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衍生自n,n’-雙(羥烷基)-均苯四甲酸二酰亞胺的共聚酯酰亞胺以及由其制成的膜的制作方法_4

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16] 對于PET共聚酯的分析結(jié)果如下。
[0117]
[0118]實施例 2 :PET 共 PDI-5
[0119] 4 NMR(400MHz,CDC13:TFA(2:1)) δ (ppm)8.40(s,Hf),8. 17(s,Ha),8. 10(s,Hc), 4. 84(s,Hb),4. 70(s,Hd),4. 29(s,He),13C 匪R(100MHz,CDC13:TFA(2:1)) 167. 85 ((^), 166. 98 (C10),137. 09 (Cn),133. 31 (C2),133. 11 (C6),130. 05 (C3),119. 33 (C12),63. 92 (C4), 63. 50(C8),37. 67(Cg),Tg= 88〇C,Tcc= 170°C,T n= 243〇C,T c= 156〇C, n inh= 0. 58dL g
[0120] 實施例 3 :PET 共 PDI-10
[0121]NMR (400MHz,CDC13: TFA (2 : 1) ) δ (ppm) 8. 40 (s,2Hf),8. 17 (s, 2Ha),8. 09 (m,2HC),4. 84 (s,4Hb),4. 70 (s,4Hd),4. 29 (s,4He),13C NMR(100MHz, CDC13:TFA(2: 1)) 167. 84((^),166. 91 (C10),137. 09 (C"),133. 32 (C2),133. 12(C6), 130. 05 (C3),119. 33 (C12),63. 92 (C4),63. 49 (Cs),37. 66 (C9),Tg= 96 °C,T cc= 158 °C,T n = 232〇C,Tc= 159〇C,n inh=0. 69dLg
[0122] 實施例 4 :PET 共 PDI-15
[0123]NMR (400MHz,CDC13: TFA (2 : 1) ) δ (ppm) 8. 40 (s,2Hf),8. 17 (s, 2Ha),8. 08 (m,2HC),4. 83 (s,4Hb),4. 70 (s,4Hd),4. 29 (s,4He),13C NMR(100MHz, CDC13:TFA(2: 1)) 167. 80((^),166. 93 (C10),137. 08 (C"),133. 31 (C2),133. 10(C6), 130. 04(C3),119. 33(C12),63. 92 (C4),63. 51 (C8),37. 65 (C9),Tg= 106°C, Tcc= 171 °C, T n= 247〇C,Tc= 176〇C, n inh= 1. 02dL g
[0124]實施例 5 :PET 共 PDI_2〇
[0125]NMR (400MHz,CDC13: TFA (2 : 1) ) δ (ppm) 8. 39 (s,2Hf),8. 17 (s, 2Ha),8. 08 (d,2HC),4. 83 (s,4Hb),4. 70 (s,4Hd),4. 29 (s,4He),13C NMR(100MHz, CDC13:TFA(2: 1)) 167. 85 ((^),166. 93 (C10),137. 08 (C"),133. 30 (C2),133. 09 (C6), 130.04(C3),119.34(C12),63.92(C4),63.51(Cs),37.64(C9),Tg= 102Γ,n inh=〇.45dL g丄。
[0126] 實施例 6 :PET 共 PDI-25
[0127] NMR (400MHz,CDC13: TFA (2 : 1) ) δ (ppm) 8· 39 (s,2Hf),8· 17 (s, 2Ha),8. 08 (d,2HC),4. 84 (s,4Hb),4. 70 (s,4Hd),4. 29 (s,4He),13C NMR(100MHz, CDC13:TFA(2: 1)) 167. 69 (0^ , 166. 87 (C10) , 137. 10 (Cn) , 133. 35 (C2) , 133. 14 (C6), 130.04(C3),119.28(C12),63.89(C 4),63.47(Cs),37.67(C9),Tg=97°C,n inh=0.30dL g \ IR(vnax cm "2956,1717,1457,1405,1388,1340,1263,1251,1119,1102。
[0128] 用共聚單體(I)替代不同量的BHEN,正如下表3中所示,提供PEN與不同摩爾分?jǐn)?shù) 的共聚單體(I)的共聚酯。
[0129]表 3
[0130]
[0131] PET共聚酯的分析結(jié)果如下。
[0132]
[0133] 實施例 7 :PEN 共 PDI-5
[0134] 4 NMR (500MHz,CDC13:TFA (2:1)) δ (ppm) 8.70 (s,Ha),8.62 (s,He),8.40 (s,H), 8. 14(d,J = 8. 5Hz,Hb),8. 06(d,J = 8. 5Hz,Hc),8. 02(m,Hg),7. 94(s,Hf),4. 92(s,Hd), 4.74(s,Hh),4.32 (s,私),13C 匪R (125MHz,CDC13: TFA (2:1) ) 168. 87 ((^),166.98((^), 137. 14 (C17),135. 01 (C4),134. 87 (Cn),131. 59 (C3),130. 25 (C5),128. 46 (C2),128. 17 (C9), 125. 84 (C6),125. 70 (C13),119. 36 (C1S),64. 00 (C7),63. 47 (Cs),37. 78 (C9),Tg= 130 °C,T n = 256〇C, ninh= 〇. 49dL g
[0135] 實施例 8 :PEN 共 PDI-10
[0136] 4 MMR(400MHz,CDC13:TFA(2:1)) δ (ppm)8. 71 (s,2Ha),8. 60(m,2He),8. 40(s, 2Η),8·13((1,J = 8.4Hz,2Hb),8.05(d,J = 8.8Hz,2Hc),8.02(s,2Hf,2Hg),4.91(s,4H d), 4. 74(s,4Hh),4. 320,4?),13C 匪R(100MHz,CDC13:TFA(2:1)) 168. 89((^),166. 98(C16), 137. 10 (C17),134. 98 (C4),131. 58 (C3),130. 23 (C5+12),128. 40 (C2),128. 14 (C9),125. 79 (C6), 125. 68(C13), 119. 36(C18) ,64. 00(C7) ,63. 45(C8) ,37. 74(C9) ,Tg= 136〇C, n inh= 0. 52dL g
[0137] 實施例 9 :PEN 共 PDI-15
[0138] 4 MMR(400MHz,CDC13:TFA(2:1)) δ (ppm)8. 71 (m,2Ha),8. 60(m,2He),8. 40(s, 2?),8. 14(d,J = 8. 4Hz,2Hb),8. 03(m,2Hc,2Hf,2Hg),4. 91 (s,4Hd),4. 74(s,4Hh),4. 32(s, 4?),13C NMR (100MHz,CDC13: TFA (2:1)) 168. 91 (Q),166. 99 (C16),137. 10 (C17),134. 98 (C4),131. 58(C3),130. 22(C5),128. 39(C2),128. 10(C9),125. 78(C6),125. 64(C13),119. 37(C1S), 63. 98(C7) ,63. 45(C8) ,37. 76(C9),Tg= 144°C, n inh= 0. 47dL g
[0139] 實施例 10 :PEN 共 PDI-20
[0140] 4 MMR(400MHz,CDC13:TFA(2:1)) δ (ppm)8. 71 (m,2Ha),8. 60(m,2He),8. 40(s, 2?),8. 14(d,J = 8. 8Hz,2Hb),8. 03(m,2Hc,2Hf,2Hg),4. 91 (s,4Hd),4. 74(s,4Hh),4. 32(s, 4?),13C NMR (100MHz,CDC13: TFA (2:1)) 168. 90 (Q),166. 98 (C16),137. 11 (C17),134. 98 (C4), 131. 58(C3),130. 23(C5),128. 40(C2),128. 12(C9),125. 79(C6),125. 65(C13),119. 45(C1S), 63.99(C7),63.45(Cs),37.82(C 9),Tg= 148°C,ninh=〇.46dLg丄。
[0141] 實施例 11 :PEN 共 PDI-25
[0142] 4 MMR(500MHz,CDC13:TFA(2:1)) δ (ppm)8. 73(m,2Ha),8. 62(m,2He),8. 42(s, 2?),8. 16(d,J = 10. 45Hz,2Hb),8. 06(m,2Hc,2Hf,2Hg),4. 95(s,4Hd),4. 76(s,4Hh),4. 34(s, 4?),13C NMR (500MHz,CDC13: TFA (2:1)) 168. 81 (Q),166. 98 (C16),137. 11 (C17),134. 98 (C4), 134. 94 (Cn),131. 59 (C3),131. 55 (C10),130. 24 (C5+12),128. 43 (C2),128. 14 (C9),125. 83 (C6), 125.68(C13),119.35(Cls),64.00(C 7),63.48(Cs),37.76(C9),Tg=151°C,n inh=0.45dL g \ IR(vnax cm "2956,1717,1387,1339,1278,1257,1182,1132,1091。
[0143] 實施例的實驗數(shù)據(jù)總結(jié)于下表4中。對照樣品是純的PET或PEN,根據(jù)對于實施例 2-11描述的方法與步驟進(jìn)行合成,但不包含共聚單體。表4中的熔化焓和結(jié)晶度數(shù)據(jù)使用 標(biāo)準(zhǔn)(未退火)DSC方法獲得。
[0144]表 4
[0145]
[0146] 實施例 12,13 和 14
[0147] 用以上描述的合成方法以較大的規(guī)模(使用5加侖反應(yīng)器)生產(chǎn)三種分別包含 5mol%,10. 3mol%和16. 4mol%的單體(I)的PEN共聚物(在本文中稱為PEN共PDI-5,PEN 共roi-10和PEN共ro
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