超声波辐照作用下部分水解聚丙烯酰胺与甲基丙烯酸酯共…

研究了部分水解聚丙烯酰胺（ＨＰＡＭ）和一系列甲基丙烯酸酯在超声波辐照作用下的共聚反应。研究结果表明，共聚反应前期，单体的转化率随单体水溶性增大而增大，共聚反应动力学决定于单体的水溶性。通过红外光谱、核磁共振及质谱研究了共聚物的结构，证实共聚物为嵌段体。     

Fe—Al—α，α’—联吡啶催化体系催化马来酸酐与环氧环已烷开环共聚

用Fe(acac)3-Al(i-Bu)3-α，α’－联吡啶（acac=乙酰丙酮）催化马来酸酐（MA）与环氧环已烷（CHO）开环交替共聚，研究了Fe/Al、Fe/α，α’－联吡啶摩尔比对聚合的影响，用核磁共振技术研究了共聚物的交替度，测得共聚物中马来酸酐含量达33％以上。共聚物分子量用凝胶渗透色谱仪测量，分析表明共聚物分子量分散度很窄。共聚反应动力学研究表明，共聚反应速度与单体浓度呈一级关系，表观活化能为25．4kJ/mol。     

丙烯酸共聚物中凝胶含量的控制

本文研究了丙烯酸酯单体同丙烯酸酯缩小甘汪，共聚反应得共聚物中凝胶含量的变化，反应体系中加入调节剂叔十二硫酸，异丙基二硫化黄原酸酯能降低凝胶含量，共聚物在干燥及塑炼过程对凝胶也有一定影响。     

淀粉/DMDAAC-AM接枝共聚物的合成及表征

以淀粉（St）、二甲基二烯丙基氯化铵（DMDAAC）、丙烯酰胺（AM）为原料，采用Fe^2 -H2O2氧化还原引发体系，合成了接枝共聚物。研究了单体浓度和单体配比等因素对接枝体系的接枝率、单体转化率、阳离子度等因素的影响，得到了Fe^2 -H2O2-抗坏血酸引发淀粉接枝共聚反应的基本规律。采用红外光谱和核磁共振谱对接枝共聚物进行了结构分析。     

丙烯酰胺与烯丙基磺酸钠的共聚合

以ＡＰＳ为引发剂，研究了丙烯酰胺与烯丙基磺酸钠的水溶液共聚合反应，考察了单体配比、反应温度、ＡＰＳ浓度等对共聚反应的影响。用ＩＲ、＾１Ｈ－ＮＭＲ和［ｙ］对共聚物进行了表征，并用＾１Ｈ－ＮＭＲ谱测定了共聚物的组成，计算出了３０℃时共聚单体的竞聚率。     

甲基丙烯酸甲酯与丙烯酸丁酯规整接枝共聚物的合成及性能研究

采用聚丙烯酸丁酯大分子单体和甲基丙烯酸甲酯小分子单体共聚 ,合成了以甲基丙酸甲酯为主链、丙烯酸丁酯为支链的规整接枝共聚物。用红外光谱表征结构 ,研究了大单体的投料量、引发剂的用量及共聚反应温度对接枝效率的影响。并且研究了接枝共聚物的力学性能影响因素 ,当聚丙烯酸丁酯大单体的分子量大于 50 0 0 ,投料重量百分比在 6 0 %左右 ,得到性能良好的热塑性弹性体     

对二氧环己酮与丙交酯共聚反应的~1H-NMR分析

由对二氧环己酮（PDO）和丙交酯（LA）单体,在不同温度下合成了PDO-co-LA共聚物,采用核磁共振（1H-NMR）研究了共聚反应动力学和共聚物分子链结构,提出了一种链段平均序列长度的计算方法。结果显示,丙交酯在共聚反应中的聚合能力要比对二氧环己酮强;实验条件下LA/PDO投料物质的量比为2/3时,共聚物中PDO与L...     

丙烯酰胺与顺酐的共聚合反应及其产物的特性研究

考察了丙烯酰胺与顺丁烯二酸酐的共聚反应的条件,测定了单体的竞聚率。用ＩＲ、ＳＥＭ对共聚物的结构进行了表征,研究了其结构与性能的关系,得到了单体转化率高,性能好的吸水性材料。     

过硫酸钾—半胱氨酸引发丙烯腈与丝素接枝共聚反应的研究

研究了过硫酸钾－半胱氢酸氧化还原体系引发丙烯腈在丝素上的接枝共聚反应。考察了单体浓度，引发剂浓度，聚合温度对接枝共聚反应的影响。红外，电镜确证了研究所得材料为丙烯腈在丝素上的接枝共聚物。根据阿累尼乌斯公司计算出该引发体系的引发活化能和总活化能并对接枝后丝素的结晶性能和动态力学性能进行了研究。     

制备淀粉接枝共聚物的新方法

合成了丙烯酰氧基淀粉和以甲基丙烯酸羟乙酯为功能端基的聚乳酸大单体。研究了以丙烯酰氧基淀粉为母体的接枝共聚反应。制备了具有高接枝效率及单体转化率的淀粉－醋酸乙烯酯接枝共聚物。尤其是制备得到了以可生物降解的疏水性聚乳酸为接枝链的淀粉改性共聚物。     

高性能高硅烷含量硅丙复合乳液的研究

利用醇解反应，将γ-甲基丙烯酰氧基丙基三甲氧基硅烷中水解速度较快的甲氧基置换成水解速度较慢的乙氧基或异丙氧基，通过乳液共聚合成了高硅烷含量的硅丙复合乳液。用NMR，GC对硅烷单体进行了结构分析及转化率测试，并利用红外光谱对共降物进行了表征。研究了高有机硅含量对共聚物膜力学性能及吸水率的影响，证实了高含量硅烷组分能显著地提高丙烯酸酯乳液的物理性能。     

The biodegradation of poly (ester-ether-ester) block copolymers in a cellular environmentin vitro

In this paper we report about the biodegradation of tri-block poly (ester-ether-ester) copolymers obtained by reaction of preformed poly (ethylene glycol) (PEG) with two different lactone monomers, i.e. -caprolactone (CL) and L-lactide (LA). The two series of copolymers will be indicated as PCL-POE-PCL and PLA-POE-PLA. We identified and measured by HPLC analysis the amount of degradation products of the poly (ester-ether-ester) copolymers; three copolymers were tested for each series during 3–8 week experiments. The experiments were carried out both in the presence and absence of fibroblast cell populations. We evaluated at the same time the decrease of copolymer molecular mass after degradation by means of intrinsic viscosity [] measurements. From the [] measurements we can conclude that the higher the hydrophilicity of the material, the faster the rate of decrease of its intrinsic viscosity with time. The HPLC results indicate that the amount of the degradation products, i.e., respectively, the monomers 6-hydroxyhexanoic acid and L-lactic acid, is a function of both hydrophilicity of the molecule and the lateral block length. When the fibroblast cell populations were present in the same wells together with the biodegradable copolymers, signs of cellular metabolism of the degraded monomers were detected.     

甲基丙烯酸甲酯-苯乙烯共聚物的合成及对铸模性能的影响

采用悬浮聚合法合成了两种不同分子量的甲基丙烯酸甲酯(MMA)-苯乙烯(ST)共聚物．通过凝胶渗逢色谱和元素分析确定产品为无规共聚物,对可发处理后的共聚物的铸模性能进行测定,并研究了单体残留量对共聚物分子量和结构以及分子量对铸模性能的影响,结果表明,(1)随单体残留量增加,PSMMA共聚物的分子量减小,(2)同一种PSMMA共聚物珠粒,单体残留量不同,其结构也不同,(3)PSMMA共聚物的分子量愈大,发泡剂含量愈高,发泡倍率愈大,成型密度愈小,相应的发气量和灼烧后的残留量愈小．     

疏水性增透聚酯薄膜的制备及应用

以聚苯乙烯为大分子引发剂,丙烯酸聚硅氧烷酯为单体,通过原子转移自由基聚合制备苯乙烯-丙烯酸聚二甲基硅氧烷酯共聚物。将所得聚合物旋涂于聚对苯二甲酸乙二醇酯(PET)薄膜表面,研究共聚物中不同硅氧烷含量对聚酯薄膜性能的影响。通过核磁共振和红外光谱表征了丙烯酸聚硅氧烷酯单体及与苯乙烯共聚产物的结构,结果表明实验成功制备出了苯乙烯共聚物;凝胶渗透色谱结果表明聚合物的相对分子质量与设计相对分子质量相接近,并且相对分子质量分布系数均小于1.4,说明反应具有一定可控性;紫外-可见光分光光度计结果表明聚合物的折射率随着嵌段聚合物中硅氧烷含量的降低而增加;通过场发射扫描电镜(FE-SEM)对改性前后的聚酯薄膜进行观察,结果显示聚酯薄膜表面形成了蜂窝状多孔结构,从而有效改善了薄膜的透光性。总体研究结果表明,随着共聚物中硅氧烷含量的增加,聚酯薄膜的水接触角和透光率均呈先增后减的趋势。当共聚物中硅氧烷含量为19.6%时,PS-PDMS嵌段共聚物折射率为1.38,涂覆在PET表面后薄膜透光率达到92.6%,水接触角为120°。     

Poly(diphenylamine-<Emphasis Type="Italic">co</Emphasis>-aniline) copolymers for supercapacitor electrodes

Polyaniline, polydiphenylamine, and two copolymers with precursor monomers molar ratios of 1:1 and 3:1 (anilinium dodecyl sulfate (P1):diphenylamine) were synthesized via oxidative polymerization in a water/ethanol interfacial system. The morphology characterization and physicochemical properties showed that the copolymers share polyaniline or polydiphenylamine characteristics, depending on the monomer molar ratio. The electroactivity characterization indicated that the polydiphenylamine (PDPA) repeating units provided the copolymers with better cycling stability, whereas PAni repeating units reduced resistance and improved storage capacity, generating a synergistic interaction. Particularly, the copolymer with the highest content of P1, showed a specific capacitance of 341.93 F g^?1, with a 74.5% capacitance retention after 500 cycles, which suggests a feasible application in electrodes for supercapacitor design.     

线型与星型聚酰胺6-聚氨酯嵌段共聚物的性能比较

以聚醚多元醇(PPG)、二苯甲烷二异氰酸酯(MDI)以及己内酰胺为单体,在碱性催化剂条件下,通过单体浇铸(MC)工艺制备了线型和星型聚酰胺6/聚氨酯(PA 6-PU)嵌段共聚物。使用差热分析(DSC),扫描电镜分析(SEM)研究了两者的结晶和熔融行为以及微观结构,并进行了比较。研究发现,与线型PA 6-PU嵌段共聚物相比,随着PU组分含量的增加,星型PA 6-PU嵌段共聚物具有较高的熔融温度(Tm)和结晶温度(Tc),并且,两共聚物中的PU与PA的相容性好。比较两者的力学性能,结果显示,同等PU添加量时,星型PA 6-PU嵌段共聚物冲击性能的提高更为明显。     

Fluorescent molecular thermometers based on polymers showing temperature-induced phase transitions and labeled with polarity-responsive benzofurazans

Poly(N-isopropylacrylamide) in aqueous solution undergoes a phase transition at approximately 32 degrees C. The fluorescence properties of benzofurazans are affected by solvent polarity. We combine these two characteristics for the first time to develop sensitive fluorescent molecular thermometers. Five fluorescent monomers having a benzofurazan skeleton were synthesized, and the copolymers of N-isopropylacrylamide (NIPAM) and a small quantity of the fluorescent monomer were obtained to investigate their fluorescence properties. With increase in temperature, the copolymers in water showed the temperature-induced phase transition at approximately 32 degrees C and the fluorescence intensities of the copolymers concurrently increased. Especially, for the copolymer of 4-N-(2-acryloyloxyethyl)-N-methylamino-7-N,N-dimethylaminosulfonyl-2,1,3-benzoxadiazole and NIPAM, the fluorescence intensity at 37 degrees C was 13.3-fold that seen at 29 degrees C. The sensitive range of temperature of these fluorescent molecular thermometers is changed by the replacement of the NIPAM units by N-isopropylmethacrylamide or N-n-propylacrylamide units in the copolymers. The basis of these fluorescent molecular thermometers is the decrease in the microenvironmental polarities near the main chains of the copolymers with increasing temperature, as confirmed from the maximum emission wavelengths of the benzofurazan units in the copolymers. The responses from the copolymers to the change in temperature are reversible and exactly repeatable during at least 10 cycles of heating and cooling.     

聚丙烯酸盐与聚乙烯醇共混膜醇水混合物分离性能研究

将自制的丙烯酸、甲基丙烯酸Ｎ,Ｎ－二甲基氨基乙酯共聚物与聚乙烯醇（ＰＶＡ）共混蛊渗透汽化膜,研究了膜对混合液的吸收溶解性能和分离性能,发现共混膜优先透水,与ＰＶＡ膜相比,选择性有所下降而透过速率得到很大提高,尤其是分离９５％的乙醇水溶液仍有较大的渗透通量。选择合适的共聚单体比例及聚盐含量能得到性能较好的共混膜。当共聚单体比例为２、聚盐含量为１６．３％时,共混分离９５％乙醇水溶液分离系数约为９００,     

带有环氧基的反应型聚丙烯酸酯乳液的合成及表征

以甲基丙烯酸甲酯、丙烯酸-2-乙基己酯和甲基丙烯酸缩水甘油酯等为单体,制备了以PMMA-BA为"核"、PEHA-GMA为"壳"的微相复合乳液.利用透射电镜和激光动态光散射对乳胶粒子的形态和粒径分布进行了表征.研究了乳液聚合物和乳液与水溶性脲醛树脂共混物经不同温度热处理后的物理性能.结果表明,合成乳液的乳胶粒子具有预期的核-壳结构,粒度分布窄,平均粒径为132 nm;乳液聚合物和乳液与脲醛树脂共混物均随着热处理温度的升高,玻璃化转变温度升高,拉伸强度增大,断裂伸长率变小,吸水率降低.     

The incorporation of polar monomers in copolymers based on styrene and divinylbenzene obtained from glycerol suspension polymerization

Porous copolymer networks based on styrene (STY) and divinylbenzene (DVB) containing polar monomer (methacrylamide — MAM, methacrylic acid — MAA or acrylonitrile — ACN) were prepared by suspension polymerization using glycerol as a dispersant medium. Poly(styrene-co-methacrylamide-co-divinylbenzene), poly(styrene-co-methacrylic acid-co-divinylbenzene) and poly(styrene-co-acrylonitrile-co-divinylbenzene) were synthesized using mixtures of toluene with 2-butanone, toluene and 2-butanone and n-heptane with ethylacetate, respectively at different dilutions: 50%, 100% and 120% (v/v). The copolymers were characterized by bulk density, infrared spectrometry (FTIR) and elemental analysis (CHN). Morphological features of the copolymer pearls were evaluated by microscopic analysis and correlations between porous structure and parameters of reaction were found. The copolymers presented high incorporation of polar monomers. The pearl porosities and visual appearances had a strict relation with the monomer type and the dilution degree employed in synthesizing them.