 g.
이 수지를 가열맨틀에 장착된, 냉각기가 부착된 플라스크에 넣고 톨루엔 129g을 가한 후 70o℃에서 3시간 가열하고, 다시 자연냉각 시켜여과한 다음, 다시 동일한 톨루엔 세척과정을 2회 더 실시한 후 여과하여 60℃ 오븐에서 8시간 건조된 수지의 비표면적은 912 m2/g, 다공도 0.36 cc/cc, 그리고 세공반경이 200Å 이하인 세공용적이 89%, 300 Å 이상의 세공용적은 7.4% 이었다.The resin was placed in a flask equipped with a cooling mantle, added toluene 129 g, heated at 70 ° C. for 3 hours, filtered again by natural cooling, followed by the same toluene washing process twice more, followed by filtration. The specific surface area of the resin dried in an oven at 60 ° C. for 8 hours was 912 m 2 / g, porosity 0.36 cc / cc, and pore volume of 89 mm or less, 89%, and pore volume of 300 kPa or more was 7.4%.
실시예 2Example 2
상기 실시예 1과 동일한 방법, 동일한 제조조건으로 하되, 평균분자량 7,000인 폴리스티렌을 사용하여 비표면적이 870 m2/g, 다공도 0.38 cc/cc, 그리고 200 Å이하의 세공용적이 72%, 300 Å 이상의 세공용적이 8.1%인 수지를 얻었다.The same method as in Example 1, using the same manufacturing conditions, but using a polystyrene having an average molecular weight of 7,000, the specific surface area of 870 m 2 / g, porosity of 0.38 cc / cc, the pore volume of less than 200 72 72%, 300 Å or more A resin having a pore volume of 8.1% was obtained.
실시예 3Example 3
상기 실시예 1과 동일한 장치, 동일한 방법으로 평균분자량 12,000인 폴리스티렌을 사용하여 비표면적이 827 m2/g, 다공도 0.41 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 61%, 300 Å 이상의 세공용적이 13.1%인 수지를 얻었다.Using the same apparatus as in Example 1, polystyrene having an average molecular weight of 12,000, the specific surface area of 827 m 2 / g, porosity of 0.41 cc / cc, pore volume of less than 200 반경 and 61%, 300 Å or more A resin having a volume of 13.1% was obtained.
실시예 4Example 4
상기 실시예 1과 동일한 방법으로 평균분자량 1,000인 폴리스티렌을 사용하여 비표면적이 744 m2/g, 다공도 0.44 cc/cc, 그리고 200 Å 이하의 세공용적이 38%, 300Å 이상의 세공용적이 51%인 수지를 얻었다.Using polystyrene having an average molecular weight of 1,000 in the same manner as in Example 1, the specific surface area is 744 m 2 / g, porosity 0.44 cc / cc, and the pore volume of less than 200 38 38%, the pore volume of 300 Å or more 51% A resin was obtained.
실시예 5Example 5
상기 실시예 1과 동일한 방법으로 평균분자량 30,000인 폴리스티렌을 사용하여 비표면적이 675 m2/g, 다공도 0.46 cc/cc, 그리고 200 Å 이하의 세공용적이 30%, 300 Å 이상의 세공용적이 61%인 수지를 얻었다.In the same manner as in Example 1, using polystyrene having an average molecular weight of 30,000, a specific surface area of 675 m 2 / g, porosity of 0.46 cc / cc, and a pore volume of 200 mm or less is 30%, and a pore volume of 300 mm or more is 61%. A resin was obtained.
비교예 1Comparative Example 1
상기 실시예 1과 동일한 장치와 동일한 방법, 동일한 제조조건으로 하되, 단지 평균분자량 50,000인 폴리스티렌을 사용하여 수지를 제조하였다. 제조된 수지의 비표 면적이 510 m2/g, 다공도 0.52 cc/cc, 그리고 200 Å 이하의 세공용적이 51%, 300 Å 이상의 세공용적이 70%인 수지를 얻었다.Resin was prepared using the same method as in Example 1, the same method and the same production conditions, but using only polystyrene having an average molecular weight of 50,000. A resin having a specific surface area of 510 m 2 / g, a porosity of 0.52 cc / cc, and a pore volume of 200 kPa or less of 51% and a pore volume of 300 kPa or more of 70% was obtained.
비교예 2Comparative Example 2
상기 실시예 1과 동일한 장치, 동일한 방법, 동일한 제조조건으로 하되, 단지 폴리스티렌의 양을 0.91g으로 변경하였다. 제조된 수지의 비표면적이 302 m2/g, 다공도 0.16 cc/cc, 그리고 200 Å 이하의 세공용적이 94%, 300 Å 이상의 세공용적이 3%인 수지를 얻었다.The same apparatus as in Example 1, the same method, and the same production conditions, but only the amount of polystyrene was changed to 0.91g. A resin having a specific surface area of 302 m 2 / g, porosity of 0.16 cc / cc, pore volume of 200 mm 3 or less, and 94% pore volume of 3 mm or more was obtained.
실시예 6Example 6
상기 실시예 1과 동일한 반응장치와 동일한 방법으로, 탈이온수 770.7 mL, 폴리비닐알코올 1.54g, NaNO20.0033g을 균일한 수용액상으로 만들고, 이와 별도로 디비닐벤젠(순도 56.7%) 58.2 mL, 스티렌 51.9 mL, 평균분자량 5,000인 폴리스티렌 10g, 벤조일퍼옥사이드 0.56g, 톨루엔과 n-헵탄의 부피 혼합비가 1 : 3인 혼합용매 125 mL를 넣고 균일 혼합상을 만든 후 실시예 1과 동일한 과정을 통해서 수지비드를 제조하였다. 제조된 수지의 비표면적은 572 m2/g, 다공도 0.29 cc/cc, 그리고 200Å 이하의 세공반경을 가지는 세공용적이 91%, 300Å 이상의 세공용적이 3 % 이었다.In the same manner as in the same reactor as in Example 1, 770.7 mL of deionized water, 1.54 g of polyvinyl alcohol, and 0.0033 g of NaNO 2 were prepared in a homogeneous aqueous solution, and separately from 58.2 mL of divinylbenzene (56.7% purity) and styrene. 51.9 mL, 10 g of polystyrene having an average molecular weight of 5,000, 0.56 g of benzoyl peroxide, 125 mL of a mixed solvent having a volume mixing ratio of toluene and n-heptane of 1: 3 were added to form a homogeneous mixed phase, followed by the same procedure as in Example 1. Beads were prepared. The specific surface area of the produced resin was 572 m 2 / g, porosity 0.29 cc / cc, pore volume having a pore radius of 200 mm or less, 91%, pore volume of 300 mm 3 or more.
실시예 7Example 7
상기 실시예 6과 동일한 반응장치와 동일한 제조조건으로 하되, 단지 평균분자량이 7,000인 폴리스티렌을 사용하였다. 제조된 수지의 비표면적은 546 m2/g, 다공도 0.34 cc/cc, 그리고 200 Å 이하의 세공용적이 87%, 300 Å 이상의 세공용적이 5% 이었 다.Polystyrene having an average molecular weight of 7,000 was used under the same production conditions as in Example 6 with the same reactor. The specific surface area of the prepared resin was 546 m 2 / g, porosity 0.34 cc / cc, pore volume of 200 mm 3 or less, 87%, pore volume of 300 mm 3 or more 5%.
실시예 8Example 8
상기 실시예 6과 동일한 반응장치와 동일한 제조조건으로 하되, 단지 평균분자량이 12,000인 폴리스티렌을 사용하였다. 제조된 수지의 비표면적은 492 m2/g, 다공도 0.38 cc/cc, 그리고 200 Å 이하의 세공용적이 67%, 300 Å 이상의 세공용적이 5% 이었다.Polystyrene having an average molecular weight of 12,000 was used under the same production conditions as in Example 6 with the same reactor. The specific surface area of the prepared resin was 492 m 2 / g, porosity 0.38 cc / cc, pore volume of 200 kPa or less, and 67% of pore volume of 300 kPa or more.
실시예 9Example 9
상기 실시예 6과 동일한 반응장치와 동일한 제조조건으로 하되, 단지 평균분자량이 17,000인 폴리스티렌을 사용하였다. 제조된 수지의 비표면적은 444 m2/g, 다공도 0.43 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 63%, 300 Å 이상의 세공용적이 15% 이었다.Polystyrene having the same production conditions as those of Example 6 and the same production conditions, but using only 17,000 average molecular weights. The specific surface area of the prepared resin was 444 m 2 / g, porosity 0.43 cc / cc, pore volume of less than 200 mm 3 and pore volume of 63%, and pore volume of 300 mm 3 or more.
실시예 10Example 10
상기 실시예 6과 동일한 장치와 동일한 제조조건으로 하되, 단지 평균분자량이 30,000인 폴리스티렌을 사용하였다. 제조된 수지의 비표면적은 404 m2/g, 다공도 0.46 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 59%, 300 Å 이상의 세공용적이 22% 이었다.Polystyrene having an average molecular weight of 30,000 was used under the same manufacturing conditions as those of Example 6. The specific surface area of the prepared resin was 404 m 2 / g, porosity 0.46 cc / cc, pore volume of less than 200 mm 3, 59%, and pore volume of 300 m 3 or more was 22%.
비교예 3Comparative Example 3
상기 실시예 6과 동일한 장치와 동일한 제조조건으로 하되, 단지 평균분자량이 50,000인 폴리스티렌을 사용하여 수지를 제조하였다. 제조된 수지의 비표면적은 381 m2/g, 다공도 0.50 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 51%, 300 Å 이상의 세공용적이 34% 이었다.Resin was prepared using the same manufacturing conditions as those of Example 6, but using polystyrene having an average molecular weight of 50,000. The resin had a specific surface area of 381 m 2 / g, porosity of 0.50 cc / cc, and a pore volume of less than 200 mm 3 with a pore volume of 51% and a pore volume of 300 mm 3 or more and 34%.
비교예 4Comparative Example 4
상기 실시예 1과 동일한 반응장치와 동일한 방법으로, 탈이온수 700 mL, 폴리비닐알코올 1.4g, NaNO20.003g을 균일한 수용액상으로 만들고, 이와 별도로 디비닐벤젠(순도 56.7%) 52.91 mL, 스티렌 47.21 mL, 평균분자량 7,000인 폴리스티렌 0.91g,벤조일퍼옥사이드 0.5g, 톨루엔과 n-헵탄의 부피 혼합비가 1 : 3인 혼합용매 102 mL를 넣고 균일 혼합상을 만든 후 실시예 1과 동일한 과정을 통해서 수지비드를 제조하였다.In the same manner as in the same reactor as in Example 1, 700 mL of deionized water, 1.4 g of polyvinyl alcohol, and 0.003 g of NaNO 2 were prepared in a uniform aqueous solution. Separately, 52.91 mL of divinylbenzene (56.7% purity) and styrene 47.21 mL, 0.91 g of polystyrene having an average molecular weight of 7,000, 0.5 g of benzoyl peroxide, 102 mL of a mixed solvent having a volume mixing ratio of toluene and n-heptane of 1: 3 were added to form a homogeneous mixed phase. Resin beads were prepared.
제조된 수지의 비표면적은 128.5 m2/g, 다공도 0.13 cc/cc, 그리고 200Å 이하의 세공반경을 가지는 세공용적이 93%, 300Å 이상의 세공용적이 1.5 % 이었다.The specific surface area of the prepared resin was 128.5 m 2 / g, porosity 0.13 cc / cc, pore volume having a pore radius of 200 mm or less, 93%, and pore volume of 300 mm or more was 1.5%.
실시예 11Example 11
상기 실시예 1과 동일한 반응장치와 동일한 방법으로, 탈이온수 700 mL, 폴리비닐알코올 1.4g, NaNO70.003g을 균일한 수용액상으로 만들고, 이와 별도로 디비닐 벤젠(순도 56.7%) 88.18 mL, 스티렌 11.85 mL, 평균분자량 5,000인 폴리스티렌 9.1g,벤조일퍼옥사이드 0.5g, 톨루엔과 n-헵탄의 부피 혼합비가 1 : 3인 혼합용매 114 mL를 넣고 균일 혼합상을 만든 후 실시예 1과 동일한 과정을 통해서 수지비드를 제조하였다. 제조된 수지의 비표면적은 683 m2/g, 다공도 0.27 cc/cc, 그리고 200Å 이하의 세공반경을 가지는 세공용적이 91%, 300Å 이상의 세공용적이 4 % 이었다.In the same manner as in the same reactor as in Example 1, 700 mL of deionized water, 1.4 g of polyvinyl alcohol, and 0.003 g of NaNO 7 were prepared in a uniform aqueous solution. Separately, 88.18 mL of divinyl benzene (purity 56.7%) and styrene 11.85 mL, 9.1 g of polystyrene 9.1g, 0.5g benzoyl peroxide with an average molecular weight of 5,000, and 114 mL of a mixed solvent having a volume mixing ratio of toluene and n-heptane 1: 3 were added to form a homogeneous mixed phase. Resin beads were prepared. The specific surface area of the prepared resin was 683 m 2 / g, porosity 0.27 cc / cc, pore volume having a pore radius of 200 mm or less, 91%, pore volume of 300 mm or more was 4%.
실시예 12Example 12
상기 실시예 11과 동일한 반응장치와 동일한 제조조건으로 하되, 단지 평균분자량이 7,000인 폴리스티렌을 사용하였다. 제조된 수지의 비표면적은 648 m2/g, 다공도 0.30 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 84%, 300 Å 이상의 세공용적이 6% 이었다.Polystyrene having an average molecular weight of 7,000 was used under the same production conditions as in Example 11 with the same reactor. The specific surface area of the prepared resin was 648 m 2 / g, porosity 0.30 cc / cc, pore volume of less than 200 mm 3 and pore volume of 84%, pore volume of 300 mm 3 or more.
실시예 13Example 13
상기 실시예 11과 동일한 반응장치와 동일한 제조조건으로 하되, 단지 평균분자량이 12,000인 폴리스티렌을 사용하였다. 제조된 수지의 비표면적은 580 m2/g, 다공도 0.35 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 71%, 300 Å 이상의 세공용적이 19% 이었다.Polystyrene having an average molecular weight of 12,000 was used under the same production conditions as those of Example 11 except for the same reactor. The resin had a specific surface area of 580 m 2 / g, porosity of 0.35 cc / cc, and a pore volume of less than 200 mm 3 with a pore volume of 71% and a pore volume of 300 mm 3 or more at 19%.
실시예 14Example 14
상기 실시예 11과 동일한 반응장치와 동일한 제조조건으로 하되, 단지 평균분자량이 17,000인 폴리스티렌을 사용하였다. 제조된 수지의 비표면적은 542 m2/g, 다공도 0.38 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 57%, 300 Å 이상의 세공용적이 25% 이었다.Polystyrene having an average molecular weight of 17,000 was used under the same production conditions as in Example 11 with the same reactor. The specific surface area of the produced resin was 542 m 2 / g, porosity 0.38 cc / cc, pore volume of less than 200 mm 3 , and pore volume of 57 mm and 300 mm 3, respectively.
실시예 15Example 15
상기 실시예 11과 동일한 반응장치와 동일한 제조조건으로 하되, 단지 평균분자량이 30,000인 폴리스티렌을 사용하였다. 제조된 수지의 비표면적은 493 m2/g, 다공도 0.41 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 55%, 300 Å 이상의 세공용적이 25% 이었다.Polystyrene having an average molecular weight of 30,000 was used under the same production conditions as in Example 11 with the same reactor. The specific surface area of the prepared resin was 493 m 2 / g, porosity 0.41 cc / cc, pore volume of less than 200 mm 3, and 55% of pore volume of 300 mm 3 or more.
비교예 5Comparative Example 5
상기 실시예 11과 동일한 반응장치와 동일한 방법, 동일한 제조조건으로 하되, 단지 평균분자량이 50,000인 폴리스티렌을 사용하여 수지를 제조하였다. 제조된 수지의 비표면적은 451 m2/g, 다공도 0.44 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 53%, 300 Å 이상의 세공용적이 28% 이었다.Resin was prepared using the same method as in Example 11, the same method and the same production conditions, but using polystyrene having an average molecular weight of 50,000. The resin had a specific surface area of 451 m 2 / g, porosity of 0.44 cc / cc, and a pore volume of less than 200 mm 3 with a pore volume of 53% and a pore volume of 300 mm 3 or more.
비교예 6Comparative Example 6
상기 실시예 11과 동일한 장치와 동일한 방법으로 하되, 단지 폴리스티렌량을 0.91g 으로 하여 수지를 제조하였다. 제조된 수지의 비표면적은 186 m2/g, 다공도 0.16 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 88%, 300 Å 이상의 세공용적이 6% 이었다.A resin was prepared in the same manner as in Example 11, except that the amount of polystyrene was 0.91 g. The specific surface area of the prepared resin was 186 m 2 / g, porosity 0.16 cc / cc, pore volume of less than 200 mm 3, 88%, and pore volume of 300 mm 3 or more was 6%.
비교예 7Comparative Example 7
상기 실시예 1과 동일한 반응장치와 동일한 방법으로, 탈이온수 700 mL, 폴리비닐알코올 1.4g, NaNO20.003g을 균일한 수용액상으로 만들고, 이와 별도로 디비닐벤젠 26.45 mL, 스티렌 73.75 mL, 평균분자량 7,000인 폴리스티렌 9.1g, 벤조일퍼옥사이드 0.5g, 톨루엔과 n-헵탄의 부피 혼합비가 1 : 3인 혼합용매 115 mL를 넣고 균일 혼합상을 만든 후 실시예 1과 동일한 과정을 통해서 수지비드를 제조하였다. 제조된 수지의 비표면적은 98 m2/g, 다공도 0.04 cc/cc, 그리고 200Å 이하의 세공반경을 가지는 세공용적이 92%, 300Å 이상의 세공용적이 5% 이었다.In the same manner as in Example 1, 700 mL of deionized water, 1.4 g of polyvinyl alcohol, and 0.003 g of NaNO 2 were prepared in a homogeneous aqueous solution. Separately, divinylbenzene 26.45 mL, styrene 73.75 mL, and average molecular weight. Resin beads were prepared in the same manner as in Example 1 after adding 9.1 mL of polystyrene 9.1 g, benzoyl peroxide 0.5 g, toluene and 115 mL of a mixed solvent having a volume mixing ratio of 1: 3. . The specific surface area of the produced resin was 98% 2 / g, porosity 0.04 cc / cc, and the pore volume having a pore radius of 200 kPa or less was 92%, and the pore volume of 300 kPa or more was 5%.
비교예 8Comparative Example 8
상기 비교예 4와 동일한 반응장치와 동일한 제조조건으로 하되, 단지 평균분자량이 12,000인 폴리스티렌을 사용하였다. 제조된 수지의 비표면적은 87 m2/g, 다공도 0.05 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 84%, 300 Å 이상의 세공용적이 9% 이었다.Polystyrene having an average molecular weight of 12,000 was used under the same production conditions as those of Comparative Example 4 above. The specific surface area of the prepared resin was 87 m 2 / g, porosity 0.05 cc / cc, pore volume of less than 200 mm 3 and pore volume of 84%, pore volume of 300 mm 3 or more 9%.
실시예 16Example 16
상기 실시예 1과 동일한 반응장치와 동일한 방법으로, 탈이온수 700 mL, 폴리비닐알코올 1.4g, NaNO20.003g을 균일한 수용액상으로 만들고, 이와 별도로 디비닐벤젠(56.7%) 70.2 mL, 스티렌 25 mL, 메틸메타크릴레이트 4.8mL 평균분자량 7,000인 폴리스티렌 9.1g, 벤조일퍼옥사이드 0.5g, 톨루엔과 n-헵탄의 부피 혼합비가 1 : 3인 혼합용매 100 mL를 넣고 균일 혼합상을 만든 후 실시예 1과 동일한 과정을 통해서 수지비드를 제조하였다. 제조된 수지의 비표면적은 868 m2/g, 다공도 0.38 cc/cc, 그리고 200 Å 이하의 세공반경을 가지는 세공용적이 87%, 300Å 이상의 세공용적이 8.3% 이었다.In the same manner as in Example 1, 700 mL of deionized water, 1.4 g of polyvinyl alcohol, and 0.003 g of NaNO 2 were made into a homogeneous aqueous solution. Separately, 70.2 mL of divinylbenzene (56.7%) and styrene 25 mL, methyl methacrylate 4.8 mL Polystyrene 9.1 g of polystyrene having an average molecular weight of 7,000, 0.5 g of benzoyl peroxide, 100 mL of a mixed solvent having a volume mixing ratio of toluene and n-heptane of 1: 3 was added to form a homogeneous mixed phase. Example 1 Through the same process to prepare a resin bead. The resin had a specific surface area of 868 m 2 / g, a porosity of 0.38 cc / cc, and a pore volume of 87%, and a pore volume of not less than 200 mm 3, of 8.3%.
실시예 17Example 17
상기 실시예 16과 동일한 반응장치와 동일한 제조조건으로 하되, 단지 지방족 비닐모노머로서 메틸메타크릴레이트 대신 같은 부피의 아크릴로니트릴을 사용하였다. 제조된 수지의 비표면적은 882 m2/g, 다공도 0.39 cc/cc, 그리고 반경 200 Å 이하의 세공용적이 89%, 300 Å 이상의 세공용적이 7% 이었다.The same reaction conditions as in Example 16 were used, but the same volume of acrylonitrile was used as the aliphatic vinyl monomer instead of methyl methacrylate. The specific surface area of the prepared resin was 882 m 2 / g, porosity 0.39 cc / cc, pore volume of less than 200 mm 3, 89%, and pore volume of 300 mm 3 or more was 7%.
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