WO2017109411A1

WO2017109411A1 - Fatty acid methyl ester composition having a low pour point

Info

Publication number: WO2017109411A1
Application number: PCT/FR2016/053611
Authority: WO
Inventors: Stéphanie LEBRUN; Ornella ZOVI; Sylvie DESPRET
Original assignee: Arkema France
Priority date: 2015-12-21
Filing date: 2016-12-21
Publication date: 2017-06-29
Also published as: MY197228A; EP3394228A1; FR3045660B1; CN108431185A; KR20180094097A; SG11201805309VA; FR3045660A1

Abstract

The invention relates to a composition comprising: - at least 95 wt% of a castor oil fatty acid methyl ester mixture; - an additive that lowers the pour point; the maximum pour point of the composition being 0°C. The invention also relates to the use of said composition as a lubricant, formwork removal agent for concrete, degreasing agent or cleaning agent.

Description

COMPOSITION OF METHYL ESTERS OF LOW FATTY ACIDS

FLOW POINT

FIELD OF THE INVENTION

The present invention relates to a composition based on fatty acid methyl esters, derived from castor oil, having a low pour point. This composition is useful in particular as a lubricant or to facilitate the stripping of concrete.

TECHNICAL BACKGROUND

It is known to transesterify vegetable or animal oils, which are mixtures of different fatty acids, in order to produce useful products for example for lubrication.

The fatty acid composition varies considerably from one vegetable or animal oil to another, so that each transesterified oil has different properties.

A particularly useful product, especially as a lubricant or concrete release agent, is a mixture of fatty acid methyl esters derived from castor oil. This product contains predominantly methyl esters of C1-C22 fatty acids, the main ones being methyl linoleate and methyl oleate. This product also contains two specific compounds that are generally not found in products derived from other vegetable oils, namely 10-undecylenic acid and methyl ricinoleate.

This product is in particular marketed by Arkema under the designation Oleris® Esterai A. However, a disadvantage of this product is that it has a relatively high pour point, around + 6 ° C. (according to ASTM D97). . As a result, the use of the product is difficult in cold weather.

It is known to use pour point depressant additives to reduce the pour point of various products derived from vegetable or animal oils. Thus, the documents EP 0543356, EP 0626442, US 6,409,778, US 6,051, 538 and US 201 1/296743 describe various compositions in which pour point depressant additives are used.

However, in general, the possibility of lowering the pour point of a product derived from a vegetable or animal oil to allow its use in cold weather depends on the nature and properties of this product. Therefore, there is a need to improve a mixture of fatty acid methyl esters derived from castor oil so as to allow its use in cold weather.

SUMMARY OF THE INVENTION

The invention firstly relates to a composition comprising:

at least 95% by weight of a mixture of methyl esters of castor oil fatty acids;

a pour point depressant additive;

the pour point of the composition being less than or equal to 0 ° C. According to one embodiment, the pour point of the composition is less than or equal to -5 ° C, preferably less than or equal to -9 ° C.

According to one embodiment, the mixture of methyl esters of castor oil fatty acids has an iodine number of 100 to 120 g / 100 g and comprises, in mass proportions:

from 5 to 20%, preferably from 8 to 12% of methyl stearate;

from 20 to 40%, preferably from 25 to 35% of methyl oleate;

from 30 to 50%, preferably from 35 to 45% of methyl linoleate; less than 10%, preferably less than 8.5% of methyl palmitate;

from 1.5 to 4%, preferably from 2 to 3% of methyl ricinoleate;

from 0.4 to 1.5%, preferably from 0.6 to 1% of 10-undecylenic acid.

According to one embodiment, the composition comprises a mass proportion of pour point depressant additive of 1 to 2%, preferably from 1.2 to 1.8%.

According to one embodiment, the pour point depressant additive is an acrylic polymer (preferably according to the general formula presented below) dissolved in an oil, the proportions preferably being from 60 to 100 parts of acrylic polymer. for 15 to 40 parts of oil.

According to one embodiment, the oil is a paraffinic distillate.

According to one embodiment, the additive has: a viscosity at 100 ° C. according to ASTM D445 of 200 to 500 mm ² / s, preferably of 300 to 400 mm ² / s;

- a pour point according to ASTM D97 less than or equal to -30 ° C, preferably less than or equal to -36 ° C;

an acid number according to ASTM D974 less than or equal to

0.6 mg KOH / g, preferably less than or equal to 0.5 mg KOH / g. The invention also relates to the use of the above composition as a lubricant, concrete release agent, degreasing agent or cleaning agent.

The present invention overcomes the disadvantages of the state of the art. It provides more particularly a mixture of fatty acid methyl esters derived from castor oil which can be used in cold weather.

This is accomplished by the use of an additive which makes it possible to lower the pour point of the mixture to less than 0 ° C, preferably to less than -5 ° C or less than -9 ° C.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 represents the kinetics of crystallization of various compositions, estimated by the thickness of the crystal layer formed (in ordinate, in mm) as a function of the temperature (in abscissa, in ° C). Details are in Example 1 below.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The invention is now described in more detail and without limitation in the description which follows.

The composition according to the invention is obtained by mixing a mixture of fatty acid methyl esters derived from castor oil and a pour point depressant additive.

The mixture of fatty acid methyl esters derived from castor oil is obtained by transesterification of a castor oil with methanol. The transesterification rate of the mixture is not necessarily 100%, which means that the mixture of methyl esters in question may comprise a certain proportion of unesterified fatty acids.

The mixture of fatty acid methyl esters derived from castor oil is preferably characterized by a pour point according to ASTM D97 of 5 to 8 ° C; and / or an iodine value of 100 to 120 g / 100 g. The iodine number can be determined according to ISO 3961. The mixture of fatty acid methyl esters in question preferably comprises:

from 5 to 20%, preferably from 8 to 12% of methyl stearate (C18: 0);

from 20 to 40%, preferably from 25 to 35% of methyl oleate (C18: 1);

from 30 to 50%, preferably from 35 to 45% of methyl linoleate (C18: 2);

less than 10%, preferably less than 8.5% of methyl palmitate (C16: 0);

from 1.5 to 4%, preferably from 2 to 3% of methyl ricinoleate (C18: 1 (OH));

from 0.4 to 1.5%, preferably from 0.6 to 1% of 10-undecylenic acid (C1 1: 1).

The pour point depressant additive is selected such that it makes it possible to lower the pour point of the composition according to the invention below 0 ° C. (preferably below -1 ° C. C, or -2 ° C, or -3 ° C, or -4 ° C, or -5 ° C, or -6 ° C, or -7 ° C, or -8 ° C, or -9 ° C, according to ASTM D97).

This may include an acrylic polymer (which includes acrylic copolymers) dissolved in an oil. The relative proportions are preferably from 60 to 100 parts of acrylic polymer for 15 to 40 parts of oil.

The acrylic polymer is preferably a polyalkylmethacrylate of the general formula:

wherein n is an integer, which is preferably from 200 to 2000, and each R is independently a C1-C22 alkyl group.

The oil can for example be obtained by catalytic hydrogenation of a petroleum fraction and comprise predominantly predominantly saturated C15 to C30 hydrocarbons, and have a viscosity of less than 19 cSt at 40 ° C. It can in particular be the oil referenced under the number CAS 64742-55-8. The oil can also be obtained by catalytic hydrogenation of a petroleum fraction and comprise predominantly C20 to C30 hydrocarbons, predominantly saturated, and have a viscosity greater than 19 cSt at 40 ° C. It may especially be the oil referenced under the number CAS 64742-54-7.

The oil can also be obtained from a petroleum fraction, by removing paraffins by crystallization in a solvent and comprising predominantly C20 to C30 hydrocarbons, and have a viscosity of greater than 19 cSt at 40 ° C. It may especially be the oil referenced under the number CAS 64742-65-0.

It is also possible to use a mixture of the above oils.

Preferably the additive has:

a viscosity at 100 ° C. according to ASTM D445 of 200 to 500 mm ² / s, preferably of 300 to 400 mm ² / s; and or

- a pour point according to ASTM D97 less than or equal to -30 ° C, preferably less than or equal to -36 ° C; and or

an acid number according to ASTM D974 less than or equal to 0.6 mg KOH / g, preferably less than or equal to 0.5 mg KOH / g.

A particularly suitable additive is the product marketed by Evonik under the reference VISCOPLEX® 1 -21 1.

The additive may be present in the composition in a weight ratio of 0.1 to 5%, and preferably 1 to 2%. Preferred ranges of contents are: from 1.0 to 1.1%; from 1, 1 to 1, 2%; from 1, 2 to 1, 3%; from 1, 3 to 1, 4%; from 1.4 to 1.5%; from 1.5 to 1.6%; from 1.6 to 1.7%; from 1.7 to 1.8%; from 1.8 to 1.9%; and from 1.9 to 2.0%. A weight content of about 1.5% is particularly suitable.

The content of acrylic polymer or copolymer in the composition of the invention is preferably from 0.5 to 2%, more preferably from 0.8 to 1.4% (especially from 0.8 to 0.9%). , or from 0.9 to 1.0%, or from 1.0 to 1.1%, or from 1.1 to 1.2%, or from 1.2 to 1.3%, or from 1 to at 1, 4%).

According to one embodiment, the composition consists essentially of the mixture of fatty acid methyl esters derived from castor oil and the pour point depressant additive. According to another embodiment, the composition consists of the mixture of fatty acid methyl esters derived from castor oil and the pour point depressant additive.

EXAMPLES

The following examples illustrate the invention without limiting it. Example 1

Various pour point depressant additives are added at a level of 1 to 2.5% in a mixture of fatty acid methyl esters derived from castor oil marketed under the designation Oleris® Esterai A by Arkema (point d). flow: + 6 ° C).

The additives used are:

- VISCOPLEX® 10-310 (Evonik): Acrylic copolymer in a content greater than or equal to 60%, combined with rapeseed oil, having a viscosity of 1800 mm ² / s at 100 ° C;

- VISCOPLEX® 1 -21 1 (Evonik): acrylic polymer in a content greater than or equal to 60%, combined with a neutral oil, having a viscosity of 400 mm ² / s at 100 ° C;

- VISCOPLEX® 1 -180 (Evonik): acrylic copolymer in a content of 40 to 70%, combined with a neutral oil, having a viscosity of 300 mm ² / s at 100 ° C;

- VISCOPLEX® 1 -255 (Evonik): acrylic copolymer in a content of 15 to 40%, combined with a neutral oil, having a viscosity of 45 mm ² / s at 100 ° C.

The pour points of the compositions thus obtained are summarized in the following table:

Pour point (ASTM D97) The VISCOPLEX® 1 -21 1 additive is particularly interesting because it allows the pour point to drop to -9 ° C at a concentration of only 1.5%.

In addition, crystallization kinetics measurements were made between 5 and -3 ° C., by measuring the thickness of the crystal layer formed in a sample kept in a test tube (height of 55 mm filling). These measurements concerned four compositions manufactured with 1.5% of the four additives above; as well as on a control sample of Oleris® Esterol A. The results are shown in FIG. 1. They demonstrate that the VISCOPLEX® 1 -21 1 additive is the one that offers the slowest crystallization kinetics.

Curve 1 represents the control composition without additive, curve 2 represents the composition manufactured with VISCOPLEX® 1 -255, curve 3 represents the composition manufactured with VISCOPLEX® 1 -180, curve 4 represents the composition manufactured with VISCOPLEX ® 10-310 and curve 5 represents the composition made with VISCOPLEX® 1 -21 1.

Example 2

The consistency of various compositions prepared with the same products as in Example 1 was evaluated after storage under static conditions at -7 ° C for 7 days.

The results are shown in the table below:

Homogeneity and fluidity of products The compositions obtained with VISCOPLEX® 1 -21 1 are the most advantageous in terms of homogeneity and fluidity, for a content of additive remaining moderate (1, 5%).

Claims

Composition comprising:

at least 95% by weight of a mixture of methyl esters of castor oil fatty acids;

a pour point depressant additive;

the pour point of the composition being less than or equal to 0 ° C.

The composition of claim 1 wherein the pour point is less than or equal to -5 ° C, preferably less than or equal to -9 ° C.

A composition according to claim 1 or 2, wherein the mixture of castor oil fatty acid methyl esters has an iodine value of 100 to 120 g / 100 g and comprises, in mass proportions:

from 5 to 20%, preferably from 8 to 12% of methyl stearate;

from 20 to 40%, preferably from 25 to 35% of methyl oleate;

from 30 to 50%, preferably from 35 to 45% of methyl linoleate;

less than 10%, preferably less than 8.5% of methyl palmitate;

from 1.5 to 4%, preferably from 2 to 3% of methyl ricinoleate;

from 0.4 to 1.5%, preferably from 0.6 to 1% of 10-undecylenic acid.

Composition according to one of Claims 1 to 3, comprising a mass proportion of pour point depressant additive of 1 to 2%, preferably of 1.2 to 1.8%.

Composition according to one of claims 1 to 4, wherein the pour point depressant additive is an acrylic polymer dissolved in an oil, the proportions being preferably from 60 to 100 parts of acrylic polymer for 15 to 40 parts of oil.

The composition of claim 5, wherein the acrylic polymer is of formula:

wherein n is an integer preferably 200 to 2000, and each R is a C1 to C22 alkyl group.

The composition of claim 5 or 6, wherein the oil is a paraffinic distillate.

Composition according to one of Claims 1 to 7, in which the additive has:

a viscosity at 100 ° C. according to ASTM D445 of 200 to 500 mm ² / s, preferably of 300 to 400 mm ² / s;

Use of the composition according to one of claims 1 to 8 as lubricant, concrete release agent, degreasing agent or cleaning agent.