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Transmission Electron Microscope and other properties testing results show that the complex emulsifier system is the crucial influence factor of the polymerization process and the properties of products. It may influence the coagulum content and reaction rate of the polymerization process, the performance, particle diameter,viscosity, electrolyte stability and storage stability of the emulsion products and the contact angle of the film.The initiator mainly influences the coagulum content and reaction rate.The acrylic monomers mainly influence the solid content, Minimum Film Formation Temperature of the emulsion and the Glass Transition Temperature of the film.The organic silicone monomer mainly influences the water absorption of the film.The reaction temperature mainly influences the reaction rate and conversion.The stirring intensity mainly influences the coagulum content of the polymerization process.

透射电镜等性能测试结果显示:复合乳化剂体系是硅丙共聚乳液的聚合过程及产品性能的主要影响因素,它可以对聚合过程的凝胶率、反应速率以及乳液的外观、粒径、粘度、耐电解质稳定性及贮存稳定性,还有乳液涂膜的接触角等造成不同程度的影响;引发剂主要影响反应速率和凝胶率;丙烯酸酯单体主要影响到乳液的固含量、最低成膜温度以及涂膜的玻璃化转变温度,有机硅单体主要影响涂膜的吸水率等;聚合反应温度主要影响乳液的反应速率和转化率等;搅拌强度主要是影响到聚合过程的凝胶率。

For inverse suspension polymerization, water soluble monomer is dispersed in oil continuous phase and initiated in aqueous phase.

反相悬浮聚合是将水溶性单体分散在油溶性介质中,水溶性引发剂溶解于水相中进行聚合的方法。

They cationic monomer Acryloyloxyethyl ethyl trimethyl ammonium chloride and resource-rich, low price, low values of weathering burning coal as its main raw material, aqueous dispersion polymerization methods, through the weathered coal / cationic monomer in-situ polymerization in the international arena for the first time prepared by a high efficiency oil-bearing wastewater treatment agent; use of oil-field wastewater treatment, the waste slurry as raw material, has developed the world's first CWS dispersants and oil fields of the "three mining" using profile control plugging agent, in order to The high value of solid waste has opened up new avenues of applications; integration of related technologies, and open up for the oil field wastewater treatment, an annual output of 300 tons of sets of processes and devices for the first time realized the slop oil and drilling fluid back row of the industrialization of treatment .

他们以阳离子单体丙烯酰氧乙基三甲基氯化铵与资源丰富、价格低廉、燃烧值低的风化煤为主要原料,采用水介质分散聚合方法,通过风化煤/阳离子单体原位聚合技术,在国际上首次制备出高效含油废水处理剂;采用油田废水处理后的废弃物泥浆为原料,在国际上率先开发出水煤浆分散剂和油田"三采"用调剖堵水剂,为固体废弃物的高值化应用开辟了新途径;集成相关技术,开拓出针对油田废水处理、年产300吨的成套工艺和装置,首次实现了油田污油水和钻井返排液的工业化处理。

The effects of different factors on the laser-induced graft polymerization on the PET surface were analyzed, and the mechanisms were discussed. The factors were: 1 Monomers with smaller molecules resulted in better modification than polymeric monomers. Acrylamide monomer was chosen as hydrophilic modifier finally; 2 Higher concentration of the monomer solution favored the graft reaction; 3 With the increasing laser fluence, the surface hydrophilicity of PET films increased at first, then decreased. More laser pulses led to a more hydrophilic surface; 4 Benzophenone as a photosensitizer hindered the graft polymerization; 5 The homopolymer retardant of ammonium iron sulfate hexahydrate in a proper concentration retarded the formation of homopolymers and promotes the graft copolymerization; 6 The solvent of monomer solution also affected the graft reaction. Different solvents functioned in different ways. Ethanol can promote the graft reaction because of the activity of hydrogen in its structure; 7 pH value of the monomer solution affects the polymerization rate, and a lower pH value was favorable to the graft reaction.

这些影响因素的作用分别为:1小分子单体的表面改性效果好,确定以丙烯酰胺为亲水性改性单体;2较高的单体溶液浓度有利于接枝反应;3激光能量密度增大,薄膜表面亲水性先显著增强,后又减弱;激光脉冲次数越多,改性后表面亲水性越强;4光敏剂BP对PET表面接枝聚合反应有阻碍作用;5适当浓度的均聚物抑制剂六水合硫酸铁铵能减少单体均聚物的生成,促进接枝聚合;6单体溶液的溶剂也影响接枝聚合的反应进程,不同溶剂的影响作用原理不同,含较活泼氢的乙醇能促进接枝反应;7溶液pH值影响单体聚合速率,pH值较低有利于接枝反应。

Dealcoholization temperature markedly influences the surface area and porosity of the resultant MAO-supports. When the support was pretreated at lower or higher temperature, the corresponding MAO-support shows very low surface area;2.XRD and IR analyses indicate that MAO has reacted with the residual ethanol in the supports, which is an important manner to get MAO fixed on the carrier. Morever, XPS analyse indicates that MAO can also be coordinated with MgCl_2, which is another way to get MAO fixed on the support;3.ICP and EDX analyses indicate that dealcoholization temperature not only determined the element content on the solid catalyst, but also influences the element distribution on the carrier;4.The activities of the supported phenoxy-imine catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature. The support (MSP-5) obtained by treating MgCl_2·2.56C_2H_5OH at 160℃for 4 h, then modified by MAO is very effective for immobilizing complex 3, the resultant solid catalyst (MSPC-5) shows very high activity in ethylene polymerization, and its kinetics of polymerization is stable during the reaction process. Finally, PEs with spherical morphology and high bulk density (over 0.35g/ml) were obtained, without reactor fouling;5.In this work, polymerization conditions such as alkylaluminums, Al/Zr ratio, temperature and H_2 had a pronounced effect on the activity of MSPC-5 and properties of PE;(3). New MgCl_2-Supported Single-Site Catalysts for Ethylene PolymerizationIn this work, a kind of new MgCl_2 support was obtained by anhydrous MgCl_2 co-milled with solid MAO, and it is a creative contribution. Then some single-site catalysts were supported on the new MgCl_2 support, and the resulted solid catalysts were tested in ethylene polymerization, the results indicated that:1.XRD and IR analyses indicate that MAO does be coordinated with MgCl_2, which is in good agreement with the results obtained by XPS;2.co-mlling time had no obvious effect on the texture of support after 12 hours;3.In this work, MgCl_2 was co-milled with solid MAO for different hours, and then complex 3 was supported on these co-milled supports. It was found that co-milling time markedly influences the activity of solid catalysts, but it had negligible effect on the kinetic profile and the properties of resultant PE.

XPS研究结果表明,MAO不仅仅只和乙醇作用,MAO还与MgCl_2本身有一定的作用,这是一个极为重要的发现;3、通过ICP和EDX表征,发现载体的脱醇温度直接影响着元素在固体催化剂中的含量及分布;4、脱醇温度极大地影响着负载苯氧基亚胺类催化剂的活性和聚合物的性能,特别是原始载体经160℃活化4小时制备得到的固体催化剂MSPC-5的活性明显高于其他脱醇温度条件下制得的固体催化,并且催化剂寿命长,表现出稳定的动力学行为,最终获得了高堆密度(大于0.35g/ml)的球形聚乙烯颗粒;5、本文选择MSPC-5为研究对象,考察了聚合反应参数对催化剂的活性及其聚合物的影响,研究发现:不同的烷基铝对催化剂具有非常重要的影响,特别足TIBA对MSPC-5的助催化活性最高,烷基铝的加入量有一个较佳值,聚合温度为80度时活性最高,H_2的加入使催化剂的活性明显降低且聚合物的分子量也减小;、新型氯化镁载体负载单活性中心催化剂催化乙烯聚合本文创造性采用固体MAO与无水氯化镁直接进行共研磨,制备出了一种的新型的氯化镁载体,并将该载体用于多种单活性中心催化剂的负载化研究,研究表明:1、通过BET、XRD的表征,再次证实了MAO与MgCl_2之间具有直接作用,与XPS的研究结果相一致;2、当研磨时间高于12小时时,延长研磨时间对载体的结构没有显著的影响;3、将配合物3负载于共研磨时间不同的一系列载体上,乙烯聚合结果表明,尽管共研磨时间对负载催化剂的活性具有明显的影响,但是它对聚合物的性能以及催化剂的影响不明显。

Dealcoholization temperature markedly influences the surface area and porosity of the resultant MAO-supports. When the support was pretreated at lower or higher temperature, the corresponding MAO-support shows very low surface area; 2.XRD and IR analyses indicate that MAO has reacted with the residual ethanol in the supports, which is an important manner to get MAO fixed on the carrier. Morever, XPS analyse indicates that MAO can also be coordinated with MgCl_2, which is another way to get MAO fixed on the support; 3.ICP and EDX analyses indicate that dealcoholization temperature not only determined the element content on the solid catalyst, but also influences the element distribution on the carrier; 4.The activities of the supported phenoxy-imine catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature. The support (MSP-5) obtained by treating MgCl_2·2.56C_2H_5OH at 160℃for 4 h, then modified by MAO is very effective for immobilizing complex 3, the resultant solid catalyst (MSPC-5) shows very high activity in ethylene polymerization, and its kinetics of polymerization is stable during the reaction process. Finally, PEs with spherical morphology and high bulk density (over 0.35g/ml) were obtained, without reactor fouling; 5.In this work, polymerization conditions such as alkylaluminums, Al/Zr ratio, temperature and H_2 had a pronounced effect on the activity of MSPC-5 and properties of PE;(3). New MgCl_2-Supported Single-Site Catalysts for Ethylene Polymerization In this work, a kind of new MgCl_2 support was obtained by anhydrous MgCl_2 co-milled with solid MAO, and it is a creative contribution. Then some single-site catalysts were supported on the new MgCl_2 support, and the resulted solid catalysts were tested in ethylene polymerization, the results indicated that: 1.XRD and IR analyses indicate that MAO does be coordinated with MgCl_2, which is in good agreement with the results obtained by XPS; 2.co-mlling time had no obvious effect on the texture of support after 12 hours; 3.In this work, MgCl_2 was co-milled with solid MAO for different hours, and then complex 3 was supported on these co-milled supports. It was found that co-milling time markedly influences the activity of solid catalysts, but it had negligible effect on the kinetic profile and the properties of resultant PE.

XPS研究结果表明,MAO不仅仅只和乙醇作用,MAO还与MgCl_2本身有一定的作用,这是一个极为重要的发现; 3、通过ICP和EDX表征,发现载体的脱醇温度直接影响着元素在固体催化剂中的含量及分布; 4、脱醇温度极大地影响着负载苯氧基亚胺类催化剂的活性和聚合物的性能,特别是原始载体经160℃活化4小时制备得到的固体催化剂MSPC-5的活性明显高于其他脱醇温度条件下制得的固体催化,并且催化剂寿命长,表现出稳定的动力学行为,最终获得了高堆密度(大于0.35g/ml)的球形聚乙烯颗粒; 5、本文选择MSPC-5为研究对象,考察了聚合反应参数对催化剂的活性及其聚合物的影响,研究发现:不同的烷基铝对催化剂具有非常重要的影响,特别足TIBA对MSPC-5的助催化活性最高,烷基铝的加入量有一个较佳值,聚合温度为80度时活性最高,H_2的加入使催化剂的活性明显降低且聚合物的分子量也减小;、新型氯化镁载体负载单活性中心催化剂催化乙烯聚合本文创造性采用固体MAO与无水氯化镁直接进行共研磨,制备出了一种的新型的氯化镁载体,并将该载体用于多种单活性中心催化剂的负载化研究,研究表明: 1、通过BET、XRD的表征,再次证实了MAO与MgCl_2之间具有直接作用,与XPS的研究结果相一致; 2、当研磨时间高于12小时时,延长研磨时间对载体的结构没有显著的影响; 3、将配合物3负载于共研磨时间不同的一系列载体上,乙烯聚合结果表明,尽管共研磨时间对负载催化剂的活性具有明显的影响,但是它对聚合物的性能以及催化剂的影响不明显。

After the oxidative polymerization of DMP,styrene was in-situ polymerized under the initiation of dibenzoyl peroxide and dicumyl peroxide,finally thermodynamically compatible PPO/PS alloy was prepared.When styrene content was 50 wt%,for the synthesized PPO/PS alloy the yield and the weight-average molecular weight were determined to be 95%and 1.7×10~5 for PPO,93%and 2.0×10~5 for PS,respectively.The influence of the concentration of DMP and catalyst,molar ratio of N/Cu, oxygen partial pressure,NaOH concentration and temperature on the initial polymerization rate(R_0) of DMP was studied.It was found that the initial polymerization rate of DMP increased with the concentration of DMP and catalyst. The initial polymerization rate increased with the molar ratio of N/Cu at first and then decreased.

通过测定DMP氧化聚合过程中氧气吸收量随时间的变化,研究了DMP和催化剂浓度、N/Cu摩尔比、氧气分压、氢氧化钠浓度及温度对水介质中DMP氧化聚合初始速率的影响,发现DMP氧化聚合初始速率与氧气分压的0.1次方成正比;DMP氧化聚合初始速率随DMP和催化剂浓度及温度的增加而增加;随氢氧化钠浓度和N/Cu摩尔比的增加DMP氧化聚合初始速率先增加后降低。

After introduction of reaction mechanism of LHE water stabilizer containing polyhydroxy carboxylate in CW system and applications in other chemical plants,the author analyzes the feasibility introducing this kind of stabilizer into CW system in nitric acid plant of Sichuan Chemical Co.

介绍LHE聚合羟基羧酸盐水质稳定剂的作用机理以及在其他化工厂循环水系统中的应用实例,设想将LHE聚合羟基羧酸盐水质稳定剂用于我公司硝酸厂循环水系统,将表冷液治理后低浓度氨氮淡水作为循环水系统的补充水,达到氨氮零排放。

Secondly, according to the construction and characteristic of the N-isopropylacrylamide and the temperature-sensitivity of PNIPA hydrogel, Pdualistic hydrogel was synthesized by microwave low temperature plasma. The effects of the factors on the swelling characteristic of P dualistic hydrogel, such as treatment time and power of plasma, concentrations of crosslinking agent and total monomers, proportion of AMPS, polymerizing temperature etc, was discussed in detail. The three dimensions structure , thermostability , reversional volume , swelling/deswelling kinetics, temperature-sensitivity and pH-sensitivity of the hydrogel were also investigated. The optimal synthesizing technics of P dualistic hydrogel initiated by microwave low temperature plasma was confirmed.

在此基础上,结合NIPA的结构特征和PNIPA的温敏性,用微波低温等离子体引发聚合了P二元智能凝胶,详细探讨了微波低温等离子体处理功率、处理时间、总单体浓度、AMPS单体浓度、交联剂浓度及聚合反应溫度等因素对P二元凝胶溶胀性能的影响;并对其三维交联结构、热稳定性、失水-吸水动力学、温度敏感性、pH敏感性、体积复原性等进行了研究;确定了适合微波低温等离子体引发聚合P二元智能凝胶的最佳工艺。

In order to reflect the catalyst deactivation during the oxidative polymerization and difference of the reactivity between monomer,the oligomer soluble in water,and the oligomer unsoluble in water,a new heterogeneous kinetic model was proposed according to Flory statistical theory.It was found that the polymerization rate estimated by the new model was consistent with the calculated data.

根据DMP氧化聚合过程中催化剂随时间延长而逐渐失活,不同种类的苯氧阴离子活性不同以及非均相聚合特点,提出了水介质中DMP氧化聚合动力学模型,并采用多元非线形回归计算得到模型参数,采用模型计算得到的聚合速率与实验测定值一致,证明所提出模型的正确性。

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