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  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
  • C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
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  • C09K23/12—Sulfonates of aromatic or alkylated aromatic compounds
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/326—Coal-water suspensions
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
  • C10M135/10—Sulfonic acids or derivatives thereof
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
  • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
  • C10M2219/088—Neutral salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
  • C10M2219/089—Overbased salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/251—Alcohol-fuelled engines
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines
  • C10N2040/28—Rotary engines

Definitions

• This invention relates to novel compositions of matter and methods of making the same. More particularly, this invention relates to the alkylation of phenols by olefinic components of cracked petroleum distillates to produce novel alkylphenols; and to derivatives of the alkylphenols.
• the invention is related to the composition, separation and alkylation chemistry of olefinic cracked petroleum distillates especially of thermally cracked petroleum residua of high sulfur content.
• the invention is particularly related to the chemistry of C 8 and higher alkylphenols. It is aimed at the preparation of semilinear alkylphenols derived by alkylating phenols with the largely linear olefin components of distillates derived by the high temperature thermal cracking of petroleum residua. Furthermore, the invention is concerned with the ethoxyl ation and propoxyl ation of alkylphenols, particularly of those derived from cracked petroleum distillates, especially coker distillates. The preparation of sulfate and sulfonate derivatives of the ethoxylated and propoxylated alkylphenol products is also described. Finally, the conversion of alkyl phenols to sulfurized metal phenate overbased detergents is discussed.
• alkylation of phenols by olefins in the presence of acids to produce alkylphenols is a well known reaction.
• alkylphenols are used in a wide variety of applications.
• ortho alkylphenols are superior antioxidants compared to para alkylphenols as described in U.S. patent 3,929,654.
• the C 8 and higher branched alkylphenols are commercially used for the production of ethoxylated nonionic surfactants and their anionic sulfate and sulfonate derivatives.
• nonionic Surfactants M. J. Schick, editor, M.
• alkylphenol derivatives include automotive lubricants additives. See, for example, “Lubricants and Related Products”, D. Klamann, Verlag Chemie, Weinheim, W. Germany, 1984, particularly pages 181, 182, and 199.
• alkylphenols are used in the preparation of surfactants.
• the most frequently used alkylphenol surfactant intermediates are t-octyl phenol, t-nonyl phenol and t-dodecyl phenol. They are commonly prepared by the alkylation of phenol of diisobutylene, propylene trimer and propylene tetramer, respectively. These are highly branched alkylphenols, generally 95% being para substituted.
• linear alkylphenols In contrast to the highly branched alkylphenols, there are known so-called linear alkylphenols. When produced via low temperature alkylation at about 80°C, these alkylphenols generally consist of close to a statistical mixture of ortho and para isomers, i.e., 66 to 33. These intermediates are prepared using linear alpha olefins as alkylating agents.
• U.S. Patent 3,423,474 and Soviet Patent 882,995 disclose alkylations of phenols with alpha olefins as reactants.
• U.S. Patents 3,312,734 and 3,432,567 disclose similar alkylations with cracked wax olefins.
• U.S. Patent 3,630,918 discloses the preparation of metal dialkyl dithiophosphate derivatives from alkylphenols derived from cracked wax olefins.
• thermally cracked petroleum distillates particularly those derived from residual fuel oil by Fluid-coking and Flexicoking, contain unexpectedly major quantities of linear olefins and minor quantities of branched olefins.
• These olefins are valued below distillate fuel cost, because such cracked distillates have high concentrations of sulfur compounds and have to. be extensively hydrogenated before they can be used as distillate fuels.
• the olefin components are converted to paraffins during such hydrogenations.
• sulfur compounds in such thermally cracked petroleum distillates are mostly inert aromatic, thiophene type compounds rather than catalyst inhibiting mercaptans.
• a group preferred thermally cracked distillates comprises naphtha and gas oil fractions produced in fluidized coking units.
• Integrated fluidized coking processes such as Fluid-coking and Flexicoking represent a superior refinery method for the conversion of residual fuel oil.
• the thermal cracking step of Fluid-coking and Flexicoking is identical.
• Fluid-coking does not utilize the residual coke produced with the coker distillate while Flexicoking employs the coke by-product for the production of low thermal value gas.
• U.S. Patent Nos. 2,813,916; 2,905,629; 2,905,733; 3,661,543; 3,816,084; 4,055,484 and 4,497,705 which are incorporated as references.
• the preferred Fluid-coking and Flexicoking processes are low severity thermal cracking operations.
• Low severity is usually achieved by keeping the temperature relatively low in the range of 482 to 538°C (900 to 1000°F) while using a long residence, i.e., contact, time of about 20 to 60 seconds.
• low severity can be achieved by using high temperatures, in the order of 538 to 705°C (1000 to 1300°F) and contact times of less than 5 seconds.
• additional amounts of the desired olefin components can be produced by reinjecting the heavy gas oil distillate products into the cracking line.
• the residual fuel feeds for the above coking processes are usually vacuum residua which remain after most of the crude petroleum is removed by refinery distillation processes.
• these residua typically possess boiling points above 565°C (1050°F) and have Conradson carbon contents above 15%.
• These residua contain most of the undesirable components of the crude, .i.e. sulfur and nitrogen compounds and metal complexes.
• sulfur and nitrogen compounds and metal complexes On coking much of the sulfur ends up in the distillate products.
• major amounts of olefinic components are also formed and become major constituents of such distillates.
• such distillates In spite of their high monoolefin content such distillates generally were not considered as alkylation feeds because of their high sulfur and conjugated diolefin content. It was surprisingly found in the present invention that, in spite of the high sulfur content, the olefinic components of such feeds selectively react with added phenol to form semi linear alkylphenols.
• the semi linear alkylphenols of the present invention differ from the highly branched and linear alkylphenols of the prior art in both the branchiness and the ortho versus para isomer distribution. They contain from about 1.4 to 2 branches per alkyl substituent on the average and ortho to para alkyl substituent ratios ranging from about 10/90 to 40/60.
• FIGURES Figure 1 shows the capillary gas chromatogram of a Fluid-coker naphtha feed in the C 4 to C 12 range, with an indication of the major 1-n- olefin and n-paraffin components.
• Figure 2 shows the 400 MHz proton nuclear magnetic resonance spectrum of the olefinic protons of Fluid-coker naphtha feed, with an indication of the chemical shift regions of various types of olefins.
• Figure 3 shows the capillary gas chromatogram of the light Fluid- coker gas oil feed in the C 9 -C 15 range, with an indication of the major 1- n-olefin and paraffin components.
• Figure 4 shows the capillary gas chromatogram on a highly polar column of a C 12 fraction of light Fluid-coker gas oil, with separation of various types of aliphatic and aromatic components and sulfur compounds.
• Figure 5 shows the separation of a 1-n-olefin - n-paraffin mixture from a C 16 -C 19 Fluid-coker gas oil fraction by crystallization.
• Figure 6 shows the C NMR spectrum of a highly branched dodecyl phenol product of the prior art at the top and the spectrum of a comparatively semilinear dodecylphenol of the present invention at the bottom.
• the present invention is predicated on the discovery that phenols can be selectively alkylated with the olefin component of a thermally cracked sulfur containing petroleum distillate derived from residua in the presence of an acid catalyst to provide monoalkylphenols which have an average of less than two alkyl branches in the said alkyl group.
• the monoalkylphenols so obtained generally possess ortho to para ratios of about 10 ortho to about 90 para isomers to about 40 ortho to about 60 para isomers.
• Various derivatives of such alkylphenols are also contemplated.
• R is a C 1 to C 35 , preferably C 5 to C 35 , more preferably C 8 to C 29. most preferably C 9 to C 20 alkyl, C 9 and C 12 alkyl groups being specifically preferred; R is in an ortho and/or para position relative to the phenolic OZ group, with the proviso that at least one R is a higher C 5 to C 35 alkyl group said alkyl groups having an average of less than two but more than one branches therein, p is 1 or 2, preferably 1 with the proviso that if p is 1, the ratio of o- to p- R groups is from about 10 to 90 to about 40 to 60; preferably from about 20 to 80 to about 30 to 70;
• Z is a phenolic hydrogen or a substituent member of the group consisting of Na, K, Ca, Mg, (EO) n H, (EO) n (CH 2 ) 2 SO 3 M (EO) n (CH 2 ) 3 SO 3 M and (EO) n CH(CH 3 )CH 2 CH 2 SO 3 M wherein E is CH 2 CH 2 , CH 2 CH(CH 3 ), CH(CH 3 )CH 2 ; M is H, Na, K, ammonium, Ca, Mg and n is 1 to 30; preferably 1 to 15;
• Q is a bridging radical selected from the group consisting of S, S 2 and CH 2 with the proviso that if Q is S or S 2 , Z is H, Ca or Mg and if Q is C H2 , Z is (EO) m H; q, the number of bridging groups, is 0 to 15 with proviso that if Q is S or S 2 , q is in the range of 1 to 5; m, the number of phenolic groups is 1 to 16, m being 1 + q;
• Y is selected from the group consisting of H and SO 3 M in which it is defined as above with the proviso that if Y is SO 3 M, q is preferably 0 and Z is (EO) n H;
• the semilinear alkylphenol intermediates of the present invention are prepared according to the present process by reacting phenols with the olefin components of the high temperature cracking of sulfur containing residua, and are of the formula
• R and p is as defined before.
• 'M is H or Na, K, Ca, Mg, Co, Ni.
• preferred semilinear alkylphenols are octylphenol, nonylphenol, undecylphenol, dodecylphenol.
• the preferred semilinear monoalkyl phenol compositions possess o- to p- ratios of their alkyl groups in the range of about 10 to 90 to about 40 to 60.
• the value- of Q is O.
• the compounds generically are of the formula wherein OZ represents a phenolic group in which Z is selected from the group consisting of H, Na, K, Ca, Mg, (EO) n H and (EO) n (T) (t) (SO 3 ) u and in which E is selected from the group consisting of CH 2 CH 2 , CH(CH 3 )CH 2 and CH 2 CH(CH 3 ), n is 1 to 30, T is selected from the group consisting of CH 2 CH 2 , CH 2 CH 2 CH 2 , CH(CH 3 )CH 2 CH 2 , t is 0 or 1, m is H, Na, K, ammonium, Ca, mg, Ni , Co, or Fe, and u is 0 or 1 provided that if t is 1, u also is 1; and Y is selected from the group consisting of H and (SO 3 )M in which M is as defined above; and R is selected from the group consisting of C 5
• the present invention also is directed toward a method of preparing these compositions.
• the alkylphenols of the present invention are prepared by reacting phenol with a hydrocarbon feed containing more than 15% monoolefins having C 5 to C 35 carbon ranges. These monoolefins contain from about 30 to 50% 1-n-olefin, 15 to 30% linear internal olefin and 30 to 45% monobranched olefins and have terminal to internal unsaturation ratios being in the range of from about 1.5 to 1 to about 4 to 1.
• the hydrocarbon feed employed in the practice of the present invention be an olefin containing distillate fraction of thermally cracked hydrocarbons derived from petroleum residua. Consequently, specific mention is made hereinafter to olefin containing distillate fractions of thermally cracked residua; however, it will be appreciated that other feeds having substantially similar properties can be employed.
• the preferred cracked distillates of the present feed contain relatively high amounts of organic sulfur compounds.
• the sulfur concentrations are preferably between 0.1% (1000 ppm) and 5% (50,000 ppm) more preferably between 0.5% (5000 ppm) and 4% (40,000 ppm).
• the prevalent sulfur compounds of the preferred feeds are aromatic, mainly thiophenic.Most preferably the aromatic sulfur compounds represent more than 90% of the total. In view of this characteristic of the feed, the present finding of selective phenol alkylation is surprising since thiophenes are highly reactive and tend to polymerize under acid conditions.
• the olefin-containing reactant used as a feed in the present invention will generally have from C 5 to C 35 carbon ranges. More preferably, the carbon range in such olefin-containing fractions will be from C 8 to C 29 and most preferably from C 9 to C 20 . Additionally, it is particularly preferred in the practice of the present invention that greater than 25%, for example, 30% to 80% of the olefins in the feed be linear aliphatic olefins.
• the olefin feed is reacted with phenol. Normally at least one mole of phenol per mole of olefin will be employed; however, it is generally preferred to use excess phenol.
• the reaction of phenol and the olefinic feed is conducted at temperatures sufficient to alkylate the phenol. In general these are temperatures of about 20oC and 450°C and preferably from about 20°C to 50°C more preferably from 80 to 130°C.
• the reaction is conducted in the presence of an effective amount of an acid catalyst.
• the acid concentration in the reaction mixture will vary from about 1% to about 50% by weight and preferably from 5% to 25%.
• acid catalysts that are suitable in the practice of the present invention are strong acids such as sulfuric acid, phosphoric acid, phosphonic acid, sulphonic acid, inorganic polyacids, such as aluminosilicate clays, acidic cation exchange resins, such as sulfonic acids, based on crosslinked styrene, divinyl benzene polymers, boron trifluoride, hydrogen fluoride, tetrafluoroboric acid and other combined acids.
• Insoluble acid catalysts are preferred.
• the particularly preferred catalyst in the process of the present invention is a sulfonic acid derivative of an insoluble cross-linked styrene, divinyl resin.
• alkylphenol reaction products of the present process can be separated from unreacted feed components by standard separation techniques such as fractional distillation.
• Another aspect of the present invention is the conversion of the alkylphenol products derived from cracked distillates.
• the most important type of conversion provides novel surfactants, preferably via ethoxylation and/or propoxylation.
• such alkylphenols or their ethoxylated/propoxylated derivatives are reacted with propanesultone, butanesulto ⁇ e or sulfuric acid to produce sulfonate surfactants.
• semilinear alkylphenols are converted to overbased automotive lubricant additives, preferably by reaction with sulfur and calcium oxide plus carbon dioxide.
• semilinear alkylphenols can be also employed to prepare demulsifier additives by reacting them with formaldehyde and ethylene oxide.
• the olefinic feed of the present process is a critical factor in producing the novel alkylphenols at a low cost.
• the preferred feed is produced by thermal cracking of petroleum residua.
• Thermal cracking of petroleum residua produces hydrocarbons of more linear olefinic character than catalytic cracking does. It was found in the present invention that the percentage of olefins including 1-n- olefin components in thermally cracked petroleum distillates generally increases with increases in the cracking temperature. Therefore, the olefin containing distillate fractions derived from petroleum residua by high temperature thermal cracking processes are preferred feeds for alkylation of phenols in accordance with the present invention of the present process.
• Suitable distillate feeds can be also prepared in thermal processes employing a plurality of cracking zones at different temperatures. Such a process is described in U.S. Patents 4,477,334 and 4,487,686. Each of these thermal cracking processes can be adjusted to increase the olefin content of their products. Heavy gas oil distillates can be further cracked to increase the amount of lower molecular weight olefins.
• the olefin containing distillate fractions of thermal cracking processes may be employed as feeds in the process of the invention without prior purification; however, these distillate fractions may optionally be treated prior to their use to reduce concentrations of aromatic hydrocarbons, sulfur and nitrogen compounds if so desired.
• aromatic hydrocarbons and sulfur compounds can be selectively extracted from the olefin containing fraction by polar solvents. Mercaptan components can be removed with base. Nitrogen and sulfur compounds in general can be removed by use of absorption columns packed with polar solids such as silica, Fuller's earth, bauxite and the like.
• sulfur compounds are present as thiophenic compounds, i.e., alkylthiophenes, benzothiophenes, etc.
• High temperature fixed beds of either bauxite or Fuller's earth or clay can be used to convert sulfur compounds to easily removable H 2 S with a concurrent isomerization of the olefin components.
• the conjugated olefin components of the present feeds may be removed by prior mild hydrogenation or selective alkylation prior to use.
• the branched olefin components can be similarly removed e.g. by water, alcohol or acid addition.
• 1-n-Olefin components can be selectively reacted via hydroformylation or removed together with the n-paraffins by cocrystallization.
• the cracked refinery distillate products, light and heavy naphthas and gas oils, are preferably further fractionated prior to use in the present process.
• the preferred broad carbon ranges of the thermally cracked feeds are from C 5 to C 35 .
• a more preferred carbon range is from C 8 to C 29 .
• the most preferred range is from C 9 to C 20 . It is desirable to limit the carbon number range of any given distillate feed by efficient fractional distillation to five carbons, preferably three carbons and more preferably to one carbon to facilitate the separation of alkylphenol products of increased boiling range from the unreacted feedstock.
• preferred feeds are C 9 and C 12 cracked distillate fractions for the preparation of semilinear C 9 and C 12 alkylphenols, respectively.
• the ratio of the different types of isomeric olefin components depends on the boiling range point.
• the olefin content of the present cracked distillate feeds is about 15%, preferably above 30%, more preferably above 40%.
• the 1-n- olefins are preferably the major type components.
• R-CH CH 2
• RCH CHR
• R-C CH 2
• R-C CHR ⁇ ⁇
• the concentration Type I olefins is preferably from about 30 to 50% of the total olefin concentration. Similarly, the percentage of Type II olefins preferably from about 15 to 30%.
• n-al kyl substi tuted Type I ol efi ns i .e. 1-n-ol efi ns
• the alkylation process of the present invention comprises reacting an olefinic cracked petroleum distillate feed, preferably produced from petroleum residua by high temperature thermal cracking and containing 1-n-olefins as the major type of olefin components and organic sulfur compounds, between 0.1 and 5% sulfur, more preferably between 0.5 and 4%, with phenol or cresol, preferably phenol, employing at least one mole of excess phenol per mole olefinic reactant, preferably in the liquid phase, at least one mole of excess phenol per mole olefinic reactant, preferably in the liquid phase, at temperatures between about 20 and 450°C, preferably from 20 to 150°C, more preferably from 80 to 130°C, in the presence of effective amounts of an acid catalyst, preferably a strong acid insoluble in the reaction medium, to produce alkylphenols as the major products, preferably a C 8 to C 30 semilinear monoalkyl phenol and preferably including, in addition to said alkylation process step, the
• the branched olefin components of the feed react at a faster rate than the linear olefins due to the better stabilization of the tertiary cation intermediates; e.g. in the case of p-alkyl phenols: o
• 1-n-olefins provide not only methyl but higher alkyl branched alkylphenols dependent on the reaction conditions, e.g.
• branched olefins lead to t-alkylphenols while linear olefins provide s-alkylphenols.
• ratio of tertiary versus secondary alkylphenol products depends on the ratio of branched versus linear olefins reacted.
• the prior art isoalkylphenols derived from branched olefins are essentially all t-alkylphenols.
• Branched olefins provide mostly para tertiary alkylphenols while linear olefins lead to mixtures of ortho and para secondary alkylphenols.
• 1-n-Olefins can give an o/p isomer mixture close to statistical i.e. a 66 o 33 o/p ratio.
• the present process provides products of increasing o/p ratios with i ncreasi ng olefi n conversion of the cracked di sti l l ate feeds.
• the monoal kyl phenol products of the present process can be further al kyl ated to provide 2 ,4-di al kyl phenol s .
• 1-n-ol efins yiel d some of the fol l owing compounds :
• dialkylphenols can be suppressed by employing a large excess of the phenol reactant and relatively mild reaction conditions.
• One of the preferred catalysts of the present process is the sulfonic acid derivative of an insoluble crosslinked styrene divinylbenzene resin.
• This catalyst is preferably employed at temperatures below 150°C to avoid decomposition and the formation of soluble sulfonic acids. Insoluble solid acids can be simply removed from the reaction mixture by filtration.
• the alkylphenol products of the present process can be separated from the unreacted feed components by fractional distillation. However, it is important the all strong acids be removed or neutralized prior to distillation because at high temperature they can lead to a catalytic reversal of the alkylation reaction.
• alkylphenol products of the present invention can be derivatized to provide several different types of useful compositions.
• the monoalkyl phenol intermediates can be further converted either prior to or after separation. Derivatization of the crude monoalkyl phenol reaction products is often advantageous from the separations point of view since the derivatives are less volatile.
• the alkylphenols can be ethoxylated and/or propoxylated in the presence of acid or base catalysts to provide alkylphenyl polyoxyethyl and/or polyoxypropyl alcohols.
• the first step of such base catalyzed alkoxylation reactions is much faster than those of the subsequent steps, e.g., in case of the p-alkylphenols.
• the alkylphenol is monoethoxylated or propoxylated the high boiling products can be readily separated from the much lower boiling impurities by distillation.
• the monoalkoxylated product can then be further reacted, e.g. ethoxylated or propoxylated.
• the acid catalyzed propoxylation is further discussed in the following because it forms mixtures of primary and secondary propoxylated alcohols; e.g.
• alkylphenoxyethanol or alkyl phenoxypropanol monoalkoxylation product is isolated by distillation and then further derivatized. Further ethoxyl ation of alkyl phenoxyethanol results in a Poisson distribution of variously ethoxylated alkylphenol products. A similar behavior is observed in the propoxylation of alkyl phenoxy-2-proparol. However, in case of propoxylation the isomeric product composition depends on the presence of base versus acid catalyst.
• the base catalyzed ethoxylation and propoxylation of the present alkylphenols is preferred because of the high rate and selectivity of monoalkyoxylated product formation. Acids are poor catalysts of phenol -epoxide reactions. Selective formation of the monoalkoxylated products is particularly advantageous when the starting cracked olefin derived alkylphenol reactants are of a fairly broad boiling range and contain hydrocarbon and sulfur compounds as impurities.
• VOV _ VOV _
• Pr is CH(CH 3 )CH 2 or CH 2 CH(CH 3 ).
• These products contain propylene moieties of different orientation and possess mainly alcohol end groups.
• sodium hydroxide and potassium hydroxide are frequently used. These catalysts react with alkylphenols to form the corresponding alkali phenol ate. The latter in turn further reacts with the ethylene oxide or propylene oxide to produce a growing alkoxide moiety.
• alkali hydroxides sodium or potassium may serve as precursors of the phenol ate or alcohol ate species.
• the molecular weight of the alkoxylated product is controlled by the phenol to ethylene oxide and/or propylene oxide ratio.
• acid catalysts of alkoxylation p-toluenesulfonic acid silicon tetrafluoride, crosslinked polymeric sulfonic acids, antimony pentachloride, tin tetrachloride, trifluorometha ⁇ esulfonic acid and other strong acids can be used .
• Combi nati ons of BF3 with metal al kyl s or hydri des e.g. of Al , Ti can be also employed.
• anhydrous systems are preferred.
• Sulfonate derivatives can be also prepared by reacting the alkylphenols and their ethoxylated/propoxylated derivatives with a sulfoalkylating agent.
• a sulfoalkylating agent for example, the reaction of alkali metal derivatives with propanesultone on butanesultone lead to the corresponding sulfonate salts
• sulfoalkylating reagents are bromoethanesulfonate and vinylsulfonate salts.
• Alkylphenols can be sulfurized primarily by technical sulfur dichloride, a mixture of SCl 2 and S 2 Cl 2 , preferably at about 80°C to provide sulfur bridged condensation products having about 3 phenol moieties per molecule.
• technical sulfur dichloride a mixture of SCl 2 and S 2 Cl 2 , preferably at about 80°C to provide sulfur bridged condensation products having about 3 phenol moieties per molecule.
• the product After the removal by the purging of all the HCl by-product and unreacted components from, the reaction mixture, the product can be used as an antioxidant component of crankcase oil, an automotive lubricant. Similar products can also be used as additive intermediates.
• sulfurized 4-t-dodecyl phenol is used for the preparation of an overbased detergent additive based on monoalkylphenols.
• Dodecyl phenol is largely converted to the corresponding overbased calcium dodecyl phenol ate by reacting it in a higher alcohol solvent with elemental sulfur and calcium oxide in the presence of ethylene glycol and then carbon dioxide.
• the main course of the reaction can be indicated by the following scheme.
• the viscosity of the i-dodecylphenol intermediate of the above scheme depends on the branchiness of the i-dodecyl group. A reduced viscosity is desired for the ease of processing. The reduced branchiness of the dodecyl group of the cracked olefin derived alkylphenol. resulted in advantageously reduced viscosity and thus improved processability.
• the overbased calcium dodecylphenol ate product is used as a detergent additive component of marine engine oils and crankcase oils. As an additive it is acting not only as a detergent antioxidant but as a neutralizer of acidic oxidation by-products.
• Overbased magnesium alkyl phenol ates can be also prepared and are useful as superior detergent additives.
• the key magnesium hydroxide reactant is to be derived from a magnesium alcoholate.
• the overall process scheme is the following:
• Alkylphenols derived from cracked distillates are readily condensed with formaldehyde.
• the resulting methylene bridged condensation products are then ethoxylated and/or propoxylated, preferably in the presence of a base catalyst, to provide oligomeric surfactants useful as demulsifiers, fuel additives and coal slurry stabilizers.
• the reaction scheme is illustrated with nonyl phenol in the following:
• n is 1 to 30.
• the zinc dialkyldithiophosphate products which usually contain excess Zn as hydroxide, are high temperature antioxidants useful as lubricating additives.
• ethoxylated and/or propoxylated semilinear alkylphenol compositions are also derived by alkylating phenols with the olefin components of thermally cracked distillates in the first step. They are of the formula
• the most important derivatives of the present ethoxylated and/or propoxylated alkyl phenols are the sulfates and sulfonates. They are preferably of the formula
• T is CH 2 CH 2 , CH 2 CH 2 CH 2 , CH(CH 3 ) CH 2 CH 2 , preferably CH(CH 3 )CH 2 CH 2 ;
• t is 0 or 1;
• M is H, Na, K, Ca, Mg, Ni, Co, Fe, preferably H and Na;
• u is 0 or 1 with the proviso that if t is 1, u must be also 1, and r is 0 or 1.
• a preferred subgenus of the above compounds consists of sulfate derivatives of ethoxylated alkyphenols of the formula is a precursor of the. ethoxylated sulfonate of the formula
• the sulfate sulfonate of the above formula is a precursor of the ethoxylated sulfonate of the formula
• Another preferred type of sulfonate derivative of the present ethoxylated monoalkyl phenol is of the formula
• n 1 to 35 preferably 1 to 15.
• a specific preferred group of sulfonates of this type is
• the mono ethoxylated sodium sulfonate compound is specifically preferred: ⁇
• composition derived from the present semilinear alkylphenols comprises sulfur bridged antioxidant compounds of the formula
• R is more preferably C 8 to C 12 , most preferably C 9 alkyl
• the bridging sulfur groups are in ortho para positions relative to the phenolic hydroxyl, mostly ortho
• x is 1 or 2
• v is 0 to 6, preferably 1 to 3.
• the sulfur bridged semilinear nonyl phenol having an average value of v between 0 and 2, preferably equaling 1, is specifically preferred.
• Sulfur bridged overbased calcium and magnesium phenate derivatives of semilinear monoalkylphenols are detergent additives of a distinct type. They contain structural units of the formula
• R is a C 5 to C 35 alkyl, preferably, a C 9 to C 18 alkyl, most preferably C 12 alkyl;
• M is Ca or Mg, preferably Ca.
• Methylene bridged semilinear mono alkylphenols and their ethoxylated and/or propoxylated derivatives represent another subgenus of the present compositions. They are of the formula
• R is a C 5 to C 35 alkyl, preferably a C 8 to C 15 alkyl, most preferably a C 9 alkyl, in an ortho and/or para position relative to the phenolic group.
• the bridging methylene groups are in an ortho or para, mostly ortho, position relative to the phenolic group, p is 1 or 2, preferably 1, m is 0 to 15, preferably 1 to 10, E is CH 2 CH 2 , CH 2 CH(CH 3 )CH 2 preferably CH 2 CH 2 , n is 0 to 30, preferably either 0 to 30.
• Bis-alkylaryl dithiophosphate antioxidant additive derivatives of the present semilinear monoalkylphenols form another subgenus of the formula
• R is C 5 to C 35 preferably C 8 to C 12 alkyl, in an ortho and/or para position relative to the phenolic oxygen, M is H, (Zn) 1/2 , ZnOH, preferably Zn 1/2 .
• the key factor in producing the highly olefinic reactant feed of the present invention is high temperature thermal cracking. Another factor is the origin and prior treatment of the petroleum residua to be cracked. The presence of the major 1-n-olefin components of the cracked distillates depends on the presence of normal alkyl groups in the crude oil. These olefins are formed by the cracking and dehydrogenation of n-alkyl aromatics and n-paraffins.
• distillate fractions used as feed in the present invention were derived by the Fluid-coking of vacuum residua produced from Northwest American crude.
• the composition of these feeds in a wide carbon range is described in U.S. Patent Application Serial No. 914,802, filed on October 4, 1986 and now allowed. This application is incorporated by reference.
• the composition of the C 4 to C 12 coker naphtha distillate was analyzed by GC using a temperature programmed 50 m column.
• the key components of the mixture were identified by GC/MS, with the help of standards as required.
• the gas chromatogram obtained is shown in Figure 1 with symbols indicating the 1-n-olefin and n-paraffin components of various amounts.
• the 1-n-olefin to n-paraffin ratios range from about 1.1 to 2.1.
• the 1-n-olefins are the largest single type of compounds.
• the broad C 3 to C 12 coker naphtha fraction was fractionally distilled, using a column equivalent to 15 theoretical plates with reflux ratio of 10, to produce distillates rich in olefins and paraffins of a particular carbon number. Selected fractions were studied by proton NMR using a JEOL GX 400 MHz spectrometer.
• Figure 2 shows the NMR spectrum of the olefinic region of the naphtha with an indication of the chemical shift regions assigned to the vinylic protons of various types of olefins. A quantitative determination of the olefinic protons of the various types of olefins was used to estimate olefin linearity.
• Type I olefins i.e., monosubstituted ethyl enes
• the percentage of Type I olefins in the distillation residue is, however, reduced to less than half of the original. It is assumed that this result is due to 1-n-olefin conversion during the high temperature distillation. Minor variations, between 32 and 50%, are also observed in Type I olefin content of distillate cuts.
• the second largest olefin type present in the naphtha and its distillate consists of 1,2-disubstituted ethylenes.
• the percentage of these Type II olefins varies between 18 and 26%. Most, if not all, of these olefins are linear internal olefins.
• Type III olefins i.e., 1,1-disubstituted ethylenes were found to be present in amounts ranging from 12 to 17%.
• the major olefins of this type were 2-methyl substituted terminal olefins. Their branching occurs mostly at the vinylic carbon.
• Type IV olefin i.e., trisubstituted ethylenes, were the smallest monoolefin components of these distillates. Their relative molar concentration is in the 6 to 12% range.
• Type V olefins i.e., tetrasubstituted ethylenes, could not be determined by proton NMR.
• the NMR spectra of naphtha fractions were also analyzed in the area of aromatic and paraffinic protons to estimate the amounts of olefins. From the percentage distribution of various types of hydrogens and the elemental analyses of these fractions, the weight percentage of various types of compounds was estimated.
• the type I olefins mostly 1-n-olefins were estimated to be present in these fractions in the range of 18.7 to 28.3%. These percentages depend on both the carhon number and the particular usually
• the total olefin content of these fractions is in the 47 to 62% range as determined by NMR. It is noted that the conjugated diolefins are included in this percentage since they are converted to monoolefins under hydroformylation conditions or by a prior mild hydrogenation. Due to differences in the boiling points of olefin isomers, the relative proportion of linear versus branched olefin components is of course somewhat dependent on the boiling range of the feed. The table also shows significant and increasing amounts, up to 25%, of aromatic components in the various naphtha fractions. The aromatics are mostly hydrocarbons, i.e. alkylbenzenes and naphthalenes, but also contain significant amounts of alkylthiophenes and benzothiophenes. In the higher carbon fractions most of the sulfur is in the form of these heteroaromatic compounds.
• Table II shows the elemental composition of Billings Fluid-coker naphtha fractions. Most importantly, the data of the table indicate a high percentage of sulfur. Surprisingly, in the C 8 and higher fractions, little of this sulfur is in the form of mercaptans. According to GC/MS, most of the sulfur of the C 8 to C 12 fractions is in the form of alkylthiophenes. In the present examples, the C 8 and C 9 fractions of Billings Fluid-coker naphtha were used as alkyl ating feed. The C 4 to C 12 naphtha and C 9 to C 16 light gas oil fractions overlap. A C 12 fraction of Billings Fluid-coker light gas oil was also employed in an example.
• Figure 3 shows the capillary GC of the light gas oil in the C 9 to C 16 range. About 90% of the components are in the C 10 to C 15 carbon range. The C 11 to C 13 components are particularly large. Obviously, there is some overlap between this composition and that of the broad cut naphtha.
• the main components are the 1-n-olefins and the n-paraffins.
• concentrations of the 1-n-olefins are greater than those of the corresponding paraffins.
• the 1-n-olefin to n-paraffin ratio is apparently maintained with increasing carbon numbers.
• the light gas oil fraction was fractionally distilled to produce narrow cut distillates of a particular carbon number.
• the data of Table III show that the relative olefin percentages of the distillate cuts vary. However, the percentage of the Type I olefins, including the desired 1-n-olefins, is generally more than a third of the total. The type I and II olefins combined, which includes all the linear olefins represent more than 55% of the total. The vinylically branched olefins are present in less than 35% amounts. The percentages of the conjugated diolefins are included in the table since they are converted to monoolefins during hydroformyl ation. However, the diene structures are uncertain and as such of approximate values.
• Type III also shows the distribution of olefin types in case of four narrow cut C 12 distillate fractions. As expected varying amounts of the different types of olefins of different boiling points were found to be present. Thus the proportion of the Type I olefins changed from 45.5 to 33.8%.
• the effluent of the above polar capillary column was split and led to a flame ionization and a sulfur specific detector.
• the chromatogram of the flame ionization detector shows the distribution of the organic compounds according to polarity in the lower part of the Figure.
• the upper chromatogram produced by the sulfur specific detector shows the elution of the sulfur compounds in the order of their polarity.
• the lower GC of Figure 6 shows good separation of the aliphatic, monoaromatic and diaromatic hydrocarbon components of the C 12 fraction.
• the aliphatic components could be broken down to paraffins, olefins plus diolefins. Their percentages were 18.6 and 50.5%, respectively.
• the monoaromatics included alkyl benzenes, naphthenobenzenes and trace amounts of alkylthiophenes. The total amount of monoaromatics was 28.2%.
• the main diaromatic compounds were i ⁇ dene, nephthalene and benzothiophene.
• the upper, sulfur specific GC of Figure 4 shows that essentially all the sulfur compounds of the C 12 fraction were aromatic. The majority were alkyl thiophenes. Benzothiophene was also present in significant amounts.
• distillate fractions of light gas oil were also analyzed for elemental composition, particularly for sulfur and nitrogen compounds and mercaptans. The data obtained are summarized in Table IV.
• the total nitrogen contents of the distillates were more than an order less than that of the total sulfur.
• the mercaptan content is generally even lower. However, both the nitrogen and mercaptan contents rose sharply in the C 15 and C 16 fractions.
• Olefin-paraffin mixtures could be obtained which then could be easily processed further to separate the olefins from the paraffins via molecular sieve (Parex process).
• the olefin rich fractions resulting from these separations and others such as adsorption can be used for the alkylation of phenol, olefins, aromatic hydrocarbons and the like.
• the aromatic components can be reacted with coker distillate olefins of choice of further purified and then utilized.
• Example 1 This example illustrates the alkylation of excess phenol with a C 12 olefin containing a fraction of Fluid-coker gas oil from a thermal cracking process.
• the final reaction mixture was filtered with suction using a glass filter of medium frit to remove the catalyst.
• the catalyst was then washed with toluene and the filtrates were, combined and fractionally distilled in vacuo to separate the products and unreacted feed components.
• the monododecyl phenol product was obtained at between 122° and 145°C at 0.05 mm.
• the didodecyl phenol was distilled between 192°C and 200°C at 0.05 mm. Elemental analysis was obtained.
• C 18 H 30 O Calcd. C, 82.38%; H, 11.52% found C, 82.69%; H, 10.64%; S, 0.25%.
• didodecyl phenol C 30 H 54 O: Calcd. C, 83.65%; H, 12.64%. Pound C, 83.90%; H, 10.39%.
• the structures of the mono- and di -dodecyl phenol products were also subjected to a 13 C NMR study.
• the monododecyl phenol was determined to have 36.5% of the ortho-substituted isomer and 63.5% of the parasubstituted phenol.
• the ortho isomer is much less generally in the range of 4% to 10%.
• the branchiness of the present semilinear monododecyl phenol product was also compared with that of the highly branched isododecyl phenol on the basis of the number of methyl groups present per phenyl group.
• That number of methyl groups is two for a linear 1-n-dodecene derivative.
• Monobranched dodecenes lead to products having three methyl groups.
• Dibranched olefins provide products having four methyl groups. The degree of branchiness of these three products is defined as 0, 1 and 2.
• the NMR study of the present semilinear monododecyl phenol showed 2.9 mole methyl groups per molecule and thus a branchiness degree of 0.9.
• the commercial isododecyl phenol had 4.9 methyls and thus a branchiness of 2.9. Due to. the NMR uncertainty of CH 2 versus CH 3 group assignments these values may not be absolutely right but certainly indicate the much reduced branchiness of the novel product.
• composition of the starting C 12 light Fluid-coker gas oil fraction and the unreacted components of the same were compared by 1 H NMR spectroscopy. Percentages of different types of hydrogens were determined. Based on the hydrogen distribution weight percentages of the various types of compounds were estimated as shown by Table VI.
• the final reaction mixture was filtered using a Buchner funnel with suction.
• the Amberlyst 15 was washed twice with 400 ml n-hexane each and dried in vacuo.
• the resulting recovered catalyst weighed 462 g and thus showed a 19% weight increase.
• Example 3 The recovered catalyst was used in Example 3 which was carried out in the same manner. The results were also similar:
• the resulting reaction mixture was filtered and the catalyst was washed in the- same manner, except that toluene was used for washing.
• the use of toluene resulted in the recovery of a cleaner catalyst.
• the dried weight of the catalyst was 411 g, just 6% above the original.
• the average percentage of monononyl phenol in the above examples was: 35.6%.
• the average ratio of mono- versus dinonylphenol was 85 to 15.
• the weight of the combined product is 1845 g. This corresponds to 66.7% of the calculated yield.
• the combined filtrates and washings were fractionally distilled in vacuo to separate the unconverted reactants and products.
• the unconverted C 12 fraction was distilled at first about 40°C at 1 mm. It was a colorless liquid. This was followed by the unconverted phenol at about 60oC at 0.1 m.
• the product was distilled with minor decomposition, essentially dealkylation, apparently due to the presence of residual acid catalyst.
• Some of the crude product distillates were combined and redistilled to provide a total of 1489 g (53.8%) of monononyl phenol as an almost colorless liquid boiling in the range of 105 and 120° at 0.05 mm.
• the dinonylphenol by-product boiled between about 160 and 182°C at 0.05 mm.
• the amount of this viscous orange liquid distillate product was 204 g.
• nonyl phenol of the present example is of a more branched character than the analogous product of Example 1, it is nevertheless distinctly different from the highly branched t-nonyl phenols of the prior art. This has been determined by comparison of the 13 C NMR spectra of the product of this experiment and t-nonyl phenol.
• Example 4 This example demonstrates the alkylation of phenol with a C 8 fraction of a fluid coker naphtha containing equimolar amounts of octenes.
• a magnetically stirred mixture of 1.2 g (12.75 mmole of phenol and 2.4 g of a C 8 distillate cut of a Fluid-coker naphtha containing 60% (1.43 g, 12.75 mmole) of octenes and 0.54 g of catalyst that was used in the type of Example 1 was heated in a closed vial at 90°C for 8 hours.
• an identical reaction mixture was employed; however, the temperature used was 115°C.
• a C 8 coker naphtha was replaced by a 60/40 weight mixture of 1-octene and n-nonane.
• Example 5 This example demonstrates the alkylation of phenol 130°C with a C 9 Fluid-coker naphtha containing a small excess of olefins.
• Phenol was reacted with 10% excess of Fluid-coker nonenes at 130°C in the presence of -5 wt.% Amberlyst 15 in the manner described in Examples 2 and 3. The data indicate that the conversion was substantially complete in 4 hours. The ratio of mono-versus dinonylphenol products was found to be substantially similar to those of Examples 2 and 3 in spite of the different ratios of reactants used.
• the final reaction mixture was worked up to obtain mono- and dinonylphenol products via fractional distillation.
• the first distillate fractions containing the more branched nonylphenol isomers was obtained between 94 and 104°C at 0.05 mm.
• the latter distillate fractions with the more linear nonyl phenols were distilled between 104 and 119°C at 0.5 mm. Both sets of distillates were of similar amounts and found to be similar in composition, thus confirming their isomeric character.
• Example 10 This example shows a model compound study of phenol alkylation with 1-octene in the presence of benzothiophene.
• a catalyst precursor it was dissolved in the alkylphenol to form sodium alkyphenolate prior to being added into the tube.
• the last component to be added was ethylene oxide or propylene oxide. Appropriate molar amounts of ethylene oxide were condensed to the other components into the evacuated tube which was then closed.
• the liquid propylene oxide reactant was simply added to the mixture.
• the closed tubes containing the reaction mixtures were then heated in baths at the desired reaction temperature. At the start of the heating the mixture was shaken by hand to assure homogeneity.
• samples were periodically taken from the tubes, after cooling, for GC analyses to determine the progress of the reaction.
• Example 11 This example illustrates the ethoxylation of semilinear nonylphenol.
• the tubes were sealed and heated at 140°C. The first three mixtures were kept at that temperature for 1 hour, the last for 15 minutes. Thereafter they were analyzed by packed column GC. The GC data indicated a complete reaction of ethylene oxide with the exception of the 15 minute sample. The nonylphenol reactant was substantially converted in each case. However, the impurities in the nonylphenol, apparently nonyl thiophenes of shorter retention times, did not react.
• Example 12 This example illustrates the propoxylation of semilinear nonylpheno.
• the nonyl phenols derived in accordance with the present invention reacted with varying amounts of propylene oxide in a manner analogous to Example 11 above. These reactions were carried out in the presence of 5 mole % sodium as catalyst precursor. Propylene oxide to nonylphenol reactant ratios of 1, 2 and 10 were used. The reaction mixtures were heated at 140°C and periodically sampled for GC analyses. At the 1/1 and 3/1 oxide to phenol reactant ratios, selective propylene oxide ring opening by the phenol took place. On the basis of GC composition, the relative amounts of variously propoxylated nonylphenols were calculated. The data are shown in Table X.
• the reaction mixture contained unreacted propylene oxide.
• b Includes species of higher propoxylation.
• the data indicate that as the reaction progressed, the amounts of more highly propoxylated species increased.
• the main products were mono- and di propoxy! ate.
• the main products were di- and tripropoxylated nonylphenols. Beyond the tetrapropoxylated species, little product was formed.
• propylene oxide polymerization became a major side reaction when 10 moles of oxide were reacted with one mole of phenol at 140°C.
• Example 13 This example compares the base and acid catalyzed ring opening reactions of propylene oxide with monoethoxylated phenol as a model compound.
• Monoethoxylated phenol was reacted with propylene oxide in the presence of sodium as a catalyst precursor and 15 wt. % p-toluene sulfonic acid as a catalyst.
• the sodium was reacted with the monoethoxylated phenol to provide 5 mole % sodium alcohol ate as a catalyst.
• 2.76 g (10 mmole) monoethoxylated phenol, 2.76 g mesitylene solvent and 1.16 g (10 mmole) propylene oxide were employed. The reactions were carried out in closed pressure tubes as usual at 140°C for 1 hour.
• the acid catalyst was not soluble in the reaction mixture at room temperature but dissolved on heating. Acid catalysis was somewhat less effective and less selective than base catalysis. After one hour at 140°C, there was still 1% unconverted propylene oxide (6.5% of the original amount) in the reaction mixture. Also, there was 5.77% propylene oxide oligomer present (equivalent to 37% of the propylene oxide reactant employed) and 26.8% of monoethoxylated phenol. The major part of the propylene oxide (57.2%) reacted with the monoethoxylated phenol to form primary and secondary alcohols. The ratio of these alcohols for the monopropoxylated products according to capillary GC was the following: ) O O O O O O O O O
• Example 15 A comparative experiment (Example 15) was carried out in an identical manner, except for the acid catalyst.
• ethoxylated nonylphenol reactant (2.15 g)
• 0.37 g p-toluenesulfonic acid monohydrate was added to neutralize the sodium alkoxide base and provide a 15% concentration of the acid catalyst.
• a threefold molar excess of the propylene oxide reactant (0.75 g) was added and the sealed mixture was heated at 140°C for 1 hour.
• a subsequent GC analysis indicated that propoxylation occurred but at a lower rate and less selectively than in the case of the base catalyst.
• Example 16 This example illustrates the reaction of nonylphenol sodium compound prepared in accordance with the present invention and n- octylphenol sodium with y-butanesultone.
• n-octylphenol sodium was prepared using 0.67g (3.2 mmole) n-octylphenol, 0.14g (3.5 mmole) sodium hydroxide and about 3g of a 4/1 water/dioxane mixture with D 2 O locking solvent.
• 0.44g (3.2 mmole) Y-butane-sultone was added and sulfonate formation was followed by 13 C NMR. NMR showed that the sultone conversion was complete on standing overnight. Reaction was also indicated by the formation of product crystals.
• the mixture was heated at 70°C to obtain a homogeneous solution and then a 13 C NMR spectrum was taken at that temperature. The following characteristic chemical shift values (ppm) were found for carbon fragments of the 3-butanesulfonate group.

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