R&D Reports

FY 2001

vol. 2001 - II (2001.11.30 issue)

All the current caprolactam manufacturing processes produce large amounts of ammonium sulfate as a by-product, because oleum or sulfuric acid is used for the reaction promoter in the Beckmann rearrangement process and hydroxylamine sulfate is brought into the cyclohexanone oxime production unit. As the profitability of caprolactam production depends on the amount of ammonium sulfate, the process to avoid its generation has been a dream for many manufacturers. Recently Sumitomo Chemical Co., Ltd. developed the vapor phase Beckmann rearrangement process. In the process cyclohexanone oxime is rearranged into caprolactam using a high silica zeolite catalyst instead of sulfuric acid. EniChem in Italy developed the ammoximation process that involves the direct production of cyclohexanone oxime without producing any ammonium sulfate. Sumitomo Chemical Co., Ltd. will industrialize the combined process of vapor phase Beckmann rearrangement and ammoximation in 2003. The process does not produce any ammonium sulfate. We focus in this paper on some aspects of the vapor phase Beckmann rearrangement catalysis. It has been believed that the catalyst must possess acidity, however we have developed a catalyst with extremely week acidity, which cannot be detected by ammonia TPD measurements.
( 4-12 by Hiroshi ICHIHASHI, Masami FUKAO, Keisuke SUGITA, Tatsuya SUZUKI )

Liquid Crystalline Polymers (LCPs) ("Sumikasuper LCP" is one of them) are now used for wide varieties of electronic parts, especially SMT (Surface Mount Technology) connector for personal computers and mobile phones. However, it is sometimes difficult to apply LCPs (Sumikasuper LCP also) to the usage, because of molding problems. The most significant molding problem is warpage. In this report, we explain the basic study to solve the problem based on our own flow pattern theory. According to experimental results based on the theory, it is found that both the compound formulation and procedure are part of the key technologies to solve warpage problem and to fit flow patterns of various actual connector designs also. Thus Sumikasuper E6000HF series have been developed as connector grades. Furthermore, the effectiveness of CAE (Computer Aided Engineering) technology is introduced as a method of estimating the flow pattern and warpage analysis.
( 13-19 by Satoshi NAGANO, Hiroyasu YAMAUCHI, Manabu HIRAKAWA )

The new polypropylene (PP) suitable for blow molding has been developed. The new PP gives good controllability of parison thickness because of its very small dependence of die swell on shear rate. Furthermore, the productivity of blow molding can be improved by reducing the molding cycle time, because the cooling rate of the new PP is high. On the other hand, physical properties of the new PP has been also improved. Impact strength of the new PP is surprisingly higher than that of conventional PP and high density polyethylene for blow molding. Moreover, the new PP has advantages such as high flexibility and good transparency.
( 20-26 by Seiji SHIROMOTO, Tatsuhiro NAGAMATSU, Haruyuki SUZUKI, Toshihide OGIHARA )

The process for producing methyl esters of fatty acids by reacting fats and oils such as soybean oil and waste oil with methanol was investigated. We have found the fact that the methyl esters are obtained at a high reaction rate in the absence of a catalyst under the supercritical conditions. This process is a clean and simple process without soap by-produced in the case of using alkali catalysts. So that, the part of the process to wash soap away using water after reaction can be omitted.
( 27-31 by Fumisato GOTO, Tomoyuki SUZUKI, Toshio SASAKI, Tatsuo TATENO )

Recent developments regarding microreactors of which reaction volume is at µ rorder are reviewed from the viewpoint of system design for laboratory automation which is useful for process chemistry. Physical and chemical phenomena at µm level (size effects), structural elements , fabrication methods concerning microreactors are summarized. Applied reaction examples classified into seven categories are also surveyed. The advantages of microreactors are (1)easy of rapid and precise control of temperature, which is helpful in obtaining of heat-unstable compounds, (2)easy to reduce reaction (residence)time, (3)high yield of reaction products (one of the author's hypothesis)and (4)easy of scale-up of reaction volume by numbering-up procedures of each microreactor element without complicated calculations in chemical engineering. The productivity of chemical compounds by microreactors is much enough for cost-effective fine chemicals. The importance of combination of computer-aided synthesis design and microreactors is also pointed out to swiftly validate the candidate reaction routes presented In conclusion, microreactors have great potential for serving as a powerful tool for organic synthesis research, analytical science, and its production.
( 32-45 by Hideho OKAMOTO, Arata HASHIZUME )

Safety pharmacology is one of non-clinical evaluation aimed to assess the safety of medicinal products by examining the pharmacodynamic properties. Recently, ICH guideline for the safety pharmacological study is designed to obtain the information necessary to predict the potential adverse effects and assess the safety of the substance in humans. In this paper, we explain the circumstance of ICH guideline establishment and its summary, and describe our current practices in evaluating of vital function, chiefly cardiovascular system, are considered to be the most important ones to assess in safety pharmacological studies.
( 48-52 by Terumasa MINO, Tomohiro NODA, Shinji TsUJIMOTO, Shin-ichi SUGIMOTO, Minoru NAKANO )

Process Systems Engineering (PSE) has made progress as a new discipline to establish theories and methods for decision making at all the stages of plant life cycle (planning, design, management, operation, control and maintenance of process systems). Recently the main research field of PSE has been shifted from process design to plant operation and control in response to the change in needs of chemical process industries. This paper reviews the key technologies of PSE and their applications to industrial chemical plants, and touches upon some difficult problems and further development.
( 53-59 by Yoshinori KUTSUWA )

vol. 2001 - I (2001.5.31 issue)

Delaus® (diclocymet: (RS)-2-cyano-N-[ (R-1- (2,4-dichlorophenyl)ethyl]-3,3-dimethylbutyr-amide) is a novel fungicide for use in rice. Delaus® has systemic properties as well as long lasting effectiveness and controls both rice leaf and panicle blast infection by granular application to rice seedling boxes. Foliar treatment of Delaus® also shows excellent control of rice blast. Delaus® has been registered in April 2000 in Japan.
( 4-13 by Yukio OGURI, Akio MANABE, Yoshimi YAMADA, Masao INOUE, Minoru NAKANO, Orie KADOOKA, Hiroshi ANZAI )

Flumioxazine was discovered and developed by Sumitomo Chemical Company. Flumioxazine is used as an herbicide to control a wide variety of weeds in crop field, such as soybeans, peanut and tree fruit field, and non-crop area. Flumioxazine inhibits protoporphyrinogen oxidase of chlorophyll biosynthesis pathway. Flumioxazine has very big margin of safety against environment and human health. Flumioxazine had already been launched in South America, France, China and Japan, and registered in the United State within 2001.
( 14-25 by Eiki NAGANO, Ryo SATO, Masahiro YAMADA, Yuji FUNAKI, Ritsuko FURUTA, Takuo FUJISAWA, Satoru KAWAMURA )

Dry or semi-dry lands have essentially high potential of CO2 fixation, because they occupy about one-third of all land surface on earth. In the fundamental study to develop transgenic plants that could survive under severe environmental stress, we are investigating the light-stress tolerance of plants on the molecular basis. The model plant, Arabidopsis thaliana, showed increased tolerance to highintensity light when pre-exposed to medium-intensity light (light acclimation). Among characterized acclimation-induced genes, we identified a zinc finger protein RHL41. The transgenic plants overexpressing the RHL41 gene showed an increased tolerance to high-intensity light. RHL41 could function as a regulatory factor in the acclimation/photo-protective process.
( 26-32 by Asako IIDA, Kenji OEDA )

Nenchaku-Kun® has two formulations, Nenchaku-Kun® Ekizai (starch 5% soluble concentrate used after 100-time dilution by water) and Nenchaku-Kun® 80% starch 80% WP used after 500-time dilution by water). At spraying test in the laboratory, the starch formulations showed high efficacy against leaf-mite, Tetranychus urticae, T. kanzawai, Panonychus citri and P. ulmi. In the strawberry greenhouse, treatment by the combination of Nenchaku-Kun® Ekizai and a biotic pesticide, predacious mite, Phytoseiulus persimilis controlled T. kanzawai population over 30 days. In the citrus fields, P. citri population did not increase about 90 days by two-time spraying of Nenchaku-Kun® 80 between late-May and early-September. On the trees treated by the starch formulation, various native natural enemies of P. citri, predacious mites, mitephagous ladybirds and thrips, and Oligota spp. were observed. Since Nenchaku-Kun® had neither direct killing action nor residue effect against natural enemies, it seems that direct killing action of Nenchaku-Kun® and predation effect by natural enemies controlled increase of the density of the mites.
Nenchaku-Kun® has highly safe for various lives, for example, people, animals, fishes, bees and natural enemies. As it kills leaf-mites by physical action, no insecticide resistance develops. Therefore, Nenchaku-Kun® is an optimum material for Integrated farm system and IPM system.
( 33-37 by Masaru HONDO, Nobutaka TANAKA, Eiji SATO )

Sumitomo Pharmaceuticals successfully developed the novel serotonin-dopamine antagonis t-type antipsychotic agent, perospirone (Lullan® approved in Dec. 2000), which was discovered from studies based on the synthetic technology of the azapirone derivatives. Perospirone, unlike conventional antipsychotics, has potent antagonistic actions both for serotonin-2 and dopamine-2 receptors and showed antipsychotic effects in various animal models. It was confirmed in the clinical studies that perospirone was effective not only for the positive symptoms of schizophrenia, but also for the negative symptoms which are resistant to the conventional agents. In addition, extrapyramidal side effects of perospirone were found to be weak. These findings indicate that perospirone is the new type antipsychotic agent with a broad clinical efficacy.
( 38-45 by Yukihiro OHNO, Fujio ANTOKU, Toshiro TSUCHIYA )

Recently, imaging diagnosis plays a major role in clinical field. Especially in the brain diseases, non-invasive imaging is essential for diagnosis. X-ray computed tomography (CT) and magnetic resonance imaging (MRI) visualize the shape of tissue, in contrast, nuclear medicine with radiopharmaceuticals and special equipment provides the functional imaging such as cerebral blood flow or metabolism. Therefore, nuclear medicine provides the essentially different information with CT and MRI. For instance, in the early stage of brain stroke or dementia, MRI cannot detect any morphological changes, but nuclear medicine can detect the changes in cerebral blood flow and metabolism. Moreover, only nuclear medicine can perform the imaging of neurotransmitters and their receptors or transporters. In this review, present status of the neuroimaging by nuclear medicine and our company's challenges will be discribed.
( 46-54 by Hiroki MATSUMOTO, Akira MAEKAWA )

Sumitomo Chemical has developed the new polymer bead ABA ; "CS series", which has a narrow particle size distribution and average size of 1.1, 1.8 and 3.0μm, respectively. CS series ABA has a good affinity with polypropylene, resulting in the superior performances of OPP film (low blocking, low haziness, high transparency, and good anti-scratch), as well as in less manufacturing trouble like ABA deposition onto rolls of the machine. With CS series ABA, a tailor made surface can be designed, and superior winding characteristics of film roll is obtained.
( 55-61 by Takeshi EBARA, Hiroyuki TANIMURA, Satoru HOSODA, Kazuhiro YAMAZAKI, Tuyoshi HASHIMOTO, Hajime SADATOSHI )

In industrial chemical production it is important to have the quantitative information about safe handling, storage and transportation temperatures for the given process. An adiabatic decomposition temperature for 24 hrs (ADT24) is the temperature at which TMR (time to maximum rate) is 24 hrs derived from adiabatic measurements. A self-accelerating decomposition temperature (SADT) is the lowest ambient air temperature at which a self-reactive substance undergoes an exothermic reaction in specified commercial package in a period of seven days or less. In this article, the methodology of using the ARCR to obtain ADT24 and SADT values are described together with the ∅ correction procedures of the ARCR data.
( 62-70 by Takeshi KIKUCHI )