高分子化學(xué)浙江大學(xué)polymerMeasurementofratecoefficientsPPT學(xué)習(xí)教案

1、會(huì)計(jì)學(xué)1高分子化學(xué)浙江大學(xué)高分子化學(xué)浙江大學(xué)polymerMeasurementofratecoefficients2第1頁(yè)/共48頁(yè)3L0L0+2L0L0+2L0+3L0irradiated by a pulsed laser beam (5-20ns)Monomerphotoinitiator, (solvent & transfer agents)MW of polymer produced by PLP: L0,n=nkpMt0第2頁(yè)/共48頁(yè)4第3頁(yè)/共48頁(yè)5MRkdtMdRpp1221lnttRkMMp第4頁(yè)/共48頁(yè)6A photopolymerizable mixture p

2、asses through a capillary system, is irradiated at a specific location, and polymerizes in the capillary during a well-defined dark period until it drops into a quenching bath with an inhibitor(nitroxyl radicals).Measuring the chain length distribution by size-exclusion chromatography that allows de

3、termination of kp in accordance with the equation.L=kpMt0第5頁(yè)/共48頁(yè)7The usual procedure for measuring the chain transfer constant CT involves determination of Xn for a range of T/M values and plotting the data as 1/Xn versus T/M, that is, a Mayo plot. The value of CT is then determined as the straight

4、-line slope of this plot. MTCCRMkkXTMpptn2211第6頁(yè)/共48頁(yè)8121tkRRt tpkkttRkMM2/012 0112 tkRRt22RkdtRdtMRkdtMdRpp第7頁(yè)/共48頁(yè)9Applying pulsed laser-polymerization (PLP) in conjunction with infrared or near-infrared spectroscopic measurement of monomer conversion induced by a single laser pulse (SP-PLP) allow

5、s for the determination of the ratio of termination to propagation rate coefficients, kt/kp, in wide ranges of temperature; pressure; and monomer conversion. tpkkttRkMM2/012第8頁(yè)/共48頁(yè)10Identification and quantification of chain ends are not simple as they give only small signals (relative to the rest

6、of the polymer chain) in a spectroscopic analysis. This can be overcome to some extent by isotopic labeling of the initiator end groups by 14C or by using initiator fragments containing fluorine or phosphorus as NMR-sensitive molecules.The application of the matrix-assisted laser desorption ionizati

7、on time-of-flight mass spectroscopy (MALDI-TOF-MS) to the problem of end-group analysis of polymers brought some promising results to this field of polymerization kinetics. 第9頁(yè)/共48頁(yè)11MALDI-TOF-MS第10頁(yè)/共48頁(yè)12第11頁(yè)/共48頁(yè)13第12頁(yè)/共48頁(yè)14第13頁(yè)/共48頁(yè)15nStatistical approach (統(tǒng)計(jì)方法)nKinetic approach （動(dòng)力學(xué)法）第14頁(yè)/共48頁(yè)

8、16第15頁(yè)/共48頁(yè)17dttrppRRRRp,a polymer chain with the length n is formed by n-1 propagation steps and one chain stopping (termination or transfer) event of probability (1-p).So the probability of finding a chain of length n is: ppNNnn11number of chains of size ntotal number of chainsnumber-fraction dist

9、ribution第16頁(yè)/共48頁(yè)18weight of chains of length n: Wn=mnNnweight of all chains : W=mN0Initial number of monomersMW of monomerppNnNNnNmNmnNWWnnnn11000Since one termination results in one chain, so pNN10211pnpWWnnppNNnn11第17頁(yè)/共48頁(yè)1902000400060008000100000246810number fraction (10-4)polymerization degree

10、 p 0.999 0.9995 0.9997504000800012000160000.000.010.020.030.04weight fraction (10-2)polymerization degree p 0.999 0.9995 0.99975第18頁(yè)/共48頁(yè)20pNNXn110dttrppRRRRp,1111,kineticndttrpprobnXRRRpXaccording to definition:trdtptrdtptrdtipkineticnRRRRRRRRRRX,)22(212211RMIik第19頁(yè)/共48頁(yè)21ppnpNNnXnnn11)1 (1accordin

11、g to calculation:ppppnWWnXnnw11)1 (21221pXXnwpolydispersity index(多分散性指數(shù)), PDI第20頁(yè)/共48頁(yè)222222)1 ()1 () 1(pnpppnNNnnn There are (n-1) different ways to form a chain of length n from the combination of two chains, so 22211)1 (1pppppnmnm第21頁(yè)/共48頁(yè)23322)1 (21ppnWWnnpNNnXnn12ppWWnXnw125 . 121pXXnw22)1 (pn

12、pNNnn第22頁(yè)/共48頁(yè)2404000800012000160000.000.010.020.030.04number fraction (10-2)Polymerization degree p 0.999 0.9995 0.9997504000800012000160000.000.010.020.03weight fraction (10-2)polymerization degree p 0.999 0.9995 0.99975Molecular weight distribution curve第23頁(yè)/共48頁(yè)25Average molecular weight Disprop

13、ortionation vs CombinationpXn12ppXw125 . 1nwXXpXn11ppXw112nwXX第24頁(yè)/共48頁(yè)2602000400060008000100000.000.010.020.030.040.050.06weight fraction (10-2)polymerization degreeXn=1000 disproportionation, p=0.999 combination, p=0.998pXn12pXn11第25頁(yè)/共48頁(yè)27第26頁(yè)/共48頁(yè)28第27頁(yè)/共48頁(yè)291nkknRMRdppSTHG第28頁(yè)/共48頁(yè)30enthalpy

14、contribution Hentropy contribution S S is always negative, reflecting the loss of degrees of freedom of the monomer becoming a part of the polymer chain. S is around -105-125 J/(mol*K) for polymerization from R.T. to 100 oC, -TS is around 3042 KJ all chain polymerizations are exothermic. most free-r

15、adical polymerizations are negative with typical values ranging from 30 to 80 kJ/mol. STHGPolymerization is mainly determined by H第29頁(yè)/共48頁(yè)31CCCC350 KJ/mol610 KJ/mol2906103502 HSteric effect: -H Resonance effect: -H Styrene(69.9)butadiene(72.8) acrylonitrile (72.4) negative substitute: -H vinyl chlo

16、ride(95.8) vinylidene fluoride(129.7)tetrafluoroethylene(154.8) H bond & solvent: -H acrylic acid(66.9) methacrylic acid(42.3) -第30頁(yè)/共48頁(yè)32第31頁(yè)/共48頁(yè)33MRTGMRRRTGKRTGGnn1lnlnln01000STHGSHTc1nkknRMRdppeccMRTSTHG1ln00ccMRSHTln0000SHTcM=1.0第32頁(yè)/共48頁(yè)34第33頁(yè)/共48頁(yè)35For example: H S M at 70 oCkJ/mol J/(molK)M

17、MA 56 1184.3610-3Styrene73 104 2.0910-6-Methylstyrene45 1487.60 001lnSTHRMeeMRTSTHG1ln00equil. monomer concentration第34頁(yè)/共48頁(yè)36第35頁(yè)/共48頁(yè)37第36頁(yè)/共48頁(yè)38第37頁(yè)/共48頁(yè)39第38頁(yè)/共48頁(yè)40In this mechanism, the dormant chain is dissociated into polymer radical P and capping radical X, where X is assumed to be stable

18、 enough to undergo no reaction other than the combination with P第39頁(yè)/共48頁(yè)41第40頁(yè)/共48頁(yè)42The dormant chain is activated by the catalytic action of activator A, and the capping agent is transferred to form a stable species AX.第41頁(yè)/共48頁(yè)43The dormant chain is attacked by radical P to form the active species P and the dormant species PX. This is an exchange reaction. 第42頁(yè)/共48頁(yè)44第43頁(yè)/共48頁(yè)45SSSRRSZSRSZSSZSmonomercomonomerSSSSSSmonomercomonomerSHaminedithioestertrithiocarbonateWhat will happen if cyclic dithioester or trithiocarbonate is used?AB block polymerABAblock copolymerA