负载钛—三异丁基铝体系催化1—丁烯聚合

负载钛－Ａｌ（ｉ－Ｂｕ），催化合成的聚１－丁烯，经溶剂萃取分离和＾１３Ｃ－ＮＭＲ测试表明为全同立构和无规立构的混合物，全同立构含量约６７％，熔点为９７℃。ＰＢｔ生胶的拉伸强度９．７ＭＰａ，断裂伸长率４９０％，永久变形小于１００％，邵尔Ａ型硬度８７，是一种热塑性弹性体材料。     

负载钛-三异丁基铝体系催化1-丁烯聚合 Ⅰ.聚合条件对1-丁烯聚合的影响

考察了负载钛（Ｔｉ）－三异丁基铝（Ａｌ）催化体系聚合条件对１－丁烯（Ｂｔ）聚合的影响。实验表明，该催化体系对Ｂｔ聚合催化效率可达３４．８ｋｇ／ｇ，聚合物为全同立构和无规立构聚１－丁烯的混合物。在一定的Ｔｉ／Ｂｔ（摩尔比）下，随着Ａｌ／Ｔｉ（摩尔比，下同）的增加和温度的升高，转化率都是先升高后下降，最佳Ａｌ／Ｔｉ值为３００，温度为３０℃。聚合物的相对分子质量和全同立构ＰＢｔ含量均随Ａｌ／Ｔｉ和温度升高而逐渐下降。     

单茂钛催化1-丁烯合成聚1-丁烯

以单茂钛化合物／ＭＡＯ为催化剂催化１－丁烯聚合。产物以＾１３Ｃ－ＮＭＲ,ＧＰＣ,ＤＳＣ,ＤＭＡ表征,结果表明该聚合物是一种立体嵌段的高相对分子质量的热塑性弹性体。     

负载钛-三异丁基铝体系催化苯乙烯的聚合Ⅱ.钛系聚苯乙烯的结构与性能

对负载钛（Ti）一三异丁基铝（A1）催化体系催化合成的全同立构聚苯乙烯（iPS）进行了结构表征和性能测试。抽提分离和差示扫描量热法测试表明，其为结晶型全同立构聚合物，全同立构含量为45％～90％，熔点为215℃，维卡软化点为193℃。偏光显微镜下观察聚合物结晶形态为球晶，聚合产物中的无规部分有利于提高全同立构部分的结晶速率。聚合物拉伸强度为11．79MPa。断裂伸长率为2．1％，洛氏硬度为122。     

聚合条件对合成聚1-丁烯热塑性弹性体的影响

以1-丁烯(B t)为原料,负载钛(简称Ti)-三异丁基铝(简称Al)为催化体系,用本体聚合法合成了聚1-丁烯(PBt)热塑性弹性体(TPE)。考察了聚合条件对PBt TPE的影响,并用差示扫描量热法对聚合物进行了分析。结果表明,随着氢气压力的升高,单体转化率、催化效率呈下降趋势;随着Al/Ti(摩尔比)的增加,转化率和催化效率先升高后降低;随着Ti/Bt(摩尔比)的增加,转化率和催化效率逐渐升高;随着聚合温度的升高,转化率和催化效率先升高后降低;在氢气压力为0.2 MPa、Al/Ti为300、Ti/Bt为2×10-5、反应温度为30℃的聚合条件下,合成出转化率为80.0%的PBt TPE。随着氢气压力的升高,聚合物的特性黏数([η])和全同立构质量分数都呈下降趋势,氢气压力能较好地调节聚合物的相对分子质量;随着Al/Ti的增加,[η]逐渐下降,全同立构质量分数变化不明显;随着Ti/Bt的增加,[η]先升高后降低,最后趋于平稳,而全同立构质量分数略有降低后趋于平稳;随着聚合温度的升高,[η]和全同立构质量分数都呈下降趋势。反应温度为40℃时,PBt TPE的结晶度最高,为20.3%。     

1-十二酰胺基-1-甲基乙膦酸钠及其微乳液的缓蚀作用

用静态失重法、稳态极化曲线和扫描电镜初步研究了ＤＡＭＥＰＮａ＿２－及ＤＡＭＥＰＮａ＿２－庚烷－戊醇－自来水微乳液对２０￣＃碳钢的缓蚀性能，结果表明（１）两者都为抑制阳极为主的混合型缓蚀剂，（２）该微乳液具有较好的缓蚀性能，缓蚀率可达９９％以上，而单一ＤＡＭＥＰＮａ＿２－的缓蚀率仅为１６．２％。     

催化半氢化制备1,4-丁烯二醇

研究制备了聚－γ－氨丙基硅氧烷钯络合物催化剂ＰＣＡＬ，用于丁炔二醇（ＢＹ）的催化半氢化，半氢化产物丁烯二醇（ＢＥ）收率高达９５％。在相同试验条件下用Ｌｉｎｄｌａｒ催化剂作了催化半氢化丁炔二醇的对比，发现二者有相同的催化效果，就生成ＢＥ的选择性和催化剂寿命而言，ＰＣＡＬ催化剂具有更多优点。该催化剂是适用于炔醇催化半氢化的新品种催化剂。     

TiCl_4/MgCl_2-AlEt_3体系合成聚1-丁烯

以负载钛体系(简称Ti)为主催化剂,三乙基铝(简称Al)为助催化剂,加氢汽油为溶剂,用溶液聚合法合成了聚1-丁烯。研究了n(Ti)/n(Bt)、n(Al)/n(Ti)、反应温度、反应时间对转化率、催化效率、聚合物的特性粘数[η]及其全同立构含量的影响。结果表明,随n(Ti)/n(Bt)增加,转化率和催化效率都不断提高;随n(Al)/n(Ti)增加、反应温度升高,转化率和催化效率呈先上升后下降趋势;随n(Al)/n(Ti)、n(Ti)/n(Bt)增大和反应温度的升高,特性粘数逐渐下降,但其对全同立构含量影响较小。     

TiCl4／MgCl2-AIEt3体系合成聚1-丁烯

以负载钛体系（简称Ti）为主催化剂,三乙基铝（简称Al为助催化剂,加氢汽油为溶剂,用溶液聚合法合成了聚1-丁烯。研究了n（Ti）／n（Bt）、n（Al）／n（Ti）、反应温度、反应时间对转化率、催化效率、聚合物的特性粘数[η]及其全同立构含量的影响。结果表明,随n（Ti）／n（Bt）增加,转化率和催化效率都不断提高;随n（Al）／n（Ti）增加、反应温度升高,转化率和催化效率呈先上升后下降趋势;随n（Al）／n（Ti）、n（Ti）／n（Bt）增大和反应温度的升高,特性粘数逐渐下降,但其对全同立构含量影响较小。     

N-马来酰基-氨基丙酸丁酯均聚和共聚反应的研究Ⅰ单体N-马来酰基-氨基丙酸丁酯的合成

以刀来酸酐（ＭＡ）、氨基丙酸（Ａ１ｎ）、丁醇为原料用三步二釜法合成了Ｎ－马来酰基－Ｄ，Ｌ－氨基丙酸丁酯（ＢＡＭ），产率达５８％。并用ＰＥＲＫＩＮ－ＥＬＭＥＲＦＴＩＲ－１７１０红外光谱仪ＰＥ－２４００有机元素 对产品进行了检测。与传统方法相比，缩短了合成时间，节省大量的溶剂，降低了成本，提高了产率。     

The three-phase structure of isotactic poly(1-butene)

A detailed analysis of the three-phase structure of isotactic poly(butene) was conducted by conventional and temperature-modulated calorimetry. The development of the crystalline, mobile amorphous, and rigid amorphous fractions was analyzed as a function of thermal history, upon isothermal and non-isothermal crystallization. It was found that, under the chosen experimental conditions, the amount of rigid amorphous phase (w_RA) in PB-1 ranges from w_RA = 0.14 to 0.23, with higher values formed when the polymer is crystallized at low temperatures or at high cooling rates from the melt. Comparison of total and frequency-dependent reversing heat capacity curves suggested that the rigid amorphous phase of isotactic poly(1-butene) vitrifies after completion of the crystallization process and that its full mobilization takes place at around 50 °C. The exact temperature of complete devitrification is slightly affected by the thermal history of the material. An effort to link the mechanical properties of PB-1 to the three-phase structure was attempted, and a correlation of Young's modulus with the solid fraction at the temperature of analysis, composed of crystalline and rigid amorphous phases, was proposed.     

负载钛催化体系合成聚1-丁烯的序列结构

通过聚1－丁烯（PBt）的^13C-NMR谱图中对立体结构的实测值与Bernoulli模型计算值比较，表明该体系基本符合Bernoulli模型提出的机理，同时计算出甲苯不溶物、可溶物和空白试样BPt的全同（m）和间同（r）平均链长，并作出r和m连接的分布曲线，3个试样的间同平均链长都接近1，并且分布非常窄，而全同平均链长虽然各不相同但都较, 分布非常宽，这表明PBt的序列结构为主体嵌段结构。     

Mesophases in polyethylene, polypropylene, and poly(1-butene)

This paper contains new views about the amorphous and partially ordered phases of the three polymers listed in the title. The discussion is based on information on structure, thermodynamic stability, and large-amplitude molecular motion. Polyethylene is the basic backbone of all alkene polymers, and the other two are the first members of the vinyl polymers which have stereospecifically placed alkyl side chains. Their multiphase structures consist of metastable crystals, mesophases, and surrounding rigid and mobile amorphous fractions. All these phases have sizes ranging from micrometer dimensions down to nanometers. Besides the phase structures, information about the molecular coupling between the phases must be considered. Depending on temperature, the polymer phases can vary from solid (rigid) to liquid (mobile). New knowledge is also gained by cross-comparison of the title polymers. The experimental information was gained from (a) various forms of slow, fast, and temperature-modulated thermal analysis to identify equilibrium and non-equilibrium states, (b) measurement of structure and morphology at various length scales, and (c) tracing of the large-amplitude molecular motion, the kinetics of order/disorder changes, and the liquid/solid transitions (glass transitions). It is shown that much more needs to be known about the various phases and their coupling to characterize a given polymer and to fine-tune its properties for a given application.     

不同聚合方法合成聚1-丁烯热塑性弹性体的结构与性能

比较了分别通过溶液聚合和本体聚合所得聚1-丁烯热塑性弹性体的物理机械性能.结果表明,用溶液法制得的聚1-丁烯的物理机械性能要优于本体法,也更接近于热塑性弹性体.核磁共振和差示扫描量热分析表明,在相同的聚合条件下,用溶液法所得聚1-丁烯分子链的规整度要高于本体法聚合产物,其结晶程度也更高.     

聚1-丁烯弹性体及1-丁烯与1-己烯共聚弹性体的流变性能

采用恒速双筒毛细管流变仪研究了自制的聚1-丁烯热塑性弹性体(PB-TPE)及1-丁烯与1-己烯共聚弹性体(B-co-H)的流变性能.结果表明,相同条件下PB-TPE和B-co-H均为假塑性流体,B-co-H的非牛顿性更强,PB-TPE比B-co-H的黏流活化能高.随着1-己烯含量的增大,共聚物分子链柔顺性增加,加工性能...     

Chemical modification of poly(1-butene) resins through reactive processing

Controlled-rheology poly(1-butene) resins have been produced by chemical modification of commodity poly(1-butene) (PB-1) resins through reactive processing with an organic peroxide. Using various amounts of peroxide, samples have been produced and have been analyzed in terms of their molecular and rheological properties. Molecular weight distributions (MWD) as determined by gel permeation chromatography (GPC) indicate that polydispersity (PDI) remains approximately constant but weight-average molecular weight (M_w) decreases with increasing peroxide concentration. These trends are in agreement with predictions from a kinetic model previously developed for the production of controlled-rheology polypropylene. Linear viscoelastic measurements indicate that the modified samples are thermorheologically simple and that zero-shear viscosity decreases with increasing peroxide concentration while flow activation energy remains approximately constant. Finally, no significant variation in melting and crystallization properties was observed for the range of peroxide concentrations used. Based on these results, it is proposed that tailor-made controlled-rheology poly(1-butene) resins can be produced easily through reactive extrusion operations similar to those used for the production of controlled-rheology polypropylene (CRPP).     

Tensile properties and morphology of injection-molded poly(1-butene)

The injection-molded poly(1-butene) (PB-1) is found to be more brittle than the compression-molded PB-1. The morphologies of these specimens are examined by use of polarized optical microscopy and scanning electron microscopy (SEM). A skin layer and an oblate spherulitic structure extended to the core region are observed in the injection-molded PB-1, while typical spherulites exist in the compression-molded PB-1. Below the skin layer of the injection-molded PB-1, the fracture surface is found to consist of many aligned strip-like voids with ribbon edges propagating to the center of the specimen and perpendicular to the flow direction of injection-molding. Based on these observations, it can be inferred that shear stress induced by the melt flow during the injection-molding does not only cause the formation of skin layer, but also penetrates deeply into the central region of the injection-molded specimen causing the formation of oblate spherulites. The oblate spherulitic structure is responsible for the aligned voids during elongation of PB-1, while the existence of the skin layer and the oblate spherulites in core region is responsible for the brittleness of the injection-molded PB-1. The elongation of the injection-molded PB-1 is found to be lower than that of the compression-molded. This can be attributed not only to the presence of the skin layer but also to the oblate spherulites in the core region. The elongation can be improved by annealing at a temperature above the melting point of PB-1.     

低温合成高等规度聚1-丁烯

考察了低温聚合下三乙基铝/负载钛高效催化剂[n(Al)/n(Ti)]、n(Ti)/1-丁烯[n(Bt)]、二苯基二甲氧基硅烷[n(DDS)]/n(Ti)和氢气压力对聚1-丁烯等规度和特性黏数的影响,并用差示扫描量热仪和偏光显微镜对自制试样和日本三井化学公司的试样进行了分析比较.结果表明,当n(DDs)/n(Ti)为13.21、n(Ti)/n(Bt)为3×10-5、n(Al)/n(Ti)为200、温度为15℃及氢气压力为0.02 MPa时可以合成等规度为97.2%、特性黏数为254 mL/g的聚1-丁烯.自制试样和三井化学公司试样的熔点与熔限温度范围基本一致,二者的结晶度分别为63.90%和82.96%.二种试样均为球晶,粒径分布比较均匀,但自制试样的晶粒明显大于三井化学公司的试样.自制试样的密度、硬度、冲击强度、弯曲模量及屈服强度都低于三井化学公司的试样,而拉伸强度和扯断伸长率却高于后者,这主要是在自制试样中未添加成核剂的缘故.限温度范围基本一致,二者的结晶度分别为63.90%和82.96%.二种试样均为球晶,粒径分布比较均匀,但自制试样的晶粒明显大于三井化学公司的试样.自制试样的密度、硬度、冲击强度、弯曲模量及屈服强度都低于三井化学公司的试样,而拉伸强度和扯断伸长率却高于后者,这主要是在自制试样中未添加成核剂的缘故.     

复合引发剂引发GMA熔融接枝聚1-丁烯

采用复合引发剂用Haake流变仪研究了甲基丙烯酸缩水甘油酯(GMA)-苯乙烯(St)多组分单体熔融接枝高全同聚1-丁烯(iPB)。用傅里叶变换红外光谱对接枝物进行了分析,并分别考察了复合引发剂比例、GMA用量、引发剂总用量和St用量对接枝的影响。结果表明:在复合引发剂引发下,GMA和iPB可熔融接枝,接枝率最高可达1.74%;St作为共单体可明显提高GMA的接枝率和接枝效率,当n(St)/n(GMA)为1.5时,接枝率为单独使用GMA时的2.3倍。     

成核剂对丙烯-1-丁烯无规共聚物结构与性能的影响

研究了成核剂NA21对丙烯-1-丁烯无规共聚物(PP-R)性能的影响。采用偏光显微镜、差示扫描量热仪、小角X射线散射仪、动态力学分析仪表征了PP-R的结构。添加成核剂使PP-R球晶尺寸减小,从而使雾度从45.93%降至14.46%,弯曲模量从1.14 GPa提高到1.32 GPa,23℃下的Izod缺口冲击强度从32.9 J/m提高至41.0 J/m,热变形温度从81.7℃提高到87.3℃。加入成核剂对片晶熔点、结晶温度、片晶和非晶区厚度分布以及非晶区的玻璃化转变温度均产生影响,但对结晶度和平均长周期的影响不明显。