United States Patent Office E

Total Page:16

File Type:pdf, Size:1020Kb

United States Patent Office E Unitede States- Patent- Office 3,845,059E. 1. 2 The reaction of biuret with diethanolamine to form PREPARATION OF N,N'-DIETHANOL3,845,059 PIPERAZINE N,N'-diethanol piperazine can be illustrated as follows: Alvin F. Beale, Jr., Lake Jackson, Tex., assignor to The Dow Chemical Company, Midland, Mich. 2(HOCH)NH -- NH2CONHCONH --> No Drawing. Filed June 19, 1972, Ser. No. 264,704 5 CHO Int, C. C07d51/70 U.S. C. 260-268. SY 8 Claims /N al-woman-mamm CH, CH, ABSTRACT OF THE DISCLOSURE + 2CO. 1 + 8NHat Diethanolamine is reacted with urea or a urea pyrol- lo Y yzate (e.g. biuret, triuret, or cyanuric acid) to form N,N'-diethanol piperazine. The following chart illustrates the balanced stoichiom BACKGROUND OF THE INVENTION la etry for reacting diethanolamine with urea, biuret, triuret, N,N'-diethanol piperazine has been previously prepared and cyanuric acid. Reaction products Moles of Empirical Moles N,N'- Moles of formula of of diethanol Moles Moles (HOCH)NH Name of reactant reactant reactant piperazine of Co2 of NH3 2---------------------- Urea------------------------ CHNO 2 2 4. 2- ---. Biuret---. C2HNO2 2 3 6-- --- Triuret.----- ... C3HNO3 2 3. 6 8 6.----- ... Cyanuric aci - C3H3NO3 2 3. 6 6 by the condensation of piperazine with ethylene chloro- The reaction has been found to be specific for dieth hydrin as reported in J. Am. Chem. Soc., Vol. 55, p. 3823 anolamine since analogous dialkanolamines do not give (1933). The compound has been reported to have phar- corresponding dialkanol-substituted cyclic structures con macological properties as an anesthetic or sedative in 30 taining nitrogens within a carbon ring. Heterocyclic Compounds, Vol. 6, published by John The reaction of diethanolamine with reactants urea, Wiley & Sons, Inc. of New York. biuret, triuret, or cyanuric acid may be carried out using SUMMARY OF THE INVENTION only one of said reactants or may be a combination of two or more of said reactants. It has now been found that N,N-diethanol piperazine 3.5 The reaction may be carried out in an inert solvent is efficiently and inexpensively prepared by reacting di- or diluent or may be carried out using an excess of the ethanolamine with urea or a urea pyrolyzate. diethanolamine as the reaction medium. Urea pyrolyzates are obtained by thermally condensing When excess diethanolamine is employed as the reac urea to form, principally, biuret, triuret, and/or cyanuric tion medium, it can be cycled back to the reactor and em acid; ammonia is driven off as the urea condenses. Other ployed along with make-up diethanolamine and fresh cyclic urea pyrolyzates (besides cyanuric acid) such as urea or urea pyrolyzate added. When an inert carrier or isocyanuric acid, ammelide, ammeline, etc. are also pre- solvent is employed as the reaction medium, it can be pared by autocondensation of urea. The thermal con- re-cycled back to the reactor after the product is sub densing of urea to form pyrolyzates is a well known re stantially removed. action and requires no further description herein. In 45 It will be understood by persons skilled in the art that Chemical Reviews, Vol. 56, pp. 95-197, there is a review inert carriers useful in the present invention may be sol titled "Biuret and Related Compounds” by Frederick vents for either the diethanolamine or the urea (or urea Kurzer which describes the condensation of urea to biuret pyrolyzates) or both. They may also be solvents for the and other compounds. 50 desired product (viz., N,N'-diethanol piperazine). It is also easily understood that the solubilizing ability of an DETALED RESSESN OF THE inert carrier will usually vary with the temperature. It is advisable to perform the present process in a medium in The reaction of urea with diethanolamine to form which the desired product is easily precipitated while N,N'-diethanol piperazine can be stoichiometrically illus- keeping the reactants in a non-precipitated state. Inert trated by the following balanced equation: 55 liquids which are not solvents for the reactants or the desired product may be employed as the reaction medi 2(HOCH)NH -- 2NH2CONH - um, but are not preferred. CHO . The reaction product, N,N'-diethanol piperazine, is easily precipitated from the reaction solution by cooling /S 60 or by adding a non-solvent which is miscible with the pH, (H, 2CO 4N reaction solvent, depending on the situation. Preferably, CH, CH -- f -- s the reaction is carried out in a medium in which the re N/ actants are soluble, but in which the desired product (di N ethanol piperazine) will precipitate when formed or when CEO cooled, - - - - - 3,845,059 3 4. The ratio of the reactants to each other is not critical the mixture was cooled and it was filtered out and washed as the reaction proceeds according to the stoichiometrical with acetone. The dried ppt. weighed 1 lb. 12 oz. and equation illustrated hereinbefore. Ordinarily an excess of was analyzed as N,N'-diethanol piperazine. The yield is the diethanolamine is employed, either because the di calculated as about 61% (theoretical). ethanolamine is to serve as the reaction medium or be cause it is usually more soluble, in whatever reaction EXAMPLE 3 medium is used, than the urea (or urea pyrolyzate) or The filtrate from Example 2 above (12 lbs., 3 oz.) was the desired product. This helps in separating the product mixed with 1 lb. 7 oz. of tetraethylene glycol dimethyl from residual diethanolamine. It is best to select condi ether, 1 lb. 3 oz. of urea, and 2 lb. 2 oz. of diethanolamine. tions in which all the urea or urea pyrolyzate is con The mixture was heated under a N purge, with stir sumed, thus simplifying the purification of the product. 10 ring, at 135 C. for 24 hours, then at 145 C. for 19 As the reaction progresses, CO and NH3 are evolved hours. The mixture was cooled, the precipitate was filtered and released from the reaction. An inert gas purge or out, washed with acetone, dried and found to weigh 1 lb. sparge may be employed to speed the release of CO2 and 6 oz. It was analyzed as N,N'-diethanol piperazine. The NH3. Reduced pressure may also be employed in some 5 yield is calculated as about 79.5% (theoretical). instances to speed the release of the CO2 and NH3 from EXAMPLE 4 the reaction. , Even though the reaction will proceed at sub-atmos A stirred mixture of 105 gms. of diethanolamine and pheric, atmospheric, or super-atmospheric pressures, at 60 gms. of urea was heated under a N purge at 150 C. mospheric pressures are preferably employed for econom for about 7 hours. During this time the evolving NH ic reasons and also to provide for easy purging of the 20 was passed through an acid scrubber and was sufficient to evolved CO2 and NH3. Super-atmospheric pressures re neutralize 225 ml. of 7.6N HSO4. tard the release of CO2 and NH from the reaction mix The mixture was cooled and 100 ml. of triethylene gly ture, thus are not preferred. col dimethyl ether was added. The precipitate was filtered As will be readily apparent to those skilled in the art, out and washed with acetone. The amount of dried prod the vapors and gasses leaving the reactor can be easily 25 uct obtained (N,N'-diethanol piperazine) represented a trapped by conventional methods either for re-cycling or 15%' yield (theoretical). for preventing contamination of the ambient atmosphere. Broadly speaking the reaction can be carried out at EXAMPLE 5 temperatures ranging from about 70° C. to about 268 30 A stirred mixture of 130 gms. of diethanolamine and C. (the boiling point of diethanolamine). At 70° C. the 60 gms. of urea was heated under a N purge at 150 C. reaction is very slow and it would take many days to get for 8 hours. During this time the evolving NH neutralized an appreciable yield of desired product. For best opera 235 ml. of 7.6N HSO4 in a scrubber. After cooling, tion, a range of about 110-175 C., preferably about 50 ml. of triethylene glycol dimethyl ether was added, 130-165 C. should be used for urea, biuret, and triuret. the precipitate was filtered out, washed with acetone, The reaction proceeds as slower rates at lower tempera and dried. The dried ppt., analyzed as N,N'-diethanol tures; at higher temperatures the reaction is accelerated piperazine, weighed 24.5 gms. which was about 28% but the tendency to form undesirable side-products is also yield (theoretical). encountered. EXAMPLE 6 When cyclic urea pyrolyzates, such as cyanuric acid, 4. In similar manner to the above Example 5, 158 gms. are used in the reaction, the temperature should be main of diethanolamine and 60 gms. of urea were reacted at tained in the range of about 165-265 C., and prefer 50° C. for 22 hrs. with 255 ml. of 7.6N HSO being ably about 215-240° C. Here again, one finds that at neutralized by the evolving NH3. Mixture was cooled, lower temperatures the reaction is quite slow and at higher 100 ml. of triethylene glycol dimethyl ether was added, temperatures, the formation of unwanted side products 45 the precipitate was filtered out, washed with acetone, is likely to be encountered. and dried. The dried product (N,N'-diethanol piperazine) In those instances in which an inert carrier is used as weighed 33 gms. which represented about 38% yield the reaction medium, the boiling point of the carrier (theoretical). may limit the reaction temperature. For this reason, a EXAMPLE 7 carrier should be selected which has a boiling point at least as high as the desired operating temperature.
Recommended publications
  • This Item Was Submitted to Loughborough University
    This item was submitted to Loughborough University as an MPhil thesis by the author and is made available in the Institutional Repository (https://dspace.lboro.ac.uk/) under the following Creative Commons Licence conditions. For the full text of this licence, please go to: http://creativecommons.org/licenses/by-nc-nd/2.5/ LOUGHBOROUGH UNIVERSITY OF TECHNOLOGY LIBRARY AUTHOR/FILING TITLE . -------------~§'~£~~~-~-;::r------_...: __________ i , ----------------!.------------------------ -- ----- - .....- , ACCESSION/COPY NO. --------------___ _L~~~~~/~~-----~- _____ ______ _ VOL. NO. CLASS MARK ISO C YA N I C ACID B Y D. J. BEL SON N .rkl ' A'~OCIORAL THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR , . ." , THE AWARD OF ~,_~,.' , ~ kf\S-r.. tt ; ~eCTeR OF PHILOSOPHY OF THE LOUGHBOROUGH UNIVERSITY OF TECHNOLOGY - 1981\ SUPERVISOR: DRI A, N, STRACHAN DEPARTMENT OF CHEM I STRY © BY D. J. BELSON J 1981. ..... ~- ~~c. \0) 'to 'b/O"2- .-'-' , C O,N TEN T S Chapter 1 Intr6duction .. 1 2 Preparation and storage of isocyanic acid.­ 3 3 Physical properties and structure of isocyanic acid. 11 4 Methods of analysis for isocyanic acid. 17 5 The polymerisation of isocyanic acid. 21 6 Pyrolysis and photolysis of isocyanicacid. 34 7 Reactions in water. 36 8: Reaction 'with alcohols. 48 9 Reactions with ammonia and amines. 52 10 Other addition reactions across th'e N=C double bond. 57· 11 Addition of isocyanic acid to unsaturated molecules. 65 12 Summary and conclUsions. 69 Acknowledgements. 82 Ref erenc es. 83 Figures Opposite Page 1 Van't Hoff equation plot for the gas- 23 phase depolymerisation of cyanuric acid. 2 Values of pKfor isocyanic acid 37 dissociation~;'- plotted against temperature.
    [Show full text]
  • ) (51) International Patent Classification: A01N 43/58
    ) ( 0 (51) International Patent Classification: Declarations under Rule 4.17: A01N 43/58 (2006.01) A01P 15/00 (2006.01) — as to applicant's entitlement to apply for and be granted a (21) International Application Number: patent (Rule 4.17(H)) PCT/EP20 19/055007 — of inventorship (Rule 4.17(iv)) (22) International Filing Date: Published: 28 February 2019 (28.02.2019) — with international search report (Art. 21(3)) (25) Filing Language: English (26) Publication Language: English (30) Priority Data: 18159322.9 28 February 2018 (28.02.2018) EP (71) Applicant: BASF SE [DE/DE]; Carl-Bosch-Str. 38, 67056 Ludwigshafen am Rhein (DE). (72) Inventors: NESVADBA, Peter; Klybeckstrasse 141, 4002 Basel (CH). CUNNINGHAM, Allan Francis; Klybeck¬ strasse 141, 4002 Basel (CH). NAVE, Barbara; Speyerer Strasse 2, 67 117 Limburgerhof (DE). WALLQUIST, Olof; Klybeckstrasse 141, 4002 Basel (CH). WISSEMEIER, Alexander; Speyerer Strasse 2, 671 17 Limburgerhof (DE). HINDALEKAR, Shirang; 1st Floor, VIBGYOR Towers, Plot C62, 40005 1 Mumbai (IN). POTHI, Tejas; G Block, Bandra Kurla Complex, 40005 1 Mumbai (IN). (74) Agent: MAIWALD PATENTANWALTS- UND RECHTSANWALTSGESELLSCHAFT MBH; Eva Dbrner, Postfach 33 05 23, 80065 Mtinchen (DE). (81) Designated States (unless otherwise indicated, for every kind of national protection available) : AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IR, IS, JO, JP, KE, KG, KH, KN, KP, KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
    [Show full text]
  • Thermodynamics and Reaction Mechanism of Urea Decomposition† Cite This: Phys
    PCCP View Article Online PAPER View Journal | View Issue Thermodynamics and reaction mechanism of urea decomposition† Cite this: Phys. Chem. Chem. Phys., 2019, 21,16785 a b b b Steffen Tischer, * Marion Bo¨rnhorst, Jonas Amsler, Gu¨nter Schoch and Olaf Deutschmann ab The selective catalytic reduction technique for automotive applications depends on ammonia production from a urea–water solution via thermolysis and hydrolysis. In this process, undesired liquid and solid by-products are formed in the exhaust pipe. The formation and decomposition of these Received 18th March 2019, by-products have been studied by thermogravimetric analysis and differential scanning calorimetry. Accepted 5th July 2019 A new reaction scheme is proposed that emphasizes the role of thermodynamic equilibrium of the DOI: 10.1039/c9cp01529a reactants in liquid and solid phases. Thermodynamic data for triuret have been refined. The observed phenomenon of liquefaction and re-solidification of biuret in the temperature range of 193–230 1Cis rsc.li/pccp explained by formation of a eutectic mixture with urea. Creative Commons Attribution-NonCommercial 3.0 Unported Licence. 1 Introduction and ammonium ISE (ion-selective electrode) measurements. Concluding from experimental results and literature data, 23 Air pollution by nitrogen oxides from Diesel engines is a major possible reactions including urea and its by-products biuret, problem concerning the environment and society. Therefore, cyanuric acid, ammelide, ammeline and melamine are presented. governments follow the need to regulate emissions by law (e.g., Further, cyanate and cyanurate salts and cyanamide are 715/2007/EG, ‘‘Euro 5 and Euro 6’’).1 The favored method to proposed as possible intermediates of high temperature urea reduce nitrogen oxides is selective catalytic reduction (SCR) decomposition.
    [Show full text]
  • Asian Journal of Chemistry Asian Journal of Chemistry
    Asian Journal of Chemistry; Vol. 27, No. 9 (2015), 3149-3151 ASIAN JOURNAL OF CHEMISTRY http://dx.doi.org/10.14233/ajchem.2015.16726 Synthesis and Antimicrobial Activities of 2-S-Hepta-O-benzoyl lactosyl-1-aryl-5-hepta-O-benzoyl-β-lactosyl-2-isothiobiurets * REENA J. DESHMUKH and SHIRISH P. D ESHMUKH P.G. Department of Chemistry, Shri Shivaji College, Akola-444 001, India *Corresponding author: E-mail: [email protected] Received: 20 April 2014; Accepted: 14 March 2015; Published online: 26 May 2015; AJC-17213 A series of novel 2-S-hepta-O-benzoyl lactosyl-1-aryl-5-hepta-O-benzoyl-β-lactosyl-2-isothiobiurets have been synthesized by the interaction of S-hepta-O-benzoyl lactosyl-1-arylisothiocarbamides and hepta-O-benzoyl-β-D-lactosyl isocyanate. These compounds were screened for their antibacterial and antifungal activities against Escherichia coli, Proteus vulgaris, Salmonella typhimurium, Staphylococcus aureus, Pseudomonas aeruginosa and Aspergillus niger. The newly synthesized compounds have been characterized by analytical and IR, 1H NMR and mass spectral studies. Keywords: Arylisothiocarbamides, Lactosyl thiocyanate, Isothiobiurets. INTRODUCTION an efficient synthetic route to novel lactosyl isothiourea derivatives and their antimicrobial activities are reported. A number of thiourea derivatives have been reported to 1 2 exhibit antibacterial , herbicidal and fungicidal activities. EXPERIMENTAL Sugar thioureas3 has synthetic applications in neoglycocon- jugate synthetic strategies4, including neoglycoproteins5, Melting points determined are uncorrected. IR Spectra glycodendrimers6, glycoclusters7 and pseudooligosaccharides8. were recorded on Perkin-Elmer spectrum RXI FTIR spectro- Thiobiurets (mono and di) are also important derivatives meter. 1H NMR was obtained on Bruker DRX-300 MHz NMR of (thio) urea which may increase the biological activity of Spectrometer.
    [Show full text]
  • Spray Foam Event 2013, Session a Presentations Contents List
    Spray Foam Event 2013, Session A Presentations Contents List 1. Introduction to Spray Polyurethane Foam (Click to go to PDF Page 2) 2. OSHA’s Isocyanates National Emphasis Program (Click to go to PDF Page 58) 3. EOLWD On-site Consultation Program (Click to go to PDF Page 76) 4. Essential Resources and Training, American Chemistry Council (Click to go to PDF Page 109) 5. Safe Spray Foam (Click to go to PDF Page 126) 6. EPA Safe Use of Polyurethane Products (Click to go to PDF Page 137) Return to Contents List Introduction to Spray Polyurethane Foam This presentation will provide important background information on SPF, including history, product categories and delivery methods and applications. It will also address chemical concerns and include tips for a quality installation, and briefly cover environmental impacts of the product COPYRIGHTED MATERIALS This presentation is protected by US and International copyright laws. Reproduction, distribution, display and use of any part of this presentation without written permission of the speaker is prohibited. © 2013 Spray Polyurethane Foam Alliance Presentation Content 1. History 2. Product Categories 3. Basic Chemistry 4. Delivery Methods 5. Chemical Concerns 6. Environmental Impact 7. Quality Installation 8. Summary History of SPF in Buildings in construction for 50 years • Late 60’s ‐ Medium Density (agricultural and industrial) • Mid 70’s ‐Roofing ‐ Medium Density (general const.) ‐ Sealants • Mid 90’s ‐ Low Density (residential) Product Category Four general categories of SPF Spray Foam
    [Show full text]
  • United States Patent (19) 11 Patent Number: 4,822,624 Young (45) Date of Patent: Apr
    United States Patent (19) 11 Patent Number: 4,822,624 Young (45) Date of Patent: Apr. 18, 1989 54 PRESERVATIVE FOR HARVESTED CROPS 4,033,747 7/1977 Young ................................... 426/69 (75) Inventor: Donald C. Young, Fullerton, Calif. 4,426,396 l/1984 Young .... ... 426/69 73 Assignee: Union Oil Company of California, FOREIGN PATENT DOCUMENTS Los Angeles, Calif. 117171 1/1976 German Democratic Rep. ... 426/69 Appl. No.: 1191470 5/1970 United Kingdom.................. 426/69 (21) 79,347 Primary Examiner-R. B. Penland 22 Filed: Jul. 30, 1987 Attorney, Agent, or Firm-Michael H. Laird; G. Wirzbicki Related U.S. Application Data (57) ABSTRACT 60 Continuation of Ser. No. 568,067, Jan. 4, 1984, aban doned, which is a division of Ser. No. 272,687, Jun. 11, The growth of microorganisms in stored crops, and 1981, Pat. No. 4,426,396. especially in animal feedstuffs, is inhibited by the appli (51) Int. C.'................................................ A23K 1/22 cation of a preservative composition which comprises (52) U.S. C. ........................................ 426/53; 426/69; ammonia, urease enzyme urea and/or urea polymers in 426/332; 426/532; 426/623; 426/630; 426/636; . a fluid medium. Urea polymers which are useful include 426/807 biuret, triuret, cyanuric acid, urea cyanurate and other (58) Field of Search ................... 426/53, 69,332, 532, compounds which decompose to form ammonia. The 426/623, 630, 807, 636 effect of treatment with the preservative composition is to provide an immediate microorganism-inhibiting am 56) References Cited monia level, which, due to delayed decomposition of U.S. PATENT DOCUMENTS the urea and urea polymers, is sustained to some signifi 1,702,735 2/1929 Legendre ...........................
    [Show full text]
  • Biuret Applications in Beef and Dairy Rations
    The Technical Edge Biuret has Practical Applications in Beef and Dairy Rations Feed grade biuret, an economical source of non-protein nitro- gen (NPN), is an ADM Alliance Nutrition® exclusive. It can be Table 1 Nutrient Composition of Biuret used in ruminant diets and is approved for use in dairy lactation Item % AF % DM diets. Prior to May 2003, biuret was not approved for use in dairy DM, % 99 — rations. ADM was instrumental in getting biuret approved for use in dairy rations. Numerous research articles were reviewed and Protein, % 246 248.5 summarized. On May 27, 2003, ADM received an approval letter RDP, % CP 100 100 from the Food and Drug Administration (FDA) allowing biuret to 1 be formulated into dairy rations. SIP , % CP 100 100 Biuret is formed by the controlled decomposition of urea, con- NPN, % SIP 100 100 densing two molecules of urea into a single molecule of biuret, NRC, 2001 A Protein, % CP 100 100 which retains three of the nitrogen atoms (see Figure 1). Feed- 1 grade biuret is a mixture containing biuret and urea (maximum of For use in formulation; biuret is slowly soluble. 14%) with small amounts of triuret and cyanuric acid. Typically, biuret contains a minimum of 35% nitrogen with a crude protein fed in confinement. The slower degradation and physical proper- value of 246% (See Table 1). ties assist in forming a high-quality, self-fed supplement. Biuret Biuret is less soluble than urea. The combination of structural is at least 7.3 times less toxic than urea, making it ideal when and physical characteristics slows the rumen digestion of biuret.
    [Show full text]
  • Attachment A
    Attachment A Proposed 15-Day Modifications California Code of Regulations, Title 17, Division 3, Chapter 1, Subchapter 7.7, Article 1 Note: This document shows proposed modifications to the originally proposed amendments to the Regulation for the Reporting of Criteria Air Pollutants and Toxic Air Contaminants, as presented during the November 19, 2020, meeting of the California Air Resources Board. At that meeting, the Board directed staff to make modifications to the proposed amendments based on public comments received, and to provide these updates for public comment for a period of at least 15 days. The pre-existing regulation text is set forth below in normal type. The original proposed amendments are shown in underline formatting to indicate additions and strikeout to indicate deletions. The additional proposed modifications made available with the notice of public availability of modified text dated March XY, 2021, are shown in double- underline to indicate additions and double-strikethrough to indicate deletions. The symbol “***” means that intervening text not proposed for amendment is not shown. Proposed Amendments to the Regulation for the Reporting of Criteria Air Pollutants and Toxic Air Contaminants California Code of Regulations, Title 17, Division 3, Chapter 1, Subchapter 7.7, Articles 1 and 2 Amend Subchapter 7.7, Article 1, and sections 93400, 93401, 93402, 93403, 93404, 93405, 93406, 93407, 93408, 93409, 93410, title 17, California Code of Regulations, and adopt new Subchapter 7.7, Article 2, sections 93420, 93421, and new Subchapter 7.7, Article 2, Appendices A and B to title 17, California Code of Regulations, to read as follows: Subchapter 7.7: Regulation for the Reporting of Criteria Air Pollutants and Toxic Air Contaminants Article 1.
    [Show full text]
  • United States Patent Office Patented Feb
    3,367,956 United States Patent Office Patented Feb. 6, 1968 1 2 3,367,956 or cycloaliphatic hydrocarbons. When following the pro PREPARATION OF BIURET POLYISOCYANATES cedure of the present invention, it is critical to elevate Hans Joachim Hennig, Cologne-Starnmheim, and Otto the temperature at least in the later stage of the reaction Bayer, Erwin Windemuth, and Wilhelm Bunge, Lever ' to about ISO-250° C. to bring about formation of mono kusen, Germany, assignors to Farhenfabriken Bayer isocyanate which must be continuously removed substan Aktiengesellschaft, Leverkusen, Germany, a German corporation tially as soon as it is formed, preferably by operating at N0 Drawing. Filed Apr. 1, 1964, Ser. No. 356,650 the elevated temperature at a reduced pressure or by Claims priority, application Germany, Apr. 13, 1963, using a carrier gas to remove the organic monoisocyanate F 39,482 from the reaction mixture substantially as soon as it is 6 Claims. (Cl. 260—453) formed. Then the well-de?ned biuret polyisocyanates of the invention are formed instead of high molecular weight This invention relates to organic polyisocyanates and condensation products. Thus, it is an essential feature of more particularly to a process for the preparation of this invention to carry out the process under such tem biuret polyisocyanates. Moreover, this invention provides perature conditions that a monoisocyanate is split off and a new and unexpected way of preparing biuret polyiso the reactants may recombine to form a biuret polyiso cyanates which may also contain carbamyl groups with cyanate. Instead of high molecular weight condensation out the formation of undesirable by-products.
    [Show full text]
  • Risk-Based Closure Guide Draft
    Risk-based Closure Guide July 1, 2021 Office of Land Quality Indiana Department of Environmental Management Disclaimer This Nonrule Policy Document (NPD) is being established by the Indiana Department of Environmental Management (IDEM) consistent with its authority under IC 13-14-1-11.5. It is intended solely as guidance and shall be used in conjunction with applicable rules or laws. It does not replace applicable rules or laws, and if it conflicts with these rules or laws, the rules or laws shall control. Pursuant to IC 13-14-1-11.5, this NPD will be available for public inspection for at least forty-five (45) days prior to presentation to the appropriate State Environmental Board, and may be put into effect by IDEM thirty (30) days afterward. If the NPD is presented to more than one board, it will be effective thirty (30) days after presentation to the last State Environmental Board. IDEM also will submit the NPD to the Indiana Register for publication. 2 Table of Contents 1 Introduction ..................................................................................................................................... 7 1.1 Applicability .............................................................................................................................. 8 1.2 Types of Closure ...................................................................................................................... 9 1.3 Process Overview ...................................................................................................................
    [Show full text]
  • NMR Analysis to Identify Biuret Groups in Common Polyureas
    Chinese Journal of POLYMER SCIENCE ARTICLE https://doi.org/10.1007/s10118-018-2130-y Chinese J. Polym. Sci. 2018, 36, 1150–1156 NMR Analysis to Identify Biuret Groups in Common Polyureas Wei-Guang Qiu, Fei-Long Zhang, Xu-Bao Jiang*, and Xiang-Zheng Kong* College of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China Abstract Polyureas (PU) are well known as a class of high impact engineering materials, and widely used also in emerging advanced applications. As a general observation, most of them are only soluble in a very limited number of highly protonic solvents, which makes their chemical structure analysis a great challenge. Besides the presence of abundant hydrogen bonding, the poor solubility of PU in common organic solvents is often ascribed to the formation of biuret crosslinking in their molecular chains. To clarify the presence of biuret groups in PU has been of great interest. To this end, two samples, based on hexamethylene diisocyanate (HDI) and toluene diisocyanate (TDI) respectively, were synthesized by precipitation polymerization of each of these diisocyanates in water-acetone at 30 °C. Their chemical structures were analyzed by high resolution magic angle spinning (HR-MAS) NMR, and through comparison of their NMR spectra with those of specially prepared biuret-containing polyurea oligomers, it was concluded that biuret group was absent in all the PU prepared at 30 °C. In addition, this NMR analysis was also applied to a PU obtained by copolymerization of TDI with ethylene diamine (EDA) and water at 65 °C in EDA aqueous solution. It was confirmed that biuret unit was also absent in this PU and that EDA was more active than water towards TDI.
    [Show full text]
  • Chemicals Subject to TSCA Section 12(B) Export Notification Requirements (January 16, 2020)
    Chemicals Subject to TSCA Section 12(b) Export Notification Requirements (January 16, 2020) All of the chemical substances appearing on this list are subject to the Toxic Substances Control Act (TSCA) section 12(b) export notification requirements delineated at 40 CFR part 707, subpart D. The chemicals in the following tables are listed under three (3) sections: Substances to be reported by Notification Name; Substances to be reported by Mixture and Notification Name; and Category Tables. TSCA Regulatory Actions Triggering Section 12(b) Export Notification TSCA section 12(b) requires any person who exports or intends to export a chemical substance or mixture to notify the Environmental Protection Agency (EPA) of such exportation if any of the following actions have been taken under TSCA with respect to that chemical substance or mixture: (1) data are required under section 4 or 5(b), (2) an order has been issued under section 5, (3) a rule has been proposed or promulgated under section 5 or 6, or (4) an action is pending, or relief has been granted under section 5 or 7. Other Section 12(b) Export Notification Considerations The following additional provisions are included in the Agency's regulations implementing section 12(b) of TSCA (i.e. 40 CFR part 707, subpart D): (a) No notice of export will be required for articles, except PCB articles, unless the Agency so requires in the context of individual section 5, 6, or 7 actions. (b) Any person who exports or intends to export polychlorinated biphenyls (PCBs) or PCB articles, for any purpose other than disposal, shall notify EPA of such intent or exportation under section 12(b).
    [Show full text]