KR101234274B1 - Amide and Ester Copolymers from Poly(Styrene-Alkyl Acrylate-Maleic Anhydride) as a Dispersant - Google Patents

Abstract

The present invention relates to a dispersant comprising an amide and ester copolymer of poly (styrene-alkyl acrylate-maleic anhydride).
The poly (styrene-alkyl acrylate-maleic anhydride) amide and ester dispersant of the present invention have a hydrocarbon group, a carboxylic acid group, and an amide / ester structure in a molecular structure at the same time to be included in fuel oils, oils, inks, paints, coatings, and the like. Various kinds of carbons, pigments and the like can be effectively dispersed.

Description

Amide and Ester Copolymers from Poly (Styrene-Alkyl Acrylate-Maleic Anhydride) as a Dispersant}

The present invention relates to a dispersant that effectively disperses carbon, pigments, and the like, and more particularly, styrene and anhydrous, which can be used as a dispersant that can disperse carbon, pigments, etc. contained in fuel oils, oils, inks, paints, coating agents, and the like. A dispersant comprising an amide and ester copolymer of poly (styrene-alkyl acrylate-maleic anhydride) synthesized through copolymerization from monomers such as maleic acid and alkyl acrylate.

The dispersant has a structure in the form of an oil-soluble surfactant, which disperses polar deposits in fuel oil and dissolves and disperses substances attached to nozzles inside the engine. Usable as dispersants include amides, amines, polybutenesuccinimides, polyolefin amines, polyether amines and the like. The dispersant is used in a state diluted in a solvent, and about 300 ppm of these compounds are added to diesel.

Korean Laid-Open Patent Publication No. 2005-0010718 and Japanese Laid-Open Patent Publication No. 2005-42113 include a paraffinic dispersant and a block copolymer which are derivatives of fatty amines, and improve the low temperature properties of mineral oil and mineral oil distillate. Additives and fuel oils in which such additives are formulated are described. Korean Patent Laid-Open Publication No. 2005-0025070 describes a diesel fuel composition containing a metal additive stabilized for phase separation, which diesel fuel is used for stabilizing the dispersed or solubilized metal catalyst compound and the metal catalyst compound. It contains an organic compound as a stabilizer. WO 02/12417 A1 describes additives for improving the combustibility of diesel oils, including metal oxidation catalysts, organic nitrates and dispersants, but the dispersants are intended to increase the activity of a mixture of metal oxidation catalysts and organic nitrates. As used, polyolefin amines or alkylaryl amines and the like are described as such dispersants. In addition, Korean Patent Laid-Open Publication No. 2005-0010718 discloses controlling mass% of unsaturated and saturated acids without using polycyclic acids or derivatives thereof in order to improve low temperature behavior and filterability of fuel oil. have.

U.S. Pat.No. 5,567,211 also relates to gasoline engine cleaners, in particular intake valve deposition inhibitor additives, which additives contain a condensation product of 4-alkyl-2-morpholinone and alkylphenoxypolyoxyalkylene amines. It also discloses that it contains a mixture of alkanolamines and polyisobutylene amines.

It is an object of the present invention to provide a dispersant for effectively dispersing various kinds of carbon, pigments and the like contained in fuel oil, oil, ink, paint, coating agent and the like.

The present invention provides a dispersant comprising an amide and ester copolymer of poly (styrene-alkyl acrylate-maleic anhydride).

The dispersant comprising the amide and ester copolymer of the poly (styrene-alkyl acrylate-maleic anhydride) of the present invention has a hydrocarbon group, a carboxylic acid group and an amide / ester structure at the same time in the molecular structure, so that the fuel oil, oil, ink It can effectively disperse various kinds of carbon, pigments and the like contained in paints, coatings, and the like.

Figure 1 shows the dispersibility of the dispersant of the present invention on activated carbon.
Figure 2 shows the dispersibility of the blue pigment of the dispersant of the present invention.

The present invention relates to a dispersant comprising an amide and ester copolymer of poly (styrene-alkyl acrylate-maleic anhydride) represented by the formula (1).

In Formula 1, R ₁ is hydrogen or a methyl group, R ₂ is C ₁ Is a C ₃₀ alkyl group and R ₃ is hydrogen or C ₁ It is a C- ₃₀ alkyl group, l is 0.1-0.89, m is 0.1-0.89, n is 0.01-0.04, and o is 1-5.

More preferably in Formula 1, R ₁ is a methyl group, R ₂ is C ₁₀ C ₂₀ is an alkyl group and R ₃ is C ₁₂ It may be a C ₂₀ alkyl group.

Amides and esters of poly (styrene-alkyl acrylate-maleic anhydride) represented by Formula 1 include polyamines of the poly (styrene-alkyl acrylate-maleic anhydride) copolymer represented by Formula 2 below: It can be prepared to have an amide and an ester group in the molecule of the formula (1) by ring-opening at 150 ~ 250 ℃. The weight average molecular weight (Mw) of the copolymer thus prepared may be 2,000 to 20,000 g / mol, preferably 2,000 to 7,000 g / mol. The molecular weight distribution (Mw / Mn) of the copolymer may be 1.0 to 5.0, preferably 1.1 to 3.0. Particularly, the preferred copolymer has a content of 10 to 85 mol%, preferably 30 to 60 mol%, an alkyl (meth) acrylate unit of formula 5 to 10 to 85 mol%, Preferably 30 to 60 mol%, the content of the ring-opening reaction amide and ester in the maleic anhydride unit of formula 6 is 1 to 30 mol%, preferably 5 to 20 mol%.

In Formulas 2 and 3, R ₁ is hydrogen or a methyl group, R ₂ is C ₁ Is a C ₃₀ alkyl group and R ₃ is hydrogen or C ₁ It is a ~ C ₃₀ alkyl group, l is 0.1 ~ 0.89, m is 0.1 ~ 0.89, n is 0.01 ~ 0.04, o is 1-5.

In Formula 5, R ₁ is hydrogen or an alkyl group of C ₁ ~ C ₃ , R ₂ is C ₁₀ - an alkyl group of C _20.

As the polyamine represented by Formula 3, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, pentaethylenehexaamine, hexaethyleneheptaamine, etc. having an o value of 1 to 5 may be used. The amount of polyamine represented by Chemical Formula 3 may be 0.5 to 2.0 molar ratio with respect to the copolymer represented by Chemical Formula 2, and preferably 0.6 to 1.0 molar ratio. If the polyamine is used in less than 0.5 molar ratio, dimers are produced, resulting in poor cleanliness, and when the polyamine is used in excess of 2.0 molar ratio, excess polyamine remains, resulting in deterioration in oxidation stability and solubility. The ring-opening reaction is carried out in an amount of 10 to 50% by weight relative to the weight ratio of maleic anhydride contained in the copolymer and the copolymer obtained in the presence of a solvent and the polyamine of the formula (3) for 4 to 24 hours at a reaction temperature of 150 to 250 ℃ Can be. Examples of the solvent that can be used in the ring opening ring reaction include aliphatic hydrocarbons or aromatic hydrocarbons such as toluene, n-hexane, tetrahydrofuran, xylene, benzene and the like.

The reaction temperature is preferably 150 to 250 ° C, more preferably 180 to 230 ° C. If the reaction temperature is less than 150 ° C, the kinematic viscosity of the reactants is too large to facilitate a smooth reaction and difficult to obtain a dispersant of the formula (1). In addition, when the reaction temperature exceeds 250 ° C oxidized reaction is a concern for the production of soot and solubility in diesel oil is a problem.

The poly (styrene-alkyl acrylate-maleic anhydride) copolymer represented by Formula 2 may be prepared by radical polymerization of styrene of Formula 4, alkyl (meth) acrylate of Formula 5, and maleic anhydride of Formula 6. The weight average molecular weight (Mw) of the copolymer thus prepared may be 1,000 to 10,000 g / mol, preferably 2,000 to 5,000 g / mol. The molecular weight distribution (Mw / Mn) of the copolymer may be 1.0 to 5.0, preferably 1.1 to 3.0. In particular, preferably 10 to 85 mol%, preferably 30 to 60 mol% of the styrene units of the following formula (4), 10 to 85 mol%, preferably 30 to 60 mol of the alkyl (meth) acrylate units of the formula (5) %, Maleic anhydride unit of formula 6 may be prepared using 1 to 30 mol%, preferably 5 to 20 mol%.

[Formula 4]

[Chemical Formula 5]

In Formula 5, R ₁ is hydrogen or an alkyl group of C ₁ ~ C ₃ , R ₂ is C ₁₀ - an alkyl group of C _20.

[Formula 6]

The copolymer represented by Chemical Formula 2 may be prepared by administering the monomer mixture represented by Chemical Formulas 4 to 6 to a solvent, adding a chain transfer agent thereto, and then performing a radical polymerization reaction using a free radical initiator. Can be.

The alkyl (meth) acrylate represented by the formula (5) is specifically methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and isobutyl (meth) acrylate, hexyl (meth) ) Acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylic Latex, octadecyl (meth) acrylates or comonomers thereof.

The free radical initiator that can be used in the above production process preferably includes a peroxide or an azo compound. Specific free radical initiators include, for example, benzoyl peroxide, t-butyl peroxy acetate, di-t-butyl peroxide, t-butyl peroxy pivalate, t-butyl peroxy-2-ethyl as peroxide compounds. Hexanoate, t-butyl peroxy neodecanoate, t-butyl peroxy isobutyrate, t-butyl peroxy benzoate, t-amyl peroxy neodecanoate, t-amyl peroxy pivalate, t- Amyl peroxy-2-ethyl hexanoate can be used and 2,2'- azo bisisobutyronitrile (AIBN), 1,1'- azobiscyclohexanecarbonitrile, 2,2 'as an azo compound can be used. -Azobis-2-methylpropionamidine and the like can be used. The free radical initiator may be added in a form dissolved in a solvent or in a form dissolved in a monomer by a method known in the art.

The amount of the free radical initiator used is 0.05 to 10% by weight, particularly preferably 0.5 to 1% by weight, based on the weight of the monomer mixture of Chemical Formulas 4 to 6.

As said solvent, an aliphatic hydrocarbon or aromatic hydrocarbons, such as toluene, n-hexane, tetrahydrofuran, xylene, benzene, etc. are mentioned, for example.

The chain transfer agent may use n-dodecyl mercaptan or n-butyl mercaptan.

The process of preparing the amide and ester copolymer of poly (styrene-alkyl acrylate-maleic anhydride) represented by Chemical Formula 1 may be briefly summarized as in Scheme 1 below.

[Reaction Scheme 1]

The present invention also relates to a fuel oil comprising the dispersant.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are merely to illustrate the present invention, but it should be understood that the present invention is not limited thereto.

Manufacturing example  : Poly (Styrene- Alkyl Acrylate -myriad Maleic acid Synthesis of Copolymer

0.5 wt% of initiator bisisobutyronitrile (AIBN) was placed in a 100 ml round container, vacuumed, and filled with nitrogen. 70% by weight of toluene was added as a solvent in a nitrogen atmosphere and stirred until the initiator completely dissolved. The initiator was completely dissolved and styrene, lauryl methacrylate and maleic anhydride were injected into the vessel in a nitrogen atmosphere at a weight ratio of 6: 3: 1. 0.5 wt% of a chain transfer agent, n-dodecyl mercaptan, was injected to appropriately control the molecular weight. The freeze-thaw was carried out three times to remove the oxygen in the solution. The vessel was immersed in an oil bath, and the reaction temperature was adjusted to 60 ° C to carry out a polymerization reaction. The proportion of monomers in all experiments was calculated by weight ratio and injected.

After the completion of the polymerization, the reaction temperature was lowered to room temperature, and then the polymerization reaction product was dissolved in a small amount of tetrahydrofuran and precipitated in an excess of nonsolvent methanol. The obtained polymer was allowed to settle, the supernatant was removed, dissolved in a small amount of tetrahydrofuran, and the excess was added again to recover by precipitating methanol. The recovered polymer was dried in a vacuum oven at 30 ° C. for 24 hours, and the obtained polymer was analyzed for molecular weight through GPC. The molecular weight of the prepared polymer is shown in Table 1 below.

Example  One

The solution obtained by dissolving 182 g of the copolymer obtained in the above preparation in 130 g of xylene was added to a round flask and 32 g of tetraethylenepentaamine (TEPA) was added dropwise with stirring, followed by reaction at 180 ° C. for 6 hours, and then heated to 220 ° C. The reaction was carried out for 4 hours. After the reaction, the temperature was cooled to 150 ° C., and 150 mL of cyclohexane was added to filter the carbonized component, and the filtrate was evaporated in vacuo to synthesize a final copolymer dispersant in 95% yield. The elemental analysis of the copolymer showed that the nitrogen element content was 2.1% and TBN was 47 mg KOH / g.

FT-IR (KBr, ν cm ^-1 ): 1732 (C = O), 1702 (C = O), 1230 (CO)

Example  2 to 11

To prepare a polymer in the same manner as in Example 1 by varying the composition of the monomer as shown in Table 1.

Comparative example  One

Comparative Example 1 is the gas oil itself without containing a polymer.

Weight ratio Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Styrene 6 6 5 5 5 5 4 4 - - - - Lauryl
Methacrylate 3 - 4 - 3 - 4 - 6 5 4 - Stearyl
Methacrylate - 3 - 4 - 3 - 4 3 4 4 - Maleic anhydride One One One One 2 2 2 2 One One 2 - TEPA 4 4 4 4 4 4 4 4 4 4 4 - Molecular Weight M _n 2,000 2,500 2,300 2,600 2,600 2,500 2,600 2,600 2,100 2,400 2,500 - M _w 4,400 5,100 4,800 5,800 5,700 5,900 5,600 5,900 4,500 5,200 5,300 - PD 2.2 2.0 2.1 2.6 2.6 2.4 2.2 2.3 2.1 2.2 2.1 - Solubility ¹ Transparency Transparency Transparency Transparency Transparency Transparency Transparency Transparency Transparency Transparency Transparency -

Experimental Example

Dispersibility of the synthesized copolymer was evaluated by the STEM ^™ -Technology (Space- and Time-resolved Extinction Profiles) technique using a LUMiSizer LS610 Dispersion Analyzer (LUM GmbH, Berlin Germany) tester. As in the mass cylinder method, the sample was prepared by dispersing 0.08 g of activated carbon (or blue pigment) in 80 mL of a diesel oil (ULSD) solution diluted with 500 ppm of synthetic copolymer, and then rotating the rotor at 1500 rpm. Transmittance% was measured and the sedimentation time was measured when the transmittance was 20, 40, 60, 80 100% to evaluate the dispersibility. Dispersibility evaluation results are shown in Table 2 and FIGS. 1 and 2.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Activated Carbon Settling Time (sec) 20% 24.7 32.3 43.9 53.1 24.6 23.7 23.1 15.4 0 0 0 0 40% 144.7 92.4 144.0 143.2 84.8 84.0 73.1 75.4 30.8 22.4 20.8 10.1 60% 204.8 192.4 204.0 193.2 174.7 173.9 123.1 135.4 48.4 42.4 30.8 19.9 80% 285.0 272.4 244.1 223.3 244.8 244.1 163.2 191.6 50.9 62.4 60.8 29.9 100% 395.0 382.7 354.2 333.4 324.8 324.1 323.3 275.6 70.9 82.4 80.8 50.2 Blue Pigment Settling Time (sec) 20% 35.4 24.7 24.0 21.6 22.4 22.3 23.0 22.8 20.9 11.5 10.8 10.0 40% 155.6 134.8 144.0 111.7 122.4 102.2 84.5 74.0 60.8 51.5 50.7 40.0 60% 225.5 194.7 203.9 171.6 172.4 142.2 175.0 122.9 110.9 100.4 70.7 60.0 80% 295.5 254.7 253.9 231.6 232.4 192.2 245.1 163.8 140.9 131.5 100.7 90.0 100% 355.5 314.7 313.9 291.6 282.3 242.2 323.9 324.0 170.8 171.4 150.6 120.1

As a result of Table 2 and the results of FIGS. 1 and 2, it can be seen that the settling time of activated carbon and blue pigment is much higher than that of the comparative example, and the dispersant of the present invention is very excellent. In addition, it can be confirmed that the dispersant of Examples 1 to 8 in which the composition of the monomer is adjusted as compared with Examples 9 to 11 is excellent.

Claims (9)

A dispersant comprising an amide and ester copolymer of poly (styrene-alkyl acrylate-maleic anhydride) represented by Formula 1 below:
[Formula 1]

In Formula 1, R ₁ is hydrogen or a methyl group, R ₂ is C ₁ Is a C ₃₀ alkyl group and R ₃ is hydrogen or C ₁ It is a ~ C ₃₀ alkyl group, l is 0.1 to 0.89, m is 0.1 to 0.89, n is 0.01 to 0.04, o is 1 to 5.
The method according to claim 1, wherein in Formula 1 R ₁ is a methyl group, R ₂ is C ₁₀ C ₂₀ is an alkyl group and R ₃ is C ₁₂ ~ C ₂₀ Alkyl group, characterized in that the dispersant.
The dispersant according to claim 1, wherein the weight average molecular weight of the dispersant is 2,000 to 20,000 g / mol, and the molecular weight distribution is 1.0 to 5.0.
According to claim 1, wherein the copolymer represented by the formula (1) has a content of 10 to 85 mol% of the styrene unit of the formula 4, 10 to 85 mol% of the alkyl (meth) acrylate unit of the formula (5), Dispersant, characterized in that the content of the ring-opened amide and ester in the maleic anhydride unit of the formula (6) is 1 ~ 30 mol%.
[Chemical Formula 4]

[Chemical Formula 5]

In Formula 5, R ₁ is hydrogen or an alkyl group of C ₁ ~ C ₃ , R ₂ is an alkyl group of C ₁₀ ~ C ₂₀ .
[Chemical Formula 6]

The poly (styrene-alkyl represented by the following Chemical Formula 1 including ring-opening reaction of the poly (styrene-alkyl acrylate-maleic anhydride) copolymer represented by the following Chemical Formula 2 at 150 to 250 ° C. Process for the preparation of amide and ester copolymers of acrylate-maleic anhydride):
[Formula 1]

(2)

(3)

In Formulas 1 to 3, R ₁ is hydrogen or a methyl group, R ₂ is C ₁ It is a ~ C ₃₀ alkyl group, R ₃ is hydrogen or a C ₁ ~ C ₃₀ alkyl group, l is 0.1 ~ 0.89, m is 0.1 ~ 0.89, n is 0.01 ~ 0.04, o is 1-5.
6. The poly (styrene-alkyl acrylate) according to claim 5, wherein the polyamine represented by Chemical Formula 3 is diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, pentaethylenehexaamine or hexaethyleneheptaamine. A process for the preparation of amide and ester copolymers of maleic anhydride).
6. The amide and ester copolymers of poly (styrene-alkyl acrylate-maleic anhydride) according to claim 5, wherein the molar ratio of the polyamine represented by Chemical Formula 3 and the copolymer represented by Chemical Formula 2 is 0.5 to 2.0. Method of preparation.
The poly (styrene-alkyl acrylate) according to claim 5, wherein the copolymer represented by Chemical Formula 1 has a weight average molecular weight of 2,000 to 20,000 g / mol and a molecular weight distribution (Mw / Mn) of 1.0 to 5.0. A process for the preparation of amide and ester copolymers of maleic anhydride).
A fuel oil comprising the dispersant of any one of claims 1 to 4.

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