TW205067B - - Google Patents

Description

A 6 B6 ^ 0500? 5. Description of the invention () Field of invention (please read the precautions on the back before filling in this page) This invention is based on a lubricating oil composition and a fuel lubricating mixture for a two-stroke engine. This invention also includes a method of controlling piston wear. Introduction of the invention Over the past few decades, the ignition of two strokes (two strokes) inside. The use of combustion engines has increased. They are now found in more powerful weeders and other garden equipment that requires power operations, power key saws, pumps, energetic hairsprings, outboard naval engines, snowmobiles, motorcycles and the like . The increase in the use of these two-stroke engines and the increase in the number of operations that must be matched by the two-stroke engine printed by the Cooperative Society of the Ministry of Economic Affairs of the Central Standards Bureau have led to an increase in the need for oil to adequately lubricate this engine. Among the problems is the piston's wetness, wear or scarring. This condition is generally caused by a relatively high viscosity oil (greater than or equal to 100 micro toes (cent is toke) (cSt), temperature 4010) or light-colored high-viscosity moisturizing oil (br i ght St ock) to control, the action of this higher viscosity oil and light-colored high viscosity lubricating oil can increase the viscosity and prevent the piston from seizing. The problem with the use of these materials is to sink in the combustion chamber or paint Formation, which may lead to pre-ignition (pre i gn iti on). High molecular weight polymers can be used to replace some or all of the light-colored high-viscosity lubricants used in two-stroke engines. This polymer can increase viscosity and prevent piston seizure. * About light-colored high-viscosity lubricating oil or high-viscosity oil or high-molecular-weight polymer 81. 5. 20.000 (H) This paper scale is used in the S National Standard (CNS)肀 4 specifications (210x297 male dragon) ^ 0500 ^ Λ 6 Β6 V. The description of () The problem is that these products tend to cause damage to the spark plugs of the one and two stroke engines. Aminophenols are useful for two-stroke engines. US patents 4, 32 0, 020 and 4, 3 2 0, 021 were issued to Lange regarding aminophenols and their use as lubricants. Aminophenols have been used to combine dispersants and detergents. U.S. Patent Nos. 4,100,082 and 4,200,545 relate to two-stroke lubricants. Aminophenols are used to combine neutral or ageing metal salts with amine dispersions. U.S. Patent 4, 3 79, 065, issued by Lange, is used in combination with ash-free ester dispersants. Meipu Patent No. 4,425, 1 38. Pseudo-aminophenol was used as a lubricant-fuel mixture in a two-stroke engine. Printed by Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before writing. This page) U.S. Patent Nos. 4,663,063 and 4,724,091, issued by Davis, is a combination of a alkylphenol and a cabinet compound in a two-stroke engine, which is related to the former A slap alkylphenol and an ammonia compound instead of an aminophenol. The latter concerns one-pitch alkylphenol and one aminophenol. The only problems and techniques regarding the lubrication of two-stroke engines have been recognized by people who are familiar with the lubrication techniques of two-stroke engines as a different type of lubricant. Refer to, for example, US registered patent 3,085,975; 3, 004 , 837; and 3, 753, 905. The ingredients of the present invention are effective in controlling piston wear. These benefits are obtained by using light-colored high-viscosity lubricating oils or high-viscosity oils that do not require high molecular weight polymers. . This paper scale uses the Chinese Standard (CNS) A4 specifications (210X297 public goods) 81. 5. 20.000 (H) Printed by the Employees ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ 6 Β6 V. Description of invention () Summary of invention This invention is related to a two-stroke lubricating oil composition, which includes: at least one lubricating viscosity oil, which is a free-flowing oil, which is a free-flowing oil and has a viscous viscosity, which is greater than or equal to 100c at 40 St, a compound that can sufficiently reduce or prevent the amount of piston wear: (A) at least a phenol selected from the reaction products of (A-1) -aminophenol and (A-2) -nitrophenol and an ammonia compound , And (B) at least one ashless dispersant. These compositions may also contain up to about 10% by weight of (C) at least one polyolefin, having a value average molecular weight of from about 400 to about 2500. Because the lubricating oil composition of the two-stroke engine is often mixed with fuel before or during burning, the invention of Shen Shen also includes a fuel lubricating oil mixture. The applicant has found that the above composition of the present invention can control the control piston At the same time, it also contributes to the lubrication of the piston, the control of Shen Dianwu, the protection of the ring defense, reducing the blocking of the exhaust port and reducing the tangible smoke emissions. These lubricating oil compositions use oils that generally have a lower viscosity than oils conventionally used. In another embodiment of the present invention, the lubricating oil composition is free-flowing isostearic acid, or a derivative thereof. Detailed description of the invention The term "hydrocarbyl" includes sulfonated hydrogen, and a group of hydrogen atoms in general. In general, the sulfonated hydrogen group group describes the group paper containing non-master hydrogen substituents. The national standard (CNS) A 4 specification (210X297 male dragon) is used in the paper. 81. 5. 20,000⑻ (please read the back Please pay attention to this page and then fill out this page) Binding-Order_ Λ6 B6 05067 Fifth, the invention description () base, it will not be affected by the support of this master hydrogen group. (Please read the precautions on the back before filling this page.) Examples of hydrocarbon groups include the following: (1) Master hydrogen substituents, that is, aliphatic (e.g., alkyl or olefin Group), alicyclic (eg, alkyl, cycloalkenyl) substituents, aromatic, aliphatic- and alicyclic monosubstituted aromatic group substituents, and analogs thereof, and ring substitutions Group, in which the ring becomes complete by other parts of the molecule (ie, for example, any two specifically indicated substituents, which can be taken together to form an alicyclic group); (2) substituted The hydrogen substitution of the master, that is, those containing non-master hydrogen group, in the specification of the present invention, it does not change the main hydrogen substitution of the master; those skilled in the neck skills will Pay attention to these groups (eg halogen (especially atmosphere and fluorine), hydroxyl, alkane, thiol, alkyl thiol, nitro, nitroso, sulfo, etc.). (3) Heterocyclic substituent printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Also has the main hydrogen substituent in the specification of the present invention, including other carbon atoms different from the ring or other components. The hard atoms, suitable heterocyclic atoms will be obvious to those with ordinary skills, including: for example, sulfur, gas, nitrogen and these substituents are: eg pyridyl, furanyl, thiazyl, azole Base, etc. Roughly speaking, only about 2; preferably 1, a non-hydrogenated hydrogen substituent will exist in every tenth atom of this hydrocarbon group. Typically, there will be no such non-generated hydrogen atom in this hydrocarbon group. Therefore, this hydrocarbon group is pure hydrogen. When a substituent is defined by an average number of atoms with a large number of atoms, this paper uses the Chinese National Standard (CNS) A4 specification (210x297 male dragon) 81. 5. 20t000 (H) ^ 0500 ^ Λ6 __B6_ 5 2. Description of the invention () The average number of sulfonic atoms is based on the number average molecular weight. However, this substituent does not require an average number of atoms. This substituent may have a single single atom number of the master atom, e.g. 18, the master atom. (A) Phenol The composition of the present invention contains a reaction product of mononitrophenol or monoaminophenol and monoamine compound. The use of this name "phenol" in the Japanese manual is a common definition acceptable in its field, and it represents a hydroxy-aromatic compound that has at least one hydroxy group directly bonded to the main atom of the aromatic ring. The aminophenol used in this invention contains at least one of each of the following substituents: a hydroxyl group and an R group as defined herein. Each value in the group below must be connected to a value atom, which is part of the aromatic core in the group Ar. However, if there is more than one aromatic core in the Ar group, they do not need to be connected to the same aromatic ring each. The aromatic group of aminophenol and nitrophenol can be a single aromatic core, such as: benzene core, an atridine core, a core of thiobenzene, a 1, 2, 3, 4- Tetrahydronaphthalene core, etc., or printed by an employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Multi-nuclear aromatic group base. The basic energy of these multinuclear groups is a condensed ring; also, at least two aromatic nuclei are fused to other nuclei at two points, such as naphthalene, anthracene, aza naphthalene, etc. It has been found that these polynuclear aromatic group groups can also be of the type of bonding, in which at least two cores (single or multicore) are connected to each other via a bridge bond. These bridging bonds can be selected from the following group-based options, including master-to-shuttle single bonds, ether bonds, and the paper standard General Chinese National Standard (CNS) A 4 specifications (210x297 public goods) 81. 5. 20, 〇〇 ( η) Printed by the Employees ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Λ 6 Β6 V. Description of invention () Ketone bond, sulfide bond, polysulfide bond of 2 to 6 sulfur atoms, sulfite bond , Sulfonamide bond, methylene bond, olefin bond, di- (lower alkyl) methylene bond, lower olefin ether bond, olefin ketone group bond, lower order The olefin sulfonate bond, the lower olefin polysulfide bond, contains 2 to 6 sulfon atoms, the amine group bond, the polyamino bond and a mixture of these divalent bonds. Under certain circumstances, in Ar *, the bridging group between aromatic nuclei can exist for more than one hull. For example, a fluorine core has a benzene core bonded by a methylene bond and a covalent bond. These cores are considered to have 3 cores, but only 2 are aromatic. Normally, Ar will contain only one atom at the core of each aromatic group. This single cyclic aromatic nucleus that can be used as an Ar group group can be represented by the general formula: ar (Q) m, where ar represents a single cyclic aromatic core (eg benzene), with 4 to 10 large atoms , Each slap Q independently represents a lower alkyl group, a lower alkane group, methyl alcohol or a lower hydrogen atom-based substituted methyl alcohol, or a halogen atom , And m are 0 to 3, preferably 2. The term "lower" used in the scope of patent applications in the specification or later refers to a group of radicals having 7 or less, preferably 1 to about 3 atoms, like lower alkyl And lower alkoxy. Halogen atoms include fluorine, gas, bromine and iodine atoms; usually, the halogen atoms are fluorine and atmosphere atoms. Examples of single cyclic Ar group groups include benzene group groups, such as 1, 2, 4 monophenyl triyl group; 1, 2, 3-phenyl triyl group; 3-methyl mono 1, 2, 4-phenyl group Three bases; 2-methyl- 5-ethyl-1, 3, 4- -9- This paper scale is easy to use Chinese National Standard (CNS) A 4 specifications (210x297 public goods) 81. 5. 20.000 (H) ( Please read the precautions on the back before filling in this page) Binding-Bookbinding-Λ 6 B6 V. Description of invention () Phenyltriyl; 3. — Propoxy-1, 2, 4, 5, 5-phenyltetrayl; 3-chloro-1,2,4-phenyltriyl; 1, 2, 3, 5-phenyltetrayl; 3-cyclohexyl-1,2,4-phenyltriyl; and 3-azo Cyclopentyl-1,2,5-phenyltriyl, and pyridinyl, like 3,4,5- azabenzene; and 6-methyl-3,4,5-azabenzene. When Ar is an aromatic group group of a polynuclear condensed ring, it can be represented by this general formula: arl ^ artniMCl) 丨 ', where ar, Q and η are as defined above, and π' is 1 To 4, and each Y represents a pair of fused bonds, fused two rings, prepared the part of two β atoms in the ring of each slap two adjacent rings • and bid 'are β and Β The special examples of the Ar group of the thickened aromatic group include: 1, 4, 8—naphthalene; 1, 5, 8—Cai; 3,6-dimethyl-4,5, 8 (1 —couple gas Cai); 7 — methyl- 9-methanyl 1, 2, 5. 9 — pain tetrayl; 3, 10 — phenanthrene; and 9 monomethoxy-phenanthrene 5, 6, 8, 12 — Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy. When this aromatic group base Γ is a multi-linked aromatic group base, it can be represented by this general formula: ar (Lng — ar) w (d) aw where w is an integer from 1 to about 20, a Γ is as defined above, except that it has at least 3 values of unsaturated (i.e. free) covalent in all ar group groups The keys .Q and · are as defined above, ^ is the sum of the face and ^ and each L n g is a tilt or inveterate above bonded chains. When Ar is bonded to a multi-nuclear aromatic group, its special examples include: 3, 3 ', 4, 4', 5-diphenyltetrayl; di (3, 4 -10- 81. 5. 20,000 (H) (Please read the precautions on the back before filling in this page) This paper is used in China National Standard (CNS) Grade 4 (21〇X297mm) ^ 0500 ^ ^ 0500 ^ Staff of Central Bureau of Standards, Ministry of Economic Affairs Printed by cooperatives of Xiaotiao Λ 6 Β6 V. Description of the invention () monophenyl) acid; 2,3-phenyl-2,6-the first house; and 3-methyl, 9H-fluoro-1, 2, 4, 5,8-yl; 2,2-bis (3,4-phenyl) propane; sulfur-coupled 3-methyl-1,2,4-phenyltriyl (having 1 to about 10 thio groups Methylphenyl group); 3-methyl 1, 2, 4-phenyltriyl (with 1 to about 100 aminophenyl groups) coupled to an amino group. The Ar group group is usually unsubstituted, except for the R and OH group groups (with any bridging group). For reasons of cost, availability, effectiveness, etc., the Ar group is normally a benzene core, a lower-level olefin bridged benzene core, or a core. Therefore, a typical Ar group is a benzene or naphthalene core, with 3 to 5 unsaturated covalent bonds, so that one or two of the covalent bonds can be saturated by a hydroxyl group, so that The remaining unsaturated covalent bond may be in an ortho or para position with this hydroxyl group. Preferably, Ar is a benzene core with 3 to 4 unsaturated covalent bonds, so one can be saturated with a hydroxyl group, and the remaining 2 or 3 quats are ortho and para positions with this hydroxyl group. . (A-1) Aminophenol As described above, the present invention includes monoaminophenol. Preferably, the aminophenol is represented by the general formula: (〇H) c (R),-Ar- (NH2) b -11- The paper size is generally in accordance with the Chinese National Standard (CMS) A 4 specification (210X297 Cheng) 81. 5. 20.000 (H) (Please read the precautions on the back before filling in this page) Binding &Order; L050G7 A 6 B6 V. Description of invention () where R is a hydrocarbyl substituent with an average of about 10 Up to about 400 Yuan Shuoyuan; (a), (b) and (c) respectively represent integers, from 1 to 3 times the number of aromatic cores in Ar, the prerequisite is (a) plus (b) plus (c ) Cannot exceed the number of unsaturated covalent bonds of Ar; Ar is a very aromatic group, which is substituted by from 0 to 3 groups selected from the group consisting of: lower alkyl, alkoxy , Nitro, halogen, or a combination of two or more. In the above Ar, the number of aromatic nuclei, fusion, bonding, or both play a role in determining the values of a, b, and c. For example, when Ar contains a single aromatic nuclei, a, b, And c are 1 to 4 respectively. When Ar contains two aromatic nuclei, a, b, and c can be integers from 1 to 8, respectively, up to 3 times the number of aromatics present (2 for naphthalene). For a three-core aromatic group (Ar), a, b, and c can each be an integer from 1 to 12. For example, when Ar is a bisphenyl or naphthyl group, a, b, and c can be integers 1 to 8, respectively. The values of a, b, and c are limited by the total number of unsaturated covalent bonds whose sum cannot exceed Ar. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page). The phenol compounds used in this invention include, directly bonded to the aromatic group group Ar, — at least about 10 Atomic hydrocarbyl groups (R), usually, the hydrocarbyl group has at least about 30, more typically, at least about 50-th aliphatic aliphatic atoms, and up to about 400, more typically, up to about 300 sulfonic atoms. In one embodiment, the hydrocarbon group has a number average molecular fi from about 400f to about 3000, preferably from about 500 to about 2500, more preferably from about 700 to about 1500. -12- This paper scale is printed in China National Standard (CNS) Grade 4 (210x297); > i) 81. 5. 20.000 (H) Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, “Λ 6 __Β_6_ V. Inventions Description () contains at least ten Shuo atoms, the description of the hydrocarbon group is η-decyl, n-dodecyl, tetrapropyl, η-octadecyl, oil-based, gas-octadecyl, thirty-two Shuo Hospital bases, etc. Generally speaking, this hydrocarbon group R is the source | polyolefin, this polyolefin is the same or multimer (eg copolymer, trimer) of single and di-olefins like ethylene, propylene, butylene Ene-1, isobutylene, butadiene, isopropylene, 1-hexene, 1-octene, etc. Typically, these olefins are 1-monoolefins. This R group group can also be derived from these polyolefin analogs Halide (es chloride or bromide), however, this R group can be derived from other sources, such as single-molecule high-molecular-weight olefins (e.g. 1-tetracontene) and its aerobic analogs and Hydrochlorinated analogues, the petroleum component of aliphatics, are to be distinguished from stone scallions and broken and climatic analogues and hydrochlorinated species Substances, white oil, synthetic olefins, such as those produced by the Zieg 1 er — Nat ta method (es poly (ethylene) grease) and other sources known to those skilled in the art. The unsaturation in the R group group can be reduced or eliminated by hydrogenation through a conventional procedure. Examples of the determination of a hydrocarbon group (R) containing an average number of more than about 30 atoms are shown below: a value of about 3 A mixture of poly (ethylene / propylene) groups of 5 to about 70 atoms; a mixture of poly (ethylene / propylene) groups that can be chemically or mechanically degraded, which has about 35 to about 7 °. Master atoms; a mixture of poly (propylene / 1-hexene), which has about 80 to about 150 atoms; and a mixture of polybutene groups, with an average of 50 to 75 atoms, this group R一 -13- (please read the precautions on the back before filling in this page) -installed- • V *. Thread · The paper size is free to use China National Standard (CNS) A4 specifications (210x297 public) 81. 5. 20,000 (H) Printed A6 by Beigong Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs ___ B6 V. Description of Invention ) The preferred source is polybutene »It is a white C 4 refining gas stream with 3 5 to 7 5 weight percent butene component and 3 0 to 60 weight percent isobutene component (Γ efi η e Γ y S t Γ eam) Polymerization »This reaction is in the presence of Le W is an acid catalyst, like aluminum trichloride» Boron trifluoride. Aromatic group A Γ of the phenolic phenol used in the invention The hydrocarbon group R can be converted into 1 by one of the methods known to many industry. 7 A special suitable method is F Γ iede 1 — Craft anti-plaque • where olefin (e • g • a polymer containing an olefin bond »or halogenated or Hydrohalogenated analog) • Reaction with phenol $ This reaction takes place in the presence of Lewis acid (e • g • Boron trifluoride and its complex with acid «phenol < hydrofluoride» etc. • Aluminium oxychloride »Aluminum bromide 9 Zinc dichloride t, etc.) Execute this The corresponding methods and m pieces are the 0 reference that the industry is familiar with * For example * The discussion named "A 1 ky 1 ati 〇η 〇f P he η 〇1 99 in this article • i η K irk — 0 thme Γ η E η C y C 1 〇P edia 〇f C hem • ca 1 T e C h η 〇1 〇gy ”t second sales * V 〇1 1» page 8 9 4 a 8 9 5 see I η te Γ S 1 e η C e P ub 1 i S he Γ S »J 〇hn W i 1 ey and C ο m P anyt N • y ♦ 9 branching mechanism $ 1 9 6 3 ο Other equally well-known appropriate and convenient The method of connecting this m group group R to the aromatic group group A Γ is easy and well-known to those skilled in the art. As mentioned above > this aromatic group group (A Γ) may contain Up to 3 奤 m -14- (Please read the precautions on the back before writing this page) Binding · Order · The paper size is free to use China National Standard (CNS) A 4 specifications (210X297) and 81. 5. 20.000 ( H) Λ6 B6 V. Description of invention () Selectively take Group, which is a lower alkyl group, a lower alkoxy group, a master alkoxy methyl alcohol or a lower alkyl group substituted methyl alcohol, nitro, nitroso, halogen, amino, Or a combination of two or more of these selective substituents. These substituents can be attached to a single atom, which is part of the aromatic core of Ar *. However, if there is more than one ring in Ar, they need not be attached to the same aromatic ring. In a preferred embodiment, the aminophenol used in the present invention contains each of the aforementioned substituents (ie, a, b, and c are each tilt), and Ar * is a single aromatic ring. Jia is benzene. This better aminophenol grade can be represented by the following formula: (Please read the notes on the back before filling this page)

Printed by the S Industry and Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy where R is as defined above; R 'is a group selected from the group consisting of the following: lower alkyl, master alkyl, nitroso, and halogen; X is 0 or 1 •, and z is 0 or 1. Generally speaking, the R group is located in the ortho-position or para-position with the hydrocarbon group, and z is usually 0. In most cases, the aminophenol used in the present invention has only one atmosphere group, that is, X is equal to 0. The aminophenols of the present invention can be prepared by many synthetic routes, for example, aromatic hydrocarbons or monophenols can be alkylated and then nitrified to form an intermediate -15- Chinese paper standard (CNS) A4 Specification (210x297 public) 81. 5. 20.000 (H) ο r'o ο

66 AB V. Description of Invention () Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 0 This intermediate can be produced by any conventional method. The nitrated intermediate of the aromatic hydrocarbon group can react with water to form a hydroxyl group-Nitrification Institute Aromatics »Then, as is known, the original aminophenol Ο m The technique of acidifying phenols is known 1 Reference> For example, t K i Γ k — 0 thme Γ, E η C y C 1 Ο Ρ ediaof C hem • ca 1 T e C h η 〇1 〇gy η second seller • V o 1 • 1 3 9 Article titled P9 N it Γ 〇Ρ he η Ο 1 ff article t 8 8 8 »etseq And these discussions η A romatic S ubst • tuti ο η • 9 Ν * tratj ο nand Η a 1 〇senat • 〇η 99 9 by P • B • D • D e L a M a Γ e and J • Η • R idd • N • Y • 9 A cadem ί c Ρ Γ e S s * 1 9 5 9 l ”N * t Γ at • ο na η d A Γ ο mat • 1 c R ea C ti V ity ”by J • G * H osset > L ondon > cambrid 8 e U n • V e Γ sity P ress $ 1 9 6 1 ♦ and” T he G hemistry ο fthe Ν * t Γ oand N ί tros OG rou P ”t Η e η τ * y F euert E ditor * I nte Γ S c ♦ 1 ence P ub 1 ishe Γ s, N • Y • t 1 9 6 9 O Aromatic nitro compound reduced to equivalent Amine is also a known t reference »For example> an article titled n A mi η ati ο η by Reductio η η $ in K i Γ k 一 0 thmer E n -16- (please read the notes on the back first (Fill in this page) The size of this paper is in accordance with China National Standards (CNS) Grade 4 (210x297 mm) 81. 5. 20,000⑻ * Λ 6 _ Β6 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy ) C y C 1 〇P ed 1 a 〇f C hemi C a IT e C h η 〇1 〇S y ,, — the second vendor in the book 9 V ο 1 • 2, page 7 6 — 9 9 page 0 — * Generally ... V- 1 This also The original reaction can be carried out using, for example, t hydrogen »monogasification m or hydrazine» (or a mixture thereof) in the presence of a gold catalyst, such as: rake 9 and its gasifier »锞 * copper chromite» Etc. 0 Co-catalysts »such as • • or alkaline earth gold hydrogen compounds or amines (including m-based phenols) can be used in the reduction reaction of these philophiles. Nitro can be obtained by Z Ϊ η • η reaction lotus origin 9 which is discussed On 9 »0 Γ S a η • CR ea C ti 〇η S η» V 〇1 • 2 0 t J 〇h η W i 1 ey & S 〇η S 9 N ♦ Y • minus 1 9 7 3 * Page 4 5 5 $ et S eq 〇 In general and • The Z i η i η reaction involves the reduction of a mononitro group and a divalent negative sulfur compound »Like the alkali metal sulfide 9 polysulfide and hydrosulfide The 〇 group of nitro groups can be reduced by the action of electrolysis. Refer to, for example, coax the above title “A mi η ati 〇η by R ed UC t 〇η η Article 0-Typical > The aminophenol used in the present invention can be obtained by reduction of nitrobenzene with hydrazine or hydrogen »in the presence of a metal catalyst. These metal m media are As discussed above, this reduction reaction is usually carried out at a temperature in the range of about 1 5-2 5 0 t, typically between about 5 0-1 5 0 V «When using hydrogen * The pressure of hydrogen is about 0 A 2 0 0 0 between PS i S 1 is typically about 5 0-2 5 0 P S i S. The time of the reaction is usually between about 0 5 to 5 0 small time fluctuations 9 Generally speaking t Inert liquid thinner-17- (Please read the precautions on the back before filling in this page) Packing- -3- This paper uses the Chinese National Standard (CNS) A4 specifications (210 father 297 mm) 81. 5. 20,000 (H) A 6 B6_ V. Description of the invention () and solvents, such as ethanol, cyclohexane, etc., can be used to accelerate this reaction. This aminophenol product can be prepared by conventional techniques, such as: steaming, extraction, extraction, etc. The reduction reaction is carried out until at least about 50%, usually about 80% of the nitro products present are converted to amino groups. The above-mentioned typical route from the present invention to phenols can be summarized as (1) nitration of at least one compound of formula (R) a-Ar — (OH) c with at least one nitrating agent, where a, c and Ar * are as above As defined, and Ar has 0 to 3 selective substituents (R ′), as described above, and (2) In the reaction mixture, at least about 50% of this nitro group is reduced to an amino group. The following special illustrative examples illustrate the preparation of the aminocere used in the composition of the present invention. In the following examples and the scope of patent applications and specifications, unless otherwise indicated, the portion is by weight, the temperature is pert, the pressure is atmospheric sink 〇Example A _ 1 Printed by the Ministry of Economic Affairs, Central Standards Bureau employee Xiao # Cooperative (please read the precautions on the back before writing this page) A mixture, including 4578 parts of polybutene substituted phenol, which is composed of three Fluorinated phenol boron is obtained by catalyzing alkylation of polybutene with a number average molecular weight of approximately 100 0 (calculated from the gas phase osmotic pressure), 3 0 5 2 parts of 100 natural ground oil, and 725 parts Fabric distillate (t extile spirits), heat it to 60Ό, to obtain a homogeneous material, when cooled to 30¾, add 3 19. 5 parts of 16 mol of nitric acid and 600 parts of water in this mixture, Continue to cool to keep the temperature of this mixture below 40¾, where the mixture is 1 18-this paper scale is universal Chinese National Standard (CNS) A 4 specifications (210x297 g; Ji) 81. 5. 20,000 (H)

Λ 6 Β6_ V. Description of the invention () (please read the notes on the back before filling in this page) After stirring for another 2 hours, a full divisor of 3,710 copies is transferred to a second vessel, the second vessel The reaction vessel was treated with 127.8 parts of 16 mol of nitric acid / 130 parts of water at a temperature of 25-30 C, and the reaction mixture was stirred for 1.5 hours, and then stripped to 22〇υ / 30 torr, after filtering Get the oil solution of the desired intermediate. A mixture, including 810 parts of the above-prepared intermediate oil solution, 405 parts of isopropanol and 405 parts of toluene, which was filled into an autoclave of appropriate size, adding vaporized platinum catalyst (0. 8 1 part), and the autoclave was evacuated and purified four times with nitrogen to remove any air, hydrogen was fed into the autoclave at a pressure of 29-55PS is, while stirring this ingredient and heating to 27-92Ό, a total of 13 hours, the residual excess hydrogen is removed from the reaction mixture through nitrogen evacuation and purification four times, and then the reaction mixture is filtered through diatomaceous earth, and the filter liquid is stripped to obtain the desired aminophenol oil Solution, the solution contains 0.58% nitrogen. Example A-2 in a mixture, containing 361.2 parts of ten (propylene) one take the phenol printed by the Ministry of Economic Affairs Central Standards Bureau employee consumer cooperatives and 270.9 parts of glacial acetic acid, the temperature is 7-171, add A mixture containing 90.3 parts of nitric acid (70-71% HN〇3) and 90.3 parts of glacial acetic acid. The addition was completed within 1.5 hours, while the reaction mixture was externally cooled to maintain the temperature within the range of -17 ¾; the cooling bath was removed, and the reaction was stirred at room temperature for 2 hours, and then at 1 341 Stripping this reaction under / 35 t 〇rr 81. 5. 20.000 (H) The paper size is used in China National Standard (CNS) A 4 specifications (210X297 Gonglu) A 6 B6_ V. Description of invention (), after filtering , A desired nitrification intermediate can be obtained, which is a filtrate with a nitrogen content of 4.65%. A mixture containing 150 parts of the above intermediate and 50 parts of ethanol was added to an autoclave, the mixture was purged of nitrogen, and 0.75 parts of the rake catalyst on the Jiao Shuo was added, The autoclave was purged and pressurized with nitrogen several times, and then placed in an environment with a hydrogen pressure of 100 ps ig, keeping the anti-mixture at 95 to 100 Ό 2.5 hours, the same hydrogen pressure changed from 100 to 20 ps is, when hydrogen When E drops below 30 PS ig, transfer back to IOOps ig, Zhao Xu reacts for 20.5 hours, then re-open the autoclave, and add 0.5 parts of the rake catalyst on Jiao Shuo. After the nitrogen blanket was removed (3 times), the pressure of this autoclave was restored to 100 psig with hydrogen, followed by a sickle reaction of 16. 5 hours, and a total amount of 2.0 mol of hydrogen was added to the autoclave and filtered This reaction mixture is stripped to 130t: / 16t〇rr, the second filtration can obtain the amino product, which is in the form of a filtrate, mainly having the amino group adjacent to the hydroxyl group, and the ten (propylene) substituent pair located in the hydroxyl group Press product only. Example A-3 Printed in a mixture of the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, containing 3685 parts of polybutene-substituted phenol (wherein the polybutene substituent contains 40 to 45 nitrile atoms), and 140,000 parts Textile steams (textile spirits), adding 790 parts of nitric acid (70%), keeping the temperature of the reaction mixture below 501, stirring for about 0.7 hours, the reaction mixture was poured into a 5000 parts of ice, Keep it for 16 hours, the separated organic -20- 81. 5. 20,000 (H) (please read the precautions on the back before filling in this page) This paper scale is universal Chinese National Standard (CNS) A 4 specification (210x297 public name) )

Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Λ 6 Β6_ V. Description of the invention () The phase layer is washed twice with water, and then combined with 1000 parts of benzene. This solution is stripped to 17〇υ, and the residue is over Obtain the desired filtrate intermediate mixture-containing 130 parts of the above intermediate, 130 parts of ethanol, and 0.2 parts of vaporized platinum (86.4% Pt〇2), put it in a hydrogenation bomb In the reactor, this reactor was purged with hydrogen several times, and then loaded with hydrogen to 54 ps ig, the reactor was shaken for 24 hours, and then loaded with hydrogen to 70 pS ig, held and shaken for another 98 hours, and stripped the reaction mixture. To 145 ^ / 760torr to provide half the solid residue of the desired aminophenol. Example A-4 A mixture containing 105 parts of the intermediate of Example A-3, 3 03 parts of cyclohexane and 4 parts of commercial Raney nickel catalyst, put it into a hydrogenation reactor of appropriate size, The pressure of this reactor was pressurized with hydrogen to 1 OOOp sig, and stirred at about 50P for 16 hours. The reactor was added to 1 1 0 0 P color ig, and mixed for another 2 4 hours, and then opened In this reactor, filter the reaction mixture, and then put a new 4 parts of Raney nickel bracelet medium into the reactor, pressurize the pressure of the reactor to 1 100ps ig, and stir for 24 hours, stripping the reaction mixture. To 951/28 t 〇rr to provide half-solid residue aminophenol. Example A — 5 in a mixture, containing 400 parts of polybutene-substituted phenol (-2 1- (please read the precautions on the back before writing this page) Binding-Order _ Line · The paper size General Chinese Standards (CNS) A 4 specifications (210x297 gong) 81. 5. 20,000 (H) A 6 B6 ^ 05067 5. Description of invention () (please read the precautions on the back before writing this page) where , This polybutene substituent contains about 100 atoms), 12 5 parts of fabric steamer (text i 1 esp iri ts), and 266 parts of diluted mineral oil, temperature 28t, slowly add 22.8 Parts of nitric acid (70%) / 50 parts of water, time is 0.33 hours, the mixture is stirred at a temperature of 28t: _34lC for 2 hours, and stripped to 1 58t: / 30 torr, after filtration can get what you want An oil solution (40%) of a cat phenol intermediate with a nitrogen content of 0.88%.

T-mixture, containing 93 parts of the above intermediate and 93 parts of a mixture of toluene and isopropanol (50/50, by weight), put it into a hydrogenation reactor of suitable size to exclude the gas and Purified with nitrogen, add 0.3 1 parts of commercial gasified platinum catalyst (86. 4%

Pt02), pressurize the reaction vessel to 57ps ig, and maintain it at 50t: to 60Ό2 for 1 hour, a total of 0.6 mole hydrogen is introduced into the reaction vessel, and then the reaction mixture is filtered, and the filtrate is stripped to produce The desired aminophenol product is obtained as an oil solution containing 0.44% nitrogen. Example A-6 The Ministry of Economic Affairs, Central Bureau of Standards, Staff and Consumers Cooperative printed an anti-mole container, containing 750 parts of 100 natural diluent oil and 1,000 parts of a polybutene-substituted phenol, which is derived from a polybutene (The number average molecular weight is equal to 940). This mixture was heated to 4510-65Ό, 89.5 parts of a 62% nitric acid solution was added to the reaction mixture, maintaining the reaction temperature at 60¾-6 5t: two hours, under nitrogen, the reaction mixture was heated to 155TC — 165C, added -22- 81. 5. 20.000 (H) This paper uses the Chinese National Standard (CNS) A 4 specifications (210x297 public goods) Λ6 Β6 V. Description of the invention () hydrazine hydrate (71 copies ) In this reaction mixture, the time is 6.5 hours, the reaction mixture is filtered through silica bath under nitrogen, the filtrate is the desired product, and has a total of 23, 0. 55% nitrogen, and 40% Neutral mineral oil. (A-2) Reaction product of nitrophenol and monoaminophenol compound In another embodiment, the composition of the present invention includes the reaction product of nitrophenol and diaminophenol compound. This nitrophenol can be reacted as follows The formula represents: (〇H) c (R) a -Ar- (NO,) b where a, b, c, r and Ar are as defined above, the preferred implementation of the nitrophenol used in the present invention For example, it contains a single aromatic chen, and in most cases it is a benzene ring. This preferred nitrophenol grade can be represented by the following formula: (please read the notes on the back before filling this page)

T Printed by the Central Bureau of Standards of the Ministry of Economic Affairs

OH

(R '): where R, R' and z are as defined above-23- This paper scale uses Chinese Standards (CHS) A 4 specifications (210x297 male dragons) for free use of this paper scale 81. 5. 20,000 (H) A 6 B6 V. Description of the invention () The nitrophenol used in the present invention can be synthesized by several conventional synthetic methods, and various ways of preparing nitrophenol have been discussed above. The nitrophenol of the present invention is reacted with a monoamine compound. The atmosphere compound may be a single or polyamine, including hydroxy monoamine, hydroxy polyamine, amine concentrate, alkane gasification sickle polyamine, heterocyclic polyamine, And dispersant. The monoamine usually contains from 1 to about 24 atoms, preferably from 1 to about 12, more preferably from 1 to about 6. Examples of the monoamine used in the present invention include methylamine, ethylamine, propylamine, butylamine, octylamine, and dodecylamine. Examples of secondary amines are dimethylamine, diethylamine, dipropylamine, dibutylamine, methylbutylamine, ethylhexylamine, etc. Tertiary amines include trimethylamine, tributylamine, methyldiamine Ethylamine, ethyldibutylamine, etc. In another embodiment, the atmosphere compound may be a hydroxylamine. Typically, the hydroxylamine is a primary, secondary, or tertiary alkane enzyme or a mixture thereof. These amines may be represented by the following formula: H2N-R &quot.; -OH, (Please read the precautions on the back before writing this page) Binding-Order _ Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

81. 5. 20.000 (H) This paper scale is used in the ® National Standard (CNS) A 4 specifications (210x297 male dragon) V. Description of invention ()

-R " — OH wherein Ri is independently a hydrocarbon group of one to about 8 stoichiometric atoms, or a hydroxy hydrocarbon group of one to two to about 8 stoichiometric atoms, preferably 1 to about 4 stoichiometric atoms, and R ′ ^ is A bivalent hydrocarbon group having from about 2 to about 18 large atoms, preferably from 2 to about 4. An R '' -OH group represents a hydroxy hydrocarbon group in this chemical formula, R '' may be an acyclic, alicyclic, aromatic, typically, R '' is an acyclic straight bond or Branched-chain olefin groups, like ethylene. 1,2-propene, 1,2-butene, 1,2-octadecene, etc., when two Ri groups exist in the same molecule, they can It is directly connected by carbon-shuojun or through a heteroatom (es, gas, nitrogen, or sulfur) to form a 5-, 6-, 7_ or 8-printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Atomic ring structure. Examples of these heterocyclic amines include N- (hydroxyl lower alkyl) oxoline, thioxoline, monopiperidine, oxazolidine, thiazolidine, and the like Thing. However, typically Ri is methyl, ethyl, propyl, butyl, pentyl, or hexyl, respectively. Examples of these alkanols include monodione and triethanolamine, diethylethanolamine, ethylethanolamine, butyldiethanolamine, and the like. This hydroxyamine can be an ether N_ (hydroxyhydrocarbyl) amine, these are the hydroxy poly (hydrocarbyl monooxygen) analogs of the aforementioned hydroxyamines (these analogs also include hydroxy-substituted gas olefin analogs), N- ( Hydroxyalkyl) amine-25- 81. 5. 20,000 (H) (please read the precautions on the back before filling in this page) The paper size is easy to use Chinese a family standard (CNS) A 4 specifications (210X297 mm) ^ 0506 ^ A 6 B6 ^ 0506 ^ V. Description of the invention () It can be conveniently prepared by the reaction of epoxide and amine, this amine can be represented by the following general formula: H2N —— (R " 〇h-Η,

(Please read the precautions on the back before filling out this page) Binding-Ordering-Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy where x is a mark from about 2 to about 15, ^ 1 and 11 '* as before As mentioned, Ri may also be a group of monohydroxy poly (hydrocarbon-based gas). The amino compound may also be an ammonium cation derived from a polyamine. The polyamine may be aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples of such polyamines include olefin polyamines, including hydroxyl groups of & amines, aromatic polyamines, and heterocyclic polyamines. -2 6-This paper scale uses the Chinese National Standard (CNS) Grade 4 (210X297); ¢ 81. 5. 20.000 (H) V. Description of invention Hydrocarbon Λ 6 Β 6 (Please read the precautions on the back before filling in this page) Installed--* tT- Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs N 1 R Η Hydrocarbon 2

2 R η Λ / ζ N 1R where η has an average value between about 1 and about 7, preferably about 2 to about 1 to about 10 atoms, more preferably about 2 to about 4. Rz independently of the hydroxy-substituted aliphatic group, preferably, Rz has the same as these olefin polyamines including methylene polypropylene polyamine, pentene polyamine, and the like. Specific examples of cyclic amines, such as polyamines such as Dalton and N-aminoalkanes, are ethylene s- (2aminoethyl) amine, propylene tetramine, tetraethylene pentamine, and hexaethylene heptane by condensation of two or more ( Poly) and two or more of the aforementioned polyamines of ethylene polyamines, like some of these polyamines are described in detail in this article titled E t hy, in s '' Encylopedi 1 Technology ”-27 Between about 10 *, preferably between about 2 and about 5 * and the "olefin" η is preferably about 2 to about 6% f, more preferably argon, or one aliphatic or may be as high as about 3 0 master atoms 〇 definition 〇amine 9 ethylene polyamine t butene polyamine 9 this higher homologous and related hetero group substitutions are also included 0 diamine, triethylenetetramine> t Γ i di Amine 9 Trimethylene diamine 9 Tripropyleneamine> pentaethylenehexylamine »etc. The higher homologues of the above olefins are mixtures and are also useful. The above discussion is The K i Γ k 0 thme Γ 9 a 〇f C hemi C a of the $ 1 e η e A mi η e S used is the second paper f V ο 1 7, the first paper standard of China National Standards (CNS) A 4 specifications (210X297 g) 81. 5. 20.000 (H), ΟδΟΟ A 6 Β6 Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy V. Description of inventions (2 2-37 shers The most convenient one is ethylene glycol grea Compression products of these reactions. After the polyamine mixture is stripped ο 1 yam L ·-polymer to be prepared), boiling a typical D 〇w chemical 5.6 t: when the ratio of nitrogen and stoke 9 3% For example, 2% TET of pentaethylene has a ring-compressed ethylene tetraamine and a page, Interscience Publi, New York (1965). These polyamines are prepared from the reaction of ethylene dicarbide and ammonium • or through the reaction of an amine and a ring-opening reagent (r i ng open i η gent), such as water, ammonium, etc. If the resulting γ compound mixture of polyolefin polyamines, including rings, as described above, the mixture of ethylene polyamines is a useful compound, and other useful types of remnants are left behind. It is less than inebott. Secondly, the sample which usually points at about 200C is obtained from the company of Freep, and has a viscosity of 1 s when it is named with a specific gravity of 1.016 40¾. Terminals of these samples are airborne "(most A, 21.74% tetraamines and higher (with heavy products such as piper < and diethyl and its analogues. Since the upper polyamine base is roughly (The ethylene poly Te is w E-100 type are those commonly referred to as "ms", less than 1%, these ort 8, 33 2 1 withdrawal history color layer is divided into DE vinylamylamine meter) .15 torr (c analysis contains TA) and 7 6 of some olefins are higher than those of the polyamine blending section described above (P, olefins are calculated by weight of X as " at the bottom of the amine, at 1 weight percent enti Approximately 0., 0.7 .61% Polyamine bottom strip, three (please read the precautions on the back before filling this page) Pack--, τ · 28 This paper scale is used in the national standard (CNS) A 4 specifications (210X297 Gonglong) 81. 5. 20.000 (H) Printed by the Beigongxiaot Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ 6 _Β_6 V. Description of the invention () The bottom of these polyolefin polyamines can be reacted with nitrophenol alone, or Used with other amines, polyamines, or mixtures of them. Another useful polyamine is one containing at least one hydroxyl compound and at least one polyamine reactant Condensation reactant, this polyamine reactant contains at least-grade amine or secondary amino group. The hydroxyl compound is preferably polyhydroxylase and amine. These polyhydric alcohols are described below. Preferably, the hydroxyl compound is poly Hydroxylamines and polyamines include any of the above-mentioned monoamines (e.g. ethylene oxide, propylene vapors, butene vapors, etc.) that react with Japanese olefin vapors, with two to about 20 large atoms, Preferably, there are two to about 4 slap atoms. Examples of polyhydroxy include tris (hydroxypropyl) amine, tr 〖s— (hydroxymethyl) aminomethane, 2-amino-2-methyl-1 , 3-propanediol, N, Ν, Ν ', Ν'-tetrakis (2-hydroxypropyl) ethylene diamine, and Ν, Ν, Ν', Ν'-tetrakis (2-hydroxyethyl) Ethylenediamine, preferably tris (hydroxymethyl) aminomethane (THAM). Polyamine reactant, which reacts with this polyhydric alcohol or amine to form this concentrated product or concentrated amine is as described above, Preferred polyamine reagents include triethylenetetramine (TETA), tetraethylenepentylamine (TEPA), pentaethylenehexylamine (PEH) Α), and a mixture of polyamines, like the "amine bottom" as described above. The concentration reaction between the polyamine reactant and the hydroxyl compound is at a high temperature, usually about 60¾ to about 265C, (preferably at (Approximately 220 υ to about 25 〇〇) and the presence of acid catalyst. This amine concentrate and the method of preparing this amine concentrate are described in PC Τ-2 9- (please read the notes on the back first (Fill in this page again) 装 · This paper scale uses the Chinese National Standard (CNS) A4 specifications (210x297 public) 81. 5. 20,000 (H) Λ6 B6 (〇5〇 ^ V. Description of invention () (please first Read the precautions on the back and fill out this page) Shen Yu W086 / 05501, here it is used as a reference to show the concentrate and the preparation of this substance. The preparation of these polyamine concentrates can be carried out in the following manner: In a 4-neck 3-liter round-bottom flask, the device is equipped with a glass stirrer, a warmer, and an N2 inlet under the liquid surface. Dean-St ark 拼And Fr * i edr ich condenser, filled with: 1299 grams of HPA Taft amine (an amine bottom commercially produced by Union Carbide Co. company, basically it has 34.1% by weight of nitrogen and 12.3 stone Weight percent primary amine, 14.4% heavy child percentage of secondary limbs and 7.4% weight percent of tertiary amine nitrogen distribution), and 727 grams of 40% tris — (hydroxymethyl) aminomethane (THAM) aqueous solution, this mixture was heated to 60C, and 23 grams of 85% H3P〇4 was added. Then the mixture was heated to 120Π within 0.6 hours, wiped with N2, and then the mixture was heated to 150t within 1.25 hours, and then to 235tJ for another hour, then kept at a temperature of 230-235 C 5 hours long, then heated to 24〇υ in a time of 0.75 hours, and maintained at 240-24510, 5 hours long Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the product is cooled to 150 " C Then use diatomite as a supplementary rib. Yield: 84% (1221 g). In another embodiment, the atmosphere-based compound is a hydroxyl group-containing polyamine, a hydroxyl monoamine-containing hydroxyl group-containing polyamine analog In particular, alkoxylated olefin polyamines (eg N, N (diethanol) ethylene diamine) will be used. These polyamines can be made from the above-mentioned olefin amines and one or more of the above-mentioned -30- 81. 5. 20.000 (H) The paper size is easy to use China a home standard (CNS) A 4 specifications (210x297 g; ¢) Economy Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards

^ 〇5〇GV A6 ___B_6____ V. Description of the invention () Prepared by the reaction of olefin gasification, similar olefin oxide alkanolamine reaction products will be used, like the aforementioned primary, secondary or tertiary alkanolamine and The reaction products of ethylene, propylene, or higher ring gasification compounds at a molar ratio of 1.1 to 1.2, and the ratio of reactants to carry out these reactions are inversely known to those skilled in the art. Examples of the determination of alkylene gasified olefin polyamines include N- (hydroxyethyl) ethylenediamine, N, N-bis (2-hydroxyethyl) monoethylenediamine, 1- (2-hydroxyethyl) piper Mono (hydroxypropyl) substituted tetraethylene monoamylamine, N- (3-hydroxybutyl) -tetramethylene diamine, etc. Higher analogues can be prepared by concentrating the above-mentioned hydroxyl-containing polyamines, which are equally useful via amino groups or via hydroxyl groups. Concentration via amino groups will result in higher amines, accompanied by the elimination of ammonium, but via hydroxyl groups Concentration will result in products containing ether bonds, and with the elimination of water, any two or more of the aforementioned mixtures may also be used. In another embodiment, the amino compound may be a cation from a heterocyclic polyamine, the heterocyclic polyamine includes 1-azacyclopropene (az ir idines), azetidines (azetidines), Li Ni Yuan (Azo i idines), tetra- and di-pyridine, pyrrole, indole, piperidine, myrazole, di- and tetrahydroimidazole, thiophene, isoindole, purine, morpholine, thiomorpholine, N-aminoalkylmorpholine, N_aminoalkylthiomaline, N-aminoalkylpiperidine :: Ν, Ν'-diaminoalkylpiperidine · azep i nes, Azocins (azocines), azine (azonine), -31- This paper standard is used in aa family standard (CNS) A 4 specifications (210x297 public) 81. 5. 20,000 (H) (please read the back first Please pay attention to this page and then fill out this page) Install &Order; Printed by Beigong Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs

^ 〇50GV A 6 _____B6_ V. Description of the invention () azec ines, and each of the above-mentioned substances of four, two one and highly hydrogenated derivatives, and these heterocyclic amines of two or more mixtures, compare Preferred heterocyclic amines are saturated 5- and 6-atom heterocyclic amines, which only contain nitrogen, gas and / or sulfur atoms on the heterocyclic ring, especially piperidine, nifefa, thiomorpholine, morpholine , Pyrroline, and analogs thereof; shovelidine, aminoalkyl substituted piperidine, piperidine, aminoalkyl substituted shoveline, aminoalkyl substituted morpholine, pyrroline, and aminoalkyl substituted pyrrole Porphyrin is better. Usually the aminoalkyl substituent is part of a heterocyclic atom on the nitrogen atom. Examples of these heterocyclic amines include N-g-propylpropylmorpholine, N-aminoethylneline, and N , Ν'-Diaminoethyl reported. Hydroxyheterocyclic polyamines are also useful, and examples include N- (2-hydroxyethyl) cyclohexylamine, 3-hydroxycyclopentylamine, p-hydroxyaniline, N-hydroxyethyl sulfonate, and the like. In another embodiment, the amino compound may be derived from a dispersant, the dispersant includes: a nitrogen-containing carboxylic acid dispersant, an amine dispersant, a nitrogen-containing ester dispersant; a Mannich dispersant ; And dispersant viscosity modifiers and their mixtures. These dispersants will be discussed below. In order to prepare the reaction product of a nitrophenol and an amino compound, at least one nitrophenol must be condensed with at least one of the above amines. This reaction is a concentration reaction, which will continue until the reaction product is substantially free of nitro groups. This reaction Generally speaking, it is carried out at a temperature between 2 51C and the decomposition temperature of other components. Generally speaking, this temperature is below 250t :, preferably between 50 and 175. -32- The size of this paper is free to use the Chinese standard (CNS) A4 specification (210x297) 81. 5. 20.000 (H) (please read the precautions on the back before filling out this page) Printed by the Cooperative Society of the Bureau of Standards ^ 05067 Λ 6 _ Β6_ V. Description of the invention () When each nitro group in the nitrophenol contains less than about 15 mega atoms per molecule, at low temperature (eg, ΟΊΟ Up to 50¾) It is necessary to handle the condensate of the concentrate, and must be careful, because there may be a violent reaction. In general, use at least half an equivalent of nitrophenol for each equivalent of ammonia compound, usually more than three equivalents of nitro compound for each equivalent of amino compound, or more than 8 equivalents for each equivalent of nitrophenol The amino compounds are unfavorable. In a typical embodiment, the amount of conjugated nitrophenol and amino compound in the concentration reaction is in proportion, and each mole of nitrophenol is about 0.5 to 10 equivalents of amino compound, preferably About 1.0-5. The following example concerns the reaction product of mono-nitrophenol and mono-amino compound. Example A-7 Monoalkylated alcohols are prepared by reacting phenol with polybutene having a number average molecular weight of about 1000 (vp〇) in the presence of boron difluoride monophenol complex catalyst. The resulting product was stripped under vacuum to 230 ° C and 76 ° tor, and then 205t / 50t〇r to provide a polybutene-substituted alcohol. This polybutene-substituted phenol (4578 parts), 3052 parts of 100 neutral mineral oil and 725 parts of fabric steamed dumplings (text i 1 e sp iri ts) were heated to 60t under IS mixing and cooled to After 3〇r, a mixture, including 319.5 parts of 16-mole nitric acid and 600 parts were slowly added to this mixture, during which is outside -33- the paper standard universal 3 national standard (CNS) A4 specifications (210x297 g; lir) 81. 5. 20.000 (H) (please read the precautions on the back before filling out this page). Packing · Thread _ Printed by the Ministry of Economic Affairs Central Standards Bureau Beigong Consumer Cooperative 0506 · / Λ 6 2_B_6_ 5. Description of the invention () Partial cooling method keeps the temperature at 40t. After stirring this mixture for 2 hours, 3710 parts were transferred to the second reactor vessel, and the remaining material was stripped to 150t: / 43t〇r, cooled to 1 10 seven, and then filtered through diatomaceous earth to provide the desired nitrophenol overlying liquid, this substance has a nitrogen content of 0.53%. The above nitrophenol (1353 parts) was added to 61.5 parts of a mixture of commercial polyethylene polyamines, which contained 33.5% nitrogen, and was roughly equal to the experimental formula of tetraethylenepentamine. Heat the anti-alcohol mixture to 8 ΟΌ1.5 hours. Then store at 25P for 16 hours, then heat to the inside within 15 hours to 30-1 60t :, and finally stripped to 160/30 tor. Residue through diatomaceous earth The product can be obtained containing 1.5% nitrogen. Example A-8 A mixture containing 1600 parts of polybutene-substituted phenol, which is prepared from polybutene having a number average molecular weight of 1400 (gel permeation chromatography) by the method described in Example A, 10 One part of aqueous solution of hydrogen radon acid and 33 parts of paraformaldehyde were heated under nitrogen to a temperature of 9 Ot for 20 hours, and were stored at room temperature intermittently. Then add 500 parts of fabric distillate, followed by 9 1.3 parts of concentrated nitric acid and 100 parts of water. During the period of addition of nitric acid, maintain a temperature of 1 30-1 38υ by external cooling method. The eaves was mixed with the eaves at a temperature for 2 hours, then the polyethylene polyamine of Example A was slowly added, the reaction mixture was heated to a temperature of 1 601C for 7 hours, and then stripped to 1 60 ° C and 30 t 〇-34- ( Please read the precautions on the back before filling out this page) Binding · Line-This paper uses the Chinese National Standard (CNS) A 4 specifications (210X297 male dragon) 81. 5. 20.000 (H) Λ6 B6 Central Bureau of Standards, Ministry of Economic Affairs Employee Consumer #Cooperative printed five. Description of the invention () r, this residue is passed through diatomite, which can produce a product with a nitrogen content of 0.88%. Example A-9 An oil solution of nitropolybutene-substituted phenol prepared by the method described in Example A, which contains 60% by weight of the oil solution, was added to a reaction containing 134 parts of triethanolamine In the container, this addition is completed within 1.5 hours. By maintaining the temperature of the reaction mixture at 2 001C for 12 hours, the reaction mixture was stripped to 200t: / 20t or, and then cooled to 100t :, and the reaction mixture was passed through diatomaceous earth to obtain a product containing 0.97% nitrogen. (B) Ashless dispersant The ingredients of the present invention also include a ashless ashless dispersant. This dispersant includes a nitrogen-containing carboxylic acid dispersant, an amine dispersant, an ester dispersant and a Mannich )Dispersant. In one embodiment, the dispersant may be substituted with succinic anhydride, nitrile, carbamide, boron compound, phosphorous compound such as urea, thiourea * sulfide disulfide, aldehyde, ketone, carboxylic acid, hydrogen compound. Wait for processing. Dispersants containing carboxylic acids containing nitrogen. Dispersants containing carboxylic acids containing nitrogen include the reaction products of hydrocarbyl-substituted carboxylic acid hydroformylation agents, like substituted carboxylic acids or their derivatives, such as the amines described above. The amine is a polyamine, and the preferred amine is vinylamine, amine base or amine concentrate. This hydrogen-substituted carboxylic acid acetylating agent may be derived from monocarboxylic acid or polycarboxylic acid -35 (please read the precautions on the back before filling out this page) Standard (CNS) A4 specifications (210x297 public waste) 81. 5. 20,000 (H) 〇5〇 & A6 B6 Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (), polycarboxylic acid is usually Preferred derivatives of this kind »Like halide t esters > Aldehyde 9 is more preferably m type 〇 Optimizing agent 〇 This hydrocarbon-substituted carboxylic acid acetylated hydrocarbon-based reagents, special features of this polyolefin > It is preferred to have a value of at least about 3 5% to about 3 0 0 Atomic atom% 0 Atomic atom 0 (in one embodiment the average molecular weight) is at least about the hydrocarbon's characteristic is Μ η value is about 50 In about 8 0 0 to about 2 5 0 0 the value changes from about 5 0 0 to 1 2 0 in another embodiment »This is about 1 3 0 0 to about 5 0 0 • 5 to about 4 polyolefin f better better Is about 2 • 5 to about 3 • Chemical 9 where the substituent is derived. Described in US Patent 4 »2 3 4 Reference 〇 This polyolefin includes polymerizable (h 〇m 〇Ρ 〇1 yme Γ P 〇1 yme Γ S) »The acylating agent may be a carboxylic acid or an aldehyde of the carboxylic acid, etc., preferably an acid, an ester, or the carboxylic acid acetylating agent is a succinic acid enzyme including one derived from 値The emblem of the polyolefin contains at least about 8 衏 硪 原 0 value, more preferably at least about 3, preferably 200 value, more preferably 10, the characteristic of this polyolefin is Mn (number is 500, generally In particular, the polyene is between 0 and about 5000, preferably, in another embodiment, the Mn 0 or 1 3 0 0 〇 hydrocarbon group is derived from having a Mn value of at least 0, and Mw / Mn value in From about 1 is from about 1.8 to about 3. 6, 2. For a substituted succinic acid polyolefin, the preparation and application is No. 435, which is shown here as a combined olefin monomer The homogeneous polymer s) and inter-polymer (inter hydrocarbon monomers contain from about 2 to about 16-36- (please read the note on the back Item and then fill in this page)

This paper uses the Chinese standard (CNS) A4 specifications (210X297 male dragon) 81. 5. 20.000 (H) Λ 6 Β6 V. Description of invention () Sulfur atom, usually about 2 to about 6® , Preferably 2 to about 4, more preferably 4 values. This olefin can be a monoolefin, like ethylene, propylene, 1-butene, isobutylene, and 1-octene; or a polyolefin monomer, preferably a diolefin monomer, like 1,3-butadiene And isoprene, preferably, the polymer here is a homogeneous polymer, an example of a preferred homogeneous polymer is a polybutene, preferably a polybutene, which is about 50% of this The polymer is derived from isobutylene, and this polyolefin can be prepared by conventional procedures. The hydrocarbyl-substituted carboxylic acid acetylating agent can be prepared by reacting one or more polyolefins with reverse- or multi-porous unsaturated carboxylic acid reagents. The unsaturated diacid reagents usually contain monoolefin unsaturated monomers. The carboxylic acid test preparation of the Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperative can be carboxylic acid, and its functional derivatives, such as anhydrides, esters, amide compounds, amide imine compounds, salt, aldehyde halide, and nitrile These carboxylic acid reagents can be monobasic or polybasic in nature. When they are polybasic, although tri- and tetracarboxylic acids can also be used, dicarboxylic acids are preferred and useful single-aged unsaturated carboxylic acids The specific examples are acrylic acid, 2-methacrylic acid, cinnamic acid, crotonic acid, 2-phenylacrylic acid, and so on. Examples of polyhydric acids include maleic acid, fumaric acid, mesaconic acid, itaconic acid, and maleic acid. Generally speaking, the unsaturated carboxylic acid or its derivative is maleic anhydride, or maleic acid or fumaric acid or ester, preferably maleic acid or wild acid, more preferably Maleic anhydride. This polyolefin can be reacted with various carboxylic acid reagents, such as reagents having at least 1 mole for 1 mole of poly-smoke, preferably an excess amount of reagent is used, and the excess amount is usually about 5% to about 2 Between 5%. -3 7-81. 5. 20,000 (Η) (Please read the precautions on the back before filling in this page) This paper is generally compliant with China National Standard (CNS) A 4 specifications (210x297 public waste) Λ 6 Β6 Central Standard of the Ministry of Economy Printed by the Bureau ’s staff cooperative. 5. Description of the invention () In another example > The acetylating agent is prepared by reacting the above-mentioned polyolefin with an excess of maleic anhydride »to provide — substituted Succinic acid hydroformylation agent> where the number of succinic acid group groups per substituent group is at least 1 • 3 »the maximum value will not exceed 4 • 5 1 suitable range is from 1 • Between 4 and 3 • 5 $ especially for each — when the weight of the substituent is from about 1 • 4 to about 2 • 5 m succinic acid group group. In this example f this The polyolefin preferably has a Μ η value from about 1 3 0 0 to about 50,000 and a MW / Μ η value of at least about 1 «5 t as described above 9 Μ η value Fortunately, it is between about 1 3 0 0 and 5 0 0 0 > For Μ η value »A preferred range is from about 1 5 0 0 to about 2 8 0 0 1 Μ η value is the best range It is from about 1 5 0 0 to about 2 4 0 0 0 Reaction acid reagent-polyolefin conditions> such as temperature search 9 Solvent 9 and its species are well known to the industry 0 Description Preparation of useful chemical agent Examples of patents for various steps are US Patent 3 9 2 1 5 »7 0 7 (re η S e) 3 > 2 1 9» 6 6 6 (Ν 〇Γ ma η eta 1) • 9 3 t 2 1 3 t 5 8 7 (R e η S e); 3 * 9 1 2 »7 6 4 (P a 1 me Γ)» 4 »1 1 Q» 3 4 9 (C ο he η) 9 and 4 9 2 3 4 • 4 3 5 (Μ e ί η ha Γ dteta 1) 9 and U • Κ • 1 9 4 4 0 f 2 1 9 0 These patents are shown and incorporated herein by reference. Amine dispersant This dispersant can be a Amine dispersant > Amine dispersant is a hydrocarbyl substituted amine 9 -3 8 _ (Please read the precautions on the back before filling in this page) This paper uses the Chinese National Standard (CNS) A 4 specifications (210x297 gong) 81. 5. 20,000 ⑻ L0G0G7 Λ 6 B6 Central Standard of the Ministry of Economic Affairs Printed by the bureau employee cooperative. V. Description of the invention () These amines substituted by these hydrocarbon groups are shown in the United States, 7 5 7; 3, 3, 7 5 5, 4 It is also revealed that hydrocarbons, amine dispersants are composed of mono- Or polyamine) This amine can be any of the above) amine; N, N -0: 5 0 molar ratio of ethyl) a N-polybutenamine; N _ (butene) ethylene di (butene) di Vinylamine; N, N-didiamine and its analog ester dispersant in another dispersant can be obtained by dispersing this ester in the case of one less organic hydroxylation reaction. This organic hydroxylamine is for those who are accustomed to this country's patent 3) 2 7 5 f 4 5 4 * 5 5 5 3 3 3 = and 3 »8 2 2 prepared by the reaction of olefin and olefin polymerization 〇 This polyene can be the amine-amine dispersant dimethyl-N — poly (monomer of Example B) polybutene polybuteneamine * N — (2 polybutene — aniline> N — amine 9 N — Poly (propylene) triamine N y, N 9 — methyl — N ——, poly (propylene embodiment, this dispersant is at least one of the above-mentioned hydrocarbon-based complexes and the selective amine preparation is reacted by this aldehyde Compounds including the general formula R4-39- are well known to those skilled in the art. 5 5 4; 3, 4 3 8, 5 6 5, 8 0 4;, 2 8 9. References to these patented methods. Typical materials ( Polyolefin) and amines (any of the polyolefins. Examples include poly (propylene / propylene) amines, (5 amines; N, N—di (hydroxy-hydroxypropyl) -N-polybutene Morpholine; N-polytrimethylenediamine; N-poly (butene) tetraethylenepentene) -1,3-propene Ester dispersant, the esterified carboxylic acid hydroformylation agent and prepared. In another implementation and the above hydroxylamine preparation of (Ο H) m compound, (please read the precautions on the back before filling this page ) Packing-This paper standard universal SS home sample standard (CNS) A 4 specifications (2K1X297 male dragon) 81. 5. 20,000 (H) Λ6 Β6 V. Invention description () where R4 is a monovalent or multivalent organic group , Connected to a group of 〇Η group through a sulfone atom, a is an integer from 1 to about 10, wherein the hydrocarbon group contains at least about 8 aliphatic sulfon atoms, this hydroxy compound is an aliphatic compound, like monohydroxy and Polyhydric alcohols, or aromatic compounds like phenol and naphthol. This ester-forming aromatic hydroxy compound can be illustrated by the following special examples: Phenol./9 Mononaphthol, α-naphthol, cresol, m Hydroquinone, hydroquinone, ρ, Ρ'—dihydroxydiphenyl, 2-gasified phenol, 2,4-dibutyl gallophenol, etc. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to form esters The alcohols preferably contain up to about 40 aliphatic monatomic atoms, preferably from 2 to about 30, more preferably from 2 to about 10 These atoms are monohydric alcohols, such as methanol, isooctyl alcohol, dodecanol, cyclohexanol, etc. In one embodiment, the hydroxy compound is polyhydric alcohol, like olefin polyol, preferably The polyhydric alcohol contains from 2 to about 40 atoms, more preferably from 2 to about 20 values; and from 2 to about 10 hydroxyl groups, more preferably from 2 to about 6 values. Polyhydric alcohols include ethylene glycol, including di-, tri-, and tetra-propylene glycol; glycerol, butylene glycol, hexylene glycol, sorbitol, arabitol, mannitol, sucrose; fructose; glucose ; Cyclohexanediol; Pentaerythritol, and pentaerythritol, including di- and tripentaerythritol, preferably diethylene glycol, diethylene glycol, propylene glycol, and alcohol. , Pentaerythritol and erythritol. Assuming that at least one hydroxyl group remains unesterified, the polyhydric alcohol may be esterified with a monocarboxylic acid having from 2 to about 30 monatomic atoms, preferably from about 8 to about 18 monocarboxylic acids Examples include acetic acid, propionic acid, butyric acid-4 〇- 81. 5. 20,000 ⑻ (please read the precautions on the back before writing this page). 4 Specifications (210 > < 2 Machi Kosumi) The Ministry of Economic Affairs, Central Standards Bureau, Employee Consumer Cooperative printed Λ6 B6_ V. Description of invention () and fatty carboxylic acid, this fatty monocarboxylic acid has from about 8 to about 30 sulfonate Atom, and includes caprylic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid and tall oil acid. Specific examples of these esterified polyhydric alcohols include sorbitol oleate, including mono- and dioleate, sorbitol stearate, including mono- and di-stearate, glycerol oleate塩, including glycerol single, di- and dioleate and erythritol octanoate. . The carboxyl ester dispersant can be prepared by any conventional method. This method is preferred because of its convenience and the properties of the ester produced, which is wider than the reaction of the above-mentioned carboxylic acid aldolizing agent with one or more alcohols or phenols. For each equivalent of the acetylating agent, The ratio is from about 0.5 equivalents to about 4 equivalents of the hydroxy compound. The ester reaction is usually carried out at a temperature higher than 10 °, preferably between 150 ° C and 300 ° C. As the esterification proceeds, the water formed from the by-products can be removed by distillation. The preparation of useful carboxylic acid ester dispersants is described in U.S. Patent Nos. 3,522,179 and 4,234,435. The carboxylate dispersant can further react with at least one of the above-mentioned amines, preferably with at least one polyamine above. In one embodiment, the amount of amine reaction is sufficient to neutralize any unesterified carboxylic acid The amount of group groups, in a preferred embodiment, this nitrogen-containing carboxylate dispersant, for each equivalent of the hydroformylation agent, is from about 1.0 to 2.0 equivalents, preferably about 1. 0 至 1. 8equivalents of hydroxy compounds, and high to about 0.3 equivalents, preferably about 0.02 to about 0.25 equivalents of polyamine prepared. In another embodiment, this carboxylic acid acylating agent can be used with alcohols and amines _ 4 1-(please read the precautions on the back before filling in this page) 装 · * 1T_ 线-This paper size is common in China National Standard (CNS) A4 specifications (210x297 male dragon) 81. 5. 20,000 (Η) A6 B6 V. Description of the invention () Reaction, although the equivalent of each equivalent of the hydroformylation agent, the combined equivalent of amine and alcohol is at least about 0 5, but usually has at least about 0.01 equivalent of alcohol and at least about 0.01 equivalent of amine. These deuterium-containing carboxylate dispersant compositions are well known to those skilled in the art, and the preparation of many of these derivatives is described in, for example, US Patent Nos. 3, 9 5 7, 854 and 4, 2 3 4 , 43 No. 5, used here as a reference. -The method of preparing these materials by this carboxylate dispersant is well known in this field, and it is shown in US Patent 3, 219, 666; 3, 3 8 1, 0 2 2; 3, 5 2 2, Nos. 179 and 4, 234, 4 and 35, the description of which is prepared for these carboxylic acid ester dispersants is here taken as a reference of the present invention.

MANNICH DISPERSA NTS This dispersant can be a Manley phase dispersant, which can be prepared by reacting at least one aldehyde, at least one of the above amines and at least one hydroxy aromatic compound. This reaction is carried out in the range from room temperature to 2 2 5¾, usually from 50P to about 200¾. (75¾-125¾ is the best printed by the Ministry of Economic Affairs Central Standards Bureau Beigongxiao # Cooperative), the amount of reagent is The molar ratio of hydroxyaromatic compound to formaldehyde and to amine is in the range from about (1: 1: 1) to about (1: 3: 3). The first reaction reagent on the shanghai is a hydroxyaromatic compound. This term includes phenol (which is preferred), phenol, gas, sulfur, and nitrogen. A bridged phenol and its analogues and via covalent bonds Linked phenol (for example: 4, 4 '1-4 2- 81. 5. 20.000 (H) (please read the precautions on the back before filling this page) This paper is also used in China National Standard (CNS) A 4 Specifications (210X297 g; ¢)

Printed Λ6 B6 by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention () bis (naphthyl) diphenyl), a mesogenic compound derived from fused ring hydrocarbons (eg, Tsai alcohol and its analogs) •, and polyhydroxy compounds, such as benzene dioxane, m-phenyl dioxane and p-phenylene dichloride. As the first reactant, a mixture of lean or multiple lean compounds can be used. The hydroxyaromatic compounds are those substituted with at least one, and preferably no more than two, aliphatic or cycloaliphatic groups. These aliphatic or cycloaliphatic group groups have at least about 6 (usually at least about 30, more preferably at least about 5〇) Value carbon atoms and up to about 400 0 atoms, preferably 300, more preferably 200. These groups are derived from the above-mentioned polyolefins. In one embodiment, the hydroxy aromatic compound is substituted with an aliphatic or alicyclic hydrocarbon group. The hydrocarbon group has a Mn value of about 420 to about 10, 〇. 〇〇. The second reagent is a hydrocarbyl aldehyde, preferably a lower aliphatic aldehyde. Suitable aldehydes include formaldehyde, benzaldehyde, acetaldehyde, butyraldehyde and hydroxybutyrol, and gengxing, and the The precursors (precursors), which are like aldehydes under the reaction conditions, such as para-S, polyacetaldehyde, formalin, and metha 1. Xue and its precursors are preferred (e.g., formaldehyde, trioxane), and mixtures of aldehydes can also be used for the second reagent. The third reagent is any of the above amines. Preferably, the amine is the above-mentioned polyamine. Manly phase dispersants are described in the following patents: US patents 3, 98 0, 5 6 9; 3, 8 7 7, 8 9 9; 4, 454, 0 5 9 (herein for Manly phase dispersants For reference). -4 3-(Please read the precautions on the back before filling the nest page) Binding-Binding-Thread-This paper standard is common in the national standard (CNS) A 4 specifications (210x297 g) 81. 5. 20,000 (H ) A 6 B6 V. Description of the invention () The following fixed illustrative examples describe the preparation of an example dispersant (B) used in the composition of the invention. Example B-1 A mixture, including 1500 parts of atmospheric poly (isobutylene) (molecular weight is about 950, and has a nitrogen content of 5.6%), 285 parts of olefin polyamine, with an average stoichiometry S, which is equal to four Ethyl amylamine, and 12Q0 parts of benzene, were heated under reflux, and then the temperature of this mixture rose slowly to 17 Ot in the interval of 4 hours: benzene was removed, and the cooled mixture was equal Dilute a mixture of hexane and absolute ethanol (1: 1), heat the mixture under reflux, and add 1/3 volume of 10% aqueous solution of sodium strontium. After stirring, let the mixture cool and separate the chicken. 5%。 By washing the portion of the organic phase layer with water and stripping, the desired polyisobutylene polyamine can be obtained, which has a nitrogen content of 4.5%. Example B — 2 The Ministry of Economic Affairs Central Standards Bureau employee Xiao # Cooperative printed a mixture consisting of 140 parts of toluene and 400 parts of polyisobutylene succinic anhydride (made from poly (isobutylene) with a molecular weight of about 850 and vapor phase infiltration) Obtained), which has a saponification number of 109, and 63.6 parts of a mixture of vinylamine, which has an average chemical composition equal to that of tetraethylenepentylamine, heated to 150t :, during which the water / toluene azeotrope is removed . The reaction mixture is then heated to 15 ° V under reduced pressure, preferably until the toluene has stopped distilling out. This residual amide polyamine has a nitrogen content of 4.7%. Example B — 3 -4 4 _ 81. 5. 20,000 (Η) (please read the precautions on the back before filling this page) This paper is for standard use China National Standards (CNS) A 4 specifications (210x297 g: 2 :): Λ 6 Β6 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy V. Invention Instructions (1) A reaction vessel, containing 820 copies of 100 neutral mineral oil And 1000 parts of polybutene substituted T diacid, which is derived from polybutene (number average molecular weight is equal to 9 6 0), the mixture is heated to 1 10 it, during which 85 is added to the reaction mixture · 0 parts of ethyl amine mixture, which has an average composition stoichiometry equal to tetraethylene pentamine, heat the reaction mixture to 15 〇t: _ 1 6 〇C, and maintain this temperature for 4 hours, cooling the reaction mixture , And · Passing through the diatomaceous earth, the wave solution has a total base number of 35, 1.56% nitrogen and 40% 100% neutral rock oil. Example B-4 A reaction vessel filled with 400 parts of 100 neutral mineral oil, and 1 000 parts of polybutene succinic anhydride described in Example B-3, 'heat this mixture to 88 hp, in between To the reaction mixture, 152 parts of concentrated amine (prepared by the reaction of HP A Taft amine and tr is (hydroxymethyl) aminomethane (TH AM) of Un i on Carbide company) was added, and the reaction temperature was increased to 152Ί0, And maintained for 5.5 hours, the reaction mixture was cooled to 145 ^, and then filtered through diatomaceous earth, then the filtrate contained 40% 100 neutral mineral oil and 2.15% nitrogen. Example B_5 In a mixture, containing 50 parts of polypropyl substituted phenol (having a molecular weight of about 900, the vapor phase layer is penetrated), 500 parts of mineral oil (from a viscosity of 100 SUS at 100T Solvent obtained by refining the oil of panax oil) and 130 parts of 9.5% dimethylamine solution-4 5-(please read the precautions on the back before filling in this page). Install. '^ Τ_ Line-This paper The scale uses the Chinese standard (CNS) A4 specification (2Κ) × 297 g. Pan) 81. 5. 20.000 (H) Λ6 B6 V. Description of the invention () Aqueous solution (equal to 12 parts of amine), to In the form of droplets, 22 parts of 37% aqueous formaldehyde solution (equal to 8 parts of aldehydes) was added in the interval of 1 hour. During the addition, the reaction temperature slowly increased to 100 t: and maintained at that temperature During 3 hours, the reaction mixture was blown with nitrogen. To the cooled reaction mixture, 100 parts of toluene and 40 parts of mixed butyl alcohol were added, and the organic phase layer was washed three times with water until the litmus paper was Until neutral, and the organic phase layer is filtered and stripped to 200C / 5-10 torr, the residue is the oil solution of the final product Square containing 0.5% nitrogen. Example B — 6 A substantially hydrocarbyl-substituted succinic anhydride, which consists of a polybutene with a molecular weight of 1 000 to an atmosphere content of 4.5%, and then 1. The 2 mol part of maleic anhydride is prepared by heating at a temperature in the range of 150-220¾. The resulting succinic anhydride has an acid number of 130, a mixture, including 874 g (1 Mo Ear) of this succinic anhydride and 104 g (1 mol) of neopentyl glycol in the condition of 240 — 250 ^ / 3 0mm for 12 hours, the residue is a ester of this diol-S or Erjian 2%。 Hydroxy vinegar mixture, the saponification number is 101, and the content of alcoholic hydroxyl group is 0.2%. Example B-7 is prepared by heating 65 8 'parts of a carboxylic acid having an average molecular weight of 1 Q 1 8 (prepared by the reaction of chlorinated polybutene and acrylic acid) and 22 parts of pentaerythritol Ester, during which the temperature is maintained at 180 — 20 -4 6-81. 5. 20.000 (H) (please read the precautions on the back before filling this page) This paper standard is common to China National Standards (CNS) A 4 specifications (210x297 public and)

A 6 B6 Printed by the Consumer Labor Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention () Within the scope of 51C for 18 hours, and nitrogen is constantly blowing through this mixture. The mixture is then filtered and the filtrate is the desired ester. (C) Polyolefin The composition of the present invention may optionally contain up to 10% by weight having a number average molecular weight of from about 400, preferably about 500, more preferably from 600 to about 2500, preferably About 1500, more preferably about 1300 polyolefin. This polyolefin has been described above, and is preferably a polybutene. The polyolefin is present in an amount of up to about 10% by weight, preferably up to about 7%, more preferably about 5% And even better is about 3% by weight. In one embodiment, the presence of the polyolefin (C) is up to about 3% by weight, preferably about 0.5% to about 1.5% by weight, the polyolefin can improve lubricity and The anti-wear properties of this lubricant. The lubricating oil composition of the present invention also contains at least one substantially inactive, normally liquid organic diluent up to about 25% replacement percentage. This diluent generally improves aminophenol and dispersant and The miscibility of the selective polyolefin that lubricates the fuel. The diluent may be the fuel itself, Stoddard solvent, kerosene, naphtha, jet fuel, and the like. The amount of the organic diluent is generally from about 5% to about 25% by weight, preferably about 10% to about 20% by weight. As mentioned above, the present invention provides a two-stroke engine lubricating oil mixture to improve the protection of piston wear and abrasion. The lubricating oil group of the present invention -47- (please read the precautions on the back before filling this page) ; Stranding. The size of this paper is in accordance with Chinese National Standard (CNS) A 4 specifications (210x297 male clam) 81. 5. 20.000 (H) Λ 6 Β6 V. Description of invention () The finished product can contain up to about 3% The replacement percentage of light-colored high-viscosity lubricating oil or high-molecular-weight polymer, preferably, the composition contains up to about 1.5% by weight, preferably 1% by weight, more preferably up to About 0.5% by weight of light-colored high-viscosity lubricating oil or polymer-based polymer, in another embodiment, the lubricating component is selectively free of light-colored high-viscosity lubricating oil and high molecular weight Polymers, which will cause pollution of exhaust ports, spark plug sockets and unclean engines. The term "free of" used in the scope of specification and patent application is defined as the absence of a substance, Except for the amount of impure substances, such as very small , Typical, in this embodiment, will be present in an amount of less than about 0. This composition is 01% by weight of the composition. The lubricating oil composition of the present invention may not contain isostearic acid or its derivatives. The present invention relates to a lubricating oil composition and lubricating fuel for a two-stroke engine. This lubricating oil composition for a two-stroke engine will contain a main weight-weight percentage of at least one lubricating viscosity oil and a small amount sufficient to control piston ring viscosity Scrap and reduce iron formation to improve general engine cleaning. Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. This oil composition and the method of the present invention are applied to a lubricating viscosity oil, including natural or synthetic lubricating oils and mixtures thereof. Natural turbidity contains animal oil, vegetable oil, mineral lubricating oil, soluble or acid-treated mineral oil, and oil derived from coal or shale. Synthetic lubricating oils include hydrogenated hydrogen oils, halogen-substituted hydrogenated hydrogenated oils, olefin gas polymer, esters of dicarboxylic acids and polyols, esters containing phosphoric acid, polytetrahydrofuran and silicon-based oils. Special examples of these lubricating viscosity oils are described in US Patent 4, 3 2 -4 8-81. 5. 20,000 (H) (please read the precautions on the back before filling in this page). This paper is used in the national standard (CNS) A4 specifications (210x297 gongs) V. Description of invention () A6 B6 Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 6 9 7 2 and European Patent 1 0 Description of lubricating viscosity oil as a reference to the description of viscosity oil 1 The article appears where it appears »tt LU b Γ i C a η” V 〇1 U me 4 3 9 th h V »1 9 8 7 0 Here, this is the reference of the present invention. —— * 兰兰 于 patent 4 t 5 8 2 6 1 8 ♦ line 6 3) > Here it is generally speaking > the composition of Runming of the present invention 9 which is sufficient to control the life promotion and general engine cleaning. Normal and (B)- Jhrf Μ ash dispersant mixed 30% 9 is preferably about 5% to the total weight 〇General and 1. > Phenolics (A) 0 • 0 5% • preferably about 1 3 0% f is better Is 2 0% > The amount of this lubricating oil composition exists in the present invention and is also used in other applications. 9 These additives include »Example inhibitor 9 pole JJit m pressure agent > Anti-wear No. 7, 282, here is the mole 5 $, a basic, brief description of lubrication, which was published by DV Brookt Engineering 1 84-1 85. The Marc article on lubricating viscosity oil appears as a slippery viscosity oil in the United States (Cabinet 2, Lines 37 to 3 are shown in the Lubricating Viscosity Oil as a reference. The sliding viscosity oil contains a large amount of viscosity of this hair plug ring. To reduce iron formation and properties, use (A)-the general manager It is about 0.1% to about 20% of the total amount of the lubricating oil composition and the dispersant (B) is an amount from%, more preferably about 2.5% to about more preferably about 15 % By weight 〇Additives combined with the composition of this invention, such as corrosion and gasification inhibitors, pour point damage, color stabilizers and anti-foaming agents 4 9- (please read the precautions on the back and then this page) ) This paper uses the Chinese standard (CNS) standard 4 (210x) 297 Gonglong) 81. 5. 20,000 (H) Coffee 06 'Λ6 B6 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () 〇 Extreme pressure agent and corrosive gas that can be used for the subsidy of the lubricant of the present invention Examples of chemical inhibitors include examples of chlorinated aliphatic hydrogen compounds, such as gasification pans and gasified aromatic compounds; organic sulfides and polysulfides; sulfurized alkylphenols; phosphorous sulfide sulfohydrogen compounds; phosphoric esters ; Mainly contains the phosphides of the second master hydrogen compound and the third master hydrogen compound, and the metal thiosulfonate. Many of the extreme pressure additives and corrosion-gasification inhibitors of the aforementioned auxiliary ribs can also be used as anti-wear agents, and dialkylphosphorodisulfate is a well-known example. Pour point dispersants are a particularly useful additive type and are often included in the lubricating oils described here. The use of these pour point dispersants in this oil-based composition improves the low temperature properties of this oil-based composition at This field is a common knowledge, reference, for example, "Lubr i cant Add i tives" page 8, by CV Smalheer and R. Kennedy Smit. H, (Lezius — Hi 1 es Co. Publishers, Cl eve 1 and, Ohio, 1967). Examples of useful pour point dispersants are poly-2-methacrylic acid esters; polyacrylic acid esters; polypropylene imines; concentrated products of halide worms and aromatic compounds; vinyl carboxylate polymers; and dialkyl fumars Acid salt, terpolymer of vinyl ester of fatty acid and alkyl vinyl ether. For the purpose of the present invention, pour point dispersants, techniques for preparing these dispersants and their use are described in US Patent 2, 3 8 7, 501; 2, 015, 7 4 8; 2, 6 5-5 0-(please Read the precautions on the back and then fill out this page) Pack ..... Available-line &r; r This paper size is common in S δ home standard (CNS) A 4 specifications (210x297 mm) 81. 5. 20.000 (H )

V. Description of the invention () Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5 i 4 7 9; 1 > 8 1 5 0 2 2; 2 > 1 9 1 »4 9 8 > 2 1 6 6 6 7 4 6 2 * 7 2 1 t 8 7 7 9 2 9 7 2 1 I 8 7 8 and 3 > 2 5 0 t 7 1 5 9 The relevant description is here taken as reference of the present invention 0 Anti-foaming agent Used to reduce or prevent the formation of stable foams. Typical anti-foaming agents include polysiloxanes or organic polymers. Other anti-foaming agent compositions are described in F 〇am C 〇η tr 〇1 A ge η t S 9P 1 by Η e η ty T * K e Γ η e Γ (N 〇ye SD ata C 〇Γ P 0 Γ at ί ο η f 1 9 7 6) »No. 1 2 5 — 1 6 2 Page 〇 Anti-wear and lubricity modifiers »Especially sulfurized spermacete oil derivatives and other fatty acids and vegetable oils» Like Μ sesame oil »is used in other situations like bb race and very high fuel / lubricating oil bb Case Next 〇Remove the bow or burn the deposition modifier is sometimes used to improve the life of the better Mars plug »and remove the large deposits 0 dentifying compounds and / or m-containing substances can also be used in this case. The composition of the present invention can be directly added to this lubricating oil. 9 However, 9 is preferably > they are diluted with-roughly neutral 9 normal organic diluent 9 like mineral oil naphtha benzene 9 toluene or xylene »to form Concentrate of an additive * This concentrate usually contains from about 30% to about 90% t of the weight of the composition of the present invention and in addition f may contain one or more other substances described in this field Additives in internal knowledge 0 The rest of the concentrate is roughly a neutral liquid diluent that is neutral to humans. ○ -51- (please read the precautions on the back before filling out this page) National Standard (CNS) 4 specifications (210X297 g) 81. 5. 20.000 (H) 5. Description of the invention () Because it is well known to those who are used to this technology, two-stroke engine lubricating oil is usually added directly to the fuel. A mixture of lubricating oil and fuel, which is then directly introduced into the engine cylinder, is included in the scope of the present invention. These lubricant-fuel mixtures typically contain about 10, preferably about 15, more preferably about 20 to about 100, and most preferably up to about 50 parts of fuel for each part of the lubricant. The fuel printed on the two-stroke engine by the Beigongxiaot Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is well known to those skilled in this technology, and usually contains a major portion of normal liquid fuel, such as petroleum sulfonate Distillate fuel (e.g. automotive gasoline as defined by ASTM specification D — 43 9 to 7.3. These fuels can also contain non-hydrogen compounds such as alcohols, ethers, organic-nitro compounds and the like, (e.g. : Methanol, ethanol, diethyl ether, methyl acetic acid, nitromethane) are also included in the scope of the present invention. Oils derived from vegetable or mineral sources, such as corn, a 1 afa, yan and coal, also contain Within the scope of the present invention. Examples of these fuel mixtures are combinations of gasoline and alcohols, diesel or ether, gasoline and nitromethane, etc. Particularly preferred is gasoline, ie, having an ASTM boiling point at 10% Distillate is 60C, 90% distillate is a mixture of sulfohydrogen compounds at 250C. The two-stroke fuel also contains other additives well known in the art, these may contain ethers, like ethyl-t -Butyl ether, methyl-t-butyl , And its analogues, alcohols, such as ethanol and methanol, lead cleaners, like ketone (such as: ethylene dichloride and ethylene dibromide), dyes, cetyl pentane to -52- 81. 5. 20,000 (H) (Please read the precautions on the back before writing this page) The size of this paper uses the Chinese National Standard (CNS) T4 specifications (210 father 297 male dragon) Λ 6 Β6 1 V. Description of invention () quality agent, Anti-gasification agent, like 2, 6-di-tert-butyl-4-methyl, raw 4 inhibitors, like alkylated succinic acid and anhydrides, bacteriostatic agent, glue inhibitor, metal deactivator, Buffers, lubricants for higher cylinders, anti-icing agents, and the like. The invention can be used for lead-free and lead-containing fuels. Concentrates containing the composition of the invention are also within the scope of the invention. The concentrate generally includes one or more of the above oils and about 50% to about 90% of the invention comprising (A) at least one phenol, (B)-ashless dispersant and optionally (C) a polyolefin mixture of the present invention Composition. The following example relates to the lubricating oil composition of the present invention, and the amount of the ingredient is a percentage by weight. The amount includes any diluent in the product. (Please read the precautions on the back before filling in this page) Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -53- 81. 5. 20,000 (Η) This paper size is used with ease ® National Standard (CNS) A 4 specifications (210x297 g; ii)

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Claims (1)

• Ί / a, A7 B7 C7 D7 »The Ministry of Economy ’s standard« ΛIndustry and Consumer Cooperation Du Printed VI. Patent application for Fan Garden 1. A lubricating oil composition for two-stroke engines, including at least 50% At least one lubricating viscosity oil, which at 4 ου temperature, does not have an oil with a viscosity greater than or equal to 100c St, a mixture sufficient to reduce or prevent piston wear, including from 0.05% to 3090 (A) At least one phenol selected from the reaction product of (A-1) -aminophenol and (A-2) -nitrophenol and an ammonia compound, wherein the aminophenol (A-1) is represented by the following formula: (〇H ) e (31),-AT-(HH,) b and wherein the nitrophenol is represented by the following formula:. (Strict): (H),-Ar-(NO mountain where each R is an independent representative A hydrocarbon group with 0 to 400 macro atoms; a, b and c are integers, respectively, 1 to 3 times the number of aromatic nuclei present in Ar, but the sum of a, b and c does not exceed Ar ’s Saturated valence; and each one of Ar · Chalid is an aromatic group, which is substituted by a substituent selected from the group consisting of 0 to 3, lower alkyl, alkane, nitro , Halogen, or both Or more compositions, and from 0.05% to 30% (B) at least one ashless dispersant, in which dispersant (please read the notes on the back before filling this page) 丨 装 _ Order · • Line · This paper scale is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) α A7 B7 C7 D7 ". Patent application Fanyuan (B) is a one-man period dispersant, a amine dispersant, one contains Nitrocarboxylic acid dispersant, or monoester dispersant, wherein the ashless dispersant contains a hydrocarbon group derived from a polyolefin having a number average molecular weight of from about 5,000 to about 1,500. 2. As The composition of patent application No. 1 item, wherein the phenol (A) is an aminophenol (A-1). 3. If the patent application is the first from at least one having a molecular weight from 50 〇4. If applying for a patent The naphthalene nucleus, benzene nucleus, or mixtures thereof. 5. If the composition of patent application item 1 is a, b, and c are 1. 6. If the composition of patent application item 1, Wherein the ammonia compound is a polyamine or a hydroxy monoamine. 7. If the composition of item χ of the patent scope is applied for, the splitting agent (B) is an amine dispersion prepared by reacting an amine and a polyolefin. The composition of item, wherein the composition of the dispersant item, wherein R is a polyolefin derived from 2 500 0 '. The composition of which. Ar is one (please read the precautions on the back before writing this page). I install and order. Line. The Ministry of Economy Central Standards Bureau employee consumer cooperative printed «8. If you apply for a patent model park No. 1 ( B) is a nitrogen-containing carboxylic acid dispersant, prepared from a substituted carboxylic acid awakening agent. 9. If applying for patent No. 8 polyamine, and the awakening agent is succinic acid 10. If the patent application, the first agent (B) is a Manley phase dispersion, which is composed of the reaction of an amine and a The hydrocarbon-based composition, wherein the amine is a hydroformylation agent. The composition of item 1, wherein the dispersion is based on the reaction of the substituted hydroxy group. The paper standard is applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) A7 B7 C7 D7 Cooperate with Du Printing. 6. It is obtained from the application of patented aromatic compounds, monoaldehyde and polyamine. 1 1 _ The composition as claimed in item i of the patent application, wherein the dispersing thin I (B) is a monoester dispersant, which is prepared by reacting a polyhydroxy compound and an acidulant with a selective monoamine . xl 2. The composition as claimed in item 1 of the defamation patent scope, which further includes: (C) up to 10 weight percent of polyolefin having a number average molecular weight from 400 to 250,000. 13. The composition as claimed in item i2 of the patent application, wherein the poly (C) has a number average molecular weight from 500 to 1,500. 14. The composition as described in item 12 of the patent application, where the polyolefin (C) is a polybutene. 15. The composition according to item 12 of the patent application scope, wherein the polyolefin (C) is present in an amount up to 3% by weight > 16. The composition according to item 1 of the patent application scope, wherein the composition contains Up to 3% by weight of light-colored high-viscosity lubricants. 17. The composition as claimed in item 1 of the patent scope, in which the composition does not contain light-colored high-viscosity lubricating oil. 18. The composition as claimed in item 1 of the patent scope, wherein the composition does not contain isostearic acid or its derivatives. 19. If the composition of item 1 of the patent application scope, it also includes at least one substantially neutral, normal organic liquid thinner with a replacement percentage of up to 25%. 2 0. —A type of lubricating oil composition for two-stroke engines, including: (Please read the precautions on the back before writing this page) i installed 'Order 丨 line · This paper standard is used in BB home «standard ( CNS) T 4 specifications (210 X 297 mm) 6. At least one lubricating viscosity oil with a patent scope greater than 5 Q96, which does not have oil having a viscosity greater than or equal to 100 cSt at a temperature of 4 Ot :, an amount sufficient to reduce or prevent piston wear, This mixed tree includes (A — 1) at least one aminophenol, which is represented by the following formula: < Please read the note on the back ^ item before filling out this page) Install. 0Ξ Where R is a hydrocarbon group with an average of 30 to 400 aliphatic monatoms; R 'is a group selected from the group consisting of: lower alkyl, lower alkoxy, nitro , And halogen; and z is 0 or 1, and (B) at least one ashless dispersant, wherein the ashless dispersant (B) is a Manley phase splitter, an amine dispersant, a nitrogen-containing carboxylic acid A dispersant, or a monoester dispersant, wherein the ashless dispersant contains two hydrocarbon groups derived from a polyolefin having a number average molecular weight from 50,000 to 1500. 21. The composition of claim 20, wherein R is a hydrocarbon group derived from a polyolefin having a number average molecular weight of from 500 to 2500. 2 2. The composition as claimed in item 21 of the patent scope, wherein the polyolefin has a number average molecular weight of from 600 to 1500. The size of this paper is in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297 mm). · T «Jibu Central Standards R R & C Cooperative Printed by A7 B7 C7 D7 βJibu Central Prototype House ΛGong Consumer Cooperative印 六. Applying for a patent fan garden 23. If the composition of item 20 of the patent application is applied, where z is 0 〇24. If the composition of item 20 of the patent application is applied, the ashless dispersant (B) It is a cyanic acid-containing carboxylic acid dispersion, which is prepared from a carboxylic acid acylating agent substituted with an amine and a hydrocarbon group. 25. The composition as claimed in item 24 of the patent scope, wherein the amine is a polyamine and the sulfonamide is a succinic acid awakening agent. 26. If the composition claimed in item 20 of the patent scope, it further contains at least one substantially neutral, normal liquid plaque organic diluent up to a replacement percentage of 25%. 27. The composition as claimed in item 20 of the patent specification, which further contains polyolefin with a number average molecular weight of 500 to 1500, with t (C) as high as about 1% by weight. 28. The composition as claimed in item 20 of the patent scope, wherein the composition contains up to 3 percent replacement light oil with high viscosity and high viscosity. 29. The composition as claimed in item 20 of the patent scope, in which the composition does not contain light-colored high-viscosity lubricating oil. 30. The composition as claimed in item 20 of the patent scope, wherein the composition does not contain isostearic acid or its derivatives. 3 1.-Lubricant-fuel composition, for each application, the lubricating oil in item 1 of the patent scope contains from 10 to 200 parts of at least one fuel. (Please read the precautions on the back before filling in this page) -Installation_ Order.: 皋-This paper size is applicable to the BS family standard (CNS) A 4 specifications (210 X 297 mm). Six, apply for patent Fan Garden A7 B7 C7 D7 Please go to Shen's part ο one ο every 2 to the right ο, 1 thing from the combined package, the material is oil-smooth-the oil-smooth item is moisturized 2 1 1. 第 o '2 Enclosure 3 Fan Shuangli has a few special skills, the combination of operation methods and combination of oil-damaged slippery lubricating oil-engine material ignition process line item 2 1 prevention 3 pre-registration or surrounding low fan down special types. Shen〇3 as engine 3 To cite this package, the combination of the operation method and the combination of damage to the oil mill sliding plug Run I Li material, the ignition line line 2 2 prevention 3 pre-regulation or surrounding low-range descending species are specific. 申 〇4 Ruqing 3 To quote the package (please read the precautions on the back before filling in this page) --installation. Order. --Line · * Zhangshi " printed by the Ministry of Economic Affairs of the Ministry of Economic Affairs of the Ministry of Economics and Trade Co., Ltd. 4 now) 5 NC / V Standard I Home Country I Middle Use »Male 7 9 2 X 10