COPU/PBMA交联共聚物网中游离末端对性能的影响

制备出一系列具有不同蓖麻油游离末端含量的样品,研究了它们的力学性能、转变与松弛行为以及形态结构。结果表明,全部样品在动态力学谱上只有一个T_g,呈现出一相行为;而用透射电子显微镜观察到的却是具有微相分离的两相体系。游离末端含量的增加使T_g移向低温,明显地增加了低温区的阻尼因子,使微相分离增大,相区大小约从3.5nm增加到20nm。次级松弛与游离末端含量无关。

酚氧树脂/蓖麻油交联聚氨酯

使2.2-(4’-羟基苯基)丙烷(双酚A)与环氧氯丙烷反应制得了带端羟基的酚氧树脂(HBA),将其与蓖麻油共混,用2.4-甲苯二异氰酸酯(TDI)作固化剂,制得了一系列交联聚氨酯。DSC和DMA测试结果表明,这种聚氨酯只有一个T_g。改变NCO/OH摩尔比及HBA/(HBA+蓖麻油)比可制得具有较好阻尼性能的聚氨酯材料。

交联对聚己二酸乙二醇酯聚氨酯/甲基丙烯酸甲酯交联聚合物的力学阻尼、相容性及形态的影响

用紫外光聚合方法制备出一系列端乙烯基聚己二酸乙二醇酯聚氨酯(PEAPU)和甲基丙烯酸甲酯(MMA)AB交联聚合物(ABCP)。用粘弹谱仪、透射电子显微镜(TEM)和平衡溶胀法研究了AB交联聚合物的动态力学性能、玻璃化转变温度、形态和交联密度、观察到相应于聚氨酯和PMMA相两个玻璃化转变温度,TEM照片中的微相分离是更明显的,ABCP中的两个T_g内移表明,两种成分的化学交联增加了相互的可混性、与ABCP具有相同组成的IPN有比ABCP大得多的相区。氢键能够影响ABCP的相容性、形态和动态力学性能。

高聚物玻璃化转变温度和分子参数的关系 Ⅱ.分子量对玻璃化转变温度的影响

根据前文提出的理论模型,本文推导出下述表征高聚物数均分子量(M_n)与玻璃化转变温度T_8关系的理论公式: T_g=T_g~∞-K_g/M_n K_g=T_g~∞·σ~2(T_g)·M_u十几种高聚物的K_g理论计算位能较好地和实验值吻合。应用理论关系式具体计算了聚苯乙烯、聚氯乙烯、聚二甲基硅氧烷和聚α-甲基苯乙烯的T_g随分子量的变化,其结果是令人满意的。

钼体系1,2-聚丁二烯橡胶的屈服行为及其转变

本工作发现钼体系1,2-聚丁二烯橡胶的屈服强度(σy)与其[η]呈线性关系,方程式为:[η]=Kσy+C(未加分子量调节剂时为[η]=0.46σy+1.39)。方程式的斜率K随温度降低由正值变为负值。该胶料的T_g和应力-应变受分子量调节剂的影响,且后者影响明显。分子量调节剂用量一般控制在0.25—0.75质量份。

顺丁橡胶/低密度聚乙烯的共混

比较了未交联和动态交联不同组成PB/LDPE共混物的力学性能。共混物的T_g、T_m和T_d不随组成而变化,表明PB和LDPE不具有相容性。但共混物中PE的γ转变向高温方向位移,说明PE非晶部分的分子短链和PB有界面相互作用。形态研究表明,未交联体系中量多的组份形成连续相,动态交联体系在PB/LDPE≤70/30时,PE呈连续相,交联的PB为分散相。

三元乙丙橡胶的γ—辐射交联

本文报道了三元乙丙橡胶(EPDM)经~(60)Co γ—辐照后的辐射交联规律。由于EPDM中含有不饱和双键,经25K Gy剂量辐照后,凝胶分数可达30％。EPDM具有优良的介电性能,无论是未辐照的还是辐照的样品介电常数ε′在2.2左右。介电损耗因子ε′在10~(-4)～10~(-3)数量级。EPDM的T_g(?)辐照剂量增加而增加。剂量位于30K Gy附近,抗张强度T_s和伸长率E达到极大值,以后随剂量增加Ts和E逐渐下降。

稀土-其它过渡金属混合催化剂用于共轭双烯烃的聚合——Ⅲ.关于两种活性中心及其聚合机理的探讨

研究了(NdCl_3+FeCl_3)r phen-HA_2(i-Bu)_2体系聚合丁二烯。通过固定催化剂中稀土(或铁)含量而改变铁(或稀土)含量的方法,证明了此聚合体系中存在两种不同的对丁二烯聚合有很高催化活性的活性中心,即能使丁二烯聚合成高顺式产物的Nd活性中心,和使丁二烯聚合成几乎是等二元(cis-1,4和1,2构型),聚合物的Fe活性中心。所得产物具确两个T_g和产物分级后可得到cis-1,4为92％和1,2含量为54％的级分,为以上结论也提供了旁证。两种活性中心的催化活性受铝比、聚合温度等的影响,稀土活性体对聚合条件比过渡金属活性体有较宽的适应范围。对其聚合机理进行了探讨,认为两种活性中心分别按各自的聚合机理进行聚合反应。

蓖麻油聚氨酯基网状聚合物的动态力学性质

研究了蓖麻油聚氨酯基AB型交联聚合物(ABCP)及同步法合成互穿聚合物网络(IPN)的动态力学谱。ABCP的两组分近似互容,在动态力学谱上呈现出单一T_g松弛,用透射电子显微镜观察,聚氨酯相区尺寸小于 2 nm;而其化学组成相同的 IPN则呈现出两相结构,其动态力学谱上有两个 T_g松弛,两组分间虽有链段互穿,但其相容性仍次于 ABCP。

乙丙共物聚的结晶速率与序列结构

本文用(体)热膨胀计法研究了共聚物组成、催化体系对乙丙共聚物结晶速率的影响。结果表明,同一催化体系乙丙共聚物的最大结晶速率(1/t_((1/2)(max)))随共聚物中乙烯含量的增加而增大。不同催化体系对二元乙丙共聚物的1/t_((1/2)(max))次序为:VOCl_3~->V_(5-9~-)>V_((aca?)3~-)。加入活化剂ETCA的各催化体系的二元乙丙共聚物的1/t_((1/2)(max))为VOCl_3~-ETCA>V_(5-9~-)ETCA>V_((ocac)~-)ETCA。结合结晶度、T_g、以及不同序列分布共聚物组成的测定,可推测VOCl_3~-体系乙丙共聚物具有较长的聚乙烯序列结构,V_(5-9~-)体系次之,V_((acac)_3~-)体系的乙丙共聚物分子链有更多的无规结构。

动、静态硫化(NR+SBR)/PE共混体系的结构与性能

用TEM研究了(NR+SBR)/PE共混体系经动、静态硫化后的形态结构及其与力学性能的关系。未硫化和静态硫化体系的形态结构与其组成有关,均以含量大的组份为连续相;对动态硫化体系,当(NR=SBR)/PE<70/30时,均以PE为连续相,其性能主要依赖于构成连续相组份的性质。 动态硫化体系的T_g值低于静态体系,随PE组份含量的增加变化不大,而静态硫化体系的T_g值则随PE含量增加向高温方向迁移。用DSC测得动态硫化体系的结晶度比静态体系的大。前者的应力-应变性能也低于后者。

环形聚苯乙烯的玻璃化温度

环形聚苯乙烯是两端带活性基团的线形聚苯乙烯径环化反应,使两端以化学键相连而合成。线形聚合物的玻璃化温度(T_g)已得到广泛深入的研究,但环形聚合物的玻璃化温度却

Decay of imprinted surface waves in polymers

CONCLUSIONS The focus of this work was the investigation ofanomalies in Tg and dynamics at polymer surfaces. Thethermally induced decay of hot-embossed polymer gratings isstudied using laser-diffraction and atomic force microscopy(AFM). Monodisperse PMMA and PS are selected in the Mwranges of 4.2 to 65.0 kg/mol and 3.47 to 65.0 kg/mol,respectively. Two different modes of measurement were used:the one mode uses temperature ramps to obtain an estimate ofthe near-surface glass temperature, Tdec,0; the other modeinvestigates the dynamics at a constant temperature aboveTg. The temperature-ramp experiments reveal Tdec,0 valuesvery close to the Tg,bulk values, as determined bydifferential scanning calorimetry (DSC). The PMMA of65.0 kg/mol shows a decreased value of Tg, while the PS samples of 3.47 and 10.3 kg/mol (MwT_g,bulk(c1=16)tend to be smaller than Tdec,0 and Tg,bulk fromtemperature-ramp and DSC measurements, but confirm thecourse of the values with increasing Mw. The comparison of the fragilities (temperaturedependence of the polymer properties at Tg) near the surfaceand in the bulk shows a higher fragility for PS near thesurface, a lower one for PMMA with molecular weights of 4.2and 65.0 kg/mol. The different surface behavior of PS istraced back to a lower degree of cooperation and a largerfree volume fraction.

Dielectric relaxation of polysiloxanes and kerr effect of p-phenylene vinylene oligomers

The dielectric relaxation behaviour of a series of cyclic and linear poly(dimethylsiloxanes) with overline nn in the range 28 to 99 has been studied, as a function of temperature (142.0K-157.5K) and frequency (12-105Hz). Activation energies for the -relaxation process, Davidson-Cole empirical distribution factors, , and mean-square dipole moments per repeat unit, < 2> , have been calculated. Differences in values of H_act reflected restricted dipolar rotation for the cyclic structures, compared to the linear structures, over the range of molecular weights studied. The dielectric relaxation behaviour of a series of linear oligomers of methyl phenyl siloxane, with n in the range 4 to 10, a series of linear fractions of poly(methyl phenyl siloxane), with overline n_n in the range 31 to 1370, and a cyclic oligomer of mehyl phenyl siloxane, with n = 10, has been studied as a function of temperature (155.5K-264.0K) and frequency (12-105Hz). Activation energies for the -relaxation process, Davidson-Cole and Cole-Cole empirical distribution factors, and , respectively, and mean-square dipole moments per repeat unit have been calculated. The reduced flexibility of short methyl phenyl siloxane chains, compared to dimethyl siloxane chains, was apparent from a comparison of dipole moment ratios. The dilectric relaxation behaviour of poly(methyl hydrogen siloxane) and poly(n-hexyl methyl siloxane) has been studied as a function of temperature and frequency. A polysiloxane liquid crystal has been synthesised and its dielectric relaxation behaviour has been studied, as a function of temperature and frequency, in the liquid crystalline phase and below T_g. Poly(p-phenylene vinylene) and related oligomers have been synthesised and characterised by a variety of experimental techniques. The Kerr effect of two oligomeric fractions, in solution in PPG 2025, has been measured. The electrical conductivities of the undoped and I_2-doped polymer and oligomers have been measured.