钼体系聚1,2-丁二烯分子量及其分布

本文用粘度法和GPC法研究了MoCl_4R-i-Bu_2AlOR′催化体系合成的聚1,2-丁二烯的分子量及其分布,发现该体系聚合物分子量分布非常窄,且与聚合温度呈直线关系;利用外推法估计,在-18℃左右该体系有可能引发活性聚合。聚合温度为30—70℃时,聚合物分子量分布宽度指数为1.5—2.0。本文还研究了调节聚合物分子量及其分布的方法,发现烯丙基卤可以大幅度调节聚合物分子量,对分子量分布也有一定的调节作用,其中烯丙基碘的效果最好。     

A COMPARISON OF POLYACETYLENES PREPARED WITH VARIOUS CATALYST SYSTEMS

A comparison of polyacetylenes (PA) prepared with rare earth(Ln) and titanium(Ti) basedcatalyst systems in regard to the isomerization rate, conductivity and doping behaviour is presented.It is found that PA synthesized with Ln-catalyst showed the lower isomerization rate than Ti-PA.Room temperature conductivity of I_2-doped Ln-PA is higher than that of Ti-PA under the sameconditions, this might related to the uniform conjugation length of Ln-PA. The difference in thedoping behaviors was observed for cis and trans PA films. and the complicated doping behavioursof cis-PA could be attributed to the simultaneously occurring isomerization reaction during doping.     

THE CHAIN STRUCTURE OF 1,2-POLYBUTADIENES PREPARED WITH MOLYBDENUM CATALYST SYSTEMS

The chain structure of 1,2-polybutadienes prepared with molybdenum catalyst systems has been studied by IR, ~(13)C-NMR and T_g method, and the method to regulate the chain structure investigated. It was found that some polar additives, e. g., allyl halides, are able to regulate not only the content of 1,2-units in the polymer, but also its configuration and sequence distribution. Attempt has been made to estimate the sequence length of stereo-isomers of 1,2-units by statistical theory.     

SYNTHESIS AND-CHARACTERIZATION OF THE SOLUBLE, HIGH MOLECULAR WEIGHT AND LADDERLIKE POLYHYDROSILSESQUIOXANE AND ITS COPOLYMERS

The high molecular ladderlike polyhydrosilsesquioxane (LPHSQ) and its copolymer, ladderlike random copolymethylhydrosilsesquioxane (LR-PMHSQ) and ladderlike block copolymethylsilsesqui-oxane(LB-PMHSQ) have been synthesized by a preaminolysis reaction of the corresponding trichlorosilane with 1 ,4-phenylene diamine(PDA) then by hydrolysis and polycondensation reactions The thermographs of these polymers measured by DSC method indicate that these macromolecular backbones are very rigid as seen from the DSC curves which are almost horizontal from room temperature until 350 ~C without noticeable glass transition. The content of Si—H group in the polymers can be regulated by changing the composition of the two copolymerized monomers. So the ladderlike polymers including its copolymers can be the useful precursors for the functional polymers, especially such as fishbone-like liquid crystalline polymers.     

球形MgCl_2负载钛催化剂催化苯乙烯等规聚合与产物分子量分布研究

采用球形高效负载ZieglerNatta催化体系(TiCl4MgCl2AlR3二苯基二甲氧基硅烷(DPDMS)合成等规聚苯乙烯(iPS),催化效率最高可达7.7×103gPSgTi·h.通过多个SchulzFlory最可几分布对产物的分子量分布曲线拟合分峰来研究iPS的分子量及分子量分布的变化,AlEt3能使产物中低分子量部分含量增加,Al(iBu)3则倾向于形成高分子量的活性中心.体系中加入氢气不仅能显著提高催化效率,而且使iPS的分子量分布显著增宽.     

球形MgCl2负载钛催化剂催化苯乙烯等规聚合与产物分子量分布研究

采用球形高效负载Ziegler-Natta催化体系(TiCl4-MgCl2/AlR3/二苯基二甲氧基硅烷(DPDMS)合成等规聚苯乙烯(iPS),催化效率最高可达7.7×103 gPS/gTi·h.通过多个Schulz-Flory最可几分布对产物的分子量分布曲线拟合分峰来研究iPs的分子量及分子量分布的变化,AlEt3能使产物中低分子量部分含量增加,Al(i-Bu)3则倾向于形成高分子量的活性中心.体系中加入氢气不仅能显著提高催化效率,而且使iPS的分子量分布显著增宽.     

GPC-多检测联用技术测定聚己内酯分子量及其分布

介绍一种用于生物可降解高分子材料聚已内酯(PCL)及其改性高分子的分子量和分子量分布测定的GPC-示差折光(RI)-示差黏度(DV)-直角光散射(RALLS)多检测联用技术.叙述了该方法的实验原理,并对测试过程中的有关技术及实验结果进行了讨论.该方法可准确测定聚己内酯(PCL)及其改性高分子的分子量及其分布、特性黏度分布、Mark-Houwink方程系数以及高分子尺寸等重要参数.通过对窄分布PS标样验证,分子量测定结果的相对误差在1%之内.     

EFFECT OF POLYMERIZATION CONDITIONS ON THE MOLECULAR WEIGHT OF POLYPHENYLSILSISQUIOXANE

Samples of polyphenylsilsisquioxane (PPSQ)using CaF_2 or MgF_2 as the main catalysts hadbeen prepared under different polymerization conditions. The results were treated on anorthogonal design L_9 (3~4). All weight-average molecular weights (M_W ) of PPSQ had beenmeasured by gel permeation chromatography (GPC). Effects of polymerization conditionsincluding reaction temperature, composition of the dual catalysts (CaF_2 or MgF_2 and DCC),mixture of solvents and reaction time on M_W of PPSQ have been discussed. The quantity of thecatalysts is the most important factor that affects M_W of PPSQ. Reaction temperature is thesecond important factor. Appropriate polymerization condition has been established to get PPSQwith high M_W.     

SYNTHESIS OF NEW HIGH MOLECULAR WEIGHT AND REACTIVE LADDERLIKE POLYSILSESQUIOXANES*

Ladderlike polychloropropylsilsesquioxane (CP-T) was first synthesized by "stepwise coupling polymerization".The molecular weight of CP-T is as high as 1.7×10~5. It is a tough, elastic reactive ladderlike polymer and has good heat-resistant and adhesive properties. CP-T can further react with many nucleophilic reagents to generate new ladderlike reactivepolysilsesquioxanes, which can be used as potential precursors in the synthesis of functional ladderlike polymers.     

METALLOCENE POLYETHYLENES WITH BROAD OR BIMODAL MOLECULAR WEIGHT DISTRIBUTION

Seven new binuclear titanocenes with different linking bridges, unsubsti-tuted or substituted on the Cp rings, were synthesized and tested for their effect on ethylenepolymerization in the presence of MAO. The polyethylenes thus obtained had broad MWDor even bimodal GPC curves, as compared with that from two reference mononuclear ti-tanocenes. This is explained by the difference in degree of steric hindrance around the activecenter sites imposed by the bulky substituted ligands assuming different configurations inthe rotation of the catalyst molecules. Lower polymerization temperatures alleviate theeffect of these configuration differences, as reflected in change in MW and M_w/M_n. Thiseffect is not caused by decomposition or disproportionation of the binuclear titanocenes asevidenced by the stability of the catalyst.     

钼催化体系制备的聚1,2-丁二烯链结构

本文利用红外光谱、~(13)C-NMR和线膨胀等方法研究了钼体系聚1,2-丁二烯的链结构,并研究了链结构的调节方法。发现烯丙基卤等极性添加剂既可以调节1,2-链节含量,又可以调节链节的立体构型。最后,利用统计理论估计了1,2-链节的各种异构体的平均序列长度。     

A STUDY OF LOW-TEMPERATURE CRYSTALLIZATION BEHAVIOR THE cis-1,4 POLYBUTADIENE PREPARED WITH RARE-EARTH CATALYST SYSTEM

The effects of molecular weight and temperature on crystallization processes at low tempera-ture for cis-1,4 polybutadiene prepared with rare-earth catalyst (Ln-PB) have been studied by WAXDmethod. In the range of molecular weight from     

聚2,6-二甲基苯醚树脂分子量分布及其与冲击强度关系的研究

本工作建立了室温下用凝胶色谱法(GPC)测定聚2,6-二甲基苯醚(PPO)树脂分子量、分子量分布的方法。淋洗剂不采用文献申报道的毒性较大者,也不在较高柱温下进行,而采用甲苯(或氯仿)在室温下测定。对样品在甲苯中溶解温度、浓度和稳定性等都进行了系统研究,找到了最优化条件。GPC数据结合改性PPO(MPPO)产品性能测定结果,经仔细分析找到了影响MPPO产品质量的一个重要因素是PPO树脂中低分子量部分含量。它与产品冲击强度有明显的依赖关系。提出了一个从CPC谱图确定低分子量部分含量的方法。     

INFLUENCE OF MOLECULAR WEIGHT OF CHITIN AND ITS THREE DERIVATIVES ON CRITICAL CONCENTRATION OF LYOTROPIC LIQUID CRYSTALLINE PHASE TRANSITION*

The critical concentration of lyotropic liquid crystalline phase transition for chitin derivatives was determinedusing a polarization microscope. The influence of molecular weight on critical concentration of liquid crystalline solution forchitin, chitosan, cyanoethyl chitosan and propionyl chitin successively increases as the chain rigidity decreases. Therefore itcan be used as an indicator of the chain rigidity.     

SYNTHESIS AND CHARACTERIZATION OF NEW STABILIZERS WITH OPTIMAL MOLECULAR WEIGHT*

Over 2×10~8 tons of polymers are produced every year, and a large portion of polymers faces the degradationproblem. There are many effective methods to protect polymers against degradation and the addition of stabilizers to polymerremains the most convenient and effective way of enhancing polymer life and performance. In this article, a series of effectivestabilizers with optimal molecular weight (MW), including common, monomeric and polymeric stabilizers (antioxidant andlight stabilizer) were synthesized using isocyanation, controlled isocyanation, hydrosilylation, epoxide addition, macro-reaction of stabilizing functional compounds and polymerization of monomeric stabilizers. The structure and performance ofthese new stabilizers were characterized by using IR, NMR, MS, UV-spectra XPS and elemental analysis. The currentdevelopment of stabilizer synthesis was also reviewed.     

DYE-SENSITIZED PHOTOLYSIS OF o-Cl-HEXAARYLBIIMIDAZOLE AND PHOTOPOLYMERIZATION KINETICS STUDY OF THE LONG WAVE-LENGTH DYE/HEXAARYLBIIMIDAZOLE SYSTEMS*

o-Chloro-hexaarylbiimidazole (o-Cl-HABI) can be sensitized efficiently by the dyes 1-ethyl-3'-methyl thiacyaninebromide (C 1), 3,3'-diethyl thiacarbocyanine iodide (C 2), and cyclopentanone 2,5-bis[2-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)ethylidene] (C 3) through electron transfer proceses. When exposed to a xenon lamp (filtered by Pyrex glass),the photosensitive systems composed of o-Cl-HABI and the above dyes can produce free radicals which initiate thepolymerization of MMA. The photopolymerization kinetics equation was obtained for the o-Cl-HABI/C2 system, R_p=K [C2]~(0.75)[o-Cl-HABI]~(0.44)[MTA]~(0.12)[MMA]~(10). A comparison of the influence of different dyes on the conversion of MMA photopolymerization was conducted.     

STUDIES ON RADICAL POLYMERIZATION OF METHYL METHACRYLATE INITIATED WITH ORGANIC PEROXIDE-AMINE SYSTEMS

Radical polymerization of methyl mcthacrylate (MMA) initiated with various diacyl peroxideamine systems was studied. Benzoyl peroxide (BPO) and lauroyl peroxide (LPO) were used as diacyl peroxide component, N,N-dimethyl aniline (DMA) and its para substituted derivatives, i.e., N,N-dimethyl-p-toluidine (DMT), p-hydroxymethyl-N,N-dimethyl aniline (HDMA), p-nitro-N,N-dimethyl aniline (NDMA) and p-dimethylamino benzaldehyde (DMAB) were used as amine components. It was found that the peroxide-DMT systems give higher rates of bulk polymerization R_p of MMA than the organic hydroperoxide-DMT systems with the following descending order BPO-DMT>LPO-DMT>CHP (cumene hydroperoxide)-DMT>TBH (tert-butyl hydroperoxide)-DMT. The aromatic tertiary amines possess obvious structural effect on the R_p values in the diacyl peroxideamine system. The overall activation energy of MMA polymerization was determined and thekinetics of polymerization of MMA initiated with BPO-DMT system was investigated.     

A SIMPLE METHOD FOR THE INCORPORATION OF LOW MOLECULAR WEIGHT DYES IN ULTRATHIN FILMS

A simple method for the fabrication of ultrathin films containing low molecular weight dye material is introduced(post-adsorption technique). The chromophore used is 4-nitro-4'-decyloxy azobenzene quaternary ammonium salt (azo-10Q).In classical layer-by-layer (LBL) procedures, where the substrate is dipped alternately into the chromophore solution and thecomplementary polyelectrolyte, the chromophore tends to desorb from the film during subsequent immersion in thepolyanion solution, and there is little or no indication of multilayer growth. The extent of desorption depends somewhat onthe selection of polyelectrolyte, the ionic strength and the pH of solution. An alternative approach is to first prepareconventional LBL films from a pair of oppositely charged polyelectrolytes, and then to soak this film into the chromophoresolution, where adsorption by penetration into the LBL film may take place. In preliminary results, a linear dependence ofUV absorbance on layer number of LBL film thus prepared was found, demonstrating the apparent effectiveness of the post-adsorption technique for the preparation of azo-10Q-containing ultrathin films.     

STUDIES ON THE ORGANIC PEROXIDE-DITERTIARY AMINE INITIATION SYSTEMS

Radical polperization of methyl methacrylate (MMA) initiated with organic peroxide-ditertiaryamine binary systems was studied. Benzoyl peroxide (BPO), lauroyl peroxide (LPO), t-butyl hydro-peroxide (TBH), and t-butyl peroxybenzoate (TBPB) were used as organic peroxide components,aromatic ditertiay amine 4, 4′-tetramethyldiaminodiphenylmethane (TMDAPM) an d aliphatic di-tertiary amine tetramethylethylenediamine (TMEDA) were used as amine components. The polymeri-zation rate R_P, the overall activation energy of polymerization E_a, the rate equation of MMA poly-merization, and the end group of polymer formed were determined.     

甲基丙烯酸甲酯聚合动力学和分子量及分布的开放控制

在甲基丙烯酸甲酯聚合过程中 ,凝胶效应会导致转化率在短时间内出现突变 ,这对工业反应器非常危险 ,同时也导致分子量剧增、分子量分布加宽 .为了使聚合反应速度、分子量及分布同时得到控制 ,提出 3个控制目标 ,即热荷分布指数、预定分子量及变化、分子量分布指数 .在甲基丙烯酸甲酯半间歇聚合动力学和分子量模型的基础上 ,通过单体、溶剂和链转移剂 3种物料的流量和加料方式的仿真计算 ,对动力学、分子量及分布进行开放控制 ,并进行优化 ,得到热荷分布指数和分子量分布指数分别小于 2 0和 2 2的控制策略 ,且分子量达到预定要求 .选择两种优化策略进行实验验证 ,结果与开放控制仿真结果一致