JPS58176288A - Low-temperature fluidity improver - Google Patents

Abstract

PURPOSE:A low-temp. fluidity improver giving fuel oil excellent low-temp. fluidity, which comprises an adduct of a reaction product between a specified alpha- olefin and maleic anhydride with an aliph. alcohol or a salt thereof, and a reaction product between low-molecular PE and maleic anhydride. CONSTITUTION:A reaction product of a weight-average degree of polymn. of 1-100 obtd. by reacting (i) an alpha-olefin of an average carbon atom number of 10-30 with (ii) maleic anhydride in a molar ratio of 1:1-2 is reacted with (iii) an aliph. alcohol of an average carbon atom number of 6-28 to obtain an adduct or a salt thereof in which the sum of an average carbon number of the longest alkyl chain of component (i) and that of component (iii) is 21-40. Then to 1pt.wt. component A is added 0.1-10pts.wt. reaction product (B) between low- molecular PE of a weight-average MW 300-20,000 and maleic anhydride to obtain a low-temp. fluidity improver. This improver is added in an amt. of 10- 10,000ppm to a hydrocarbon fuel oil.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a low temperature fluidity improver, and more particularly to an additive for improving the low temperature fluidity of hydrocarbon fuel oil.

Hydrocarbon fuel oils, such as light oil and heavy oil, contain n-paraffin wax, so in cold regions in winter,
Precipitation of n-paraffin wax often occurs,
This causes major problems with the fluidity of fuel oil at low temperatures, such as blockage of oil pipes and clogging of strainers installed in the fuel supply circuit of internal combustion engines.

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-KOKAI Flit-/Tough No. 106;
The long-chain alcohol esterified product of a copolymer of an ethylenically unsaturated dicarboxylic acid and an α-olefin described in JP-A No. 7, and the copolymer of an ethylenically unsaturated dicarboxylic acid and an α-olefin described in JP-A No. 7 Aliphatic amine-modified copolymers are known. However, these effects cannot be said to be sufficient.

Recently, methods have been proposed to incorporate a third component or a third component in order to supplement the effect of adding fl'5. For example, as described in Japanese Patent Application Laid-open No. Sho Tag-/6-Lis, an aliphatic amine modified product of a copolymer of ethylenically unsaturated dicarboxylic acid and α-olefin described in Japanese Patent Laid-open No. Sho J4T-71307 A method in which a co-component such as an ethylene-vinyl acetate copolymer is used in combination with the method, and US Patent No. 9t2/θ
As described in the specification of Dako ρ, a method has been proposed in which n-paraffin wax and a nitrogen-containing compound are used together as second and third components in an ethylene-vinyl acetate copolymer, but these methods are also It does not work effectively on heavy light oil or heavy oil obtained from heavy crude oil containing a large amount of paraffin such as Minas oil.

Regarding the low-temperature fluidity of fuel oil, the present inventors have discovered the following interesting phenomenon in their research into the relationship between the form of wax that precipitates from fuel oil at low temperatures and the effect of additives. I found it.

In other words, in order to improve the low-temperature fluidity of fuel oil, (1)
To suppress the crystal size of wax that precipitates at low temperatures as small as possible. (2) To stably disperse the precipitated wax crystals in oil. These two points are important, and rather than the conventional method of combining these separate functions with a single compound, we will develop separate compounds with each function, namely (1) Wax. (2) A compound with the function of microcrystallizing (microcrystallization agent) and (2) a compound with the function of stably dispersing wax crystals in oil (dispersant).
We have found that the method of combining species is more rational and effective.

Based on these discoveries, the present inventors searched for compounds and combinations thereof that are effective as microcrystallization agents and dispersants,
The low-temperature fluidity improver of the present invention has been achieved.

That is, the gist of the present invention is as follows.

(A) The amount average degree of polymerization of the α-olefin having an average number of carbon atoms of io to 30 and maleic anhydride is / − / 00
and an aliphatic alcohol having an average carbon number of 6 to 2r, the average number of carbon atoms of the longest chain alkyl group of the α-olefin and the average carbon atom of the longest carbon chain of the aliphatic alcohol. and (B) a reaction product of low molecular weight polyethylene with a weight average molecular weight of 300-2000θ with maleic anhydride. be.

The present invention will be explained in detail below.

Component A of the fluidity improver of the present invention has an average number of carbon atoms of 10 to
It is an adduct of a reaction product of 30 α-olefin and maleic anhydride and a higher alcohol, and as a reaction product of α-olefin and maleic anhydride, it is an adduct of the l double In addition to the adduct, the amount average degree of polymerization io
.

Hereinafter, Fia preferably includes the following copolymers. If the weight-average degree of polymerization exceeds 100, the solubility in fuel oil will be poor and the low-temperature fluidity effect will also be poor, which is not preferable.

The α-olefin used as a raw material for component A in the present invention is an olefinic hydrocarbon having a double bond at the α-position of a hydrocarbon having an average number of carbon atoms of io to 30;
Even when olefin is a single product, α- has different carbon numbers.
It may also be a mixture of olefins.

The copolymerization reaction of α-olefin and maleic anhydride is carried out in the presence of a radical initiator using a suitable solvent such as benzene, toluene, xylene, methyl isobutyl keto/dioxane, etc., or without a solvent. to
−/roc.

The adduct of α-olefin and maleic anhydride corresponding to te polymerization degree lK can be obtained by heating α-olefin and maleic anhydride in the absence of a solvent until l≦O-co3θC according to a conventional method. I can do it.

After the reaction is completed, the target compound is obtained by removing the solvent, unreacted α-olefin/and maleic anhydride by distillation under reduced pressure.

The constituent molar ratio of the reaction product α-olefin and maleic anhydride obtained in the reaction of α-olefin and maleic anhydride is usually in the range of /:/−/:, and any of these can be used.

The reaction product of the α-olefin and luic anhydride is then reacted with an aliphatic alcohol having one hydroxyl group. This alcohol has an average carbon atom number of 6 to 2r, preferably 7 to 2r.
Those having one straight chain or one branched chain can be used. These alcohols may be used alone or as a mixture of alcohols with different numbers of carbon atoms, but in the present invention, the average number of carbon atoms in the longest carbon chain of the alcohol and the longest alkyl group of the α-olefin (polymerized The sum of the average number of carbon atoms of the portions (which will later become side chains) must be in the range of 27 to 0, preferably 0 to 3. The total number of carbons is 2
When it is less than 1, or when it exceeds 0, almost no effect can be expected.

The reaction between the reaction product of α-olefin and maleic anhydride and the alcohol can be carried out according to a conventional method, optionally using an acid catalyst, in a suitable solvent such as benzene, toluene, xylene, methyl ethyl ketone, dioxane, etc. It is carried out without solvent by heating to ≦Q~/9tOC.

The reaction molar ratio of alcohol is suitably 7 to 2 times molar to the acid anhydride group in the reaction product of α-olefin and maleic anhydride. The reaction product preferably contains an average of 0, r to 8 nanomoles of alcohol per mol of acid anhydride group.

After the reaction is completed, the acid catalyst is washed away with water, and then the solvent and unreacted alcohol are removed by distillation to obtain the desired alcohol adduct (hereinafter simply referred to as the adduct).

Salts of the above adducts can be obtained by conventional methods. For example, hydroxide salts such as potassium hydroxide, sodium hydroxide, ammonium hydroxide, etc. are obtained in solvents such as benzene, toluene, xylene, etc. or without solvents.

The adduct and its salt thus obtained are used as a wax microcrystallization agent and (4) described below, and function as a dispersing agent for microcrystallized wax.

As the wax microcrystallization agent (component B), a reaction product of low molecular weight polyethylene with a weight average molecular weight of 300 to 000 and maleic anhydride is used. The resulting α-olefin, polyethylene wax, or grease wax produced as a by-product during the production of high-molecular-weight polyethylene is used.If the weight average molecular weight of low-molecular-weight polyethylene is less than 100, it may be difficult to combine with the wax contained in fuel oil. Microcrystallization is less effective due to insufficient interaction;
Moreover, if the weight average molecular weight exceeds 20,000, the solubility in fuel oil will be poor, which is not preferable.

The reaction product of low molecular weight polyethylene and maleic anhydride is prepared by mixing low molecular weight polyethylene and maleic anhydride in an amount of θ, /~a o wt % with respect to the low molecular weight polyethylene, in the presence of a radical initiator. heated in the absence of
It can be obtained by carrying out a copolymerization reaction or a grafting reaction.

The ratio of component B to component A used is o,/~i.

Weight times, preferably 0. A range of 2 times the weight is appropriate.

The low-temperature fluidity improver composed of component B and component B obtained in this way has a range of /0 to / for hydrocarbon fuel oil.
0.000 ppm, preferably / 00- / 0
001) The addition of PI and K can significantly improve the fluidity at low temperatures. It can impart excellent low-temperature fluidity to oil.

The present invention will be explained below with reference to Examples.

The method for measuring the amount-average degree of polymerization and the method for testing low-temperature fluidity are shown below.

(1) Method for measuring amount-average electric power (Pw) Gel permeation chromatograph (G.

P, C1) method, it was calculated from the following formula using a standard polystyrene calibration curve.

However, the number of molecules Pl: 1 is the molecular weight average degree of polymerization of PW, and the polymerization degree of the molecule is 1. For the measurement, a high performance liquid chromatograph HLO-/r02 UR manufactured by Toyo Soda Kogyo ■ is used. It was done on condition.

Solvent: THF column 2000, 3000, 2000×2 (
East 1st column) Temperature: 9toC Flow rate: t, 2II//Kaku (2) Low temperature fluidity test method Low temperature fluidity evaluation is as follows: Measure the pour point by fXB K-16 "Petroleum product pour point test method" or an automatic overflow clogging point tester TEM MIO-cypp-A1 that complies with the IF 309/7≦ standard! ! CFPF (001dfi) using
This was done by measuring the 1t6r plugging point and determining the 2nd plugging point.

That is, a glass test tube covered with a stainless steel tube was immersed in a glass tank maintained at -1 aC, a sample arB/ was placed inside and cooled, and a stainless steel mesh (filter) with a 3JO mesh (pore diameter lc hiromu) Insert the glass pipette at the tip into the sample and aspirate the sample into the pipette under reduced pressure of 200 μ water column. 0PPP with temperature
Expressed as a value. The lower the 0FPP value (temperature), the lower the temperature at which clogging of the filter occurs. That is, it shows good low-temperature fluidity.

Example [Mu-■] Production table of reaction product of α-olefin and maleic anhydride-/ , θ mole and in experiment A/ toluene 3
．． 0 mol was used. ) into a flask, and after purging with nitrogen gas, adjust the temperature to 100C and add tertiary-butyl peroftate (purity yrs) while stirring.
6. Octopus f (0.02 mol) was added and reacted for 6 hours. Next, xylene is distilled off by increasing the temperature, and unreacted α-olefin and maleic anhydride are removed under reduced pressure.
-Olefin O maleic anhydride copolymer was obtained. (Experiment/%/-/) The weight-average degree of polymerization of the obtained copolymer was determined by gel vermiacetin chromatography, and α-
The copolymerization molar ratio of olefin and maleic anhydride was determined by elemental analysis and is shown in Table 7.

0 mol of α-olefin having 1r carbon atoms and 0 mol of maleic anhydride were charged into a flask, and after replacing the flask with nitrogen, the temperature was raised to 00C with stirring and reacted at the same temperature for 2 hours. . Next, unreacted α-olefin and maleic anhydride were distilled off while gradually increasing the degree of vacuum to obtain α-olefin and maleic anhydride adduct 2701. α−
The addition molar ratio of olefin and maleic anhydride was determined by measuring the acid value. The results are shown in Table-7.

(Note) Dialene is a registered trademark of Sano Kasei Kogyo.
Dialene l≦l is a mixture of α-olefins with carbon atoms /4 and /r, Dialene 201 is a mixture of α-olefins with carbon atoms -0 to r, and the others have a single number of carbon atoms. It is an α-olefin.

(Reaction product of the α-olefin produced in A-11 Component Mu [Mu-I] and maleic anhydride (Experiment 4.r) Cobb 0.! f (amount containing 〇 mole to acid anhydride group) , a synthetic alcohol with 13 carbon atoms (Diadol/J (trademark), manufactured by Mitsubishi Chemical Industries, Ltd.) and xylene l-1,jf were placed in a flask 11, heated to 100Cyc with stirring, and reacted for a feeding time at the same temperature. Let me.

Half-esterified product of the reaction product of α-olefin and maleic anhydride 6/! , 2F was obtained. The degree of esterification of the obtained adduct was determined as bait lS from the acid value measurement.

Also, [Mu-I] Experiment/I6! The α-olefin/maleic anhydride copolymer obtained with and the number of carbon atoms/! An adduct with alcohol (Diadol TR (trademark), manufactured by Mitsubishi Chemical Industries, Ltd.) and potassium hydroxide in an amount equivalent to the hydroxyl group contained in the adduct are heated in a flask with stirring to 13°C to 2°C to form a The water was removed from the reaction system, and an appropriate amount of xylene was added to adjust the concentration to produce the potassium salt of the adduct.

Adducts with alcohols and salts thereof shown in Table 1 were produced in a similar manner and used as components of the low temperature fluidity improver of the present invention. Table 3 shows the components produced.

Table 3 CB-1) Production of component B-7 α-olefin with an average number of carbon atoms (manufactured by Mitsubishi Chemical Industries, Ltd., Dialene 30 (trademark)) 600f and maleic anhydride de0. After charging the flask with nitrogen and purging with nitrogen, di-tertiarybuternomonooxide e and t4f were added under stirring at a temperature of 1roC, and a reaction was carried out for a period of time. Next, unreacted maleic anhydride is distilled off while gradually increasing the degree of vacuum, and the α-olefin
Maleic anhydride copolymer 6901 was obtained (B-7). The weight average degree of polymerization of the obtained copolymer was determined to be lco, j by gel permeation chromatography.

Similarly, α-olefin/maleic anhydride copolymers (B-co and B-J) were produced by changing the amount of maleic anhydride charged or the type of α-olefin. Result line table -
Shown at @.

α-olefin/maleic anhydride adducts (B7g and 7g) were prepared in the same manner as above, except that di-tert-butyl oxidite was added and the reaction was carried out for 2 hours in 2 OCs. Manufactured. The results are shown in Table D.

Table-Hiro CB-11) Production of component B-2 Low molecular weight polyethylene with a number average molecular weight of about 3100 (grease wax by-product during polyethylene production) 10001 and maleic anhydride! Prepare Of into a 2A flask,
After nitrogen substitution, it.

Di-tertiary-butyl peroxide at 2.2 F was added to the mixture under stirring at a temperature of 2.2° C., and the mixture was allowed to react for a feeding time. Next, unreacted maleic anhydride was distilled off while gradually increasing the degree of vacuum, and a low molecular weight polyethylene/maleic anhydride copolymer (B-6) having a weight average molecular weight of about 100 g/7 was distilled off.
I got an F.

Similarly, by changing the amount of maleic anhydride or the type of low molecular weight polyethylene, low molecular weight polyethylene/maleic anhydride copolymers (B-7, B-r and B-ta) were produced.
was manufactured. The results are shown in Table-rK.

Table - Number average molecular weight, 2) Weight average molecular weight (0-13 Low temperature fluidity test-7 Commercially available light gas oil (specific gravity 0 IJt4, sulfur content θ, 10, sulfur content, feed, pour point + 22.C1 flammability) Point/l!4tC1
Kinematic viscosity //, 610st/suOC> by weight ratio 10:2
It00ppm of the previously produced component in the fuel oil blended with
and/or component B! 00 ppm was added to evaluate the low temperature fluidity. The results are shown in Table 4.

Table - ≦ 17 indicates the amount of component M and portion B added, respectively / t
o ppm.

[C! -II) Low-temperature fluidity test-2 Component A and component B produced previously were added to Minas A heavy oil having a pour point jc, and the pour point was measured. The results are shown in Table-7.

Table −?

Claims (1)

[Claims] (1) (A) Average number of carbon atoms lO to α- of JO
The amount average degree of polymerization of olefin and maleic anhydride is l~
100 reactants and an average number of carbon atoms of 4 to . 21 with an aliphatic alcohol, the sum of the average number of carbon atoms of the longest chain alkyl group of the -1 olefin and the average number of carbon atoms of the longest carbon chain of the aliphatic alcohol is co/- 0 and (B) a reaction product of a low molecular weight polyethylene having a weight average molecular weight of 100 to J12000 with maleic anhydride.