Korean Chemical Engineering Research

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(1)Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005, pp. 21-26. 5Ï ¿û×Ç ¿ô§ /@| +ÏÛ Monolith g». <SË /X. †. z ¬H/ ÄdHàHz zQ C Ä¢ 100 ¸ ö ³ [¤, 2004¸ 11ö 17³ >). 608-739 (2004 9 15. Preparation of Porous Polymer Monoliths in Supercritical Carbon Dioxide Se Ran Kang and Chang Sik Ju† Division of Applied Chemical Engineering, Pukyong National University, San 100, Yongdang-dong, Nam-gu, Busan 608-739, Korea (Received 15 September 2004; accepted 17 November 2004). ß È. ð»ª «d!õ «ÄGñ à Ê~É Hô-)õ fÆG2 Y×J õCõ }Gñ,

(2) ÜÍQ OYä ÆQË« @ æ2 Ê~É Hô-) í Ñ Âj2 s Y×Jk³ Æ G. OYäo ä« ,}æ2 8 äí ¡dõ îûO ¤ À´ ²«´ s zôK ÊF ä, Ñ ,}æÉk,

(3) Í kÎ o Îõ fGÊ2 ä, z=Q ³K QÆGÊ à ¯ Ê~É Hô-)õ »És ¤ À É. @ æ2 Ê~É Hô-) 9 ,

(4) Jo äHYí O

(5) Q OYä FtÑ ¶ ÍGk, ,ªJ ã2 Ýãf MMAõ ÍGñ ¬Q ¤ ÀÉ. Abstract − Experimental researches on the preparation of porous polymeric monoliths in supercritical carbon dioxide have been performed and the effects of monomer and polymerization parameters on the physical properties of the monolith prepared were examined. Polymerizations were carried out in the high pressure stainless steel reactor with sapphire window to show the phase change during the polymerization reaction, and continuous and dry porous monolithic polymer could be obtained. The specific surface area of monolithic polymer increased with monomer contents in reaction mixture and reaction pressure. The Rockwell hardness could be enhanced by the addition of co-monomer MMA in reaction mixtures. Key words: Porous Polymeric Monolith, Supercritical, Carbon Dioxide. 1.. C «. ¸Ñ [´Ë

(6) ñ6 õg¤« Ê~É Y ê Íà ~tÑ ð»ª Kõ «ÄK Î¤K õg êËs ÝÊGD QÊG [3-7]. « ~t õg2 ð»ª «d!Ñ ¬K Ê~É Ä gÑ îK õg, Ê~É Y Ú ß DgÑ îK õg, Ê~É 9Ã(bead) 2 Â§ ½É fÆÑ îK õg -Ê à Ê~ É fÆÑ îK õg Ù« ?Íõ «PÊ À. Rindfleisch Ù[8]o ð»ª «d!Ñ ¬K Ê~ÉË Ägõ Æ K õgÑ 9 Ê~ÉË ð»ª «d!Ñ ¬K Äg 2 Ê~Éõ dGM÷(fluorinating) Ê~É ? 1(backbone) Ñ bs ÍG

(7) ÍQ ¤ ÀÊ ÝÊK à À. O’Neill Ù[9-10]o ð»ª Ñ siloxane ªù

(8) Ë ~ OYs Æ Gñ ½É _ DgQ ½É DgÑ îK õg êõ è,K à ÀÊ, Galia Ù[11]o 9v ªù

(9) Ë ~ O YÑ ¬g ÝÊK à À. Cooper Ù[12]o ð»ª «d!õ «ÄGñ Ê ÍGY s ä2 Ê~É Â§½Éõ fÆG2 Y×s }Gñ, ä HYíÑ 8_fõ ÍG

(10)

(11) Â§K ½ÉÍ fÆæÊ ¿DQ ½ 1990. ð»ª Kº ÊK»ªY « Ftê 5Ñ ÊéG

(12) D ê K K eª¤, Y Ù Mí s äÊ U ê 97K Êõ Í(2 D·U

(13) Kõ SK[1-2]. ð»ª KÍ ¤ HYí O U_ ~Ñ ¬Gñ >J¯ ~-Dts ÷2 Ù U«K ùòHJ Ms ä22 Yo 1ÖMz <s ÀÉ k÷, 1970¸¬Ñ [´Ë

(14) ÆñQ ¡dÑ Î½´ ð»ª K à_o _ÊdH, R\, H -Ê Ñw( Æ ÙÑ Y³ K Ä ÍD s (r Y0J¯ ¬ à_k³ ¬&æD QÊG. ð»ª K D¬o o Ägt, I YQ Ê eª¤³ ¯K Kñ z· Ùê ço ð»ª K ßYs «ÄG2 D¬³, DÊ ä Ú ~g, , _d, ¤, ô, QÆ, §_ Ù M HÇ dHà_Ñ D¬J ´sÞs gO ¤ À2 *³Ò D¬³ ?IçÊ À. † To. whom correspondence should be addressed. E-mail: [email protected] 21.

(15) ã§ºö? R. 22. ~¯2 8_f Ñ ¿j s ç22 as ÝÊG. LeleQ Shine Ù[13]o ð»ª Ê~É ÄUs H§îs 0Gñ è Qÿ2 ör(RESS)k³ Ê~É Â§ ½Éõ fÆG2 õgõ }K à À. CooperQ Holmes[14]2 ð»ª KÑ Ñ Ägæ2 Í(

(16) õ ÄGñ ð»ª Ñ à Ê~Éõ fÆG2 Y×s }Gñ, ä HYí O

(17) Í ÍO¤´ @ æ2 à Ê~É Æ)« jÊg(Ê §à ¿DÍ Ê4 9 ,

(18) J « ÍK2 õg êõ ÝÊG. ð»ª Kõ «ÄGñ à Ê~É monolithõ fÆGD .g2,

(19) 2 ð»ª «d!Ñ ¬K ÄgÍ ¿Ê @ æ2 Ê~É2 ÄgÍ Jo í0s >K. >ê

(20) õ í QfQ Wÿ ÊF äDÑ Ê ð»ª =Ñ Ê~É Y ä s ,}Qÿ

(21) ð»ª ÄUÑ ¬K ÄgÍ Jo Ê~É í0« @ ê. « Ê~É í0o ßG

(22) ½É k³ ð»ª K Ñ æ

(23) ³ 4Gñ à Ê~É monolithÍ @ æ 2 ak³ <s À[15-17]. á õgÑ2 ð»ª «d!õ Äk³ ÄGñ ¿³K Ö) column £M í0[18-19], D 2 KD Äk ñê k Ùk³ lÄæ´ àÆJ ÍjÍ o à Ê~É monolithõ f ÆG2 Y×J õgõ }G.

(24) ÜÍQ ÆÊ¡¤Ë« @ æ2 Ê~É monolith í Ñ Âj2 s Æ GÊ, ð»ª Kõ «ÄGñ à Ê~Éõ fÆG2 à_Ñ îK MäJ¯ Æ õ G. 2.. / . /ð£ á õgÑ2

(25) Q OYä íQf Ú ð»ª «d! õ ÄGñ à Ê~É monolithõ fÆGD .Gñ Fig. 1Ñ ÷ àQ ço ð»ª OYä ßjõ fÊG. ð»ª OYä ßj2 «d! Y1

(26) , I5¤Æ, ÊFÄ hand pump, ]5¤Æ Ú äD -Ê 5Q Ft ÆQD Ù z ß 9³ g æÉ. Î ß9Ëo 1/8" ÊFÄ stainless îk³ õæÉ k, 1®K ÞÑ ÷ 1 Ú 8M-s jG. Ä

(27) 66 ml äD2 ÊF äs ¤}O ¤ À´ stainless steel³ fÊæÉ k, @ ê monolithõ ò ¬³ ¡¤O ¤ À´ \Ñ ñ6 õ jG. ½g ä¬\ ñ6Ñ2 ä« ,}æ2 8 z ¡dõ îûO ¤ À´ sapphire windowõ zôG. ä D ½gÑ2 quick connectorQ õ jGñ äDõ ÍF = Ñ OYä ßj³z j ~-, ßôO ¤ À´ G. 2-2. Monolith£ g» Z Ïh á õgÑ2

(28) ³ TRM(trimethylol propane), EDMA(ethylene glycol dimethacrylate), DVB(divinyl benzene)õ, OY íQf³2 AIBN(2,2'-azobis (isobutyronitrile))s, OY Äk³2 ð»ª «d! õ ÄGñ à Ê~É monolithõ fÆG. -Ê @ æ 2 monolith õ ¬QÿD .g 1®K ÎÑ2 à

(29) ³ MAA(methacrylic acid 2-diethyl aminoethyl ester)õ ÄG. Sapphire windowÍ zôê ÊF äDÑ Y Ñ ÄO

(30) , íQfõ £MGÊ OYä ßjÑ ßôK. äDQ OYä 2-1.. ¤@¤ C43× C1 2005 2. Fig. 1. Schematic diagram of experimental apparatus. 1. CO2 bomb 17. Pressure gauge 2. Valve 18. Vent 3. Cooler bath 19. Quick connector 4. Hand pump 10. Check valve 5. 1/8" tube 11. Reactor 6. Safety valve 12. Water bath. ßj z õ fMGD .g «d!õ Ik³ 15~ Ñ 1 {, ÊFÄ hand pumpõ ÄGñ äD z Ft s »ªFt « (100 bar)k³ ÍFK. äD ?. õ 4 äD z Fts K(K =Ñ quick connectorõ ÄG ñ äDõ OYä ßj³z ~-K. ~-ê äDõ ñ6 d Ë´ ä HYí« è³Gj HYæ´ T4(2 as sapphire windowõ 0Gñ e¯K. äDõ Q OYä ßjÑ ßôG Ê, ÊFÄ hand pumpQ ]5 ¤Æõ ÄGñ äD 5Q F ts òG2 =³ ÆQK. Sapphire windowõ 0Gñ äD z ¡dõ îûG

(31) O Y äs ,}Q. 20QÑ « äQ á äDõ 40 C³ ÎQÿÊ, äD zQ OYä ßj «d!õ gõ 0Gñ ¾ Q. «d!Í UM¾ æ

(32) äD \ ñ6õ T´ @ ê Ê~É monolithõ äDÑ ¡¤K. fÆê Ê~É monolith2 MÉ Â (SEM)ê 9 ,

(33) J +_ ßj(BET)õ ÄGñ í-J U s Æ GÊ, DªJ 2 Rockwell ªõ ÄGñ +_G. 9 ,

(34) J +_QÑ2 Qs ~GÑ K ,

(35) J Íõ ö(G D .g, @ ê Ê~É monolithõ 2 mm « ¿D³ ~GK á BETõ ÄGñ +_G. á õgÑ fÆK à Ê ~É monolithÍ ùÑ kÎ uK as Ý8Gñ, Ms- MÑ Q0 Dà ¤~s èGD Ò acetonek³ ¬K á 120 CÑ 24QÑ 8 M s-G. o. o. 3.. ûG Z +{. 3-1. /@| monolith£ <

(36)

(37) ÜÍQ , Y ä Ft Ú 5, Y ä QÑ Ù s ¡dQÿ

(38) ð»ª Ñ à Ê~É monolithõ fÆG 2 Y×s }K ê, ä HYí O

(39) Í 10% «G¯ Îõ fGÊ2 á õgÑ >K HÇ Y×ÆQÑ äD.

(40) ð»ª «@õ «ÄK à Ê~É Monolith fÆ. z =Q ³K + à Ê~É monolithõ »s ¤ ÀÉ. fÆê monolith z s ÷Ê À2 Fig. 2õ Ý

(41) ,

(42) Í Ã ÎÑ2 äD z =Q ³K ò? monolithÍ fÆæ÷,

(43) Í Êo Î(>10%)Ñ2 ÍÒ) z~« ~-ê monolithÍ fÆæÉ. «6K o ð»ª Ñ Ê~ÉË« @ æ2 ê_s ]gÝ

(44) g« ÍDG. OYä« ,}öÑ ¶ ð»ª «d!Ñ Äg Í Jo Ê~ÉËo ßG

(45) æ´ 1ó ½Éõ GÊ, « Ë« ª ßG

(46) ³ YGñ monolithõ Gj ê. « ê_Ñ

(47) Í (÷jj k

(48) @ æ2 Ê~ÉË« äD M àÑs Î( \Gñ ÍÒ) z~« ~-ê s äj æ2 ak³ gO ¤ À. 97K õgõ }K ñ } õgÉË Î[14]Ñ2 OYä íQ MÑ äHYís GäGD .g äD zÑ É Gä ós ÉD )éÑ fÆê Ê~É monolith2 Gäók³ ¯Gñ UMK s Í0 ¤ ÇÉ. á õgÑ2 É GäD ÄÑ ñ «6K éfYs gGD .g äD ½gÑ jK quick connectorõ «ÄGñ äDõ ð»ª =Ñ Y ä ßj³z ~-Gñ ä HYís HYK á éßôG2 örs >Wk ³ UMK = à Ê~É monolithõ »s ¤ ÀÉ. 3-2. ÿË @ ·» fÆê à Ê~É monolith z gÆQ §à =õ SEM k³ îûK êõ Fig. 3ê 4Ñ ÷É.

(49) ³ TRMs ÄK Î ä HYí O

(50) . Fig. 2. Representative photos of porous polymeric monolith produced 7 at different monomer contents (a) 50 vol% (b) 5 vol%.. 23. Í z Ñ Âj2 s ÷Ê À2 Fig. 3s Ý

(51) , @ ê monolith2 ¤Qo 1ó ½É Yk³ «P´, à gÆ ³ æ´ À2 as < ¤ À.

(52) Í 30 vol%³ ¬J k³ o Fig. 3(a) ÎÑ2 9GJ Ã 1ó ½ÉË³ g ê í h §àgÆõ Í(,

(53) Í 70 vol%³ o Fig. 3(c) ÎÑ2 4? Êo 1ó ½ÉË Yk³ «P´ À2 jÊ K gÆõ ä2 ak³ ÷

(54) . ¶ ä HYí O

(55) . Í ÍG

(56) @ æ2 Ê~É monolithõ g G2 1ó ½ÉQ §à ¿D2 ÝGÊ Æ)« jÊg(2 as < ¤ ÀÉ.. Äê

(57) ÜÍÍ @ æ2 monolith z Ñ Âj2 s ÷Ê À2 Fig. 4õ Ý

(58) , EDMA÷ DVBõ

(59) ³. ÄK ÎÑ2 ço ÆQÑ TRMs

(60) ³ ÄK Î(Fig. 3(b))Ý monolithõ g GÊ À2 1ó ½É ¿DÍ ÊÊ Æ) « jÊK ak³ ÷

(61) . «6K Ëo monolith Y Ñ Äê

(62) Q @ æ2 Ê ~É ½É Äg³ O ¤ À. á õgÑ ÄK TRM, EDMA Ú DVB

(63) 2 ð»ª «d!Ñ ¬K ÄgÍ ¿D )éÑ OY ä MÑ2 ä HYí« è³K s ä(O, OY ä« ,}æ´ Ê~ÉÍ @ æ

(64) ð»ª «d!Ñ ¬K Äg 2 Gj ÝGj ê. ¶ ½É Ê~ÉË« ÏI GÊ «Ë« ßG

(65) ³ YGñ monolithõ Gj ê. OY äs 0g ßG2 Ê~É

(66) Ñ ¬K Äg2 ð»ª «d!Ñ ¬K ÄgÑ 9Gñ ¬Jk³ ¿³, ä HYí O

(67) Í s ÎÑ2 ßG2 Ê~É ~-Í

(68) Í o ÎÑ 9Gñ ¬Jk³ Ej ³´÷j ê. -Ê ~-Í ³´ÿ ) @ ê ÊÊ Qo õ J¯ 1ó ½ÉË« ³ YGñ jÊK Æ) monolithõ @ Qÿ2 ak³ gê. ä HYí O

(69) Í s ÎÑ2 ßG2 Ê~É ½É ~-Í ¬Jk³ o MdSÑ ³´÷j æÊ, « ³ ¯Gñ Â§K 1ó ½ÉË« ê. 1ó ½ÉË« ê á Ñ

(70) Ñ g èOê 1ó ½É2 OYäs 0K ßs ( GÊ, ð»ª «d! zÑ OYäo ªê. «³ ¯Gñ Ê~É ½ÉËo ßGÊ ½ÉË « §ào î, Ã 1ó ½ÉË« 4ê gÆ monolithõ Gj ê. «6K êËo CooperQ Holmes[14] õg êQ Ñ ³j G2 a«.. Fig. 3. SEM images showing the internal structure of porous polymer monoliths produced from TRM in supercritical CO2 at different monomer concentrations (50 oC, 310 bar). (a) 30 vol% (b) 50 vol% (c) 70 vol%. Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005.

(71) 24. ã§ºö? R. Fig. 5. The effect of monomer concentration on the specific surface area of porous polymeric monolith prepared from TRM (50 oC, 310 bar).. Fig. 4. SEM images showing the internal structure of porous polymer monoliths produced from different monomers in supercritical CO2 (50 vol%, 50 oC, 310 bar). (a) EDMA (b) DVB.. 3-3. §¿L ð»ª «d! Ñ @ æ2 à Ê~É monolith 9 ,

(72) JÑ ?³ s Âj2 ¯É2 ä HYí O

(73) . Q OYä Ft¯ ak³ ÷

(74) .

(75) ¡dÍ @ æ2 Ê~É monolith 9 ,

(76) JÑ Âj2 s ÷Ê À2 Fig. 5õ Ý

(77) , ä HYí O

(78) Í ³_j(TRM Î 40%, EDMA Î 30%) «G ³ ÎÑ2 9,

(79) J« kÎ ÊÊ

(80) s M ç ( :2 as < ¤ À. 6÷ « òÑ2

(81) Í ÍO¤´ @ æ2 monolith 9 ,

(82) J« ¾ ÍG2 as < ¤ À. «6K o

(83) Í ÍO ¤´ ßG2 Ê~É ½É ~-Í (õæ´, Êo 1ó ½É Q Â§K Dàs Gñ o 9,

(84) Js Í(j æD )é¯ ak³ gê. EDMAÍ TRMÝ 9 ,

(85) J« ¿Ê s çD QÊG2 Í o ao EDMA ÄgÍ TRMÑ 9g ¬Jk³ ¿D )é«¶ _ê.. ¤@¤ C43× C1 2005 2. Fig. 6o OYä Ft ¡dÍ @ æ2 à Ê~É monolith 9 ,

(86) JÑ Âj2 s ÷ a«. Fig. 6s Ý

(87) , OYä Ft« ÍO¤´ @ æ2 Ê~É monolith 9 ,

(88) J« Í G2 as < ¤Í À. «6K ê2 ð»ª Ñ Ft« ÍG

(89) ð»ª KÑ ¬K Ê~É ½É ÄgÍ ÍGÊ, «Ñ ¶ Ê~É ½É ~-Í (õæ´ Êo 1ó ½ÉÍ @ æÊ «Ë« Â§K Dàs G2) D¯G2 ak³ gO ¤ À. Fig. 5Q Fig. 6 ê³z @ æ2 Ê~É ½É ä HY íÑ ¬K ÄgÍ Ç¤´ Â§K 1ó ½É³ g ê jÊK Æ) monolithÍ @ ê2 as < ¤ ÀÉ. 3-4. Rockwell ð»ª «d! Ñ @ æ2 Ê~É monolith Rockwell Ñ Âj2

(90) ¡d s Fig. 7Ñ ÷É. Fig. 7 s Ý

(91) ,

(92) Í ÍO¤´ Rockwell Í ÍG2 s ÷Ê À. «2

(93) Í ÍG

(94) @ æ2 monolithÍ Â§K 1ó ½É³ g æ´ Æ)« jÊg(Ê ÊÍ ÍGD )é¯ ak³ gO ¤ À.. Fig. 6. The effect of reaction pressure on the specific surface area of porous polymeric monolith prepared from TRM (50 oC, 310 bar)..

(95) ð»ª «@õ «ÄK à Ê~É Monolith fÆ. OYä Ft« @ æ2 Ê~É monolith Rockwell Ñ Âj2 s ÷Ê À2 Fig. 8s Ý

(96) , 200 bar «G IF Ñ2 OYä Ft« ÍG

(97) Rockwell Í ÍG2 s ÷D2 G(O « Ft p.Ñ2 Ft s M ç( :2 ak³ ÷

(98) . «2 OYä Ft« @ æ 2 Ê~É ÄgÑ s ÂjD2 G(O, ÁêÍ

(99) . Ý ÊD )é¯ ak³ _ê. OYä QÑ« @ æ2 à Ê~É monolith Rockwell Ñ Âj2 s ÷Ê À2 Fig. 9õ Ý

(100) , OYä QÑ « ÍO¤´ Í ÍG2 as < ¤ À. @ æ2 à Ê~É monolith àHJ Ä s ¬Q IJk³, monolith Rockwell õ ³ ¤ À2 örÑ ¬K Y×J õgõ }G. Fig. 7-9b( êÑ »´, MÊ õ »s ¤ À2 ÆQs JÄGÊ, Ýãf³ à

(101) MAA õ ÍGñ MMA ÍÍ @ æ2 Ê~É monolith í Ñ Âj2 s Æ G. OY HYí O M

(102) 2 50 vol%³ Ê_Q ÆQÑ,

(103) ³ TRMOs ÄGñ OY K monolithQ ?

(104) TRMê à

(105) MAA z) 9õ ¡ dQ- fÆK àOY monolith Rockwell ¡dõ Fig. 10. 25. Fig. 9. The effect of reaction time on the Rockwell hardness of porous polymeric monolith prepared from TRM (50 oC, 310 bar).. Fig. 10. The effect of co-polymer content in the reaction mixture on the Rockwell hardness of porous polymeric monolith prepared from TRM (50 oC, 310 bar).. Fig. 7. The effect of monomer concentration on the Rockwell hardness of porous polymeric monolith prepared from TRM (50 oC, 310 bar).. Ñ 9GGñ ÷É. Fig. 10s Ý

(106) , @ æ2 Ê~É monolith Rockwell 2 Íæ2 à

(107) MAA Í 33 vol%Í î )b( ÍG2 as < ¤ ÀÉ. 3-5. ô/ ¬?F @ æ2 Ê~É monolith Äk ¤tÑ Âj2

(108) s ÷Ê À2 Fig. 11s Ý

(109) ,

(110) Í ÍO ¤´ Äk ¤t« ¾ ÝG2 as < ¤ À. « ê

(111) Í ÍO¤´ @ æ2 Ê~É monolith ÊÍ ÍG2) D¯G2 ak³ gê. Äk ¤tÑ Âj2 ñ ÆÊ¡¤Ë o M Ç2 ak ³ ÷

(112) . 4.. Fig. 8. The effect of reaction pressure on the Rockwell hardness of porous polymeric monolith prepared from TRM (50 oC, 310 bar).. û «. àÆJk³ lÄ ÍjÍ o à Ê~É monolithõ fÆG 2 D¬s íèGD .g ð»ª «d! Ñ à Ê~É monolithõ fÆG2 Y×J Æ õ 0Gñ »o ·o {ê ç. Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005.

(113) ã§ºö? R. 26. Fig. 11. The effect of monomer concentration on the solvent absorption ratio of porous polymeric monolith prepared from TRM (50 oC, 310 bar).. (1) ä HYí O

(114) Í kÎ o Î(10% «G) õ fG

(115) á õgÑ >K HÇ ÆÊ ÆQÑ

(116) Ü ÍÑ îªÇ« äD z =Q ³K + õ à Ê~É monolithõ fÆO ¤ ÀÉ. (2) ä HYí O

(117) Q OYä Ft« ÍG

(118) @ æ2 Ê~É monolith2 Êo 1ó ½É³ g æÊ Æ)« j Êg(2 ak³ ÷

(119) . (3) @ æ2 à Ê~É monolith 9 ,

(120) Jo ä HYí O

(121) Q OYä Ft« ÍO¤´ ÍG2 ak³ ÷

(122) . (4) @ æ2 Ê~É monolith Rockwell 2 ä HYí O

(123) Q OYä QÑ« ÍO¤´ ÍG2 ak³ ÷

(124) . ä HYíÑ Ýãf MAAõ ÍGñ fÆG

(125) monolith Rockwell õ ÍQ ¤ ÀÉ. (5) monolith Äk ¤to

(126) Í ÍO¤´ Ý GÊ, OYä QÑ« ÍO¤´ ÍG2 ak³ ÷

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