DOCSLIB.ORG

Phosgene-Free Synthesis of Diphenyl Carbonate

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Phosgene-Free Synthesis of Diphenyl Carbonate TECHNISCHE UNIVERSITÄT MÜNCHEN Lehrstuhl II für Technische Chemie Phosgene-free Synthesis of Diphenyl Carbonate Bo Peng Vollständiger Abdruck der von der Fakultät für Chemie der Technischen Universität München zur Erlangung des akademischen Grades eines Doktor-Ingenieurs (Dr.-Ing.) genehmigten Dissertation. Vorsitzender: Univ.-Prof. Dr.-Ing. Kai-Olaf Hinrichsen Prüfer der Dissertation: 1. Univ.-Prof. Dr. techn. Johannes A. Lercher 2. Univ.-Prof. Dr. mont. Dr. rer. nat. h. c. Ewald Werner Die Dissertation wurde am 22.12.2015 bei der Technischen Universität München eingereicht und durch die Fakultät für Chemie am 12.04.2016 angenommen. 天行健，君子以自强不息。地势坤，君子以厚德载物。 Heaven moving forward and forever, superior person shall accomplish excellence with perseverance. Earth featuring vast and grand, superior person shall embrace objects with virtues. ——《易经》 — Classic of Changes «Мне не нужны доказательства. Законы природы исключений не терпят и этим явно отличаются от правил и правильностей, подобных, например, грамматическим.» “I have no need of proof. The laws of nature, unlike the laws of grammar, admit of no exception.” — Дмитрий Иванович Менделеев — Dmitri Ivanovich Mendeleev 谨以本论文纪念我已故的外祖父母黄蕴璞先生（1921 ～ 1980）和姚同玉女士 （1922 ～ 2011）。 The present thesis is sincerely dedicated to the memory of my beloved maternal grandparents, Mr. Yunpu Huang (1921 ~ 1980) and Mrs. Prof. Tongyu Yao (1922 ~ 2011), who passed away too early to witness the completeness of my doctoral work. 彭博 Bo Peng 2015 年 8 月 August 2015 Acknowledgement First, my sincere appreciation is expressed to the supervisor of my doctoral work, Prof. Dr. Johannes A. Lercher. Thank you for offering me a position in your international research group and giving me the opportunity to work on challenging and interesting project. During these years, your warm encouragement and thoughtful guidance have always enlightened me. You taught me a lot not only with wisdom and knowledge, but also with maturity of conducting. I am very grateful to senior scientist Dr. Erika E. Ember. Thank you for your efforts on coordination of every project-related activity and correction of every project-related document. The discussions with you throughout my doctoral work, on the topics of science, food, religion and cat, are really memorable. Furthermore, thank you for all your helps during my adaptation to the culture of Central Europe. I am gratitude especially to your respect on cultural tradition from another continent. Inside the small team of “small molecule activation”, a close and successful collaboration has been made, owing to the efforts from everybody in the team. Dr. Anastasia V. Pashigreva, Dr. Jieli He, Claudia B. Himmelsbach, Navneet K. Gupta and Benjamin Felkel are acknowledged for their supports and inputs in my work. Senior members in Chair II of Chemical Technology, both scientific and non-scientific, are important for the smooth and efficient running of organization, supervision, administration, etc. Prof. Dr. Andreas Jentys, Prof. Dr. André van Veen, Prof. Dr. Chen Zhao, Dr. Oliver Y. Gutiérrez and Dr. Maricruz Sanchez are acknowledged for their scientific inputs. Franz-Xaver Hecht, Martin Neukamm and Andreas Marx are acknowledged for their technical supports. Stefanie Seibold, Helen Brenner, Heidemarie Hermann, Katharina Thies, Bettina Federmann, Karen Schulz and Ulrike Sanwald are acknowledged for their administrative helps. A friendly and cooperative circumstance is always positive for office and laboratory. Dr. Herui Dou, Dr. Jeongnam Kim, Dr. Luis F. Gonzalez-Peña, Dr. Yue Liu, Dr. Wenhao Luo, Dr. Hui Shi, Dr. Stefan Schallmoser, Dr. Maximillian W. Hahn, Murat Küçükdişli and Sebastian Müller are acknowledged for scientific discussions. Dr. Despina Tzoulaki, Dr. Yanzhe Yu, Dr. Sonja Wyrzgol, Dr. Baoxiang Peng, Dr. John Ahn, Dr. Sarah Maier, Dr. Christian Gärtner, Dr. Xianyong Sun, Dr. Stefanie Simson, Dr. Robin Kolvenbach, Dr. Yuchun Zhi, Dr. Nathan Hould, Daniela Hartmann, Jennifer Hein, Linus Schulz, Yuanshuai Liu, Edith Berger, Yu Lou and Marco Peroni are acknowledged for supportive helps in the lab. Dr. Lin Lin, Dr. Wenji Song, Dr. Udishnu Sanyal, Dr. Ricardo Bermejo de Val, Monica Markovits, Moritz Schreiber and Kai Sanwald are acknowledged for being good officemates. In an international research group, without going into details, all following colleagues in Chair of Chemical Technology II are acknowledged for sharing their time with me. Prof. Dr. Xuebing Li, Dr. Yongzhong Zhu, Dr. Roberta Olindo, Dr. Eszter Baráth, Dr. Márta Dömök, Dr. Elena Kondratieva, Dr. Vishnuvarthan Muthusamy, Dr. Yulia Martynova, Dr. Michael Salzinger, Dr. Tobias Förster, Dr. Sabine Scholz, Dr. Florian Schüßler, Dr. Ana Hrabar, Anna Lubinus, Eva Schachtl, Phillip Wallis, Elisabeth Hanrieder, Pamina Andrä, Sebastian Grundner, Tobias Berto, Sebastian Foraita, Stanislav Kasakov, Sebastian Eckestein, Manuel Wagenhofer, Martina Braun, Guoju Yang, Yang Song, Peter Hintermeier, Sylvia Albersberger, Matthias Steib, Daniel Melzer, Andreas Ehrmaier, Wanqiu Luo, Takaaki Ikuno and Ferdinand Vogelgsang together with our external members – visiting scholars, Prof. Dr. Gary Haller, Prof. Dr. Mirosław Derewiński, Prof. Dr. Xiangyun Guo, Dr. Rino Mukti and Dr. Bruno Dalla Costa, thank you all! External experimental supports from Division of Physical Chemistry and Chair I of Chemical Technology are acknowledged. Prof. Dr. Sebastian Günther, Dr. Florian Schweinberger, Dr. Robert Reichelt and Dr. Cornelia Ablasser, thank you for your contributions. I am impressed by your scientific and technical expertise as well as your patience during the time of my measurements. The work packages of INCAS project from European Commission are acknowledged for financial support and opportunity given to young scientists. The young scientists involved in INCAS project, Dr. Katia Barbera, Dr. Salvatore Abate, Dr. Christina Popa, Dr. Miguel Palomino, Leone Frusteri, Alejandro Prieto and Emila Kertalli, are especially appreciated for exchanging scientific ideas. The inputs from industrial partners, Prof. Dr. Leslaw Mleczko, Dr. Stefan Roggan, Dr. Stefan Grasser, Dr. Konstantinos Metaxas, Dr. René Bos, Dr. Herman Kuipers, Dr. Erik Abbenhuis and Dr. Eoghan McAlpine, are also acknowledged. During my work for doctoral thesis, I have obtained the supplementary supports from my students. They have transferred their talents and enthusiasms into their theses or internship works with me, being extra supports of my work. Dominik Göppert, Jialei Wu, Sandy Lama, Thilo Kögl, Kenny Yeo, Yizhou Shen, Karan Singh, Xaver Müller and Rasyiqa Mohd, thank you all for your contributions! Last but not least, I want to express my gratitude to my family for their ceaseless encouragements and supports. The scientific suggestion from my paternal grandfather Mr. Acad. Prof. Shaoyi Peng, the mental support and understanding from my parents and parents-in-law, Mr. Li Peng, Mrs. Xiaomu Huang, Mr. Brig. Prof. Qing Pan and Mrs. Xiaoqing Zhang are acknowledged. Finally, I am indebted to my dearest wife, Mrs. Yuan Pan, for the unconditional love, support, encouragement and understanding. I appreciated and will always cherish the time with you. Thank you! Bo Peng August 2015 Abstract Using a mechanistically guided approach, a two-step synthesis route of diphenyl carbonate has been developed, combining methanol carboxylation to dimethyl carbonate with its transesterification with phenol. The equilibrium constraints are overcome by the selective removal of water or methanol using novel zeolite modifications. The catalytic efficiencies of both steps have been advanced based on mechanistic insights gained from kinetic and spectroscopic studies. Zusammenfassung Unter Verwendung einer mechanistisch geführten Herangehensweise wurde eine zwei-stufige Syntheseroute von Diphenylcarbonat entwickelt, die über eine Carboxylierung von Methanol zum Dimethylcarbonat führt und dessen Umesterung mit Phenol die Reaktionssequenz abschließt. Die Gleichgewichtslimitierungen wurden durch selektive Abtrennung von Wasser oder Methanol mittels neuer Zeolithmodifikation überwunden. Die katalytische Effizienz beider Schritte wurde durch mechanistische Erkenntnisse weiterentwickelt, die aus kinetischen und spektroskopischen Untersuchungen gewonnen wurden. Table of contents Introduction .................................................................................................................. 1 1.1 Polycarbonates ......................................................................................................... 2 1.2 Brief history of PCs production ............................................................................... 2 1.3 Principal synthetic route for PCs production ........................................................... 3 1.4 Alternative pathways for sustainable PCs production ............................................. 5 1.4.1 Overview of possible routes........................................................................... 5 1.4.2 Catalytic DMC synthesis from methanol and CO2 ........................................ 9 1.4.3 Catalytic DPC synthesis from phenol and DMC ......................................... 12 1.4.4 Zeolites as solid state sorbents ..................................................................... 16 1.4.5 Molecular diffusion in zeolites .................................................................... 18 1.5 Main challenges and opportunities on sustainable DPC synthesis ........................ 19 1.6 Scope of the thesis ................................................................................................
Load more

Recommended publications
  • Reaction of Dialkyl Carbonates with Alcohols: Defining a Scale of the Best Leaving and Entering Groups*
    Pure Appl. Chem., Vol. 81, No. 11, pp. 1971–1979, 2009. doi:10.1351/PAC-CON-08-12-02 © 2009 IUPAC, Publication date (Web): 30 October 2009 Reaction of dialkyl carbonates with alcohols: Defining a scale of the best leaving and entering groups* Pietro Tundo1,2,‡, Fabio Aricò1,2, Anthony E. Rosamilia1, Maurizio Rigo1, Andrea Maranzana1,3, and Glauco Tonachini3 1Interuniversity Consortium “Chemistry for the Environment”, Via delle Industrie, 21/8 30175 Marghera, Venice, Italy; 2Department of Environmental Sciences, Ca’ Foscari University of Venice, Dorsoduro 2137-30123, Venice, Italy; 3Department of General Chemistry and Organic Chemistry, University of Torino, Corso Massimo D’Azeglio 48, I-10125 Torino, Italy Abstract: A series of dialkyl and methyl alkyl carbonates has been synthesized and their re- activity investigated. The behavior of preferential leaving and entering groups for the newly synthesized carbonates has been accurately investigated. Both experimental and computa- – – ≥ tional studies agreed that the scale of leaving groups follows the trend: PhCH2O , MeO – – – – – EtO , CH3(CH2)2O , CH3(CH2)7O > (CH3)2CHO > (CH3)3CO . Accordingly, the scale of the entering group has the same trend, with t-butoxide being the worst entering group. A preliminary attempt to rationalize the nucleofugality trends, lim- – – ited to the (CH3)3CO and CH3O groups, has indicated that a likely origin of the observed trends lies in the different entropic contributions and solvation effects. Keywords: computational studies; dimethyl carbonate; green chemistry; synthesis; theoreti- cal chemistry. INTRODUCTION Since the 1980s, when dimethyl carbonate (DMC) was synthesized for the first time using a green process [1], its exploitation both in industrial [2] and laboratory scale [3] has grown exponentially.
    [Show full text]
  • Environmentally-Friendly Synthesis of Carbonate-Type Macrodiols and Preparation of Transparent Self-Healable Thermoplastic Polyurethanes
    polymers Article Environmentally-Friendly Synthesis of Carbonate-Type Macrodiols and Preparation of Transparent Self-Healable Thermoplastic Polyurethanes Seon-Mi Kim 1,†, Seul-A Park 1,†, Sung Yeon Hwang 1,2, Eun Seon Kim 1, Jonggeon Jegal 1, Changgyu Im 3, Hyeonyeol Jeon 1,*, Dongyeop X. Oh 1,2,* ID and Jeyoung Park 1,2,* ID 1 Research Center for Bio-Based Chemistry, Korea Research Institute of Chemical Technology (KRICT), Ulsan 44429, Korea; [email protected] (S.-M.K.); [email protected] (S.-A.P.); [email protected] (S.Y.H.); [email protected] (E.S.K.); [email protected] (J.J.) 2 Advanced Materials and Chemical Engineering, University of Science and Technology (UST), Daejeon 34113, Korea 3 Department of Chemical Engineering, Hanyang University, Ansan 15588, Korea; [email protected] * Correspondence: [email protected] (H.J.); [email protected] (D.X.O.); [email protected] (J.P.); Tel.: +82-52-241-6324 (H.J.); +82-52-241-6316 (D.X.O.); +82-52-241-6315 (J.P.) † These authors contributed equally to this work. Received: 16 October 2017; Accepted: 29 November 2017; Published: 30 November 2017 Abstract: Carbonate-type macrodiols synthesized by base-catalyzed polycondensation of co-diols and dimethyl carbonate as an environmentally-friendly route were subsequently utilized for the preparation of transparent and self-healable thermoplastic polyurethanes (TPUs) containing a carbonate-type soft segment. Three types of macrodiols, obtained from mono, dual and triple diol-monomers for target molecular weights of 1 and 1.5 kg mol−1, were analyzed by 1H NMR integration and the OH titration value.
    [Show full text]
  • Method for Making Organic Carbonates
    Office europeen des brevets (fi) Publication number : 0 507 546 A2 @ EUROPEAN PATENT APPLICATION @ Application number : 92302826.0 © Int. CI.5 : C07C 69/96, C07C 68/00 (22) Date of filing : 31.03.92 (30) Priority: 01.04.91 US 678411 @ Inventor: King, Joseph Anthony, Jr. 927 Vrooman Avenue Schenectady, New York 12309 (US) @ Date of publication of application : Inventor : Faler, Gary Ray 07.10.92 Bulletin 92/41 34 St. Stephens Lane Scotia, New York 12302 (US) Inventor : Krafft, Terry Edward (S) Designated Contracting States : 7456 Parklane Road DE ES FR GB IT NL Longmont, Colorado 80503 (US) © Applicant : GENERAL ELECTRIC COMPANY @ Representative : Pratt, Richard Wilson et al 1 River Road London Patent Operation G.E. Technical Schenectady, NY 12345 (US) Services Co. Inc. Essex House 12/13 Essex Street London WC2R 3AA (GB) (54) Method for making organic carbonates. (57) A method for making diphenyl carbonate free of color bodies is provided by reacting an organic hydroxy compound, such as phenol with carbon monoxide and oxygen in the pre- sence of an effective amount of a palladium catalyst, in the form of a palladium material which is used in combination with a quaternary ammonium salt, an inorganic cocatalyst, such as cobalt diacetate and an organic cocatalyst such as benzophenone or 1,10-phenanthroline. Recycling of catalyst values is also provided. CM < CO 10 h- o 10 LU Jouve, 18, rue Saint-Denis, 75001 PARIS 1 EP 0 507 546 A2 2 Reference to Copending Applications Although the aforementioned methods for making organic carbonates are of interest because they do Reference is made to copending applications of not require the use of phosgene which is a toxic and T.C.T.
    [Show full text]
  • Umted States Patent [191 [111 4,139,721
    UmtedI States Patent [191 [111 4,139,721 Campbell [45] Feb. 13, 1979 [54] PROCESS FOR PREPARING DIPHENYL [56] References Cited HALOETHYLENES us. PATENT DOCUMENTS ' 3,247,265 4/ 1966 Speziale et a1. ........... .. 260/613 R X [75] Inventor: John R. Campbell, Clifton Park, NY. 3,642,910 2/ 1972 Holan ......................... .. 260/613 R ‘ 3,663,602 5/1972 Steinxnann .... .. 260/613 R X 3,760,007 9/1973 Steinmann .... .. 260/613 R X [73] Assignee: General Electric Company, 3,991,120 11/1976 Ladd ....... .. .. 260/613 R Schenectady, N_y_ 4,073,814 2/1978 Kinson et a1. .. 568/726 Primary Examiner-Bernard Helf _ Attorney, Agent, or Firm-Joseph T. Cohen; Charles T. [21] Appl. No.. 901,515 watts 22 Fl (1 M 1 1978 [57] ABS Cr [ 1 1e ' 8y ' Diphenyl chloroethylenes are prepared by the reaction of either phenol or anisole with a trihaloethylene com [51] Int. C1.2 ..................... .. C07C 37/00; C07C 41/00 pound. [52] US. Cl. ................................ .. 568/641; 568/726 , V [58] Field of Search ................... .. 568/726; 260/613 R 10 Claims, No Dt-awings 4,139,721 1 2 is obtained in acceptable yield by this route, substantial PROCESS FOR PREPARING DIPHENYL amounts of by-products are obtained in the form of the - HALOETHYLENES ortho, para-isomer (two stereoisomers) of the formulas This invention is concerned with a process for pre paring diphenyl haloethylenes. More particularly, the (V) invention is concerned with a process for making a ', diphenyl haloethylene compound of the general for~ ' and .' mula Cl-C-H 01-] 15 HQ“ which comprises effecting reaction between an aryl compound of the general formula In addition to these ortho, para-isomers having possible 20 harmful effects on polymers made from the para, para isomer, this process also uses an expensive starting ma terial, namely, the dichloroacetaldehyde diethylacetal that is not readily available at present.
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 7,687,595 B2 Brunelle Et Al
    USOO7687595 B2 (12) United States Patent (10) Patent No.: US 7,687,595 B2 Brunelle et al. (45) Date of Patent: Mar. 30, 2010 (54) SULFONATED TELECHELIC (58) Field of Classification Search ................... 528/86, POLYCARBONATES 528/171, 196, 198, 199, 373 See application file for complete search history. (75) Inventors: Daniel J. Brunelle, Burnt Hills, NY (US); Martino Colonna,s Bolognas (IT): (56)56 Refeeees Citede Maurizio Fiorini, Anzola Emilia (IT): U.S. PATENT DOCUMENTS Corrado Berti, Lugo (IT). Enrico 5,162.405 A 1 1/1992 Macleay et al. Binassi, Bologna (IT) 5,412,061 A 5/1995 King, Jr. et al. 5,644,017 A 7/1997 Drumright et al. (73) Assignee: SABIC Innovative Plastics IP B.V., 5,650,470 A 7/1997 McCloskey et al. Bergen op Zoom (NL) 5,807,962 A 9/1998 Drumright et al. 6,303,737 B1 10/2001 Lemmon et al. (*) Notice: Subject to any disclaimer, the term of this 6,323,304 B1 1 1/2001 Lemmon et al. patent is extended or adjusted under 35 6,376,640 B1 4/2002 Lemmon et al. U.S.C. 154(b) by 197 days. 6,930,164 B1 8, 2005 Brunelle et al. 2003, OOSO427 A1 3/2003 Brunelle et al. (21) Appl. No.: 11/834,417 Primary Examiner Terressa M Boykin (22) Filed: Aug. 6, 2007 (57) ABSTRACT (65) Prior Publication Data A sulfonated telechelic polycarbonate is described which is US 2009/OO43071 A1 Feb. 12, 2009 produced by melt synthesis. A dihydroxy compound is reacted with a sulfobenzoic acid salt, then with an activated (51) Int.
    [Show full text]
  • Diphenyl Carbonate Cas N°: 102-09-0
    OECD SIDS DIPHENYL CARBONATE FOREWORD INTRODUCTION DIPHENYL CARBONATE CAS N°: 102-09-0 UNEP PUBLICATIONS 1 OECD SIDS DIPHENYL CARBONATE SIDS Initial Assessment Report For SIAM 19 19–22 October 2004, Berlin, Germany 1. Chemical Name: Diphenyl carbonate 2. CAS Number: 102-09-0 3. Sponsor Country: Germany Contact Point: BMU (Bundesministerium für Umwelt, Naturschutz und Reaktorsicherheit) Contact person: Prof. Dr. Ulrich Schlottmann Postfach 12 06 29 D- 53048 Bonn 4. Shared Partnership with: 5. Roles/Responsibilities of the Partners: • Name of industry sponsor Bayer AG, Germany /consortium Contact person: Dr. Burkhardt Stock D-51368 Leverkusen Building 9115 • Process used The BUA Peer Review Process : see next page 6. Sponsorship History • How was the chemical or by ICCA-Initiative category brought into the OECD HPV Chemicals Programme ? 7. Review Process Prior to last literature search (update): the SIAM: 13 April 2004 (Human Health): databases medline, toxline; search profile CAS-No. and special search terms 18 March 2004 (Ecotoxicology): databases CA, biosis; search profile CAS-No. and special search terms 8. Quality check process: As basis for the SIDS-Dossier the IUCLID was used. All data have been checked and validated by BUA. A final evaluation of the human health part has been performed by the Federal Institute for Risk Assessment (BfR) and of the ecotoxicological part by the Federal Environment Agency (UBA). UNEP PUBLICATIONS 2 OECD SIDS DIPHENYL CARBONATE 9. Date of Submission: Deadline for circulation: 23 July 2004 10. Date of last Update: Last literature search: IUCLID Chapters 1-4: 2003-10-08 Chapter 5: 2004-01-22 11.
    [Show full text]
  • Development and Industrialization of a Novel Process for Polycarbonate Production from CO2 Without Using Phosgene
    Polymer Journal, Vol. 39, No. 2, pp. 91–114 (2007) #2007 The Society of Polymer Science, Japan AWARD ACCOUNTS: SPSJ AWARD (2005) Green and Sustainable Chemistry in Practice: Development and Industrialization of a Novel Process for Polycarbonate Production from CO2 without Using Phosgene y Shinsuke FUKUOKA,1; Masahiro TOJO,2 Hiroshi HACHIYA,3 Muneaki AMINAKA,3 and Kazumi HASEGAWA3 1New Business Development, Asahi Kasei Corporation, Kojima-Shionasu, Kurashiki 711-8510, Japan 2Central Research & Development Laboratories, Asahi Kasei Corporation, 2-1 Samejima, Fuji 416-8501, Japan 3Technology Licensing Department, Asahi Kasei Chemicals Corporation, Kojima-Shionasu, Kurashiki 711-8510, Japan (Received October 27, 2006; Accepted November 22, 2006; Published January 16, 2007) ABSTRACT: This review focuses on the world’s first process succeeded in development and industrialization by 1 Asahi Kasei Corp. for producing an aromatic polycarbonate (PC) using CO2 as starting material. The carbonate group of PC links directly to the residual aromatic groups of the bisphenol. Until Asahi Kasei’s new process is revealed, all of carbonate groups of PC in the world were derived from CO as starting material. Furthermore, more than about 90% of PC has been produced by so-called ‘‘phosgene process’’, and the PC contains Cl-impurities. It needs to use not only highly toxic and corrosive phosgene made from CO and Cl2 as a monomer, but also very large amounts of CH2Cl2 and water, and needs to clean a large amount of waste water. The new process enables high-yield production of the two products, Cl-free and high-quality PC and high-purity monoethylene glycol (MEG), starting from ethylene oxide (EO), by-produced CO2 and bisphenol-A.
    [Show full text]
  • Biodegradation of Bisphenol-A Polycarbonate Plastic by Pseudoxanthomonas Sp
    Journal of Hazardous Materials 416 (2021) 125775 Contents lists available at ScienceDirect Journal of Hazardous Materials journal homepage: www.elsevier.com/locate/jhazmat Research Paper Biodegradation of bisphenol-A polycarbonate plastic by Pseudoxanthomonas sp. strain NyZ600 Wenlong Yue a, Chao-Fan Yin a, Limin Sun b, Jie Zhang b, Ying Xu a, Ning-Yi Zhou a,* a State Key Laboratory of Microbial Metabolism, Joint International Research Laboratory of Metabolic & Developmental Sciences, and School of Life Sciences & Biotechnology, Shanghai Jiao Tong University, Shanghai 200240, China b Instrumental Analysis Center, Shanghai Jiao Tong University, Shanghai 200240, China ARTICLE INFO ABSTRACT Editor: Dr. Shaily Mahendra Bisphenol-A polycarbonate (PC) is a widely used engineering thermoplastic and its release has caused damage to the ecosystem. Microbial degradation of plastic represents a sustainable approach for PC reduction. In this study, Keywords: a bacterial strain designated Pseudoxanthomonas sp. strain NyZ600 capable of degrading PC was isolated from Bisphenol-A polycarbonate activated sludge by using diphenyl carbonate as a surrogate substrate. Within a 30-day period of incubating with Biodegradation strain NyZ600, PC films were analyzed with atomic force microscopy, scanning electron microscope, water PC contact angle, X-ray photoelectron spectroscopy, fourier transform infrared spectroscopy, differential scan Plastic waste Depolymerization calorimeter and thermogravimetric analysis technique. The analyses results indicated that the treated PC films were bio-deteriorated and formed some “corrosion pits” on the PC film surface. In addition, strain NyZ600 performed broad depolymerization of PC indicated by the reduction of Mn from 23.55 to 16.75 kDa and Mw from 45.67 to 31.97 kDa and two degradation products bisphenol A and 4-cumylphenol (the two monomers of PC) were also found, which established that PC were biodegraded by strain NyZ600.
    [Show full text]
  • As a Platform Molecule for the Synthesis of Different
    www.nature.com/scientificreports OPEN From D-sorbitol to fve-membered bis(cyclo-carbonate) as a platform molecule for the synthesis of Received: 19 March 2018 Accepted: 31 May 2018 diferent original biobased Published: xx xx xxxx chemicals and polymers Pierre Furtwengler & Luc Avérous Bis(cyclo-carbonate) was successfully synthesized from D-sorbitol (Sorb-BisCC) through an environmentally friendly process with dimethyl carbonate (DMC) as a reactant. In agreement with green chemistry principles, solvent free reactions were catalyzed and took place at low temperature. The reaction yield was increased until 50%, with the use of 1.3.5-triazabicyclo[4.4.0]dec-5-ene as catalyst and a continuous DMC feed to limit the side-reactions or the loss of reactant by azeotropic fux with a reactional subsidiary product. The obtained Sorb-BisCC is a remarkable platform molecule which could compete with others polycyclic platform molecules (isosorbide). Sorb-BisCC can be e.g., used to synthesize diferent chemicals such as short and long polyols, or novel biobased non- isocyanate polyurethanes (NIPU). Two Sorb-BisCC molecules have been coupled to obtain novel cyclic diols with pendant side chains. Polyether polyols were also obtained by anionic ring opening polymerization. According to the synthesis conditions, these synthetized polyether polyols range from partially to highly cross-linked materials. Finally, NIPU were synthesized with short and biobased fatty diamines. These diferent modifcations and synthesis highlight the versatility of the Sorb-BisCC and demonstrated its high potential as building block. Sorb-BisCC can be considered as a platform molecule to open the way to diferent original and biobased chemical architectures.
    [Show full text]
  • MSDS Vivak.Pdf
    A & C Plastics, Inc. Phone Numbers Email Addresses 6135 Northdale Sales: 713.645.4915 [email protected] Houston, TX Fax: 1.800.627.5899 [email protected] 77087-5095 Toll Free: 1.800.231.4175 VIVAK Material Safety Data SheetMaterial Safety Data Sheet Vivak Copolyester Sheet Service. It’s what we deliver. Pg. 1 1.800.231.4175 www.acplasticsinc.com VIVAK Material Safety Data Sheet 3. HAZARDS IDENTIFICATION (Continued) --------------------------------------- ROUTE(S) OF ENTRY..................: Inhalation; Skin Contact; Eye Contact HUMAN EFFECTS AND SYMPTOMS OF OVEREXPOSURE: ACUTE EFFECTS OF EXPOSURE.....: Material is a non-reactive solid. Mechanical irritation (i.e. abrasion) to the eyes may occur due to exposure to fines. Eyes may become red and scratchy and may tear. NOTE: Gases and fumes evolved during the thermal processing or decomposition of this material may irritate the eyes, skin or respiratory tract. At recommended processing conditions, the primary fume constituents evolved are water, carbon dioxide (CO2), diphenyl carbonate, and monochlorobenzene. CHRONIC EFFECTS OF EXPOSURE...: None known CARCINOGENICITY NTP.........................: Not listed as a carcinogen IARC........................: Not listed as a carcinogen OSHA........................: Not listed as a carcinogen MEDICAL CONDITIONS AGGRAVATED BY EXPOSURE......: None known EXPOSURE LIMITS...............: For product fines, the OSHA-PEL for nuisance dust of 15 mg/m3 total dust, 5 mg/m3 respirable dust is recommended. In addition, the ACGIH-TLV for Particulates Not Otherwise Classified (PNOC) of 10 mg/m3 is recommended. Observe a more stringent limit for product fines if applicable. Refer to section 2 for any other applicable exposure limits. At temperatures above decomposition (716 F (380 C)), phenol and other chemicals listed in the hazardous decomposition products can be generated.
    [Show full text]
  • Synthesis and Trans-Ureation of N,N'-Diphenyl-4, 4
    J Polym Res (2012) 19:9754 DOI 10.1007/s10965-011-9754-8 ORIGINAL PAPER Synthesis and trans-ureation of N,N’-diphenyl-4, 4′-methylenediphenylene biscarbamate with diamines: a non-isocyanate route (NIR) to polyureas Hsueh-Yung Chen & Wen-Chen Pan & Chao-Hsing Lin & Chun-Ying Huang & Shenghong A. Dai Received: 25 May 2011 /Accepted: 25 August 2011 /Published online: 22 February 2012 # Springer Science+Business Media B.V. 2012 Abstract A non-isocyanate route (NIR) of making polyureas Keywords Non-isocyanate route . Trans-ureation . of high molecular weight has been found through trans- Polyurea . N,N’-diphenyl-4,4′-methylenediphenylene ureation of N,N’-diphenyl-4,4′-methylenediphenylene biscar- biscarbamate . N,N’-dimethyl-4,4′-methylenediphenylene bamate (4,4′-DP-MDC) with a variety of diamines and mixed biscarbamate . Diphenyl carbonate diamines. The preparation of 4,4′-DP-MDC was achieved readily by carbonylation of 4,4′-methylenedianiline (4,4′- MDA) with diphenyl carbonate (DPC) using organic acids as catalysts. It was found that the highest yield (99%) of pure Primary intermediate synthesized Specifications Abbreviation 4,4′-DP-MDC can be isolated in a toluene solution under mild N,N’-diphenyl-4,4′- Mw:438.47 4,4′-DP-MDC conditions co-catalyzed by benzoic acid and tertiary amine. methylenediphenylene ′ biscarbamate Trans-ureation of 4,4 -DP-MDC with aliphatic amines indi- N,N’-dimethyl-4,4′- Mw:314.34 4,4′-DM-MDC cated that the process is a highly solvent dependent process methylenediphenylene and was found to be extremely facile in dimethyl sulfoxide biscarbamate ′ (DMSO) at 80 °C and in tetramethylene sulfone (TMS) at 4,4 -diphenylmethanebis- Mw:372.42 [DPMHU] [(2-hydroxyethyl)urea] 140 °C in absence of any catalyst.
    [Show full text]
  • Immunotoxicity and Allergic Potential Induced by Topical Application of Dimethyl Carbonate (DMC) in a Murine Model
    HHS Public Access Author manuscript Author Manuscript Author ManuscriptJ Immunotoxicol Author Manuscript. Author Author Manuscript manuscript; available in PMC 2015 November 19. Published in final edited form as: J Immunotoxicol. 2013 ; 10(1): 59–66. doi:10.3109/1547691X.2012.691124. Immunotoxicity and allergic potential induced by topical application of dimethyl carbonate (DMC) in a murine model Stacey E. Anderson, Jennifer Franko, Katie L. Anderson, Albert E. Munson, Ewa Lukomska, and B. Jean Meade National Institute for Occupational Safety and Health (NIOSH), Morgantown, WV, USA Abstract Dimethyl carbonate (DMC) is an industrial chemical, used as a paint and adhesive solvent, with the potential for significant increases in production. Using select immune function assays, the purpose of these studies was to evaluate the immunotoxicity of DMC following dermal exposure using a murine model. Following a 28-day exposure, DMC produced a significant decrease in thymus weight at concentrations of 75% and greater. No effects on body weight, hematological parameters (erythrocytes, leukocytes, and their differentials), or immune cell phenotyping (B- cells, T-cells, and T-cell sub-sets) were identified. The IgM antibody response to sheep red blood cell (SRBC) was significantly reduced in the spleen but not the serum. DMC was not identified to be an irritant and evaluation of the sensitization potential, conducted using the local lymph node assay (LLNA) at concentrations ranging from 50–100%, did not identify increases in lymphocyte proliferation. These results demonstrate that dermal exposure to DMC induces immune suppression in a murine model and raise concern about potential human exposure and the need for occupational exposure regulations.
    [Show full text]