Process oil and rubber composition comprising same

Abstract

A process oil and a rubber composition comprising the process oil are provided, the process oil comprising a polymer including: a unit (A) derived from an ethylenically unsaturated monomer containing an ester group; and a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group. Regarding the rubber composition, mixing processability is improved, and due to the low viscosity and glass transition temperature of the process oil, low-temperature properties can be improved.

Description

Process oil, rubber composition containing same

[0001] The present invention relates to a process oil and a rubber composition containing the same.

[0002]

[0003] In general tire manufacturing, a green tire is completed from a tire forming composition containing a curing agent and rubber molecules, and the green tire is placed in a curing mold, and cured for a certain period of time while applying heat and pressure to the inside and outside of the green tire, thereby crosslinking the curing agent and the rubber molecules contained in the tire forming composition to obtain stable, inherent properties of tire rubber.

[0004] During this curing process, a thin, sack-like layer of tire rubber is used inside the green tire to determine the tire's appearance. Because tire rubber is used under harsh conditions of high temperature and high pressure, it requires unique properties compared to other rubbers. Under these circumstances, the development of tire rubber with superior performance and long life can directly lead to cost savings. Therefore, research and improvement efforts on tire rubber have been continuously conducted.

[0005] Additionally, various additives are used in tire rubber to improve or strengthen the physical properties required for tires. Among these additives, process oil is used to improve the mixing load when mixing rubber and various additives (chemicals). The process oil acts as a softener, reducing the mixing energy loss required when mixing tire rubber composition components, and improving the dispersion and compatibility between the various materials used in the rubber composition, such as rubber, chemicals, and fillers.

[0006] Process oils used in tire rubber compositions are typically viscous oils composed of hydrocarbon compounds, including aromatic, paraffinic, and naphthenic components. Petroleum-based paraffinic oils are widely used in butyl rubber compounding processes. Castor oil is often blended with them to improve production efficiency and the physical properties of butyl rubber products.

[0007] Meanwhile, hydrocarbon compounds commonly used in process oils are petroleum-based, and their potential for environmental pollution and other issues has been consistently pointed out. In particular, with the growing social demand for environmentally friendly raw materials and products utilizing them, particularly those related to Environment, Social Governance (ESG) and Sustainability, there is a growing need to develop tire process oils using these environmentally friendly raw materials.

[0008]

[0009] The technical problem to be solved by the present invention is to provide a process oil prepared using environmentally friendly materials and a rubber composition containing the same.

[0010]

[0011] One aspect of the present invention relates to a process oil comprising a polymer comprising a unit (A) derived from an ethylenically unsaturated monomer containing an ester group and a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group.

[0012] Another aspect of the present invention relates to a rubber composition comprising the process oil.

[0013]

[0014] The process oil according to the present invention comprises a polymer comprising a unit (A) derived from an ethylenically unsaturated monomer containing an ester group and a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group, so that the process oil can easily implement excellent blending processability.

[0015] In addition, the process oil has low viscosity and glass transition temperature, so that the low-temperature properties of a rubber composition including the process oil can be improved.

[0016]

[0017] Below, various aspects and various implementation examples of the present invention are described in more detail.

[0018] Terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0019] The terminology used herein is merely used to describe specific embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In the present invention, it should be understood that the terms "comprise" or "have" are intended to specify the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0020] Specifically, one aspect of the present invention provides a process oil comprising a polymer comprising a unit (A) derived from an ethylenically unsaturated monomer containing an ester group and a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group.

[0021] For example, the process oil can easily realize excellent blending processability by including a polymer including a unit (A) derived from an ethylenically unsaturated monomer containing an ester group and a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group.

[0022] In addition, since the process oil has low viscosity and glass transition temperature, a rubber composition including the process oil may have excellent low-temperature properties.

[0023] According to one embodiment, the ethylenically unsaturated monomer containing the ester group may be represented by the following chemical formula 1, and the ethylenically unsaturated monomer containing the carboxyl group may be represented by the following chemical formula 2.

[0024] <Chemical Formula 1>

[0025]

[0026] <Chemical Formula 2>

[0027]

[0028] Among the above chemical formulas 1 and 2,

[0029] R 11 Inland R 14 and R 21 Inland R 24 are independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and R 15 Inland R 16 and R 25 are independently an alkyl group having 1 to 20 carbon atoms, a11 and a21 are independently integers of 1 to 20, and a13 and a23 are independently integers of 1 to 50.

[0030] According to one embodiment, among the chemical formulas 1 and 2, R 11 Inland R 14 and R 21 Inland R 24 are independently hydrogen, methyl or ethyl, and R 15 Inland R 16 and R 25 can be independently a methyl group, an ethyl group or a propyl group.

[0031] According to one embodiment, among the chemical formulas 1 and 2, R 11 Inland R 14 and R 21 Inland R 24 are hydrogen, and R 15 Inland R 16 and R 25 can be independently a methyl group, an ethyl group or a propyl group.

[0032] According to one embodiment, in the chemical formulae 1 and 2, a11 and a21 can independently be an integer of 1 to 15, an integer of 1 to 12, an integer of 1 to 9, an integer of 1 to 6, an integer of 1 to 5, or an integer of 1 to 3.

[0033] According to one embodiment, in the chemical formulae 1 and 2, a13 and a23 can be independently an integer of 1 to 50, an integer of 1 to 45, an integer of 1 to 40, an integer of 1 to 35, an integer of 1 to 30, an integer of 1 to 25, an integer of 1 to 20, an integer of 2 to 50, an integer of 4 to 50, an integer of 5 to 50, or an integer of 5 to 20.

[0034] According to one embodiment, the ratio of the number of moles of units (A) derived from the ethylenically unsaturated monomer containing an ester group to the number of moles of units (B) derived from the ethylenically unsaturated monomer containing a carboxyl group in the polymer may be 1 to 20.

[0035] For example, the ratio of the mole number of units (A) derived from the ethylenically unsaturated monomer containing an ester group to the mole number of units (B) derived from the ethylenically unsaturated monomer containing a carboxyl group in the polymer may be 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 to 10, 1 to 8, 2 to 20, 2 to 10, 3 to 20, 3 to 10, or 3 to 8.

[0036] According to one embodiment, at least one of the ethylenically unsaturated monomer containing an ester group and the ethylenically unsaturated monomer containing a carboxyl group may be derived from edible oil.

[0037] For example, the edible oil may include fatty oils that are liquid at room temperature, such as rapeseed oil or salad oil, and fats that are solid at room temperature, such as palm oil or hydrogenated oil. For example, the edible oil may be waste cooking oil. Waste cooking oil may refer to cooking oil remaining after use.

[0038] According to one embodiment, the ethylenically unsaturated monomer containing an ester group and the ethylenically unsaturated monomer containing a carboxyl group can each be derived from edible oil.

[0039] For example, if each of the ethylenically unsaturated monomer containing an ester group and the ethylenically unsaturated monomer containing a carboxyl group is derived from edible oil, the polymer may be a self-polymer of the edible oil. For example, the self-polymer of the edible oil may mean a polymer formed by polymerizing the ethylenically unsaturated monomer containing an ester group and the ethylenically unsaturated monomer containing a carboxyl group contained in the same edible oil. For example, the self-polymer means a polymer formed by polymerizing the ethylenically unsaturated monomer containing an ester group and / or the ethylenically unsaturated monomer containing a carboxyl group contained in the edible oil. For example, self-polymerization means that the ethylenically unsaturated monomers contained in the edible oil are polymerized with each other.

[0040] According to one embodiment, the polymer may be a dimer. For example, the dimer may be a polymer in which two monomer molecules are bonded. For example, the dimer may refer to a polymer in which two molecules of an ethylenically unsaturated monomer contained in the edible oil are bonded. For example, the ethylenically unsaturated monomer contained in the edible oil may include an ester group or a carboxyl group.

[0041] According to one embodiment, the polymer may include two or more of a dimer including a unit (A) derived from an ethylenically unsaturated monomer containing an ester group; a dimer including a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group; and a dimer including a unit (A) derived from an ethylenically unsaturated monomer containing an ester group and a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group.

[0042] The polymer may include a dimer comprising a unit (A) derived from an ethylenically unsaturated monomer containing an ester group; a dimer comprising a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group; and a dimer comprising a unit (A) derived from an ethylenically unsaturated monomer containing an ester group and a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group.

[0043] According to one embodiment, the ratio of the number of moles of the dimer comprising the unit (A) derived from the ethylenically unsaturated monomer containing the ester group; the number of moles of the dimer comprising the unit (B) derived from the ethylenically unsaturated monomer containing the carboxyl group; the number of moles of the dimer comprising the unit (A) derived from the ethylenically unsaturated monomer containing the ester group and the unit (B) derived from the ethylenically unsaturated monomer containing the carboxyl group; may be 1 to 35:1 to 35:50 to 98.

[0044] The number of moles of a dimer including a unit (A) derived from an ethylenically unsaturated monomer containing an ester group is the number of moles excluding a dimer including a unit (A) derived from an ethylenically unsaturated monomer containing an ester group and a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group among dimers including a unit (A) derived from an ethylenically unsaturated monomer containing an ester group.

[0045] The molar number of the dimer including the unit (B) derived from the ethylenically unsaturated monomer containing the carboxyl group is the molar number excluding the dimer including the unit (A) derived from the ethylenically unsaturated monomer containing the ester group and the unit (B) derived from the ethylenically unsaturated monomer containing the carboxyl group among the dimers including the unit (B) derived from the ethylenically unsaturated monomer containing the carboxyl group. For example, the molar number of the dimer including the unit (A) derived from the ethylenically unsaturated monomer containing the ester group among the polymers is 1 to 35 mol%, 1 to 30 mol%, 1 to 25 mol% or less, 2 to 25 mol%, 2.5 to 25 mol%, 3 to 25 mol%, 1 to 23 mol%, 1 to 22 mol%, 1 to 17 mol%, 2.5 to It can be 17 mol% or 3 to 16 mol%.

[0046] For example, the molar number of the dimer including the unit (B) derived from the ethylenically unsaturated monomer including the carboxyl group in the polymer may be 1 to 35 mol%, 1 to 30 mol%, 1 to 25 mol%, 5 to 30 mol%, 5 to 25 mol%, 7 to 30 mol%, 7 to 25 mol%, 10 to 30 mol%, 12 to 30 mol%, 14 to 30 mol%, 1 to 25 mol%, 1 to 23 mol%, 1 to 20 mol%, 1 to 18 mol%, 6 to 23 mol%, or 7 to 18 mol% with respect to the total molar number of the polymer.

[0047] For example, the molar number of the dimer including a unit (A) derived from an ethylenically unsaturated monomer containing an ester group and a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group among the polymers may be 50 to 98 mol%, 50 to 90 mol%, 50 to 87 mol%, 50 to 85 mol%, 50 to 80 mol%, 55 to 90 mol%, 56 to 90 mol%, 66 to 90 mol%, 67 to 90 mol%, 66 to 79 mol%, or 67 to 78 mol% with respect to the total molar number of the polymer. For example, the polymer may be a dimer including two units (A) derived from an ethylenically unsaturated monomer containing an ester group; a dimer including two units (B) derived from an ethylenically unsaturated monomer containing a carboxyl group; And a dimer each including one unit (A) derived from an ethylenically unsaturated monomer containing an ester group and one unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group; may include two or more of the following: a dimer including two units (A) derived from an ethylenically unsaturated monomer containing an ester group; a dimer including two units (B) derived from an ethylenically unsaturated monomer containing a carboxyl group; and a dimer including one unit (A) derived from an ethylenically unsaturated monomer containing an ester group and one unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group.

[0048] According to one embodiment, the ratio of the number of moles of the dimer including two units (A) derived from the ethylenically unsaturated monomer including the ester group; the number of moles of the dimer including two units (B) derived from the ethylenically unsaturated monomer including a carboxyl group; the number of moles of the dimer including one unit (A) derived from the ethylenically unsaturated monomer including the ester group and one unit (B) derived from the ethylenically unsaturated monomer including a carboxyl group; may be 1 to 35:1 to 35:50 to 98.

[0049] For example, the mole number of the dimer including two units (A) derived from the ethylenically unsaturated monomer including the ester group among the polymers may be 1 to 35 mol%, 1 to 30 mol%, 1 to 25 mol%, 2 to 25 mol%, 2.5 to 25 mol%, 3 to 25 mol%, 1 to 23 mol%, 1 to 22 mol%, 1 to 17 mol%, 2.5 to 17 mol%, or 3 to 16 mol% with respect to the total mole number of the polymer.

[0050] For example, the molar number of the dimer including two units (B) derived from the ethylenically unsaturated monomer including the carboxyl group among the polymers may be 1 to 35 mol%, 1 to 30 mol%, 1 to 25 mol%, 5 to 30 mol%, 5 to 25 mol%, 7 to 30 mol%, 7 to 25 mol%, 10 to 30 mol%, 12 to 30 mol%, 14 to 30 mol%, 1 to 25 mol%, 1 to 23 mol%, 1 to 20 mol%, 1 to 18 mol%, 6 to 23 mol%, or 7 to 18 mol% with respect to the total molar number of the polymer.

[0051] For example, the molar number of the dimer each including one unit (A) derived from an ethylenically unsaturated monomer containing an ester group and one unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group among the above polymers may be 50 to 98 mol%, 50 to 90 mol%, 50 to 87 mol%, 50 to 85 mol%, 50 to 80 mol%, 55 to 90 mol%, 56 to 90 mol%, 66 to 90 mol%, 67 to 90 mol%, 66 to 79 mol%, or 67 to 78 mol% with respect to the total molar number of the polymer.

[0052] According to one embodiment, the polymer may include two or more of the compounds represented by the following chemical formulas 3 to 5.

[0053] <Chemical Formula 3>

[0054]

[0055] <Chemical Formula 4>

[0056]

[0057] <Chemical Formula 5>

[0058]

[0059] Among the above chemical formulas 3 to 5,

[0060] L 31 , L 32 , L 41 , L 42 , L 51 and L 52 are independently a single bond; or an alkylene group having 1 to 20 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms,

[0061] R 31 Inland R 36 , R 41 Inland R 46 and R 51 Inland R 56 are independently hydrogen or an alkyl group having 1 to 20 carbon atoms,

[0062] R37 , R 38 , R 47 , R 48 , R 49 , R 57 , R 58 , R 59a and R 59b are independently an alkyl group having 1 to 20 carbon atoms,

[0063] a31, a32, a41, a42, a51 and a52 are independently integers from 1 to 50.

[0064] According to one embodiment, among the chemical formulas 3 to 5, L 31 , L 32 , L 41 , L 42 , L 51 and L 52 can be independently a single bond, a methylene group, an ethylene group, or a propylene group.

[0065] According to one embodiment, among the chemical formulas 3 to 5, R 31 Inland R 36 , R 41 Inland R 46 and R 51 Inland R 56 can be independently hydrogen, methyl, ethyl or propyl.

[0066] According to one embodiment, among the chemical formulas 3 to 5, R 37 , R 38 , R 47 , R 48 , R 49 , R 57 , R 58 , R 59a and R 59b can be a methyl group, an ethyl group, a propyl group, or a butyl group.

[0067] According to one embodiment, in the chemical formulae 3 to 5, a31, a32, a41, a42, a51 and a52 can independently be an integer of 1 to 50, an integer of 1 to 45, an integer of 1 to 40, an integer of 1 to 35, an integer of 1 to 30, an integer of 1 to 25, an integer of 1 to 20, an integer of 2 to 50, an integer of 4 to 50, an integer of 5 to 50 or an integer of 5 to 20.

[0068] For example, the compound represented by the above chemical formula 3 may be a compound in which two molecules of the ethylenically unsaturated monomer containing the carboxyl group are bonded. For example, the compound represented by the above chemical formula 4 may be a compound in which the ethylenically unsaturated monomer containing the carboxyl group and the ethylenically unsaturated monomer containing the ester group are bonded. For example, the compound represented by the above chemical formula 5 may be a compound in which two molecules of the ethylenically unsaturated monomer containing the ester group are bonded.

[0069] According to one embodiment, the polymer may include a compound represented by the above chemical formula 3 and a compound represented by the above chemical formula 4. For example, the polymer may include a compound represented by the above chemical formula 3 and a compound represented by the above chemical formula 5. For example, the polymer may include a compound represented by the above chemical formula 4 and a compound represented by the above chemical formula 5. For example, the polymer may include a compound represented by the above chemical formula 3, a compound represented by the above chemical formula 4, and a compound represented by the above chemical formula 5.

[0070] According to one embodiment, the polymer includes a compound represented by the chemical formula 3, a compound represented by the chemical formula 4, and a compound represented by the chemical formula 5, and a ratio of the number of moles of the compound represented by the chemical formula 3 to the number of moles of the compound represented by the chemical formula 4 to the number of moles of the compound represented by the chemical formula 5 may be 1 to 35: 1 to 35: 50 to 98.

[0071] For example, the mole number of the compound represented by the chemical formula 3 among the polymers may be 1 to 35 mol%, 1 to 30 mol%, 1 to 25 mol%, 2 to 25 mol%, 2.5 to 25 mol%, 3 to 25 mol%, 1 to 23 mol%, 1 to 22 mol%, 1 to 17 mol%, 2.5 to 17 mol%, or 3 to 16 mol% with respect to the total mole number of the polymer.

[0072] For example, the mole number of the compound represented by the chemical formula 4 among the polymers may be 1 to 35 mol%, 1 to 30 mol%, 1 to 25 mol%, 5 to 30 mol%, 5 to 25 mol%, 7 to 30 mol%, 7 to 25 mol%, 10 to 30 mol%, 12 to 30 mol%, 14 to 30 mol%, 1 to 25 mol%, 1 to 23 mol%, 1 to 20 mol%, 1 to 18 mol%, 6 to 23 mol%, or 7 to 18 mol% with respect to the total mole number of the polymer.

[0073] For example, the mole number of the compound represented by the chemical formula 5 among the polymers may be 50 to 98 mol%, 50 to 90 mol%, 50 to 87 mol%, 50 to 85 mol%, 50 to 80 mol%, 55 to 90 mol%, 56 to 90 mol%, 66 to 90 mol%, 67 to 90 mol%, 66 to 79 mol%, or 67 to 78 mol% with respect to the total mole number of the polymer.

[0074] According to one embodiment, the weight average molecular weight (Mw) of the process oil may be 500 to 8,000 g / mol, and the number average molecular weight (Mn) of the process oil may be 100 to 5,000 g / mol.

[0075] For example, the weight average molecular weight (Mw) of the process oil may be 600 to 8,000 g / mol, 800 to 8,000 g / mol, 1,000 to 8,000 g / mol, 500 to 7,000 g / mol, 500 to 6,000 g / mol, 500 to 5,000 g / mol, 500 to 4,000 g / mol or 1,000 to 4,000 g / mol.

[0076] For example, the number average molecular weight (Mn) of the process oil may be 100 to 5,000 g / mol, 200 to 5,000 g / mol, 400 to 5,000 g / mol, 500 to 5,000 g / mol, 100 to 4,500 g / mol, 100 to 4,000 g / mol, 100 to 3,500 g / mol, 100 to 3,000 g / mol, or 500 to 3,000 g / mol.

[0077] According to one embodiment, the kinematic viscosity (cst, 40°C) of the process oil may be 20 cSt to 70 cSt, the glass transition temperature of the process oil may be -90°C to -60°C, the iodine value (gI2 / 100g) of the process oil may be 60 to 120, and the acid value (mgKOH / g) of the process oil may be 0.1 to 10. For example, the kinematic viscosity (cst, 40°C) was measured according to ASTM D 445. For example, the glass transition temperature was measured using differential scanning calorimetry (DSC). For example, the iodine value (gI2 / 100g) was measured according to ASTM D 5768.

[0078] According to one embodiment, the process oil can be prepared by polymerizing an ethylenically unsaturated monomer containing the ester group and an ethylenically unsaturated monomer containing the carboxyl group.

[0079] According to one embodiment, the polymerization may be carried out in the presence of an acid catalyst. For example, the acid catalyst may include an organic acid catalyst, an inorganic acid catalyst, or a Lewis acid catalyst.

[0080] According to one embodiment, the organic acid catalyst may include an alkylsulfonic acid having 1 to 6 carbon atoms, an arylsulfonic acid having 6 to 14 carbon atoms, an alkylarylsulfonic acid having 7 to 20 carbon atoms, or an arylalkylsulfonic acid having 7 to 20 carbon atoms.

[0081] According to one embodiment, the inorganic acid catalyst may include sulfuric acid, hydrochloric acid, nitric acid, boric acid, or phosphoric acid.

[0082] According to one embodiment, the Lewis acid catalyst may include boron 3-chloride (BCl3), aluminum chloride (AlCl3), tin 4-chloride (SnCl4), titanium 4-chloride (TiCl4), vanadium 5-chloride (VCl5), iron 3-chloride (FeCl3), boron 3-fluoride (BF3), and the like, as well as organic aluminum compounds such as chlorodiethyl aluminum (Et2AlCl), dichloroethyl aluminum (EtAlCl2).

[0083] According to one embodiment, the acid catalyst may include sulfuric acid, hydrochloric acid, nitric acid, boric acid, phosphoric acid, sulfonic acid, or para toluenesulfonic acid.

[0084] According to one embodiment, the content of the catalyst may vary depending on the type of catalyst. For example, when the catalyst is a homogeneous catalyst, the content of the catalyst may be 0.01 to 5 wt%, 0.01 to 3 wt%, 1 to 5 wt%, or 2 to 4 wt% based on the total weight of the reactants. For example, when the catalyst is a heterogeneous catalyst, the content of the catalyst may be 5 to 200 wt%, 5 to 100 wt%, 20 to 200 wt%, or 20 to 150 wt% based on the total weight of the reactants.

[0085] For example, the polymerization can be performed at 40°C to 100°C, 45°C to 100°C, 50°C to 100°C, 40°C to 90°C, 40°C to 80°C, 40°C to 70°C, 40°C to 60°C, or 50°C to 60°C.

[0086] For example, the polymerization can be carried out for 1 hour to 10 hours, 2 hours to 10 hours, 3 hours to 10 hours, 4 hours to 10 hours, 5 hours to 10 hours, 1 hour to 8 hours, 1 hour to 6 hours or 5 hours to 6 hours.

[0087] For example, the process oil may be a process oil for tires. The process oil for tires may be mixed with rubber during tire manufacturing to prepare a rubber composition.

[0088] Another aspect of the present invention provides a rubber composition comprising raw rubber and the process oil described above.

[0089] According to one embodiment, the rubber composition may be a rubber composition for a tire. For example, a tire or tire tread may be prepared from the rubber composition for a tire.

[0090] According to one embodiment, the raw rubber may include at least one of, for example, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, isoprene-styrene rubber, isoprene-butadiene-styrene rubber, isobutylene, and ethylene-propylene diene rubber (EPDM).

[0091] According to one embodiment, the content of the process oil may be 10 to 50 wt%, 10 to 40 wt%, 10 to 30 wt%, or 15 to 25 wt% based on the total weight of the rubber composition.

[0092] According to one embodiment, the rubber composition further comprises a tackifier, and the content of the tackifier may be 1 to 10 wt% based on the total weight of the rubber composition. For example, the rubber composition may include the process oil described above, thereby reducing the content of the tackifier included in the rubber composition.

[0093] For example, the adhesive may include rosin or rosin derivatives, such as gum rosin, wood rosin, and tall oil rosin, and hydrogenated and disproportionated forms thereof, as well as various derivatives, such as alkyl-phenolic compounds, acetylene-phenolic compounds, and combinations thereof. For example, the adhesive may include condensation products of alkyl phenols, such as butyl phenol, and acetylene, alkylphenol acetylene resin adhesives, and colorless transparent gum rosins. For example, the adhesive may include alkylphenol resin adhesives.

[0094] According to one embodiment, the rubber composition may further include, in addition to the process oil or the raw rubber, at least one of a reinforcing filler, a vulcanizing agent, a vulcanization accelerator, a crosslinking activator (e.g., zinc oxide or stearic acid), and a deterioration inhibitor such as a wax. For example, those commonly used in the rubber industry may be appropriately blended into the rubber composition.

[0095] For example, reinforcing fillers may include carbon black, silica, titanium dioxide, clay, layered silicate, tungsten, talc, or syndiotactic-1,2-polybutadiene (SPB).

[0096] According to one embodiment, the content of the reinforcing filler may be 10 to 90 parts by weight, 30 to 90 parts by weight, or 50 to 90 parts by weight based on 100 parts by weight of the raw rubber.

[0097] For example, the vulcanizing agent may contain sulfur. For example, the content of the vulcanizing agent may be preferably 1 to 5 parts by weight per 100 parts by weight of the raw rubber.

[0098] For example, the vulcanization accelerator may include at least one of a sulfenamide-based vulcanization accelerator (e.g., CBS (2-Benzothlazolesulfenamide, N-cyclohexyl)), a thiuram-based vulcanization accelerator, a thiazole-based vulcanization accelerator, and a guanidine-based vulcanization accelerator (e.g., DPG (Diphenylguanidine)). The content of the vulcanization accelerator may be 0.1 to 7 parts by weight or 0.5 to 5 parts by weight based on 100 parts by weight of the raw rubber.

[0099] For example, the crosslinking activator may include zinc oxide or stearic acid. For example, the content of the crosslinking activator may be 1 to 10 parts by weight or 2 to 7 parts by weight based on 100 parts by weight of the raw rubber.

[0100]

[0101] Hereinafter, the present invention will be described in more detail through examples. These examples are intended solely to illustrate the present invention more specifically, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

[0102]

[0103] Manufacturing Example 1: Manufacturing of process oil

[0104] In a 1 L superconducting kettle equipped with a reflux device, 100 g of toluene was charged, and a monomer containing a methyl ester group extracted from waste cooking oil and a monomer containing a carboxyl group extracted from waste cooking oil were added at a molar ratio of 6:1. 1.25 ml of BF3-phenoate as a catalyst was added and stirred at 40°C. After self-polymerization at 60°C for 6 hours, the temperature was raised to 80°C. After this, 200 g of water was added and stirred for 20 minutes while maintaining 80°C. Stirring was then stopped and the mixture was allowed to separate. Once the layers separated, the lower layer (water) was removed, leaving only the upper layer (toluene and reactants). The mixture was heated to 180°C to remove toluene and depressurized to completely remove any remaining volatile substances. The mixture was then cooled to 40°C to prepare process oil.

[0105] The mole number of compound (a) containing carboxyl groups at both terminals included in the above process oil: the mole number of compound (b) containing a carboxyl group at one terminal and an ester group at the other terminal: the mole number of compound (c) containing ester groups at both terminals = 1:2:11.

[0106] The mole ratio of the compound (A) containing an ester group at both ends in the above process oil: the mole ratio of the compound (B) containing an ester group at one end and a carboxyl group at the other end: the mole ratio of the compound (C) containing a carboxyl group at both ends was measured through structural analysis using HNMR.

[0107]

[0108] Manufacturing Example 2

[0109] 50 g of toluene as a solvent was added, and a polymerization reaction was performed at 50°C for 6 hours. Process oil was prepared in the same manner as in Manufacturing Example 1, except that the molar ratio of the monomer containing a methyl ester group extracted from waste cooking oil and the monomer containing a carboxyl group extracted from waste cooking oil was 7.5:1.

[0110] The mole number of compound (a) containing a carboxyl group at both terminals included in the above process oil: the mole number of compound (b) containing a carboxyl group at one terminal and an ester group at the other terminal: the mole number of compound (c) containing an ester group at both terminals = 1:6:27.

[0111]

[0112] Manufacturing Example 3

[0113] Process oil was prepared in the same manner as in Manufacturing Example 1, except that 200 g of toluene as a solvent was added and the molar ratio of the monomer containing a methyl ester group extracted from waste cooking oil and the monomer containing a carboxyl group extracted from waste cooking oil was 3:1.

[0114] The mole number of compound (a) containing carboxyl groups at both terminals included in the above process oil: the mole number of compound (b) containing a carboxyl group at one terminal and an ester group at the other terminal: the mole number of compound (c) containing ester groups at both terminals = 1:1:4.

[0115]

[0116] Manufacturing Example 4

[0117] Process oil was prepared in the same manner as in Manufacturing Example 1, except that 200 g of toluene as a solvent was added and the molar ratio of the monomer containing a methyl ester group extracted from waste cooking oil and the monomer containing a carboxyl group extracted from waste cooking oil was 2:1.

[0118] The mole number of compound (a) containing carboxyl groups at both terminals included in the above process oil: the mole number of compound (b) containing a carboxyl group at one terminal and an ester group at the other terminal: the mole number of compound (c) containing ester groups at both terminals = 2:2:5.

[0119]

[0120] Manufacturing Example 5

[0121] Process oil was prepared in the same manner as in Manufacturing Example 1, except that 200 g of toluene as a solvent was added and the molar ratio of the monomer containing a methyl ester group extracted from waste cooking oil and the monomer containing a carboxyl group extracted from waste cooking oil was 9:1.

[0122] The mole number of compound (a) containing carboxyl groups at both terminals included in the above process oil: the mole number of compound (b) containing a carboxyl group at one terminal and an ester group at the other terminal: the mole number of compound (c) containing ester groups at both terminals = 1:1:13.

[0123]

[0124] Ester: Compound with carboxyl at both ends (a): Compound with carboxyl + ester (b): Compound with ester at both ends (c) Manufacturing example 16:11:2:11 Manufacturing example 27.5:11:6:27 Manufacturing example 33:11:1:4 Manufacturing example 42:12:2:5 Manufacturing example 59:11:1:13

[0125] Evaluation Example 1: Evaluation of physical properties of process oil

[0126] The kinematic viscosity (cst, 40°C) of the process oil according to Manufacturing Examples 1 to 5 was measured according to ASTM D445, the iodine value (gI2 / 100g) according to ASTM D5768, the glass transition temperature (°C) using a differential scanning calorimeter (DSC), and the acid value (mgKOH / g) according to ASTM D 664, and the results are listed in Table 2 below.

[0127] The weight average molecular weight and number average molecular weight were measured using GPC (Gel permeation chromatograph).

[0128]

[0129] [Viscosity measurement]

[0130] The kinematic viscosity (cst, 40°C) of the above process oil was measured using a viscometer (Cannon-Fenske Routine Viscometer). The process oils according to Preparation Examples 1 to 5 were each injected into the viscometer so that the lower spherical space of the viscometer was approximately half-filled, and each viscometer was stored in a 40°C constant-temperature water bath for more than 30 minutes. Then, the measurement sample was raised to a certain height of the viscometer using a syringe, and the movement time for the measurement sample to descend to a certain height was measured to calculate the viscosity. The kinematic viscosity (cst, 40°C) of the above process oil was calculated by multiplying the movement time by the viscosity constant of the above process oil.

[0131]

[0132] [Acid value measurement]

[0133] Process oils according to Manufacturing Examples 1 to 5 were injected into a 100 ml Erlenmeyer flask. 30 ml of toluene, a neutral solvent, was added to each flask and stirred to dissolve the process oils. 4 to 6 drops of PP (Phenolpthalein) indicator were added dropwise. Titration of the sample containing the process oil was started with 0.1 N alcoholic KOH. The titration was continued until the sample containing the process oil exhibited discoloration and lasted for more than 10 seconds (end point).

[0134] The acid value was calculated according to the following equation 1.

[0135] Formula 1: V(ml) * F * 56.11 * 0.1 / (Process oil weight (g))

[0136] V is the titer of 0.1N alcoholic KOH,

[0137] F is the 0.1N alcoholic KOA correction factor.

[0138]

[0139] [Iodine value measurement]

[0140] Each 0.2 g of the process oils according to Manufacturing Examples 1 to 5 were weighed into a 250 ml Erlenmeyer flask. 10 ml of cyclohexane was added, and the oils according to Manufacturing Examples 1 to 5 were dissolved by stirring. 25 ml of WIJS solution was added and placed in a dark place at 20 to 30°C. When the iodine value was less than 100, it was placed in a dark place for 30 minutes, and when it was 100 or more, it was placed in a dark place for 1 hour. After placing, 20 ml of KI (10 wt%) solution and 100 ml of distilled water were added and completely dissolved. 4 to 6 drops of 1% starch solution were added dropwise as an indicator. Titration was performed with a 0.1 N Na2S2O3 solution until colorless. A blank test was performed using the same method.

[0141] The iodine value was calculated from Equation 2 below.

[0142] Equation 2: Iodine value = (AB)*1.260*F / (Process oil weight (g))

[0143] A is the consumption of 0.1 N Na2S2O3 solution in the blank test (ml),

[0144] B is the consumption of 0.1 N Na2S2O3 solution in the actual test (ml),

[0145] F is the correction factor (1) of 0.1 N Na2S2O3 solution.

[0146] WIJS solution is a solution (1 L) prepared by adding acetic acid to 7.9 g of trichloroisocyanurate (ICl3) and 8.7 g of iodine and stirring.

[0147] Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Kinematic viscosity (cst, 40℃) 3965252480 Iodine value (gI2 / 100g) 987011551118 Tg (℃) -80-65-85-86-63 Acid value (mgKOH / g) 6.5 9.5 4.5 4.4 9.5 Weight average molecular weight (g / mol) 1,8541,9501,7501,7201,980 Number average molecular weight (g / mol) 1,0801,2001,0501,0101,220 Crystallinity (25℃) None None None Yes

[0148] Example 1: Preparation of rubber composition

[0149] A rubber composition was prepared by mixing 100 g of styrene butadiene rubber (SBR), 80 g of silica, 8 g of silane, 35 g of the above-mentioned process oil prepared above, 1.5 g of sulfur as a vulcanizing agent, 2 g of CBS (2-Benzothlazolesulfenamide, N-cyclohexyl) and 2 g of DPG (Diphenylguanidine) as vulcanizing accelerators, and 3 g of zinc oxide and 2 g of stearic acid as crosslinking accelerators.

[0150]

[0151] Examples 2 to 5

[0152] A rubber composition was manufactured in the same manner as in Example 1, except that the type of process oil was corrected as shown in Table 3 below.

[0153]

[0154] Comparative Examples 1 to 3

[0155] A rubber composition was manufactured in the same manner as in Example 1, except that the type of process oil and the content of the adhesive were corrected as shown in Table 3 below.

[0156] SBR(g) Process Oil Type Content Example 1100 Manufacturing Example 135 Example 2100 Manufacturing Example 235 Example 3100 Manufacturing Example 335 Example 4100 Manufacturing Example 435 Example 5100 Manufacturing Example 535 Comparative Example 1100 TDAE35 Comparative Example 2100 RAE35 Comparative Example 3100 Waste Cooking Oil35

[0157] TDAE: Treated Distillate Aromatic Extract (petroleum aromatic oil)

[0158] RAE: Residual Aromatic Extract

[0159]

[0160]

[0161] Evaluation Example 2. Evaluation of physical properties of rubber composition

[0162] Mooney viscosity (100°C), T05 (125°C), T35 (125°C), rheometer (160°C), mechanical properties, hardness and dynamic characteristics of the rubber compositions for tires according to Examples 1 to 5 and Comparative Examples 1 to 3 were measured and recorded in Tables 4 and 5 below.

[0163] [Mooney viscosity (100℃)]

[0164] Mooney viscosity is used to evaluate the processability of rubber. The flow resistance of a rubber sample was measured while the rotor rotated at a speed of 2 rpm at a measurement temperature (100℃). When the resistance applied to the rotor is 84.67 kgfcm, the Mooney viscosity is defined as 100, and the Mooney viscosity of each of the tire rubber compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 was calculated from the torque applied while the rotor rotated at a speed of 2 rpm. The displacement is 2.54 mm from 0 to 100 M.

[0165] [T05(125℃)]

[0166] For each of the rubber compositions for tires according to Examples 1 to 5 and Comparative Examples 1 to 3, the time elapsed from the time the minimum Mooney viscosity (Vm) was reached at 125°C until the vulcanization reaction began and the minimum Mooney viscosity (Vm) increased by 5 M (12.7 mm) was measured.

[0167] [T35(125℃)]

[0168] For each of the rubber compositions for tires according to Examples 1 to 5 and Comparative Examples 1 to 3, the elapsed time (t1) from the time when the minimum Mooney viscosity (Vm) reached at 125°C until the vulcanization reaction began and the minimum Mooney viscosity (Vm) increased by 35 M (88.9 mm) was measured, and then T35 (125°C) was measured from the time obtained by subtracting the elapsed time (t2) from the elapsed time (t1) until the minimum Mooney viscosity (Vm) increased by 5 M (12.7 mm).

[0169] [Rheometer measurement (160℃)]

[0170] The rheometer is used to evaluate the optimal vulcanization conditions (temperature, time) of rubber. At 165°C, the rubber compositions for tires according to Examples 1 to 5 and Comparative Examples 1 to 3 were subjected to shear by vibrating the lower die at an angle of ±1°, and the vulcanization reaction of the rubber compositions for tires according to Examples 1 to 5 and Comparative Examples 1 to 3 was performed. Depending on the progress of the vulcanization reaction, the torque (lbfin) was measured by a sensor connected to the upper die.

[0171] ① Rheometer (160℃) Toq.(min) and Toq.(max): From the Rheometer Curve measured from the above sensor, the minimum torque value (Toq.(min)) and maximum torque value (Toq.(max)) were measured, respectively. The lower the Toq.(min), the lower the Mooney viscosity tended to be, and the higher the Toq.(max), the higher the hardness and modulus tended to be.

[0172] ② Rheometer (160℃) T 90 (optimal vulcanization time): The time when the torque value is 90% of the maximum torque value was measured.

[0173] [Mechanical property evaluation]

[0174] In order to evaluate the mechanical properties after vulcanization of the rubber compositions for tires according to Examples 1 to 5 and Comparative Examples 1 to 3, Stress (force per unit area) and Strain (strain per unit length) were measured using a Load Cell that converts physical quantities such as force or load into electrical signals and measures them. 0

[0175] ① Tensile strength: The maximum stress per unit area (kg / cm) when the vulcanized rubber specimens according to Examples 1 to 5 and Comparative Examples 1 to 3 are pulled and broken 2 ) was measured.

[0176] ② Elongation: The rubber specimens according to the vulcanized examples 1 to 5 and comparative examples 1 to 3 were pulled at a constant speed and the elongation ratio was measured by comparing the length at break with the initial length.

[0177] ③ 100% elasticity and 300% elasticity: The rubber specimens according to the vulcanized examples 1 to 5 and comparative examples 1 to 3 were pulled to determine the stress (kg / cm) for a specific elongation (100%, 300%). 2 ) was measured.

[0178] [hardness]

[0179] The hardness of the vulcanized rubber specimens according to Examples 1 to 5 and Comparative Examples 1 to 3 was measured. The hardness was measured using a Shore A type durometer. The durometer has a scale ranging from 0 (very flexible) to 100 (stiff), and the load was applied to the rubber specimens in the form of a static load and a spring.

[0180] [Dynamic characteristics]

[0181] In order to evaluate the viscoelastic behavior of the rubber specimens according to the vulcanized examples 1 to 5 and comparative examples 1 to 3, a vibrating force or deformation was applied to each of the rubber specimens, and the elastic modulus (Modulus) and energy loss (Damping) were measured, and the Tanδ value and Tg value according to temperature change were measured.

[0182] ① Tanδ(0℃): Tanδ value at 0℃ is a measure of wet grip performance.

[0183] ② Tanδ(25℃): Tanδ value at 25℃ is a measure of dry grip performance.

[0184] ③ Tanδ(60℃): Tanδ value at 60℃ is a measure of cloud resistance.

[0185] ④ Tg(℃): The temperature at which the Tanδ value is maximum. The Tg of the vulcanized rubber specimens according to Examples 1 to 5 and Comparative Examples 1 to 3 is measured using DMA Q800(TA) in Multi-Frequency-Strain mode under the following conditions.

[0186] - Preload force: 0.01N

[0187] - Poisson's ratio: 0.44

[0188] - Clamp type: Tension film

[0189] - Frequency: 11Hz

[0190] - Measurement temperature range: -50℃ (maintained for 5 min) to 75℃,

[0191] - Heating rate: 3℃ / min

[0192]

[0193] Example 1 Example 2 Example 3 Example 4 Example 5 Mooney viscosity (100℃) 7273706878T05 (125℃) 2319232225T35 (125℃) 35.829.8343330Rheometer (160℃) Toq. (max) 29.233.127.625.432Rheometer (160℃) Toq. (min) 7.17.56.56.47.4Rheometer (160℃) T909.18.28.88.88.3Hardness 7375727075 100% Elastic modulus (kg / cm) 2 )4553434253300% Elasticity (kg / cm) 2 )145165139134164Tensile strength (kg / cm) 2 )200210190185212Elongation (%)405380420450375Tg(℃)-27-23-30-30-23Tanδ(0℃)0.26050.29130.22800.22 400.2915Tanδ(25℃)0.17170.17750.16220.16200.1782Tanδ(60℃)0.13330.14040.12520.12500.1408

[0194] Comparative Example 1 Comparative Example 2 Comparative Example 3 Mooney viscosity (100℃) 808 178 T5 (125℃) 262 322 T35 (125℃) 38.3 34.8 39 Rheometer (160℃) Toq. (max) 39.2 35.6 25.8 Rheometer (160℃) Toq. (min) 8.8 7.9 6.1 Rheometer (160℃) T90 10.5 10.2 10.3 Hardness 777 667 100% Elastic modulus (kg / cm) 2 )605428300% Elasticity (kg / cm) 2 )18316678Tensile strength (kg / cm) 2 )177211172Elongation (%)299370588Tg(℃)-20-18.6-36Tanδ(0℃)0.35140.36830.2308Tanδ(25℃)0.20570.21580.1622Tanδ(60℃)0.14970.14590.1252

[0195] Referring to the above examples and comparative examples, Examples 1 to 5 had lower Mooney viscosity than Comparative Examples 1 to 3, thereby improving the distribution processability. In addition, Examples 1 to 5 had lower glass transition temperatures than Comparative Examples 1 to 2, thereby exhibiting excellent low-temperature properties and being more easily applicable to winter tires.

[0196] In addition, Examples 1 to 5, which polymerized monomers extracted from waste cooking oil, showed improved mechanical properties, such as improved hardness, 100% elasticity, 300% elasticity, tensile strength, and elongation, compared to Comparative Example 3, which used waste cooking oil as is.

[0197]

[0198] The above-described examples and comparative examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Those skilled in the art will be able to implement the present invention by making various modifications based on the examples provided. Therefore, the technical protection scope of the present invention should be defined by the appended claims.

Claims

1. Unit (A) derived from an ethylenically unsaturated monomer containing an ester group, and A process oil comprising a polymer comprising a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group.

2. In paragraph 1, The ethylenically unsaturated monomer containing the above ester group is represented by the following chemical formula 1, The ethylenically unsaturated monomer containing the above carboxyl group is a process oil represented by the following chemical formula 2: <Chemical Formula 1> <Chemical Formula 2> Among the above chemical formulas 1 and 2, R 11 Inland R 14 and R 21 Inland R 24 are independently hydrogen or an alkyl group having 1 to 20 carbon atoms, R 15 Inland R 16 and R 25 are independently an alkyl group having 1 to 20 carbon atoms, a11 and a21 are independently integers from 1 to 20, a13 and a23 are integers from 1 to 50, independently of each other.

3. In paragraph 2, Among the above chemical formulas 1 and 2, R 11 Inland R 14 and R 21 Inland R 24 are independently hydrogen, methyl or ethyl groups, R 15 Inland R 16 and R 25 Process oil, which is independently a methyl group, an ethyl group or a propyl group.

4. In paragraph 2, A process oil wherein the ratio of the number of moles of units (A) derived from an ethylenically unsaturated monomer containing an ester group to the number of moles of units (B) derived from an ethylenically unsaturated monomer containing a carboxyl group among the polymers is 1 to 20.

5. In paragraph 1, A process oil, wherein at least one of the ethylenically unsaturated monomer containing the ester group and the ethylenically unsaturated monomer containing the carboxyl group is derived from edible oil.

6. In paragraph 1, A process oil comprising two or more of a dimer comprising a unit (A) derived from an ethylenically unsaturated monomer containing an ester group, a dimer comprising a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group, and a dimer comprising a unit (A) derived from an ethylenically unsaturated monomer containing an ester group and a unit (B) derived from an ethylenically unsaturated monomer containing a carboxyl group.

7. In paragraph 1, The above polymer is a process oil comprising two or more compounds represented by the following chemical formulas 3 to 5: <Chemical Formula 3> <Chemical Formula 4> <Chemical Formula 5> Among the above chemical formulas 3 to 5, L 31 , L 32 , L 41 , L 42 , L 51 and L 52 are independently a single bond; or an alkylene group having 1 to 20 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms, R 31 Inland R 36 , R 41 Inland R 46 and R 51 Inland R 56 are independently hydrogen or an alkyl group having 1 to 20 carbon atoms, R 37 , R 38 , R 47 , R 48 , R 49 , R 57 , R 58 , R 59a and R 59b are independently an alkyl group having 1 to 20 carbon atoms, a31, a32, a41, a42, a51 and a52 are independently integers from 1 to 50.

8. In paragraph 7, The above polymer is a process oil comprising a compound represented by the above chemical formula 3, a compound represented by the above chemical formula 4, and a compound represented by the above chemical formula 5.

9. In paragraph 8, The mole number of the compound represented by the above chemical formula 3 is 1 to 35 mole% with respect to the total mole number of the polymer, The mole number of the compound represented by the above chemical formula 4 is 1 to 35 mole% with respect to the total mole number of the polymer, A process oil in which the mole number of the compound represented by the above chemical formula 5 is 50 to 98 mole% with respect to the total mole number of the polymer.

10. In paragraph 1, The weight average molecular weight (Mw) of the above process oil is 500 to 8,000 g / mol, Process oil having a number average molecular weight (Mn) of 100 to 5,000 g / mol.

11. In paragraph 1, The kinematic viscosity (cst, 40℃) of the above process oil is 20 cSt to 70 cSt, The glass transition temperature of the above process oil is -90°C to -60°C, The iodine value (gI2 / 100g) of the above process oil is 60 to 120, The process oil has an acid value (mgKOH / g) of 0.1 to 10.

12. In paragraph 1, The above process oil is a process oil for tires.

13. Raw rubber; and A rubber composition comprising a process oil according to any one of claims 1 to 12.

14. In paragraph 13, A rubber composition comprising the above raw rubber, butyl rubber, natural rubber, styrene butadiene rubber, or butadiene rubber.

15. In paragraph 13, A rubber precursor, wherein the content of the process oil is 10 to 50 wt% based on the total weight of the rubber composition.

16. In paragraph 13, A rubber composition further comprising at least one of a reinforcing filler, a vulcanizing agent, a vulcanization accelerator, a crosslinking activator, and a deterioration inhibitor.

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