KR101027160B1 - Pour point depressant including nano particles and preparation method thereof - Google Patents

Abstract

The present invention relates to a fluid lowering agent used for improving the fluidity of lubricating oils, such as engine oil, gear oil, transmission oil, hydraulic fluid, and the like, and more particularly, in the process of preparing a polyalkyl methacrylate fluid lowering agent. The present invention relates to a fluidity lowering agent having improved fluidity lowering performance by adding nanoparticles and a method of manufacturing the same. The present invention does not require a complicated process because it does not use a mixture of various monomers to improve the pour point drop performance, as in conventional lubricant additives, and it is simple to add nanoparticles when preparing a polyalkyl methacrylate copolymer. Through the process, it is possible to provide a pour point lowering agent having improved pour point dropping performance and a manufacturing method thereof.

Pour point depressant, polyalkyl methacrylate, nanoparticles, lubricants, pour point drop performance

Description

Pour point depressant added with nanoparticles and preparation method thereof {POUR POINT DEPRESSANT INCLUDING NANO PARTICLES AND PREPARATION METHOD THEREOF}

The present invention relates to a pour point lowering agent used to improve the fluidity of the lubricating oil at low temperatures and a method for preparing the same, and more particularly, pour point lowering performance by adding nanoparticles in the process of preparing a polyalkyl methacrylate-based pour point lowering agent It relates to a pour point lowering agent and a method for producing the improved.

It is practically preferable that lubricating oils such as engine oil, gear oil, transmission oil and hydraulic oil flow freely at low temperatures. These various types of lubricants require a pour point depressant to flow freely at low temperatures, and additives such as pour point depressants are well known in the art.

Pour point depressants of the prior art have been studied in the direction of improving pour point drop performance using certain types of polymers.

For example, U.S. Patent Application Publication No. 2005-0003974 used a copolymer of isoprene and butadiene to prepare a pour point depressant.

U.S. Patent No. 3,910,77 discloses additives for improving flow, including alkyl aromatics and ethylene-containing polymers and N-aliphatic hydrocarbyl succinic acid, which are condensation products of chlorinated wax and naphthalene.

US Patent Publication No. 2007-0094920 discloses additives for improving low temperature flow characteristics produced using copolymers of α-olefins, vinyl esters and esters of α, β-unsaturated carboxylic acids.

In Korean Patent No.0258294, a graph having a structural unit formed from an oil-soluble polymer (a) made of an olefin-based polymer, and a structural unit formed from a polymer (b) having a peroxide bond or a polymer (c) having a peroxide bond and a predetermined functional group Disclosed is a viscosity index improver containing a copolymer.

EP 0872539 discloses a viscosity index improver using a copolymer of a soluble polymer comprising an olefin polymer and a monomer having a hydrogen peroxide bond with methacrylate or 2-hydroxyethyl (meth) acrylate.

The prior art for preparing the above-mentioned pour point depressant can obtain a low temperature pour point drop effect by copolymerizing two or more types of monomers. Since these methods require the use of a large number of monomers, they have to go through different complicated purification processes, resulting in an increase in manufacturing cost. When copolymerizing these monomers at an appropriate blending ratio, it is difficult to control polymerization conditions and separate unreacted materials after the completion of polymerization. There is a problem that must go through the purification process.

The present inventors have been intensively researched to solve the above problems, during the manufacture of the polyalkyl methacrylate-based copolymer for the pour point depressant when the pour point lowering agent is prepared by adding nanoparticles to the low temperature pour point drop performance without complex process It has been found that the present invention can be improved to the present invention.

SUMMARY OF THE INVENTION An object of the present invention is to provide a pour point lowering agent capable of improving low temperature pour point lowering performance without using various types of monomers as in the conventional method of preparing the pour point lowering agent.

Another object of the present invention is to provide a method for preparing a pour point lowering agent which can improve the low temperature pour point lowering performance by adding nanoparticles in the process of preparing a polyalkyl methacrylate copolymer for the pour point lowering agent.

In order to achieve the above object, the present invention comprises the steps of synthesizing an alkyl methacrylate monomer through an alcohol decomposition reaction using a fatty alcohol and methyl methacrylate (step 1); And alkyl methacrylate monomer synthesized in step 1; Methylmethacrylate; Provided is a method for preparing a pour point lowering agent to which nanoparticles are added, comprising a step (step 2) of polymerizing a polyalkyl methacrylate copolymer by radical polymerization of a mixture of a radical polymerization initiator and an organic solvent in which nanoparticles are dispersed. do.

The mixture in step 2 is 49 to 90% by weight alkyl methacrylate monomer; 9-50 weight percent of methyl methacrylate; And 0.1 to 1% by weight of the radical polymerization initiator may be prepared by mixing the organic solvent in which the nanoparticles are dispersed.

Polymerizing the polyalkyl methacrylate copolymer of step 2 It is preferably carried out for 65 to 85 ℃, 2 to 16 hours in a nitrogen atmosphere.

In addition, the present invention is based on the total weight of the polyalkyl methacrylate copolymer It provides a pour point lowering agent to which nanoparticles are added, characterized in that the nanoparticles are contained in an amount of 0.05 to 1% by weight.

Nanoparticles that can be used in the present invention may be used, such as silica nanoparticles, titanium dioxide (TiO ₂ ) nanoparticles and carbon nanotubes.

The present invention does not require a complicated process because it does not use a mixture of various monomers to improve the pour point drop performance, as in conventional lubricating oil additives, and does not require a complicated process, the nanoparticles in the preparation of the polyalkyl methacrylate copolymer for the pour point depressant The addition can provide a pour point depressant and a method of manufacturing the same to improve the pour point drop performance.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention comprises the steps of synthesizing an alkyl methacrylate monomer through alcohol decomposition using fatty alcohol and methyl methacrylate (step 1); And alkyl methacrylate monomer synthesized in step 1; Methyl methacrylate; Provided is a method for preparing a pour point lowering agent to which nanoparticles are added, comprising a step (step 2) of polymerizing a polyalkyl methacrylate copolymer by radical polymerization of a mixture of a radical polymerization initiator and an organic solvent in which nanoparticles are dispersed. do.

Hereinafter will be described in detail step by step the manufacturing method of the pour point lowering agent added nanoparticles according to the present invention.

Step 1 is a step of synthesizing an alkyl methacrylate monomer through an alcohol decomposition reaction using fatty alcohol and methyl methacrylate. Synthesizing the alkyl methacrylate monomer through alcohol decomposition using the fatty alcohol and methyl methacrylate can be easily carried out by those skilled in the art to which the present invention pertains.

The fatty alcohol may be capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoseryl alcohol, but are not limited thereto.

In the step 1, the process of synthesizing the alkyl methacrylate monomer is preferably performed by adding a polymerization inhibitor such as hydroquinone, methylene blue, hydroquinone monomethyl ether, and petosazine to prevent polymerization between monomers in the presence of an acid catalyst. Do.

Acid catalysts that may be used in step 1 may include sulfuric acid, p-toluenesulfonic acid, hydrochloric acid, diaminohexyl cyclocarbodiamide, and the like, but are not limited thereto.

Synthesis of the alkyl methacrylate monomer through an alcohol decomposition reaction is preferably performed for 6 to 24 hours.

If the process of synthesizing the alkyl methacrylate monomer is carried out for less than 6 hours, there is a problem that the complete reaction does not occur, if the polymerization is carried out for more than 24 hours there is a problem that the polymerization reaction between the synthesized trace monomers.

Step 2 is an alkyl methacrylate monomer synthesized in step 1; Methyl methacrylate; It is a step of polymerizing a polyalkyl methacrylate copolymer by carrying out a radical polymerization reaction of the mixture which mixed the radical polymerization initiator and the organic solvent in which the nanoparticles were disperse | distributed.

More specifically, in Step 2, 49 to 90% by weight of the alkyl methacrylate monomer synthesized in Step 1; 9-50 weight percent of methyl methacrylate; And 0.1 to 1% by weight of a radical polymerization initiator in an organic solvent in which nanoparticles are dispersed, to synthesize a polyalkyl methacrylate copolymer to which nanoparticles are added through a radical polymerization reaction.

In the present invention, in order to add the nanoparticles to the polyalkyl methacrylate copolymer synthesized in the present invention, a polymerization reaction is performed using an organic solvent in which the nanoparticles are dispersed.

The organic solvent in which the nanoparticles are dispersed may be prepared by mixing the nanoparticles with an organic solvent such as benzene, toluene, and xylene, followed by ultrasonication.

Nanoparticles that can be used in the present invention may be used, such as silica nanoparticles, titanium dioxide (TiO ₂ ) nanoparticles, carbon nanotubes. The added nanoparticles prevent the paraffin crystals in the lubricating oil formed as the ambient temperature decreases to form a mesh structure with each other, thereby helping to lower the pour point of the lubricating oil.

The nanoparticles are based on the total weight of the polyalkyl methacrylate copolymer. It is included in an amount of 0.05 to 1% by weight. When the nanoparticles are included in an amount of less than 0.05% by weight based on the total weight of the polyalkyl methacrylate copolymer, the effect of improving the pour point drop performance may be insignificant. If it is included in excess of the weight percent it is difficult to evenly distribute the nanoparticles, which may cause the pour point drop performance degradation.

As the radical polymerization initiator that can be used in the polymerization reaction of step 2, t-butylperoxy pivalate, t-hexyl peroxy pivalate, t-butyl peroxy neodecanoate, t-butyl perbenzoate, t- Butyl peroctoate, cumene hydroperoxide, t-octylperoxy neodecanoate, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-hex Silperoxy-2-ethylhexanoate, t-octylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, lauroyl peroxide, benzoyl peroxide, 3,5,5-trimethylhexanoyl Peroxide, diisobutyryl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1- Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,2'-azobisisobutyronitrile, ammonium persulfate, and the like may be used, but It is not limited.

Polymerizing the polyalkyl methacrylate copolymer of step 2 It is preferably carried out at 65 to 85 DEG C, for 2 to 16 hours under a nitrogen atmosphere.

When the process of polymerizing the polyalkyl methacrylate copolymer is performed at less than 65 ° C., there is a problem in that the polymerization does not occur because the radical polymerization initiator is not decomposed and radicals are not generated. When the polymerization is performed above 85 ° C., methyl methacrylate is used. And there is a problem in that some of the organic solvent including nanoparticles are not reacted by vaporization. In addition, when the process of polymerizing the polyalkyl methacrylate copolymer is less than 2 hours, there is a problem that complete polymerization does not occur, and since the complete reaction is performed for 16 hours, no further polymerization process is necessary.

In the present invention, the polyalkyl methacrylate copolymer of step 2 may be polymerized, followed by further purification using methanol or chloroform to obtain a polyalkyl methacrylate copolymer to which nanoparticles are added.

The present invention synthesizes an alkyl methacrylate monomer through an alcohol decomposition reaction using a fatty alcohol and methyl methacrylate, 49 to 90% by weight of the synthesized alkyl methacrylate monomer; 9-50 weight percent of methyl methacrylate; And a mixture of 0.1 to 1 wt% of a radical polymerization initiator in an organic solvent in which nanoparticles are dispersed, to prepare a polyalkyl methacrylate copolymer through a radical polymerization reaction, thereby providing a pour point lowering agent to which nanoparticles are added. .

Synthesized alkyl methacrylate monomers through alcohol decomposition using fatty alcohols and methyl methacrylate, and then synthesized alkyl methacrylate monomers; Methyl methacrylate; And radical polymerization initiators The process of preparing the polyalkyl methacrylate copolymer by polymerizing the mixture mixed with the organic solvent in which the nanoparticles are dispersed is performed in the same manner as the method for preparing the pour point lowering agent of the present invention.

In another aspect, the present invention provides a pour point lowering agent to which the nanoparticles are added, characterized in that the nanoparticles are contained in an amount of 0.05 to 1% by weight based on the total weight of the polyalkyl methacrylate copolymer.

The nanoparticles may be silica nanoparticles, titanium dioxide (TiO ₂ ) nanoparticles, carbon nanotubes, and the like.

Pour point lowering agent according to the present invention can be prepared by adding nanoparticles can be improved pour point drop performance.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

< Example >

Example  One

Hexadecyl methacrylate monomer was synthesized by 110 ml of cetyl alcohol and 79 ml of methyl methacrylate at 90 ° C. for 18 hours. The synthesis was carried out by the addition of acid catalysts sulfuric acid and hydroquinone. After the synthesis was completed, hydroquinone was removed using methanol. In order to polymerize the polyhexadecyl methacrylate copolymer, a mixture of 87 wt% of hexadecyl methacrylate monomer, 12 wt% of methyl methacrylate, and 1 wt% of AIBN as an initiator was mixed at 70 ° C. in a nitrogen atmosphere for 4 hours. Silica nanoparticles were dispersed in toluene and added to the sonicated solution, followed by polymerization. After completion of the polymerization reaction, a polyhexadecyl methacrylate copolymer to which silica nanoparticles, which can be used as a pour point lowering agent, was obtained through a purification process using methanol.

Example  2

An octadecyl methacrylate monomer was synthesized through the alcohol decomposition reaction of 110 ml of stearyl alcohol and 70 ml of methyl methacrylate at 90 ° C. for 18 hours. The synthesis was carried out by the addition of acid catalysts sulfuric acid and hydroquinone. After the synthesis was completed, hydroquinone was removed using methanol. In order to polymerize the polyalkyl methacrylate copolymer, a mixture of 88% by weight of octadecyl methacrylate monomer, 11% by weight of methyl methacrylate and 1% by weight of AIBN as an initiator was mixed at 70 ° C. in a nitrogen atmosphere for 4 hours. Nanoparticles were dispersed in toluene and added to the sonicated solution, followed by polymerization. After the polymerization reaction was completed, a polyoctadecyl methacrylate copolymer to which silica nanoparticles which can be used as a pour point lowering agent was obtained through a purification process using methanol.

Comparative example  One

Polyhexadecylmethyl methacrylate (PHDMMA) was prepared in the same manner as in Example 1 except that silica nanoparticles were not added.

Comparative example  2

Polyoctadecylmethyl methacrylate (PODMMA) was prepared in the same manner as in Example 2 except that silica nanoparticles were not added.

Experimental Example  Pour point measurement experiment

0.1 wt% of the copolymer containing the nanoparticles obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was dissolved in lubricating base oil and then lubricator according to the KS M2016 method using a pour point tester (MPC-602, TANAKA). Significant pour point was measured.

TABLE 1

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Pour point of base oil (℃) -36 -25 -24 -22

As shown in Table 1, compared with Example 1, Comparative Examples 1 and 2 and Comparative Example 2, the polyhexadecylmethyl methacrylate (PHDMMA) added to the silica nanoparticles of Example 1 is compared Pour point drop performance was improved compared to polyhexadecylmethyl methacrylate (PHDMMA) of Example 1, and polyoctadecylmethyl methacrylate (PODMMA) to which silica nanoparticles of Example 2 were added was also polyoctata of Comparative Example 2. It can be seen that the pour point drop performance is improved compared to decyl methyl methacrylate (PODMMA).

Claims (16)

Synthesizing an alkyl methacrylate monomer through alcohol decomposition using fatty alcohol and methyl methacrylate (step 1); And Alkyl methacrylate monomer synthesized in step 1; Methyl methacrylate; A method for producing a pour point lowering agent to which nanoparticles are added, comprising a step (step 2) of polymerizing a polyalkyl methacrylate copolymer by radical polymerization of a mixture of a radical polymerization initiator and an organic solvent in which nanoparticles are dispersed. The method of claim 1, The process of synthesizing the alkyl methacrylate monomer in the step 1 is a method for producing a pour point lowering agent added to the nanoparticles, characterized in that is carried out by adding an acid catalyst and a polymerization inhibitor. The method of claim 2, Wherein said acid catalyst is selected from the group consisting of sulfuric acid, p-toluenesulfonic acid, hydrochloric acid and diaminohexyl cyclocarbodiamide. The method of claim 2, The polymerization inhibitor is a hydroquinone, methylene blue, hydroquinone monomethyl ether and fetocyazine is a method for producing a pour point lowering agent to which nanoparticles are added, characterized in that selected from the group consisting of. The method of claim 1, Synthesizing the alkyl methacrylate monomer through the alcohol decomposition reaction of step 1 is carried out for 6 to 24 hours, characterized in that the manufacturing method of the pour point lowering agent added to the nanoparticles. The method of claim 1, The fatty alcohol is nanoparticles, characterized in that selected from the group consisting of capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lignoceryl alcohol Process for the preparation of the pour point depressant. The method of claim 1, The organic solvent in which the nanoparticles are dispersed is prepared by mixing the nanoparticles with an organic solvent selected from the group consisting of benzene, toluene and xylene, followed by ultrasonication. The method of claim 7, wherein Said nanoparticles are silica nanoparticles, titanium dioxide (TiO ₂ ) nanoparticles and carbon nanotubes are added. The method of claim 1, With respect to the total weight of the polyalkyl methacrylate copolymer Method for producing a pour point lowering agent to which nanoparticles are added, characterized in that the nanoparticles are contained in an amount of 0.05 to 1% by weight. The method of claim 1, The mixture is 49 to 90% by weight alkyl methacrylate monomer; 9-50 weight percent of methyl methacrylate; And 0.1 to 1% by weight of a radical polymerization initiator is prepared by mixing an organic solvent in which the nanoparticles are dispersed. The method of claim 1, The radical polymerization initiator is t-butyl peroxy pivalate, t-hexyl peroxy pivalate, t-butyl peroxy neodecanoate, t-butyl perbenzoate, t-butyl per octoate, cumene hydroperoxide t-octylperoxy neodecanoate, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-octylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, lauroyl peroxide, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, diisobutyryl peroxide, Diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3, Nanoparticles, characterized in that selected from the group consisting of 3,5-trimethylcyclohexane, 2,2'-azobisisobutyronitrile and ammonium persulfate Process for the preparation of added pour point depressant. The method of claim 1, Polymerizing the polyalkyl methacrylate copolymer of step 2 Process for producing a pour point lowering agent to which nanoparticles are added, characterized in that carried out at 65 to 85 ℃, 2 to 16 hours in a nitrogen atmosphere. The method of claim 1, After the polymerization of the polyalkyl methacrylate copolymer of step 2 and the purification step using methanol or chloroform further comprising the step of preparing a pour point lowering agent added nanoparticles. Synthesized alkyl methacrylate monomers through alcohol decomposition using fatty alcohols and methyl methacrylate, and then 49 to 90 wt% of the synthesized alkyl methacrylate monomers; 9-50 weight percent of methyl methacrylate; And a radical polymerization reaction of 0.1 to 1% by weight of a radical polymerization initiator in an organic solvent in which nanoparticles are dispersed to prepare a polyalkyl methacrylate copolymer. Polyalkyl methacrylate copolymer Pour point lowering agent to which nanoparticles are added, characterized in that the nanoparticles are contained in an amount of 0.05 to 1% by weight. The method of claim 15, The nanoparticles are pour point lowering agent added to the nanoparticles, characterized in that selected from the group consisting of silica nanoparticles, titanium dioxide (TiO ₂ ) nanoparticles and carbon nanotubes.