JPH03237195A - Additive for oil and oil containing the additive - Google Patents

Abstract

PURPOSE:To provide a new oil additive containing a compound having an atomic group containing CN double bond and bonded to the molecular chain, imparting fuel oils and lubrication oils with excellent low-temperature fluidity and clean dispersibility and effective in improving the viscosity index. CONSTITUTION:The objective additive contains a compound having the atomic group containing the bond of formula and bonded to the molecular chain (e.g. a polymer having a heterocyclic structure introduced into the molecular chain using a compound having unsaturated bond, a polymer. containing oxazinium salt or oxazolium salt monomer unit in the molecular chain or a polymer produced by reacting an organic compound with a polymer having an alkali or alkaline-earth metal bonded thereto and containing said bond on the molecular chain terminal or in the molecular chain).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel oil additive suitable for fuel oils and lubricating oils, and to oils to which this additive is added.

(Prior Art) Fuel oil and lubricating oil are required to have many functions and characteristics depending on their use. In order to meet these demands, it is necessary to add various additives to the base oil of fuel oils and lubricating oils to improve the properties of the base oil or to impart functions to the base oil.

For example, fuel oils such as light oil and A heavy oil contain n-paraffin wax, so in cold winter regions, this n-paraffin wax often precipitates, causing blockage of oil pipes and damage to internal combustion engines. This causes major problems in the fluidity of fuel oil at low temperatures, such as clogging of the strainer installed in the fuel supply circuit.

To solve this problem, additives commonly called cold flow improvers are used. Various types of low-temperature fluidity improvers have been studied and proposed, including ethylene-vinyl acetate copolymers.

For example, the copolymer of ethylenically unsaturated dicarboxylic acid and α-olefin described in JP-A-54-157106, and the copolymer of ethylenically unsaturated dicarboxylic acid and α-olefin described in JP-B-50-15005. Known are long-chain alcohol esters of polymers, and aliphatic amine-modified copolymers of ethylenically unsaturated dicarboxylic acids and α-olefins as described in JP-A-5481307. However, the effects of adding these substances are still far from being sufficient.

In addition, requirements for fuel oil such as gasoline have become increasingly sophisticated as the performance of internal combustion engines for automobiles and the like has improved. One example of these is polybutenyl succinic anhydride, polyamine polybutenyl succinimide, barium polybutenyl (thio)phosphonate, etc., which are used as cleaning dispersants and sludge dispersants for the purpose of cleaning fuel systems. However, there is a problem that these additives are ineffective unless used in large amounts.

Lubricating oils, such as gear case oils for internal combustion engines, contain polyisobutyne, polymethacrylate, polyalkylstyrene, partially hydrogenated butadiene-styrene copolymers, or amorphous ethylene-propylene copolymers to increase the viscosity index of the oil. Polymeric substances act as viscosity index improvers, and polyvalent metal sulfonates, organic phosphoric acids, etc. are used as cleaning agents to disperse sludge generated in the oil and keep the inside of the gear case clean. as polybutenyl succinate,
Polybutenyl succinate etc. are added as a dispersant.

Incidentally, recently, (co)polymers and graft polymers of maleimide, vinylimidacillin, vinylpyrrolidine, vinylpyridine, etc., have been proposed as additives that simultaneously improve the viscosity index and disperse sludge. However, it also has other properties, such as acting as an oxidative deterioration inhibitor to impart thermal stability to the oil and stabilizing metals in the sludge (which promote oxidative deterioration of the oil). There is a need for multifunctional additives that have the following properties.

(Intelligence to be Solved by the Invention) In view of the above background, the present invention, etc. has been developed as a result of intensive research to develop new additives for oil, especially additives for fuel oil and lubricating oil. It was discovered that this functional compound is effective as a multifunctional additive for both fuel oil and lubricating oil, and the present invention was completed.

(Means for Solving the Problem) Φ According to the present invention, there is provided an oil additive characterized in that it contains a compound in which an atomic group having/having a C=N bond is bonded to a molecular chain, and the above-mentioned compound. Provided with added oil.

The configuration of the present invention will be explained below.

(Additive) The additive of the present invention is a compound in which an atomic group having the bond is bonded to a molecular chain. The bond may or may not be present in a heterocyclic structure.

The compound present in the bond or heterocyclic structure can be formed by (1) using a compound having at least one unsaturated bond in the molecule to form an atomic group ( Heterocyclic structure) (Ia) to (IVb) (1a) (Ib) (Ila) (IIb) (I[Ia) (IIIb) R2 (IVa) 2 (IVb) (R, -R, in the formula They may be the same or different and represent a hydrocarbon group.R and -R3 are at least partially substituted with a substituent such as a halogen atom, nitro group, epoxy group, carboxyl group, hydroxyether group, or phenyl group. ) introduced into the molecular chain (compound A
), (2) The following general formula (V) (Vl
) A polymer having an oxazinium salt or oxacillium salt monomer fAfL (compound B).

8 (V) Oxazinium salt (VJ) Oxacillium salt (
In the formula, R4 to R8 represent hydrogen or a hydrocarbon group. ) (3) A polymer (compound) having the bond at the end or in the molecular chain obtained by reacting a polymer to which an alkali metal or alkaline earth metal is bonded, such as a living anionic polymer, with a specific organic compound. C) etc. are included.

(1) The additive containing the compound A having a specific heterocyclic structure of the present invention has carbon-carbon atoms such as carbon-carbon double bonds or triple bonds at the end of the molecular chain or in the molecular chain. It can be produced using a compound having a carbon unsaturated bond as a raw material.

As a raw material compound having an unsaturated bond at the end of the molecular chain,
For example, α-olefins having long chain alkyl groups such as 1-decene, l-dodecene, 1-tetradecene, 1-hexadecene, l-eicosene, 1-tridecene; low molecular weight polyethylene, liquid or low molecular weight polypropylene, α - Low molecular weight polymers or oligomers such as oligomers of olefins; polymers such as polybutene, polyisobutylene, polyethylene glycol dimethacrylate, polyethylene glycol diarylate, polypropylene glycol diarylate, polypropylene glycol dimethacrylate, polystyrene methacrylate, polystyrene allylad, etc. can be mentioned.

Examples of raw material compounds having unsaturated bonds in branch chains other than those mentioned above include 1.9-decadiene, 2,3-dimethylbutene, 2,5-hexadiene, 7-tetradecene, tricosene, 2.4.4- ) organic compounds having -C=C- bonds such as trimethyl-2-pentene, and also polymers of butadiene, isoprene, piperylene, dicyclopentadiene, ethylidenenorbornene or the monomers mentioned above and vinyl monomers, such as styrene, acrylonitrile,
Examples include unsaturated polymers such as copolymers with (meth)acrylate and the like. Examples of copolymers include styrene-
Butadiene random copolymer, styrene-isoprene random copolymer, acrylonitrile-isoprene copolymer, styrene-butadiene block copolymer (A-B type, A-B-A type, B-A-B type, etc.) ), styrene-isoprene block copolymer (same as left, A indicates polystyrene block, B indicates polybutadiene block or polyisoprene block), acrylonitrile-butadiene copolymer, butadiene-methyl methacrylate copolymer, partial hydrogen thereof and ethylene-propylene-diene monomer copolymers.

Examples of compounds having a -CmiC- bond include organic compounds such as 1-dicine, 3,3-dimethyl-1-butyine, heveine, hexine, 1,8-nonadiine, and octiine.

The compound that can be used as a raw material in the present invention may be any compound having a carbon-carbon unsaturated bond in its molecular chain, and there is no particular restriction on the molecular weight, and it may range from low-molecular organic compounds, oligomers to high-molecular weight solid polymers. (For example, high molecular weight polymers having a molecular weight of about several hundred thousand).

The method for producing the compound A having a heterocyclic structure of the present invention is not particularly limited, but some typical production methods are described below.

(i) The compound having the carbon-carbon unsaturated bond at the end of the molecular chain or in the molecular chain disclosed in JP-A No. 61-225202 is treated with the general formula Rq-CH in the presence of a Lewis acid.
There is a method of reacting an organic compound (I) represented by =N-R,o (in the formula, Rq, R, represents an organic atomic group) with an organic halide.

Examples of the organic compound (1) include benzylideneaniline and benzylidenebutylamine, and examples of the organic acid nolide include acetyl chloride and benzoyl chloride.

Lewis acids include BF3, BF30(C,H3),
AlC1,,TtC/! , ,5nCI! a, 5
Examples include bC13 and AgBF4.

Reaction conditions are not particularly limited, but usually benzene,
In an inert solvent such as toluene or cyclohexane, 20 to 8
React at 0°C for about 1 to 2 hours. Organic compound (1
) and the organic acid halide are usually about 1 to 1.5 mol per mol of the unsaturated compound, and the Lewis acid is about 0.1 to 1 mol per mol of the organic acid halide. When the unsaturated compound is a polymer, the amount of organic compound (1) and organic acid halide used is 0 per 100 parts by weight of the polymer.
．． It is about 1 to 30 parts by weight (for details, see Japanese Patent Application Laid-open No. 61225
(See Publication No. 202).

(ii) The above-mentioned compound having a carbon-carbon unsaturated bond is reacted with an N-hydroxymethyl acetate compound (N-methylol compound) in the presence of a free sol Tarafluorocatalyst, and if necessary, an alkyl halide or p -There is a method of reacting with methyl toluenesulfonate or the like to achieve N-alkylation.

An N-hydroxymethylaldehyde compound is a reaction product of an amide compound and an aldehyde compound. As the aldehyde compound, aliphatic and aromatic aldehydes such as formalin, butyroaldehyde, valeraldehyde, and benzaldehyde are used. Examples of the amide compound include acetamide, benzamide, methoxybenzamide, nitrobenzamide, N-methylbenzamide, butyroagodo, phthalamic acid, glutaric acid amide, and the like.

A copolymer containing N-methylolacrylamide monomer as one component can also be used as the N-hydromexymethylamide compound.

Examples of alkyl halides include benzyl bromide, benzyl chloride, bromohexane, bromopropane,
-Chloroethyl ether, chloromethyl ether, chloropentane, etc. are mainly used.

As the free sol cod fluorine catalyst, commonly known ones can be used. Typical examples thereof are metal or metalloid halides, such as B, Af,
5iSP, Ti, V, Fe, Zn, Mo, S
n.

Elements such as Sb, Te, W, or po, so□,
These include halides of oxygen-element bonds such as vo, organic halides, and complexes thereof.

More specifically, BF3, BhO(CJs)z, B
CI! 3, AlIC1,y, TiCfa, 5nCj
! , ,FeC15,WCfi,POCf,(CzH
s) zA j2, etc.

The reaction conditions are not particularly limited (details of this reaction can be found, for example, in the 5YNTFIESIS of C. Giordano et al.
, 92 (1971)).

(iii) After reacting the unsaturated bond with nitrile oxide, nitrile imine, or nitrile ylide, which is known as a 1.3-dipole addition reaction, to the above-mentioned compound having a carbon-carbon unsaturated bond, alkyl halide or There is a method of reacting with dimethyl sulfate or the like to achieve N-alkylation.

1. For the 3-dipole addition reaction, see Huisgen, Anges, Chevs, 'i5.604 (163
) details are published in the paper.

Regarding the introduction reaction of isoxazoline ring with nitroxide, see the literature of Kyokuni, Numata et al. (Japan Rubber Association Journal,
43, 996 (170)) ni tsuka ivy.

(1v) The above compound having a carbon-carbon unsaturated bond is reacted with a halohydroxy compound in the presence of an HCI removing agent such as anhydrous sodium carbonate. If necessary, a method of further reacting with an alkyl halide, dimethyl sulfate, etc. to achieve N-methylation. Halohydroxyimino compounds are T, L, J, C, S of Christ et al.
Cheap, Commun, 1090 (1979
), or by reacting hydroxylamine hydrochloride with the α-haloaceto compound described in A, 0g1
J, Org, Chem, U, S, of oblin et al.
S, R, ±1370 (1965).

The synthesis of an oxazine compound by the reaction of an olefin and a halohydroxyimino compound shown in the synthesis example is T, L, 1
J, Chem, Soc, Per of i1christ et al.
Kin Trans.

1, 1275 (1983).

The synthesis of other oxazine compounds is described by H, E. Zaugg et al., 5ynthesis, 85 (1984), 5yn.
thesis, 182 (1984), 5ynthes
IS, 49 (1970), the other examples given in the example of the precepts followed this.

(2) The additive containing compound B having a specific heterocyclic structure of the present invention is produced by the following method.

(i) A polymerizable monomer having an oxazinium ion or an oxacillium ion in its molecule is polymerized alone or together with other polymerizable monomers.

Examples of the polymerizable monomer having an oxazinium ion in the molecule include 2-vinyl-2-oxazinium ion, 2-
vinyl-4-methyl-2-oxazinium ion, 2-
vinyl-4-ethyl-2-oxazinium ion, 2-
isopropenyl-2-oxazinium ion, 2-isopropenyl-4-methyl-2-oxazinium ion,
2-isopropenyl-4-ethyl-2-oxazinium ion, 2-isopropenyl-4,5-dimethyl-2-
Examples include oxazinium ion. The counter anion is not particularly limited, but one that stabilizes the salt is preferred.

Examples of polymerizable monomers having oxacillium ions in the molecule include 2-vinyl-2-oxaturium ions, 2-
Vinyl-4-methyl-2-oxacillium ion, 2-
Vinyl-4-ethyl-2oxacillium ion, 2-isopropenyl-2-oxacillium ion, 2-impropenyl-4-methyl-2-oxacillium ion, 2
Examples include isopropenyl-4-elti-2-oxacillium ion, 2-isopropenyl-4,5-dimethyl-2-oxacillium ion, and the like. Although the counter anion is not particularly limited, it is preferable to stabilize the salt.

Monomers used as necessary with these monomers are not particularly limited as long as they can be copolymerized, such as styrene monomers such as styrene, p-methylstyrene, and p-methoxystyrene; acrylic acid Acrylic acid or methacrylic acid monomers such as , methyl acrylate, butyl acrylate, stearyl acrylate, methacrylic acid, methyl methacrylate; ethylene, propylene, vinyl chloride, vinyl acetate, acryl oxide, acrylonitrile, N-vinyl Examples include pyrrolidone, and one or more of these may be used.

In particular, higher alcohol ester monomers such as ethylene, acrylic acid, and methacrylic acid are preferred because they are easily soluble in the base oil.

In the case of copolymerization, the amount of the monomer having the above-mentioned ion in the molecule is in the range of 0.01 to 10% by weight based on the total monomer mixture. If the amount is less than 0.01% by weight, the effect of the additive will not be sufficient, and if it is used in excess of 10% by weight, the effect will be saturated. Preferably it is 0.1 to 5% by weight.

As the polymerization initiator used for polymerization, commonly used oil-soluble peroxide-based or azo-based initiators can be used.

For example, peroxide initiators such as benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,2゛-azobisisobutyronitrile, 2,2゛-Azobis-(2,4-dimethylvaleronitrile), 2.2'-azobis-2,2,3-)limethylputyronitrile, 1.1'-azobis-(cyclohexane-1-carbonitrile) , 4.4'-3azobis-
There are peroxide-based initiators such as 4-cyanovaleric acid and dimethyl-2,2'-azobisisobutyrate. The polymerization initiator is preferably used in an amount of 0.05 to 10% by weight based on the polymerizable monomer.

Examples of the polymerization solvent include acetonitrile, nitromethane, toluene, benzene, and xylene, which may be used alone or in combination. Polymerization temperature is usually -20°
It is carried out at a temperature of C to 150°C, preferably 0°C to 120°C.

In addition to the radical polymerization described above, the polymer can also be produced by anionic polymerization using an anionic polymerization catalyst such as organolithium. Anionic polymerization can also be carried out using conventional methods.
There are no particular restrictions.

(11) In a polymer of a polymerizable monomer having an oxazine group or an oxazoline group in the molecule, the nitrogen atom of the group is
A polymer containing oxane ions or oxacillium ions can be obtained by ammonium-forming.

Examples of monomers having an oxazine group in the molecule include 2-vinyl-2-oxazine, 2-isopropenyl-2-oxazine, 2-vinyl-4-methyl 2-oxazine, and 2-isopropenyl-4-methyl-2 -Oxazine and the like.

Examples of monomers having an oxazoline group in the molecule include 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, and 2-isopropenyl-4-methyl-2 -oxazoline and the like.

The monomers copolymerizable with these monomers and the polymerization method are the same as in the case of (i) above.

A method for converting the nitrogen atom of the group in the polymer into a quaternary ammonium is alkylation using an N-alkylating agent.

Examples of the N-alkylating agent include methyl tosylate, alkyl halide, dimethyl sulfate, and the like.

The alkylation reaction may be carried out according to a conventional method and is not particularly limited. The content of ionized monomeric units within the polymer or copolymer ranges from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight.

In addition to the above (i) and (ii), methods for producing oxacillium ion-containing polymers include 2-oxazoline, 2-methyl-2-oxazoline, 5-methyl-2
- A method of cationically polymerizing 2-oxazolines such as oxazoline and terminating the polymerization reaction with a nucleophilic solvent to obtain a polymer in which oxacillium ions are bonded to the end of the polymer chain; a halogen atom is used as a cationic polymerization catalyst. ,
There is also a method of polymerizing 2-oxazolines using a polymer having a proton-donating group such as a sulfoxyl group.

(3) The additive containing the compound C of the present invention is a polymer to which alkali metals and/or alkaline earth metals are bonded, that is, living anionic polymers, or alkali metals and/or alkaline earth metals are bonded by post-reaction. The added polymer is reacted with a bond represented by the general formula -C-N (where X is oxygen or 1 o)aldehyde, N-substituted amino(thio)ketone, etc., and the reaction product is hydrolyzed. (For details, see JP-A-58-162604 and JP-A-60-137913).

The anionic polymer used in this method is obtained by polymerizing monomers that can be polymerized with an anionic polymerization catalyst such as an alkali metal and/or alkaline earth metal-based catalyst, and the above-mentioned metal is present at at least one end of the molecular chain. Combined polymer (
(including oligomers to high molecular weight polymers), and
Polymers (including oligomers and high molecular weight polymers) to which the metals have been added through post-reactions (addition reactions) are produced by adding the metals to polymers having double bonds in their molecular chains using known methods. can do.

Monomers that can be polymerized with an anionic polymerization catalyst include 1
．． Conjugated dienes such as 3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene (sulfur atom) N-substituted amino compounds, aromatic vinyl compounds such as divinylbenzene, trivinylbenzene, and divinylnaphthalene, unsaturated nitriles such as acrylonitrile, esters of (meth)acrylic acid, and vinylpyridine. It is not limited to.

As the polymer, these polymers and copolymers are used, and specifically, polybutadiene rubber, polyisoprene rubber, butadiene-isoprene random and block copolymers, butadiene-styrene random copolymers, Butadiene-styrene block copolymer (A-B type, A-
B-A type etc.

A and B are the same as above), isoprene-styrene block copolymer (same as above), and the like.

Polymers (including oligomers to high molecular weight polymers) used to add the metal by addition reaction can be polymerized using the aforementioned metal-based catalyst, solution polymerization using a Ziegler catalyst, etc., or polymerization using a redox type catalyst, etc. Diene-based polymers obtained by polymerizing or copolymerizing the above-mentioned conjugated diene monomers or conjugated diene monomers and monomers copolymerizable therewith by a normal polymerization method such as emulsion polymerization, specifically polybutadiene, polyisoprene, Butadiene-styrene random and block copolymers, isoprene-styrene random and block copolymers, butadiene-isoprene random and block copolymers, polypentadiene, butadiene-piperylene copolymers, butadiene-propylene alternating copolymers, ethylene -propylene-diene monomer copolymer and the like.

The metal-based polymerization catalyst used in the polymerization and addition reaction is not particularly limited, and any catalyst conventionally used in anionic polymerization can be used.

As the alkali metal-based catalyst, n-butyllithium, 5
Representative examples include organic lithium compounds having 2 to 20 carbon atoms such as ec-butyllithium.

As an alkaline earth metal-based catalyst, JP-A-51-115
Publication No. 590, JP-A-52-9090, 17591
, 30543, 48910°98077, JP-A-56-112916, . Examples include, but are not limited to, catalyst systems containing compounds such as barium, strontium, and calcium as main components disclosed in Japanese Patent Application Laid-open No. 118403 and Japanese Patent Application Laid-open No. 57-100146. The polymerization reaction and the alkali metal and/or alkaline earth metal addition reaction are carried out using hydrocarbon agents conventionally used in anionic polymerization, such as tetrahydrofuran, tetrahydrobilane,
It is carried out in a solvent that does not destroy the metal-based catalyst, such as dioxane.

The amount of the metal-based catalyst used for producing high molecular weight polymers from oligomers is usually 0.1 to 100 g of monomer.
It is in the range of 200 mmol. In the addition reaction, the amount of the metal to be added varies depending on the amount of the metal to be added, but it is usually about 0.1 to 10 mmol per 100 g of the polymer.

Polymerization is usually carried out in the presence of polar compounds such as ether compounds, amine compounds, phosphine compounds, etc. as randomizers and vinylizing agents. Polar compounds are also commonly used in addition reactions.

The conditions for polymerization and addition reaction are not particularly limited as long as they follow the conditions of these conventional methods.

The living anionic polymer obtained by the above method and the organic compound to be reacted with the metal-added polymer are as follows.

) as a compound having an atomic group represented by N
-Methyl-β-propiolactam, N-butyl-β
-Propiolactam, N-phenyl-β-propiolactam, N-methoxyphenyl β-propiolactam, N
-naphthyl-β-propiolactam, N-methyl-2-
Pyrrolidone, N-t-butyl-2-pyrrolidone, N-phenylpyrrolidone, N-methoxyphenyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-benzyl-2
-pyrrolidone, N-naphthyl-2-pyrrolidone, N-methyl-5-methyl-2-pyrrolidone, N-t-butyl-
5-methyl-2-pyrrolidone, N-phenyl-5-methyl-2-pyrrolidone, N-methyl-3,3-dimethyl-
2-pyrrolidone, Nt-butyl-3,3-dimethyl-
2-pyrrolidone, N-phenyl-3,3°-dimethyl-
2-pyrrolidone, N-methyl-2-piperidone, N-t
-Butyl-2-piperidone, N-phenyl-2-piperidone, N-methoxyphenyl-2-piperidone, N-vinyl-2-piperidone, N-benzine-2-piperidone, N-naphthyl-2-piperidone, N- Methyl-3,3
゛-Dimethyl-2-piperidone, N-phenyl-3,3
゛-Dimethyl-2-piperidone, N-methyl-ε-captractam, N-phenyl-ε-captractam, N-methoxyphenyl-ε-captractam, N-vinyl-ε-
captolactam, N-benzyl-ε-captolactam,
N-naphthyl-ε-captractam, N-methyl-ω-
N-substituted such as laurirolactam, N-phenyl-ω-laurirolactam, N-t-butyl-ω-laurirolactam, N-vinyl-ω-laurirolactam, N-benzyl-ω-laurirolactam, etc. Lactams and their corresponding thiolactams: 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone,
1-methyl-3-ethyl-2-imidazolidinone, 1,
3-dimethylethyleneurea, 1,3-diphenylethyleneurea, 1,3-di-t-7'thylethyleneurea, 1.
Examples include N-1F substituted cyclic ureas such as 3-divinylethylene urea and corresponding N-substituted cyclic thioureas.

In addition, other organic compounds include 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4-dimethylaminobenzophenone, and 4-dimethylaminobenzophenone.
-di-t-butylaminobenzophenone, 4-diphenylbenzophenone, 4,4'-bis(dimethylamino)
Benzophenone, 4.4'-bis(diethylamino)benzophenone, 4.4"-bis(di-t-butylamino)benzophenone, 4.4"-bis(diphenylaξ)
) Benzophenone, 4,4'-bis(divinylamino)
Benzophenone, 4-dimethylaminoacetophenone,
N-substituted aminoketones such as 4-diethylaminoacetophenone, 1,3-bis(diphenylamino)-2-propanone, 7-bis(methylethylamino)-4-heptanone and the corresponding N-IF-converted ξ-nothioketones Kind:
N-7-substituted aminoaldehydes such as 4-dimethylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-divinylaminobenzaldehyde and the corresponding N
-substituted aminothioaldehydes.

The amount of these organic compounds used is usually 0.05 to 10 mol per mol of the metal bonded to the polymer. The reaction between a living anionic polymer, etc. and an organic compound is carried out in a solution of a solvent that dissolves both, but since the reaction occurs rapidly, the reaction temperature and reaction time can be selected within a wide range.
- For boat fishing, the temperature ranges from room temperature to 100°C for several seconds to several hours. After the reaction is completed, the reaction product is hydrolyzed, for example, by adding alcohol such as methanol or isopropyl alcohol to the reaction mixture as a coagulant, or by subjecting the reaction mixture to steam stripping, etc.
; The additive of the present invention is obtained in which an atomic group having a c=Ng bond is bonded.

The following is an example of the reaction between an anionic polymer having a Li-terminated terminal and 4,4'-bis(dimethylamino)-benzophenone as an organic compound.

〜Polymer chain twisting regret ℃, so itjy) Counterfeit money 09 reference) 9 The additives obtained by the methods (1) and (2) explained above are fuel oil, that is, at 40 to 500℃. Petroleum middle distillate fuel oils with boiling points in the range (e.g. gasoline, diesel oil, kerosene,
It is used as an additive in diesel fuel oil, jet fuel oil, A heavy oil, etc.) and lubricating oils.

When used as an additive for fuel oil, it functions as a dispersant and a low-temperature fluidity modifier (pour point depressant). It is only necessary to select a compound or a combination of compounds that maximizes the function of the compound, and there are no particular restrictions on the type of compound. Likewise, there are no restrictions on the molecular weight, and it includes everything from low-molecular organic compounds to high-molecular weight polymers. .

The number of heterocycles containing the bond or the number of bonds in the additive varies depending on the molecular weight of the additive, but is usually (weight average molecular weight)/(number of the heterocycle or bond per molecule). is preferably 200,000 or less, more preferably 100,000 or less, more preferably 100,000
It is as follows. However, when i,ooo or less, the effect becomes saturated.

The amount of this additive added is usually o, ooi% by weight or more, preferably 0.01 to 5% by weight, more preferably 0.01 to IIrf%, based on the fuel oil.

This additive can be used in combination with other additives, such as antioxidants, combustion improvers, antifogging agents, antiknock agents, colorants, ash modifiers, surfactant type additives, and the like.

In addition, when adding the dispersant-cold flow modifier of the present invention to fuel oil, a diluting solvent such as kerosene,
It can be dissolved in a light lubricating base material, heavy aromatic naphtha, etc. and then mixed into the fuel oil.

When the additive of the present invention is used as an additive for lubricant oil, it exhibits multiple functions such as a viscosity index improver, a low-temperature fluidity modifier (pour point depressant), a detergent dispersant, and an antioxidant. Ru.

Lubricating oils include various lubricating oils based on mineral oils and synthetic groups (α-olefins, esters), such as engine oils (for gasoline and diesel), gear oils, turbine oils, hydraulic oils, and rubber compounded oils. (process oil) and waxes.

The additive of the present invention may be selected from compounds soluble in lubricating oil, or a combination of compounds that maximizes the above functions, and the type of compound is not particularly limited. There is no restriction, and it includes from low molecular weight organic compounds to high molecular weight polymers.

The additive of the present invention is usually 0.00% relative to lubricating oil (base oil).
It is added in an amount of 1% by weight or more, preferably 0.001 to 30% by weight, more preferably 0.01 to 20% by weight.

The additive of the present invention can be used in combination with other additives, such as antifoaming agents, corrosion inhibitors, extreme pressure agents, oiliness improvers, and the like.

(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and percentages in Examples and Comparative Examples are based on weight unless otherwise specified.

The low temperature fluidity of petroleum middle distillate fuel oil is JIS K-220.
4 pour point and JIS K-2288 clogging point (C
FPP) was used. In addition, the evaluation of cleanliness and dispersibility is based on JIS K.
The adhesion state of the lacquer to the varnish rod was evaluated according to the lubricating oil oxidation stability test of No.-2514.

Additive production example 1 100g of each polymer shown in Table 1 was mixed with benzene 500111.
in a vessel equipped with a stirrer, an internal heating device, a vapor condenser and a liquid-solid feed inlet, and heated to 60° C. with stirring. Reagent A and Reagent B shown in Table 1
0.1 mol of each were added and reacted for about 1 hour (in some cases, 0.15 mol of reagent C was added). Then, a small amount of methanol was added to stop the reaction, and 1j
! The reaction mixture was poured into methanol to solidify the product.

The obtained product was dried in a vacuum dryer. The obtained additives are referred to as Additives I to ①.

Additive production example 2 Contents a2j! After cleaning and drying the stainless steel polymerization reactor and purging it with dry nitrogen, 150 g of 1,3-butadiene was added.
, 50 g of styrene and 820 g of benzene.

0.5 mmol of tetramethylethylenediamine and 1.8-5 mmol of n-butyllithium (n-hexane solution) were added, and polymerization was carried out at 40° C. for 1 hour while stirring the contents.

After the polymerization reaction was completed, 1.0 mmol of N-methylpyrrolidone was added and reacted for 10 minutes with stirring.

Then 2.6-di-t-butyl-p-cresol2.
The contents of the reactor were poured into a 0% methanol solution to solidify the resulting polymer, which was then dried under reduced pressure at 60° C. for 24 hours. This polymer is referred to as additive (2).

Further, a polymer was produced under the same conditions as above except that N-methylpyrrolidone was not reacted. Add this as an additive■(*)
shall be.

Additives IV and IV (*) have a bound styrene content of 25%, GP
The weight average molecular weight in terms of polystyrene measured at C is 15
It was 10,000.

Additive Production Example 3 1 mol each of α-olefin or polybutene shown in Table 2 and 300 mf of benzene were mixed with a stirrer, an internal heating device,
It was placed in a vessel equipped with a vapor condenser, and a liquid-solid feed inlet.

Add 1 mol each of Reagent A and Reagent B shown in Table 2,
The reaction was carried out at 5°C for about 1 hour. Methanol was added to stop the reaction. Furthermore, 0.5 to 1 l of methanol was added, and the mixture was cooled in a refrigerator, and the resulting precipitate was washed with methanol and dried to obtain the desired additive. These are referred to as additives V to ■. Also, α in Table 2 which is a reaction starting material
- Additives V (*) to ■ (*) for olefins and polybutenes
shall be.

Additive production example 4 Ethylene-propylene-diene copolymer (Mitsui Petrochemical Co., Ltd. X-4010, Ml, t, , 100°C = 10
) and 31 g of benzene were placed in a vessel equipped with a stirrer, an internal heating device, a vapor condenser, and a liquid-solids feed inlet. 20 mmol of benzylidene butyl chloride, 20 mmol of acetyl chloride, and 20 mmol of acetyl chloride were added as benzene solutions, and the reaction was carried out at 45° C. for about 1 hour. Methanol was added to stop the reaction.

Further, 0.5 to 11 methanol was added, cooled in a refrigerator, and the resulting precipitate was washed with methanol and dried to obtain the desired additive. This is called additive (■). Also, the starting material is an additive (*).

Additive Production Example 5 3 parts of N-methyl-isopropenyloxacillium tosylate and 97 parts of methacrylic acid stearate were dissolved in 250 parts of toluene in a flask equipped with a stirrer, N2 gas introduction tube, reflux condenser and thermometer. 10 parts of benzono(-oxide) was added.N2 gas was blown in and the mixture was heated to 80-100°C, and polymerization was carried out for 5 hours while stirring in this state.The mixture was returned to room temperature and the solvent was removed by evaporation. Thereafter, the mixture was poured into 500 parts of methanol, coagulated, and dried to obtain a polymer having an oxacillium ion structure as a functional group.This polymer was designated as Additive X.

When the resulting polymer was partially dissolved in chloroform and the UV-visible spectrum of the polymer component was measured using GPC connected to a UV-visible multi-wavelength spectrometer (MULTI-330 manufactured by JASCO Corporation), UVmax was −310 parts m. Absorption that was attributed to oxacillium was obtained.

It was confirmed that the obtained polymer contained an oxacillium ion structure.

300 parts of benzene was dissolved in 100 parts of the similarly obtained clay tyrene/vinyl oxazoline (97 parts by weight) copolymer, 5 parts of methyl chloride and 1 part of sodium iodide were added, and the mixture was reacted under reflux for 12 hours. I let it happen. The obtained reaction solution was poured into 1,000 parts of methanol, reprecipitated, and then dried.

A portion of the obtained polymer was dissolved in chloroform, and a UV/visible multi-wavelength spectroscopic detector (MULTI-330 manufactured by JASCO Corporation) was used.
When the ultraviolet-visible spectrum of the polymer component was measured using a GPC connected to the UV max = 31 On, an absorption believed to be attributable to the proverbial oxathurium was obtained. It was confirmed that the obtained polymer contained an oxalium ion structure.This polymer was designated as Additive XI.

Example 1 Additives manufactured in Additive Production Examples 1 and 2 - IV, I
Add 300ppm or 500pp of V(*) to the following fuel oil.
- added to evaluate cold flowability and clean dispersibility. The results are shown in Table 3.

Fuel oil A: 20% boiling point 268°C, 90% boiling point 345°C,
Soft point 373°C Fuel oil B: 20% boiling point 22 boiling point 221° sea 190 Table 3 shows that the fuel oil additive of the present invention is an additive that has the functions of a low-temperature fluidity modifier and a dispersant. ing.

Example 2 5 parts of any one of additives 1 to 1 and 2 (*) to 2 (*) were added to 95 parts of hydrorefined paraffinic mineral oil. The viscosity index (ν, ■,) of the obtained lubricating oil is determined by JIS
K2283 and shear stability JPI-55-
Evaluation was made based on the viscosity loss rate (calculated using the formula below) due to ultrasonic irradiation in accordance with 29-88.

Vo: kinematic viscosity (cst) before ultrasonic irradiation (cst), kinematic viscosity (cst) after ultrasonic irradiation (cst) The results are shown in Table 4.

Further, the cleaning dispersibility was evaluated based on the degree of lacquer adhesion to the varnish rod according to JIS K2514. The results are shown in Table 5.

Table 5 From Table 4, it can be seen that the viscosity index (V, 1.) is significantly improved by using the lubricating oil additive of the present invention.

Furthermore, Table 5 shows that the lubricating oil additive of the present invention has an excellent function as a detergent and dispersant.

All lubricating oils after the test had changed color to blackish brown and had a rating of 10
Even when the lubricating oil of the present invention was left in a refrigerator at °C for one week, no sludge sedimentation was observed, but the sludge of the comparative lubricating oil was sedimented after one day.

The above results indicate that the lubricating oil additive of the present invention is a multifunctional additive having the functions of a viscosity index improver and a detergent/dispersant.

(Effects of the Invention) The oil additive of the present invention provides fuel oil with superior low-temperature fluidity and clean dispersibility as compared to the prior art. Furthermore, it is a multifunctional additive for lubricating oils that improves the viscosity index and imparts cleansing and dispersion properties.

Therefore, fuel oils and lubricating oils to which the additives of the present invention have been added have significantly improved properties as compared to conventional oils.

Claims (7)

[Claims] (1) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ An oil additive characterized by containing a compound in which an atomic group with a bond is bonded to a molecular chain. (2) The additive according to claim 1, wherein the compound is a compound having a heterocyclic structure containing the bond. (3) The additive according to claim (1), wherein the oil is fuel oil. (4) The additive according to claim (1), wherein the oil is a lubricating oil. (5) An oil to which the oil additive according to claim (1) is added. (6) The oil according to claim (5), wherein the oil is a fuel oil. (7) The oil according to claim (5), wherein the oil is a lubricating oil.