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第二章 离子型聚合反应 配位聚合反应及开环聚合反应. 学习目的:        学习基本概念        学习基本原理        掌握基本规律        掌握基本应用. §2-1  一般性阐述. ● 定义: 单体在阳离子或阴离子作用下,活化为带正电荷或带负电荷的活性离子, 再与单体连锁聚合形成高聚物的化学反应,统称为离子型聚合反应 ( ionic polymerization) 。 属于连锁聚合反应的一种。      阳离子聚合        离子型聚合反应阴离子聚合            配位离子型聚合 ● 特征: 〆 对单体的选择性高; - PowerPoint PPT Presentation

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  • 2-1(ionic polymerization)

  • 2-1

  • 2-2P

    CH2CCHCCH3CHCH2CH2CH2

  • 2-2

  • 2-2 BF3HOHHBF3OH

    HBF3OHCH2CCH3C BF3OH

    CH2C BF3OH CH2C CH2C CH2C BF3OH

    CH2C BF3OH CH2C CH2C CH3C BF3OH

  • 2-2 CH2C BF3OH CH2C CH2C CH3CH

    CH2C BF3OH CH2C H

    CH2C BF3OH CH2C OH H

  • 2-2

    CH2C BF3OH CH2C OH BF3

    CH2C BF3OH XB CH2C B X

    Lewis BF3>AlCl3>TiCl4>TiBr4>BCl3>BBr3>SnCl4AlCl3>AlRCl2>AlR2Cl>AlR3

  • 2-2SnCl4HCl>CH3COOH>CH3CH2NO2>C6H6OH>H2O>CH3OH>CH3COCH3

    BF3-H2O BF3+H2OHBF3OH H3OBF3OH0.185mol/LSnCl4++--

  • 2-24078TiCl4-H2OCM

    CCl4CHCl3C2H4Cl2C6H6C7H8C3H8C6H14C6H5NO2CH3NO2

  • 2-3Qe A B C DCH2CHCH2CHCH2CHCH2CCN

    Q 1.0 0.42 1.78 12.6 e 0.80.60 1.202.10

  • 2-3

    abABCcddAABCDabcd

  • 2-3n-C4H9LiCH2CH C4H9CH2CHLi

    CH2CHLi CH2CH CH2CHCH2CHLi

    CH2CHLi CH3OH CH2CH2 LiOCH3

  • 2-3KNH2NaNH2RLiRMgX-RLiRMgXCLiKNH2NaNH2KNH2 KNH2K NH2 NH2 CH2=CH H2NCH2CHK

    LiKNa-Li CH2CHCH2CHLi

  • 2-32CH2CHLi LiCHCH2CH2CHLi

    Na Na

    Na CH2CH CH2CHNa

    2CH2CHNa NaCHCH2CH2CHNa

    THF

  • 2-3

    MA MA M A

    H

  • 2-3MH AOHMH AXMH AOCH3MH RCOOAMAMCOOAMCOOH AMOOA2MOA2MOH 2A

    MCH2CH2OAMCH2CH2OH AMCNRNCOMCONHRNH2 AOH CO2

  • 2-3

    OHCOOHSH

  • 2-3

    COOHOH

  • 2-3

    CH2CCH2CHKCH2C

    SBSnS Sn SnSm SnBmSi SnBmSiABBA2AnBmLiBr(CH2)6BrAnBm+1(CH2)6Bm+1An 2LiBrCH3CH3COOCH3COCHCH2PMMAPS1,2,4,5-PSRLimBiS

  • 2-3sec-C4H9Lii-C3H7Lit-C4H9Lii-C4H9Lin-C4H9LiC2H5Lisec-C4H9Lii-C3H7Li n-C4H9LiC2H5Li i-C4H9Li t-C4H9Li

    RLiRNaRKRLiLiR

  • 2-3

  • 2-4--ZieglerGNattaPPHDPEPSBREPR

  • 2-4C2H4O---

  • 2-4

    -1,4--1,4-

  • 2-4

    CH2CCH2CCH2CCH2CCH2CCH2C

    DLRSdlrsddddddlllllldldl

  • 2-4

  • 2-4-

    CHCH2RR CH3C2H5 CHCH2 CH2CH2CH(CH3)2 OCH3 OCH2 CH(CH3)2 C6H5

  • 2-4-

    IUPAC

  • 2-41-Zieger-NattaZiegerNatta

    Zieger-Natta Zieger-Natta-TiVMoWCrClBrIMoCl5WCl5CoNiRuRh

  • 2-4Zieger-Natta

    Zieger-Natta-

  • 2-4

  • 2-4

    TiCl3AlEt3

  • 2-4

  • 2-4

  • 2-4AlR3

  • 2-4

    TiCl3

  • 2-4Zieger-NattaAl(C2H5)2H Al(C2H5)3 Al(C2H5)2Cl Al(C2H5)2Br Al(C2H5)2I Al(OC2H5)2C2H5 Al(C2H5N)C2H5 Al(i-C4H9)2H Al(i-C4H9)3 Al(i-C4H9)2Cl Al(i-C4H9)2[(CH3)2CCHCH2] Al(i-OC4H9)3R

  • 2-4

    TiCl3AlEt2ClAl/Ti1.52.5

  • 2-4Zieger-NattaNPOII%

    70O2CO2H2H2OCHCH

  • 2-41,3-Zieger-NattaTiV14V14CrMo1,23,4NiCo1,4--NiURh-

  • 2-41,41,41,2TiCl3()TiCl3()

  • 2-4Ni(OOCR)2Al(C2H5)2BF3OC2H5nCH2CHCHCH2

  • 2-5

    nR XRX

    X-

  • 2-5

  • 2-5

    YZ

  • 2-5

  • 2-5

    CH2CH2NaOHHOCH2CH2ONaHOCH2CH2ONanCH2CH2HOCH2CH2CH2CH2ONaCH2CH2ONaCH2CH2O C9H19CH2CH2O C9H19NaOH

  • 2-5BF3-H2O

    OCH2OCH2CH2OH(BF3OH)HOCH2OCH2OC(BF3OH)OCH2OCH2CH2O(BF3OH)HHH

  • 2-5

    HOCH2O CH2O C(BF3OH)HHH(BF3OH) H2OHOCH2OCH2OCH2OCH2OH3n

  • 2-5

    3,3-3,3-Al(C2H5)3-H2O

    HOCH2OCH2OOCH2OCH2OH (CH3CO)2OCH3COCH2OCH2OOCH2OCH2OCCH3H[Al(C2H5)3OH]

  • 2-5

    ClCH2 CH2ClCH2 CH2CO[Al(C2H5)3OH] HH2O

  • 2-5

    3,3-NaNaHH[Al(C2H5)3OH] NaHH2

  • 2-5

    KOH

    CH3SiOSiCH3CH3SiOSiCH3KOH

  • 2-5

    115200 n