KR101278872B1 - Norbornene dialkyl ester containing dialkyl dithiocarbamate compounds, antiwear additives and lubricant comprising the same - Google Patents

Abstract

(식 중, R₁ 은 각 경우에 동일하거나 상이하며, 탄소수 1 내지 10 의 알킬기이고, R 은 각 경우에 동일하거나 상이하며, 탄소수 4 내지 20 의 알킬기 또는 알케닐기임). The present invention relates to a norbornene dialkyl ester compound containing a novel dialkyl dithiocarbamate group represented by the following formula (1), an antiwear agent and a lubricant comprising the same:
[Formula 1]

(Wherein R ₁ is the same or different at each occurrence and is an alkyl group having 1 to 10 carbon atoms, and R is the same or different at each occurrence and is an alkyl group or alkenyl group having 4 to 20 carbon atoms).

Description

NOBORNENE DIALKYL ESTER CONTAINING DIALKYL DITHIOCARBAMATE COMPOUNDS, ANTIWEAR ADDITIVES AND LUBRICANT COMPRISING THE SAME}

The present invention relates to norbornene dialkyl ester compounds having novel dialkyl dithiocarbamate groups, antiwear agents and lubricating oils comprising the same.

Recently, with the development of the industry, precision instruments and various industrial parts are required to operate under harsher environmental conditions, and in order to satisfy this, additives having excellent wear resistance are used.

Such an anti-wear agent is an anti-wear agent that exhibits a load carrying capacity by forming a film on the metal surface to prevent wear caused by contact between the metal and the metal. Abrasion resistance has the advantage of improving the efficiency of the machine, reducing fuel consumption and reducing energy by reducing wear caused by metal-to-metal contact.However, if oil is leaked during use, it causes soil pollution and water pollution. Due to the disadvantage that you need to reduce the usage.

As the anti-wear agent used to improve the wear resistance acts as a wear-resistant agent according to the chemical structure and the elements of the compound contained in the anti-wear agent, since the anti-wear agent is used to form a film on the metal surface. Significantly reduces the energy generated by friction, which shows effective and good abrasion resistance.

Among them, the anti-wear agents for improving the wear resistance, which are widely known, contain molybdenum. Patents related to such anti-wear agents containing molybdenum include Al. tea. Vanderbilt's organic molybdenum compound and manufacturing method (US Patent No. 4,889,647, US Patent No. 5,137,647, US Patent No. 5,412,130), Organic Molybdenum Complex (JP-A-5-247075), Exxon Research & Engineering Friction Reduction Organic Molybdenum Abrasion Resistant Additive (US Pat. No. 4,164,473), Multifunctional Additive for Lubricant (US Pat. No. 4,474,674), Method for Manufacturing Lubricant Additives of Mobil Oil Corporation (US Pat. No. 4,259,254), of Ethyl Corporation Antioxidant System of Lubricant Base Oils (U.S. Patent No. 5,840,672), Lubricant Coated with Molybdenum Compounds (e.g. U.S. Patent No. 6,174,842), Molybdenum Compounds as Multifunctional Additives of Oil-soluble Molybdenum Mixtures and Lubricant Compositions (European Patent No. 1,136,496 B1) , Soluble Molybdenum Coating Composition (European Patent No. 1,136,497 B1), Asahi Denka Kokyo K. Lubricating oil composition containing molybdenum of K. (US Patent No. 4,692,256), oil-soluble molybdenum multifunctional friction additive (U.S. Patent No. 6,103,674) for lubricating composition of Uniroyal Chemical Company, Lubricant additive of TEXACO Corporation Patent 4,765,918) and the like are known.

However, known antiwear agents have limited solubility in oils, are expensive in terms of cost, and for phosphorus-containing compositions can cause corrosion of metals, and when used in rubber-like elastomers Can cause a phenomenon.

In addition, since the anti-wear agent contains heavy metals such as molybdenum and zinc and phosphorus with poisoning phenomenon of the exhaust gas catalyst of the internal combustion engine, there is a possibility of causing environmental pollution. Therefore, the development of a new concept of next-generation anti-wear agent that does not cause environmental pollution is difficult. There is an urgent need.

An object of the present invention is to provide a norbornene dialkyl ester compound having a novel dialkyl dithiocarbamate group and a process for producing the same.

Another object of the present invention is to use a novel norbornene dialkyl ester compound, having a wear resistance equal to or higher than that of a conventional antiwear agent, and excellent thermal stability, in particular heavy metals such as molybdenum, zinc and toxic substances such as phosphorus It is to provide a wear-resistant lubricant and lubricants that do not contain much improved environmental friendliness.

In addition, an object of the present invention is to provide an anti-wear agent and a lubricating oil which are excellent in solubility in oil and do not contain phosphorus and do not exhibit corrosion phenomenon of metal.

In order to achieve the above object, the present invention provides a norbornene dialkyl ester compound having a dialkyl dithiocarbamate group represented by the following formula (1) and a method for preparing the same:

[Formula 1]

(Wherein R ₁ is the same or different at each occurrence and is an alkyl group having 1 to 10 carbon atoms, and R is the same or different at each occurrence and is an alkyl group or alkenyl group having 4 to 20 carbon atoms).

The present invention is a method for preparing a norbornene dialkyl ester compound having a dialkyl dithiocarbamate group prepared according to Scheme 1, by reacting dialkyl maleate (Formula 5) and dicyclopentadiene (Formula 6) Preparing a norbornene dialkyl ester (Formula 2) (step S1); And addition reaction of the norbornene dialkyl ester (formula 2) with carbon disulfide and dialkylamine (formula 4) (step S2), to provide a process for producing a norbornene dialkyl ester compound. .

The present invention also provides an anti-wear agent comprising a norbornene dialkyl ester compound having the dialkyl dithiocarbamate group and a lubricating oil comprising the same.

The antiwear agent comprising a norbornene dialkyl ester compound having a novel dialkyl dithiocarbamate group of the present invention has a wear resistance equivalent to or more than that of a conventional antiwear agent, and is excellent in biodegradability, particularly with heavy metals such as molybdenum and zinc. It does not contain toxic substances such as phosphorus, which is more environmentally friendly than conventional antiwear agents, has excellent solubility in oil, and does not contain phosphorus, which does not exhibit corrosion phenomenon of metal.

The present invention relates to a norbornene dialkyl ester compound having a dialkyl dithiocarbamate group represented by the following formula (1).

[Formula 1]

In Formula 1, R < 1 _> Is the same or different at each occurrence, and is an alkyl group having 1 to 10 carbon atoms, and R is the same or different at each occurrence, and is an alkyl group or alkenyl group having 4 to 20 carbon atoms. If the carbon number of R ₁ exceeds 10, there may be a problem of wear resistance. If the carbon number of R is less than 4, the solubility in oil is poor, and if the carbon number exceeds 20, it is measured by a 4-ball anti-wear tester. There may be a problem that the diameter of the four-ball wear scar increases (a decrease in wear resistance) and an uneconomical problem.

More preferably, in Formula 1, R ₁ is an alkyl group having 1 to 4 carbon atoms, and R is an alkyl group or alkenyl group having 6 to 18 carbon atoms.

In one embodiment of the present invention, an example of a norbornene dialkyl ester compound having a dialkyl dithiocarbamate group represented by Formula 1 is dioctyl-5-dibutylcarbamo-thionyl-thio-bicyclo [2,2,1] heptane-2,3-dicarboxylate, bis (2-ethylhexyl) -5-dibutylcarbamo-thionyl-thio-bicyclo [2,2,1] heptane-2 , 3-dicarboxylate, bis (11-methyldodecyl) -5-dibutylcarbamo-thionyl-thiobicyclo [2,2,1] heptane-2,3-dicarboxylate, dododecyl -5-Dibutylcarbamo-thionyl-thio-bicyclo [2,2,1] heptane-2,3-dicarboxylate, dioctyl-5-dioctylcarbamo-thionyl-thio-bicyclo [2,2,1] heptane-2,3-dicarboxylate, bis (2-ethylhexyl) -5-dioctylcarbamo-thionyl-thio-bicyclo [2,2,1] heptane-2 , 3-dicarboxylate, bis (11-methyldodecyl) -5-dioctylcarbamo-thionyl-thio-bicyclo [2,2,1] heptan-2,3-dicarboxylate, dido Decyl-5-di Octylcarbamo-thionyl-thio-bicyclo [2,2,1] heptane-2,3-dicarboxylate, dioctyl-5-bis (2-ethylhexyl) carbamo-thionyl-thio-bi Cyclo [2,2,1] heptane-2,3-dicarboxylate, bis (2-ethylhexyl) -5-bis (2-ethylhexyl) carbamo-thionyl-thio-bicyclo [2,2 , 1] heptane-2,3-dicarboxylate, bis (11-methyldodecyl) -5-bis (2-ethylhexyl) carbamo-thionyl-thio-bicyclo [2,2,1] heptane -2,3-dicarboxylate, dododecyl-5-bis (2-ethylhexyl) carbamo-thionyl-thio-bicyclo [2,2,1] heptane-2,3-dicarboxylate and the like This is preferred.

Hereinafter, a method for preparing a norbornene dialkyl ester compound having a dialkyl dithiocarbamate group according to the present invention will be described with reference to Scheme 1 below.

[Reaction Scheme 1]

First, the dialkyl maleate (Formula 5) may be prepared by a condensation reaction of maleic anhydride (Formula 7) and a fatty alcohol (Formula 8).

[Chemical Formula 5]

Wherein R is the same or different at each occurrence and is an alkyl or alkenyl group having 4 to 20 carbon atoms;

[Formula 7]

;

;

[Formula 8]

Wherein R is the same or different at each occurrence and represents an alkyl or alkenyl group having 4 to 20 carbon atoms.

The dialkyl maleate can be prepared through a condensation reaction method known in the art, using maleic anhydride and a fatty alcohol as starting materials. The condensation reaction may be performed by heating maleic anhydride and a fatty alcohol in the presence of an organic solvent and an acid catalyst.

At this time, the heating temperature is preferably 100 ~ 150 ℃, the reaction time is 10 to 20 hours, it is preferable to remove the water with the Dean-Stark apparatus with heating.

The organic solvent that can be used in the condensation reaction is not particularly limited, but toluene and xylene may be preferably used. The acid catalyst is Amberlyst-15, Ti (OBu) ₄ , pTSA, which is an ion exchange resin manufactured by Sigma Aldrich. H ₂ O and the like can be used, of which Amberlyst-15, pTSA.H ₂ O can be preferably used.

Next, as shown in Scheme 1, dialkyl maleate (Formula 5) and dicyclopentadiene (Formula 6: DCPD) are reacted at a high temperature to prepare a norbornene dialkyl ester (Formula 2) (S1). step).

[Formula 6]

;

;

[Formula 2]

Wherein R is the same or different at each occurrence and represents an alkyl or alkenyl group having 4 to 20 carbon atoms.

The norbornene dialkyl ester (Formula 2) may be carried out through a conventional method of heating and reacting dialkyl maleate (Formula 5) and dicyclopentadiene (Formula 6: DCPD). The heating temperature is preferably 170 to 200 ° C., and when the heating temperature exceeds 170 ° C., a side reaction occurs, and when the heating temperature reaches 170 ° C., it is preferable to maintain the reactor temperature at 200 ° C. or less by controlling the reaction heat through a cooling device. High pressure may be generated by cyclopentadiene (CPD) generated during the reaction, but a pressure of 1.5 to 2.5 bar is preferable, and the reaction time is preferably 10 to 20 hours.

After the heating step, norbornene dialkyl ester may be obtained through a step of distillation under reduced pressure for 10 to 15 hours at a temperature of 10 to 20 ℃ lower than the heating temperature.

Next, a norbornene dialkyl ester compound having a dialkyl dithiocarbamate group (Formula 1) by addition reaction of norbornene dialkyl ester (Formula 2) with carbon disulfide (Formula 3) and dialkylamine (Formula 4) ) Is prepared (step S2).

(3)

[Formula 4]

(Wherein R ₁ is the same or different at each occurrence and is an alkyl group having 1 to 10 carbon atoms);

[Formula 1]

(Wherein R ₁ is the same or different at each occurrence and is an alkyl group having 1 to 10 carbon atoms, and R is the same or different at each occurrence and is an alkyl group or alkenyl group having 4 to 20 carbon atoms).

The addition reaction may proceed through the dropwise addition of dialkylamine, stirring the reactants, cooling and washing.

First, at a low temperature of 5 to 15 ° C., dialkylamine (formula 4) is slowly added dropwise to norbornene dialkyl ester (formula 2) and carbon disulfide, followed by stirring at a temperature of 105 to 120 ° C. for 15 to 20 hours. desirable.

Thereafter, the mixture is cooled to room temperature, volatiles are removed by distillation under reduced pressure, and washed with aqueous HCl solution and distilled water.

Through such a step, a norbornene dialkyl ester compound having a dialkyl dithiocarbamate group (Formula 1) may be prepared.

As described above, norbornene dialkyl ester compounds having a dialkyl dithiocarbamate group (Formula 1) are norbornene dialkyl esters (Formula 2), carbon disulfide (Formula 3), dialkylamine (Formula 4) It synthesize | combines through addition reaction of, and the yield at this time shows 90% or more.

The nucleophilic reaction for synthesizing the norbornene dialkyl ester compound having the dialkyl dithiocarbamate group (Formula 1) can be carried out by controlling the heat of reaction generated at a low temperature, the control of the heat of reaction by putting a reactor in an ice water bath It can be carried out through a control method.

Substitution reaction of Scheme 1 is generally carried out in the technical field to which the technology of the present invention belongs, but through a series of processes norbornene dialkyl ester compound having a dialkyl dithiocarbamate group of the present invention is more efficient Can be obtained.

The present invention also provides an anti-wear agent comprising a norbornene dialkyl ester compound having the dialkyl dithiocarbamate group, and the anti-wear agent according to the present invention may exhibit thermal stability and wear resistance equivalent to or more than those of conventional anti-wear agents.

In addition, the present invention provides a lubricating oil comprising the anti-wear agent.

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 not to limit the present invention.

Example  1: butyl Carbamate Nobonen Dioctyl  Ester ( C4 - DTC - NBDE - C8 )

(One) Dioctyl Maliate  Preparation-Formula 5 (R = C8 )

Install a thermometer, stirrer, Dean-Stark trap, condenser in a two-necked reactor, then maleic anhydride (10.0 g, 102 mmol), 1-octanol (R = C8) (35.5 mL, 224 mmol), Amberlyst-15 (0.500) g), toluene (volume: 40 mL) was added to the reactor and stirred at 110 ° C. for 15 hours. The reaction solution was cooled to room temperature, filtered to remove solids, distilled under reduced pressure to remove remaining alcohol, and a colorless liquid (33.1 g, yield 95%) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 6.23 (s, 2H), 4.17 (t, 4H, J = 9.06 Hz), 1.71-1.62 (m, 4H), 1.38-1.19 (m, 20H), 0.90 -0.86 (m, 6 H).

(2) Nobonen Dioctyl  Preparation of Ester-Formula 2 (R = C8 )

Dicyclopentadiene (DCPD) (40.6 g, 307 mmol) and dioctyl maleate (R = C8) (205 g, 602 mmol) were put in an autoclave, and it heated at 185 degreeC for 14 hours. After cooling to room temperature, the remaining cyclopentadiene (CPD) and dicyclopentadiene (DCPD) were removed by simple distillation at 170 ° C. for 12 hours to obtain a yellow liquid (243 g, yield 99%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 6.25-6.20 (m, 2H), 4.11-3.90 (m, 4H), 3.27-3.08 (m, 3H), 1.62-1.28 (m, 27H), 0.90- 0.86 (m, 6 H).

(3) Butyl Carbamate Nobonen Dioctyl  Preparation of Ester-Formula 1 (R = C8 , R _One = C4 )

Norbornene dioctyl ester (5.00 g) and CS ₂ (1.12 mL, 18.5 mmol) were added to the autoclave, and dibutylamine (2.49 mL, 14.8 mmol) was slowly added dropwise at 10 ° C. The temperature was raised to room temperature, and the autoclave was completely sealed and stirred at 115 ° C. for 18 hours. Then, after cooling to room temperature, the volatile substance was removed by distillation under reduced pressure, diluted with EtOAc, washed twice with 1N HCl aqueous solution, and washed twice with distilled water. EtOAc was removed via distillation under reduced pressure to give a brown liquid (7.15 g, yield 95%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 4.16-3.97 (m, 4H), 3.96-3.81 (m, 4H), 3.65-3.57 (m, 2H), 3.32-3.25 (m, 1H), 2.92- 2.80 (m, 2H), 2.63-2.59 (m, 1H), 2.21-2.00 (m, 1H), 1.76-1.50 (m, 8H), 1.48-1.22 (m, 32H), 0.99-0.88 (m, 6H ).

Example  2: butyl Carbamate Nobonen Diisooctyl  Ester ( C4 - DTC - NBDE - iC8 )

(One) Diisooctyl Maliate  Produce Formula 5 (R = iC8 )

Install a thermometer, stirrer, Dean-Stark trap and condenser in a two-necked reactor, then use maleic anhydride (30.0 g, 306 mmol), 2-ethylhexyl alcohol (105 g, 673 mmol), Amberlyst-15 (1.50 g), toluene (Volume: 122 mL) was added to the reactor and stirred at 110 ° C. for 15 hours. The reaction solution was cooled to room temperature, filtered to remove solids, and distilled under reduced pressure to remove remaining alcohol to obtain a colorless liquid (82.8 g, 79%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 6.23 (s, 2H), 4.11-4.03 (m, 4H), 1.61-1.53 (m, 2H), 1.40-1.29 (m, 16H), 0.91-0.87 ( m, 12H).

(2) Nobonen Diisooctyl  Preparation of esters Formula 2 (R = iC8 )

Dicyclopentadiene (DCPD) (11.7 g, 88 mmol) and diisooctyl maleate (bis (2-ethylhexyl) maleate; 60 mL, 166 mmol) were placed in an autoclave and heated to 190 ° C. for 12 hours. It was. After cooling to room temperature, the remaining cyclopentadiene (CPD) and dicyclopentadiene (DCPD) were removed by simple distillation at 170 ° C. for 12 hours to obtain a yellow liquid (67.2 g, 99%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 6.25-6.21 (m, 2H), 4.07-3.95 (m, 2H), 3.89-3.78 (m, 2H), 3.28 (t, 2H, J = 1.92 Hz) , 3.16-3.07 (m, 2H), 1.56-1.45 (m, 3H), 1.40-1.21 (m, 17H), 0.91-0.85 (m 12H).

(3) Butyl Carbamate Nobonen Dioctyl  Preparation of Ester-Formula 1 (R = iC8 , R _One = C4 )

Norbornene diisooctyl ester (10.0 g, 24.5 mmol) and CS ₂ (2.97 mL, 49.2 mmol) were added to an autoclave, and dibutylamine (4.97 mL, 29.5 mmol) was slowly added dropwise at 10 ° C. The temperature was raised to room temperature, the autoclave was completely sealed and stirred at 115 ° C. for 18 hours. Thereafter, after cooling to room temperature, the volatile substance was removed by distillation under reduced pressure, diluted with EtOAc, washed twice with 1N HCl aqueous solution, and washed twice with distilled water. EtOAc was removed via distillation under reduced pressure to give a brown liquid (14.6 g, 97%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 4.15-3.97 (m, 4H), 3.95-3.80 (m, 4H), 3.66-3.58 (m, 2H), 3.31-3.26 (m, 1H), 2.89- 2.75 (m, 2H), 2.64-2.60 (m, 1H), 2.20-2.06 (m, 1H), 1.98-1.91 (m, 1H), 1.76-1.50 (m, 7H), 1.45-1.26 (m, 20H ), 1.02-0.87 (m, 18 H).

Example  3: butyl Carbamate Nobonen Diisotridecyl  Ester ( C4 - DTC -NBDE-iC13)

(One) Diisotridecyl Maliate  Produce Formula 5 (R = iC13 )

Install a thermometer, stirrer, Dean-Stark trap, condenser in a two-necked reactor, then maleic anhydride (20.0 g, 204 mmol), isotridecanol (123 g, 612 mmol), pTSA (1.94 g, 10.2 mmol), toluene (Volume: 408 ml) was added to the reactor and stirred at 110 ° C. for 15 hours. After cooling to room temperature, the reaction solution was filtered and diluted with EtOAc. After saturated NaHCO ₃ The solution was washed twice with an aqueous solution, twice with distilled water, dried over Na ₂ SO ₄ , and filtered. The residual alcohol was distilled off under reduced pressure to obtain a colorless liquid (89.4 g, 91%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 6.24 (s, 1H), 6.21 (s, 1H), 4.09-3.793 (m, 4H), 3.28-3.08 (m, 2H), 1.56-1.10 (m, 34H), 0.90-0.80 (m, 18H).

(2) Nobonen Diisotridecyl  Preparation of esters Formula 2 (R = iC13 )

Dicyclopentadiene (DCPD) (7.01 g, 53 mmol) and diisotridecyl maleate (bis (11-methyldodecyl) maleate; 50.0 g, 104 mmol) were added to an autoclave, followed by 12 hours at 190 ° C. Heated during. After cooling to room temperature, the remaining cyclopentadiene (CPD) and dicyclopentadiene (DCPD) were removed by simple distillation at 170 ° C. for 12 hours to obtain a yellow liquid (56.8 g, 99%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 6.24 (s, 1H), 6.21 (s, 1H), 4.09-3.79 (m, 4H), 3.28-3.08 (m, 3H), 1.56-0.82 (m, 53H).

(3) Butyl Carbamate Nobonen Dioctyl  Preparation of Ester-Formula 1 (R = iC13 , R _One = C4 )

Norbornene diisotridecyl ester (13.0 g, 23.8 mmol) and CS ₂ (2.00 mL, 33.3 mmol) were added to an autoclave, and dibutylamine (4.81 mL, 28.5 mmol) was slowly added dropwise at 10 ° C. The temperature was raised to room temperature, the autoclave was completely sealed and stirred at 115 ° C. for 18 hours. Thereafter, after cooling to room temperature, the volatile substance was removed by distillation under reduced pressure, diluted with EtOAc, washed twice with 1N HCl aqueous solution, and washed twice with distilled water. EtOAc was removed via distillation under reduced pressure to give a brown liquid (17.3 g, yield 97%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 4.12-35 (m, 10H), 3.29-3.24 (m, 1H), 2.85-2.57 (m, 4H), 2.13-1.89 (m, 2H), 1.78- 1.49 (m, 12H), 1.41-1.06 (m, 26H), 0.99-0.73 (m, 26H).

Example  4

1% by weight of butyl carbamate norbornene dioctyl ester obtained in Example 1 was dissolved in mineral oil-based lubricant base oil (100N BO) A wear resistant agent comprising the same was prepared.

Example  5

1 wt% of butyl carbamate norbornene diisooctyl ester obtained in Example 2 was dissolved in mineral oil-based lubricant base oil (100N BO) to prepare an antiwear agent comprising the same.

Example  6

1% by weight of butyl carbamate norbornene diisotridecyl ester obtained in Example 3 was dissolved in mineral oil-based lubricant base oil (100N BO) A wear resistant agent comprising the same was prepared.

The results of elemental analysis and ¹ H-NMR spectrum of each compound according to the present invention prepared in Examples 1 to 3 are summarized in Table 1 below.

division EA
(%) ¹ H-NMR
(ppm) C H N O S Example
One 66.43
(66.73) 10.50
(10.05) 2.00
(2.29) 10.60
(10.46) 10.47
(10.48) δ 4.16-3.97 (m, 4H), 3.96-3.81 (m, 4H), 3.65-3.57 (m, 2H), 3.32-3.25 (m, 1H), 2.92-2.80 (m, 2H), 2.63-2.59 ( m, 1H), 2.21-2.00 (m, 1H), 1.76-1.50 (m, 8H), 1.48-1.22 (m, 32H), 0.99-0.88 (m, 6H) Example
2 66.50
(66.73) 9.89
(10.05) 2.43
(2.29) 10.34
(10.46) 10.84
(10.48) δ 4.15-3.97 (m, 4H), 3.95-3.80 (m, 4H), 3.66-3.58 (m, 2H), 3.31-3.26 (m, 1H), 2.89-2.75 (m, 2H), 2.64-2.60 ( m, 1H), 2.20-2.06 (m, 1H), 1.98-1.91 (m, 1H), 1.76-1.50 (m, 7H), 1.45-1.26 (m, 20H), 1.02-0.87 (m, 18H) Example
3 70.05
(70.25) 10.55
(10.85) 1.93
(1.86) 8.70
(8.51) 8.77
(8.53) δ 4.12-35 (m, 10H), 3.29-3.24 (m, 1H), 2.85-2.57 (m, 4H), 2.13-1.89 (m, 2H), 1.78-1.49 (m, 12H), 1.41-1.06 ( m, 26H), 0.99-0.73 (m, 26H) () Is the theoretical value

Experimental Example  1: Biodegradation evaluation

The biodegradability of the compound obtained in Examples 1 to 3 and Mo-DTC as a comparative example was evaluated by the OECD 301C method, and the results are shown in Table 2 below.

division Biodegradability (%) Example 1 78% Example 2 82% Example 3 80% Comparative Example
(Mo-DTC, Sakura-165) 30%

As shown in Table 2, it was confirmed that the compounds of Examples 1 to 3 according to the present invention exhibited a biodegradability in the range of 78 to 82%, and the biodegradability of the comparative material Mo-DTC was almost 30%. It was shown that no biodegradation occurred.

Experimental Example  2: solubility evaluation

The solubility of mineral oil and vegetable oil of the compounds obtained in Examples 1 to 3 was measured and shown in Table 3 below.

division Solubility 100N BO
(Mineral oil) Rapeseed Oil
(Vegetable oil) Example 1 Dissolved Dissolved Example 2 Dissolved Dissolved Example 3 Dissolved Dissolved

As shown in Table 3, the compounds obtained in Examples 1 to 3 according to the present invention can be found to be well dissolved in mineral oil (100N BO) and vegetable oil.

Experimental Example  3: Wear resistance  evaluation

1% of the compounds obtained in Examples 1 to 3 were added to mineral oil (100N BO), and the frictional wear test was evaluated by ASTM D4172 method using a 4-ball abrasion resistance tester (Stannhope-seta, UK). Table 4 shows. At this time, the rotation speed is 1200 ± 10 rpm, the test temperature is 75 ± 1.7 ℃, the load is 40 kg, the test time was 60 ± 1 min. The amount of wear was measured as three ball trace diameters after the test was completed.

Wear resistance (4-ball WSD, mm) @ 100N BO Example 1 0.5122 Example 2 0.5162 Example 3 0.5167 Comparative Example
(Mo-DTC, Sakura-165) 0.5260

As shown in Table 4, the diameter of the 4-ball wear scars at 100N BO of the compounds obtained in Examples 1 to 3 was 0.5122 to 0.5167 mm, which was slightly better than 0.5260 mm of the control group, but the difference was large. No ordinary wear resistance is affected.

Claims (7)

Norbornene dialkyl ester compounds represented by the following general formula (1) having a dialkyl dithiocarbamate group:

(Wherein R ₁ is the same or different at each occurrence and is an alkyl group having 1 to 10 carbon atoms, and R is the same or different at each occurrence and is an alkyl group or alkenyl group having 4 to 20 carbon atoms). The Novo according to claim 1, wherein R ₁ is the same or different at each occurrence, and is an alkyl group having 1 to 4 carbon atoms, and R is the same or different at each occurrence, and is an alkyl or alkenyl group having 6 to 18 carbon atoms. Nene dialkyl ester compound. The norbornene dialkyl ester compound of claim 1 is a dioctyl-5-dibutylcarbamo-thionyl-thio-bicyclo [2,2,1] heptane-2,3-dica. Recarboxylate, bis (2-ethylhexyl) -5-dibutylcarbamo-thionyl-thio-bicyclo [2,2,1] heptane-2,3-dicarboxylate and bis (11-methyldode Nor) -5-dibutylcarbamo-thionyl-thiobicyclo [2,2,1] heptane-2,3-dicarboxylate. As a method for producing a norbornene dialkyl ester compound having a dialkyl dithiocarbamate group prepared according to Scheme 2 below,
Reacting a dialkyl maleate represented by Formula 5 with a dicyclopentadiene represented by Formula 6 to produce a norbornene dialkyl ester represented by Formula 2 (S1); And
Method of producing a norbornene dialkyl ester compound comprising the step of reacting the norbornene dialkyl ester with carbon disulfide and dialkylamine represented by the following formula (S2):
[Reaction Scheme 2]

(In Formula 1-5, R <_1> is the same or different in each case, is a C1-C10 alkyl group, R is the same or different in each case, and is a C4-C20 alkyl group or an alkenyl group.). 5. The norbornene dialkyl ester compound according to claim 4, wherein the dialkyl maleate represented by Formula 5 is prepared by a condensation reaction of maleic anhydride represented by Formula 7 with a fatty alcohol represented by Formula 8. Manufacturing method of:
(7)

;
[Chemical Formula 8]

Wherein R is the same or different at each occurrence and represents an alkyl or alkenyl group having 4 to 20 carbon atoms. An anti-wear agent comprising the norbornene dialkyl ester compound according to claim 1. Lubricating oil comprising an antiwear agent according to claim 6.