2.2 DVB DVB 2.3 DSC 13 C-NMR GC/MS DVB DVB BPA DVB 850 ( ) BPA 190 KH-130 KH-150 ( ) BPA 2E4MZ % 150 C C DVB Table 1

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1 New Phenolic Resins by the Reaction between Phenols and Divinylbenzene Mori Kunio, Inoue Tadashi and Ikeda Takashi A phenolic resin with a new structure was synthesized by reacting phenols and divinylbenzene (\DVB"), a compound with two vinyl groups in its molecule, using the electrophilic substitution reaction of the vinyl group to the nuclear phenol. DVB purity, phenol types, and catalysts together with reaction mechanism, structural analysis and evaluation as epoxy hardener are discussed. DVB selectively reacts with various phenols without self-polymerizing, by the electrophilic substitution reaction of a cation, which forms on the carbon of the vinyl group, to the high-electron-density site of the nuclear phenol. Compounds formed due to this mechanism were detected by 13 C-NMR and GC/MS. Also, the molecular weight distribution was controlled by adjusting the molecular ratio, catalyst, and temperature of the reaction. An epoxy resin cured by this resin has low water absorption, and BPA1DVB resins were also enhanced in heat resistance. It also has features of low heat expansion, therefore, it is expected to withstand thermal strains and exhibit good oxidization resistance which is attributed to the low heat weight decrease caused by the low oxygen content. With these features, a wide range of applications in new elds is expected. 1 1) DVB 2;3) Fig.1 DVB DVB 1 DVB DVB/P 0.7 4) 2 DVB DVB/P DVB DVB/P 0.7 Fig.1 The model reaction scheme of phenol1dvb resin. DVB DVB 130 C 130 C DVB C C DIC Technical Review No.5/

2 2.2 DVB DVB 2.3 DSC 13 C-NMR GC/MS DVB DVB BPA DVB 850 ( ) BPA 190 KH-130 KH-150 ( ) BPA 2E4MZ % 150 C C DVB Table 1 (DVB/P) Table 1 Reaction Conditions of Synthesis of Phenol1DVB Resin Exp.No Molar ratio Purity Solvent Catalyst Reaction Treatment (DVB/P) of DVB(%) P 0 01 P 0 02 P 0 03 P :7 65 PTSA A 2 SO 4 AlCl 3 Oxa: acid 130 C 2 3Hrs: 130 C 2 3Hrs: 190 C; Vac: dist: 99K not reacted P 0 05 P 0 06 P 0 07 P 0 08 P 0 09 P 0 01 P 0 07 P 0 10 P 0 11 P 0 12 P 0 07 P :5 0:6 0:7 0:8 81 PTSA 130 C 2 3Hrs: 190 C; Vac: dist 0:7 55 PTSA 130 C 2 3Hrs: 190 C; Vac: dist :7 81 PTSA 0:2wt%=P 130 C 2 3Hrs: 190 C; Vac: dist 0:5wt%=P 2wt%=P Table 2 Reaction Conditions of Synthesis of Phenol Derivative1DVB Resin Exp.No Molar ratio Purity Solvent Catalyst Reaction Treatment (DVB/Pd) of DVB(%) B-01 0:5 81 MIBK 3 PTSA 130 C 2 3Hrs: 90 C; Vac: dist: (BPA base) C-01 0:6 (Cresol case) N-01 0:5 MIBK 3 (-Naph base) D-01 0:5 MIBK 3 (2; 7-DON base) *MIBK/Phenolics=50wt% 32 DIC Technical Review No.5/1999

3 DVB DVB DVB ES ES ES DVB Table 2 DVB Fig.2 Table BPA - 2,7-2,6- DVB Fig.2 Chemical structure of the series of phenol1dvb resin. 3.2 DVB DVB DSC (Fig.3) 160 C Table 3 Fundamental Property of Phenols1DVB Resin Exp.No Appearance SP( C) 31 Vis 32 Mn 33 Mw 33 ES-P 34 o-/p- 35 P-01 P-02 P-03 Yellow solid G G F :5 5:7 5:3 1:18 1:28 1:41 P-05 P-06 P-07 P-08 P-09 P-01 P-07 P-10 P-11 P-12 P-07 P-13 B-01 C-01 N-01 D-01 KH-130 KH-150 Yellow solid Yellow solid Yellow solid Yellow solid Brown solid Yellow solid *1 Ball & Ring method A B-C D S-T K G D B F E D D C-D B-C C E *3 Molecular weight measured by GPC *4 Contents of Ethylstyrene-Phenol addact(wt%) *5 measured by NMR :5 3:5 2:9 2:4 5:8 5:5 2:9 1:5 3:3 3:0 2:9 2:5 16:8 (-Naph) 14:5 (2; 7-DON) 44 (BPA) 39 (BPA) *2 Gardner Vis.(50%n-BuOH soln.) DIC Technical Review No.5/

4 Fig.4 13 C-NMR GC/MS (Fig.5) DVB Table 4 Fig.6 DVB DVB (o-) (p-) DVB DVB o- p- o- p NMR Fig.3 Comparison of DSC chart. Fig.4 Assignment of 13 C-NMR spectrum of phenol1dvb resin. 34 DIC Technical Review No.5/1999

5 Fig.5 MASS spectrum of phenol1dvb resin. Table 4 Assignment of GC/MS MW Phenol DVB Eth.Sty o- p- 5) Fig.7 - DVB 1 3 DVB (Fig.8 Fig.9) Fig.6 Reaction mechanism of phenol1dvb resin. 2,7- DVB DVB Table DVB DVB BPA DVB DVB DIC Technical Review No.5/

6 57 DVB DVB Fig.8 Chemical structure of -naphtol1dvb resin. Fig.7 Chemical model structure of phenol1dvb resin and phenol aralkyl resin. Fig.9 Chemical structure of 2,7-dihydroxy naphtharene1 DVB resin Table 5 Evaluation on Performance of Hardened Epoxy Resins Using Phenols1DVB Resins as Hardner for Epoxy Resin Phenolics BPA Novolac Phe1DVB BPA1DVB Cre1DVB No. KH130 KH150 P-06 P-07 P-08 P-10 B-01 C-01 EPOXY RESIN Epi-850 Epi-850 Epi-850 Epi-850 Flexural Str. RT (MPa) 100 C HDT C Water Absorp. 1Day % 7Day (BOIL) 1Hr Hr Hr Insulation Resist Anb A Boil,2hr Tg(TMA) 1st scn ( C) 2nd scn Tg(DMA) ( C) E'(Pa) 50 C 1.8E9 3.2E6 2.4E9 2.1E9 2.3E9 1.9E9 2.0E9 2.2E9 Tg+40 C 1.8E9 6.6E6 4.0E6 3.5E6 2.7E6 4.6E6 5.7E6 3.2E6 Tan Max Therm.Expansion L (E-5/ C) M H Weight Loss 400 C by TGA % 500 C DTA Max Temp. ( C) DIC Technical Review No.5/1999

7 BPA DVB 3.4 DVB Fig.10 Fig.10 BPA DVB 2 DVB o- 4 1 DVB 2 3DVB ES ES DVB 4 DVB DVB o- p- 5DVB 13 C-NMR GC/MS DVB ES 6 DVB DSC 160 C DVB 7 2;3) DVB DVB 6;7) Fig.10 Bending strength in phenol1dvb resin and BPA epoxy. DIC Technical Review No.5/

8 Vol.19 No.1(1998) 1) Y. A. Knop, L. A. Pilato: \Chemistry and Application of Phenolic Resins", P. 244(1980) 2), US Patent (1993) 3), Europian Patent (1997) 4), \", ( ), P. 50(1986), 5),,,,30, (9), P ),, 42,41(1992) 7),, 92,2E07, P (1992) Mori Kunio Inoue Tadashi Ikeda Takashi 38 DIC Technical Review No.5/1999