DOCSLIB.ORG

Synthesis and Trans-Ureation of N,N'-Diphenyl-4, 4

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read 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. Particularly, the most DMSO/80 effective polymerization process was developed using tetra- methylene sulfone (TMS) as the solvent under reduced pres- sure for concurrently distilling off phenol from the reaction mixture during the polymerization in a shifting equilibrium Introduction towards polyurea. However, this solvent-assisted trans- ureation was found to be in-efficient when N,N’-dimethyl- Polyurea and polyurea elastomers have been known to 4,4′-methylenediphenylene biscarbamate (4,4′-DM-MDC) possess many outstanding mechanical properties. Since intro- was used in a similar condition for comparison. Thus, an duced commercially in the 1970s, polyurea elastomers have efficient green-chemistry process has been developed based been widely applied in polyurethane-urea reaction injection on 4,4′-DP-MDC in making urea prepolymers, urea elasto- molding (RIM) processes [1–5] and spray-coating systems mers and urea plastics all in excellent yields without using [6–8] to harness their fast polymerization rates and outstand- reactive methylenediphenylene diisocyanate (MDI) or any ing mechanical properties. Currently, two important polyurea catalysts in the trans-ureation polymerizations. commercial markets are automotive and construction applica- tions [9–12]withfamiliarfinishedproductssuchasbumpers, fascia, waterproofing linings, thermal insulation materials, : : : : industrial flooring and sports facilities. However, due to the H.-Y. Chen W.-C. Pan C.-H. Lin C.-Y. Huang S. A. Dai (*) high reaction rates of diisocyanates such as methylenedipheny- Department of Chemical Engineering, lene diisocyanate (MDI) and diamines, the synthesis and pro- National Chung-Hsing University, Taichung, Taiwan cessing of polyurea and polyurea elastomers have been heavily e-mail: [email protected] dependent upon the assistance of RIM-machine or high- Page 2 of 11 H. Chen et al. pressure mixing equipments. Synthesis of polyureas in bulk polyureas in nature, high cost of di-tert-butyl tricarbonate and through more controllable step-wise manners has rarely been carbonyl biscaprolactam seems limiting their wide-spread reported and will be highly prized for polyurea formulation applications. development [13–16]. If the synthesis of polyurea can com- Since the 1980s, biscarbamates of methylenediphenylene pletely avoid using diisocyanates such as MDI or toluene diisocyanate (MDI) such as 4,4′-DM-MDC or N,N’-diethyl- diisocyanate (TDI) as the raw materials, it would become 4,4′-methylenediphenylene biscarbamate (4,4′-DE-MDC) have even more attractive because of the elimination of highly toxic been touted as the most important precursors for non-phosgene and reactive diisocyanates in the overall synthetic scheme. synthesis of MDI [21–23]. These bis-carbamates are synthesized (Scheme 1) by the condensation of mono-phenylcarbamate (Scheme 1)with Recently, non-isocyanate synthesis of polyurea and formalin. The mono-phenylcarbamates were prepared by oxida- polyurethanes has been explored with reactions of diamines tive carbonylations of aniline (Asahi’ Process) or reductive with new intermediates. For example, Meijer used di-tert-butyl carbonylation (ARCO’sProcess)ofnitro-benzene.Boththese tricarbonate and diamine terminated poly(tetrahydrofuran) as carbonylations involved carbon monoxide and precious metal raw materials for making thermoplastic elastomers (TPEs) [17, catalyses. However, high dilution and high temperature thermol- 18] of urea segmented block copolymers. Another approach for ysis of biscarbamates in excess of 250 °C are both required for preparing polyureas without isocyanate chemistry was reported MDI generation. As a consequence, those severe conditions in Mtilhaupt’s studies [19, 20] where a carbonyl biscaprolactam make the overall process unattractive due to energy cost, safety served as a non-halogen building block that could convert the concerns and process difficulties. Except for isophorone diiso- terminal amine-groups of functional polymers into the cyanate (IPDI) productions, no commercial diisocyanates (MDI corresponding caprolactam-blocked isocyanates. Although or TDI) has been diverted to the biscarbamate process so far [24, these approaches appear to be non-isocyanate processes to 25]. Therefore, non-phosgene routes (NPR) to diisocyanates NH2 NO2 O aniline nitrobenzene + H H Pd/NaI formaldehyde Pt.Se NHCOOCH3 H2N NH2 4,4'-methylenedianiline N-methyl phenylcarbamate O O O + + O H H diphenyl carbonate formaldehyde O O O O H C CH O N N O 3 O N N O 3 H H H H N,N'-diphenyl-4,4'-methylene diphenylcarbamate(4,4'-DP-MDC) N,N'-dimethyl-4,4'-methylene diphenylcarbamate(4,4'-DM-MDC) pyrolysis non-isocyanate route to polyurea non-isocyanate route to polyurea O O O O R R N N N N OCN NCO N N N N n H H H H H H H H n polyurea 4,4'-methylenediphenyl diisocyanate polyurea high molecular weights low molecular weights excellent mechanical performance O O O O R R O N N O N N N N n H H H H H H n polyurethane polyurea Scheme 1 Overall scheme of NIR route to polyurea. (The solid-line portions are carried out successfully in the study) Non-Isocyanate Route (NIR) to Polyurea through DP-MDC Page 3 of 11 such as MDI or TDI have remained a long-term un-met goal yet Since improved synthesis for 4,4′-DP-MDC from car- to be achieved in the polyurethane/urea fields. bonylation reaction of 4,4′-methylenedianiline (4,4′-MDA) However, in a non-isocyanate route (NIR) to polyurea, with diphenyl carbonates have been accomplished recently the approach based on MDI-biscarbamates seems promising by Harada’s[33]andbyBosetti’s[34]studies,wehave because no high-temperature condition is required through initiated a feasibility study of NIR-polyurea process using trans-esterification or trans-ureation. In fact, several attempts 4,4′-DP-MDC and 4,4′-DM-MDC as key intermediates to have tried to use carbamates, or biscarbamates directly as react with diamines. Our present study has established precursors for polyurethane (PU) and polyurea synthesis that there are tremendous advantages of using 4,4′-DP- bypassing isolation of diisocyanate completely [26]. In MDC over 4,4′-DM-MDC in trans-ureation reaction in 2000, ring-opening isomerization of cyclic-urethane [27–29] making polyurea. Our results show that the polymeriza- and trans-esterification [30, 31] to make PU are notable exam- tion using 4,4′-DP-MDC and diamines can lead to high ples. However, both produce low molecular weight polymers. molecular weight polyurea in dimethyl sulfoxide (DMSO) Metal or Lewis acid catalyzed trans-esterifications of diols and or tetramethylene sulfone (TMS). This NIR trans- diamines with biscarbamates also have been studied in recent ureation process is efficient and is achieved in absence reports with some success [32]. of any catalyst. Experimental section Materials and reagents Materials and reagents Specifications Suppliers Abbreviation Concentrated hydrochloric acid 37% Tedia Con. HCl Formaldehyde 37% Tedia – 1,6-Hexanediamine analytical grade Acros 1,6-HDA m-Xylylenediamine analytical grade TCI m-XDA Isophorondiamine analytical grade Acros IPDA 4,4′-Diaminodicyclohexylmethane analytical grade Alfa H12MDA 4,4′-Methylenedianiline analytical grade Acros 4,4′-MDA 2-Aminoethanol analytical grade Tedia AE Tetramethylene sulfone analytical grade Acros TMS Dimethyl sulfoxide HPLC grade Tedia DMSO Amine terminated PPG-2000 Jeffamine D-2000, Mw: 2000 Huntsman PPG-DA-2000 Amine terminated PPG-230 Jeffamine D-230, Mw: 230 Huntsman PPG-DA-230 Polyether diamine based on a predominantly PEG backbone Jeffamine ED-2003, Mw: 2000 Huntsman PEG-DA-2000 1,8-Diamino-3,6-dioxaoctane Jeffamine EDR-148, Mw: 148 Huntsman DADO N-Methyl-2-pyrrolidinone analytical grade Mallinckrodt NMP Diphenyl carbonate analytical grade Acros DPC Pyridine analytical grade Tedia – 1,4-diazabicycle[2, 2, 2]octane
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]
  • 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]
  • Download This Article PDF Format
    RSC Advances View Article Online PAPER View Journal | View Issue Highly effective transformation of methyl phenyl carbonate to diphenyl carbonate with recyclable Pb Cite this: RSC Adv.,2019,9,20415 nanocatalyst† Songlin Wang,ab Hongying Niu,a Jianji Wang,b Tong Chen, *c Gongying Wangc and Jiamin Zhanga Diphenyl carbonate (DPC) is a type of versatile industrial chemical, and the disproportionation of methyl phenyl carbonate (MPC) is a key step to produce DPC. However, the design and formulation of a catalyst for the efficient synthesis of DPC is a major challenge due to its small equilibrium constant. The support material is a critical factor influencing the performance of Pb nanocatalysts. Thus, a series of Pb-based catalysts over MgO, ZrO2, SiO2, TiO2 and Al2O3 were prepared to investigate the effect of the support materials on the physicochemical properties and catalytic performances for the conversion of MPC to effectively synthesize DPC. The catalysts were well characterized by XRD, BET, TEM, XPS, ICP-OES, H2- Creative Commons Attribution 3.0 Unported Licence. TPR, Py-IR and NH3-TPD. The results showed that the nature of the support obviously affected the structural properties and catalytic performances, and Pb was dispersed better on SiO2, TiO2, ZrO2 and MgO than on Al2O3, and showed stronger metal-support interaction over MgO and ZrO2. The activity results revealed that PbO/MgO and PbO/ZrO2 exhibited higher catalytic activities because they contained higher Pb dispersion and more Lewis acid sites, and the catalytic activities followed the order PbO/MgO > PbO/ZrO2 > PbO/SiO2 > PbO/Al2O3 > PbO/TiO2. On the contrary, PbO/MgO and PbO/ZrO2 Received 24th May 2019 exhibited better reusability due to strong interaction between the highly dispersed Pb and the supports, Accepted 12th June 2019 and the activity decrease in the case of PbO/SiO2, PbO/Al2O3 and PbO/TiO2 mainly resulted from the Pb DOI: 10.1039/c9ra03931g leaching loss.
    [Show full text]