JPH0710982B2 - Fluidity improver - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a fluidity improver, and more particularly to a fluidity improver used for petroleum products such as liquid fuels to improve their flow characteristics at low temperatures.

2. Description of the Related Art With the recent increase in the weight of crude oil and the increase of middle distillates in petroleum products, the use of oil with a high boiling fraction has become an issue.
Since oils with a high boiling fraction have poor fluidity at low temperatures, removal of wax (dewaxing), which greatly affects fluidity at low temperatures, and use of fluidity improvers have been performed. While dewaxing requires large equipment and is economically very disadvantageous, the fluidity improver does not require special equipment and is an economically advantageous method, and various conventional methods have been proposed. Has been done.

Conventionally, as a fluidity improver, an ethylene-hinyl acetate copolymer (JP-B-39-20069, JP-B-43-16153, JP-B-43-16755, JP-B-48-23165,
JP-A-55-137193), a compounding system of an ethylene-vinyl acetate copolymer and another compound (JP-A-53-124515, JP-A-56-93796), alkenylsuccinamide ( JP-A-49-63702, JP-A-56-43391) and the like are known, but these are not yet sufficient in performance, and in particular, curing to a fuel oil in a narrow distillation range is extremely small. For the purpose of compensating for this drawback and improving the fluidity for narrow boiling oils, JP-A-57-177092 proposes a fluidity improver containing a specific polyoxyalkylene ester or ether or ester ether. However, this compound has a problem that the effect on oil having a wide distillation range is low.

Therefore, the present inventors have developed a polyester derivative compound as a fluidity improver that exerts an effect of improving fluidity with respect to both wide boiling oil and narrow boiling oil, and disclosed in JP-A-60-31799.
Filed as an issue. However, this compound alone is not used for CFPP (cold plugging temperature; cold filter plugging point).
t) is effective, but PP (pour point; Pour Poin
There is a problem that the effect against t) is low, and as a solution to it, a copolymer of ethylene-vinyl acetate, a copolymer of chlorinated wax and naphthalene, polyacrylate, alkenyl succinamide, maleated oleic amide. It was proposed to be used in combination with.

The object of the present invention is to use PP, CF for both wide boiling oil and narrow boiling oil.
It is intended to provide a fluidity improver that exhibits an improving effect together with PP.

Structure of the Invention The fluidity improver of the present invention is characterized by containing the following components (A) and (B).

(A) Polyester derivative compound represented by the following general formula (I): 0.01 to 10 parts by weight, R ¹ COO (A ¹ O) l {COYCOO (A ² O) _m } _n COR ² (I) (wherein , R ¹ , R ² , A ¹ , A ² , Y, l, m and n represent the following.

_R ^1: C 9~29 hydrocarbon group R ^2: hydrocarbon group _C 9~29 A ^1: A ^2: alkylene group having C _{2 to 4} Y: 2 divalent group of aliphatic or aromatic l:. 1 to 50 m: 1 to 50 n: 1 to 10) (B) Ethylene-vinyl acetate copolymer having a molecular weight of 500 to 10,000 and a vinyl acetate content of 10 to 50% by weight: 90 to 99.99 parts by weight As a result of investigation, it was found that, when a specific polyester derivative compound was combined with an ethylene-vinyl acetate copolymer, even if a small amount of this polyester derivative compound was used, its additive effect was exhibited at all. . The fluidity improver is added and consumed in combustion oil, and its cost reduction is desired.
The polyester derivative compound as the component (A) is described in Japanese Patent Application No.
As described in No. 60-31799, although it has an excellent effect of improving fluidity, it is complicated to manufacture and relatively expensive.

Hereinafter, the present invention will be described in more detail.

In the polyester derivative compound as the component (A), R ¹ and R ² in the general formula (I) are preferably aliphatic hydrocarbon groups, and linear alkyl is particularly preferable. These may be introduced as a linear fatty acid residue ^{(R 1 CO-, R 2 CO-} ). As the fatty acid, n-decanoic acid, n-dodecanoic acid (lauric acid), n-pentadecanoic acid, n-heptadecanoic acid, n-hexadecanoic acid (palmitic acid), n-octadecanoic acid (stearic acid), n-eicosanoic acid , N-
Docosanoic acid (behenic acid), n-pentaeicosanoic acid,
n-heptaeicosanoic acid, n-hexaeicosanoic acid, n
-Saturated straight chain aliphatics such as -octaicosanoic acid and n-triacontanoic acid can be used, and these can be used alone or in combination. Further, mixed fatty acids derived from natural products such as fish oil fatty acids, beef tallow fatty acids, coconut fatty acids and the like can also be used, and hydrogenated fatty acids of these are preferably used.

A ¹ and A ^{2 in} the general formula (I) are an ethylene group, a propylene group, a tetramethylene group, etc., and are introduced from ethylene oxide, propylene oxide, tetrahydrofuran or the like.

Y in the general formula (I) represents an aliphatic residue such as an alkylene group or an alkenylene group or an aromatic residue such as a phenylene group, and these are dicarboxylic acid residues (-CO-Y-CO-).
Can be introduced as. As cigarbonic acid,
Oxalic acid (when Y is a C ₀ alkylene group, that is, when CO and CO are directly bonded), malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, terephthalic acid , Fumaric acid, naphthalic acid or their anhydrides.

l and m each represent the number of moles added to the oxyalkylene group (A ¹ O) and (A ² O), and are 1 to 50, preferably 1
~ 25. For example, (A ¹ O) 1 can be introduced by adding a single alkylene oxide such as ethylene oxide, or by sequentially adding ethylene oxide and propylene oxide, or by adding a mixed alkylene oxide thereof. It is also possible to introduce in the form of block addition, random addition, etc.

n shows the number of 1-10, Preferably it is 1-5.

The polyester derivative compound used in the present invention includes, for example, first adding an alkylene oxide to a fatty acid, then adding a dibasic acid and further adding an alkylene oxide, and if necessary, a step of adding the dibasic acid and the alkylene oxide is performed. Repeatedly, finally, it can be produced by crosslinking the obtained alkylene oxide adduct with a dibasic acid. In addition, a method in which a polyoxyalkylene glycol and a dibasic acid are previously reacted to obtain a polyester polyol having a hydroxyl group at the terminal, and further esterification of the terminal hydroxyl group with a fatty acid is carried out. Any method such as a method of producing an ester polyether having a hydroxyl group in and crosslinking the ester polyether with a dibasic acid can be used.

As the ethylene-vinyl acetate copolymer as the component (B),
A number average molecular weight of 500 to 10,000, preferably 10,000 to 5,000 is used. In addition, the structural unit derived from vinyl acetate is 10
Those which occupy 50 to 50% by weight, preferably 15 to 45% by weight are used. It is not possible to sufficiently improve the filter passability and the pour point where the number average molecular weight and the vinyl acetate content deviate.

The blending ratio of the above components (A) and (B) is (A) polyester derivative compound: 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, (B) ethylene-vinyl acetate copolymer: 99.99 to 90 Parts by weight, preferably 99.9 to 95 parts by weight. By adding a small amount of the polyester derivative compound (A) to the ethylene-vinyl acetate group polymer (B), these act in a complementary manner, and both narrow boiling oil and wide boiling oil are added.
CFPP and PP can be greatly reduced.

The fluidity improver of the present invention is used for petroleum products including liquid fuel, and is suitable for middle distillates such as jet fuel, light oil and heavy oil A.

The amount of the fluidity improver of the present invention added to fuel oil is 10 by weight.
〜5000ppm is suitable, preferably 50〜1000ppm. If the addition amount is less than 10 ppm, a sufficient effect cannot be obtained. On the other hand, if the addition amount exceeds 5000 ppm, the addition effect is saturated and the effect is not so large.

The method for adding the fluidity improver of the present invention to fuel oil is not particularly limited, and includes (A) polyester compound and (B)
The ethylene-vinyl acetate copolymer may be added after mixing in advance, or may be added separately.

Also suitable solvents such as petroleum fuel oils, aromatic solvents,
It can also be used after diluting it with an aliphatic solvent or the like.

EFFECTS OF THE INVENTION The fluidity improver of the present invention comprises a polyester compound (A) and an ethylene-vinyl acetate copolymer (B) in a specific ratio, so that it can be used for both narrow boiling and wide boiling distilled oils at low temperatures. The plugging temperature (CFPP) and pour point (PP) can be greatly reduced. Therefore, by adding the fluidity improver of the present invention to the fuel oil, it is possible to improve the filter passability and prevent the filter from being clogged in a diesel engine or the like, and the pour point is greatly lowered. Therefore, it becomes easy to transport the high boiling point oil containing wax at a low temperature and to use it in a diesel engine. As a result, it is possible to expand the use frame of fuel oil and increase the production amount. In addition, the above-mentioned effects are exhibited even if the amount of the relatively expensive (B) polyester compound derivative used is small, which is extremely advantageous industrially.

Hereinafter, the effects of the present invention will be described more specifically with reference to Examples. First, prior to this, a synthesis example of the polyester derivative compound as the component (A) is shown.

Synthesis Example 1 0.5% by weight of potassium acetate was charged into an autoclave with respect to 341 parts by weight of behenic acid, and after dissolution, nitrogen substitution and deaeration, 150-1
200 parts by weight of ethylene oxide was subjected to an addition reaction at 90 ° C. to obtain a monoester polyether of polyoxyethylene behenate (average number of moles of ethylene oxide added: 4.5, hydroxyl value: 107, acid value: 2.9).

This monoester polyether was charged with succinic anhydride in an amount equivalent to the hydroxyl value (based on the acid value) in a flask,
Add paratoluenesulfonic acid 0.5% by weight, 140-160 ℃
Then, a dehydration reaction was performed while flowing nitrogen to obtain a polyester ether of succinic acid-di (polyoxyethylene behenate) ester (ester conversion rate 93%). Here, the esterification reaction was expressed by the rate of decrease with respect to the acid value when the reaction was charged.

Hereinafter, synthesis was performed in the same manner except that the reagents shown in Table 1 were used to obtain Synthesis Examples 2 to 7. The results are shown in Table-1.

Synthesis Example 8 73 parts by weight of adipic acid (molar ratio: PEG / adipic acid = 2) based on 600 parts by weight of polyethylene glycol (average molecular weight 600)
/ 1) in the presence of 0.5% by weight of paratoluenesulfonic acid
A dehydration reaction was carried out at 40 to 160 ° C while flowing nitrogen to obtain a polyester polyether (hydroxyl value 86, average degree of polymerization 1).

Further, to this polyester polyether, behenic acid having an equivalent amount (acid value standard) to the hydroxyl value was added, and 0.5% by weight of paratoluene sulfone was added to the polyester polyether while flowing nitrogen.
Esterification reaction was carried out at ~ 160 ° C to obtain an end-capped polyester polyale (reaction rate 97%). Here, the reaction rate is indicated by the rate of decrease with respect to the acid value at the time of charging.

The following synthesis was performed in the same manner to obtain Synthesis Examples 9 to 12. The results are shown in Table-2.

Synthesis Example 13 To 341 parts by weight of behenic acid, 150 parts of triethylene glycol was added.
In the presence of 0.5% by weight of paratoluenesulfonic acid, 140 parts by weight of
A dehydration reaction was carried out at ˜160 ° C. while flowing nitrogen to obtain triethylene glycol monobehenate (hydroxyl value 123, acid value 2.8).

Further, with respect to this triethylene glycol monobehenate, phthalic anhydride having a hydroxyl value and an equivalent amount (based on an acid value) was used, and paratoluenesulfonic acid was added at a temperature of 140 to 160 ° C.
The dehydration esterification reaction was carried out in the presence of 5% by weight while flowing nitrogen to obtain phthalic acid-di (triethylene glycol monobehenate) ester (reaction rate 96%).

Here, the reaction rate is indicated by the rate of decrease with respect to the acid value at the time of charging.

Then, synthesis was performed in the same manner to obtain Synthesis Examples 14 to 18. The results are shown in Table-3.

Example (A) of the present invention obtained in the above Synthesis Example was added to light oil having the following properties.
The polyester derivative compound and (B) ethylene-vinyl acetate copolymer were added, and CFPP and PP were measured. The results are shown in Table-4.

Claims (1)

[Claims] 1. (A) General formula (I) R ¹ COO (A ¹ O) 1 {COYCOO (A ² O) _m } _n COR ² (I) (wherein R ¹ , R ² , A ¹ , A ² , Y, l, m and n represent the following: R ¹ : C _9-29 hydrocarbon group R ² : C _9-29 hydrocarbon group A ¹ , A ² : C _2-4 Of the alkylene group Y: a divalent group of an aliphatic or aromatic residue 1: 1 to 50 m: 1 to 50 n: 1 to 10): 0.01 to 10 parts by weight and (B) a molecular weight of 500 A fluidity improver comprising an ethylene-vinyl acetate copolymer having a vinyl acetate content of 10 to 50% by weight: 90 to 99.99 parts by weight.