JPS63500718A - Sulfur-containing compositions and concentrated additives, lubricating oils, metalworking lubricants and asphalt compositions containing the compositions - 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] Sulfur-containing compositions and concentrated additives, lubricating oils, metalworking lubricants and asphalt composition [Description of related application] This application is U.S. Patent Application No. 760,186, filed July 29, 1985. This is a joint application based on .

Regarding this application, we request that the filing date of the earlier application be cited. The disclosure of the earlier application is All of the above are accepted as cited documents.

Technological field of escape from light The present invention is soluble in hydrocarbons or dispersible in lubricating oils, metals, etc. Sulfur-containing compounds useful as additives for processing lubricants and asphalt compositions relating to things. More specifically, the present invention uses dithiocarbamic acid salts and mercury as catalysts. Fatty acid esters, fatty acids using captobenzothiazoles and mixtures thereof , to an improved method for sulfiding other olefinic compounds and mixtures thereof. related.

[Background of the invention]

Sulfidation of various organic compounds, more particularly olefins and olefin-containing compounds Various compositions made by is known in the art. For example isobutyne, diimbutene and triisobutene It is made by reacting olefins such as sulfur with sulfur under various conditions. Typical various sulfurized compositions are listed in Chemica IReview 6. 5237 (1965). These olefins are treated with hydrogen sulfide and and elemental sulfur to form mercaptans as the main products; Sometimes various sulfides, disulfides and higher polysulfates are produced as by-products. The formation of phyids has been described in other references. J, Am, Che m.

Soc, 60.2452 (1938) and U.S. Patent No. 3,221,056, ibid. No. 3,419,614 and Publication No. 4,191,659 are cited. US special Publication No. 3,419,614 describes the reaction between olefin compounds and hydrogen sulfide and sulfur. By carrying out reactions at high temperatures in the presence of various basic substances, A method for increasing the yield of butane is described. U.S. Patent No. 4,191,659 In the publication, olefins are mixed with a mixture of sulfur and hydrogen sulfide in the atmosphere in the presence of a catalyst. By reacting at pressures exceeding the pressure and further treatment with alkali metal sulfides, It has been described that a sulfurized composition can be prepared using the following methods. Various natural or synthetic sulfurized oils In this technology, e.g. As suggested in Patent No. 2,299,813 and Patent No. 4,360,438, etc. There is.

In the past, sulfurized whale oil was used as gear oil, worm gear and spur gear or Additives in many lubricating oil compositions, such as lubricating waxes, are used as dynamic transmission fluids. It has been widely used as an additive and as an additive for metal processing. sulfurized whale oil has excellent sliding properties and other properties, especially in engine oil, gear lubricant, and rolling oil. is useful in providing a degree of rust protection and improving extreme pressure performance. . However, in recent years, the supply of sulfurized whale oil has decreased and the cost has increased. Consequently, it has been replaced by various other sulfurized compositions. Sulfidation as mentioned above Polyolefins consistently exhibit the degree of lubricity required in many applications. Not necessarily.

In this technical field, sulfurized fatty oils, such as sulfurized lard, are Although mentioned, sulfurized lard is generally paraffin-based. It does not have a suitable degree of solubility for use in standard oils. sulfurized during the last millennium Several patents have been issued suggesting solutions to lard's solubility problems. Ta. Some of those prior art techniques suggest fatty oils like lard, soybean It consists of sulfiding a mixture of oil and various olefin compounds.

For example, U.S. Patent Nos. 3,953,347 and 3.92 to 822 contain at least one fatty acid ester and about 8 to about 36 carbon atoms At least one or more aliphatic olefins, and optionally at least one or more A sulfurized composition made by reacting a mixture of fatty acids with sulfur Compositions useful as lubricating oil additives are described. This sulfurization The composition is made by sulfurizing a mixture as described above of a fatty acid ester and a fatty acid olefin. It is made by heating with yellow at a temperature from 65° to about 200°C. . In addition to the above reagents, the reaction mixture may also include, for example, phosphites. It may also contain sulfidation accelerators such as phosphorus-containing agents and surfactants such as lecithin. can. An example of a phosphorous ester listed in these patent publications is triphenyl ester. It is ruphosphite.

U.S. Pat. No. 2,012,446 describes a method for sulfurizing pine tree oil, It is reported to be useful as an additive for lubricating oil production.

U.S. Pat. describes the sulfidation product obtained by sulfurizing an olefin with Ru. These products are e.g. contaminated lard in winter or extremely contaminated lard. sulfidation of olefins together with lard with a high free acid content, such as lard It shows improved solubility in paraffin oil compared to the product obtained when It has been reported. The co-sulfurized product contains about 5 to 25% by weight sulfur. obtained, and which is reported to be useful as a metalworking oil additive. Ru. sulfur, lard oil and at least one pair of maximally dense geminals with polyisobutylene oligomers containing methyl groups (e.g. tetraisobutylene) The production of various synthetic sulfurized oils by reaction is described in U.S. Pat. No. 4,166,795. It is stated. In addition, a U.S. patent for the production of synthetic sulfurized oil, which is useful as a substitute for sulfurized whale oil, is patented. No. 843,534, No. 3, 825.495, No. 166.795, Same No. 4, 166.796, Same No. 4,166.797, Same No. 4, 321.15 No. 3, No. 4,456,540, and No. 4.48'1 (described in Publication No. 705) has been done. Generally sulfidation is carried out with elemental sulfur, and simultaneous sulfidation and salt Chlorination can be effected by reaction with sulfur monochloride. These patent publications describes the phosphosulfurization reaction, and this causes the sulfurized mixture to contain a small amount of This can be carried out by adding an amount of phosphorous sulfide and then heating.

Cheap raw materials are generally used to produce sulfurized compositions for use as lubricating oil additives. It is desirable to obtain the product by the cheapest method using raw materials. Obtained sulfide composition The color of the product is preferably light and the sulfur contained in the product is not active sulfur. It has to be something.

The invention is also suitable for use in metalworking operations, and more particularly during such operations. Also relates to lubricants.

Includes industrial metal materials. This composition comprises a major amount of lubricating oil and a minor amount of lubricating oil made in accordance with the present invention. and at least one or more sulfurized compositions.

For example, rolling, forging, hot pressing, sheet punching, bending, stamping, drawing, In metal processing operations such as cutting, punching, spinning, etc. Lubricants are used to aid in the process. Lubricants reduce the power required for such work. It is possible to prevent seizure and wear of dies and cutting tools, etc. Greatly improves work efficiency. In addition, they are often Provides rust prevention effect.

Many currently known metalworking lubricants contain relatively large amounts of active sulfur as additives. It is an oil-based lubricant containing active sulfur. (meaning sulfur chemically combined in a mottling manner).

Active sulfur tends to contaminate copper as well as other metals including brass and aluminum. And its existence is harmful.

However, its existence is the ultimate in the processing of active sulfur-containing compositions, especially ferrous metals. It was often necessary to optimize the properties of the limiting pressure.

The use of sulfur in asphalt is known.

Sulfur is commonly added to asphalt compositions as elemental sulfur.

In the asphalt composition according to the invention Roads, driveways, parking lots, etc. 1; Useful. In practice and during use Fast curing of sphalt cement to quickly make the laid surface available for use Often preferred for. However, excessive hardening of the asphalt surface loss of flexibility and flexibility can rapidly reduce its useful life. Januszk e is for magazine “Industrial Engineering Chemis try Product Research and Dive1opment'' 10 (1971) 209-213 to prevent undesirable hardening. It is noted that lead and zinc salts of ethyldithiocarbamic acid were effective.

In some geographic areas, such as the sand slicks of the western United States and western cities, asphalt roads Road deterioration can occur quickly and is often extensive. road surface embrittlement and cracking often occur.

Excessive curing of paving asphalt can result in the formation of e.g. lead or zinc salts of dithiocarbamic acids. that can be reduced by using certain antioxidants such as is known. The above-mentioned document by Januszke is about the durability of asphalt pavement. discusses the evaluation of the effects of 24 antioxidants on the Incorporated as a cited document for teaching on methods and problems of evaluation of agent behavior. .

Sulfur and sulfur-containing compounds as spreading materials for asphalt cement and their durability It is also known in the art to employ such methods to increase the

[Summary of the invention]

The sulfurized composition contains a sulfurizing agent and (A) at least one polyhydric alkali at high temperature. (B) at least one kind of fatty acid, -alcohol fatty acid ester; and (C) at least one kind of fatty acid ester or a mixture thereof. with other olefins, or [F]) the above (A), (B) and ricc> A mixture of two or more of any two or more, (E) the following formula ■ R, (R2)N-CSSH(r) (In the above formula, R1 and R2 each independently represent a hydrocarbyl group) at least one salt of at least one dithiocarbamic acid, (F) at least one salt The above mercaptobenzothiazoles, and &i (G) above (F) and (C) A compound made by reacting a mixture in the presence of the required amount as a catalyst. It is explained that

More generally, the present invention combines the sulfiding agent with (A) a polyhydric alcohol at an elevated temperature. (B) about 100 parts by weight of at least one fatty acid ester of About one or more fatty acids, fatty acid esters of -hydric alcohols or mixtures thereof about 200 parts by weight of O, and (C) about 0 or more of at least one other olefin. about 400 parts by weight, and (E) the following formula %formula%() (In the above formula, R1 and R2 each independently represent a hydrocarbyl group) one or more salts of at least one or more dithiocarbamic acids, or CF) at least also one or more mercaptobenzothiazole or (G) above (E) and above (F) ) with a catalytically effective amount of a mixture of relating to things.

The employment of the above-mentioned catalysts leads to sulfurized compositions characterized by a high sulfur content and this composition resulted in the production of sulfuric acid produced without such a catalyst. It has a lighter color and less odor than the composition.

The sulfurized compositions made in accordance with the present invention are common antioxidant and friction agents for lubricant compositions. It is useful as a modifier and as an additive in metalworking lubricants. mentioned above Sulfurized compositions made with or without catalysts are asphalt. It is useful as an additive for compositions.

[Detailed description of preferred embodiments]

The component (A) to be sulfurized according to the present invention is at least one polyhydric alcohol. It is a fatty acid ester of

The term "fatty acid" used in this specification and claims refers to naturally occurring fatty acids. Acids such as those obtainable by hydrolysis of vegetable or animal fats .

These are usually in the C16 to C2o range, and palmitic acid, stearic acid acids, oleic acid, lyluic acid, etc. To be used as this component (A) The resulting fatty acid ester is a fatty acid ester of polyhydric alcohol. Appropriate polyvalent a Examples of alcohols include ethylene glycol, globylene glycol, and trimethylene glycol. Examples include len glycol, neopentyl glycol, and glycerol. Guri Fatty oils and similar naturally occurring esters of cerol and the long-chain carboxylic acids listed above. Synthetic esters having the structure can be used. In the method according to the invention Usually preferred fatty acid esters are unsaturated acids, especially oleic acid and lyluic acid. Fatty oils derived from tall oil, lard oil, peanut oil, cottonseed oil, soybean oil , naturally occurring animal and vegetable oils such as sunflower oil, corn oil, and the like.

Mature sunflowers with particularly high oleic acid content (e.g. 80% oleic acid or more by weight) Oils can be sulfided according to the method of the invention. This kind of oil is oh w ickliffe's SVO Enterprises Corp, from TRl5U It is commercially available under the general trade name of N (registered trademark).

prepared according to the method of the present invention using only fatty acid esters of one type of polyhydric alcohol. Although the various compositions described above are soluble and useful as oil additives, the various Preference is given to using mixtures of polyhydric alcohol fatty acid esters. Among them, few at least about 50% by weight lard oil, generally from about 50 to about 80% by weight lard oil A mixture of polyhydric alcohol fatty acid esters containing a desired high sulfur content This results in the formation of a sulfurized composition, which is relatively inexpensive. Moreover, the original Sulfurized materials made according to the Ming method have reduced undesirable coloration and odor. characterized by the presence of Examples of mixtures based on lard oil include e.g. A mixture of 50 parts by weight lard oil and 50 parts by weight soybean oil, 75 parts lard oil and 2 Mixture with 5 parts of soybean oil and mixture with 60 parts of lard oil and 40 parts of peanut oil→ At least one fatty acid or fatty acid ester of m alcohols, or A mixture of these may also be used.

The above types of fatty acids can be used and the commonly used fatty acids are oleic acid unsaturated fatty acids such as phosphoric acid or lyluic acid. It can be obtained from tall oil It can be obtained by hydrolyzing eel, peanut oil, soybean oil, sunflower oil, etc. Mixtures of eel fatty acids can also be used. monovalent containing up to about 20 carbon atoms Fatty acid esters obtained from alcohol can be used alone or in combination with various fatty acids. can be used as the above component (B). Useful in the composition of fatty acid esters Examples of m alcohols are methanol, ethanol, n-glopanol, and inglo. Panol, butanols, etc. Used as component (B) in the method of the invention Specific examples of m-alcohol fatty acid esters that can be Methyl acid, ethyl oleate, lauryl oleate, methyl lyluate, stear Examples include oleyl phosphate and cetyl lyluinate.

Compositions that can be sulfurized according to the invention include other olefinic compounds CC''). There can be, for example, aliphatic, araliphatic or cycloaliphatic olefin carbonization Hydrogen containing at least 3 or more carbon atoms, at least one or more Dealing with an aliphatic conjugated aliphatic diene and at least one genophile These include Sualder addition products and at least one terpene compound. So These olefin compounds contain at least one terpene compound. So These olefin compounds contain at least one non-aromatic double bond. ” Contains two olefinic double bonds. In other words, this double bond is two fats. bonding group carbon atoms.

In one specific example, the olefin used as the component (C) has the following formula: %formula%() (However, in this formula, each of R1, R2, R3 and R4 is a small number of these. hydrogen or organic groups, provided that at least one of them must be an organic group. can be defined as Generally, each R in the above formula is where each R5 is independently hydrogen, alkyl, alkenyl, aryl, alkylaryl, substituted alkyl or substituted It is alkenyl. However, any two R5 groups are alkylene groups or substituted atom groups. can be a lekylene group, thereby making a ring of up to about 12 carbon atoms may be formed. Ar has up to about 12 carbon atoms in the aryl group or substituent Substituted aryl group containing children. M is a metal cation (preferably e.g. sodium Group 1 or Group II cations such as rum, barium, calcium ), and X is a chloro, bromo, or iodo group. ), and Y represents an oxygen or divalent sulfur group. .

Also, any two of these R1, R2, R3 and R4 are alkylated together. ・may form a nitrogen group or a substituted alkylene group, i.e. its olefinicization The compound can be cycloaliphatic.

The nature of each substituent in the above-mentioned substituted compounds is generally not critical to the invention; is compatible with the lubricating environment or asphalt composition and under the reaction conditions. Either can be used as long as it does not cause any problems.

That is, substituted compounds that are unstable enough to cause harmful decomposition under the reaction conditions used are Not included. However, certain substituents such as keto groups or aldehydes can be subject to change. Choosing the appropriate substituent is a matter of skill in the art. or can be determined by routine testing. Placement like this Typical examples of substituents include any of the groups listed above as well as hydroxyl groups, carboxyl groups, etc. Boxyl group, carbalkoxy group, amidine group, ami7 group, sulfonyl group, sulfonyl group Finyl group, sulfonic acid group, nitro group, phosphoric acid group, phosphorous acid group, alkali metal mer Examples include capto group.

Usually, in olefin compounds, each non-hydrogen R group is independently alkyl or alkyl. such as rukenyl or (rarely) a correspondingly substituted group.

modiolefinic and diolefinic compounds, the former being preferred and especially In the monoolefinic hydrocarbon compound, that is, R3 and R4 are hydrogen. R1 and R2 are alkyl (i.e. the olefin is aliphatic). ) compounds are preferred. having at least about 3 or more carbon atoms, especially about 3 Olefinic compounds having from to about 36 carbon atoms are preferred. Approximately 8 pieces Olefins containing up to 24 carbon atoms are particularly useful. This olefinic The compound can also be an araliphatic compound, especially if the aryl group is phenyl or a substituted phenyl group. A special example is Ren, α-methylstyrene, vinyltoluene, 4-ethylvinylbenzene, etc. can be lost.

Propylene, isobutyne and their dimers, trimers, tetramers and the like The above oligomers as well as mixtures thereof are useful olefinic compounds.

Examples of olefins that can be used include inbutene, 1-butene, l -hexene, 1-octene, diimbutene, cyclohexene, triisobutyne, Commercially available higher aliphatic α-olefins, especially 1-hexadecene and 1 - those in the C1□ and C3O range, such as octadecene, and commercially available mixtures thereof, such as C15 to C2o α-olefins, Cl6 α- Olefins, Cl5-C1,8 α-olefins, C2□-028 α-olefins Examples include lefins.

Polymers of olefins, such as imbutene, as well as their sulfur derivatives The conductor is compatible with other components and its sulfidation products do not lose the desired properties. It can be used as long as possible.

Generally, the olefinic compound (C) is a compound containing at least about 3 or more carbon atoms. at least one aliphatic, arylaliphatic or cyclic It is an aliphatic olefinic compound. from about 3 to about 36 carbon atoms, and and more preferably olefinic compounds containing from about 8 to about 24 carbon atoms. is particularly useful. Using a mixture of such olefin compounds as component (C) This is because mixtures of these are commercially available. Ru.

The olefinic compound can also be an internal olefin. internal olef The fin is expressed by the following general formula % formula % ([11) (Here, n and m are each independently an integer from 0 to about 15, and the carbon atoms are the total number of children is at least 8) .

Examples of internal olefins that can be used in the present invention include 2-octene , 2-dodecene, 4-dodecene, 9-octadecene, 7-titradecene, 7-to Included are xadecene and 11-eicobcene. α-olefins and internal olefins Mixtures of two or more olefins can be used, including mixtures with olefins. .

One way to make such mixtures of olefins is to use commercially available α-olefins. and the products of this isomerization reaction are I, 2, It is a mixture of olefins in which double bonds exist at positions such as 3° and 4. olefin Class mixtures can also be used to mix or fractionate olefins of different types and molecular weights. It is also possible to obtain it by Isomerization of terminal olefins For example, use a mild acid such as Amberlist 15. This is achieved by heating with a chemical catalyst. Among them, about 10 to about 20 alpha-olefins containing carbon atoms are preferred. Mixture of such olefins are commercially available and are particularly desirable for use in the present invention.

In another embodiment, this olefin (c) is a Diels-Alder addition product. It is a product. Diels-Alder addition products are produced by diene synthesis or Diels-Alder addition products. A group of compounds obtained by the Alder reaction, identified in a well-known technique. It is one of the compounds. A review of the prior art regarding this group of compounds is provided by A. chenk.

Paper on the Soviet Union by “Dienovyi 5 intes”: Izdat elstwo Akademi i Nauk 5SSR (1963) (L, Mandel, translated into English by Daniel Davey in 1964. and Co, Inc. = A, S, 0nischenko from Knee York. Found in publication as diene synthesis j. This paper and the documents listed here are the subject of this application. It is adopted as a cited document in the specification.

Numerous Diels-Alder addition products that can be used in the present invention The manufacture is described in U.S. Reissue Patent No. 2"J331, the disclosure of which is hereby incorporated by reference. This is adopted as a cited document.

Basically, diene synthesis (Diels-Alder reaction) involves at least one Conjugated diene (c=c-c=c) and at least one ethylenic or acetylene This includes reactions with compounds of cyclic unsaturation (-C=C- or =CmiC-); These latter compounds are known as genophiles. This reaction is It can be expressed as

Products A and B above are commonly referred to as Diels-Alder addition products. It is something. Sulfurized Diels-Alder adduct used in the present invention It is these that are used as starting materials for the production of the products.

A typical example of such a 1,3 diene is the following formula (in this formula, R to R5 are Each independently, alkyl /%0, alkoxy, alkenyl, alkenyloxy Cy, carboxy, cyan, amine, alkylamino, dialkylamino, phenyl and phenyl substituted with 1 to 3 substituents corresponding to R to R5, It is selected from the group. However, one of the groups of R on the adjacent carbon atom The condition is necessary that the pair does not form yet another double bond in the diene.

) or aliphatically conjugated diolefins. Preferably R or at least one of not more than three of R5 is other than hydrogen. The above is hydrogen. The total number of carbon atoms in the diene does not exceed 20. Preferences of the present invention In one specific example, both R2 and R3 are hydrogen, and the remaining R groups are Addition products are used in which at least one or more of is also hydrogen. preferred or these R to R5 groups, if these are not hydrogen, the number of carbon atoms is It is better if it is 7 or more. In this most preferred group of compounds, the above R, R', R Dienes in which ' and R5 are hydrogen, chlorine or lower alkyl groups are particularly preferred. Useful.

Specific examples of these R to R5 groups include methyl, ethyl, tolyl, and the like. So Among the dienes used to make these Diels-Alder addition products, pipette Rylene, isoprene, methylisoprene, chloroprene and 1,3-butadiene is preferred.

In addition to these linear 1,3-conjugated dienes, cyclic dienes are also It can be used as a reactant in the preparation of da-addition products. These annular Examples of dienes are cyclopentagenes, fulpenes, and 1,3-cyclohexadiene. M, l, 3-cyclohebutadienes, 1,3.5-cycloheptatrienes, Includes cyclooctatetraenes and 1,3.5-cyclononatrienes.

Various substituted derivatives of these compounds are also used in diene synthesis.

Suitable for reacting with the above dienes to form addition products used as reactants The genophile obtained is expressed by the following formula [however, in the above formula, K to 3 are the same as in the above formula (m). have the same meaning as R to R5, except that one pair of these K to 3 Additional carbon-carbon-7 bonds may be formed, i.e. 2 at -C=C-. However, this does not necessarily have to be the case. This can be expressed as

One of the preferred groups of genophiles has at least one of the above formulas OK to 3. For example, formyl, cyano, nitro, carboxy, carbohydrocarbyloxy , hydrocarbyl carbonyl, hydrocarbylsulfonyl, carbamyl, acrylic Lucarno (mil, N-acyl-N-hydrocarbylcarbamyl, N-hydrocarbyl Electron-accepting groups such as vilcarbamyl and N,N-dihydro-rubylcarno (mil) A compound selected from the group of Of those K or 3, Those that are not child-accepting groups are hydrogen, hydrocarbyl, or substituted hydrocarbyl groups. It is. Usually these hydrocarbyl groups and substituted hydrocarbyl groups are Each contains no more than 10 carbon atoms.

Hydrocarbyl groups present as N-hydrocarbyl substituents are preferably unmodified. an alkyl group of from 1 to 10 carbon atoms; of this group Typical genophiles include, for example, 1-nitrobutene-111-nitropene. Thene-1,3-methyl-1-nitrobutene-1,1-nitrohebutene-1,1- Nitroalks such as nitrooctene-1,4-ethoxy=''-nitrobutene-1 Kens, such as butyl acrylate, butyl methacrylate, decyl acrylate alkyl acrylates such as decyl methacrylate and α-methyl acrylate. alkyl acrylates (i.e. alkyl methacrylates) and di(n- α,β- such as butyl)-maleate and di(tert-butyl-maleate) Ethylenically unsaturated aliphatic carboxylic acid esters, acrylonitrile, meth Lyretrile, β-nitrostyrene, methyl vinyl sulfone, acrolein, acrolein, Acrylic acid, e.g. acrylamide, N,N-diptylacrylamide, methacrylate such as lylamide, N-dodecylmethacrylamide, and N-pentylcrotonamide. α,β-ethylenically unsaturated aliphatic carboxylic acid amides, and also chlorinated tonaldehyde, crotonic acid, β, β-dimethyldivinyl ketone, methylvinyl These include ketones, N-vinylpyrrolidone, halogenated alkenyls, and the like.

One of the preferred groups of genophiles is at least one of the above OK to 3, However, not more than two groups are =C(0)O-Ro, where R8 is about 4 It is the residue of a saturated aliphatic alcohol of up to 0 carbon atoms. That is, for example, K's At least one of the groups is a carboethoxy group, a carbobutoxy group, etc. A bohydrocarbyloxy group, in which the aliphatic alcohol serving as the group of Ro is, for example, a alkylene glycol, alkanol, aminoalkanol, alkoxy-substituted alkaline Canol, ethanol, ethoxyethanol, globanol, β-diethylamide Noethanol, dodecyl alcohol, diethylene glycol, tripropylene recall, tetrabutylene glycol, hexanol, octatool, inoc It can be a monohydric or polyhydric alcohol such as chill alcohol etc. It is something.

In this particularly preferred group of genophiles, more than two of the above three are present. What is not possible is a group =C(0)-0-R8, and the remaining ones are hydrogen or e.g. Lower alkyl such as methyl, ethyl, propyl, isopropyl, etc.

Special examples of the types of genophiles listed above include those listed above or at least three of the above. One of the following groups: hydrogen, methyl, ethyl, enyl, HOOC-1 HC(0)-1CH2=CH-1H×-1CH2(:0)O-1CI CH2- 1HOCH2-, Cl-Biridyl, -No2, CI, Br, Propyl, Isobuty It is a compound that is one of the groups such as

In addition to those ethylenically unsaturated genophiles, e.g. Do, methyl ethynyl ketone, propyl ethynyl ketone, flobenylethinyl ketone globiolic acid, globiolic acid nitrile, ethyl gloviolate, tetro acid, glopargyl aldehyde, acetylene dicarboxylic acid, acetylene dicarboxylic acid Many available like dimethyl ester of bonic acid, dibenzoylacetylene etc. There are acetylenically unsaturated genophiles.

Cyclic genophiles include cyclopentadione, coumarin, 3-cyclocoumarin, and di Methyl maleic anhydride, 3,6-nindomethylene-cyclohexenedicarbone Including acids etc. Unsaturated dicarboxylic acid anhydride derived from linear dicarboxylic acids (e.g. maleic anhydride, methyl maleate, chloroanhydride 71/inic acid) Except for this group of cyclic genophiles due to limited availability and other economical There are limits to its practical usefulness based on such considerations.

The reaction products of these dienes and genophiles have the following general formula: (However, in the above formula, R to R5 and K to 3 are as defined above. ).

If the genophilic component involved in the reaction is not ethylenic but acetylenic, In the case of K to 3 groups, two K groups bonded to each carbon atom forms another carbon-carbon double bond. diene compound and/or geno If the fill compound is itself a cyclic compound, its addition product is clearly dicyclic. They can be cyclic, bicyclic, or fused cyclic, as shown below.

reaction 3 Typically, the addition product involves the reaction of equimolar amounts of diene and genophile. However However, if the genophile has two or more ethylenic bonds, It is possible to react additional dienes when present in the reaction mixture.

The addition products and methods of making these addition products are further illustrated by the following examples. Ru. In these examples and the rest of this specification, as well as in the claims. All parts and percentages are by weight unless otherwise stated.

Example" - Seiji".

Equipped with a stirrer, a nitrogen gas inlet pipe and a reflux condenser cooled with dry ice. 400 parts of toluene and 66.7 parts of aluminum chloride were added to a 2U flask. charge a mixture of Maintain the temperature of this AlCl3 slurry at 37-58℃. 640 parts (5 moles) of butyl acrylate and 240.8 parts of toluene The second mixture is added during 0.25 hours. Next, 313 parts (5.8 moles) of but The temperature of the reaction mixture was increased from 50 to 50°C by external cooling during 2.75 hours. Add to the slurry while maintaining the temperature at 61°C. Nitrogen gas was added to the reaction mixture at 0.0%. Bubble for 33 hours, then transfer to a 4 volume separatory funnel for 11 hours. Wash with a solution of 150 parts of concentrated hydrochloric acid in 0.00 parts of water. Then the product is Two additional washes with 100 parts of water each. This washed reaction product The material is then distilled to remove unreacted butyl acrylate and toluene. This first 1 distillation step residue from 9 to b 785 parts of the desired product are collected at a temperature of 115°C.

Long-tongued L varnish 136 parts isoprene, 160 parts acrylonitrile in a shaking autoclave and 0.5 part of hydroquinone (polymerization inhibitor) to give a isoprene and acrylonitrile by heating for 16 hours in the temperature range of °C. make an addition product with The reactant was removed from this autoclave and its supernatant was The liquid is decanted, resulting in 240 parts of a pale yellow liquid.

This liquid was stripped at a temperature of 90°C and a pressure of 10n+mHg; The desired liquid product is obtained as a residue.

Second time to Tsuyoshi Following the procedure of Example DA-2 above, 136 parts of isoprene, 172 parts of methyl acetate Acrylate and 0.9 parts of hydroquinone with isoprene-methyl acrylate Convert to processed products.

Kenihe 2A Following the procedure of Example DA-2 above, 104 parts of liquefied butadiene, 166 parts of Charge methyl acrylate and 1 part hydroquinone to a shaking autoclave. , and heated to 130-135°C for 14 hours. The product is then decanted and Stripping is performed to obtain 237 parts of addition product.

To Kenji 139 parts (1 mole) of the addition product of butadiene and methyl acrylate are Transesterification with 158 parts (1 mol) of alcohol. those reactants Add to reaction flask and to this add 3 parts sodium methoxide. Next The reaction mixture is heated to a temperature of 190 DEG-200 DEG C. for 7 hours. This reaction mixture was washed with lO% sodium hydroxide solution and then 250 parts of naphtha were added. Add. This naphtha solution is washed with water. When the washing is finished, 150 parts of toluet and the reaction mixture was stripped at 150°C under a pressure of 28 parts. Ping. A dark brown liquid product (225 parts) is recovered.

This product is fractionally distilled under reduced pressure, whereby 0.45-0. Product 17 boiling in the temperature range 130-133°C at a pressure of 6 mmHH Eight copies are collected.

Example J Shihe 22dan The previous procedure was repeated with the only exception that 270 parts (5 moles) of butadiene were included in the reaction mixture. Repeat the general operations of Example DA-1.

As already mentioned, the other olefin compound (C) contains at least one terpene compound. It can be a chemical compound.

The term "terpene compound" used in the specification and claims of this application includes, for example, Species with empirical formula 010816 such as turpentine, pine tree oil and dipentenes various terpene hydrocarbon isomers and their naturally occurring or synthetic oxygen-containing conductors. shall be included. Generally mixtures of these various compounds are used, among others e.g. Used when using natural products such as tree oils and turpentine. For example, pine Pine tree oil obtained by decompositionally distilling tree waste using superheated steam is α-terpineol. Le, β-terpineol, α-fenchol, camphor, borneol/iso Borneol, fenchone, estragole, dihydro-α-terpineol, Contains anethole and other monoterpene hydrocarbons. Some given pine tree oil The overall proportions of the various components and their amounts in the do.

Is Verculnos Incorporated a special product derived from a group of pine tree oils? It is available as a commercial product. Available from Hercules Incorporated Refined pine resin oil, commonly known as terpene alcohol, is the sulfur of the present invention. It has been found to be particularly important for producing chemical products. products like this An example of this is α-terpineol containing about 95-97% α-terpineol. High purity tertiary terpene alcohols, generally containing 96.3% tertiary alcohols terpineol, which is obtained by dehydrating terpene hydrate. about 60-65% by weight of α-terpineol and 15-20% by weight of α-terpineol. of β-terpineol and 18-20% of other tertiary terpene alcohols Delvineol 318 Prime, which contains can be used Other mixtures and grades of pine tree oil are also available, such as Yarmor 302, Herco Vine oil, Yarmor 302 W, Yarmor F and Yarmor It is available from Percules under the trade name 60.

of use in preparing the sulfurized compositions of the present invention.

Terpene compounds that can also be sulfurized terpene compounds, sulfurized terpene compounds a mixture containing at least one terpene compound and at least one sulfur compound; It can be a mixture of lupene compounds. Sulfurized terpene compounds are called terpe sulfur, halogenated sulfur, or sulfur or halogenated compounds as described in detail later. can be made by sulfurization using a mixture of sulfur dioxide and hydrogen sulfide. Ru. Sulfidation of various terpene compounds has also been described in the prior art.

For example, U.S. Patent No. 2,012,446 describes the sulfurization of pine tree oil. .

Compositions that can be sulfurized according to the invention include two of the above-mentioned (A), (B) and (C). The above mixture (D) may also be used. That is, (A) at least one fatty acid A mixture of an ester and (C) at least one olefin is prepared by the method of the present invention. can be sulfurized. Other compositions include a combination of (^) and (8), The combination of (B) and (C) and the combination of (A), (B) and (C) are listed. It will be done.

In one preferred embodiment, the sulfiding composition of the invention is free of sulfiding agents at elevated temperatures. , (A) about 100 parts by weight of at least one polyhydric alcohol fatty acid ester and (B) from about O to about 200 parts by weight of at least one fatty acid, -alcohol. and (C) from about 0 to about 400% by weight. (E) at least one or more other olefins up to the amount of at least one other olefin. Notation %formula%() (In this formula, R4 and R2 each independently represent a hydrocarbyl group) or (F) at least one salt of dithiocarbamic acid. A mixture containing putobenzothiazole or a mixture (G) of the above (E) and (F) It is created simply by reacting with an object. Preferably these mixtures contain at least 2 Part (B) Contains fatty acid or fatty acid ester. The preferred range is 1 above (^) The range of (B) above is from about 2 parts to about 100 parts per 00 parts. other preferred The mixture contains at least 25 parts of aliphatic olefin (C). This feature of (C) The preferred range is between about 25 parts of (C) per 100 parts of (A) and about 100 parts of (C). It is. In another preferred embodiment the mixture to be sulfided is Contains all three components (A), (B) and (C).

The sulfurization reaction of the present invention is carried out using at least one type of (E) the following formula 8 formula % (1) (In this formula, R1 and R2 each independently represent a hydrocarbyl group) in the presence of at least one dithiocarbamic acid salt. The above formula Drocarbyl groups R and R2 are alkyl groups, cycloalkyl groups, aryl groups, alkyl groups, The alkaryl group can be an aralkyl group. R1 and R2 are also the same and constitutes a group consisting of a polymethylene group or an alkyl-substituted polymethylene group. This can also form a nitrogen-containing cyclic compound. Generally the alkyl The group has about 1 to about 20 carbon atoms, and more usually about 2 to about 1 carbon atoms. Contains up to 0 carbon atoms. The above salts are metal salts, ammonium salts or amine salts It may be.

Metal saltsMetals can be monovalent metals or polyvalent metals, but polyvalent metals are more preferred. Generally, they are more oil-soluble than alkali metal salts and are therefore preferred. As a preferred polyvalent metal For example, alkaline earth metals, zinc, cadmium, magnesium, tin, molybdenum Examples include iron, copper, nickel, cobalt, chromium, and lead. Group ■ metals preferable.

Ammonium salts and amine salts have the following general formula (% formula %) (In this formula, R1 and R2 are the same as defined in formula 1 above, and R3, R4 and R5 are each independently hydrogen or the same hydrogen as R1 and R2 above. drocarbyl group). this Such salts can be made by methods known in the art. For example, dithiocarbamic acid with ammonia or R3R4R6N substituted amine can be processed with. A special example of such salts is dimethylcyclo Hexylammonium, dibutylthiocarbamate and piperidinium pentamate Examples include tylene dithiocarbamate. These salts also have the following reaction formula: %formula%) The reaction between excess amine (e.g. R, RNH) and carbon disulfide as shown by You can also make it directly from scratch.

In such a case, the two R groups in the salt are the same and the two R groups in the product are the same. The two R2 groups are also the same.

Mixtures of metal salts, mixtures of amine salts and metal salts and amines of dithiocarbamic acids Mixtures with salts can also be used in the present invention. Such a mixture is first First make a mixture of dithiocarbamic acids and then convert these acid mixtures into salts. Alternatively, you can make different dithiocarbamates and then mix them together. The desired product can be made by

Mixtures that can be used in the compositions of the invention therefore include different dithiocarbons. It may be a simple physical mixture of rubamates or the same polyvalent metal raw material. It may also be in the form of a salt of different dithiocarbamic acid residues attached to a compound.

Examples of alkyl groups are ethyl, propyl, butyl, amyl, hexyl, heptyl. octyl, decyl, dodecyl, tridecyl, pentadecyl and hexadecyl or their isomers. An example of a cycloalkyl group is cyclo Examples of aralkyl groups include hexyl and cyclohebutyl groups, but benzyl and Examples of polymethylene groups include pentamethylene and hexyl groups. An example of an alkyl-substituted polymethylene group is methylpentane. Examples include methylene group and dimethylpentamethylene group.

Dithiocarbamic acid that can be used as component (E) in the composition of the present invention Specific examples of metal salts are bismuth dimethyl didiocarbamate, calcium diethyl Dithiocarbamate, Calcium Cyamyldithiocarbamate, Cadmium Diesel Tyldithiocarbamate, copper dimedithiocarbamate, zinc diethyldithio Carbamate, zinc dibenzyldithiocarbamate, zinc dibutyldithiocarba mate, zinc cyamyl dithiocarbamate, zinc di(2-ethyl-hexyl)- Dithiocarbamate, cadmium dibutyl dithiocarbamate, cadmium geocarbamate Cutyl dithiocarbamate, cadmium octyl butyl dithiocarbamate, Gnesium dibutyldithiocarbamate, magnesium dioctyldithiocarba mate, cadmium diethyldithiocarbamate, sodium cyamyldithiocarbamate Rubamate, sodium diisopropyldithiocarbamate, etc.

The various metal salts of dithiocarbamic acids used in the compositions of the invention are well known in the art. It is known in the field and can be made by known techniques.

The catalyst for the sulfidation reaction may also be (F) at least one mercaptobenzothiazo These can be mercaptobenzothiazole itself or analogs. It may also be a conductor such as a metal salt thereof. The metal of the metal salt is Any of the metals listed for the metal salt (E) of ocarbamic acid may be used. child These metal salts are known in the art, and in this art they are metal salts are known, and these group Ⅰ metal salts are used in the sulfurization reaction of the present invention. It is preferable as a medium for

A mixture of dithiocarbamic acid salts and mercaptobenzothiazole salts is It can be used as a medium. However, in general, dithiocarbamate It is preferable to use only

The amount of catalyst (E), (F) or (G) used in the above reaction The amount is sufficient to carry out the reaction. Generally, the above (A), (B) and (C) Amounts of catalyst from about 0.0001 to about 5% by weight, based on total weight, are sufficient.

Generally, this sulfurization reaction is carried out from about 50°C to about 350°C, more preferably from about 50°C to about 350°C. It is carried out at elevated temperatures of up to about 200°C. This reaction is carried out with sufficient stirring. It is generally carried out under an inert atmosphere such as nitrogen gas. too However, if any of the reaction components are significantly volatile at the reaction temperature, The reaction vessel may be hermetically sealed and held under pressure. Also this anti For example, alcohol, ether, used in the reaction, such as hydrocarbons, aliphatic hydrocarbons, halogenated aromatic hydrocarbons, etc. It can also be carried out in the presence of an inert solvent that is liquid within the temperature range. Ru.

Sulfiding agents that can be used in the method of the invention include elemental sulfur, hydrogen sulfide, halogen Includes sulfur genide, sodium sulfide, etc. A preferred sulfiding agent is elemental sulfur.

It is often advantageous to add such sulfiding agents batchwise to a mixture of other reactants. Ru. When using elemental sulfur as the sulfiding agent, this reaction is exothermic in some cases. After all, this can be used for cost-saving benefits. Add to reaction mixture The amount of sulfur or sulfiding agent added can vary within a wide range, but The amount present in the reaction mixture is such that a sulfided product containing the desired amount of sulfur is formed. generally at least about 10% by weight.

Following the sulfidation reaction, the reaction vessel is typically opened and flushed with gas, such as nitrogen gas. This is carried out by blowing inert gas, vacuum distillation, or stripping. Preferably, qualitatively all low-boiling substances are removed. Insoluble side reaction products are If necessary, it may be removed by filtration, generally at elevated temperatures of about 80-120°C. stomach.

Another optional step in preparing this sulfurized composition is obtained as described above. By treating the sulfidation products to reduce any active sulfur that may be present. be. One of the typical methods is treatment with alkali metal sulfides.

Improving product quality, e.g. odor, color and color mottling of the sulfurized composition Other optional processes may also be employed to do so.

The production of the sulfurized composition of the present invention will be described below with reference to Examples. These examples and specifications In the claims and claims, all parts and percentages are by weight unless otherwise stated. and temperatures are in degrees Celsius.

Example I Commercially available Cl5-18 alpha olefin 71000 parts, sulfur TR 137 parts and silica Prepare a mixture of 10 parts of zinc amyl dithiocarbamate and heat to a temperature of 150 °C did. The mixture was kept at this temperature for a total of about 12 hours and filtered through a filter aid. . The filtrate has the desired sulfur-containing composition containing 1269% sulfur (theoretical value 11.94). It was a thing.

Example 2 Commercially available Cl5-18 alpha olefin/900 parts, pine oil 100 parts, sulfur 14 A mixture of 1 part of zinc cyamyl dithiocarbamate and 10 parts of zinc cyamyl dithiocarbamate was prepared and heated to 130°C. Heat it up and let it cool. The mixture was kept at this temperature with stirring for a total of about 12 hours and filtered. Filtered through superant. The filtrate contains sulfur 1'2. ．． 61% (theoretical value 12.25) The desired product contained .

Example 3 561 parts of 1-octene, 160 parts of sulfur and 1 part of zinc cyamyl dithiocarbamate 0 parts of the mixture was prepared and heated to about 130°C. The mixture was brought to this temperature for about 6 hours. It was filtered for a while. The filtrate contains 23.2% sulfur (theoretical value 22-224) This was the desired product.

Example 4 The product of Example 3 (500 parts) was heated under vacuum to 100°C and then to 130°C. I stripped. The residue (367 parts) contains the desired product containing 30.31% sulfur. It was a product.

Example 5 1052 parts of 1-decene, 360 parts of sulfur and 1 part of zinc cyamyl dithiocarbamate 5 parts of the mixture were prepared and heated to 130°C. The mixture was left stirring for a total of 9 hours. The temperature was then maintained at 150° C. for 6 hours.

Then, the temperature was lowered to 100°C and filtered. The filtrate contains sulfur 2s, s% (theoretical value) The desired product contained 2s, 4g).

Example 6 1052 parts of isomerized 1-decene (isomerized by treatment with Amberlyst 15), preparing a mixture of 360 parts of sulfur and 15 parts of zinc cyamyl dithiocarbamate; It was heated to 130°C. The mixture was kept at this temperature for 9 hours and then at 150° C. for 6 hours. I kept it. The mixture was cooled to 90°C and filtered. The filtrate contains sulfur 2s, 6s % (theoretical value 25.5) of the desired product.

Example 7 1000 parts of commercially available C16-18 alpha-olefin, 137 parts of sulfur and sia A mixture of 10 parts of zinc mildithiocarbamate was prepared, purged with nitrogen, and heated to 130°C. Heated. The mixture was kept at 130°C for 6 hours, cooled to 100°C and filtered. filtrate is the desired product containing 11.85% sulfur (theoretical value 12..15). It was.

Example 8 700 parts of commercially available Cl6-18 alpha olefin, 1647 parts of sulfur and cyami Prepare a mixture of 7 parts of zinc ludithiocarbamate, purify with nitrogen, and heat to 130°C. did. The mixture was kept at this temperature for about 12 hours and then at 150° C. for 6 hours.

The mixture was cooled to 100°C and filtered. The filtrate contains 18.9% sulfur (theoretical value 1 The desired product contained 9.08).

Example 9 Commercially available C16-18 alpha olefin I 000 parts, sulfur 235.2M A mixture of 10 parts of zinc and cyamyl dithiocarbamate was prepared, and the atmosphere was replaced with nitrogen. Heated to 30°C. The mixture was kept at this temperature for about 12 hours and at 150° C. for 6 hours. Finally, it was kept at 180°C for 3 hours. After cooling to 100°C, the mixture was filtered. filtrate was the desired product containing 17.4% sulfur (theoretical 19.08).

Example lO 100 parts of commercially available Cl6-18 alpha-olefin, 4 parts of H5lK255 and A mixture of 10 parts of zinc and cyamyl dithiocarbamate was prepared, and the atmosphere was replaced with nitrogen. Heat it to 0℃. The mixture was held at this temperature for a total of about 12 hours and then for about 3 hours at 1 It was kept at 50°C. After cooling to 100°C, the mixture was filtered. The filtrate contains sulfur 2 The desired product contained 0.66% (theoretical value 20.37).

Example 11 6638 parts of soybean oil, 301.4 parts of commercially available Cl5-18 alpha olefin, A mixture of 34.8 parts of leic acid, 118 parts of sulfur and zinc cyamyl dithiocarbamate. The mixture was prepared, purged with nitrogen, and heated to 130°C. This mixture was heated for a total of about 9 hours. It was kept at this temperature and filtered. The filtrate contains 10.1% sulfur (theoretical value 10.6 g) ) was the desired product containing.

Example 12 The procedure of Example 11 was repeated except that 1242 parts of sulfur were mixed into the mixture.

The product obtained by this method contains sulfur ss, o% (theoretical value 18.26) Contained.

Example 13 1056 parts of soybean oil, 124.6 parts of sulfur and 1 part of zinc cyamyl dithiocarbamate 0.6 part of the mixture was prepared, purged with nitrogen, and heated to 130°C. This mixture It was kept at this temperature for about 9 hours, cooled to 100°C and filtered.

The filtrate is the desired product containing 10.2 parts of sulfur (theoretical value 10.6 s). It was.

Example engineering 4 1000 parts sunflower oil, 118 parts sulfur and 1 part zinc cyamyl dithiocarbamate 0 parts of the mixture was prepared, purged with nitrogen, and heated to 130°C. Add this mixture to about 1 It was held at this temperature for 2 hours and at 150° C. for 3 hours.

After cooling to about 110°C, the mixture was filtered. The filtrate contains 9.91% sulfur (chemical The desired product contained a theoretical value of 10.6 g).

Example 15 900 grams of the Diels-Alder adduct of Example DA-6, 149 parts of sulfur and A mixture of 9 parts of zinc cyamyl dithiocarbamate and Heated to 0°C. The mixture was kept at this temperature for approximately 6 hours. After cooling to about 95℃ , the mixture was filtered. The filtrate contains 11.81 sulfur (theoretical value 13.9 s). It contained the desired product.

Ichiichikubo 4------ Example 16 The general procedure of Example 15 was repeated except that the mixture contained 320 parts of sulfur. Ta. The product obtained in this way contained 22.6% sulfur (theoretical value 26).

Example 17 1000 parts of commercially available Cl6-18 alpha-olefin, 225.4 parts of sulfur and Cyamyldi obtained by the reaction of 2 moles of cyamylamine and 1 mole of carbon disulfide A mixture of 14.7 parts of amine salt of thiocarbamic acid was prepared, the atmosphere was replaced with nitrogen, and 130 parts of amine salt was prepared. heated to ℃. The mixture was kept at this temperature for a total of 12 hours and at 150°C for an additional 6 hours. I kept it.

After cooling to 100°C, the mixture was filtered. The filtrate contains 20.1% sulfur (theoretical value) The desired product contained 20.30).

Example 18 1000 parts of commercially available Cl6-18 alpha olefin, 255.4 parts of sulfur and A mixture of 8.9 parts of copper dibutyldithiocarbamate (5) was prepared, and the mixture was replaced with nitrogen. It was heated to 130°C. The mixture was kept at this temperature for a total of 12 hours and an additional 6 hours i. It was kept at 0°C. After cooling to about 100°C, the mixture was filtered. The filtrate contains sulfur 20 ．． The desired product contained 5% (theoretical value 20.4).

Example 19 Commercially available Oc, 1000 parts of 8 alpha olefin, 137 parts of sulfur, 2-merca A mixture of 10 parts of putobenzothiazole and 10 parts of zinc oxide was prepared and heated to 130°C. heated to. The mixture was kept at this temperature ratio for 6 hours and at 150°C for an additional 6 hours. . After cooling, the mixture was filtered. The filtrate contains 11.26 T sulfur (theoretical value 11.94 ) was the desired product containing.

Sulfur-containing compositions of the present invention include natural and synthetic lubricating oils and mixtures thereof. do. A general study of lubricating viscosity in various lubricating compositions based on various oils. It can be used as an antioxidant, extreme pressure and friction modifier. Lubrication above The composition is suitable for automotive and trunk engines, two-cycle engine lubricants, aviation Spark ignition and compression in piston engines, marine and railway diesel engines, etc. Includes crank-case lubricants for ignited internal combustion engines. However, automatic transmission oil , transaxle lubes, gear lubes, metalworking lubes, hydraulic fluids and other lubricants. Lubricant and grease compositions also benefit from incorporating the above compositions of the present invention. can receive.

The compositions of the present invention can be added directly to lubricating oils. However, preferred Preferably, the composition contains a substantially inert, normally liquid organic diluent, such as mineral oil, Additive concentrate by diluting with phthalate, benzene, toluene, or xylene, etc. to form. These concentrates typically contain the sulfur-containing compositions of the invention at about Contains 20 to 90% by weight, and also contains one or more other known additives listed below. You can also. The remainder of the concentrate is a substantially inert and usually liquid dilute solution. It is a diluent.

The lubricating oil compositions of the present invention include natural and synthetic lubricating oils, and mixtures thereof. It consists mostly of oil with a lubricating viscosity.

Natural oils include animal and vegetable oils (e.g. castor oil, lard oil, etc.), and Paraffin, naphthene or paraffin-nanthene liquid petroleum and solvents Includes treated or acid-treated mineral oil lubricants. Moisture derived from coal or sierre Oils with a slippery viscosity are also useful. Synthetic lubricating oils are hydrocarbon oils and substituted carbon Hydrogenated oils, such as polymerized and copolymerized olefins (e.g. polybutylene, poly propylene, propylene-isobutylene copolymer, chlorinated polybutylene, etc.); poly(1-hexene), poly(1 octene), poly(r-decene), and mixtures thereof; alkylbenzenes (e.g. dodecylbenzene, tetradecyl benzene, dinonylbenzene, di(2-ethylhexyl)-benzene, etc.); Polyphenyls (e.g. biphenyls, terphenyls, alkylated polyphenyls) alkylated diphenyl ether and purkylated diphenyl sulfide and derivatives, analogs and homologues thereof.

The terminal hydroxyl group has been modified by esterification, etherification, etc. Alkylene oxide polymers and copolymers and their derivatives may be used. They constitute another class of known synthetic lubricants.

Examples of these are: by polymerization of ethylene oxide or propylene oxide The resulting oil, alkyl and aryl of these polyoxyalkylene polymers ether (e.g. methylpolyisopropylene with an average molecular weight of about 1000) Glycol ether, polyethylene glyco having a molecular weight of about 500-1000 polypropylene diphenyl ether with a molecular weight of about 1000-15000 diethyl ether of lene glycol, etc.) or their mono- and poly- Carboxylic acid esters, such as CI3 oxyacid diethyl esters of tetraethylene glycol Stell's acetate ester and a combination C3-C8 fatty acid ester can be mentioned.

Another suitable synthetic lubricant that may be used is a dicarboxylic acid (e.g. Talic acid, co-phosphoric acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, Zelaic acid, speric acid, sebacic acid, fumaric acid, adipic acid, liluic acid dimer malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) and various alcohols. (e.g., -y) thyl alcohol, hexyl alcohol, dotesyl alcohol , 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol Consists of esters with monoethers (propylene glycol, etc.). These Specific examples of ster include dibutyl adipate, di(2-ethylhexyl) mono( cate, di-n-hexyl fumarate, dibutyl adipate, diisooctyla Gelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate 2-ethylhexyl diester of diecosyl heptabacate, lyluic acid dimer 1 mole of sebacic acid and 2 moles of tetraethylene glycol and 2-ethyl alcohol. Examples include complex esters produced by reacting with 2 moles of xanonic acid. can be done.

Esters useful with synthetic lubricating oils include 05-C12 monocarboxylic acids and polyesters. Obtained from oar, and Hineohentyl glycol, trimethylolpro Nosine, pentaerythritol, dibe/taerythritol, tripentaerythritol It also includes polyol ethers such as toll.

Polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy - Silicone oils, such as siloxane oils and silicate oils, are another class of Synthetic lubricating oils (e.g., tetraethyl silicate, tetraisopropyl silicate) , tetra-(2-ethylhexyl/I/) silicate, tetra-(4-methyl-hexyl) xyl) silicate, tetra-(p-t-butyl-phenyl) silicate, hexyl Sil-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxane siloxane, poly(methylphenyl)siloxane, etc.). Other synthetic lubricants , liquid esters of phosphorous acids (e.g. tricresyl phosphate, trioctyl phosphate) phosphate, diethyl ester of decanephosphonic acid, nato), polymerizable tetra Hydrofuran, etc.

Natural or synthetic, unrefined, refined and rerefined oils (and Mixtures of two or more of these can also be used in the composition of the present invention. unrefined oil are obtained from natural or synthetic sources without further purification treatment.

For example, directly from petroleum or ester processes obtained directly by retort separation operations. Ester oils obtained and used without further treatment are unrefined oils. purification Oil is unrefined unless it is further processed in one or more refining steps to improve one or more properties. Similar to oil refining. Solvent extraction, secondary distillation, acid or base extraction, filtration, percolation Many such purification techniques are known, such as sorption. Re-refined oil is refined oil. A method similar to that used to obtain refined oils and applied to already used refined oils. obtained by the method described. Such rerefined oil is also known as recycled oil. and is often further treated with additives and oil breakdown product removal techniques. It will be done.

The sulfur-containing compositions of the present invention contain from about 0.001% to about 2% of the particular oil used therein. Only 0% by weight is typically used in lubricating compositions of the present invention. Used in certain lubricants The optimum amount will of course depend on the other contents of the particular lubricating composition, the operating conditions being processed. and depending on the particular additives used. Lubricating composition for marine diesel engines In lubricating compositions used under severe adverse conditions, such as It can be present in the lubricating oil in an amount greater than about 30% by weight of the total weight of the lubricating composition.

Other additives can be used in the present invention in the lubricating oil compositions of the present invention. child Additives such as those normally used in lubricating oils, such as detergents, dispersants, and acids. anti-fouling agents, pour point depressants, extreme pressure agents ts), anti-wear agents, color stabilizers, and antifoaming agents.

Examples of ash-forming detergents include alkali or alkaline earth metal sulfonic acids or can include oil-soluble neutral or basic salts with carboxylic acids. like this The most commonly used salts of acids are sodium, potassium, lithium, and calcium. of aluminum, magnesium, strontium and barium.

The term "basic salt" refers to salts in which the metal is stoichiometrically more abundant than the organic acid groups. Indicates metal salts such as The method commonly used to produce basic salts is the production of acid minerals. Addition of metal oil solutions to metal oxides, hydroxides, carbonates, bicarbonates, or sulfides. The resulting raw material is heated at a temperature of about 50°C with a stoichiometric excess of neutralizing agent. filtration of the product. In the neutralization process that promotes the incorporation of large excess amounts of metals. It is also known to use "accelerators" to Examples of compounds useful as such promoters include , phenol, naphthol, alkylphenol, thiophenol, sulfur-containing alcohol Phenolic substances such as lukylphenol and formaldehyde and phenol Condensation products with system substances; methanol, 2-globanol, octyl alcohol , cellosolve, calpitol, ethylene glycol, stearyl alcohol, Alcohols such as cyclohexyl alcohol; and aniline, phenyl diamines, phenothiazines, phenyl-beta naphthylamines, and Examples include amines such as silamine. Particularly for producing the basic salt An effective method comprises adding an acid to an excess of a basic alkaline earth metal neutralizing agent and at least one the mixture with an alcohol promoter and carbonate the mixture under elevated temperature, such as 60-200°C. Consists of chlorination.

Due to their composition, ashless cleaning agents and dispersants do not oxidize during combustion. Although non-volatile substances such as borons can be produced, they usually do not contain metals and Despite the fact that it does not produce metal-containing ash upon combustion, Called. Various types of lubricant compositions are known, all of which can be used as the lubricant composition of the present invention. It is suitable for use in Examples may include: (1) a carbon containing at least about 34, preferably at least about 54 carbon atoms; Rubonic acid (or its derivatives) and nitrogen-containing compounds such as amines, phenols and and organic hydroxy compounds such as alcohols, and/or basic inorganic substances. reaction product. Examples of these "carboxyl dispersants" are described in British Patent No. 1,306. , 529, as well as in a number of the following US patents:

3.163,603 3,351552 3,541,0123.215,70 7 3,399,141 3,542,6803.271,310 3,433 ,744　3,574,1013.281,357　3,448,048　3, 63+19043.311,558 3,451,933 a632,5113 ．． 340,281 3,462668 3,725,4413.34 (3,49 33,52λ179 Re26,433(2) Relatively high molecular weight aliphatic or Reaction of a cycloaliphatic halide with an amine, preferably a polyalkylene polyamine thing. These are characterized as "amine dispersants", examples of which are listed below in the US As stated in the patent: 3.275,554 3,438,757 3,454,5553565.80 4 (3) Sulfalkylphenol whose alkyl group has at least about 30 carbon atoms and aldehydes (especially formaldehyde) and amines (especially polyalkylene polymers). is a reaction product characterized as a ``Mannich dispersant''. What to do. The features described in the following US patents are exemplary: λ459,112 3,44λ808 3,591,5982.984,550 3,454497 3,634.5153.166.516 3,461.1 72 3.6925743355.270 3,539,633 3,725, 4803413.347 Turtle 586,629 3980.569 (4) Calbo Xyl, amine or Mannich dispersants can be added to urea, thiourea, carbon disulfide, alkaline Dehydes, ketones, carboxylic acids, hydrocarbon-substituted cono-phosphoric anhydrides, nitriles, epoxy Products obtained by post-treatment with agents such as cid, boron compounds. this Examples of species are described in the following US patents: 303G, 003 3200, 107 3,254. ．． 025327&550 3,281,428 3,282,9553.366.569 3373.11 + 3,442,8083455.832 3,493520 3,513,0 933.539,633 3,579,450 3,600,372639, 242 3,649,659 3.69Z5743.703,536 3.70 a422 (51 decyl methacrylate, vinyl decyl ether and high molecular weight Oil-soluble monomers such as lefins and monomers containing polar substituents, e.g. Noalkyl acrylate or acrylamide and poly-(oxyethylene) - Copolymers with substituted acrylates.

These can be characterized as "polymeric dispersants", examples of which are listed below. Described in US Patent: 3.329,658 3,449,250 3,5 19,5653.666.730 3.68'14849 3,702,300 The above patents are cited herein for their disclosure regarding ashless dispersants.

Auxiliary extreme pressure agents and corrosion and antioxidants that can be included in the lubricating oils of the present invention Examples include chlorinated aliphatic hydrocarbons such as chlorinated waxes; do, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, oleyl sulfurized methyl esters of acid, sulfurized alkylphenols, sulfurized dipentene, and can include organic sulfides and polysulfides such as pentene sulfide . Group I metal salts of phosphorodithioic acids are also included in some of the above lubricating oils.

An example of a useful metal salt of phosphorodithioic acid is dicyclohexylphosphorodithioic acid. Zinc acid, barium dioctylphosphorodithioate, cadmium dinonylphosphorodithioate and phosphorus trisulfide and isopropyl alcohol and n-hexyl alcohol. List the zinc salts of phosphorodithioic acids obtained by reaction with equimolar mixtures of be able to. If it is desirable to prepare lubricating oils containing small amounts of phosphorus, , such phosphorodithioates should be avoided if possible.

Many of the auxiliary extreme pressure agents and corrosion-oxidation inhibitors listed above are also useful as antiwear agents. . Zinc dialkylphosphorodithioates are well known examples.

Pour point depressants are particularly useful additives often included in the lubricating oils of the present invention. . The use of such pour point depressants in oil-based compositions can improve the low-temperature properties of oil-based compositions. Good things are conventionally well known (for example, C0V, Smalheer, “Lubricating Oil Additives J” by R.Kennedy Sm1th See page 8 (Lezius-Hiles) Co, publishers, C1eveland, 0hio.

1967)).

Examples of useful pour point depressants include polymethacrylates; polyacrylates; Acrylamide; condensation product of haloparaffin wax and aromatic compound: vinyl carboxylate polymers; and dialkyl fumarates), vinyl esters of fatty acids. Examples include terpolymers of sterohyalkyl vinyl ethers. Eyes of the invention A US special report on pour point depressants, their manufacturing technology, and their uses. Permit No. 2.381501; O1,5,748; 2.655.47 No. 9; No. 1, 815.022; No. 2.191.498; No. 2,666.74 No. 6; No. 2,721.877; No. 2.721. , No. 878; and No. 3.25 No. 0.715, these patents are incorporated herein by reference for their related disclosures. Cited in the specification.

Defoamers are used to reduce or prevent the formation of stable foam. teenager Typical antifoam agents include silicones or organic polymers. Other antifoaming agent groups The composition is "Foam Control Agents" Pages 125-162, Author Henry T. Kcrner (NoyesDat e Corporation, 1976).

The sulfur-containing composition of the present invention is suitable for metal processing when imparting excellent extreme pressure properties to lubricating oils. It has been found to be particularly effective as an additive to industrial lubricating oils. (@ stainless steel Ingredients that are often preferably incorporated into the metalworking lubricants of the present invention (for steel) are: , at least one chlorinated wax, especially a chlorinated paraffin wax. the salt The bleached wax preferably has a molecular weight of about 350 to about 700, with a molecular weight of about 30 to about 7 Contains 0% chlorine by weight.

Other additives that may be selectively present in the metalworking lubricant used in the present invention include: , antioxidants, mainly hindered phenols; surfactants, usually oxyalkyl nonionic surfactants such as phenols; and corrosion, wear and rust prevention including agents.

As a friction modifier, an alkyl or alkenyl group having about 10 to about 40 carbon atoms an alkyl or alkenyl phosphate or phosphite having an atom and its metal salts, especially zinc salts C10-20 fatty acid amides; C10-20 alkaline Killamines, especially tallow amines and their ethoxylated derivatives; partially esterified with an amine, as described above. boric acid or phosphorus Salts with acids such as C10-2゜alkyl-substituted imidacillins and similar nitrogen complexes. Exemplifying nitrogen compounds (nitogenhet, erocycles) Can be done.

The metalworking lubricants used in this invention generally contain about 0% of the sulfur-containing composition of this invention. ．． 5 to about 15 parts by weight, preferably about 1 to about 10 parts by weight. As mentioned above Other ingredients are metals with properties such as antioxidant, anti-corrosion, anti-wear, anti-rust properties Present in sufficient quantities to provide a chemical lubricant.

Examples of the concentrate and lubricating oil of the present invention are as follows. Especially bright Unless otherwise noted, parts and sections are by weight of the total amount of the composition. Also for mineral oil All amounts in the examples exclude oil present as a diluent, except for .

Mineral oil 50 Product of Example 5-50 Mineral oil 60 Product of Example 6 40 Product of mineral oil 95 95 96 96 95 Example] 5 --- --- - -1 Product of Example 2 -5 -----1 Product of Example 4 ----4--1 Product of Example 7 ----4-- Product of Example 15 ----------Table 5 ■ Mineral oil 93.48 93.68 93.995 Product of Example 6 5.0 - Product of Example 16 5.0 4.0 0.0-di(CI2-14 alkyl) 1.0 0.8 1. s phosphorodithio zinc salt of acid Poly(alkyl methacrylate) o, so, so, s pour point depressant Silicone defoamer 0.02 0.02 0.005 Mineral oil 95.0 93. 0 94.0 Product of Example 6 15-2.0 Product of Example 16 35- Chlorinated (chlorine approx. 42 parts) Paraffin 2.5 3.5 3.0 Wax Triphenyl phosphate 10 Any metal to be worked can be treated by the method of the present invention. the money Examples of the genus include metals including iron, aluminum, copper, magnesium, and titanium. These include zinc and manganese. Contains or contains other elements such as silicon Examples of suitable alloys include yellow Copper and various types of steel (e.g. stainless steel) are widely used.

The metalworking composition used in the method of the present invention can be prepared in a suitable manner before or after the processing operation. can be applied to the metal workpiece during operation. The composition covers the entire surface of the metal or can be applied to that portion of the surface where contact is desired. For example, lubricating oil It can be brushed or sprayed onto the metal, or the metal can be soaked in a lubricating oil bath. You may. In high speed metal forming operations, spraying or dipping is preferred.

In an exemplary embodiment of the method of the invention, the ferrous metal workpiece is lubricated with lubricating oil before the machining operation. Cover. For example, if the workpiece is to be cut, connect the workpiece with a cutting tool. Can be coated with lubricant before touching. (The present invention is particularly applicable to cutting operations. Useful. ) applying lubricating oil to the workpiece when it contacts the cutting tool Alternatively, the lubricating oil can be applied to the cutting tool itself and transferred to the workpiece upon contact. It is also within the scope of the invention. Thus, in a comprehensive sense, the method of the invention comprises: If the workpiece is coated with the above-mentioned lubricant, regardless of how it is applied, Consists of metal processing operations such as:

Certain special properties added to asphalt cement or asphalt concrete compositions Certain sulfur-containing compositions reduce degradation and improve ductility of the asphalt composition. I also learned that.

Sulfur-containing compounds useful in reducing deterioration of asphalt and asphalt-containing compositions. The sulfurizing agent is added to at least one type of fat of (A) a polyhydric alcohol at an elevated temperature. Fatty acid ester, or (B) at least one type of fatty acid, monohydric alcohol fatty acid ester, or mixture thereof, or (C) at least one other olefin, or (D) a mixture of two or more of (A), (B) and (C), selectively ( E) Formula: R1(R2)N-C3SH (wherein R1 and R2 are independently hydrocarbons) at least one of at least one dithiocarbamic acid represented by salt of seeds, or (F) at least one mercaptobenzothiazole, or (F) at least one mercaptobenzothiazole, or ( c) Produced by reacting a mixture of (E) and (F) in the presence of a catalytic amount will be built.

Curing agent and Nilemene) A to G are as described above.

When the agent to be sulfurized is only the olefin (C) and the catalysts (E) and (F) are If not used, it is preferred that the olefin is a monoolefin.

Stabilized asphalt compositions contain a large amount of asphalt and a small amount of stabilization-improving amount. It consists of at least one kind of sulfur-containing composition described above.

The present invention also includes a large amount of at least one aggregate and a stabilized asphalt composition. Includes asphalt concrete consisting of a small amount of asphalt cement. do.

U.S. Pat. No. 4,119,549 uses a mixture of sulfur and hydrogen sulfide, A method for producing sulfur compounds is disclosed. In U.S. Reissue Patent No. 21331, Sulfurized Diels-Alder adducts are disclosed. U.S. Patent No. 3926.82 No. 2 contains fatty acid esters and certain olefins and optionally fatty acids. A sulfurized material obtained by sulfiding a mixture is disclosed.

This disclosed herein with respect to the sulfurization reaction and the products obtained thereby et al. and other patents are cited herein for their disclosures.

Sulfidation of unsaturated organic compounds is well known and is described by Kirk-Othmer, Enc. yclopedia of Chemical Technology”.

3rd Edition, John WiIey & 5ons, 198 3, Volume 22, pp. 255-266, which is also cited here. has been done.

As mentioned above, the sulfurizing agent may be sulfur, and the reaction is carried out by stirring the substance to be sulfided well. while in an inert atmosphere (e.g. nitrogen) at elevated temperatures, often 100-250°C. , usually by heating with sulfur at about 150 to 210°C.

It is often advantageous to add the sulfur to the substance to be sulfurized in portions. . The reaction involves alcohols, ethers, esters that are liquid at the reaction temperature used. , aliphatic hydrocarbons or -logenated aromatic hydrocarbons. can.

Following the reaction, insoluble by-products are removed by filtration, usually at elevated temperatures (approximately 80-120°C). can be removed.

The filtrate is the desired sulfurized product.

The sulfur-containing asphalt composition of the present invention comprises at least one type of sulfur-containing asphalt composition other than asphalt. Consists of sulfurized organic compounds.

A wide range of sulfurized organic compounds can be utilized in the asphalt compositions of the present invention; These compounds generally have the formula:%Formula%() (wherein S is sulfur, X is an integer having a value from engineering to about 10, R and R1 can be the same or different organic groups) Ru.

This organic group can be a hydrocarbon group or an alkyl, aryl, aralkyl, or alkali group. alkanoates, thiazoles, imidazoles, phosphorothioates, base It is a substituted hydrocarbon group containing a terketoalkyl group, etc. In fact, the hydrocarbon group is , halogen, amine, hydroxy, mercapto, alkoxy, aryloxy, Other substituents such as thio, nitro, sulfonic acids, carboxylic acids, and carboxylic esters can contain.

Specific examples of Wt gold-containing compositions useful for use in the asphalt compositions of the present invention include aromatic, alkyl or alkenyl sulfides and polysulfides, sulfides Olefins, sulfurized carboxylic acid esters, sulfurized ester olefins, sulfurized oils, and and mixtures thereof. The method for producing such sulfur-containing compositions is It is mentioned in the dedication.

The sulfurized organic compound used in the asphalt composition of the present invention is dibenzyl sulfur. dixylyl sulfide, dicetyl sulfide, shibara fin wax sulfide aromatic and alkyl sulfides and polysulfides, such as cracked wax oleum 5ulfid es) etc. One method of producing aromatic and alkyl sulfides is Condensation of a chlorinated hydrocarbon with an inorganic sulfide, whereby each from two molecules The chlorine atom of is replaced and the free valence from each molecule bonds to the divalent sulfur atom. .

Generally, the reaction is carried out in the presence of elemental sulfur.

Examples of dialkenyl sulfides useful in the compositions of the present invention are described in U.S. Patent No. 2.446. It is described in No. 072.

These sulfides are olefinic hydrocarbons containing 3 to 12 carbon atoms. and elemental sulfur in the presence of zinc or a similar metal, generally in the form of an acid salt. It can be obtained by using An example of this type of sulfide is 6.6 fudithiobis(5-methyl-4-nonene), 2-butenyl monosulfide and and 2-methyl-2-butenyl monosulfide and disulfide, and 2-methyl-2-butenyl monosulfide and disulfide. Fido can be given.

In addition to the sulfur compounds described above, the following examples show that the asphalt compositions of the present invention Non-limiting examples of useful sulfide materials.

Example 20 Commercially available CI 5-2° Mixture of 60 parts of alpha olefin and ioo parts of lard oil The mixture was heated to 160° C. under nitrogen atmosphere and 12 parts of sulfur was added. 16 of the mixture It was heated to 5° to 200°C and 65 parts of sulfur was added. After heating for 4 hours, the mixture The mixture was cooled to 100°C and filtered to yield the desired product containing 9.0% sulfur.

Example 21 Soybean oil at 165°C1. Add nitrogen to a mixture of 0 parts O and 50 parts of 1-hexadecene. Under an elementary atmosphere, 20.6 parts of sulfur was added over 20 minutes with stirring. Departure A thermal reaction occurred and the temperature rose to 200°C. Heat to 175°-200°C for 6 hours The mixture was cooled to 100° C. and filtered to obtain the desired product containing 11.1% of sulfur. .

Example 22 A mixture of 100 parts of soybean oil and 50 parts of commercially available CI6 alpha olefin was mixed with nitrogen. It was heated to 175°C in an elementary atmosphere, and 17.4 parts of sulfur was gradually added, but no emissions occurred. The temperature rose to 205°C due to the thermal reaction. The mixture was heated at 188°C to 200°C for 5 hours. ℃, gradually cooled to 90℃ and filtered to give a solution containing 10.13% sulfur. The desired product was obtained.

Example 23 According to the procedure of Example 22, 100 parts of soybean oil, commercially available C15-18 alpha A sulfided product was obtained from 50 parts of monoolefin and 17.4 parts of sulfur. The product is sulfur It contained 10.1 pieces of yellow.

Example 24 According to the procedure of Example 22, the product having a sulfur content of 10.3.3% was added to soybean oil. 100 parts, 50 parts of commercially available Cl5-20 alpha olefin and 17.9 parts of sulfur. Obtained by reaction of part.

Example 25 According to the procedure of Example 22, the product having a sulfur content of 9.69 o parts, 100 parts of commercially available C2°-28 alpha-olefin and 232 parts of sulfur obtained from the department.

Example 26 Following the procedure of Example 22, the product having a sulfur content of 1016 cm was injected into 1 l of cottonseed oil. 00 parts, commercially available CI 5-20 alpha olefin 33.3 parts and sulfur 15 ．． Obtained from Part 6.

Example 27 Following the procedure of Example 22, a product with a sulfur content of 881 cm was converted to an iodine number of 85 100 parts of -95 triglyceride, commercially available Cl5-18 alpha-olefin 2 5 parts and 14.5 parts of sulfur.

Example 28 100 parts of soybean oil, 50 parts of commercially available Cl5-48 alpha-olefin, triphenyl Under a nitrogen atmosphere, a mixture of 1.17 parts of sulfur and 17.4 parts of sulfur was added to Heated at 45° to 165°C for 16 hours. Then, it was cooled to room temperature and heated to 100 ℃, filter aid was added and filtered. The filtered product contains 10.23% sulfur Contained.

Example 29 100 parts of soybean oil, 3.7 parts of tall oil acid and commercially available Cl5-18 alpha oleaf A mixture of 46.3 parts of sulfur and 17.4 parts of sulfur was heated to 165° C. under a nitrogen atmosphere. was added.

The temperature of the mixture rose to 191°C. Maintained at 165°~200°C for 7 hours. , then cooled to 90°C and filtered. The product contained 10.13% sulfur.

Example 30 Following the procedure of Example 29, a product containing 10.39% sulfur was added to soybean oil. 100 parts, 4 parts of tall oil acid, commercially available C, 46.3 parts of 5.8 alpha olefin, and and 20.6 parts of sulfur.

Example 31 According to the procedure of Example 29, the product containing 10.6% sulfur was injected into soybean oil 1 00 parts, 5.25 parts of tall oil acid, 44.0 parts of commercially available Cl5-18 alpha olefin. 8 parts and 17.4 parts of sulfur.

Example 32 Following the procedure of Example 29, the product containing 1O34% of sulfur was 100 parts of oil, 5.26 parts of tall oil acid, commercially available Cl5-18 alpha-olefin 4 5 parts and 17.5 parts of sulfur.

Example 33 According to the procedure of Example 29, a product containing 1241% sulfur was added to 11% soybean oil. 00 parts, 5.35 parts of tall oil acid, 46.0 parts of commercially available Cl5-18 alpha olefin. 3 parts and 26.8 parts of sulfur.

Example 34 Following the procedure of Example 29, the product containing 9.98% sulfur was added to soybean oil i 0 parts, 4.11 parts of tall oil acid, and a mixture of Cl2-+6 fractions from the polymerization of inbutene. 44.8 parts of sulfur and 20.8 parts of sulfur.

Example 35 Following the procedure of Example 10, except using a temperature range of 135° to 165°C, A product containing 13.7% sulfur, 100 parts of soybean oil, 5.4 parts of tall oil acid, city 746.2 parts of commercially available Cl5-18 alpha olefin, triphenyl phosphite 1.5 parts and 25 parts of sulfur.

Example 36 According to the procedure of Example 29, the product containing 9.54% sulfur was injected into soybean oil 1 00 parts, 553 parts of tall oil acid, 50.0 parts of commercially available Cl5-Il+alpha olefin. 2 parts, 3.18 parts of lecithin and 184 parts of sulfur.

Example 37 Soybean oil was prepared according to the procedure of Example 29, except that the temperature was 150° to 165°C. 100 parts, 5.4 parts of tall oil acid, 46 parts of commercially available Cl5-18 alpha olefin, The product was obtained from 3 parts and 248 parts of sulfur. The product contains 136% sulfur. Ta.

Example 38 (a) Isoprene methacrylate of Example DA-3 heated to 110° to 120°C Sulfur flower s 3 y (1,6 smol) was added over 15 minutes. Heat at 130'-160℃ for 4.5 hours continued. After cooling to room temperature, the reaction mixture was passed through a moderately calcined glass funnel. Filtered. The filtrate consists of the desired sulfur-containing product 3012.

(b) In (a) above, the ratio of sulfur to adduct was 1:1. This example and the ratio is 5:I. Therefore, 170 moles of sulfur flower 6402 (20 moles) Heated in a 3 liter flask at 0.degree. C. for about 0.3 hours. Next, Example DA-3 Isogrene-methacrylate adduct 600y (4 mol) was heated at 174° to 198°C. was added to the molten sulfur while maintaining the temperature at . Cool to room temperature and transfer the reaction contents above. Filtered as follows. The filtrate was the desired product.

(c) The adduct 7502 (5 mol) used in (a) and (1)) above was refluxed. It was heated to 105° C. under these conditions. Add sulfur flower 320y (10 moles) to the heated adduct. for 0.75 hours while maintaining the temperature of the reaction contents at ~112°C. , was added in 5 portions. Nitrogen at a rate of 0.25-0.5Nft3/hr Heat the reaction mixture for 6 hours at 150° to 155°C while blowing through the reaction contents. It was hot. The reaction contents were then cooled and filtered at room temperature to yield the desired product 1005' I got f.

Example 39 (a) Diels-Alder adduct of butyl acrylate and isogrene 1 Reaction mixture consisting of x7ss+ (6 mol) and sulfur flower 384f (12 mol) was passed through the reaction mixture at a rate of 0.25 to 0.5 N ft3/hr. 0.5 hours at 108° to 110°C and 6 hours at 155° to 165°C while blowing It was heated for a while. At the end of the heating period, it was cooled and filtered at room temperature. Then the product is 2 It was left for 4 hours and refiltered. The 1278y filtrate was the desired product.

(1)) Example 39 (According to the operation of al, adduct 1275y (6,s The desired sulfur content is 1421 reacted products were obtained.

(C) Again, according to the method of (a), imprene and butyl acrylate 2.4502 (12-5 mol) of adduct of s mol) to give the desired sulfur-containing product.

Example 40 (a) Sulfur (4, s mol) and imprene-methyl-methacrylate (4, s mol) s mol) at room temperature and reacted at a rate of 0.25 to 0.5 N ft3/hr. The mixture was heated at 110°C for 1 hour while blowing nitrogen through it. Then nitrogen blow While continuing to heat the reaction mixture, the temperature was increased to 15°C to 155°C for 6 hours. It was hot. After heating, the reaction contents were allowed to stand for several hours while cooling to room temperature, and then filtered. did. The filtrate was 842 g of the reaction mixture of the desired sulfur-containing product.

fb) Using the method of (a), add 796 moles of sulfur and isoprene-methyl-methane. Reaction with 3.98 moles of tacrylate adduct gave 857 moles of product.

Example 41 (a) 700 y (s, 04 mol) of butadiene and methyl methacrylate The addition salt of The mixture was mixed in the presence of 3% by weight hydroquinone. The reactants are introduced into the reaction interior using nitrogen. The mixture was heated to reflux while bubbling. Heating was performed gradually at first. (first 1 o'clock temperature from room temperature to 110℃ during the period, and 110"C to 140"C during the next hour. It was hot. ) Furthermore, the reaction mixture is heated to a temperature within the range of 150"C to 160"C. for 6 hours, then cooled to room temperature and filtered twice. The filtrate is for the purpose of 930y. It consisted of sulfur-containing products.

(b) A method similar to that in (a) was carried out at a temperature of 71 to 78°C with 18 Add boiling distilled butadiene-methyl acrylate addition salt under pressure of ~19°C. I used it as a seasoning and returned it. Reactants, i.e. 550 units of the above adduct (4.0 mole) ) and 2562 sulfur powder (8.0 mol) were prepared using a reflux condenser and a nitrogen gas supply port. I put it in the flask that I bought. The mixture was heated at a temperature within the range of 350-160'C. Heating under live reflux conditions for an hour, during which time bubbles of nitrogen gas were introduced into the inside of the tube by 0.5 standard cubic meters. The air was blown at a rate of 1-7 hours. After cooling to room temperature, filter the product. 810 g of the desired product was obtained as a filtrate.

Example 42 2562 (1 liter) flask equipped with a stirrer, reflux condenser, and nitrogen inlet. mol) of butadiene and indecyl acrylate adduct, and 642 (2 mol) ) and then heated at 200°C for 12 hours. Leave it for 21 hours The desired product was obtained as a filtrate by filtration at room temperature.

Example 43 (al　420　P　C1.5mol) of isoprene and decyl acrylate The adduct was reacted with 96 mol (30 mol) of sulfur powder as in Example 5. , 4662 was obtained.

(b) Using the same reactants as in (al) above, changing the manufacturing conditions, The ratio of yellow to adduct was increased from 2:1 to 7:1. 22 in a 2g flask Add 4 mol (7.0 mol) of sulfur powder and heat to 120°C to melt the sulfur. I changed it to that of Next, the adduct of 2802 is added, and during this time the temperature inside the reaction is The temperature was raised to 200°C. The reaction mixture was further heated at a temperature of 200° to 244°C for 11 hours. It was semi-heated. Upon cooling, a dark red sticky liquid of 3662 consisting of the desired reaction product was obtained. Ta.

Example 44 fa) 45505' (25 mo#) with butadiene-butyl acrylate Addition and xsoor (s 0 mol) of sulfur powder were mixed in a stirrer, a reflux condenser and The mixture was placed in a No. 121 flask equipped with a nitrogen inlet tube. The reaction mixture was heated to 150° to 155° heating for 7 hours at a temperature in the range of °C while nitrogen was added at a rate of 0.5 cubic feet/hour I passed it. After heating, the contents are cooled to room temperature and filtered to remove the sulfur-containing filtrate. The product was obtained.

1002, the product of Example 44 fa) obtained before filtration was placed in a reflux condenser and The mixture was heated to 100° C. in a 31° flask equipped with a stirrer and a stirrer. This addition under high speed While stirring, add 1.　Sodium sulfide solution of OOO9 for 1 minute and the contents were cooled to 38°C.

The resulting mixture was heated to 50°C using an infrared lamp and further heated to 42° to 50°C. It was kept in the 0°C range for 1 hour.

On standing, the reaction mixture separated into organic and aqueous layers. lower or aqueous layer I pulled it out. Filtration of 440 parts of the organic phase yields 4012 parts of the desired product. A corresponding filtrate was obtained. The remaining portion of the organic phase was washed with 5002 water at 40”C for 10 minutes. After washing, the phases were separated.

The organic phase weighed 358y and was stripped to remove water. remove water The product after this was 3222. Sodium sulfide treated sulfur-containing adducts A first wash of the product obtained by direct filtration and the sodium sulfide-treated adduct. The adducts obtained by purification are the same and both contain IJum. It was something that they did not have.

Φ) Following the procedure of Example 44(a), xo92y (6 moles) was -butyl acrylate adduct and 1922 (6 mol) sulfur powder at 150°~ Heating was carried out at a temperature of 155° C. for 7 hours. After cooling and filtering, the product is 1. A clear, yellow liquid filtrate of 2179 was obtained.

Example 45 The butadiene-butyl acrylate adduct was prepared using a stirrer, a reflux condenser and a nitrogen inlet. 5132 (4 mol) of butadiene-1,3 was put into a No. 21 flask equipped with an entry tube. Manufactured by To this butadiene, 504 aluminum chloride ( AlCl5) for 1 min while stirring the reaction mixture at a temperature ranging from 25 to 28 °C. It was added over a period of time. A colorless and transparent solution was obtained. React the butadiene contents to 28~ This aluminum chloride-butyl acrylate was heated at a temperature of 59°C for 1.75 hours. blown into the rylate mixture. The reaction contents were then maintained at a temperature of 41-52°C. After stirring for 2 hours, a solution consisting of 150 g of concentrated hydrochloric acid and ioor of water was added to the reactants. was added to hydrolyze aluminum chloride. The aqueous phase of the reaction was discarded. organic phase was washed with 100 m/ml of water at 40°C, discarding the resulting aqueous phase and adding the desired addition of 7352. The organic phase of the product was obtained.

The above product of 2002 (1.1 mol) and the sulfur powder of 7052 (22 mol), The mixture was mixed in a 1 liter flask equipped with a stirrer and a reflux condenser. 1500~ It was heated at 160°C for 7 hours. During this reaction, nitrogen gas is introduced into the reactants at 0.25 standard Blows in at the rate of cubic feet/hour. 2602 obtained slightly orange The strained liquid was placed in a 31 flask equipped with a stirrer and a reflux condenser.

Mix 1732 toluene and 26.02 hexagonal sodium sulfide aqueous solution to this. After addition, high-speed stirring was performed at room temperature for 1 hour.

After separation into two phases, an organic phase 4057 with a pale yellow color was obtained. Reduce this organic phase. Stripping under pressure removed water and toluene. 2357 residue is thin Filtration through a pale yellow oil yields 210 g of the desired purified product as a sieve residue. Ta.

Example 46 By a procedure similar to that in Example 45, 5462 (3 mol) of Butaje Diels-Alder adduct of butyl acrylate and 1922 (6,0 mole) sulfur powder) in the presence of triamylamine 559 as a sulfurization catalyst. I responded. The product is filtered and the desired sulfur-containing product is clear and dark yellow. A slightly sticky oil 6592 was obtained as a filtrate.

Example 47 782 (4.3 mol) of Diels acetate of butadiene and butyl acrylate A mixture of the Ruder adduct and 138y (4.3 mol) sulfur powder was heated for 1 hour. Heat gradually from room temperature to 150°C over half a hour, then heat to 150° to 160°C. It was kept at ℃ for 6 hours. The reaction product was cooled to room temperature and then left for 12 hours. Generate The material was filtered to yield the desired sulfur-containing reactant, filtrate 8692.

Example 48 Sulfur (526 parts, 16,4 mol) was added to the jacket with stirrer and internal cooling coil. into a high-pressure reactor. Prior to the introduction of gaseous reactants, cooled brine was added to the reactor. It was circulated through the coil for cooling. After sealing the reactor, heat up to approximately 2 Torr. After cooling, 920 parts (16.4 moles) of isobutyne and 279 parts (8 , 2 moles) of hydrogen sulfide was charged to the reactor. νInstalling the outer jacket Heat to 182"C (360"F) by team for approximately 1.5 hours. child to a maximum pressure of 1350 psig at 168"C (33s"F) during heating. Reached.

Before the peak reaction temperature is reached, the pressure begins to drop and the gaseous reactants are consumed continues to decline steadily. After 10 hours at a reaction temperature of 182°C, the pressure is 3 10 to 340 psig, and the rate of pressure change was 5 to 10 psig/hour. . Unreacted hydrogen sulfide and isobutyne were exhausted to a recovery system. The pressure inside the reactor is normal pressure or The sulfided mixture was recovered as a liquid.

The mixture was blown with nitrogen at 100°C (212″F) to remove unreacted isobutyne and mel. Low boiling materials containing captan and monosulfides were removed. nitrogen bro - The residue after 5% superfiltrol - The mixture was stirred together and then filtered using diatomaceous earth filter aid. The filtrate is 42.5% The desired sulfurized composition contained sulfur.

Examples 49-63 Examples 49-63 omitted the acid clay treatment following the normal procedure of Example 48. The experiments were carried out by varying the ratio of reactants, reaction temperature, and composition of the reaction mixture. Example 49~ In 62, low-boiling substances are first separated by nitrogen blowing and then by vacuum stripping. By performing vacuum distillation in Example 63, vacuum distillation was performed without nitrogen blowing. This was done by When water is present in these examples, the crude product is After separation from the aqueous phase, the mixture was worked up according to conventional methods.

The details of the experiment and the results obtained are summarized in Table 4. reactant, mercap Tan and monosulfide proportions were determined by gas chromatography. .

Table 4 49 1:I:0.4 +71 None -1173,743,65501:I: 0.4 +93 None -11,54,544,22511:1.2:0.8 +93 None -15,05,05+,4352 1:1.2:0.4 +71 None -IL4 15 4117531:l:0.5182 H2O5% 118 1.5 -54 1:I:0.5 +71 Na S O, 00 Simo ν ”9.6 0,8 47.655 1:I:0.5 182 NH,OH0, 0057-' 9.6 1,4 47.0561:I:0.5171 n-C, H,NH2O,0005e 11.1 0.75 46.557 t:+:o, s 171 8H, (anhydride) o, oos Moya 59 1:1.2:0.5 + 71 n-C4H, NH, o, oos (sire 5.22 1.0! ML561 1:I:0.517I P, S, 2chi --Note) 1) Percentages are based on the weight of the reactants. This is based on a standard, and 1 mole is the amount per mole of imbutene.

2) Added as an 18% aqueous solution.

3) Added as a 28% aqueous solution.

4) Added as an approximately 30% mixture with the sulfurized product from the previous step.

Examples 64-78 Various olefinic compounds were sulfurized by the method of Example 48. each implementation The catalyst in the example includes n-butylamine (0.34% of the olefinic compound). % )It was used. The separation step was performed by vacuum distillation. Details are summarized in Table 5.

Table 5 Example Olefin compound Molar ratio 1) Temperature 64 inbutene in the product ;1-fan I:1:0.5 171 46.965 1-octene I:1 ．． 5:0.5 171 34.366 Isobutyne; l-octene 3) l:1: 0.5 171 44.67 Diynbutene l:1.5:0.5 171 4 1゜68　C,6-C,8(1-A-refui:yl:1.5:0.5　171 20.669 Cyclohexene l:1:0.5 171 31.870 I Sobutine; 1-hexene 2) I:1:0.5 171 39.571 Olein Acid Methyl/L/L: 1.5: 0.5 171 16.572 α-methyl Styrene 1:1:0.5 171 39.273 Isobuty y; Futaha 3) i:i:o,s 171 47.274 Polyisobutyne 4) l:1.5:0. 5 171 2.675 Triinfan l:1.5:0.5 17176 1-Buchi:/1:1:0.5 138-171 49.577 Inde’// V7 Acrylate 1:0.5:0.5 17+ 13.178 Butadiene and Bu Chilacrylic I:1.5:0.5 171 25.11) Olefin compound: S: H2S molar ratio.

2) With a molar ratio of 1:l.

3) 0.9:0.1 molar ratio.

4) Those having an average molecular weight of about 1000 as determined by vapor pressure osmometry.

5) No separation process.

For use in the asphalt compositions of the present invention, (E), (F) or ( G), sulfur compositions produced using other catalysts or without the addition of catalysts; Either of the prepared sulfur compositions may be used. As already mentioned, the catalyst (E) , (,F) or (G), the sulfurized compositions prepared using such catalysts It has less odor when compared to compositions made without it. asphalt composition When manufacturing asphalt, mixing is usually done at elevated temperatures, so depending on the situation, asphalt It is undesirable to use odorous sulfur compounds in paint compositions. Therefore, touch A sulfurized composition produced in the presence of a medium amount of catalyst (E), (F) or CG) Desirably, it is used to prepare the asphalt compositions of the present invention.

The sulfur composition of the present invention can be used in asphalt compositions as preferred for asphalt cement. preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, and most preferably 0.01 to 20% by weight. It is suitably present in an amount of 0.5 to 5% by weight.

Asphalt is defined by ASTM as a material whose main components are naturally occurring or petroleum-processed. A dark to black cementite-like substance consisting of bitumen obtained during mining. It is defined as. About Asphalt/+/T, its production area, uses, and asphalt characteristics. Regarding gender etc., please refer to the edition of Jnhn Wi Iey & 5ons published in 1983. Kirk-Othmer's “Encyclopedia of Ch. emical Technology J (x Ncyclobedia Op Chemical Technology) Volume 3, pages 284-327. Sara In the 7th edition of the Asphalt Institute, published in September 1974, A　Br1ef　Introduction　t.

Asphalt and Some of its UsesJ (Avery Introduction Two Asphalt Antsome of You It is also described in the Giz) Manual Series A5 (MS-5). present invention Both publications shall be cited as references.

Asphalt cement usually does not contain aggregates such as stone or gravel.

Asphalt concrete contains both asphalt cement and aggregate. It is something.

The liquid asphalt cement treated with the sulfurized composition of the present invention is Chalfornia Tilt-Oven Asphalt 　Asphalt) Under very severe aging as exemplified by durability tests Being able to maintain flexibility even when exposed to temperature has a great advantage. acceleration The test blocks exposed to experimental aging showed a significantly lower aging tendency to harden. reduce After accelerated experimental aging, the low temperature elastic modulus was measured and showed that sulfidation It has been found that the presence of the composition provides a significant improvement.

Asphalt cement is often of 5tate HighwayTransportationOffi cialsJ (American Association Off-State Highway Transportation Officials (AASHTO)) A R Viscosity Gray defined by the code rating system. The specifications for the two sets are as follows: be.

AA, SHTO-M-226 Viscosity @140”F, f, 4 250 500 1000 2000 30004 000's (AASHTOT-+-50+-Zoo +-200+-400+-6 00+-800 viscosity @275″F, 125 175 250 300 350 400C8T, minutes (AASHTO (AASHTOT-49) Outflow point, COC325350425450450450 minimum value T Ductility after TFOT 100 100 75 50 40 25 (AASHTOr =179) @77’F, 5 (y outside, minimum value @140″F, Boyz minimum value AASHTOM-226 Test ARlooOAR2000AR4000AR8000AR1600 viscosity @1.40”F, Poise 1000 2000 4000 8000 16 000 (AASHTOT-202) +-250+-500+-1000+-2 000+-4000 viscosity @275”F, C3T Minimum value 140 200 275 400 550 (AASHTOT-201) Penetration @77'F, minimum value 65 40 25 20 20 (AASHTOT- 49) Percentage of original needle humanity @776F --40455052 rate minimum value Ductility 077″F minimum value, 100 100 75 75 755 α/min Example M Asphalt cement (CV-AR400I) was mixed with a double layer of the product of Example 11. It was processed using a weight scale and 4 weight scales.

Asphalt cement satisfies AAH3TOAR4000 standards. Asfa Rutocement is widely distributed throughout the Western California Valley. It is alto cement.

Modified asphalt cement is exposed to oxidizing conditions and the same asphalt without treatment compared with cement.

The test is Rolling-Thin Film 0ven Te5t (Lori (ASTM D2872) semi-hard Evaluate the effects of heat and air on the film (asphalt of the body) v l - Transfer of substances The test was carried out using a standard test method. Asphalt material transfer film, 32 Heat in a special reflux oven at 5A for 75 minutes. heated air into each container It was injected once per cycle.

Amount of cure determined from changes in physical measurements taken before and after oven treatment did. ASTM Procedure D-2872 is incorporated herein by reference.

The test results are shown in Table 6 below.

Table 6 0-ring thin film open test results (ASTM-D2872 ) CV-AR4000CV-AR4000CV-AR4000+2 example + 4fy example Properties tested Untreated 11 products 11 products Viscosity @ 140°C (void ) 2105 1655 860-Before aging Viscosity @ 140℃ (Boys) 3625 2340 1660 - After aging Viscosity increase (voids) 1520 685 800 Aging ratio 1.7 1.4 1. 9 Viscosity 0275″F (C8T) 347 225 195-Before aging Viscosity 0275″F (C3T) 539 302 255-After aging Increase in viscosity 192 77 60 Aging ratio 1.6 1.3 1.3 Needlemanship @77”F (ddm) 37 57 90 - before aging Penetration @77'F (ddm) 28 43 60 - After aging Loss of penetration 9 14 30 Retention rate (chi) 75.7 75.4 66.7 Ductility @77″F (Sm) +5o +150+150+-before aging Ductility @77″’F (cIn) 1.50 + 150 + 150 +- After aging Example N Two types of asphalt cement (CV-AR40o and CC-AR400 0) to which various amounts of the product of Example 11 were added.

The asphalt cement tested was California Valley Asphalt Cement. (CV) and California Coastal Asphalt Cement (CC). .

Both of these are widely distributed throughout the western United States.

Modified asphalt cement is exposed to oxidizing conditions and the same asphalt without treatment compared with cement.

The test method is an accelerated laboratory test that simulates outdoor aging in hot weather. Developed by California Department of Transportation officials to establish procedures The California Tilt-Open asphalt durability test method was adopted.

Methods and data on experimental and outdoor aging are available in the hands of AAPTl 981. listed in the order. The title is ``Asphalt Durability in Outdoor and Experimental Environments'' "Comparisons in the Borderlands" and the authors are Glenn R. Kemp and Nelson. H, Predoehl. This test situation consisted of 24 hours in a hot moorland climate. This corresponds to 2 months. This method uses ASTM D28720-Ring Thin film open 168 hours using the equipment required for the test 235”F (113 table 7 california tinto - opena Sphalt durability test test results Viscosity @140″F (boys) 2+34 1415 910 1080 s+u -Before aging Viscosity @+40’F (Boys) 20336 14045 10170 8702 0 145837 after aging Increase in viscosity (Boise) 18202 12630 9260 85940 14 002 Aging ratio 9.5 9.9 11.2 80.6 24.1 Needle strength @77' F (ddm) 36 64 95 9+ 189・- before aging Penetration @77]: (ddm) +0 16 +719 35-After aging Loss of penetration (ddm) 26 48 78 72 154 Retention rate (ch) 27 ．． 8 25 + 7.9 20.9 18.5 ductility @ 77h grave) 蒐50 迿 +s o+ 150+ 1201 1501-before aging Ductility @ 77T (cm) 'λ5 150 + 150÷ 8892 - After aging Loss of ductility (m) 137.5 + OOII+, 2 + 580℃) The only change was to expose the falt to the wind and rain. In the present invention, ASTM D2872 Cite it as a reference. The test results are shown in Table 7.

Noticeable improvement in flexibility @77”F after this very severe experimental aging treatment This is something worth noting. This means that it remains flexible and flexible even after long periods of exposure to the elements. This allows you to extend the lifespan of the product.

Example 0 Adding 2% by weight of the product of Example 30 in asphalt corresponding to AR4000 An asphalt composition was produced by.

Tests for engineering properties were carried out by adding the product of Example 11 at various loadings. The test was carried out on four types of asphalt cements, either by adding or not adding it.

The test was conducted using two types of aggregate. Asphalt cement is as mentioned above. It is something.

Testing includes Marshall stability and flow tests before and after accelerated laboratory curing. After accelerated experimental curing, an indirect tensile test at 39.2 T was performed.

The values for Marshall stability and flowability are ASTM D1 cited in this invention. Determined using a Marshall loading device as described in No. 559. compressed A load was applied to the specimen at a constant deformation rate of 2 inches/min at 140'F. , record the load and the corresponding vertical deformation.

Static indirect tensile test To evaluate the tensile strength of asphalt mixtures, indirect Perform a tensile test.

A cylindrical test specimen is loaded parallel to the vertical diametric plane by the 5 compression loading method. trial Through a 0.5 inch wide steel load strip bent to fit the A load distributed over the so that The specimen eventually fails by cracking along the vertical diameter do. Tensile strength evaluation is calculated from the load applied at failure and the dimensions of the specimen. Ru.

Example P Initial tests were conducted using standard laboratory aggregates.

This is an aggregate mix commonly used in Northeast Ohio. That is #8 It is a mixture of Canadian limestone and lake sand. Details are shown in Table 7. The mixture is Performed in a Hobart mixer at 280″F. Mechanical Marshall Twenty blows with the hammer brought the air voids of the specimen to 7-9%. The test is added For Marshall stability and flow properties both before and after accelerated laboratory curing (Table 9), Furthermore, the indirect tensile test (Table 10) conducted at 39.2”F after accelerated aging It was carried out.

Table 8 (Standard aggregate mix design for experiment) component dark change Warm sand 5o, 8chi $4 60.0 $16 46.5 #50 10.8 #200 1.8 Asphalt cement content 6.5% by weight Table 9 CV-AR40010559790+23141.0CV-AR4000+ 4 % Real 407 474 +67 16.5 Example 11 Product MCA-AC206871244+557 81.0 MCA-AC20+ 4chi Implementation of 514 711 + 197 38.3 Example 11 Product Note) 14 days at -1,04F Table 10 Tensile strength Strain elasticity 1) CV-AR4000253Z2 228800CV-AR4000+4% fruit 191 3.9 98000 Product of Example 11 Example 1 of MCA-AC201666, 650300MCA-AC20+2chi 39 8.7 Product of 3260011 MCA-AC20+ 4% Example 122 7.4 3320011 product (note) 1) Elastic modulus is the secant modulus at failure assuming Poisson's ratio to be 0.33. It is calculated as follows.

Example Q In addition, the California Department of Transportati tested on aggregate provided by on. This is in the Sacramento area. It is an aggregate mixture that can be obtained from Details are shown in Table 11. Mixing is hover 20 strokes of a mechanical Marshall hammer. A test specimen with 3 to 4 air voids was used by performing a blow/side test.

Table 11 Aggregate mix design in the Caltrans area Component concentration 84-1408 (3/4'-1/2 15%84-1409 (1/2'- 3/8") 2o person 84-1.410 (3/8"-#4) 15% 84-141 2 (#4-Dust) 45chi 84-1312 (Sand) 5chi Passing through the stairs #4 53.0 #8 41.0 #16 29.0 #30 21.0 #50 13.0 #100 9.0 #200 6.0 5.3% by weight Mixture Before aging After aging Change Change Before aging After aging CV-AR4000189 62196+30015.8 12 14.0CV-AR4000212921 Example of 46+17 0.8 12 13.0+2chi 11 products CV-AR400018711992+121 6.5 14 16.0+4chi Example of 11 products C0-AR400012141431+21717.9 12 16.0CC- Example of AR400011621246+84 7.2 15 18.0+4% 11 products CC-AR400010461240+19418.5 14 14.0+4chi Example of 11 products Tensile strength Strain Elastic modulus 0 CV-AR40003604,4165,400CV-AR4000+2% fruit 242 4.2 117,100 Product of Example 11 Generation of CV-AR4000+4% actual 188 5゜2 72,000 Example 11 thing ・Elastic modulus is the secant modulus at failure assuming Poisson's ratio Q 0.33 It was calculated as

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Claims (33)

[Claims] 1. At elevated temperature, a sulfurizing agent and (A) one or more fatty acid esters of polyhydric alcohols, or (B) One or more fatty acids, fatty acid esters of monohydric alcohols, or mixtures thereof. compound, or a mixture of two or more of (D) (A), (B) and (C), one or more and other olefins, (E) Formula R1(R2)N-CSSH (In the formula, R1 and R2 are each independently a hydrocarbyl group.) one or more metal salts of one or more dithiocarpamic acids, or (F) one or more mercaptopenzothiazoles or metal salts thereof, or (G) Mixture of (E) and (F) A sulfurized composition prepared by reacting in the presence of a catalytic amount of. 2. an alkyl group in which R1 and R2 each independently contain 1 to 20 carbon atoms; one or more types of olefins (C) having 3 or more carbon atoms. Claim No. 2 is an aliphatic, araliphatic or alicyclic olefin hydrocarbon The sulfurized composition according to item 1. 3. Other olefins (C) include propylene, butylene or isobutylene and These dimers, trimers, tetramers and low molecular weight polymers may The sulfurized composition according to claim 1, which is an aliphatic olefin. 4. At elevated temperature, a curing agent and (A) about 100 parts by weight of one or more fatty acid esters of polyhydric alcohols; (B) One or more fatty acids, fatty acid esters of monoalcohols, or mixtures thereof. about 0 to 200 parts by weight of the compound and (C) a mixture consisting of about 0 to 400 parts by weight of one or more other olefins; volume of medium (E) One or more formulas R1(R2)N-CSSH (wherein R1 and R2 are each independently a hydrocarbon containing 1 to 20 carbon atoms) It is a rubyl group. ) One or more metals of one or more dithiocarpamic acids represented by salt, or (F) one or more mercaptopenzothiazoles, or metal salts thereof, or (G) Mixture of (E) and (F) A sulfurized composition obtained by reacting in the presence of. 5. the mixture contains about 2 to 200 parts of one or more other olefins (C); , wherein the olefin contains 10 to 20 carbon atoms. The sulfurized composition described. 6. At elevated temperature, a sulfiding agent and (A) about 0 to 100 parts by weight of one or more fatty acid esters of polyhydric alcohols; (B) One or more fatty acids, fatty acid esters of monohydric alcohols, or these about 0 to 200 parts by weight of the mixture, and (C) a mixture consisting of about 100 parts by weight of one or more other olefins in a catalytic amount of, (E) One or more formulas R1(R2)N-CSSH (wherein R1 and R2 are each independently a hydride containing 1 to 20 carbon atoms) dithiocarpamic acid or (F) one or more metal salts of one or more mercaptopenzothiazoles or (G) Mixture of (F) and (G) such that the mixture consists of 2 parts by weight or more of (A) and/or (B) in the presence of A sulfurized composition produced by reacting. 7. The sulfurizing agent is sulfur, and the olefin (C) is an aliphatic α-olefin or an aliphatic α-olefin. aliphatic α-olefin or one or more terpene compounds, and a catalyst is a group II metal salt of the periodic table of dithiocarpamic acid, and the reaction is about 50 to 35 The sulfurized composition according to claim 1, 4 or 6, which is carried out at a temperature of 0°C. . 8. Aliphatic olefin in which the olefin (C) contains about 3 to 36 carbon atoms Claim 1 which is. The sulfurized composition according to item 4 or 6. 9. The olefin (C) is composed of one or more dienophiles and one or more aliphatic conjugated gels. Claims 1 to 6 are one or more Diels-Alder adducts with The sulfurized composition described in . 10. dienophile is α,β-ethylenically unsaturated aliphatic carboxylic acid ester, Carboxylic acid amides, halides, nitriles, aldehydes, ketones or mixtures thereof. It is a compound, and the aliphatic conjugated gene has the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R to R5 are each independently hydrogen, alkyl, halo, alkoxy, alkenyl , alknyloxy, carboxy, cyano, amino, alkylamino, dialkyl phenyl and 1 to 3 substituents corresponding to R to R5. phenyl, or R, R2, R3 and R5 are as above and R1 R4 is an alkylene group in which R4s are successively formed into a cyclic compound. ) A composition according to claim 9 corresponding to. 11. The dienophile further contains 1 to 2 -C(O)ORo (Ro is 40 or less It is characterized by containing a carbon atom (a residue of a saturated aliphatic alcohol), and Piperylene, isoprene, methyl isoprene, chloroprene, 1,3-putage 11. The composition according to claim 10, which is a mixture thereof. 12. The dienophile is an ester of acrylic acid or methacrylic acid; 12. A composition according to claim 11, wherein the compound is 1,3-ptadiene. 13. Fatty acid (B) is tall oil or other fatty acid mixture containing oleic acid. 7. The sulfurized composition according to claim 6, which is a compound. 14. a substantially nonvolatile, normally liquid diluent, and from 20 to 90% by weight of the claimed An additive composition comprising the sulfurized composition described in item 1, 3, 5 or 6 of the box. Centrate. 15. The main amount of oil for lubricant viscosity and the characteristic improvement amount of the secondary amount in Claims 1 and 2. A lubricating oil composition comprising the composition according to item 4 or 6. 16. consisting of using the lubricating oil composition according to claim 15 on metal, A method of lubricating metal in operation. 17. Claims wherein the composition also contains small amounts of one or more chlorinated waxes The method according to paragraph 16. 18. It consists of a major amount of asphalt and a minor amount of an improved effective amount of a sulfurized composition. The composition is treated with a sulfiding agent at an elevated temperature. (A) one or more fatty acid esters of polyhydric alcohols, or (B) one or more fatty acid esters of fatty acids or monohydric alcohols, or (C) one or more other olefins, or (D) (A), (B) and (C). A mixture of two or more types, if necessary, in a catalytic amount. (E) Formula R1(R2)N-CSSH (Wherein R1 and R2 are each independently a hydrocarbyl group.) one or more salts of one or more dithiocarpamic acids, (F) mercaptopenzothia sol or a mixture of (G) (E) and (F) An asphalt composition obtained by reacting in the presence of. 19. Sulfiding agents include elemental sulfur, hydrogen sulfide, sulfur halides, sodium sulfide, and and one or more selected from the group consisting of a mixture of hydrogen sulfide and sulfur dioxide. and the other olefin (C) is one or more fats containing 3 or more carbon atoms. Claim 18 which is an aliphatic, araliphatic or alicyclic olefinic hydrocarbon. The asphalt composition described. 20. Other olefins (C) include propylene, butylene or isobutylene and and aliphatic olefins such as these dimers, trimers, tetramers and low molecular weight polymers. 19. The asphalt composition according to claim 18, which is a reflex. 21. Consisting of a major amount of asphalt and a minor stability-improving amount of a sulfurized composition, The sulfurizing composition is heated with a sulfurizing agent, (A) about 100 parts by weight of one or more fatty acid esters of polyhydric alcohols; (B) About 0 to 200 parts by weight of one or more fatty acids or monohydric alcohols; stell or mixtures thereof, and (C) about 0 to 400 parts by weight of a mixture consisting of one or more other olefins. volume of medium (E) Formula R1(R2)N-CSSH (wherein R1 and R2 are each independently a hydrogen atom containing 1 to 20 carbon atoms. It is a drocarbyl group. ) One or more dithiocarpamic acids represented by salt, or (F) one or more mercaptopenzothiazoles or salts thereof, or (G) produced by reacting in the presence of a mixture of (E) and (F) asphalt composition. 22. Claim 18 or 21, wherein the salt of (E) or (F) is a metal salt. The asphalt composition described in . 23. the mixture contains about 2 to 200 parts by weight of one or more other olefins (C); and the olefin contains 10 to 20 carbon atoms. The asphalt composition according to item 21. 24. comprising a major amount of asphalt and a minor, stability-improving amount of a sulfided composition; The sulfiding composition is heated with a sulfiding agent, (A) about 0 to 100 parts by weight of one or more fatty acid esters of polyhydric alcohols; (B) About 0 to 200 parts by weight of one or more fatty acids or dihydric alcohols; and (C) about 100 parts by weight of one or more other olefins. compound and a catalytic amount of (E) Formula R1(R2)N-CSSH (wherein R1 and R2 are each independently a hydrogen atom containing 1 to 20 carbon atoms) It is a drocarbyl group. ) One or more dithiocarpamic acids represented by salt, or (F) one or more metal salts of one or more mercaptopenzothiazoles or (G) Mixture of (E) and (F) An asphalt composition obtained by reacting in the presence of. 25. A main amount of one or more aggregates and a vice amount of claim 18, claim 21 or is an asphalt cement containing the stabilized asphalt composition according to item 24. Asphalt concrete consists of 26. the sulfurizing agent is sulfur, the olefin (C) is one type of aliphatic α-olefin, one isomerized aliphatic α-olefin or one or more terpene compounds; Periodic Table II, where the medium is dithiocarpamic acid or mercaptopenzothiazole Group metal salts, and the reaction is carried out at a temperature of about 50 to 350°C. The asphalt composition according to item 18, item 21 or item 24. 27. The method according to claim 26, wherein the sulfurizing agent further comprises hydrogen sulfide. Sufalto composition. 28. Aliphatic olefin in which olefin (C) contains 3 to 36 carbon atoms The asphalt composition according to claim 18, 21 or 24, which is . 29. Olefin (C) is one or more dienophiles and one or more aliphatic conjugated gels. claim 18 or one or more Diels-Alder adducts with is the asphalt composition according to item 24. 30. dienophile is α,β-ethylenically unsaturated aliphatic carboxylic acid ester, Carboxylic acid amides, halides, nitriles, aldehydes, ketones or mixtures thereof. It is a compound, and the aliphatic conjugated gene has the formula R▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R to R5 each independently represent hydrogen, alkyl, halo, alkoxy, alkyl Nyl, alkenyloxy, carboxy, cyano, amino, alkylamino, dia substituted with lucylamino, phenyl, and 1 to 3 substituents corresponding to R to R5. R, R2, R3 and R5 are as above, and R1 and R4 is an alkylene group that connects with each other to form a cyclic diene. ) The asphalt composition according to claim 29, which corresponds to. 31. The dienophile further contains 1 to 2 -C(O)ORo (Ro up to 40) It is the residue of a saturated aliphatic alcohol with a carbon atom. ). As a sign of Claim 30 which is prene, 1,3-ptadiene or a mixture thereof. asphalt composition. 32. dienophile is an ester of acrylic acid or methacrylic acid; 32. The asphalt composition according to claim 31, wherein ene is 1,3-ptadiene. . 33. Fatty acid (B) is tar oil or other fatty acid mixture containing oleic acid. The asphalt composition according to claim 24, which is a compound.