JPS598790A - Improving agent for fluidity at low temperature of fuel oil - Google Patents

Abstract

PURPOSE:An improving agent for the fluidity characteristics and fluidity at low temperatures containing a specific succinic acid amide derivative and a specific ethylene-ethylenically unsaturated ester copolymer, and applicable to a relatively wide range of types of petroleum middle distillate fuel oils. CONSTITUTION:An improving agent for the fluidity at low temperatures containing (A) a succinic acid amide derivative of formula I [R is 8-28C unsaturated hydrocarbon; one of X1 and X2 is NY1Y2, and the other is OH(NHY1Y2)n (Y1 and Y2 are H or 1-30C hydrocarbon; n is 0 or 1)] and (B) a copolymer of (i) ethylene and (ii) 50wt% or less ethylenically unsaturated ester of fomula II (R1 is H or CH3; R2 is OCOCH3, etc.) having 3,000-7,000 number-average molecular weight, <=5.0 molecular weight distribution and <=6, based on 100 methylene groups, methyl terminated side chains in addition to the methyl groups in the ester groups. The amount of the above-mentioned improving agent to be added to the fuel oil is usually 50-5,000ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a low-temperature fluidity improver for fuel oil, in which C is a succinamide derivative and a specific J-ethylenically unsaturated ester co-combination. Regarding the low temperature fluidity improver that can improve the low temperature fluidity and flow characteristics of seven types of petroleum middle distillates and fuel oils.

When petroleum middle distillate fuel oil, such as diesel oil, is exposed to low temperatures in winter or in cold areas, the waxy substances contained therein precipitate and damage the engine's fuel piping system. If the filter is clogged and this causes problems such as starting the engine, the fuel oil itself becomes semi-solid or solid, loses its fluidity, and causes problems such as oil pipes becoming clogged. This problem is likely to increase further due to the recent trend of commercialization of crude oil or the tight supply of kerosene and diesel oil, and appropriate countermeasures are desired.

Therefore, many efforts have been made to solve this problem, but nothing that is fully satisfactory has yet been found.

Conventionally, for example, succinic acid ami)-' derivatives, which are the reaction products of acid anhydrides of succinic acid derivatives and alkyl amines [f
l + compound] is the pour point (pp
) Excellent effect on reducing It is known to have.

However, is this the cryogenic filter plugging point (CFPP) that has been attracting attention in recent years? In order to compensate for this, various polymers are used as low-temperature fluidity improvers. These polymers include ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, branched polyethylene, and chlorinated polyethylene. , alkylnaphthalene polymers are known.

These polymers generally co-crystallize with wax in fuel oil or adsorb to wax crystals to change the shape and size of wax M crystals, thereby improving the fluidity of fuel oil at low temperatures. It is something. However, petroleum distillate 1. There are various kinds of oils depending on the production area and oil field of Toyo oil, such as mafko distillation and concentrated injection, and as a result, the wax content (wax content) 4% and wax molecular weight distribution are also different. However, it does not exhibit good low-temperature fluidity for a wide range of fuel oils.

Under these circumstances, the present inventor conducted intensive research on polymers that exhibit excellent effects when used in combination with the above-mentioned succinic acid amide derivatives, and found that a specific ethylene-ethylenic unsaturated ester copolymer has a wide range of properties. The wax crystals generated at low temperatures for these types of fuel oils are made fine and stable, and furthermore, the formation of three-dimensional mesh packing crystals due to the enlargement of fine crystals into hair dyes is significantly inhibited, and succinic acid amide derivatives and When used together, a low-temperature fluidity improver can be obtained.Is this the invention? completed.

That is, the present invention provides the following components (al and (bl, (a
l General formula +11, R-CH-COXl 1 (J) CH2-COX2 [In the formula, R represents a hydrocarbon group r having 8 to 28 carbon atoms and 0 or 1 olefinic unsaturated bond, X1A)
and x2 are -NY, Y2 (Yl and Y2 are hydrogen atoms or hydrocarbons having 1 to 60 carbon atoms?
The other is a succinic acid amide derivative represented by 10H(NHYIY2)n (nk'f-0 has 1 value, Yl and Y2 have the above-mentioned value), (bl ethylene and the following general Formula (b), [wherein, R1
indicates H or CH3, R2 is OCOCH3 father is COO
A copolymer with an ethylenically unsaturated ester represented by R3 (R3 is an alkyl group having 1 to 1 B carbon atoms), with an ethylenically unsaturated ester monomer content of 50% by weight or less, number average Molecular weight 3,000-7.00D, molecular weight distribution 5.0 or less, methyl terminal side chains (hereinafter referred to as degree of branching) of 6 or less per 100 methylene groups in addition to the methyl group of the ester group. It is a low temperature fluidity improver for fuel oil containing an ethylene-ethylenically unsaturated ester copolymer.

In this specification, [Number average molecular weight -1 is determined by vapor phase osmotic pressure method (VPO), [Molecular weight distribution -1 is determined using tetrahydrofuran solvent, Boliennale 7''
Determined by rvermission chromatography (GPC) using I + Cole standard, mafko 1-
The degree of branching is determined by nuclear magnetic resonance (NMR).

The succinic acid amide derivative as component (a) of the present invention can be produced by reacting a monoolefin with maleic anhydride to form an acid anhydride of the succinic acid derivative, which is then reacted with amines (NH
YIY2) '<Produced by reacting.

In the reaction between a monoolefin and maleic anhydride, oligomers may be produced as both organisms, but these may be used either with removal or with the presence of the oligomers. As the monoolefin, those of 08 to 02B, especially 015 to C22 are preferable, such as decene, dodecene, tetradecene, hexadecene, eicosene, tocosene, tetradecene, tetrapropylene, tetraisobutylene, hexapropylene, etc. The position of the double bond in these monoolefins may be at the α position or internally.

As amines, both ¥1 and Y2 are C1,4-C2
Hydrocarbons of No. 2 are particularly preferred, such as simiristylamine, civalmitylamine, distearylamine,
Examples include zoeikon luamine, sialkyl (hydrogenated beef tallow) amine, etc.

These succinic acid amide derivatives are amine salts (NHY,
Y, ) can also be used in history. This amine salt is
For example, zo-nibutylamine, he-1'f-ylamine, dodecylamine, octadecylamine, tert-butylamine,
Examples include diethylamine.

Ethylene-ethylenically unsaturated ester copolymer of component (b)? The constituting ethylenically unsaturated ester represented by the formula fl11 includes vinyl acetate, acrylic acid, or methacrylic acid ester, and examples of the ester include methyl, ethyl, valmitoyl, lauryl ester, and the like.

The copolymer of ethylene and the above-mentioned ethylenically unsaturated ester must contain 50 tlt% or less of the latter,
Preferably, it contains 10 to 50 it% of ethylene and 90 to 50% by weight of ethylenically unsaturated ester.

In order to improve the low-temperature fluidity of fuel oil, it is desirable that the copolymer has enalene chains corresponding to wax molecules, but as mentioned above, the molecular weight distribution of wax in fuel oil varies. So, is the molecular weight distribution of the copolymer spread to some extent? Must hold. However, if the molecular weight distribution of the copolymer is too wide, the copolymer having a molecular weight corresponding to the high molecular weight distribution of wax will be reduced, so an appropriate range is necessary. It is preferably 5.0 or less.

In addition, the degree of branching of the copolymer is one of the important factors in the phase-q interaction with the wax in the fuel, and for copolymers containing the same ethylenically unsaturated ester, The smaller the degree of branching, the better the crystallinity and the easier eutectic formation with wax molecules, and the higher the degree of branching, the greater the quality and the difficulty in eutectic formation with wax. It is preferable that the degree of branching is 6 or less.

Furthermore, its low temperature fluidity for a wide range of fuel types? In order to improve the performance, the number of molecules of the copolymer is also important, and in the present invention, the number average molecular acid is 6.000 to 7.
．． (J [J O is preferred.

Such article￥￥F? The ethylene-ethylenically incompatible ester copolymer is, for example, disclosed in Japanese Patent Publication No. 39-2L106.
No. 9, No. 48-23165, according to the free radical polymerization method described in Reference Example.

The low temperature fluidity improver of the present invention comprises the components (alk1 to 1[J
It is preferable to polymerize the composition at a ratio of 1 to 20 parts, component + 1 to 20 parts, and the above-mentioned known polymers may be used in combination with the song. The low-temperature fluidity improver of the present invention is added to fuel oil with a 50 to 5
．． By adding J 00 ppm to the blend, the fluidity at low temperatures can be improved.

Next example? List and explain - 1bo The same ethylene-ethylenically unsaturated ester co-merchandising was produced as in Tsuka examples 1 to 7, and the phosphoric acid amide conductor was produced in accordance with references 18 to 90. 〇Reference example 1 Using an autoclave polymerization device and using benzene as the solvent?
Use toilet, pressure 1i Q jcg 7cm2, temperature 10c
By using zolauroyl peroxide as an initiator under the conditions of 1'C, a compound containing hynyl acetate of 27% by weight and a number average molecular weight of 3820. Ethylene vinyl acetate copolymer with a degree of branching of 2.6 and a number average molecular weight ratio of 2-1! !
! ! 1 piece built.

Reference Example 2 Using autoclave polymerization equipment, bare (!
"L for 7 '2 IIE, pressure 110M1il/C
rrL'', dilauroyl peroxide as an initiator under the conditions of temperature 1[10''C? Depending on the material used, the vinyl acetate content is 19%, the number average molecular weight is 44%, and the degree of branching is 6%. An ethylene vinyl acetate copolymer having an O1 molecule distribution of 2.5 was produced.

Reference Example 3 Using an autoclave polymerization apparatus, using benzenone as a solvent, using zolauroyl peroxide as an initiator under conditions (pressure 210 times per day, temperature 90°C), the ethyl acrylate content was 23. Tonnage weight: 3900, branching If: 3.2, molecular weight distribution: 2
．． An ethylene-ethyl acrylate copolymer of No. 4 was prepared.

Reference Example 4 Using an autoclave polymerization apparatus i#w, using benzene as a bath agent, the pressure was 50-210 K9/(, VF6"
By using zolauroyl peroxide as an initiator at a temperature of 70 to 110"C, a rg: acid vinyl content of 268ij!%, a number average molecular weight of 265o, a degree of branching of 2.8, and a molecular weight distribution of 5.6 were obtained. Ethylene vinyl acetate copolymer was produced.

Reference example 5 Autoclave polymerization station? Use the pressure cuff oo to q/ (
7n2 and a temperature of 225°C, by using t-butyl peroxyben 7ate as an initiator and Zorobirenge as a chain transfer agent, the vinyl acetate content was 31% by weight and the number average molecular weight was 3120. Ethylene vinyl acetate copolymer with branching K 8.2 and molecular weight distribution 4.0? Manufacture (-ta)

Reference Example 6 Using an autoclave polymerization apparatus, using Tehenzen as a solvent, under the conditions of a pressure of 210 kg/cm'' and a temperature of 95°C, and using dilauroyl peroxide as an initiator, the vinyl acetate content was 4210. An ethylene vinyl acetate copolymer with an average molecular weight of 7100, a degree of branching of 3.2, and a molecular weight of f52.1 was produced.

Reference Example 7 Using an autoclave polymerization apparatus, using benzene as a solvent, under the conditions of a pressure of 55 cm/cIrL2 and a temperature of 95°C,
Dilauroyl peroxide as an initiator? Depending on the use, vinyl acetate-containing snacks have a slip coefficient of 22 and a number average molecular weight of 18.
10, an ethylene vinyl acetate copolymer ycH with a degree of branching of 6.6 and a molecular weight distribution of 2.5 was prepared.

Reference Example 8 1 mole of alkenylsuccinic anhydride obtained from an isomerized product of an α-olefin having 15 to 20 carbon atoms and maleic anhydride was mixed with 1.6 mole of sialkyl (carbon #16 = 18) amine at 80°C. The carbon number distribution of the isomerized α-olefin used here is as follows.

Reference Example 9 #4 Same as in Example 8, 1 mole of alkenylsuccinic anhydride was reacted with 1.1 mole of stearylamine at 265°C for 90 minutes to produce γ-alkenylsuccinic acid amyl (sample B).

Example 1 A low temperature fluidity improvement test for a petroleum middle distillate fuel oil was conducted on the blend of the copolymer and co-phosphoric acid amide derivative prepared in Reference Example. Shoko (polymer is added at 100 ppm, succinic acid amide derivative is added at 300 ppm, evaluation is based on CFPP (British Standard RP-309) and p
p (JIS K-2269)
I went by It'C. The results are shown in Table 1.

Margin below

Claims (1)

[Claims] 1. Components (al and fbl (,)) General formula % Formula % [In the formula, R is a hydrocarbon having 8 to 28 carbon atoms and 0 or 1 olefinically unsaturated bond] One of the radicals 2, Xl and
OH(Nl(YlYg)n (n represents 0 or 1, Yl
and Y2 represents the above-mentioned phosphoric acid amide derivative, (l) ethylene and the following general formula [wherein R1 is H or C] , shows, ) (2 is ○CC
) CH3 or 000R3 (R3 is an alkyl group having 1 to 18 carbon atoms))], and when combined with 1 l of a small saturated varnish, the ethylenic non-direct ester f7 Body agency anger 50
% of the army, number -1/- uniform molecular spear 3.1 JOO ~ 7. [
J 00, ethylene-ethylenic unsaturated ester copolymer with a molecular weight distribution of 5.0 or less, having not more than 6 methyl-terminated side chains per 100 methylene groups in addition to the methyl groups of the ester groups; A low-temperature fluidity improver for fuel oil, characterized by containing: 2. Claim 1 containing component (a) Y1-IO[J'tt part, component blY1-20 parts by weight
Low-temperature fluidity improver for fuel oil on Mound H Pi.