高分子化学2010年度试卷 合肥工业大学(A卷)

以下问题请用中文作答。

1. Explain the following concepts (名词解释)（2×5 points）
(1)degradation of polymers (聚合物降解); (2) reactive ratio in copolymerization （共聚中的竞聚率）; (3)autoacceleration （自动加速）in radical polymerization; (4) functional polymer (功能高分子); (5) gel point (凝胶点) of crosslinking polycondensation.
2. Write the reaction formulation (方程式) of following polymers. If an initiator（引发剂）is needed, please clearly indicate it. （3×5 points）
(1) poly(vinyl acetate) (聚醋酸乙烯酯) by emulsion (乳液) polymerization;
(2) poly(methyl acrylate) (聚丙烯酸甲酯) prepared in tetrahydrofuran（四氢呋喃）solution; (3) polyurethane (聚氨酯); (4) polyethylene oxide （聚环氧乙烷）; (5) butyl rubber (丁基橡胶).
3. How would you experimentally determine whether the polymerization of an unknown monomer X was proceeding （进行）by a step or a chain mechanism? （5 points）
4. The reactivity (反应活性) of styrene (苯乙烯) is considerably higher than that of vinyl acetate, but a little amount (少量) of styrene can terminate the homopolymerization (均聚) of vinyl acetate. Please explain this phenomenon. （5 points）
5. Indicate the difference between chain polymerization and linear polycondesation according to monomer conversion （单体转化率）and degree of polymerization changing with reaction time. （5 points）
6. What is the difference in monomer structure between anionic （阴离子）polymerization and cationic （阳离子）polymerization. Please give an example. （5 points）
7. Please describe some methods which can control the degree of polymerization of linear polycondensation. If water is required to remove from the synthesis of polyester (聚酯), what processes (操作) can be applied?（9 points）
8. What is the composition (组成) of basic type of Ziegler-Natta catalyst?
How to improve (提高) the reactivity (反应活性) and stereoregularity （立构规整度） controlling of basic type of Ziegler-Natta catalyst. （6 points）9. Consider the polymerization of styrene initiated by di-t-butyl peroxide（二
特丁基过氧化氢）at 60 0C. For a solution of 0.01 mol/L peroxide and 1.0 mol/L styrene in benzene, the initial rates of initiation and polymerization are
4.0×10-11 and 1.5×10-7 mol L-1s-1, respectively. Calculate the values of (fk d), the initial kinetic chain length, and the initial degree of polymerization. （10 points）
C M = 8.0×10-5, C I= 3.2×10-4, C s = 2.3×10-6
10.Ferrocenylmethyl acrylate (FMA) has been synthesized and copolymerized with styrene, methyl acrylate, and vinyl acetate. The following monomer reactivity ratios were found: （10 points）
M1M2r1r2
FMA styrene0.02 2.3
FMA methyl acrylate0.14 4.4
FMA vinyl acetate0.840.26
(1) Construct plots showing the initial copolymer composition as a function of the comonomer feed composition for the radical copolymerizations of FMA-methyl acrylate and FMA-vinyl acetate.
(2) Is styrene monomer a more or less reactive monomer than FMA monomer toward the FMA propagating center? By what factor?
(3) List styrene, methyl acrylate, and vinyl acetate in order of increasing reactivity toward the FMA propagating center. Please give the reason.
11. A heat-resistant polymer Nomex has a number-average molecular weight of 24116. Hydrolysis of the polymer yields 39.31% by weight m-aminoaniline (间苯二胺), 59.81%
terephthalic acid（对苯二甲酸）, and 0.88% benzoic acid（苯甲酸）. Write the formula for this polymer.Calculate the degree of polymerization and the extent of reaction.
（10 points）
12. Please calculate the gel points of following reaction system by Carothers equation and the statistical approach, respectively. （10 points）
(1) Phthalic anhydride (邻苯二甲酸酐) and glycerol （丙三醇） in the molar ratio 1.5 : 1.0
(2) phthalic anhydride, glycerol, and ethylene glycol (乙二醇) in the molar ratio
1.5 : 0.5 : 0.7。