JPS63248894A - Low-temperature fluidity enhancer for fuel oil - Google Patents

Abstract

PURPOSE:To provide the titled enhancer effective with addition in small quantities to even fuel oil containing large quantities of n-paraffin or such fuel oil as to be narrow in the distillation temperature range, containing a specific (poly)urethane compound, etc. CONSTITUTION:The objective enhancer comprising (A) a urethane compound of formula (Z is mono- or polyisocyanate; R is monohydric alcohol; n is 1-6) and, if needed, (B) a second compound selected from nitrogen-contg. derivative from alkenylsuccinic acid, condensates from chlorinated paraffin and naphthalene, long chain alkylene dicarboxylic acid derivatives, nitrogen-contg. derivatives from tricarboxylic acid, polyalkyl (meth)acrylates and reaction products from diisocyanate compound and dialkylamine in the weight ratio A/B=pref. 2/98-98/2. In general, 0.0001-0.5 (pref. 0.001-0.1) wt.% of said enhancer is incorporated in a fuel oil.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a low temperature fluidity improver for fuel oil.

[Prior Art] Conventionally, as a low-temperature fluidity improver for fuel oil such as light oil and heavy oil, there is a urethane urea consisting of tolylene diisocyanate and an amine (for example, Japanese Patent Publication No. 58-2207
Publication No. 4).

[Problems to be Solved by the Invention] However, the conventional methods have problems such as not being sufficiently effective for fuel oil containing a large amount of n-paraffin or fuel oil having a narrow distillation temperature range.

[Means for Solving the Problems] As a result of intensive research by the present inventors on a low-temperature fluidity improver that is effective even for fuel oil containing a large amount of 11-paraffin and for fuel oil with a narrow distillation temperature range. , arrived at the present invention.

That is, the present invention provides (A) general formula (1) Z-(NHCOOR) n (1) (wherein Z is a residue of mono- or polyisocyanate-1, R is a residue of a monohydric alcohol, and n is (an integer of 1 to 6), and if necessary, (B) a nitrogen-containing derivative of alkenylsuccinic acid, a condensate of chlorinated paraffin and naphthalene, a derivative of long-chain alkylene dicarboxylic acid, and a tricarboxylic acid-containing compound. Nitrogen derivatives, polyalkyl (meth)acrylates, and cyisocyanates
1. A low-temperature fluidity improver for fuel oil characterized by containing a compound selected from the group consisting of a reaction product of a compound and a dialkylamine.

In general formula (1), Z is mono- or polyisocyanate! Among the isocyanates forming the residue, examples of monoisocyanates include aromatic or aliphatic monoisocyanates (phenyl monoisocyanate, stearyl monoisocyanate, etc.). As for polyisocyanate, carbon number (excluding carbon in NGO group) is 6
~20 aromatic polyisocyanates, aliphatic polyisocyanates having 2 to 18 carbon atoms, cycloaliphatic polyisocyanates having 4 to 15 carbon atoms, araliphatic polyisocyanates having 8 to 15 carbon atoms, and modified products of these polyisocyanates. (Modified products containing urethane group, carbimide group, allophanate group, urea group, biuret group, uretdione group, uretonimine group, isocyanurate group, oxazolidone group, etc.). Examples of such polyisocyanates include 1,3- and 1,4-phenylene diisocyanate, 2,4- and/or 2,6-
- tolylene diisocyanate (TDI), crude TDI,
2,4'- and/or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane] condensation product of formaldehyde with aromatic amines (anilines) or mixtures thereof; diaminodiphenylmethane with small amounts (e.g. 5-20% by weight)
Mixture with trifunctional or higher functional polyamine] Phosgenide:
Polyaryl polyisocyanate (1'API), 1,
Aromatic polyisocyanes I.
; Ethylene diisocyanate, tetramethylene diisocyanate I, dodecamethylene diisocyanate, 1,6
, 11-undecane triisocyanate, 2,2.4-
1-limethylhexane diisocyanate-1, lysing 2
Isocyanate, 2,6-diycyanatomethyl caproate, bis(2-isocyanateethyl)fumaray I, bis(2-isocyanateethyl)carbonate-1
・Aliphatic polyisocyanates such as 2-isocyanate ethyl-2,6-dicyanate hexanoate!・
;, isophorone diisocyanate, dicyclohexylmethane diisocyanate (hydrogenated MD+), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl) 4-cyclohexene-1,2-dicarboxylate, etc. Cyclic polyisocyanate; Aroaliphatic polyisocyanate-1 such as xylylene diisocyanate and diethylbenzene diisocyanate; Modified MDI (urethane-modified MDI, carbodiimide-modified MDI,)
modified polyisocyanates such as urethane-modified TD+, and mixtures of two or more thereof [e.g., combined use of modified MDI and urethane-modified TD+ (isocyanate-containing prepolymer)] can be given. Urethane-modified polyisocyanate [excess polyisocyanate 1- (TDI
.

The polyols used in the production of the free isocyanate-containing prepolymer obtained by reacting MDI, etc.) with a polyol include polyols with an equivalent weight of 30 to 200, such as glycols such as ethylene glycol, propylene glycol, and diethylene glycol; trimethylolpropane, glycerin, etc. Triols; high-functional polyols such as pentaerythyl alcohol and sorbitol; and alkylene oxide (ethylene oxide and/or propylene oxide) adducts thereof. Among these, those having 2 to 3 functional groups are preferred. The free isocyanate content of the modified polyisocyanates and prepolymers is generally 8 to 33%, preferably 10 to 30%, particularly preferably 12 to 29%.

Preferred among these mono- or polyisocyanates are the aromatic diisocyanates, particularly preferred are 2,4- and 2,6-TDI and mixtures of these isomers, crude TDI, 4,4'- and 2. ．．
4'-MDI and mixtures of these isomers, crude MD
I (PAPI).

In the general formula (1), the alcohol forming the monohydric alcohol residue of R is a linear or branched alkanol having 5 to 30 carbon atoms (2-ethylhexyl alcohol, decyl alcohol, stearyl alcohol,
Behenyl alcohol alcohol (such as oleyl alcohol), cycloalkanol (such as cyclohexyl alcohol), phenyl-substituted alkanol or alkenol (such as benzyl alcohol, phenylethyl alcohol), and alkylene oxide-added alkanol or alkenol (alkylene oxide has 2 to 4 carbon atoms, The number of moles is 1 to 3
It is 0. For example, an adduct of octyl alcohol with 10 moles of ethylene oxide). Among the -hydric alcohols, alkanols having 14 to 24 carbon atoms are preferred, and alkanols having 18 to 22 carbon atoms are particularly preferred. Preferably n is 2-3.

As a specific example of the compound represented by general formula (1), TDI
(1 mol) of stearyl alcohol (2 mol), polyurethane of TDI (1 mol) and behenyl alcohol (2 mol), and polyurethane of MDI (1 mol) and behenyl alcohol (2 mol).

The urethane compound of general formula (1) is prepared by mixing isocyanate and monohydric alcohol so that the NGO1011 ratio is substantially 1, usually from room temperature to 150°C, preferably from 40 to 1
It can be obtained by reacting at 20°C.

A catalyst is usually not required for the reaction, but if the reaction rate is slow, an appropriate catalyst can be used. As catalysts, amines (triethylamine, triethylenediamine, N-methylmorpoline, etc.), organometallic compounds (
Examples include dibutyltin dilaure I, stannous octoate, etc.

Although the reaction proceeds satisfactorily without the use of a solvent, it is also possible to use a suitable solvent that does not react with the isocyanate compound and alcohol that are the raw materials. Suitable solvents include aliphatic hydrocarbons such as paraffin, olefin, and cycloparaffin, aromatic hydrocarbons such as toluene and xylene, and petroleum solvents such as kerosene, light oil, and solvent naphtha.

The reaction product is usually solid to pasty.

In the present invention, if necessary, component (13) may be a nitrogen-containing derivative of alkenylsuccinic acid, a condensate of chlorinated paraffin and naphthalene, a nitrogen-containing derivative of long-chain alkylene dicarboxylic acid, a nitrogen-containing derivative of tricarboxylic acid, polyalkyl ( meth)acrylate, and diisocyanate-1.
Any one type or two or more types of reactants of a compound and a dialkylamine can be used in combination with the above (A). ([
3) The combined use of the components brings about the great effect of promoting pour point (hereinafter abbreviated as PP) lowering ability.

(I3) Component alkenylsuccinic acid derivative is 0
Examples include reaction products (amines and/or salts) of alkenylsuccinic acid containing a 4-C28 alkenyl group, mono- or dialkylamine, and (poly)alkylene polyamine, and preferred are alkenylsuccinic acid containing a CI4-C22 alkenyl group. It is a reaction product of an acid and a dialkylamine having two CI4 to C28 alkyl groups.

08 as a condensate of chlorinated paraffin and naphthalene
Examples include condensates of chlorinated paraffins and naphthalene. Its molecular weight usually ranges from 2000 to 8000.

Examples of the nitrogen-containing derivatives of long-chain alkylene carboxylic acids include those described in JP-A-56-36588.

Specifically, it is a reaction product of a dialkylamine and a dicarboxylic acid having an unsubstituted or alkyl-substituted alkylene group having a linear alkylene chain of C+e or more, preferably C
It is a reaction product of a dicarboxylic acid having a linear alkylene group of I4 to C22 and a dialkylamine having two alkyl groups of 014 to C22.

As a nitrogen-containing derivative of tricarboxylic acid, JP-A-56-8
Examples include those described in Japanese Patent No. 4795, and specifically, it is a reaction product of an aromatic, aliphatic or alicyclic tricarboxylic acid and a dialkylamine, preferably a reaction product of trimellitic acid and a C1a to C22 alkyl group 2 It is a reaction product with a dialkylamine having .

01-C2 as polyargyl (meth)acrylate
Homo or copolymers of (meth)acrylates having a wide range of alkyl groups of 2 (such as copolymers of CI2 and C16 alkyl methacrylates) (molecular weight 1.00
0 to 1.000.000). Preferred are polymers or copolymers containing a large proportion (for example, 80% by weight or more) of (meth)acrylates having alkyl groups of CI2 to C+s. Its molecular weight is 5,000~
The range is 200.000.

In addition, examples of the reaction products of polyisocyanate-1 compounds and dialkylamines include those described in Japanese Patent Publication No. 58-2207''1.Specifically, aromatic, aliphatic, and alicyclic polyisocyanates It is a reaction product of 1. and a dialkylamine, preferably a reaction product of 1.lylene diisocyanate and a dialkylamine having two CI4 to C22 alkyl groups.

The above (B) can be used alone or in combination with (A) as a mixture.

Among (B), preferred are nitrogen-containing derivatives of alkenylsuccinic acid.

In addition, ethylene is used as an agent to improve the low-temperature fluidity of fuel oil.
Vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, chlorinated paraffins, etc. are also used, but
When component (A) in the present invention and these fluidity improvers are used together, no effect of promoting PP lowering ability is observed, and the low temperature filter clogging point (Ir2O3) for fuel oil with a narrow boiling point range is not observed. (hereinafter abbreviated as CF) is not preferable because it lowers the descending ability.

In addition, when evaluating the low-temperature fluidity of fuel oil, conventional PP
In addition, CF is widely used as a measure of fuel operability at low temperatures.

When (A) and (B) are used together, their usage ratio can be set arbitrarily, but the preferred range is (A):(B)=2:98 to 98:2 in terms of weight ratio.

The fuel oil in the present invention is mainly a distillate fuel oil and a fuel oil obtained by mixing distillate fuel oil with residual oil, and specific examples thereof include gasoline, kerosene, light oil, and heavy oil (heavy oil, B heavy oil). Among these, preferred are kerosene, light oil and heavy oil.

When the improver of the present invention is added to fuel oil, the amount added is usually o, oooi to 0.5% (by weight, the same hereinafter), preferably 0.001 to 0.1%.

The method of adding the improver of the present invention to fuel oil is not particularly limited. In the case of an improver consisting of (A) and (B), for example, (A
) and (B) are mixed in advance and added to fuel oil, (A) and (B) are separately added to fuel oil,
Examples include a method of forming an additive consisting of (A) and (B) in fuel oil. When mixing in advance (A)
A method of heating and uniformly mixing (A) and (B);
An example is a method of dissolving at least one of B) in a solvent and then mixing. In addition, as a method for forming the improver in the above fuel oil, (A) and (B) may be added as they are, or at least one of (A) and (B) may be dissolved in a solvent and both may be added simultaneously or sequentially to the fuel oil. One method is to add it.

[Examples] The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following, parts and % do not indicate parts by weight and % by weight, respectively.

Examples 1 to 6 and Comparative Example 1.2 The compounds or formulations shown below were used in accordance with the present invention and Comparative Example 15.
It is used as a water improver.

Example 1: Urethane compound of TD+ (1 mol) and behenyl alcohol (2 mol).

Example 2: Urethane compound of TDl (1 mol) and stearyl alcohol (2 mol).

Example 3: Urethane compound of MDI (1 mol) and behenyl alcohol (2 mol).

Example 4: Improver of Example 1 = 20 parts.

Monoamide of 11-tetradecenylsuccinic acid and di(n-octadecyl)amine = 80 parts.

Example 5: Improver of Example 1: 20 parts.

Long chain alkyl methacrylate copolymer (min = 30,000):
80 copies.

Example 6: Improver of Example 2: 20 parts.

11-tetradecenylsuccinic acid and di(n-octadecyl)amine: 80 parts.

Comparative Example 1: Ethylene-vinyl acetate copolymer (ffliN
=2,500. (vinyl acetate content 30%).

Comparative Example 2: Reactant of TDI and di(n-octadecyl)amine.

The improvers of Examples 1 to 6 and Comparative Example 1.2 were added to light oils 1 to 3 having the properties shown in Table 1, and PP and CF were measured. The results are shown in Table-2.

Table-1 Table-2 (Note), l:l: 20 pp+n: :t2:
100 ppn+; 1:3: 250 + width...
[Effect of the invention]

Claims (1)

[Claims] 1. (A) General formula (1) Z-(NHCOOR)_n(1) (wherein Z is a mono- or polyisocyanate residue, R is a monohydric alcohol residue, n is an integer from 1 to 6), and if necessary, (B) nitrogen-containing derivatives of alkenylsuccinic acids, condensates of chlorinated paraffins and naphthalene, derivatives of long-chain alkylene dicarboxylic acids, tricarboxylic acids A low-temperature fluidity improver for fuel oil, characterized in that it contains a compound selected from the group consisting of a nitrogen-containing derivative of, a polyalkyl (meth)acrylate, and a reaction product of a diisocyanate compound and a dialkylamine. 2. The weight ratio of (A) and (B) is (A):(B)=2:
The improver according to claim 1, which has a ratio of 98 to 98:2.