Composition of matter for allophanate encapsulation in an aromatic-aliphatic calixarene

Abstract: p-Nonyl-co-p-phenylcalix[8]arene encapsulated mono or poly allophonates are useful as nitrogen oxide reducers in diesel fuels.

Description: The present invention relates to a composition for decreasing nitric oxide, NOx, levels. The chemicals utilized in the composition of matter are reducing agents. When these reducing agents come in contact with NOx, the latter is reduced to non-toxic or environmentally friendly substances. The present invention entails encapsulating or incorporating the reducing agent into a passive or non-reactive cavity. Moreover, encapsulating the reagent is designed to both enhance the overall thermal stability of the reducing agent and to foster its dissolution in diesel fuel. Nitrogen oxides are the oxidation products of elemental nitrogen, organic, or inorganic nitrogen and oxygen at elevated temperatures. Nitrogen oxides include nitric oxide, NO; nitrogen dioxide, NO 2 ; nitrogen trioxide, NO 3 ; dinitrogen trioxide, N 2 O 3 ; tetranitrogen pentaoxide, N 4 O 5 ; tetranitrogen hexaoxide, N 4 O 6 ; and nitrous oxide, N 2 O. Elevated temperatures required to prepare these oxidation products are routinely obtained in internal combustion engines utilizing gasoline, diesel, or aviation fuel. There are cogent ecological and environmental reasons to reduce or ideally eliminate NOx as an internal combustion oxidation product. Once produced, NOx is directly responsible for acid rain and photochemical smog. Moreover, chronic exposure to NOx has been directly linked with restricted pulmonary compliance in non-smoking healthy males; acute respiratory disease among children living in "high exposure" towns in Czechoslovakia; and a key irritant cited for the high incidence of chronic bronchitis among Japanese postal workers servicing urban centers as outlined in Medical and Biologic Effects of Environmental Pollutants by the National Academy of Sciences, 1977. Numerous physical methods have been suggested to reduce or eliminate NOx. Certain proposed techniques involve a great deal of capital outlay and require major consumption of additives, scrubbers, etc. For example, U.S. Patent 3,894,141 proposes a reaction of NOx with liquid hydrocarbons; U.S.Patent 4,405,587 proposes high temperature burning of NOx with a hydrocarbon; U.S. Patent 4,448,899 proposes reacting of NOx with an iron chelate; U.S. Patent 3,262,751 reacts NOx with a conjugated olefin. Other methods utilize reactions of NOx with nitriles (U.S. Patent 4,080,425). Application of these reactions imposes organic pollutant disposal problems along with the attendant problems of toxicity and malodorous environments. In addition, they require the presence of oxygen and are relatively expensive. Other systems are based on urea reactions. For example U.S. Patent 4,119,702 discloses the use of a combination of urea and an oxidizing agent which decomposes it, e.g., ozone, nitric acid, inter alia; U.S. Patent 4,325,924 utilizes urea in a high temperature reducing atmosphere; and U.S. Patent 3,900,554 (the thermodenox system) utilizes a combination of ammonia and oxygen to react with nitric oxide. All of these methods must deal with the problem of ammonia and its disposal. All require oxygen and other oxidizing agents. These methods also suffer from the drawback of requiring controlled environments which make them difficult to use in mobile vehicles or smaller stationary devices. Back et al, Can J.Chem. 46, 531 (1968), discusses the effect of NOx on the photolysis of isocyanic acid, HNCO, the decomposition product of cyanuric acid. Increased nitrogen levels in the presence of nitric oxide were observed utilizing a medium pressure mercury lamp for HNCO photolysis. Despite several remaining uncertainties, it was clear that nitric oxide levels were reduced when contacted with isocyanic acid. Isocyanic acid is available via the thermal decomposition or unzipping of the corresponding trimer, cyanuric acid, (HNCO) 3 . Other disclosures, especially as noted by Epperly et al in U.S. Patents 4,770,863 and 5,017,347 and Bowers in U.S. Patent 4,927,612 report the use of allophanates as another source of isocyanic acid. These methods also have limited applicability in non-stationary power generators because of their very limited solubility in non-polar solvents, most notably, diesel fuel. Thus, an object of the present invention is to provide a chemical preparation of isocyanic acid from a material that is a diesel fuel-soluble precursor for non-stationary power generators. This invention provides a composition of matter comprising one or more compounds selected from: a) p-nonyl-co-p-phenylcalix[8]arene monoallophanate; b) p-nonyl-co-p-phenylcalix[8]arene diallophanate; c) p-nonyl-co-p-phenylcalix[8]arene triallophanate; d) p-nonyl-co-p-phenylcalix[8]arene tetraallophanate; e) p-nonyl-co-p-phenylcalix[8]arene pentallophanate; f) p-nonyl-co-p-phenylcalix[8]arene hexaallophanate; g) p-nonyl-co-p-phenylcalix[8]arene heptaallophanate; and h) p-nonyl-co-p-phenylcalix[8]arene octaallophanate. The present invention provides a composition of matter comprising one or more of eight components. The process for producing such components, utilises a calixarene structurally represented as where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 8 are each hydrogen or a (C 1 -C 50 ) linear, branched, saturated or unsaturated hydrocarbon; R 7 is a mono,- di-, or polyaromatic, substituted or unsubstituted group; and b is an is an integer between 1 and 8. Moreover, it has been determined that calixarenes derived from p-nonylphenol and p-phenylphenol achieve crucial material requirements. For clarity, calix[2b]arene may be more conveniently represented in a structurally abridged form and isocyanic acid produced by the thermal decomposition of urea to generate calixarene allophanates represented by: where d is representative of the allophanate repeat unit and is an integer of between 0 and 8, preferably between 0 and 5, it is especially desirable to limit d to 1. A summary of the reaction products which make up the components of the composition of matter of this invention is provided below. Code d Product Name C 0 0 (Unmodified) p-nonyl-co-p-phenylcalix[8]arene C 1 1 p-nonyl-co-p-phenylcalix[8]arene monoallophanate C 2 2 p-nonyl-co-p-phenylcalix[8]arene diallophanate C 3 3 p-nonyl-co-p-phenylcalix[8]arene triallophanate C 4 4 p-nonyl-co-p-phenylcalix[8]arene tetraallophanate C 5 5 p-nonyl-co-p-phenylcalix[8]arene pentallophanate C 6 6 p-nonyl-co-p-phenylcalix[8]arene hexaallophanate C 7 7 p-nonyl-co-p-phenylcalix[8]arene heptaallophanate C 8 8 p-nonyl-co-p-phenylcalix[8]arene octaallophanate The composition of matter of this invention is directed to two crucial areas: solubilization of allophanates in diesel fuel and the thermal enhancement of the same in order to survive the combustion event of an internal combustion engine. It has now been found that the encapsulation of allophanates in a calixarene cavity achieves these criteria. The chemical method according to the present invention utilizes two key materials, which, when used independently are completely ineffective in reducing nitric oxides. In one case, one material is completely insoluble in diesel fuel; while in the other, the crucial intermediate is not generated. The intrinsic chemical property exploited for each of these materials is provided below. a) Alkyl-co-Aromaticcalix[8]arene Completely miscible in diesel fuel. b) Alkyl or Aromatic Allophanates Upon thermal decomposition generates the nitric oxide reducing agent, isocyanic acid, HNCO. The chemical underpinning of this invention is generating isocyanic acid, HNCO, to reduce nitrogen oxide emissions to environmentally friendly materials as depicted below (Eq. 1). Isocyanic acid is generated quantitatively by thermally decomposing cyanuric acid as shown below (Eq. 2). Eq. 1 . HNCO + NOx ---------> N 2 + CO 2 + H 2 O Isocyanic Acid Nitrogen Oxides from Stationary Source However, cyanuric acid technology has very limited applicability to non-stationary NOx power plants because of its insolubility in diesel fuel. Moreover, attempts to solubilize it in diesel fuel suffer from two fundamental flaws: a) Replacement of one or more of the acidic protons of cyanuric acid reduces the amount of isocyanic acid generated below (Eqs. 3,4, and 5); and b) Solubilization of cyanuric acid in diesel fuel cannot assure its survival during the internal combustion event. The present invention provides both the ability to utilize allophanate (I) as another isocyanic source (Eq. 6.) and to cause dissolution of the same by chemically encapsulating the allophanate (I) in a calixarene. In the structural depiction of a substituted allophanate below, R represents a homo-, co-, tri-, or tetracalixarene Substituted Allophanate (I) It appears that partial or full encapsulation of the allophanate in a calixarene cavity (II), results in enhanced thermal stability. In the structural representation of calixarenes amenable to this invention provided above, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 8 are each hydrogen or a (C 1 -C 50 ) linear, branched, saturated or unsaturated hydrocarbon; and the cavity size, b , is an integer of between 1 and 8. According to the present invention, it has been determined that calixarenes derived from p-nonylphenol and p-phenylphenol have optimized diesel fuel solubility and thermal stability as provided below (III) The present method of incorporating allophanates into the calixarene cavity utilizes urea. Thermal decomposition of urea generates the reactive intermediate, isocyanic acid, HNCO (Eq. 7). Performing this decomposition reaction in the presence of calixarenes generates the partial or fully encapsulated allophanates mixture. Moreover, the amount of encapsulated allophanate may be varied by skewing the molar ratio of reagents. Thus according to the present invention, an encapsulated allophanates mixture is produced as generically depicted (V) below in Eq.8. The generic nomenclature and structural summaries of the product mixture depicted in Eq.8. are provided below in Table I. Calixarene Allophanate Product Summary Generated By Reacting Urea And p-nonyl-co-p-phenylcalix[8]arene p-Nonyl-co-p-Phenylcalix[8]arene Allophanate d p-nonyl-co-p-phenylcalix[8]arene 0 p-nonyl-co-p-phenylcalix[8]arene monoallophanate 1 p-nonyl-co-p-phenylcalix[8]arene diallophanate 2 p-nonyl-co-p-phenylcalix[8]arene triallophanate 3 p-nonyl-co-p-phenylcalix[8]arene tetraallophanate 4 p-nonyl-co-p-phenylcalix[8]arene pentallophanate 5 p-nonyl-co-p-phenylcalix[8]arene hexaallophanate 6 p-nonyl-co-p-phenylcalix[8]arene heptaallophanate 7 p-nonyl-co-p-phenylcalix[8]arene octaallophanate 8 In order to further illustrate the present invention and its advantages, the following non-limiting examples are provided. EXAMPLE 1 Preparation of p-Nonylcalix[8]arene A three neck round bottom equipped with a magnetic stirrer, thermometer, and reflux condenser with a Dean-Stark adapter was charged with 30 parts p-n-nonylphenol, 400 parts xylene, 1 part sodium hydroxide, and 8 parts paraformaldehyde and heated to reflux for 48 hours. Sufficient hydrochloric acid was added to neutralize the residue base and the mixture vacuum distilled to remove the unreacted reagents and solvent to provide the present resinous material. The present product was redissolved in xylene and precipitated in a copious amount of 1:1 v/v methanol-water mixture, respectively. EXAMPLE II Preparation of p-Nonyl-Co-p-PhenylCalix[8]arene In this Example, a 2:5 mole-mole ratio of p-phenylphenol and p-n-nonylphenol, respectively, was substituted for the p-n-nonylphenol of Example 1, above, and the procedure thereof was used herein to produce the product of this example. EXAMPLE III Preparation of p-Nonyl-Co-p-PhenylCalix[8]arene In this Example, a 2:3 mole-mole ratio of p-phenylphenol and p-n-nonylphenol, respectively, was substituted for the p-n-nonylphenol of Example 1, above, and the procedure thereof was used herein to produce the product of this Example. EXAMPLE IV Preparation of p-Nonyl-Co-p-PhenylCalix[8]arene In this Example, a 5:1 mole-mole ratio for p-phenylphenol and p-n-nonylphenol, respectively, should be substituted for the p-n-nonylphenol of Example 1, above, and the procedure thereof was used herein to produce the product of this Example. EXAMPLE V Reaction of p-Nonyl Calix[8]arene with Urea In this Example, a 2-neck flask equipped with a magnetic stirrer and a thermometer was charged with 150 parts p-n-nonylcalix[8]arene generated in Example I and 11 parts urea. While mixing the materials were heated to 160°C for 3 hours under a blanket of nitrogen. The mixture was cooled to ambient temperature and the reaction product extracted using 500 parts n-heptane. The product was isolated as a brownish solid by flash removal of solvent. EXAMPLE VI Reaction of p-Nonyl-Co-p-Phenyl Calix[8]arene with Urea In this Example, the reaction product from Example II was substituted for the p-n-nonylphenol of Example I, and the procedure thereof was used herein to produce the product of this Example. EXAMPLE VII Reaction of p-Nonyl-Co-P-Phenylcalix[8]arene with Urea In this Example, the product from Example III was substituted for the p-n-nonylphenol of Example I, and the procedure thereof was used herein to produce the product of this Example. EXAMPLE VIII Reaction of p-Nonyl-Co-p-Phenylcalix[8]arene with Urea The product from Example IV was substituted for the p-n-nonylphenol of Example I, and the procedure thereof was used herein to produce the product of this Example. EXAMPLE IX Reaction of p-Nonyl-co-p-Phenylcalix[8]arene with Urea The product from Example III was reacted with 22 parts urea as outlined in Example V to produce the product of this Example. EXAMPLE X Reaction of p-Nonyl-co-p-Phenylcalix[8]arene with Urea The product from Example III was reacted with 33 parts urea as outlined in Example V to produce the product of this Example. EXAMPLE XI Reaction of p-Nonyl-co-p-Phenylcalix[8]arene with Urea The product from Example III was reacted with 44 parts urea as outlined in Example V to produce the product of this Example. The urea addition was made in two equal increments over a heating period of four hours. EXAMPLE XII Reaction of p-Nonyl-co-p-Phenylcalix[8]arene with Urea The product from Example III was reacted with 55 parts urea as outlined in Example V to produce the product of this Example. EXAMPLE XIII Reaction of p-Nonyl-co-p-Phenylcalix[8]arene with Urea The product from Example III was reacted with 66 parts urea as outlined in Example V to produce the product of this Example. EXAMPLE XIV Reaction of p-Nonyl-co-p-Phenylcalix[8]arene with Urea The product from Example III was reacted with 77 parts urea as outlined in Example V to produce the product of this Example. EXAMPLE XV Reaction of p-Nonyl-co-p-PhenylCalix[8]arene with Urea The product from Example III was reacted with 88 parts urea as outlined in Example V to produce the product of this Example. EXAMPLE XVI Reaction of p-Nonyl-co-p-PhenylCalix[8]arene with Urea The product from Example III was reacted with 88 parts urea as outlined in Example V, although the heating time was increased an additional two hours to produce the product of this Example. EXAMPLE XVII Reaction of p-Nonyl-co-p-PhenylCalix[8]arene with Urea The product from Example III was reacted with 88 parts urea as outlined in Examples V, although the heating time was increased an additional four hours to produce the product of this Example. EXAMPLE XVIII Reaction of p-Nonyl-co-p-PhenylCalix[8]arene with Urea The product from Example III was reacted with 100 parts urea as outlined in Example V to produce the product of this Example. The materials synthesized according to the present invention were structurally and physically evaluated. The structural property of interest was the detection of allophanates encapsulated within the calixarene matrix which detection was determined using photospectrometric methods. It was fingerprinted by its infrared absorbance at 3412 cm -1 (N-H stretch), 1710 cm -1 (C=O stretch), and 1160 cm -1 (O-C stretch). Results of the diesel fuel solubility and thermal stability of the experimental samples are summarized below in Table II. Material Diesel Fuel Solubility at Turbidity Point (wt%) 50 wt% Decomposition Temperature (deg C) 90 wt% Decomposition Temperature (deg C) Unmodified urea >.1 310 315 Unmodified biuret >.1 290 300 Unmodified triuret >.1 300 315 Phenyl allophanate >.1 420 920 n-(C9-C14 alkyl)-allophanate <15 Calix[8]arene-allophanate <45 460 960 Calix[8]arene-diallophanate <45 465 960 Calix[8]arene-triallophanate <30 480 965 Calix[8arene-tetraallophanate <30 460 965 Calix[8]arene-pentaallophanate <30 475 965 Calix[8]arene-hexaallophanate <30 480 945 Calix[8]arene-heptaallophanate <20 480 960 Calix[8]arene-octaallophanate <20 480 965

Claims: p-Nonyl-co-p-phenylcalix [8] arene encapsulated mono or poly allophanate. One or more compounds selected from: a) p-nonyl-co-p-phenylcalix[8]arene monoallophanate; b) p-nonyl-co-p-phenylcalix[8]arene diallophanate; c) p-nonyl-co-p-phenylcalix[8]arene triallophanate; d) p-nonyl-co-p-phenylcalix[8]arene tetraallophanate; e) p-nonyl-co-p-phenylcalix[8]arene pentallophanate; f) p-nonyl-co-p-phenylcalix[8]arene hexaallophanate; g) p-nonyl-co-p-phenylcalix[8]arene heptallophanate; and h) p-nonyl-co-p-phenylcalix[8]arene octaallophanate. The use of a compound as claimed in Claim 1 or Claim 2 in a fuel for the reduction of nitrogen oxides. A diesel fuel comprising a compound as claimed in Claim 1 or Claim 2.

Inventors: DE ROSA THOMAS FRANCIS, KAUFMAN BENJAMIN JOSEPH, SUNG RODNEY LU-DAI, DE ROSA, THOMAS FRANCIS, KAUFMAN, BENJAMIN JOSEPH, SUNG, RODNEY LU-DAI
Applicants: TEXACO DEVELOPMENT CORP, TEXACO DEVELOPMENT CORPORATION
Application year: 1993
Main classification: C10L1
IPC codes: C10L1, C10L10, C07C275