JPH02500978A - Alkylphenols and their derivatives via phenol alkylation with cracked petroleum distillates - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Alkylphenol and its via phenol alkylation with cracked petroleum distillate This application is filed in Application No. 922.877 on October 24, 1986. This is a partial continuation application of No.

field of invention This application relates to novel compositions and methods of making the same. More specifically, this application is a new Fermentation by olefin component of cracked petroleum distillate to produce lukylphenol The present invention relates to alkylation of phenols and derivatives of said alkylphenols.

The present invention therefore provides a method for producing olefinic cracked petroleum distillates, especially pyrolyzed petroleum residues with a high sulfur content. Concerning the composition, separation and alkylation chemistry of.

The present invention particularly relates to the chemistry of C6 and higher alkylphenols. that【 ; Phenols are extracted from mainly straight-chain distillates derived from high-temperature pyrolysis of petroleum residues. Semi-linear alkylphenols derived by alkylation with olefin components The purpose of this project is to manufacture products. Furthermore, the present invention provides alkylphenols, especially cracked petroleum distillates. Ethoxylation and propoxylation of distillates, especially those derived from coker distillates. Concerning silation. Ethoxylated and propoxylated alkylphenol products The preparation of sulfate and sulfonate derivatives of is also described. Finally, a The conversion of lukylphenol to sulfurized metal phenate-containing basic detergents is discussed.

Comparison between prior art and the present invention Phenol by olefin in the presence of acid to produce alkylphenol The alkylation of compounds is a well-known reaction. In fact, alkylphenols have a wide range of For example, orthoalkylphenols used in U.S. Patent No. 3.929 , No. 654, it has superior antioxidant properties compared to rose alkylphenols. It is an inhibitor. Cs and higher branched alkylphenols are ethoxylated non- Production of ionic surfactants and their sulfate and sulfonate derivatives It is marketed for. Regarding this, "Nonion surfactant (Nonion surfactant) ic 5urfactants)", Chic (M.

J, Sch'5ck) [, M, Dekker+ Inc. , New York.

N, Y, ), 1966. Reference is made in particular to pages 44-85. Alkylphenol The chemistry of sulfate and sulfonate derivatives also includes the ``sulfonation reaction (S ulfnation Reactions) J, Gilbert (E, E, G 11bert), Interscie Publishers (Interscie nce Publishers, New York+NY)+1965 + Reference is made in particular to pages 378, 379, 350 and 297. Ethoxylated a Sulfation and sulfonation of alkylphenols is also described in U.S. Pat. No. 9; No. 2,106,716; No. 2,184,935 and No. 3.150 It is described in No. 161. Automatic for other applications of alkylphenol derivatives Contains automotive lubricant additives. For example, “Lubricants and related products (Lubrica) nts and Re1ate’d Products) J + Craman (D .

Klamann) * Verlag Chea+ie, Weinheim, H.

As mentioned above, alkylphenols are used in the production of surfactants. most often A frequently used alkylphenol surfactant intermediate is t-octylphenol. , t-nonylphenol and t-dodecylphenol. They are usually Phenols of diisobutylene, propylene trimer and propylene tetramer respectively Produced by alkylation of These are highly branched alkylphenols , and 95% of -C is substituted by rose.

In contrast to highly branched alkylphenols, so-called straight-chain alkylphenols Are known. When prepared by alkylation at about 80"C, these alkaline Kylphenol is generally a statistical mixture of mostly ortho and para isomers, i.e. These intermediates convert linear alpha olefins into alkylated It is produced by using it as a lubrication agent. Therefore, U.S. Patent No. 3.423.474 and and Soviet Patent No. 882,995 contain phenol and alpha oxide as reactants. Alkylation with lefins is disclosed. U.S. Patent No. 3.31.2.734 and No. 3.432.561 contain analogous alkyl indigestion by cracking wax olefins. is described. U.S. Pat. No. 3,630,918 also describes decomposing wax olefin. Metal dialkyldithiophosphers from alkylphenols derived from phenols The production of derivatives is disclosed.

Olefins of 06-C1 catalytic gasoline streams in U.S. Patent No. 3,639,490 Depending on the ingredients, phenol or cresols can be alkylated to form branched chain alkyl groups. The production of phenolic antioxidants is disclosed.

However, none of the above references contain semi-linear alkylphenols, i.e. Alkylphs derived from olefins, including straight chain and small amounts of branched olefins does not teach the production of phenols, known for the production of such products. No olefin feed was present.

As part of this invention, pyrolysis petroleum distillates, especially fluid coking and flexible A surprisingly large amount of linear olefins derived from residual fuel oil by coking It was found to contain olefins and small amounts of branched olefins. These olefie The mineral must be extensively hydrogenated before it can be used as such a feedstock. Distillate fuel costs are valued below. During such hydrogenation the olefinic component is converted to paraffin.

Furthermore, in the present invention, sulfur compounds in such pyrolysis petroleum distillate inhibit the catalyst. be primarily an inert aromatic thiophene-type compound rather than a mercaptan. was discovered.

Some preferred pyrolysis distillates not previously considered as alkylation feeds Products include naphtha and gas oil fractions produced in fluid coking units. integration Fluid coking methods such as fluid coking and flexi coking are It represents an excellent refining method for the conversion of feedstock oil. Fluid caulking and flexi The pyrolysis stage of shokoking is the same. However, fluid caulking -Although it does not utilize residual coke that is produced with distillate, flexi coking by-products are used to produce low heating value gas. A discussion of these methods can be found in U.S. Pat. ．． No. 813,916; No. 2, No. 905.629; No. 2,905,733; No. 3 , 66L543; No. 3,816,084; No. 4.055.484 and No. No. 4,497.705, to which reference is made.

The preferred fluid coking and flexi coking methods are low severity pyrolysis operations. It is. Low severity typically involves lower temperatures (482-538°C (900-100°C)). 00@F) and at the same time a long residence or contact time of about 20-60 seconds. This is achieved by using or lower severity to 538-705°C (10 By using high temperatures (on the order of 00 to 1300 degrees Fahrenheit) and contact times of less than 5 seconds. can be achieved. Decomposes heavy gas oil distillate products in long residence time operations producing additional amounts of the desired olefin component by reinjection into the line; Can be done.

The residual fuel feed for the coking process described above is typically from a refinery distillation process that uses most of the crude oil. This is the vacuum residue that remains after being removed by the process.

Therefore, these residual oils typically have boiling points of 565°C (1050″F) or higher. It has a Conradson carbon content of 15% or more.

These residual oils contain undesirable components of crude oil, namely sulfur and nitrogen compounds and Contains most of the metal complexes. In coking, high levels of sulfur (in the distillate product) to go into. As a result of high temperature pyrolysis, major amounts of olefins are also formed and It becomes the main component of the product. Despite their high monoolefin content, their Distillates such as Not considered as an alkylation feed. Surprisingly, despite the high sulfur content olefinic components of such feeds react selectively with the added phenol. It has been found in the present invention that semi-linear alkylphenols are formed.

The semi-linear alkylphenols of the present invention have a high degree of branching and a distribution of ortho to paraisomers. It differs from the highly branched and straight chain alkylphenols of the prior art in both. So They average about 1.4 to 2 branches per alkyl substituent, and about 10/90 to It has an ortho to paraalkyl substituent ratio within the range of 40/60.

Drawing description Figure 1 shows the capillary gas chromatography of a fluid coker naphtha feed in the C4 to C+Z range. Matogram with indication of main 1-n-olefin and n-paraffin components show.

Figure 2 shows the 400MHz frequency of olefin protons in the fluid coker naphtha feed. Proton nuclear magnetic resonance spectra with display of chemical shifts of various types of olefins Also shown.

Figure 3 shows the capillary gas in the light fluid coker gas oil feed in the C9 to CI5 range. Lomatodalum is shown with indications of major 1-n-olefin and paraffin components. vinegar.

Figure 4 shows the capillary gas on the highly polar column of the C+Z fraction of light fluid coker gas oil. romatograms to separate different types of aliphatic and aromatic components as well as sulfur compounds. show.

Figure 5 shows the 1- Figure 2 shows the separation of n-olefin-n-paraffin mixtures.

Figure 6 shows the ``CNMR spectrum'' of the prior art highly branched dodecylphenol product at the top. , and below the spectrum of the relatively semi-directly quenching dodecylphenol of the present invention. shows the file.

Summary of the invention In its simplest sense, the present invention provides for converting phenols into pyrolytic sulfur derived from residual oils. selectively alkylated with olefinic components of yellow-containing petroleum distillates in the presence of an acid catalyst. a monoalkylphenol having an average of less than 2 alkyl branches in said alkyl group; Based on the discovery that the obtained monoalkylphyl Enols generally have about 10 ortho to about 90 isomers to about 40 ortho to about 60 isomers. It has an ortho to para isomer ratio. A variety of such alkylphenols Derivatives are also contemplated.

Therefore, broadly speaking, the present invention is based on the formula: [During the ceremony, R is 01 to C3S, preferably Cs to CIs, more preferably Cs to Cz 9, most preferably C1-C2° alkyl, C1 and C11 alkyl The radicals iR are particularly preferably ortho and/or heterologous with respect to the phenol position; but at least one R is a higher C3-CI% alkyl group; The alkyl group has on average less than two but more than one branch within it, and p is 1 or more. or 2, preferably 1, and if p is 1, the ratio of 1 to p-R groups is about 10 to 90 to about 40:60, preferably about 20:80 to about 30:70; Nor hydrogen or Na, K, Cat ML (Eo)++H9(EO)+( CH Ri! 503M, (EO), 1 (CHri $503M and (EO), lCH (CH3) CHzco zS03M (Tazoshi E is CHzCHz, C I(zcH(CHs), C3(C)Is)C)Is; M is l, Na, K+ ammonium, Ca, Mg, and n is 1 to 30, preferably 1 to 15); Q is a substituent element of the group consisting of S, S2 and CHI; a bridging group selected from the group consisting of or Mg, and Q is CH! Then Z is (EO). H; number of bridging groups q is 0 to 15, and if Q is S or S2, q is in the range 1 to 5; The number m of phenol groups is 1 to 16, m is 1+q; Y is H and SOI; is selected from the group consisting of, M is as described above, and if Y is SO3M, q is preferred. Preferably, it is 0, and Z is (EO), H. oriented to new compositions.

The semi-linear alkylphenol intermediate of the present invention can be converted into phenols by this method. Produced by reaction with olefinic components of high temperature decomposition of sulfur-containing residual oil, formula: (In the formula, the meanings of R and P are as described above, and M is H or Na+ Cat ML Con Ni). Particularly preferred semilinear alkyl Phenols include octylphenol, nonylphenol, undecylphenol, It is dodecylphenol. A preferred semi-linear monoalkylphenol composition is having a 1 to p-ratio of their alkyl groups within the range of about 10:90 to about 40:60. do.

In preferred monophenol compositions, the value of Q is zero.

In this case the compound generally has the formula [In the formula, OZ represents a phenol group, Z is H, Na + Kt Cat Mgt (EO). selected from the group consisting of H and (EO)-(T)L(SO3)-, is from CHzCRt, CH(C)Is)CHz and CH2Cl(CH3) selected from the group, n is 1 to 30, T is CHzclb, CHzCHzCH z, CH (CHs) CI (tcHz, t is O or 1) Yes, m is H, Na, Kt ammonium + Ca, Mgt Nil Co or Fe, and U is O or 1, and if t is 1, then U is also 1. ; Y is selected from the group consisting of H and (SO or M (where M is as described above); Bare; R is ortho and/or rose relative to the phenol group Z group; Cs = C3S branched alkyl with an average of about 1.4 to about 2 branches in selected from the group consisting of groups, P is 1 or 2, and when p is 1, ortho The ratio of rose to rose isomers is about 10 ortho to about 90 rose to about 40 ortho to 60 rose , preferably between about 20:80 and about 30:700].

The present invention is also directed to methods of making these compositions.

These and other features of the invention will be readily understood upon reading the following detailed description of the invention. It will be.

Detailed description of the invention The alkylphenols of the present invention include phenols and monomers having a C3 to Cps carbon range. Produced by reaction with a hydrocarbon feed containing more than 15% olefins. this The monoolefins are about 30-50% 1-n-olefins, linear internal olefins. 15-30% and 30-45% mono-branched olefins, about 1.5 to 1 to It has a terminal to internal unsaturation ratio in the range of about 4 to 1. Actually used in carrying out the present invention Hydrocarbon feeds containing olefins are pyrolyzed hydrocarbons derived from petroleum residues. The olefin-containing fraction of the pyrolysis residue is preferably With particular reference to distillate fractions, but using other feeds with substantially similar properties Let's be recognized for what we can do.

The preferred cracked distillate of this feed contains relatively high amounts of organosulfur compounds. . The sulfur concentration is preferably between 0.1% (1000ppm) and 5% (50,000ppm). p+*) between (7), more preferably Lt 0.5% (5000ppm) to 4% (40,000 ppm). The main sulfur compounds in the preferred feed are aromatic family, mainly thiophenes. Most preferably aromatic sulfur compounds account for 90% of the total This corresponds to the above. Due to this feature of the feed, this selective phenolic alkyl The discovery that thiophenes are highly reactive and tend to polymerize under acid conditions This is surprising.

In summary, the olefin-containing reactants used as feeds in this invention are Generally has a C3 to C2S carbon range. More preferably such olefin-containing The carbon range in the fraction is C3-C29, most preferably C,-C2°, and At least 25%, e.g. 30-80%, of the olefins in the feed are linear aliphatic olefins. Particularly preferred for the practice of this invention are lefins.

The olefin feed is reacted with phenol as described above.

Usually at least 1 mole of phenol is used per mole of olefin; however, The use of excess phenol is generally preferred.

450°C1 preferably about 20-50°C1 more preferably 80-130°C It's temperature.

Importantly, the reaction is conducted in the presence of an effective amount of an acid catalyst.

-a, the acid concentration in the reaction mixture is important and ranges from about 1% to about 50%, preferably 5%. It varies from % to 25%.

One of the acid catalysts suitable for the practice of this invention is a strong acid such as sulfuric acid, phosphoric acid, phosphonic acid, Sulfonic acid, inorganic polyacid e.g. aluminosilicate clay, acidic cation exchange resin example For example, cross-linked styrene, sulfonic acids based on divinylbenzene polymers, and phosphoric trifluoride. Uron, hydrogen fluoride, tetrafluoroboric acid and other combination acids. insoluble acid A particularly preferred catalyst in the process of the present invention is insoluble crosslinked styrene. , a sulfonic acid derivative of divinyl resin.

Reaction of phenols with linear olefins produces alkylphenol products, That it can be further alkylated to give dialkylphenols is As will be readily appreciated, the formation of such dialkylphenols can be made to a large extent if desired. Suppressed by the use of excess phenolic reactant and relatively mild reaction conditions can do.

It is also readily appreciated that the alkylphenol reaction products of this method are standard It can be separated from unreacted feed components by separation methods such as fractional distillation.

Another aspect of the invention is the conversion of alkylphenol products derived from cracked distillates. It is. The most important type of conversion is preferably ethoxylation and/or A novel surfactant is provided via poxylation. In other important reactions, such alkylphenols or their ethoxylated/propoxylated derivatives. Sulfonate surfactant by reacting with ropanesultone, butylsultone or sulfuric acid to produce an agent. In different reactions, semi-linear alkylphenol is preferred Overbased automobiles by reaction with sulfur and calcium oxide plus carbon dioxide It is converted into a lubricant additive for use. Furthermore, semi-linear alkylphenols also Demulsifying agent additives by reaction with formaldehyde and ethylene oxide Can be used for manufacturing. This reaction between alkylphenol and sulfur dichloride is a Provides antioxidants for lubricants.

Metal derivatives of such compounds are described by Braid et al. ・U.S. Patent No. 4 assigned to Mobil Oil Corp. Acts as an octane improver as disclosed in No. 536.192. Decasulphide Through another reaction with phosphorus pentasulfide A zinc dialkylaryldithiophosphate lubricant additive is produced.

The method of converting semi-linear alkylphenol intermediates of the present invention into products with high Calibration is carried out under prior art conditions developed for alkylphenols. death However, further conversion of this alkylphenol as part of a multi-step process is not recommended. It has additional advantages. Generally, they produce high-boiling, low-volatility products, which then alkylphenol intermediates from unreacted cracked distillate components and alkylation byproducts. Better separation is possible. Product impurities can be easily removed by vacuum distillation. can be done.

Olefin property decomposition feed This method's olefinic feed produces new alkylphenols at low cost. This is a critical factor. Preferred feeds are produced by pyrolysis of petroleum residues .

Thermal cracking of petroleum residues produces hydrocarbons with more linear olefinic properties than catalytic cracking. 9 In the present invention, the olefin containing the 1-n-olefin component in the pyrolysis petroleum distillate Olefins are generally derived from cracked oils by high temperature pyrolysis. The containing distillate fraction is the preferred method for the alkylation of phenols according to the invention. It's a nice feed.

There are two major commercial methods for producing pyrolysis petroleum distillates from residual oils.

They are the magazine, Chew, Ing.

Tech, ), N (L2.P, 101-107. 1982. It was summarized by Jens Weitkamp. These methods are Caulk visbreaking corresponds to harsh and mild decomposition methods. Lord Corki The caulking methods are flexi caulking and fluid caulking, which are the methods of this invention. of the preferred distillate feed.

Suitable distillate feeds also include thermal processing using multiple cracking zones at different temperatures. It can be manufactured in cess. Such a method is described in U.S. Pat. No. 4,477,334. No. 4.487.686. These pyrolysis methods are Each can be adjusted to increase the olefin content of those products. heavy Gas oil distillate can be further cracked to increase the amount of low molecular weight olefins .

The olefin-containing distillate fraction of the pyrolysis process can be processed in the process of the invention without prior purification. However, these distillate fractions can be used as Treat them to reduce the concentration of aromatic hydrocarbons, sulfur and nitrogen compounds before their use. It can be lowered. For example, aromatic hydrocarbons and sulfur compounds in polar solvents. can be selectively extracted from olefin-containing fractions. Mercaptan component can be removed with a base. Nitrogen and sulfur compounds are generally polar solids e.g. It can be removed by using an absorption tower filled with silica, Fuller's earth, bauxite, etc. I can do it. More than 90% of the sulfur compounds in the higher fraction are thiophene compounds, i.e. It exists as alkylthiophenes, benzothiophenes, etc.

Olefin components using a high temperature fixed bed of bauxite or Fuller's earth or clay 11. Sulfur compounds can be easily removed with simultaneous isomerization of to convert into s Can be done.

The conjugated olefin component of this feed is subjected to prior mild hydrogenation or selective oxidation prior to use. It can be removed by alkylation. Branched olefin components may also be used, e.g. It can be removed by adding water, alcohol or acid. 1-n-olefin The components can be selectively reacted by hydroformylation or cocrystallization removal along with n-paraffin by Can be done.

Cracking refinery distillate products, light and heavy naphtha and gas oils are used in the present invention It is preferably further fractionated beforehand. The preferred wide carbon range for the pyrolysis feed is They are C1 to C3S. A more preferred carbon range is C8 to CZS. most preferred The range is C5 to C2°.

Effective fractional distillation reduces the carbon number range of any given distillate feed to 5 carbons, preferably High boiling range alkyl from unreacted feedstock limited to 3 carbons, more preferably 1 carbon. separation of the phenol product can be facilitated.

Particularly preferred feeds are semi-linear C9 and CI2 alkyl phenates, respectively. C3 and CI2 cracked distillate fractions for the production of nols. within single carbon range In the case of very sensitive distillate fractions, the ratio of the different types of isomeric olefin components is Depends on the rising range point.

The cracked distillate feed has an olefin content of about 15%, preferably 30% or more; More preferably, it is 40% or more. 1-n-olefin is the main type component is preferred.

The main olefin reactant component of this feed has the following formula (R=hydrocarbyl, preferably is unbranched alkyl): In III TV Non-branched, straight chain, mono-branched, mono-branched terminal internal terminal internal The unbranched type 1 and type IV are represented by the monobranched type 1 and type IV.

The concentration of Type I olefins is preferably about 30-50% of the total olefin concentration. . Similarly, the percentage of type olefins is preferably about 15-30%. formula , R2C=CR2 type olefin is substantially absent.

n-alkyl-substituted Type I olefins, i.e. 1-n-olefins, are generally these present in the highest concentrations in the pyrolysis distillate feed.

Alkylation method of the present invention The alkylation process of the present invention is preferably produced from petroleum residues by high temperature pyrolysis, 1-n-olefin as the main type of olefin component and 0.1-5% sulfur , more preferably 0.5-4% sulfur organic sulfur compounds. petroleum distillate feed, phenol using at least 1 mole excess phenol per mole of olefin reactant. or cresol, preferably phenol, preferably in liquid phase, from about 20 to 4 At a temperature of 50°C, preferably 20 to 150°C, more preferably 80 to 130°C. , reacted in the presence of an effective amount of an acid catalyst, preferably a strong acid insoluble in the reaction medium, Alkylphenol is the main product, preferably a C3-C3° semi-linear monoalkylphenol. phenol, preferably in addition to said alkylation process step. a) ethylene oxide and/or propylene oxide Ethoxylation and (or) producing a propoxylated alkylphenol nonionic surfactant; Said nonionic surfactant, preferably it is propane sultone or butane preferentially converted to sulfonate surfactant derivatives by reaction with stage, b) Or preferably the group consisting of propane sultone and butane sultone Alkylphenoxyalkane sulfonate by reacting with a sulfoalkylating agent selected from producing a nert surfactant; C) Or, sulfurized alkylphenol oligomer oxidation by reacting with sulfur dichloride Inhibitors, mainly o,o'-bis-alkylphenyl sulfides, are formed and the acid Cot and calcium hydroxide or magnesium hydroxide in the presence of Cot. Preferentially converted to overbased metal phenate detergents by reaction in the presence of step, d) Or di-alkyl by reaction with tetraphosphorus decasulfide and zinc oxide. producing an aryldithiophosphate additive; e) Or o,o'-bis-alkyl phenylene by reacting with formaldehyde. Produces nilmethane dimers and other methylene-bridged oligomeric polyphenols and the polyphenols were added to ethylene oxide and propylene oxide, respectively. Their ethoxylation and/or purification by alkoxylation reaction with oxides converting into a ropoxylated demulsifier derivative.

In the selective phenol alkylation process of the present invention, branched olefins in the feed component is faster than linear olefins due to better stabilization of tertiary cation intermediates. For example, in the case of P-alkylphenol: In the case of linear olefins with low reactivity, such as is a common side reaction. Therefore, 1-n-olefin is not only methyl but also Higher alkyl branched alkylphenols, e.g. is given depending on the reaction conditions.

In general, branched olefins yield t-alkylphenols, whereas straight chain olefins gives S-alkylphenol. Therefore, tertiary vs. secondary alkylphenols The ratio of olefin products depends on the ratio of branched to straight chain olefins reacted. Branched Olef Virtually all prior art isoalkylphenols derived from t-alkylphenols are It is lukylphenol.

Branched olefins mainly give para-tertiary alkylphenols, whereas linear olefins The quinine yields a mixture of ortho- and para-secondary alkylphenols. 1-n- Olefins are o/p isomer mixtures that are close to statistical, i.e., o/p ratios of 66:33. can be given. Therefore, this method is suitable for olefin conversion of cracked distillate feeds. gives a product with a high o,/p ratio as the o,/p ratio increases.

The monoalkylphenol product of this process can be further alkylated to 2,4-di Can provide alkylphenols. For example, 1-n-olefin is The formation of such dialkylphenols results in the formation of a large excess of phenolic compounds. can be suppressed by the use of cold reactants and relatively mild reaction conditions.

One of the preferred catalysts for this process is an insoluble cross-linked styrene divinylbenzene resin. It is a sulfonic acid derivative. The catalyst preferably decomposes and decomposes soluble sulfonic acids. Used at temperatures below 150°C to avoid formation. Insoluble solid acids are reactive It can be easily removed from the compound by filtration.

The alkylphenol products of this method are separated from unreacted feed components by fractional distillation. can do. However, at high temperatures they cause catalytic reversal of the alkylation reaction. It is important to remove or neutralize all strong acids before distillation, as they can be.

The alkylphenol products of the present invention, especially semi-linear monoalkylphenols, It can be conductorized to provide several different types of useful compositions. monoalkyl The phenol intermediate can be further converted before or after separation. coarse monoa Derivatization of the alkylphenol reaction products is an effective method for separation due to the low volatility of the derivatives. Often advantageous from this point of view.

Alkoxylation Alkylphenols can be ethoxylated and (or ) propoxylated to form alkylphenyl polyoxyethyl and/or poly Oxypropyl alcohol can be given. Such base-catalyzed alkoxy The first step of the sylation reaction, for example in the case of p-alkylphenols, Much faster than reaction.

High-boiling formation after monoethoxylation or propoxylation of alkylphenols can be easily separated from very low boiling impurities by distillation.

The monoalkoxylated product is then subjected to further reactions, e.g. ethoxylation or can be propoxylated. Acid-catalyzed propoxylation is a and a mixture of secondary propoxylated alcohols, e.g. + , which will be further discussed next. Therefore, in the attractive process variant, Alkylphenoxyethanol or alkylphenoxydibrobanol monoalkyl The coxylated products are separated by distillation and then further derivatized. Archi Subsequent ethoxylation of luphenoxyethanol can be performed using various ethoxylated alkyl groups. resulting in a Poisson distribution of phenol products. A similar behavior is observed in alkylphenoxy-2 - Observed with propoxylation of propatool. However, in the case of propoxylation The isomeric product composition depends on the presence of base versus acid catalysts.

Generally, this base-catalyzed ethoxylation and propoxylation of alkylphenols are preferred for their high rate and selectivity of monoalkoxylated product formation.

Acids are poor catalysts for phenol-epoxide reactions. Monoalkoxyl metaplasia The selective formation of the starting decomposition olefin-derived alkylphenol reactants is significant. Wide boiling range, especially when containing hydrocarbons and sulfur compounds as impurities It's advantageous.

Propoxylation in the presence of base catalyst forms virtually only secondary alcohols However, the major product isomers in the presence of acid catalysts are primary alcohols, e.g. This is 2-alkylphenoxyethoxylpropanol-1. In the presence of acid catalyst Further propoxylation leads to the subsequent addition of primary and secondary propotool units. The general formula of the resulting ethoxylated propoxylated alcohol is shown in the following reaction scheme. Shown: [In the formula, Pr is CI (C)13) C8t or CHz (CH) CHs ] These products contain propylene moieties in various orientations and are primarily alcohol-based. It has an end group.

Sodium hydroxide and potassium hydroxide are often used as base catalysts for alkoxylation. Often used. These catalysts react with alkylphenols to form the corresponding alkali Forms rifenolate. The latter is then further treated with ethylene oxide or propylene oxide. Reacts with ren oxide to form a growing alkoxide moiety. Substitute for alkali hydroxide When sodium or potassium is a precursor of phenolate or alcolade species You can help. The molecular weight of alkoxylation products is different from that of phenol and ethylene. oxide and/or propylene oxide.

P-)luenesulfonic acid, silicon tetrafluoride, cross-linked as an acid catalyst for alkoxylation Polymeric sulfonic acid, antimony pentachloride, tin tetrachloride, trifluoromethane sulfonate phosphoric acid and other strong acids can be used. BFs and, for example, 82, Ti gold Group alkyls, or combinations with hydroxides, can also be used. Ethylene oxide Anhydrous systems are preferred to avoid polymerization of and/or propylene oxide.

Sulfation and sulfonation Decomposed olefin-derived alkylphenols and their ethoxylation/propoxylation Both sylated derivatives readily react with sulfuric acid and sulfur dioxide to form sulfate and and sulfonates. Other sulfonating agents are SCh and sodium bisulfite. It is a complex of um. The latter is a compound of halides and sulfates, Str. eekey) reaction or in addition reactions with olefin derivatives. Eto Xylated alkylphenols are first sulfated under mild conditions and then sulfonated. will be converted into an online version. The acid hydrolysis of the resulting sulfate sulfonate is carried out according to the following reaction scheme. yields the sulfonate as shown: (In the formula, the meanings of symbols R and n are the same as above.) These sulfates and Metal and ammonium salts of surfactants and/or sulfonates are useful surfactants. Ru.

Sulfonate derivatives are also used for alkylphenols and their ethoxylation/purification. Can be produced by reaction of a lopoxylated derivative and a sulfoalkylating agent . For example, the reaction between an alkali metal derivative and propane sultone or butane sultone reaction yields the corresponding sulfonate.

Other sulfoalkylating reagents are bromoethane sulfonate and vinyl sulfonic acid. It's salt.

Condensation with sulfur chloride Alkylphenols are mainly industrial sulfur dichloride, 5Cj22 and S, CI! .

3 phenolic portions per minute by sulfiding, preferably at about 80°C. A sulfur crosslinked condensation product having a For example, nonylphenol In the case of dinonylphenol mixtures the following products are formed: By purging all 11C1 by-products and unreacted components from the reaction mixture. After removal, the product can be used as an antioxidant component in crankcase oils, automotive lubricants, etc. It can be used as Similar products can also be used as additive intermediates.

As a preferred example, sulfurized 4-tert-dodecylphenol contains monoa elemental sulfur and acid Calcium chloride is reacted with ethylene glycol and then in the presence of carbon dioxide. It is mainly converted to the corresponding overbased calcium dodecyl phenolate.

Although the exact sequence of the reaction is not known, the main steps of the reaction are shown in the following diagram. can be done.

The viscosity of the 1-dodecylphenol intermediate in the above scheme depends on the degree of branching of the i-dodecyl group. Exists. Low viscosity is desirable for ease of processing in zero-cracked olefin-derived alkylene oxides. The low degree of branching of the dodecyl groups in phenol advantageously results in lower viscosity and therefore improved processing. Have reason.

Overbased calcium dodecyl phenolate products are used in marine engine oils and cranks. Used as a detergent additive component in case oil. As an additive, it is simply The detergent acts not only as an antioxidant (but also as a neutralizer for oxidation by-products).

Overbased magnesium alkyl phenolates can also be produced and have excellent Useful as a detergent additive. However, in their synthesis, free hydroxide mag The nesium should be derived from magnesium alcolade 0 e.g. persalt The overall process scheme in the case of basic magnesium dodecyl phenolate is as follows: This is the case: Alkylphenols derived from cracked distillates easily condense with formaldehyde do. The resulting methylene cross-condensation product is then treated, preferably in the presence of a base catalyst. It is ethoxylated and/or propoxylated as a demulsifier, fuel additive, etc. and oligomeric surfactants useful as quartz slurry stabilizers. reaction diagram The formula is then exemplified by nonylphenol: (wherein m is 0-15, preferably 1 ~10, and n is 1 to 30) Reaction with tetraphosphorus decasulfide The semi-linear alkylphenol of the present invention can be easily converted into tetraphosphorus decasulfide by a known method. React 0 e.g. Bench, (136ncze) in the magazine "Schmielston" Schmierstoffe un d Schmierungstechnik) J, N115, P, 4-1 6.1966, can be used. The resulting bis-alky The aryldithiophosphoric acid is then converted to the corresponding dithiophosphoric acid as shown by the following reaction scheme. Converted to zinc alkyl dithiophosphate: Typically, zinc dialkyldithiophosphate products containing excess Zn as hydroxide are It is a high temperature antioxidant useful as a lubricating additive.

Alkylphenol derived composition Ethoxylated and/or propoxylated biolinear alkylphenol composition It is also possible to alkylate phenols in one step with the olefinic component of the pyrolysis distillate. It is induced by They are the formula: %formula%) has. Particular preference is given to monoethoxylated compositions in which n is 1: this ethoxy The most important derivatives of fluorinated and/or propoxylated alkylphenols are sulfate and sulfonate. They preferably have the formula: [In the formula, the meanings of R, p, EO and n are as described above; T is C6□CHi , cozcnzcoz, CH(CH3)CH2CH2, preferably C0(CHs )ChzC)It; t is O or 1; M is H, Na, KSCa, Mg, Ni-1Co, Fe, preferably H and Na; 0 [or], and if t is 1, then U must also be 1, and r is 0 or is 1] and consists of an ethoxylated sulfonate derivative of the formula It is a precursor of The sulfate sulfonate of the above formula has the formula: is a precursor of ethoxylated sulfonates.

Other preferred sulfonate derivatives of this ethoxylated monoalkylphenol The type is an expression: (In the formula, the general meanings of the symbols R and T are the same, and n is 1 to 35, preferably 1 to 15) has. A particularly preferred group of sulfonates of this type is sulfonates. monoethoxyl Particularly preferred are sodium sulfonate compounds.

Other types of compositions derived from this semi-linear alkylphenol have the formula: (In the formula, R and p have the same meaning, R is more preferably 08 to CI2, most preferably Also preferably Co alkyl, bridging sulfur group haphenolic hydroxyl with respect to the ortho-para position, mostly ortho, and X is 1 or 2, mainly 1. , V is O-6, preferably 1-3) of sulfur-crosslinked antioxidant compounds. of V equal to 0 to 2, preferably 1 Particularly preferred are sulfur-bridged semilinear nonylphenols having average values.

Sulfur-bridged overbased calcium and magnesium semi-linear monoalkylphenols Cium phenate derivatives are a different type of detergent additive. They are the formula: (In the formula, the meaning of R is C1-C3S alkyl, preferably C9-C+++ alkyl , most preferably C+Z alkyl; M is Ca or Mg, preferably Ca ) Contains structural units of

Methylene-bridged semi-linear monoalkylphenols and their ethoxylation and/or propoxylated derivatives represent another subgenus of this composition. that are of the formula: [wherein the meaning of R is ortho and/or per C, -C,, alkyl, preferably C, ~C+s alkyl, most preferably Preferably it is C, alkyl. The bridging methylene group is ortho to the phenol group. or the para position, mainly the ortho position, p is engineering or 2, preferably 1; m is 0-15, preferably 1-1O, E is Cll2CIIt, C112C 11(C11,)C112, preferably C11□CI+2, and n is 0 to 30 , preferably 0 to 30] Rudithiophosphate antioxidant additive derivatives have the formula: (wherein R is a phenolic acid C9 to C3% in the ortho and/or para position with respect to the element, preferably C 3 to CI2 alkyl, M is Hs (Zn) Vts Zn [Ill 1 preferred Actually Zn! /z] forms another subgenus.

Example This method of phenol alkylation and its products are described below to limit the invention. Examples are provided to illustrate without limitation. Decomposition distillation as an introduction to the examples Output alkylation reactants are described. The composition of these reactants is a distinguishing feature of the invention. It is a sign.

cracked distillate feed High temperature pyrolysis is a key factor in the production of the highly olefinic reactant feed of the present invention. This was disclosed in the specification. Other factors include the origin and pretreatment of the petroleum residue to be degraded. It is. The presence of the main 1-n-olefin component in the cracked distillate is due to the presence of normal atoms in crude oil. Depends on the presence of alkyl group. These olefins are n-alkyl aromatic and n - formed by decomposition and dehydrogenation of paraffins.

In the past, the molecular structures of both petroleum residues and pyrolysis distillates were unknown. Therefore, No desirable characteristics of this distillate feed were recognized. The important steps of the invention are High resolution capillary gas chromatography (GC), magnetic resonance spectroscopy (NMR) and and combined capillary gas chromatography/mass spectrometry (GC/MS) This was a structural analysis of a composite distillate feed.

Distillate Fraction Used as Feed in the Present Invention Vacuum produced from Northwest American crude oil Induced by fluid coking of residual oil.

Other distillate feeds derived from Arabian crude oil in flexi-coking units are similar. They had similar compositions. The composition of these feeds over a wide carbon range was determined in 1986. U.S. Patent Application No. 914.802 filed on October 4th and currently allowed. It is described in. Reference is made to this application.

The composition of the 64-CI2 coker naphza distillate was determined by GC using a heated 50m column. was analyzed. The key components of the mixture are determined by GC/MS with the aid of standards if necessary. It was iff. The obtained gas chromatograms showed various amounts of 1-n-olefin and 1 with symbols indicating the n-paraffin components. Range from C6 to C+ wherein the 1-n-olefin to n-paraffin ratio is within the range of about 1.1 to 2.1. Ru. 1-n-olefins are the largest single-type compounds.

Low decomposition temperatures result in low olefin/paraffin ratios. For example, fluid coke Dirate coking carried out at a lower temperature than cooling provides a lower ratio distillate.

Analysis of the naphtha fraction from the dilate coker revealed an average of 0.3 1-n-olefins. /n-paraffin ratio.

A wide range of C1-C1□ co-carnaphtha fractions with a reflux ratio of 10 and a column equivalent to 15 theoretical plates. Distillate enriched in olefins and paraffins with a specific number of carbon atoms by fractional distillation using The selected fractions that produced the product were analyzed using a JEOL GX 400MHz spectrometer. Studied by roton NMR. Figure 2 shows the NMR spectrum of the olefin region of naphtha. Table of chemical shift regions assigned to vinyl protons of various types of olefins The constant 18N region of olefin protons of various types of olefins shown in conjunction with the diagram is shown below. This was used to evaluate the linearity of ren-yne. Relative mole fraction of olefins of various carbon numbers The amounts of olefin protons were calculated based on the amounts of various types of olefin protons. of these calculations The results and boiling ranges of the fractions are shown in Table I.

The data in Table 1 shows that I diolefins, i.e., -substituted ethylene, are present in all distillate fractions. and the main type of olefin in the starting C4-C+Z naphtha. However, the percentage of I diolefin in the distillate residue decreased below the initial It will be done. This result may be due to 1-n-olefin conversion during high-temperature distillation. Ru.

Small variations of 32-50% are also observed in the diolefin content of the distillate cuts.

The second largest olefin type present in naphtha and its distillates is 1.2-di- Consists of dichloroethylene. The percentage of these diolefins is between 18 and 26% It fluctuates. Most, if not all, of these olefins are linear internal olefins. It is in.

■ Diolefin, i.e. 1,1-disubstituted ethylene, in an amount within the range of 12-17% It was recognized that it exists. The main olefin of this type is the 2-methyl substituted terminal olefin. It was Refin. Their branching occurs primarily on the vinyl carbon.

■Diolefins, trisubstituted ethylene, are the smallest monoolefins in these distillates. It was a quinine component. Their relative molar concentrations are in the range 6-12%.

■Diolefins, i.e., tetrasubstituted ethylene, cannot be measured by proton NMR. won.

Finally, Table 1 also shows a small but significant amount (8-16%) of conjugated diolefins. show. The amounts shown for these olefins are based on the position of conjugation of the conjugated olefins. and different vinyl JC hydrogens per molecule due to the presence of branching in the vinyl moiety. It is an approximation because it can have a number.

The NMR spectrum of the naphtha fraction is also in the region of aromatic and paraffinic protons. The amount of olefin was evaluated by analysis. Percentages of various types of hydrogen in these fractions The weight percentages of various types of compounds were estimated from the component distribution and elemental analysis.

Type 1 olefins, mainly 1-n-olefins, are present in these fractions from 18.7 to 28 ．． It was estimated to exist within a range of 3%. These percentages were studied Depends on both the carbon number of the inline fraction and the typically narrow boiling range of the individual C6-C These values for Type I olefins within a 1° range are determined by GC as 1-n-olefins. corresponds approximately to the value obtained for

The total olefin content of these fractions is in the range 47-62% as determined by NMR. It is in. Conjugated diolefins are known when they are under hydroformylation conditions or before are included in this percentage because they are converted to monoolefins by mild hydrogenation. It is permitted to do so. Due to differences in boiling points of olefin isomers, linear vs. branched The relative proportions of the olefin components are of course somewhat dependent on the boiling range of the feed. also shows a significant and increasing amount of aromatics in various naphtha fractions up to 25%, Aromatics are mainly hydrocarbons, namely alkylbenzenes and naphthalenes but also contains significant amounts of alkylthiophenes and benzothiophenes .

Most of the sulfur in high carbon cuts is in the form of these heteroaromatic compounds.

The most important information showing the elemental composition of Billings fluid coker naphtha fraction in Table ■ Surprisingly, the data in the table shows a high percentage of sulfur. A small amount of this sulfur in the class fraction is in the form of mercaptans. Depends on GC/MS For example, most of the sulfur in the C3-C1t fraction is in the form of alkylthiophene.

In this example, the C3 and C9 fractions of Billings fluid coker naphtha were Used as alkylation feed. 04~CI2 naphtha and C9~c,b Light gas oil fractions overlap. Billings fluid coker light gas oil 01□ distillate chima It was used in the following examples.

A similar confirmation was produced by the same flute coking equipment that took coker naphtha. The test was carried out using a light coker diesel oil.

Figure 3 shows the capillary GC of light gas oil in the C9-C4 range, about 90% of the components are C1 ~CI5 carbon range. It is clear that this group has a particularly large C11-Cl3 component. There is some overlap between the composition of naphtha and broad-cut naphtha.

The main components are 1-n-olefin and n-paraphthalate, as indicated by the symbols in the figure. It is in. In general, the concentration of 1-n-olefins is higher than that of the corresponding paraffins. The 1-n-olefin to n-paraffin ratio, which is larger than that of held.

A light gas oil fraction was fractionally distilled to produce a narrow-cut distillate with a specific carbon number. light Quality light oil and these fractions also contain proton N? Researched by IR. Quantitative analysis This gas oil contains 88.2% of the hydrogen in the mixture on saturated carbons and 6.2% on olefins. strong aliphatic character with only 5.6% on aromatic rings and on unsaturated carbons It was shown that it has a high olefinicity.

Selected distillate cants of light gas oil were also analyzed by NMR as well. those bits The distribution of olefins was specifically studied to determine the relative amounts of the different types of olefins present. Ta. The results are summarized in Table m.

The data in Table ■ shows that the relative olefin percentages of distillate cuts vary. , but the percentage of Type I olefins containing the desired 1-n-olefins is Generally, the total I/, or more. Type I and type olefins, including all straight chain olefins Together they account for more than 55% of the total. Vinyl-branched olefins are 3 Present in an amount less than 5%. The percentage of conjugated diolefins is It is included in the table because it is converted to monoolefins during lumylation. However, Jie The structure of the equation is uncertain and therefore an approximation.

■ The type also indicates the distribution of olefin types in the case of 4 Narrow Force CI □ distillate fractions. vinegar. As expected, it is recognized that there are varying amounts of different types of olefins with different boiling points. It was. Therefore, the proportion of type I olefin varied from 45.5% to 33.8%. .

From the distribution of different types of olefinic hydrogens, we calculate the weight percentages of different types of olefins. Calculated. The total olefin rating including dienes is 50.4-61.7%.

61.7% value is observed for CI & fractions distilled with decomposition As a result of zero cracking, this fraction contains not only C14 but also low molecular weight olefins. T* C1! In the case of a range, four narrower fractions are analyzed to determine the proportion of different types of compounds. determined the change in Only modest changes were observed in the total olefin concentration (45 ．． 5-54.4%).

To show the detailed composition of this gas oil feed and its effect on the separation of polar adsorbents. In order to demonstrate the results, more details for the narrow range C+Z fraction based on GC/MS analysis are presented. data is given. Such cuts are non-polar (boiling point) methyl silicone G However, the highly polar CPSiffi 8B column (cyano (propylated and silicone stationary phase) can support different types of components depending on their polarity. Separation was observed. [This column has a high operating temperature limit (approximately 27 5°C), which was confirmed in the analysis of high-boiling fractions. Contains a group of identified components A two-capillary GC trace is shown in FIG.

Split the effluent of the polar capillary column above and analyze it with flame ionization and sulfur-specific detectors. led to. The chromatogram of the flame ionization detector shows polarity at the bottom of the figure. Shows the distribution of organic compounds. Upper chromatogram given by sulfur-specific detector shows the elution of sulfur compounds in order of their polarity.

The lower GC in Figure 6 shows the aliphatic, monoaromatic and diaromatic hydrocarbon components of the C1□ fraction. With the help of GC/MS, the aliphatic components, paraffin, and It could be classified as olefin plus diolefin. Those percentages are They were 18.6% and 50.5%, respectively. Alkylbenzene for monoaromatics , naphthenobenzene and trace amounts of alkylthiophene. monoaromatic The total amount was 28.2%. The main diaromatic compounds are indene, naphthalene and benzene. It was polythiophene.

The sulfur-specific GC at the top of Figure 4 is CI! Virtually all sulfur compounds in the distillate are aromatic The majority were alkylthiophenes, indicating that it was a family of alkylthiophenes. benzothiofe Also present in significant amounts.

C1, a similar analysis of the fraction showed an even better separation of the components according to their polarity. . In this case, the distribution of aliphatic components was similar, but the main aromatic components were dinuclear: They were methylnaphthalenes and methylbenzothiophenes.

Distillate fractions of light gas oils are also characterized in terms of elemental composition, in particular sulfur and nitrogen compounds and Mercaptans were analyzed. The data obtained are summarized in Table ■.

The percentages of carbon and hydrogen were maintained rather well with increasing molecular weight. These indicate that the aliphatic character of the gas oil was significantly maintained. Total sulfur content is C1-C I! It was kept at about 1% within the range.

Thereafter, there was a sudden increase in sulfur to 2.82% in the CI6 fraction. of these fractions It is observed that there was an increase in decomposition during distillation. C.

When the fraction was redistilled, 1-n-olefins with a wide range of molecular weights were found in the distillate. It was done. This is due to the decomposition of non-volatile aliphatic sulfur compounds to produce olefins and mercaps. This suggests that tans were produced.

The total nitrogen content of the distillate was more than an order of magnitude lower than that of total sulfur. Mercaptan content is Generally lower, but both nitrogen and mercaptan contents in CIS and It rose sharply in CI & distillate.

Separation of olefin feed components Paraffin and/or olefin rich fractions and aromatic fractions are It was assumed that it could be separated from the pyrolysis distillate derived from the oil. High 1-n- Cooling of such distillates with olefin and n-paraffin content reduces these It has been found that the main components co-crystallize and can therefore be separated. The resulting α-olefin The paraffin/paraffin mixture can be used as is or further separated in olefin reactions. Wear.

In our study of model compounds, we found that mixtures suitable for this separation consist of a series of carbon atoms. It was confirmed that it contained 1-n-olefin and paraffin with . If the 1-n-olefin and n-paraffin components are present in the single carbon fraction, They do not tend to co-crystallize or form solid solutions. n-pa with a certain number of carbon atoms The effective cocrystallization of raffins is with 1-n-olefins having two more carbons per molecule. arise. Therefore, we found that eicosane (C,...) cocrystals with tococene (Cza-). However, he admitted that eicosane and eicosene did not co-crystallize.

Experiments using the C8-C+s fraction of fluid coker light oil were conducted using 1-n-olefins and It was shown that the paraffin and n-paraffin components can be separated by crystallization. This is this According to Figure 5 showing the capillary gas chromatogram of the feed and separated mixture. shown. In the experiment illustrated by this figure, 5% methyl ethyl chloride in the feed Cool the MEK solution with dry ice, filter, and wash with cold MEK. Purify it! -n-olefin-〇-paraffin (Cゎ-+　C,.) mixture is separated did. A toluene solution of the separated crystals was then analyzed by capillary GC.

Figure 5 shows C1-+Cゎ. The component is equivalent to about 41.3% of the feed, C, ″10Cゎ ' is present in the separated crystal mixture.

This separation method could be achieved with other, perhaps more advantageous, solvents.

An olefin-paraffin mixture can be obtained, which can then be further processed Olefins can be easily separated from paraffins using molecular sieves. Let's go [Parex method].

The flexi-coker and fluid coker distillates contain polar solvents e.g. sulfonates. It is highly effective for aromatics containing sulfur compounds by selective extraction with acetonitrile and acetonitrile. It has also been found that extracts enriched in paraffin and The olefin-rich residual raffinate is highly refined with a very reduced sulfur content. This is the feed that was created. Aspirates feed rich in n-paraffins and n-olefins. Separation can likewise be achieved by deposition, for example by using zeolites. this The findings are illustrated by the following table showing the results of a single step extraction with sulfolane at 20°C. shown.

by cc Ingredients Feed Raffinate Extract%~10% Paraffin 26 29 6 Olefin 64 66 49 Aromatic 10 5 39 Olefin-rich fractions resulting from these separations and others, e.g. adsorption, are It can be used for alkylation of alcohols, olefins, aromatic hydrocarbons, etc. aromatic components can be further purified and then reacted with the coker distillate olefin of choice used. I can do it.

The invention is further described in the following illustrative examples, which however do not fall within the scope of the invention. It is provided not as a limitation of scope, but as an illustration of some aspects thereof.

Example 1 This example shows the CI2 olefin-containing fraction of fluid coker gas oil from pyrolysis process. is an illustration of the alkylation of excess phenol by

1035.2 g (11 moles, 100% excess) of phenol in a 51 flask and ca. C of fluid coker gas oil containing 0% isomeric dodecene (928 g, 5.5 mol) The stirred mixture with 51.5 g of I2 distillate fraction 1B was heated in a heating bath under nitrogen for 11 hours. It was heated to 0"C. At that temperature, the Rohm and Haas Co. Product name: Amberlyst by nd Haas Co. Dry cross-linked polystyrene sulfone 6419.9 g sold under 15 ( (equivalent to 1,97 mol sulfonic acid) was added. An exothermic reaction immediately occurs, increasing the temperature of the mixture. The temperature rose to 130°C within 2 minutes. At that point, cool the mixture to approximately 115°C and held at that temperature for 4 hours. of the mixture by packed column chromatography Periodic analysis is performed for the following percentages of monododecylphenol and didodecylphenol: Showed: 1 35, 6 7.1 2 39.6 7.7 4 44, 4 7.8 These data indicate that the majority of the reaction occurred within the first hour. Due to the excess of phenol, the ratio of mono to di-dodecyl phenol product is did not become significantly higher with increasing conversion. These two at the end of the 4 hour reaction period The products were present at a combined concentration of 52.2%. mono-pair di-dodecylphenol The final weight ratio was 85:15. Based on GO data, monododecylphenol 1282 g of mol was formed, which is 88% of the calculated yield.

Filter the final reaction mixture with suction through a medium-fritted glass filter to remove the catalyst. The removed catalyst was then washed with toluene, and the combined filtrates were fractionally distilled under reduced pressure. The product and unreacted feed components were separated. Monododecylphenol product is Obtained between 122 and 145°C at 0.05wn. Didodecylphenol is Single-element analysis values distilled between 192 and 200°C at 0.05 mm were obtained.

Monododecylphenol, CIs Hz. 5 calculated value for 0, C, 82, 38% ; Hllll, 52%, measured value, C, 82, 69%, H, 10, 64%, S, 0. 25%, didodecylphenol, for C1°H,,0: calculated value, C183,6 5%, H, 12,64%, measured value, C, 83,90%, H, 10,39%.

The structures of the mono- and di-dodecylphenol products were also determined by 13ONMR studies. I got it. Monododecylphenol has 36.5% ortho-substituted isomer and para-substituted isomer. It was determined to have 63.5% phenol. Reaction between isododecene and phenol In the case of dodecylphenol obtained by (in the range of 4-10%) of this semi-linear monododecylphenol product. The degree of branching is also based on the number of methyl groups present per phenyl group. compared with that of decylphenol. The number of methyl groups is linear 1-n-dodecene 2 for derivatives.

Monobranched dodecene yields a product with three methyl groups.

Di-branched olefins give products with 4 methyl groups.

The degree of branching of these three products is defined as 0.1 and 2. This semi-linear monod NMR studies of decylphenol show 2.9 moles of methyl groups per molecule, thus 0.9 showed the degree of branching. In contrast, commercially available isododecylphenol contains 4.9 methyl, It had a degree of branching of 2.9. Due to NMR uncertainty of CH, versus CHz group assignment , these values may not be absolutely correct, but they are certainly new It shows a very low degree of branching.

The results of a comparative NMR study of semi-linear and highly branched alkylphenols are shown in Table ■. will be shown. The data are based on the semilinearity of dodecylphenol and nonylphenol. The main differences between the Both the number of branches and the number of branches are shown.

Ortho to paraisomer ratio and degree of branching of semi-linear and branched nonylphenols. The above comparative data is qualitatively determined by their 13C NMR spectra in Figure 6 is shown. In the aromatic carbon region from 100 to 160 ppm, the figure shows semi-linearity. The product contains more 〇-substituted carbon than the high school division (C- in the range of 132 to 136 pp The less branched character of the semi-linear product indicates that it has a spectral It is indicated by the aliphatic region, O~60 ppm. Especially if the semi-linear product is between 5 and 20 It is clear that it has fewer methyl groups in the pp+m region.

The composition of the starting C+Z light fluid coker gas oil fraction and its unreacted components were Comparison was made by MR spectroscopy. The percentage of different types of hydrogen was determined. Hydrogen distribution Based on the weight percentages of various types of compounds are calculated as shown in Table ■ It was done.

The data shows that about 59.3% of the total olefins and conjugated diolefins are about 60%. Only about 0.7% of the type ■, i.e., linear internal dodecene, was recovered. It was present in the feed.

Table■ ”Comparison of semi-linear and highly branched alkylphenols by CNMR spectroscopy Alkylphenol element % ortho methyl type isomer branching Yōhazoku version Legzoku L Tenjō 1% - Drinking one Semi-linear dodecyl 37.7 62.3 18.1.36.5 0.9 techniques Decyl 33.2 66.8 26.8 5.9 2.9 Semi-linear nonyl 42 ．． 2 57.8 16.4 19.3 0.3 technique nonyl 39.5 60. 5 27.8 5.0 2.2a, methyl carbon is 22.5 ppm methylene py Calculated based on the mole fraction of saturated carbon peaks between 26 and 5 pp+m, excluding Ru.

The methyl carbon of t-butyl and neopentyl groups is not included.

Examples 2 and 3 This example shows how fluid coker gas oil is produced by excess Cm olefin-containing fraction. This is an illustration of alkylation of phenols.

591 g (6,28 mol) of phenol and approximately 60% nonene ( 1200 g, 9.51 mol) of C drop fraction in fluid coker gas oil containing 2.00 0g of the stirred mixture was heated to 110°C with a heating bath. Sulfo at that temperature 388.7 g of acid catalyst was added. The reaction mixture was heated to 115° with a mild exotherm. Periodic chromatographic analysis of product formation in the 0 reaction mixture held for 4 hours at The results are further traced and shown in the following table.

Nonylphenol,' Antique plate craft monogy 1 24.8 2.3 2 29.2 2.7 4゛36.3　6.3 The final reaction mixture was filtered with suction using a Puchner funnel. amber list 15 Twice, 400aj each! of n-hexane and dried in vacuo. The resulting collection The medium weighed 462 g, thus representing a 19% weight increase.

The recovered catalyst was used in Example 3, which was conducted in the same manner. The results were also similar: Reaction time Nonylphenol 1 21.6 1.8 2 28.0 4.0 4 34.9 3.4 The resulting reaction mixture was filtered and the catalyst was washed similarly, but the toluene was washed used for. The use of toluene resulted in a cleaner catalyst recovery, reducing the dry weight of the catalyst. The amount was 411 g, just 6% higher than the original.

The average percentage of heptanonylphenyl in the above examples was 35.6%. Mo The average ratio of di-nonylphenol to di-nonylphenol was 85:15. Based on GC data The combined weight of the product was 1845 g. This corresponds to 66.7% of the calculated yield. I guess.

The combined filtrate and washings were fractionally distilled under reduced pressure to separate unconverted reactants and products. I let go. The unconverted C+z fraction was initially distilled in one country for seven distillations at approximately 40°C. it is colorless It was liquid. The unconverted phenol was then distilled off at 0.1 m and approximately 60°C.

The product apparently undergoes a small amount of decomposition due to the presence of residual acid catalyst, but essentially dealkylation. , was distilled with Therefore some of the crude product distillate was combined and redistilled to 0. Molded as an almost colorless liquid boiling within the range 105-120°C at 0.5mm. 489 g (53.8%) of nononylphenol iH was obtained. dinonilfe The nol byproduct boiled between about 160-182°C at 0.05 mm. This viscosity The amount of orange liquid distillate product was 204g.

The analysis was as follows: Monononylphenol, C+aHzaO.

Calculated value, C181, 76%; Hll 0.98%; Measured value, C182, 90%; H210, 59%, S, 0.15%, dinonylphenol, C,, H,, O, total Calculated value, C183, 17%; H112, 22%. Measured value, C, 83, 41%; H, 10.38%, S, 0.58%.

CNMR spectroscopy study of distilled monononylphenol fraction was carried out by nonyl group. It was shown that the product of Example 1 was more branched than the dodecyl group. In this case The high branching of the alkyl groups is clearly the result of low olefin conversion. (low o In the reflex conversion, only the more branched olefin component of the cracked distillate is converted into a selected alkali. ), NMR also shows ortho-nonylphenol versus para-nonylphenol. The ratio of nylphenols was shown to be 19:81. This ortho/para ratio is 18 or less of that observed in the case of ortho- and para-dodecylphenol. Ru. Again the low ortho/para ratio is due to the high branching of the alkyl substituents.

Starting C, the composition of the fluid coker naphtha fraction and its recovered unreacted components were determined by IHN. Comparison was made by MR spectroscopy. The results are shown in Table 0. The data in the table is monochrome. isomerized to fin components, namely nonene and yne. But only some of the latter was further reacted to yield the desired alkylphenol product.

The nonylphenol of this example has more branching than the analogous product of example 1. However, it is clearly different from the highly branched t-nonylphenol of the prior art. . This is the “CNMR spectrum of the product of this experiment and t-nonylphenol. Determined by comparison of files.

Example 4 This example shows a fluid coker naphtha containing phenol and equimolar amounts of octene. C, indicating alkylation by fraction.

1.2 g (12,75 mmol) of phenol and 60% (1,43 g, 12. Fluid coker naphtha C6 distillate containing octenes (75 mmol) Magnetically stirred mixture of 2.4 g and 0.54 g of the catalyst used in the mold of Example 1 was heated at 90° C. for 8 hours in a sealed glass bottle. Similar reaction mixture in second test However, the temperature used was 115°C. In the third test, C, Co. - Instead of carnaphtha, use a 60/40 heavy mixture of 1-octene and n-nonane. Using. This mixture is then similarly reacted with phenol at 115°C to reduce the reaction. Comparative data regarding gender were obtained. 3 The mono- and di-ol formed in the reaction mixture The percentage of cutylphenol was determined periodically by GC. Obtained data is shown below.

Mono- and di-octylphenol products, % Test l Test 2 Test 3 1 13.8 0.4 33.7 2.9 28.59 2.32 18.7 1.2 42.2 5.1 33.74 4.94 25.3 1.5 36. 37”16.28 32.8 2.3 The results showed that the alkylation of phenol in the presence of Amberlyst 15 increased from 90°C to 11 It shows that it is very fast at 0°C. Reaction of coker naphtha with C, cut at 115℃ is essentially completed within 2 hours. At a similar dilution, 1-n-octene is a coker-nuff. The isomer of octene is less reactive than octene, but is effectively more dialkylated. Produces phenol.

Example 5 This example shows a C, 13 fluid coker naphtha containing a small excess of olefins. Figure 2 shows alkylation of phenol at 0°C.

Fluid coker nonene with 10% excess of phenol and 5% by weight at 130”C The reaction was carried out as described in Examples 2 and 3 in the presence of Amberlyst 15.

The data show that the conversion was essentially complete within 4 hours. The ratio of nol products was similar to that of Examples 2 and 3 despite the different ratios of reactants used. was found to be substantially similar to that of

The final reaction mixture is processed to produce mono- and di-nonylphenol products by fractional distillation. I got it. The first distillate fraction containing more branched nonylphenol isomers is 0.05 obtained at 94-104°C.

Later distillate fractions containing more linear nonylphenols are 104 to 1 at 0.5 m. It is recognized that the distillates of the 0 series distilled at 19°C are of similar amount and have similar compositions. and thus their isomeric character was confirmed.

Elemental analysis, monononylphenol, C+sHt 40° total XfJ: C18 1,76; H, 10,9B, measured value for the first distillate: C1 (Direct: C: 82. 50;H,9,84is,0.15. Dinonylphenol, C,, H, □0. Calculated value: C, 83, 17: H, 12, 22° Measured value: C, 83, 41; H, 10 , 01; S, 0.35° Example This example shows equimolar C, olefin-containing fluid coker naphtha at 150°C. The alkylation of phenol is indicated by the residual fraction.

Phenol 1.8 g (19 mmol), 60% or 2.4 g (19 mmol) 4 g of C9 distillate cut of fluid coker naphtha containing nonene of Bar list 0.29g (5% by weight) (1.4 mmol sulfonic acid equivalent) magnetically The stirring mixture was heated at 86°C for 16 hours, then at 150°C for 818 hours. Samples of the liquid reaction mixture were taken periodically during the reaction to detect mono- and di-nonylphenol. We analyzed the rules. The data obtained are shown below.

-Note 1: Nonylphenol% temperature time Knee L mono 2 85 16 14.4 150 +2 38.3 4.0 4 42.5 4.5 8 45.0 6.0 The results show that a slight reaction occurs at 85°C, but monooctylphenol occurs at 150°C. is rapidly and selectively formed.

Examples 7-9 This example shows the production of phenol from the olefinic C9 fraction of Furtoco-Carnaphtha. Figure 2 shows the effect of varying temperature and reactant ratios on the alkylation of .

C9 of Billings fluid coker naphtha with phenol and 60% nonene content Distillate cut magnetically stirred mixture carried out in the presence of 15% Amberlyst catalyst The reaction was carried out as described in Example 6 at various reaction temperatures and phenol versus nonene reactions. The chemical ratio was used.

The mixture was sampled periodically and analyzed by GC. The obtained data are shown in the table■ It is shown by.

Comparing the data from Examples 6 and 7, it appears that the reaction occurred at 130"C rather than 115°C. However, the reaction rate increases by increasing the amount of catalyst used. 15°C could be sufficient to increase the temperature, therefore, the 15% amber The rate at 115°C in the presence of 5% amberlyst in Example 4 It was observed that the rates were similar to those obtained at 130°C in the presence of .

Table■ C. Effect of reactant ratio on phenol alkylation with fluid coker naphtha Fruit Phenol - Anti-Natural Conditions - In a Mixture Example Nonene Temperature Time Nonylphenol, 0NcL JL Knee L 　Monogy 7 0.90 130 1 38.3 6.32 49.4 9.5 4 48.3 12.1 8 51.9 20.3 8 0.90 115 1 22.0 4.72 3 (L3 4.8 4 36.8 6.3 8 40.2 8.3 9 0.66 115 1 19.8 2.92 29.2 5.6 4 30 9.2 9 0.50 115 1 12.5 2.74 25.7 8.6 In Examples 7-9, the phenol to olefin ratio decreases from 0.9 to 0.5. and the reaction amount was increased to increase the 0 reactivity and selectivity resulting in low product formation. The use of phenol is clearly advantageous.

Example 10 This example demonstrates phenolic alkylation with 1-octene in the presence of benzothiophene. We present a model compound study for the synthesis.

Equimolar amounts of phenol and benzothiophene in a magnetically stirred sealed glass bottle. (0.94 g (10 mmol) phenol and 1.34 g (10 mmol) base) ] and an equivalent amount of 1-octene (1.12 g, 10 mmol). The compound was incubated at 80°C overnight in the presence of 0.17 g Amberlyst 15 (5% by weight). Made it react.

GC analysis of the reaction mixture by packed column and capillary GC shows that octene is phenolic. was shown to be selectively alkylated. According to packed column GC, the reaction mixture is 16% monooctylphenols and 1% monooctylbenzothiophenes Contained. Significant amounts of dioctylphenols or dioctylbenzothiophene A 9-capillary GC in which no species were formed showed extensive isomerization of the starting 1-octene reactant. Only 11.2% of the total octenes in the reaction mixture were 1-octene. 0 -Octylphenols and P-octylphenols are octylphenols. It comprised approximately 83% of the class. The remaining 17% is thought to be m-octylphenols. I was disappointed.

2- in the case of both 0-octylphenols and p-octylphenols. Methylhebutylphenols were the major isomers.

They accounted for about 70% of the total. Further heating of the mixture produces dioctylphenol oles are mainly formed by subsequent alkylation of 0-octylphenols. Ta. Therefore, the resulting mixture is mainly P-octylphenols and 0. p-geo It consisted of cutylphenols, and no 0-octylphenols were present.

The results of phenol alkylation with 1-octene alone at 115'C are qualitative. similar to The most obvious difference is the high isomerization of 1-octene and the Lower percentage of 2-methylhebutylphenol isomer compared to octylphenols cents, about 55%, overall, the study showed that the fluid coker olefin confirming the selective process of phenol alkylation by

Alkoxylation operation of semi-linear alkylphenol (Examples 11 to 15) Alkylphenols derived from fluid coker distillate in previous examples The ethoxylation and propoxylation of was carried out primarily in a pressure tube of approximately 9 d capacity.

These tubes are equipped with Teflon stop valves and are connected to a JEOL EX900 binuclear NMR spectrometer. suitable for use in A typical 3 g reaction mixture was used.

In a typical operation, the alkylphenol and catalyst and a fixed solvent, typically Mesitylene, typically, was added to the pressure tube. Sodium used as catalyst precursor Once added, it is dissolved in alkylphenol and added to the sodium chloride solution before adding to the tube. Lucyl phenolate was formed. The last component added is ethylene oxide or or propylene oxide. The appropriate molar amount of ethylene oxide was exhausted. The other ingredients were condensed into a tube and then sealed. Liquid propylene oxide is easy Added to the mixture. The sealed tube containing the reaction mixture is then heated in a bath to the desired reaction temperature. Ta. During the reaction, the mixture was shaken by hand at the beginning of heating to ensure homogeneity. After cooling, samples were periodically taken from the tubes for GC analysis to measure the progress of the reaction.

In many alkoxylations, starting from the monononylphenol product of Example 5 It was used as a reactant. This reactant is the initial distillate fraction and therefore 0.25% sulfur. It contained yellow in the form of alkylthiophene. Of course, the latter reacts with the epoxide No, but they tend to polymerize in the presence of strong acids.

Example 11 This example is illustrative of the ethoxylation of semi-linear nonylphenol.

2.2 of nonylphenol produced by the method of the present invention in each of the 4 pressure tubes. (10 mmol) and 2.2 g of mesitylene solvent. nonylphenol 5% of is the reaction between 0.012 g (0.5 mmol) of sodium and phenol. It existed as sodium nonylphenolate derived by reaction. After that various amounts of ethylene oxide, 15, 20, 30 and 10 mmol, respectively, into a tube Condensed inside. This is 1.3.2.3 and 10 ethylene oxide versus nonyl The phenol reactant ratio was generated.

The tube was sealed and heated at 140°C. The first three mixtures were kept at that temperature for 1 hour, and the last was held for 15 minutes. They were then analyzed by packed column GC. GC day The samples showed complete reaction of ethylene oxide except for the 15 minute sample. Nonylphenol The reactant was substantially converted in each case. However, nonylphenol Impurities within, nonylthiophenes with apparently short retention times, did not react.

GC showed the formation of ethoxylated nonylphenol product.

The ratios of various ethoxylated nonylphenols are different and clearly ethylene oxide It depended on the ratio of reactant to nonylphenol. The results are shown in Table ■.

Table■ Effect of reactant ratio on the degree of ethoxylation of semilinear nonylphenol i 50.3 1s, 17.2 11.22 49.7ゝ 76.1 3B, 5 16.235.8ゝゝ　54.3ゝ　32.4 a) A 10/1 mixture of ethylene oxide to nonylphenol was simply heated for 15 minutes. Made it react.

b) This percentage also includes higher ethoxylated species.

Due to the complexity of fluid coker nonene feed, a high number of isomeric compounds are formed It was done. Therefore, the distinction between compounds with different degrees of ethoxylation is difficult and somewhat arbitrary. Met. However, the evaluation of the total reaction mixture made similar assumptions, so the evaluation was relatively valid. Cloth data was obtained.

At a low ethylene oxide to nonylphenol ratio of 1.3, mono- and di-ethoxy Only sylated products were formed. At an oxide to phenol ratio of 3, most of the product minutes had 2 or 3 functional toxy units per molecule. In contrast, 10 oxides versus phenos A wide distribution of ethoxylated products was obtained at different ratios. The degree of ethoxylation is short, 1 Although not all the ethylene oxide was reacted during the 5 minute reaction time, 4 It spread far beyond.

Example 12 This example is illustrative of the propoxylation of semi-linear nonylphenol.

The nonylphenol derived according to the present invention is mixed with a seed amount of propylene oxide and Reacted analogously to Example 11. These reactions were carried out using 5 mol as catalyst precursor. % sodium. 1.2 and 10 propylene oxide vs. The nylphenol reactant ratio was used. The reaction mixture was heated to 140’C and the GC min. Samples were taken periodically for analysis. 1/1 and 3/1 oxide to pheno Selective propylene oxide ring opening by phenol occurred at a ratio of 1 to 3 reactants. G.C. The relative amounts of various propoxylated nonylphenols were calculated based on the composition. De The data are shown in Table X.

Table X Effect of reactant ratio on the degree of propoxylation of semilinear nonylphenol 1 89.2 83.8 58.6 11.7 5.02 10.8 16.2 41.4' 39.7 39.53 27.1 36.2 4 21.5ゝ 19.3h a) The reaction mixture contained unreacted propylene oxide.

b) Contains higher propoxylated species.

The data show that the amount of higher propoxylated species increased as the reaction proceeded. 0 nominally equimolar reactant ratio (actual ratio is greater than 1 due to impurities in the phenol) The main products were mono- and di-propoxylates. 3 times excess When using lopylene oxide, the main products are di- and tri-propoxylated compounds. It was nylphenol. Small amounts of products above the tetrapropoxylated species are formed. It was.

In contrast to the selective reaction described above at low propylene oxide to phenol ratios, Polymerization of lopylene oxide combines 10 moles of oxide with 1 mole of phenol at 140° When reacted with C, it became a major side reaction.

Example 13 This example uses monoethoxylated phenol as a model compound and propylene oxide. Compare base- and acid-catalyzed ring-opening reactions of sid.

Monoethoxylated phenol with sodium as catalyst precursor and as catalyst. and reacted with propylene oxide in the presence of 15% by weight P-)luenesulfonic acid. Ta. Sodium was reacted with monoethoxylated phenol to give 5 mol% sodium. Alcolade was given as a catalyst. 2.76 g (10 mmol) in the re-experiment of monoethoxylated phenol, 2.76 g of mesitylene solvent and 1.16 g of mesitylene solvent g (10 mmol) of propylene oxide was used. The reaction is sealed pressure as in the example The reaction was carried out in a tube at 140°C for 1 hour.

In the presence of a base catalyst, the propylene oxide conversion is completed and a highly selective ring-opening reaction occurs. general formula compounds were formed. GC analysis shows the production of various propoxylated secondary alcohols. The following distribution percentages were shown for objects: n=0:9.6; n=1:64 ．． 9;n=3:18.2;n=4:4゜5;n-5+2.8゜ The acid catalyst system was not soluble in the reaction mixture at room temperature, but dissolved upon heating. . Acid catalysts had somewhat lower effectiveness and lower selectivity than base catalysts. at 140℃ After 1 hour, still 1% of unconverted propylene oxide (6.5% of the initial amount) has reacted. was present in the mixture. Additionally, 5.77% propylene oxide oligomer (used propylene oxide (equal to 37% of the reactant) and 26.8% monoethoxy phenols were present. The main part (57.2%) of propylene oxide is mono Reacted with ethoxylated phenols to form primary and secondary alcohols.

The ratio of these alcohols to monopropoxylation products by capillary GC is: It was as follows: These two compounds represented 75% of the propoxylated product.

The other 25% consists primarily of isomeric dibroboxylation products.

Examples 14 and 15 These examples illustrate the preparation of ethoxylated nonylphenyls of the present invention in the presence of base and acid catalysts. The propoxylation of nols is described.

Ethoxylated semidirect nonylphenol was used as a reactant in these examples. there was. It contains equivalent amounts of mono- and di-ethoxylated nonylphenols. Contained in tyrene solution. (5 mol% sodium alcoholade derivative as catalyst) existed).

The results were similar to those observed with model compounds in previous examples.

In the first example, 2.15 g of the above reactants were added in a 3-fold excess (0.7 5 g) of propylene oxide. Heat the reaction mixture at 140°C for 1 hour A base-catalyzed reaction then occurred. GC analysis shows virtually all ethoxylation reactants Indicates propoxylation. Most of the propylene oxide used (90% ) is propylene oxide oligo? It reacted selectively without the formation of -.

A comparative experiment (Example 15) was similarly carried out with a butylic acid catalyst.

P-)luenesulfonic acid to ethoxylated nonylphenol reactant (2.15g) - Add 0.37 g of hydrate to neutralize the sodium alkoxide base and A concentration of 15% was given. Thereafter, a 3-fold molar excess of propylene oxide reactant (0,7 5g) was added and the sealed mixture was heated at 140°C for 1 hour. After that, GC analysis is done by professionals. Poxylation, however, occurred at a lower rate and with lower selectivity than with base catalysis. and showed.

Example 1 Examples of nonylphenol sodium compounds prepared according to the present invention and n - Illustration of the reaction of sodium octylphenol with y-butane sultone.

As a first test, 2.2 g of nonylphenol produced according to the present invention was added to 10 g of base Reacted with 2.2 g of 25% methanolic sodium methoxide containing mmol . 1.4 g (1.4 g) of y-butane sultone was added to the resulting sodium nonylphenolate solution. 0 mmol) was added to give a clear orange reaction mixture liquid. If left at room temperature A reaction occurred. It is a colorless sodium 3-nonylphenylbutanesulfonate crystal. This was indicated by the precipitation of crystals. Precipitation occurred overnight. 0.4 g of crystalline product was filtered and Separated by drying. Its structure was confirmed by 13C NMR spectroscopy.

In the second test, a class reaction was carried out with high purity n-octylphenol, and the 3- Characteristic NMR parameters of butanesulfonate were determined. These parameters - was then used as a diagnostic value in confirming the structure of the nonyl derivative.

A solution of n-octylphenol sodium was added to n-octylphenol 0.67 g (3.2 mmol), sodium hydroxide 0.14 g (3.5 mmol) and Prepared using approximately 3 g of a 4/1 water/dioxane mixture locking solvent with 0 vibrations. Manufactured. Add 0.44 g (3.2 mmol) of γ-butane sultone to this reactant solution. In addition, the sulfonate formed was followed by 13CNMR. NMR is Surt 0 reaction, which showed that the conversion was complete after standing overnight, was also due to the formation of product crystals. Shown. The mixture was heated to 70 °C to obtain a homogeneous solution, then 13CIJMR The characteristic chemical shift value (ppm) of the 0th order taken at that temperature is 3-butane. It was observed for the carbon fragment of the ruphonate group.

C1h -CH-CHz -C) IzSOi18.69 73.4 47.4 Values within the chemical shift range above are also analogs derived from semi-linear nonylphenols. Recognized for sulfonate products. .

Engraving (no changes to the content) Procedure amendment writing method) Yoshi, Commissioner of the Patent Office 1) Takeshi Moon 1. Indication of case PCT/US 871027903, person making amendment Relationship to the case: Applicant 5. Date of amendment order: December 5, 1999 International search report

Claims (47)

[Claims] 1. Phenol is alkylated with olefins in the presence of acid catalysts, thereby forming olefins. In the process for obtaining alkylphenols and paraalkylphenols, at least a stoichiometric amount of reacting the phenol with an olefin-containing feed having a C5 to C35 carbon range. the feed comprises a substantial amount of straight chain aliphatic olefins, thereby Alkylphenols having on average less than 100 side chains in the alkyl group are obtained, The ratio of ortho to para isomers of rukyphenols is about 10 ortho to 90 para to about 4 Methods within the range of 0 ortho to 60 para isomers. 2. If the feed contains 20% or more olefins, the concentration of linear alpha olefins 2. The method of claim 1, wherein: is 30% or more of the total olefin concentration. 3. The method of claim 1, wherein the olefin feed has a C6 to C29 carbon range. . 4. Claim 1 wherein the olefin feed comprises 45% or more straight chain aliphatic olefins. Method described. 5. Claim 1, wherein the olefin feed is a distillate fraction of a thermal hydrocarbon cracking process. the method of. 6. 2. The method of claim 1, wherein excess phenol is reacted. 7. An olefin-containing distillate fraction of pyrolysis petroleum residue, the fraction having C5 to C Contains at least 20% of olefins in the 35 carbon range and contains at least 20% of the total olefins present. A fraction containing 45% straight chain aliphatic olefins is treated with an alkali in the presence of an effective amount of an acid catalyst. An average of less than 2 branches in the kill substituent and within the range of 10:90 to 40:60 contact for a sufficient period of time to yield alkylphenols having a ratio of normal to para isomers. An alkylation process that involves 8. The olefin fraction and phenol are brought into contact to a temperature of about 20 to about 450°C. 8. The method according to claim 7. 9. The olefin component of the distillate is 30% or more of linear terminal olefins and 15% or more. 9. The method of claim 8, comprising a linear internal olefin as above. 10. Produced from petroleum residues by high-temperature pyrolysis, it converts 1-n-olefins into the main type. Contains organic sulfur compounds as an olefin component and at a concentration of 0.1% sulfur or higher Olefinic cracked petroleum distillate feed, phenol or cresol; in liquid phase at a temperature of 20 to 450 °C, In the presence of an effective amount of acid catalyst Let it react, Alkylation method comprising producing alkylphenols as the main product . 11. 11. The method of claim 10, wherein the feed is produced from vacuum resid. 12. Vacuum residual oil is decomposed in a fluid coker or flexi-coker equipment. 12. The method of claim 11, wherein a distillate feed for alkylation is produced. 13. Narrow boiling distillate fractions and alkylphenol products within the C3-C30 range 11. The method according to claim 10, wherein the or derivative thereof is separated by fractional distillation. 14. 11. The branched olefin component of the feed is selectively reacted. the method of. 15. the phenol reactant is used in at least 1 molar excess over the olefin reactant; 11. The method according to claim 10. 16. 11. The method of claim 10, wherein the acid catalyst is a solid insoluble in the liquid reaction medium. 17. 17. The method of claim 16, wherein the insoluble acid catalyst is a crosslinked polymeric sulfonic acid. 18. The alkylphenol product of the reaction has an average of less than 2 alkyl groups on the higher alkyl group. It is a semi-linear C3-C30 monoalkylphenol with branches, ortho to para 11. The method of claim 10, wherein the ratio of alkyl substituents is greater than 10:90. 19. Additionally, alkylphenol products can be converted into ethylene oxide, propylene oxide, etc. acid, propane sultone, butane sultone, sulfur dichloride, formaldehyde, Claim 10, comprising the step of reacting with a reagent selected from the group consisting of tetraphosphorus sulfide. How to put it on. 20. Alkylphenol with ethylene oxide and/or propylene oxide Ethoxylation and (or) producing a proboxylated alkylphenol nonionic surfactant 19. The method of claim 18. 21. Nonionic surfactants in the group consisting of propane sultone and butane sultone Alkylphenoxy alkanesulfate by reacting with a sulfoalkylating agent selected from 19. The method of claim 18, wherein a Honert surfactant is produced. 22. Reacting alkylphenol with sulfur dichloride produces o,o'-bis-alkyl Phenol sulfide and other sulfurized alkylphenol oligomer antioxidants 19. The method of claim 18, wherein: 23. Sulfurized alkylphenol oligomers with calcium hydroxide or mag hydroxide Reacted with nesium in the presence of CO2 to form an overbased metal phenate detergent. 23. The method of claim 22. 24. Dialkylaryl dithiol is produced by reacting alkylphenol with tetraphosphorus decasulfide. Ophosphoric acid is produced, and then the acid is reacted with zinc oxide to form di-alkyl aryl. 19. The method of claim 18, wherein the method is converted to a zinc dithiophosphate additive. 25. By reacting alkylphenol with formaldehyde, o,o'-bis- alkylphenol methane and then other polyphenols, the latter being ethythmically Ethoxylation by reaction with lene oxide and/or propylene oxide and/or a proboxylated polyphenol demulsifier. the method of. 26. formula, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A composition comprising a compound of During the ceremony, OZ represents a phenol group, Z represents H, Na, K, Ca, Mg, (EO)nH or and (EO)nT22(SO3)uM; E is CH2CH2 , CH(CH3)CH2 and CH2CH(CH3); T is a group consisting of CH2CH2, CH2CH2CH2, CH(CH3)CH2CH2 selected from; n is 1 to 30; t is O or 1; u is O or 1; Therefore, if t is 1, u is 1; M is H, Na, K, Ca, NH4, Mg, selected from the group consisting of Ni, Co and Fe; Y represents H or (SO3)M; and M is as described above; R represents a C1-C35 alkyl group, and at least One R has a C5-C35 carbon range, and the alkyl group is a phenol OZ group. On the other hand, ortho and para relationships have an average of less than two branches within them, and p is 1 or is 2 and when p is 1, the ratio of ortho to para isomers is approximately 10 ortho to 90 ranges from para to 40 ortho to 60 para isomers, with Q being S, S2 and CH2 a bridging group selected from the group consisting of, where Q is S or S2, Z is H; Ca or Mg, and if Q is CH2, Z is (EO)xH; bridging group The number q is from 0 to 15, and if Q is S or S2, q is within the range from 1 to 5. x is 1 to 16; m is 1+q; E is as defined above. 27. q is 0, Y is H, and Z is selected from H, Na, k, Ca, and Mg. 27. The composition of claim 26, wherein the composition is 28. Claim 2, wherein q is 0, Y is H, and Z is selected from (EO)nH. 6. The composition according to 6. 29. Y is SO3M and Z is selected from (EO)n(T)t(SO3)uM 27. The composition of claim 26. 30. Y is H, Z is selected from H, K, Na, Mg and Ca, p is 1, 27. The composition of claim 26. 31. 27. A composition according to claim 26, wherein R represents a Ca-C20 alkyl group. 32. Formulas▲Mathematical formulas, chemical formulas, tables, etc.▼(In the formula, R has less than 2 branches on average. and the ratio of ortho to para isomers ranges from about 10 ortho to 90 para to 40 ortho to 60 para. C5-C35 alkyl groups within the range of A composition comprising a mixture of alkylphenols. 33. 33. The composition of claim 32, wherein R is dodecyl. 34. formula, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R has an average of less than 2 branches and an ortho to para isomer ratio of about 10 ortho to 90 percent. a C5 to C35 alkyl group within the range of 40 ortho to 60 para; E consists of CH2CH2, CH(CH3)CH2 and CH2CH(CH3) selected from the group, n is 1 to 30) consisting of a mixture of alkoxylated semi-linear ortho- and para-alkylphenols of Composition. 35. 35. The compound of claim 34, wherein R is nonyl and E is CH2CH2. 36. 35. The monoethoxylated semi-linear nonylphenol of claim 34. 37. formula, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Ethoxylated or proboxylated semi-linear alkylphenols of sulfur or a sulfonate derivative, in the formula, R is a C1-C35 atom in ortho and/or para relationship to the phenol group; alkyl group, in which at least one R is in an ortho-para relationship to the phenol group; A higher C5-C35 alkyl group having less than 2 branches therein, and p is 1 or less. or 2, and the ratio of ortho to para isomers is about 10 ortho to para when p is 1. within the range of 90 para to 40 ortho to 60 para isomers; E is CH2CH2, C H2CH(CH3) or CH(CH3)CH2; n is 1 to 35; T is CH2CH2, CH2CH2CH2, CH(CH3)CH2CH2; t is O or 1; M is H, Na, K, Ca, Mg, Ni, Co, Fe; ri; u must be O or 1, and if t is 1, then u must also be 1; r is O or 1. 38. In the formula, p is 1, E is CH2CH2; n is 1 to 35, and t and u is O. Sulfonate derivatives. 39. formula, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [During the ceremony, R is a C5-C35 alkyl group having less than 2 branches, and said alkyl group is in ortho and/or para configuration to the phenolic group, o- versus p-isomerism The body ratio is within the range of about 10:90 to about 40:70, n is 1 to 30; T is CH2CH2, CH2CH2CH2, CH(CH3) CH2CH2, M is Na, K, Ca, Mg] ethoxylated semi-linear chain sulfonate derivatives of monoalkylphenols. 40. In the formula, R is CgH19, T is CH(CH3)CH2CH2, 3 of the ethoxylated semi-linear nonylphenols of claim 28, wherein M is Na. - Sodium butanesulfonate derivative. 41. formula, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ sulfur-bridged semi-linear alkylphenol compositions. In the formula, R is a C8-C18 alkyl group having less than 2 branches, and The alkyl group is in an ortho or para orientation to the phenol group, with o-vs. The ratio of the sexes is in the range of about 10:90 to 40:60, and the S group is also a phenolic group. in the ortho and/or para position with respect to and x are 1 and 2, and v is 0-6. 42. R is C9H19, x is 1 and 2, and v is 0 to 2, the claim 42. Sulfur-bridged semi-linear nonylphenol according to item 41. 43. Phenol is an olefin component of the distillate of high-temperature pyrolysis of sulfur-containing petroleum residues. Derived from monoalkylphenols produced by alkylation, formula , ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein R is a C3-C10 alkyl having less than 2 branches, and the alkyl The group is in an ortho or para orientation to the phenol group, with o- versus p-isomers. The ratio is in the range of about 10:90 to 40:60, where M is Ca or Mg). Sulfur-bridged overbased calcium or magnesium phenate crystals containing structural units Cleaner additive composition. 44. Sulfur crosslinking according to claim 43, wherein R is C12‖29 and M is Ca. Overbased calcium phenate detergent additive. 45. Olefin components of the distillate of high-temperature pyrolysis of phenol and sulfur-containing petroleum residues. There are formulas derived through reactions, ▲mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R is C5-C35 alkyl, and R and CH2 are both phenol in the ortho and/or para position with respect to the group; p is 1 or 2; m is 1 to 15; E is CH2CH2, CH2CH(CH3) and CH(CH3 ) CH2, and n is 1 to 30] methylene-bridged semi-linear alkylphenol compositions. 46. R is C9H19, E is CH2CH2, and n is 1 to 30, 46. The methylene-bridged semilinear monononylphenol composition of claim 45. 47. Olefin components of sulfur-containing distillates of high-temperature pyrolysis of phenol and petroleum residues There are formulas, ▲mathematical formulas, chemical formulas, tables, etc. produced through the reaction of ▼ [wherein M is C in the ortho or (and) para position with respect to the phenol oxygen 5-C35 alkyl; M is H, Zn1/2 and ZnOH] bis-alkylaryl dithiophosphates of semi-linear monoalkylphenols of Antioxidant derivatives.