Studies on Cure Behaviors and Rheological and Mechanical Properties of Epoxy/Polyurethane Blend System Initiated by Latent Thermal Catalyst / ,

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(1)Journal of the Korean Chemical Society 2002, Vol. 46, No. 3 Printed in the Republic of Korea. /

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(3) (2002. 3. 19 ) †. Studies on Cure Behaviors and Rheological and Mechanical Properties of Epoxy/Polyurethane Blend System Initiated by Latent Thermal Catalyst Jun-Gil Kang†, Soo-Han Kwon†, and Soo-Jin Park * Department of Chemistry, Chungbuk National University, Cheongju 361-763, Korea Advanced Materials Division, Korea Research Institute of Chemical Technology, Yusong, Daejeon 305-600, Korea (Received March 19, 2002) †. . (N-benzyl pyrazinium hexafluoroantiminate, BPH) !"#$% &'()* +, - ./ 012 345 6 7"8 9)5 : 4 ;< ;=> . &'()* ?@A DSC ;< ?@ B ./ CDEF ;< GH;=IJ, 345 6A $KLM N OPF Q;< GH;=8, R STU(E ) V W 0 B ;< Arrhenius X HYIZ ;=>. [, 0\ [* 9)5 :A ]^B OPF Q;< GH;=>. OP_, &'()* ` abZ c\ BPH de f gB # ab 6F hijk>. &'()* R ST U l ]^B PUR 30 wt% mRnkF o p hijkq, EPr PUW* _,IZ s tu R uB* vR owx8 cy\>. : ` ab, /!"#$% &'(, R STU, ]^B, RuB. /. c. ABSTACT. In this work, the cure kinetics and rheological and mechanical properties of diglycidylether of bispheonol A (DGEBA, EP)/polyurethane (PU) blends were investigated. The 1 wt% N-benzylpyrazinium hexafluoroantiminate (BPH) was used as a latent thermal catalyst. Latent properties were performed by measurement of the conversion as a function of reaction temperature using DSC. And the rheological properties of the blend systems were investigated under isothermal conditions using a rheometer. Crosslinking activating energies (Ec) were also determined from the Arrhenius equation based on gel time and curing temperature. The impact strengths were measured as mechanical properties of the casting specimens. The BPH in the blend systems could be an excellent latent thermal catalyst without any co-initiator. The rheological results showed that Ec was highest when PU content was 30 wt% which was in good agreement with the impact strengths. This was probably due to the intermolecular hydrogen bonding between the hydroxyl group in PU and EP, resulting in increasing the crosslinking density. Keywords: Latent Thermal Catalyst, DGEBA/PU Blends, Crosslinking Activating Energy, Impact Strength, Crosslinking Density. 233.

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(5). ´ » Û8 Þ >. 7" 8 ß ab ´, às, , á 7"8 ªâ$Ur µA ¾º Àã ä" c n8 >. 6Ò Hexafluoroantimonate 3;8 BPH abZ c z,A ?@ åBR æ¨8 xçè z,IZ éF g , êë, ìí N* ,:* z,B Rî;9 ow > -* 8À éF >. Æ >/ z, r ï" ìë N* Í b ~H #;9 ow b ðñ 8 x çè 0?@ ¥Î òó 58 ô 3Î 5> }¹F RU8 >. .x, abs BPH ; < /!"#$% &'()* semi-IPNs - B ;8, ¡Äc`õ)r $KLM ;< +, -¥ ./ BPH* 6 /!"#$% &'()* `5ö345 6 l 9)5 :F ÷ Û8 ;=>. metal halide. U ` 0 Uz* ;hJ {d| s}^Br %E, t ~H, j`, j, 7 "8 b ~H N ;< # :F RU9 ow , , C9C y, ,y* N cn8 >. ;U, U A RuBZ s;< hih (brittleness), A ^s(toughness), ` (crack resistance) o w c A F >. .x, U* 3"CB, ^B(strength), ^B(stiffness), ^sF 9 ;< 3¡

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(9) r _,F £ ;< :"5 R ¿I \>. .x, 8À cÁ ½ À(soft segment)r 0½ À(hard segment BnJ ½ ÀA À"r »Ând 3"CBr %E ÃF ÄJ, 0½ ÀA 8À ^ ÃF Å>. ab ?@£ 0Z Æ ÇÈ µA ¿?5s -É SF hij U ÊIJ, R` Æ Ë-cr µA Ì Í *Î 7 S hihBÏ Ð) nd :½Z, 0 HF one-pot curing systemIZ WÑÒ ¤ 9 ow ` 0 U* } ~H Ó* [ "F q n8 >. .x `0 U* ÔZÕ 0®F Ö;9 Î Ë l ` F RU `0 U 5;× ØÙ* ¿DIZ Gu N Morio NA aliphatic sulfoniumÚ* BF , PF ´R U* 0? @ f gB # `F Û<ÜF Ýs;=8, Crivello h Abu-Abdoun NA triarylselenonium saltsh phenacyltrithenyl phosphonium salts* 1. 2,3. 4-6. 7-8. 17. 18. 18. . 9. 10. 11-13. 14. −. 15. −. 4. 6. 17. 12. . c U(EP) B * YD-128(DGEBA, ¹B 12,000 cps, E.E.W=185~190 g/ eq, uB 1.16 g/cm ), !"#$%(PU)A Uniroyal chemical company* ADIPRENE L-100(¹B 18,000 cps, NCO õ 4.1%) H g c;=>. Z c BPH benzyl bromider pyrazine øÖ:½Z ,;< c;=>. , \ BPH c C ·fKù 1W 2~ É - ú c;=>. c\ r !"# $%, 7"8 BPH* - Fig. 1 hijk>. +,-A 100 ;< !"#$%F 10, 20, 30, 7"8 40 wt%Z 4ûIJ Å¥\ y 70 C oil bath ? ;=>. Æ, BPH ¬¥Z 2~3ü n ìë Îý ú EP/PU &'() mR;=>. Å¥\ þ±F 30ÀW ?ý ú +, H ÿ9 9ª 1;9 ;< O · f ;< 5W í9û>. 9)5 : ÀF 0[* - -\ y Kù åB 5 C/minZ ;< 120 C(1 h), 150 C(2 h), 7"8 180 C(2 h)* 0F 3U;8 ú0 Z 200 C 5W 2~ `0 û>. Æ, 0 3. 19. o. o. o. o. o. o. Journal of the Korean Chemical Society.

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(11) / !. Fig. 1. Chemical structures of EP, PU, and BPH.. ú ] ^B [A ASTM D 256 .x Å¥ ;=>. . BPH c EP/PU &'() ! "#$%* õ ./ 6F ÷Û9 ;< `À OPA ¡Äc`õ)(differential scanning calorimeter, DSC) Perkin Elmer DSC6F c;< åB 2 C/minIZ O;=>. ÛHA s *Î nkIJ, 30 ml/min* åBZ ½ fÓ; ÀF · ;=>. }%E(storage modulus), O%E(loss modulus), 7"8 damping factor NF GH;< EP/PU &'()* W ./ ¹B4r RW ./ STU ÷Û9 ;<,

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(13) £ $KLMs Rheolab MC100F c; =IJ plate W]A 0.5 mm, frequency 5 HzZ 8H ;=>. 7"8, Izod method ]^B ASTM D 256 *1;< Tinius Olsel Model 66 Izod Impact Tester ;< GH;=8, ÄcC óL0 (SEM, Hitachi S-2400)F c;< +, -¥ ./ EP/PU ,y* Ñ F »;=>. o. .

(14) . 0 ab ?@£ 0 Z O Æ jË µA ¿?5s -É S F hijU ÊIJ, UVr µA Ë* -c, R`, 9, Ù N* Ì Í *Î SF ÿ¾Î j :½Z, Ñ) d¤ > 6F U8 IJ, Ì ÍF 9 C SF hi 2002, Vol. 46, No. 3. 235. Fig. 2. Conversion of EP initiated by BPH as a function of temperature.. jU Ê ~HF hi>. 0* } ~ HA Rc W(pot life)F Q;< -c;=q, 0* RcWA 1W jJ ¥5 } ~H >8 ÷×· ¾¬:)R 5¿F 9 U ;q ¥;<, BPH * 0# +, .x 2 6 HB* } ~HF h ijk>. Fig. 2 1 wt% BPH ab 3 EP/PU &( )* DSC `À *Î W .x ¿ H; vR; 0B* CDEF hijk>. OP _ZM EP/PU/BPH &() PU* mR õ #nU Ê8 150 C B Ó] SF hijJ A CDEF hijk>. * _ ZM IZM SF hij ¿?5s ) 0r >¨ BPH EP/PU &'()B # ` } ~HF hijkIJ, 6H B S # ab£ 0F Ýs¤ k>.

(15) . 0Z ` ab ¤ 0#, r µA `0 U 0?@F Q;< A À õF "8 RU ï ¢ -Z CDnq H ¹B ¿HB ?@ W .x Ó]Ò vR>. Fig. 3A ?@BR 160 Cs EP/PU &'() ?@W .x PU õ 4 ./ ¹B 4 h i >. ?@ !9 PU* õ »)g ¹ B 4R 1* gkIh, ¿H W ú ¹BR Ó] 12,16,20. 21. o. 22. o.

(16) 236. . /!"#$% &'() ?@W .x 140, 150, 160, 7"8 170 C* ¹B4 hi >. B& Ó] ¹B 4 ¨ WA BR F Ï '(q BR FÏ VR )n W *xU9 ow>. Æ ?@ BR FÏ ?@W .x EP/PU &'()* ¹B 4R Ó]Ò · nkq r µA ` ab 0 ?@* B *+A 0R · # .x 4; EP/PU &'()* R -* 4r ») >. . R 8À * V¹A 58 9,5s -U b# z° s Z 5 34 5 GH. *Î HÝÒ _H/ >. C£5s N0 y* % 6F hij }% E(G') ¹ 6 »)R O %E(G")A ¿H Ä ; 0W* s dynamic time *Î W* Z GH\>. V¹F _H; 345 X.A \Þ q, 7 z Winter *Î ~\ V¹F _H; X.A 0¿1 2(scaling theory) 9! 38 >. V ¹ 8À * @Ù 12A >%* power law ./>. o. 21. Fig. 3. Viscosity profile of EP/PU blends initiated by BPH at 160 oC.. Ò vR;=>. V* !9Ñ) À õA & '()* cÁ }* _ ""Ò vR;=Ih, R R · # .x &'()* 3¡

(17) 5 8À R £# .x ¹BR Ó]Ò vR; óIZ Ûs>. r µA óA 0Z c ` abs BPHR Äd· B ¿H W 0 ú Ó] SF hi$ .x CDõ vR; 0R · n9 ow>. .x Äd· B ¿ H W 0 ú Ó] ¹B 4 hijJ · ; 0?@A EP/PU &'() ab£ 0 s BPH* ` 6 »Â %F ÷ >. Fig. 4 !"#$%* +,-¥R 30 wt%s . 23. –n. G ( t ) = St r ; p = p c. (1). <9, S V* ^B, t ?@ W, n A 4U (0<n<1), p ?@(·5)B 7"8 P V¹ ? @B hi>. Y (1)* S À cÁ R* 3 R uB *+5s 6J, 4U n A V¹ + ; ßM(cluster)* 9;5 - *+5s s >. Y (1)IZM V¹ ·2 *+5 s 25 CÑ %E(dynamic shear moduli)A Y (2) r Y (3) µ hi7 >. r. c. r. G′ ( w ) = I′( 1 – nr ) ⋅ cos ( nr π ⁄ 2 ) ⋅ Swnr. (2). G″ ( w ) = I′( 1 – nr ) ⋅ sin ( nr π ⁄ 2 ) ⋅ Swnr. (3). V¹ loss tangent(tan δ) frequency ô8 5sq Tung Dynes A G'r G"R 9t ¹(tan δ =1)F V¹IZ H*;=>. .x V¹A Y (4) r µ hi7 >. 24. Fig. 4. Viscosity profile of EP/PU (70:30 wt%) blends initiated by BPH.. G′′ tan ( δ) = ------- = tan ( nπ ⁄ 2 ) G′. (4). Journal of the Korean Chemical Society.

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(19) / !. 237. Fig. 5. Plots of G', G" and tan δ as a function of the reaction time measured at 140 oC with mixing ratio of (a) EP100, (b) EP90PU10, (c) EP80PU20, (d) EP70PU30, (e) EP60PU40.. G"/G'* ¥ «¿ 0# 1Û> : 6F Û ?. , % 8 1Û> )A 6F Û<Å>. 0?@ !9 « 6 Uü;< G"À hih>R ?@ · n % 8* ½ R;U G'R Uü; CD¹ K nJ ¹ F V¹x ;J, o 0) 3¡

(20) R - £;9 )>. Fig. 5 140 C* N0 -É EP/PU &'( * - 4 * 0W ./ } %E o. 2002, Vol. 46, No. 3. O %E (G'') 7"8 tan δ* 4 hi >. ¿?5IZ Ñ)z, *Î ¿dh :½* 0#, V¹A G'r G''R µU ¹, < tan δR 1 n WIZ H*nq, Fig. 5* N 0 V ¹A =>Z >;=>. 9+* ) 0s DDM(4,4'-diaminodiphenylene-methane)F c U* 0 ?@ DDM ¿H B ? @ !9M SF hijd ?" RR · # .x G', G"R W U@ .x Ò 4;J . (G'),. 25.

(21) . 238. x V¹ A tan δB 4Ò ; óF hi>. 7ßh Fig. 5ZM BPH 0Z c EP/PU &() PU õ »)g ?@ W !9 G', G'' 1* 4R g>R V¹ R;B .x Ó]Ò vR;J .x tan δB Ó] Ò ; óF hi>. Table 1A N0 -É EP/PU &'()* & V¹F hijkq, VWA BR F Ï CdU8, !"#$%* õ vR¤Ï Cd U IZ Û Br +, -¥ *+5F ÷ >. . R ?@ d ST U D9 >/ B V WF GH;< ¤ >8 ÷×E >. V¹* 5 CDE A Br ¬»;8 6F >8 RH; , V W(t )A Y (5) µ ?@* kinetic constant(k) r »ÂUF >. 29. 26. Fig. 6. Polts of gel time vs. curing temperature for EP/PU blends.. 27. Ec  k = k′ ⋅ exp  –-------- R ⋅ T. g. 1 tg = c ⋅ --k. (5). Y (5) ?@* kinetic constant Arrhenius Y *Î B* Z hij >%* YIZ >ó\>. Table 1. Gel time of EP/PU blend system Compositions EP/PU. Reaction temperature (oC). Gel time (sec). 100:0. 140 150 160 170. 1840 1180 0740 0500. 90:10. 140 150 160 170. 1580 1020 0580 0400. 80:20. 140 150 160 170. 1720 1160 0600 0440. 70:20. 140 150 160 170. 2800 1640 0900 0660. 60:40. 140 150 160 170. 3280 1940 1160 0800. (6). H";< hij >% µ>. Ec 1 ln tc = ----- ⋅ --- + C R T. (7). <9, E R STU, RA 9, 7" 8 T 0B hi>. Fig. 6 EP/PU &'()* V W 0 B r* ») hijkIJ 7F* 9G9ZM Y (7) ;< 0 STU ;< Table 2 -& S TU hijk>. Table 2ZM EP/ PU &'( R STU PU* - . x 67.1~75.9 kJ/molF hiHIJ, Sung N Û8 ) 0s DDS(4,4'-Diaminophenyl sulfone) U* R STU 61.9 kJ/molÛ > A 6F hijk>. 7"8 EP/PU &( PU* -¥R vR .x R STUR v R; A EP/PU* semi-IPNs PU* IJ K (dilution effect)r @8 K(solidification effect) * Î R -* £ U n9 owx8 cy\>. 6Ò PU 30 wt% R STUR 75.9 kJ/mol Z p6F hijkIJ, 30 wt% - p 5* + ./ À W L) *Î tu R - £;9 owx8 cynd ·>.

(22) !(SEM) "#. ] TU ¢M -j* 'A À* ·2r ;z åB* ·2 c. 28. 29. Journal of the Korean Chemical Society.

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(24) / ! Table 2. Cross-linking activation energies (Ec) of EP/PU blend system Compositions EP/PU. 1/T (×10−3 K). ln tc. Ec (kJ/mol). 100:0. 2.54 2.48 2.42 2.36. 7.52 7.07 6.60 6.21. 67.1. 90:10. 2.54 2.48 2.42 2.36. 7.36 6.92 6.36 5.99. 71.3. 80:20. 2.54 2.48 2.42 2.36. 7.45 7.05 6.39 6.08. 72.3. 70:20. 2.54 2.48 2.42 2.36. 7.93 7.40 6.80 6.47. 75.9. 60:40. 2.54 2.48 2.42 2.36. 8.09 7.57 7.03 6.65. 239. * ]^B P _ hi >. P _ V UÛ> !"#$% mR# .x ]^B vR;=>. EPr PUR semi-IPNsF £ , 3 8À * + vR .x Ñ¿ 8À +; _¹F Û4IZW &'(* RuB vR8 Æ semi-IPN - PU* ð£. ½ À :"5 R¹(Physical crosslinking point) *Î EP* 3¡

(25) ¢ - tu; R#IZ, K5IZ ] TU N;9 ow>. Æ PU õ ./ ]^B* 4 ) 0s DDMIZ 0ý EP/PU &'(r 3c 0 hiXIJ, DDM 0Û> > A ]^B 6F hijk>. 6Ò PUR 30 wt% 3\ EP/PU &'(* ]^B 12 kJ · m Z p6F hij q EP/PU &'( PU* õ 30 wt%¿ o hih p5* + ./ PU-PUr EP-PUW £ \ _, * RuB vR owx8 cy nd ·>. Fig. 8A ]^B OP ú EP/PU ,y* Ñ. F SEMIZ » _ hi >. Fig. 8 (a)* V EP* Ñ * 0# ¥5 (ßÕ >. hijJ, Fig. 8(b-e)r µ PU* õ vR .x tu ¢ -R Y Öï\ F Ýs¤ kq, Z s;< Z12 hij IZ cy\>. .x. Fig. 8(d)* R} Y Öï\ X c£* Z* £¶5 12A PU 30 wt%¿o EPr PUW tu ¢ - £ _ 0:* Z # Z [\IZ Z12 · nd p* ]^B hijk>8 cynd ·>. 31. 32. −2. 31,32. 73.2. R ¿t¤ o NnOZ ¿H W j N\ ]TUR Ï ¿5s van der Waals _,F Û> P QRS IJ, o TU* NÙA À W _,, À -, 'A À¸* ¿5s TU N *Î _Hn IZ ÷×E >. Fig. 7A Izod X.F ;< éA EP/PU &'() 30.

(26) ` abs BPH c;< &'()* 012, 345 6, 7"8 9 )5 : Lt Ã ;< -c;=>. & '( ® BPH # ` 6F hij F Ýs¤ kIJ, !"#$%* õ v R¤Ï ?@W U nkIJ ¹B Ò v R; F Ýs¤ k>. Æ, RST U 30 wt% !"#$%F 3 EP/PU &'() R} hiXIJ, A EP/PU &'() EP/PU. Fig. 7. Impact strengths with the content of PU at room temperature. 2002, Vol. 46, No. 3.

(27) 240. . Fig. 8. SEM photographs of EP/PU blend systems (a) EP100, (b) EP90PU10, (c) EP80PU20, (d) EP70PU30, (e) EP60PU40.. +,-¥R 70:30 wt%¿ o + R} #;< EPr PUc* _,IZ s tu R - £ .x p* R STU hi$F ÷ >. ]^B ] +, -¥R 70:30 wt%¿ o R} : 6F hijkq SEM »\ µ 0:* Z tu R -Z s;< # Z [\IZ Z 12 · nd # ]^B hi$F Ýs¤ k>.. 1. Lee, H.; Neviles, K. Eds., Handbook of Epoxy Resins; McGraw-Hill: New York, 1967; 1. 2. May, C. A. Epoxy resins, Chem. Technol; Marcel Dekker: New York, 1988; 551. 3. Ng, H.; Manas-Zloczower, I. Polym. Eng. Sci. 1993, 33, 211. 4. Park, S. J.; Park, W. B.; Lee, J. R. Polym. J. 1999, 31, 28. Journal of the Korean Chemical Society.

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Studies on Cure Behaviors and Rheological and Mechanical Properties of Epoxy/Polyurethane Blend System Initiated by Latent Thermal Catalyst      / ,   

Studies on Cure Behaviors and Rheological and Mechanical Properties of Epoxy/Polyurethane Blend System Initiated by Latent Thermal Catalyst / ,