07-47(2)-05(김준호).fm

w œwz, 47«2y 2010 Textile Sciece ad Egieerig Vl. 47, N. 2, 2010 ù 6 p y ½x Á½ 1 Á½ y û w q w, 1 ( ) l (2010. 1. 15. /2010. 4. 14. k) Chai Extesi f Recycled Nyl 6 ad Their Prperty Chages Hyug Gue Kim, Dae Sup Kim 1, ad J H Kim Schl f Textiles, Yeugam Uiversity, Gyegsa 712-749, Krea 1 Ace Digitech C., Ltd., Chegw 363-883, Krea (Received Jauary 15, 2010/Accepted April 14, 2010) Abstract: Nyl 6 chips recycled frm waste fishig ets were extruded thrugh filters f varius mesh sizes (150:100 µm, 250:60 µm, 325:40 µm, 400:30 µm) ad subsequetly chai extedig reacti was carried ut thrugh melt-cmpudig with chai exteders, 2,2'-bis(2-xazlie) (BOZ) ad hexamethylee 1,6-dicarbamyl dicaprlactam (HDC). The resultat chages i ash ctet, mlecular weight ad crystallizati behavir i the mdified yl 6 samples were ivestigated frm themgravimetric aalysis, itrisic viscsity measuremet, ed grup titrati, ad differetial scaig calrimetry, respectively. The thermal degradati kietics were studied usig a cvetial thermgravimetric aalysis at heatig rates f 10, 20, 30, ad 40 C/mi. Thermgravimetric curves ad their derivatives were aalyzed usig varius aalytical methds t determie the kietic parameters fr the thermal degradati f the mdified yl 6. Keywrds: yl 6, recyclig, chai extesi, thermal degradati, melt filterig 1. ù v, x xk w š p w, p ù 6 sd, ü š k, ùw š f p, v p wš. š s» z wƒ» y ü. w s» w, ³ w. y ƒ w y w ƒ. w š v w w ƒ» ƒ¾. w z wš w w ƒ. s ù swwš Crrespdece t J H Kim (j@yu.ac.kr) 2010 The Krea Fiber Sciety 1225-1089/2010-2/117-09 y ƒ š. w ù w w e œ w»» ü e scree pack w wš. w w s ù ƒ w, Ÿ w, w, g w mw wƒ w» s ù j w y w w. s ù w ü w. ƒ s ù y s ù z fq w mw ¾ z w w. ù e»» w š ¼ k k. ƒ x w š, { ƒ ƒ š w. x x e» ƒ š bis(epxides)[1], bis(cyclic 117

118 ½x Á½ Á½ y carbxylic ahydride)[2], bisxazies[3], bisxazlies[4-7]» ƒ š bis (xazlies)[8-10], bis-caprlactam[11].» ƒ ù ƒƒ yww w j z [12]. s wš w y ù 6 e vl mesh j» w wš» ƒƒ e g ù 6 w, w œ p sƒwš w š w. 2. x 2.1. y ù 6(R-Ny6) s w mw, 2,2'-bis(2-xazlie) (BOZ) (TCI C., Japa) hexamethylee 1,6-dicarbamyl dicaprlactam(hdc) w. HDC ε-ev k w p p(tci C., Japa) w w w [13]. d kj (Duksa Pure Chem. C., Krea) w,» yùp (Jusei Chemical C., Japa), 0.1 N HCl(Duksa Pure Chem. C., Krea), r (Duksa Pure Chem. C., Krea), g(kat Chemical C., Japa), j s (Duksa Pure Chem. C., Krea) r, p (Duksa Pure Chem. C., Krea) w. 2.2. R-Ny6 e œ mw ƒƒ 250, 250/150, 325/150 š 400/150 mesh m g ù 6 e(f-ny6) w. 240 C screw 468 rpm š w ww. y w» w»(tga, SDT Q-600, TA Istrumets) w 30 ml/mi» w 10 C/mi 30 C 600 C¾ d w ash ctet(%) y w. 2.3. w F-Ny6 mixig chamber 260 C» w 30 rpm 10 g. 2.4. d k R-Ny6 F-Ny6 e š š kj 0.1~0.75(g/dl) y j Ubbelhde w 25 C d w y 0% w w. ƒ e š Mark-Huwik s³ y w [14]. [ η] = K( M a ) K: 18 10 4 a: 0.654 2.5.» e» w ƒƒ 0.2 g w 10 ml g ƒwš 210 C 150 ƒ w w g. w z 25 C 15 þ k 10 ml j s ƒw v w. r (0.1% g ) w 0.1 N yùp g w.» w ƒƒ 1g w r k v 7/3 yw 30 w k z þƒ g v w. p (0.1% k ) w š, 0.02 N HCl k w. z» w w.» (eq/10 6 ( a b) N g) = ------------------------ a: v (µl) b: blak (µl) N: w (eq/l) W: ù 6 (g) 2.6. p F-Ny6 p š w» w (Differetial Scaig Calrimeter, DSC) (TA Istrumet 2010, Du Pt, USA) w. ƒƒ 2~3 mg q w» w 20 C/mi 250 C¾ jš 5 k w z þ g. 10 C/mi 0 C 250 C¾ k z 10 C/mi 0 C¾ gš, š l (T m ), y (T c ) w. 2.7. w p F-Ny6 w p y š w» w TGA w. 30 ml/mi W w œwz, 47«2y 2010

재생 나일론 의 사슬연장반응 및 그 특성 변화 6 질소 기류하에 승온속도 각각 10, 20, 30 및 40 C/mi으로 유지하고, 30 C에서 650 C까지 측정하여 각각의 열분해 반응에서 나타나는 시료의 미소 무게 변화를 연속적으로 기록한 후 다양한 방법으로 열분해 반응을 조사하였다. 3. 결과 및 고찰 용융여과 효과 Figure 1은 실험에 사용된 각각의 mesh를 광학현미경으 로 확대한 사진이다. Figure 2는 mesh의 종류에 따른 열중 량곡선을 나타낸 것으로 그림에서 보면 mesh 크기가 작아 질수록 ash ctet(%)가 감소하였다. 이것은 R-Ny6 칩 속 에 함유되어 있는 불순물이 mesh를 통과하면서 여과되었 기 때문인 것으로 보인다. 3.1. Figure 1. Optical micrscpe images ( 200) f varius mesh; (a) 150 mesh (100 µm), (b) 250 mesh (60 µm), (c) 325 mesh (40 µm), ad (d) 400 mesh (30 µm). 분자량 변화 은 실험에 사용된 사슬연장제와 F-Ny6의 사슬 연장반응을 나타낸다. Figure 3은 mesh와 사슬연장제의 종 류에 따른 F-Ny6 시료의 고유점성도를 나타낸 것이다. 전 체적으로 F-Ny6 시료의 고유점성도는 사슬연장제를 첨가 함에 따라 증가하였는데, 사슬연장의 효과는 BOZ보다 HDC 가 더 큰 것으로 나타났고, mesh 크기가 작을수록 분자량 이 더 높아졌다. 특히 BOZ와 HDC를 혼합하여 첨가하였 을 때 고유점성도가 크게 증가함을 보였다. R-Ny6 칩에 함 유되어 있는 불순물을 여과하기 위하여 다양한 mesh 크기 로 재압출한 F-Ny6의 경우 고유점성도가 낮아졌는데, 이 는 재 압출과정에서 열분해와 가수분해 등에 의해서 분자 의 분해가 일어나기 때문인 것으로 보인다. 그리고 사슬연 장제의 첨가 없이 용융시킬 경우 R-Ny6보다 F-Ny6의 고 유점성도가 더 크게 증가하였다. 이것은 분해에 의해 카르 복시기와 아민기들의 농도가 높아져 재용융과정에서 열적 분해반응 보다 축합중합반응이 더 우세하게 나타나기 때문 3.2. Scheme 1 Figure 2. TGA thermgrams fr R-Ny6 melt-cmpuded with varius mesh sizes. Scheme 1. Chai extesi reactis f yl 6 usig BOZ ad HDC. Textile Sciece ad Egieerig, Vl. 47, N. 2, 2010 119

120 ½x Á½ Á½ y Table 1. Ed grup ctet with varius chai exteders (400/150 mesh) Ed grup R-Ny6 F-Ny6 Ctrl BOZ HDC BOZ+HDC Carbxyl ctet (eq/10 6 g) 55 73 57 40 65 38 Amie ctet (eq/10 6 g) 28 28 24 22 8 10 Figure 3. Chages i itrisic viscsity f melt-cmpuded F-Ny6 with varius chai exteders thrugh differet mesh sizes.. š l w s³ 17,700 g/ml R-Ny6ƒ BOZ z 20,600 g/ ml, HDC z 24,700 g/ml, š BOZ HDC z 30,300 g/ml¾ w z ƒ w ùkü. 3.3.» y Table 1 ƒ 400/150 mesh F-Ny6» e»» y ùkü. F-Ny6 R-Ny6 e» ƒ ùkû. wƒ ù ƒ ƒw q. BOZ w e» ƒ w w š» y j ùkû. HDC w e» y,» w ùkû. BOZ HDC yww ƒw e»» ƒ w ù kû. Figure 3 BOZ HDC w š ƒ ƒ j ƒw ew. 3.4. p Figure 4 F-Ny6 y w» w DSC š. Figure 4(a), Figure 4. DSC thermgrams fr F-Ny6 (400/150 mesh) meltcmpuded with varius chai exteders; (a) heatig ad (b) clig. BOZ ƒw wš z F-Ny6 w û. w yw ³e w ù» [15]. BOZ z ƒ š HDC w û» w e ƒ. Figure 4(b) F-Ny6 y ƒ z. y ƒ ƒw ùkü. y y w w» x ƒ w» wš w y ƒ ƒw. w œwz, 47«2y 2010

ù 6 p y 121 Figure 5. TGA curves f F-Ny6 (400/150 mesh) melt-cmpuded with chai exteders at varius heatig rates; (a) F-Ny6, (b) BOZ, (c) HDC, ad (d) BOZ+HDC. Figure 6. DTG curves f F-Ny6 (400/150 mesh) melt-cmpuded with chai exteders at varius heatig rates; (a) F-Ny6, (b) BOZ, (c) HDC, ad (d) BOZ+HDC. Textile Sciece ad Egieerig, Vl. 47, N. 2, 2010

122 ½x Á½ Á½ y 3.5. w p 4ƒ w d w F-Ny6 š Figure 5 ùkü. ƒ ƒ ƒw F-Ny6 wƒ wƒ ƒ, w x ƒ ƒ x w q [16,17]. ƒƒ w F-Ny6 w yƒ y y (dα/dt) e w Figure 6 ùkü. ƒ ƒ ƒw y y ƒw, ƒ ƒw y y š wù ùkùš. l w F-Ny6 w w w» û y w [17]. w w F-Ny6 w p w w. w y w Arrheius xk ƒ w ùký. dα ------ A( 1 α) E = exp ------ dt RT», A (frequecy factr), α y, E y y (kj/ml),, R» ù kü, T t (K) (mi) ƒƒ ùkü., Kissiger [18] mw w ƒ (Tm) y y (1) l xƒ β (K/mi) w (2) ùký. dα = ------ ( A/β)exp E/RT dt ( )( 1 α) y d 2 α/d 2 T =0 Tm wš, (2) l (3). E A ---------------------------------------- = -- exp E/RT 2 RT m 1 αm β m ( ) 1 ( ) w 1 ƒ w. ( ) 2 dl β/t m E ----------------------- = ------ R d( 1/T m ) 2 lβ/t m 1/Tm Figure 7 ùkü,»» l y y w. w (1) (2) (3) (4) Figure 7. Kissiger plts f F-Ny6 (400/150 mesh) meltcmpuded with varius chai exteders. Kissiger w, w 1 ƒ ƒ w ƒ 1 j ù w š w w. wr, Friedma [19] ƒ š l y w w w w, (1) w ùký. l ------ α = la 1 α ( ) ------ E RT d dt (5) l w y w ƒ w l(dα/dt) 1/T w»» l ƒ y y y w. w r la( 1 α) (6) ùký. ( ) = la+ l( 1 α) la 1 α ƒ y r l (6) la( 1 α) l( 1 α) w»» l w. Figure 8 (5) mw 1/T l(dα /dt) w xyw»» E/R l y y w. ƒƒ y y y Figure 9 ùkü., Ozawa [20] ƒ y l y y w. A, Eƒ α A, ( 1 α), Eƒ w ƒ l w, w w (7). lgf x ( ) = lg AE ------ lgβ R + lgp ------ E RT (5) (6) (7) w œwz, 47«2y 2010

ù 6 p y 123 Figure 8. Friedma plts f F-Ny6 (400/150 mesh) melt-cmpuded with varius chai exteders; (a) F-Ny6, (b) BOZ (c) HDC, ad (d) BOZ+HDC. Figure 9. Activati eergy chages f yls up cversi accrdig t the Friedma methd. Dyle[21] E/RT 20 lgp(e/rt)ƒ y w. lgp ------ E 0.4567E 2.3151 ------------------- RT RT (7). (8) lgf( x) lg AE ------ R lgβ 2.315 ------------------- 0.4567E RT», w y w lgβ 1/T w»» l y y w. Figure 10 (9) mw lgβ 1/T w xyw»» 0.4567E/R l y y w, ƒƒ y y y Figure 11 ùkü. Table 2 w w ù kü. Table 2 ùkù 3ƒ s³ y y mw ƒw. ù» w ƒ y,»ƒ š,»ƒ w w» j ƒ y y ùkü. š (1) mw (1 α) w 1 ù» y y ƒ dα/dt û. Table 2 Friedma mw w mw ƒw (9) Textile Sciece ad Egieerig, Vl. 47, N. 2, 2010

124 ½x Á½ Á½ y Figure 10. Ozawa plts f F-Ny6 (400/150 mesh) melt-cmpuded with varius chai exteders; (a) F-Ny6, (b) BOZ, (c) HDC, ad (d) BOZ+HDC. Figure 11. Activati eergy chage with reacti cversi accrdig t the Ozawa methd.. wƒ w w. 4. s w mw y ù 6 e w mesh j» k z w ƒ p w. w j» mesh w w mesh j» ƒ ash ctet w z ùkü. BOZ HDCƒ w, BOZ HDC yww g ƒ j Table 2. Kietic parameters determied by varius aalytical methds Methd Ea (kj/ml) F-Ny6 BOZ HOC BOZ+HOC l(a) (mi 1 ) Ea (kj/ml) l(a) (mi 1 ) Ea (kj/ml) l(a) (mi 1 ) Ea (kj/ml) w œwz, 47«2y 2010 l(a) (mi 1 ) Kissiger 208.0 1.00-223.9 1.00-216.5 1.00-221.7 1.00 - Friedma 201.2 a 0.82 37.22 212.1 a 0.88 39.11 211.1 a 0.87 38.90 214.4 a 0.90 39.50 Ozawa 199.8 a - - 207.7 a - - 209.3 a - - 207.3 a - - a: average value, b: assumed value.

ù 6 p y 125 ƒw š, mesh j»ƒ z f.» BOZ g e» ƒ j w š, HDC g» ƒ j w ù, BOZ HDC w» j w š ew. F-Ny6(400 mesh) BOZ g wš ù 6 û, y w w ùkü. w TGA d w ƒƒ Kissiger, Friedma, Ozawa w w, w w w y y ƒ ƒw y w. :» x (RTI04-01-04) w. š x 1. Z. Y. Qia, X. Che, J. Xu, ad B. H. Gu, Chai Extesi f PA1010 by Reactive Extrusi by Diepxide 711 ad Diepxide TDE85 as Chai Exteders, J Appl Plym Sci, 2004, 94, 2347-2355. 2. F. L. Cai, D. S. Zhag, J. Zhag, N. D. Feg, ad S. W. Ha, Study Chai Extesi Reacti f Plyester, Plyester Id, 1994, 2, 15-21. 3. A. Duhi ad A. Fradet, Study f Bulk Chai Cuplig Reactis. III. Reacti betwee Bisxazlies r Bisxazlies ad Carbxy-termiated Oligmers, J Plym Sci, Part A: Plym Chem, 1995, 33, 691-699. 4. H. Iata ad S. Matsumura, Chai Exteders fr Plyesters. I. Additi-type Chai Exteders Reactive with Carbxyl Ed Grups f Plyesters, J Appl Plym Sci, 1985, 30, 3325-3337. 5. H. Iata ad S. Matsumura, Chai Exteders fr Plyesters. II. Reactivities f Carbxyl-additi-type Chai Exteders; Bis Cyclic-imi-ethers, J Appl Plym Sci, 1986, 32, 5193-5202. 6. H. Iata ad S. Matsumura, Chai Exteders fr Plyesters. IV. Prperties f the Plyesters Chai-exteded by 2,2'-bis(2- xazlie), J Appl Plym Sci, 1987, 33, 3069-3079. 7. H. Iata ad S. Matsumura, Chai Exteders fr Plyesters. Prperties f the Plyesters Chai Exteded by 2,2'-bis(4H- 3,1-bezxazie), J Appl Plym Sci, 1987, 34, 2769-2776. 8. L. Herve ad F. Alai, Chai-cuplig Reacti f Amietermiated Oligmers by Bis(4-msubstituted-5(4H) xazlies), Macrml Chem Phys, 1998, 199, 815-824. 9. M. Aceved ad A. J. Fradet, Study f Bulk Chai Cuplig ReactisU II. Reacti betwee Bisxazles ad Amie-termiated Plyether: Sythesis f Plyether-blckplyamides, J Plym Sci, Part A: Plym Chem, 1993, 31, 1579-1588. 10. H. Lefebvre ad A. Fradet, Bis[4-msubstituted-5(4H) xazlies] as Cuplig Agets fr Blck Cplymer Sythesis: Reacti with Amie-termiated Oligmers ad with Hydrxy-termiated/amie-termiated Oligmer Mixtures, J Plym Sci, Part A: Plym Chem, 1999, 37, 4412-4421. 11. M. K. Akkapeddi ad J. Gervasi, Chai Extesi f PET ad Nyl i a Extruder, Plym Prep, 1988, 29, 567-570. 12. L. Jakisch, H. Kmber, R. Wursche, ad I. Bhme, Multifuctial Cuplig Agets. II. Chai Extesi ad Termial Grup Mdificati f Plyamides, J Appl Plym Sci, 2004, 94, 2170-2177. 13. J. H. Hg, C. W. Chi, S. Ramasudaram, A. A. Prabu, J. S. Lee, K. J. Kim, J. H. Yag, ad D. J. Lee, Studies the Recyclig f Glyclyzed Nyl 66 Usig Nvel Chai Exteders, Plym Degrad Stab, 2008, 93, 392-400. 14. M. Fukumt, Plyamide Resi Hadbk, Chia Petrchemistry Publishig C., Beijig, 1994, p.89. 15. X. Dig, J. Rg, R. Xu, D. Yu, ad Z. Yag, Effect f a Chai Exteder the Crystallizati Behavir f Nyl 66, J Appl Plym Sci, 2004, 91, 68-71. 16. S. J. Kim, C. G. Lee, P. S. Sg, J. S. Yu, Y. Kag, J. S. Kim, ad M. J. Chi, Characteristics f Pyrlysis ad Cmbusti Kietics f Waste Plystyree, J Krea Id Eg Chem, 2003, 14, 634-640. 17. M. S. Kim, S. C. Oh, H. P. Lee, H. T. Kim, ad K. O. Y, A Study the Kietics f Thermal Degradati f Plyethylee, J Krea Id Eg Chem, 1999, 10, 548-556. 18. H. E. Kissiger, Reacti Kietics i Differetial Thermal Aalysis, Aal Chem, 1957, 29, 1702-1706. 19. H. L. Friedma, Kietics f Thermal Degradati f Charfrmig Plastics frm Thermgravimetry. Applicati t a Phelic Plastics, J Plym Sci, Part C, 1964, 6, 183-195. 20. T. Ozawa, A New Methd f Aalyzig Thermgravimetric Data, Bull Chem Sc Jp, 1965, 38, 1881-1886. 21. C. D. Dyle, Estimatig Isthermal Life frm Thermgravimetric Data, J Appl Plym Sci, 1962, 6, 639-642. Textile Sciece ad Egieerig, Vl. 47, N. 2, 2010