Composition comprising modified polybutadiene

Abstract

The present invention relates to a composition comprising a modified polybutadiene and a method for preparing the composition comprising a modified polybutadiene. Specifically, the present invention provides a composition comprising a modified polybutadiene, wherein the modified polybutadiene is a polybutadiene having 1-4 substituents represented by chemical formula 1. [Chemical Formula 1] In the formula, * is a substitution position, each R1 is independently hydrogen, deuterium, a halogen, a C1-5 alkyl group, or a C1-5 alkoxy group, at least one R1 is a C1-5 alkoxy group, each L is independently a C1-5 alkylene group, and each m is independently an integer of 1-6.

Description

Composition containing modified polybutadiene

[0001] The present invention relates to a composition comprising modified polybutadiene and a method for preparing a composition comprising modified polybutadiene.

[0002]

[0003] Rubber is a polymer material widely used in tires, conveyor belts, construction materials, automotive parts, home appliances, footwear, coatings, and medical and hygiene-related products. Rubber can be classified into natural rubber and synthetic rubber, with more than half of synthetic rubber used in tires. Synthetic rubbers include styrene-butadiene rubber (SBR), butadiene rubber (BR), ethylene-propylene rubber, nitrile rubber, polychloroprene, silicone rubber, and acrylic rubber; among these, SBR accounts for approximately 35% of total synthetic rubber production and is primarily used in tire treads. Additionally, BR accounts for about 25% of production and is mainly used in tire sidewalls.

[0004] Recently, as interest in high-performance tires for eco-friendly and energy-saving purposes has increased, research is being conducted in various ways to develop high-performance rubber that possesses dynamic properties such as rolling resistance and wetting resistance, mechanical properties, and processability, that is, can resolve trade-offs between each of these properties.

[0005] For example, JP2008-031244A is an organosilane compound OCN-R-Si(OR 1 ) x (R 2 ) 3-x This invention relates to silane-modified polybutadiene using [the method], but sufficient physical properties could not be achieved with the above prior art.

[0006] In addition, KR 10-2585427B1 introduced silica-affinity functional groups to both ends of the chain of a butadiene compound, but the silica-affinity functional groups are fixedly located only at both ends of the butadiene chain, and optimization based on the substitution value of the silica-affinity functional groups was not achieved. Therefore, there is a need for superior rubber manufacturing technology.

[0007]

[0008] Prior art literature

[0009] Japanese Patent Publication JP 2008-031244A

[0010] Korean Registered Patent Publication KR 10-2585427B1

[0011]

[0012] The present invention aims to solve the problems of the aforementioned prior art, and the objective of the present invention is to provide a composition capable of significantly improving dynamic properties, mechanical properties, and wear resistance by modifying polybutadiene.

[0013]

[0014] To solve the above-mentioned problem, the present invention provides a composition comprising modified polybutadiene, wherein

[0015] The above-mentioned modified polybutadiene provides a composition in which 1 to 4 substituents of the following chemical formula 1 are substituted on polybutadiene.

[0016] [Chemical Formula 1]

[0017]

[0018] In the above formula,

[0019] * is the substitution position, and

[0020] R 1 Each is independently hydrogen, deuterium, a halogen, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 One or more of them are alkoxy groups having 1 to 5 carbon atoms, and

[0021] L is each independently an alkylene group having 1 to 5 carbon atoms, and

[0022] m is an integer from 1 to 6, each independently.

[0023] According to one embodiment of the present invention, a composition is provided characterized in that the polybutadiene comprises one or more units of the following chemical formulas 2-1 to 2-3.

[0024] [Chemical Formula 2-1]

[0025]

[0026] [Chemical Formula 2-2]

[0027]

[0028] [Chemical Formula 2-3]

[0029]

[0030] According to one embodiment of the present invention, a composition is provided characterized in that the polybutadiene comprises 40 to 90 mol% of a unit represented by Formula 2-1 and a unit represented by Formula 2-2, and 10 to 40 mol% of a unit represented by Formula 2-3.

[0031] According to one embodiment of the present invention, a composition is provided characterized in that the polybutadiene has a number average molecular weight (Mn) of 1,000 to 60,000 g / mol and a molecular weight distribution represented by Mw / Mn of 1.5 to 8.

[0032] According to one embodiment of the present invention, a composition is provided characterized in that L is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-.

[0033] According to one embodiment of the present invention, a composition is provided characterized in that m is an integer from 1 to 3.

[0034] According to one embodiment of the present invention, a composition is provided in which the modified polybutadiene is characterized by having the following chemical formula 3:

[0035] [Chemical Formula 3]

[0036]

[0037] In the above formula,

[0038] A 1 and A 2 Each is independently any one of the following chemical formulas 4-1 to 4-3, and

[0039] [Chemical Formula 4-1]

[0040]

[0041] [Chemical Formula 4-2]

[0042]

[0043] [Chemical Formula 4-3]

[0044]

[0045] n and o are each independently integers from 0 to 2, and when n is 0, A 1 is a single bond, and if o is 0, then A 2 is a single bond, and

[0046] Above A 3 To A 5 is a substituent represented by the above chemical formula 1, and

[0047] The above p and q are integers of 0 or 1, at least one of p and q is 1, and if p is 0, A 3 is hydrogen, and when q is 0, A 4 is hydrogen, and the sum of n, o, p, and q is 1 to 4, and

[0048] Above B 1 To B 3 Each is independently of the following chemical formula 2-1, 2-2, or 2-3, and

[0049] [Chemical Formula 2-1]

[0050]

[0051] [Chemical Formula 2-2]

[0052]

[0053] [Chemical Formula 2-3]

[0054]

[0055] r, s, and t are each independently greater than or equal to 0, and if r is 0, then B 1 is a single bond, and when s is 0, B 2 is a single bond, and when t is 0, B 3 is a single bond.

[0056] According to one embodiment of the present invention, a composition is provided characterized in that the sum of n and o is 1 or 2.

[0057] According to one embodiment of the present invention, the A 1 and A 2 The present invention provides a composition characterized by each independently containing 50 mol% or more of a unit represented by Chemical Formula 4-3.

[0058] According to one embodiment of the present invention, a composition is provided characterized in that the average number of substituents of Formula 1 substituted in the modified polybutadiene is 1.3 to 3.5.

[0059] According to one embodiment of the present invention, the modified polybutadiene is prepared by reacting a radical initiator, a silane coupling agent, and butadiene, and

[0060] The above silane coupling agent is a compound shown in Chemical Formula 5 below, and

[0061] [Chemical Formula 5]

[0062]

[0063] R 2 and R 3 Each is independently an alkoxy group having 2 to 5 carbon atoms, and

[0064] L 1 and L 2 Each is independently an alkylene group having 1 to 5 carbon atoms, and

[0065] The present invention provides a composition characterized in that u is independently an integer from 2 to 12.

[0066] According to one embodiment of the present invention, a composition is provided characterized in that the average number of Si substituted in the modified polybutadiene is calculated by the following Formula 1.

[0067] [Equation 1]

[0068] {b / (a + b / 2)}×D×cM×(2 / 6)

[0069]

[0070] The above 'a' is Cis / Trans H contained in polybutadiene as shown in the following chemical formulas 6-1 to 6-3. a and H present in the vinyl location a It refers to the total sum of, and the above b is H present at the terminal vinyl position as shown in Chemical Formula 6-3 below. b It refers to the total sum of, and the above c is H bonded to a carbon adjacent to oxygen in an alkoxy group having 2 to 5 carbon atoms, as shown in Chemical Formula 6-4 below. c It means the total sum of,

[0071]

[0072] The above D represents the number of butadiene (BD) chains, and D is calculated by the following Equation 2, and

[0073] [Equation 2]

[0074] Number of BD chains (D) =

[0075] The above Mn is the number average molecular weight of the modified polybutadiene, and

[0076] The above M(s) is the molecular weight of the silane coupling agent, and

[0077] The above M(b) is the molecular weight of butadiene, and

[0078] The above M is the mole fraction of the Product, calculated by the following Equation 3, and

[0079] [Equation 3]

[0080] Mole fraction of the product (M) =

[0081] The above Mn is the number average molecular weight of the modified polybutadiene, and

[0082] The above M(s) is the molecular weight of the silane coupling agent, and

[0083] x is the remaining amount of silane coupling agent in the modified polybutadiene.

[0084] According to one embodiment of the present invention, a composition is provided characterized in that the average number of Si substituted in the modified polybutadiene is 1.3 to 3.5.

[0085] According to one embodiment of the present invention, a method for preparing a composition comprising the modified polybutadiene,

[0086] A step of obtaining a silane coupling agent radical by reacting a radical initiator and a silane coupling agent;

[0087] A step of obtaining a polymer radical by polymerizing a silane coupling agent radical and butadiene; and

[0088] The method includes the step of obtaining modified polybutadiene by reacting a silane coupling agent with the above polymer radicals, and

[0089] The above silane coupling agent is a compound shown in Chemical Formula 5 below, and

[0090] [Chemical Formula 5]

[0091]

[0092] R 2 and R 3 Each is independently an alkoxy group having 2 to 5 carbon atoms, and

[0093] L 1 and L2 Each is independently an alkylene group having 1 to 5 carbon atoms, and

[0094] u provides a method in which each is an integer from 2 to 12 independently.

[0095] According to one embodiment of the present invention, a method is provided characterized in that the average number of Si substituted in modified polybutadiene is measured by the following Formula 1.

[0096] [Equation 1]

[0097] {b / (a + b / 2)}×D×cM×(2 / 6)

[0098]

[0099] The above 'a' is Cis / Trans H contained in polybutadiene as shown in the following chemical formulas 6-1 to 6-3. a and H present in the vinyl location a It refers to the total sum of, and the above b is H present at the terminal vinyl position as shown in Chemical Formula 6-3 below. b It refers to the total sum of, and the above c is H bonded to a carbon adjacent to oxygen in an alkoxy group having 2 to 5 carbon atoms, as shown in Chemical Formula 6-4 below. c It means the total sum of,

[0100]

[0101] The above H c represents the total sum of H bonded to carbons adjacent to oxygen in alkoxy groups having 2 to 5 carbon atoms, and

[0102] The above D represents the number of butadiene (BD) chains, and D is calculated by the following Equation 2, and

[0103] [Equation 2]

[0104] Number of BD chains (D) =

[0105] The above Mn is the number average molecular weight of the modified polybutadiene, and

[0106] The above M(s) is the molecular weight of the silane coupling agent, and

[0107] The above M(b) is the molecular weight of butadiene, and

[0108] The above M is the mole fraction of the Product, calculated by the following Equation 3, and

[0109] [Equation 3]

[0110] Mole fraction of the product (M) =

[0111] The above Mn is the number average molecular weight of the modified polybutadiene, and

[0112] The above M(s) is the molecular weight of the silane coupling agent, and

[0113] x is the remaining amount of silane coupling agent in the modified polybutadiene.

[0114] According to one embodiment of the present invention, a method is provided characterized in that the average number of Si substituted in the modified polybutadiene is 1.3 to 3.5.

[0115]

[0116] According to the present invention as described above, physical properties can be improved compared to conventional butadiene rubber.

[0117] The effects of the present invention are not limited to those mentioned above, and other unmentioned effects will be clearly understood by a person skilled in the art from the description below.

[0118]

[0119] Figure 1 is for measuring the number of Si substituted in modified polybutadiene. 1 This is a diagram showing the H-NMR results.

[0120] Figure 2 shows the GPC data of modified polybutadiene, and polybutadiene was used as the reference material.

[0121] Figure 3 is a plot showing the molecular weight distribution among the GPC data of modified polybutadiene measured in the same way as Figure 2.

[0122]

[0123] The advantages and features of the present invention and the methods for achieving them will become clear by referring to the embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below but may be implemented in various different forms. These embodiments are provided merely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the present invention, and the present invention is defined only by the scope of the claims.

[0124] The terms used herein are for describing the embodiments and are not intended to limit the invention. In this specification, the singular form includes the plural form unless specifically stated otherwise in the text. As used herein, "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components in addition to the components mentioned. Throughout the specification, the same reference numerals refer to the same components, and "and / or" includes each of the components mentioned and all combinations of one or more.

[0125] Unless otherwise defined, all terms used herein (including technical and scientific terms) may be used in a meaning commonly understood by those skilled in the art to which the present invention pertains. Additionally, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless explicitly and specifically defined otherwise.

[0126] The present invention relates to a composition comprising modified polybutadiene, wherein

[0127] The above-mentioned modified polybutadiene provides a composition in which 1 to 4 substituents of the following chemical formula 1 are substituted on the polybutadiene:

[0128] [Chemical Formula 1]

[0129]

[0130] In the above formula,

[0131] * is the substitution position, and

[0132] R 1 Each is independently hydrogen, deuterium, a halogen, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 One or more of them are alkoxy groups having 1 to 5 carbon atoms, and

[0133] L is each independently an alkylene group having 1 to 5 carbon atoms, and

[0134] m is each independently an integer from 1 to 6, preferably an integer from 1 to 4.

[0135] According to one embodiment of the present invention,

[0136] The above polybutadiene may include one or more units of the following chemical formulas 2-1 to 2-3.

[0137] [Chemical Formula 2-1]

[0138]

[0139] [Chemical Formula 2-2]

[0140]

[0141] [Chemical Formula 2-3]

[0142]

[0143] According to one embodiment of the present invention, the polybutadiene may comprise 40 to 90 mol% of a unit represented by Formula 2-1 and a unit represented by Formula 2-2, and 10 to 60 mol% of a unit represented by Formula 2-3. Preferably, the polybutadiene may comprise 70 to 80 mol% of a unit represented by Formula 2-1 and a unit represented by Formula 2-2, and 20 to 30 mol% of a unit represented by Formula 2-3.

[0144] In a preferred embodiment, among the units present in polybutadiene, the proportion of Formula 2-1, Formula 2-2 and Formula 2-3 is 10 mol% or more in each case and independently of each other.

[0145] According to one embodiment of the present invention, the polybutadiene may have a number average molecular weight (Mn) of 1,000 to 60,000 g / mol, preferably 1,300 to 40,000 g / mol, but is not limited thereto. In addition, the polybutadiene may have a molecular weight distribution (PDI) represented as weight average molecular weight (Mw) / number average molecular weight (Mn) of 1.5 to 8, preferably 1.5 to 6, and more preferably 2.0 to 5.0.

[0146] According to one embodiment of the present invention, L is a linear or branched alkylene group having 1 to 5 carbon atoms, and may be -CH2-, -CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, -CH2CH2CH2CH2-, -CH2CH2CH(CH3)CH2-, -CH2CH2CH2CH(CH3)CH2-, or -CH2CH2CH2CH2CH2CH2-. Preferably, L may be -CH2-, -CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, or -CH2CH2CH2CH2CH2CH2-.

[0147] According to one embodiment of the present invention, m may be an integer from 1 to 3.

[0148] According to one embodiment of the present invention, the modified polybutadiene may be a composition characterized by having the following chemical formula 3.

[0149] [Chemical Formula 3]

[0150]

[0151] In the above formula,

[0152] A1 and A 2 Each is independently any one of the following chemical formulas 4-1 to 4-3, and

[0153] [Chemical Formula 4-1]

[0154]

[0155] [Chemical Formula 4-2]

[0156]

[0157] [Chemical Formula 4-3]

[0158]

[0159] n and o are each independently integers from 0 to 2, and when n is 0, A 1 is a single bond, and if o is 0, then A 2 is a single bond, and

[0160] Above A 3 To A 5 is a substituent represented by the above chemical formula 1, and

[0161] The above p and q are integers of 0 or 1, at least one of p and q is 1, and if p is 0, A 3 is hydrogen, and when q is 0, A 4 is hydrogen, and the sum of n, o, p, and q is 1 to 4, and

[0162] Above B 1 To B 3 Each is independently of the following chemical formula 2-1, 2-2, or 2-3, and

[0163] [Chemical Formula 2-1]

[0164]

[0165] [Chemical Formula 2-2]

[0166]

[0167] [Chemical Formula 2-3]

[0168]

[0169] r, s, and t are each independently greater than or equal to 0, and if r is 0, then B 1 is a single bond, and when s is 0, B 2 is a single bond, and when t is 0, B 3 is a single bond.

[0170] According to one embodiment of the present invention, the sum of n and o may be 1 or 2, but is not limited thereto.

[0171] According to one embodiment of the present invention, the A 1 and A 2 Each may independently contain 50 mol% or more of the unit represented by Chemical Formula 4-3, preferably 60 mol% or more. The above mol% is A 1 , A 2 It represents the content of the unit represented by Chemical Formula 4-3, for example, A 1 The meaning of containing 55 mol% of the unit represented by this chemical formula 4-3 is, A 1 This means that among the corresponding units, 55% are units represented by chemical formula 4-3, and the remaining 45% are the sum of units represented by chemical formula 4-1 and units represented by 4-2.

[0172] According to one embodiment of the present invention, the average number of substituents of Formula 1 substituted on the modified polybutadiene may be 1.3 to 3.5. The lower limit of the average number of substituents may preferably be 1.5, more preferably 2.1, even more preferably 2.3, even more preferably 2.4, and most preferably 2.6, but is not limited thereto. For example, if necessary, the lower limit of the average number of substituents may be 2.9, 3.0, or 3.1. The upper limit of the average number of substituents may preferably be 3.4, more preferably 3.3, even more preferably 3.2, even more preferably 3.1, and most preferably 2.8, but is not limited thereto. For example, the average number of substituents may be 1.5 to 3.5, 2.1 to 3.5, 2.3 to 3.5, 2.4 to 3.5, 2.6 to 3.5, 2.1 to 3.3, 2.3 to 3.3, 2.4 to 3.3, 2.6 to 3.3, 2.1 to 3.1, 2.3 to 3.1, 2.4 to 3.1, 2.6 to 3.1, 2.1 to 2.8, 2.3 to 2.8, 2.4 to 2.8, 2.6 to 2.8, 3.1 to 3.5, and 3.1 to 3.4, but is not limited thereto. When the above range is satisfied, there is an excellent effect on silica dispersion performance, and physical properties (Moony viscosity, Payne effect, wear resistance, reduction in extraction weight, crosslinking density, DMTS, etc.) are improved.

[0173] According to one embodiment of the present invention, the modified polybutadiene is prepared by reacting a radical initiator, a silane coupling agent, and butadiene, and

[0174] The above silane coupling agent is a compound shown in Chemical Formula 5 below, and

[0175] [Chemical Formula 5]

[0176]

[0177] R 2 and R 3 Each is independently an alkoxy group having 2 to 5 carbon atoms, and

[0178] L 1 and L 2 Each is independently an alkylene group having 1 to 5 carbon atoms, and

[0179] u can each independently be an integer from 2 to 12, and preferably an integer from 2 to 8.

[0180] The present invention relates to a method for preparing a composition comprising the modified polybutadiene, wherein

[0181] A step of obtaining a silane coupling agent radical by reacting a radical initiator and a silane coupling agent;

[0182] A step of obtaining a polymer radical by polymerizing a silane coupling agent radical and butadiene; and

[0183] The method includes the step of obtaining modified polybutadiene by reacting a silane coupling agent with the above polymer radicals, and

[0184] The above silane coupling agent is a compound shown in Chemical Formula 5 below, and

[0185] [Chemical Formula 5]

[0186]

[0187] R 2 and R 3 Each is independently an alkoxy group having 2 to 5 carbon atoms, and

[0188] L 1 and L 2 Each is independently an alkylene group having 1 to 5 carbon atoms, and

[0189] The method provides that u can each independently be an integer from 2 to 12, preferably an integer from 2 to 8.

[0190] The above radical initiator may be selected from di-t-butyl peroxide, benzoyl peroxide, diacetyl peroxide, t-butyl acetate, t-butyl hydroperoxide, dicumyl peroxide, or 2,2'-azobisisobutyronitrile (AIBN), but is not limited thereto.

[0191] The above silane coupling agent radical is generated by a radical generated from a radical initiator reacting with a silane coupling agent. The radical generated from the radical initiator may be a radical generated by the decomposition of the radical initiator, but it may also be a radical generated by the reaction of the radical generated by the decomposition of the radical initiator with butadiene. The radical generated from the radical initiator attacks the SS bond of the silane coupling agent, causing the SS bond to break, and as a result, a part of the silane coupling agent combines with the radical generated from the radical initiator, and the remaining part of the silane coupling agent becomes a silane coupling agent radical.

[0192] The above steps may be performed at 100°C to 170°C, preferably 130°C to 150°C, but are not limited thereto.

[0193] The weight ratio of the radical initiator and the silane coupling agent may be 1:0.5 to 20, preferably 1:1 to 10, more preferably 1:1.5 to 8, and the weight ratio of the radical initiator and butadiene may be 1:5 to 60, preferably 1:10 to 40, more preferably 1:12 to 30, but is not limited thereto.

[0194] As one embodiment of the above method, when AIBN is used as a radical initiator and Bis[3-triethoxysilyl]propyl]tetrasulfide is used as a silane coupling agent, the reaction is as follows, and the radical initiator and silane coupling agent are not limited to the above materials.

[0195]

[0196] Step of obtaining silane coupling agent radicals

[0197]

[0198]

[0199] As shown above, in the present invention, the silane coupling agent radical is generated by a radical generated from a radical initiator reacting with the silane coupling agent. The radical generated from the radical initiator attacks the SS bond of the silane coupling agent, causing the SS bond to break, and thereby a part of the silane coupling agent combines with the radical generated from the radical initiator, and the remaining part of the silane coupling agent becomes the silane coupling agent radical.

[0200] In addition, the radical generated from the above radical initiator may be a radical generated by the decomposition of the radical initiator, but as shown below, the radical generated by the decomposition of the radical initiator may be a radical generated by reacting with butadiene.

[0201]

[0202]

[0203] Step of obtaining polymer radicals

[0204]

[0205] The obtained silane coupling agent radical undergoes radical polymerization with butadiene to form a polymer radical structure, and depending on the radical formation location, the structure of B may be formed differently.

[0206]

[0207] Step of obtaining modified polybutadiene

[0208] When a silane coupling agent reacts with the obtained polymer radical structure, modified polybutadiene and silane coupling agent radicals are generated. In this case, the modified polybutadiene becomes a structure in which silane coupling agent radicals are attached to both ends.

[0209] Meanwhile, if additional silane coupling agent radicals are coupled to the double bonds within polybutadiene after the radicals of the obtained polymer radical structure are terminated by a series of reactions (e.g., a disproportion termination reaction), modified polybutadiene with a structure in which silane coupling agent radicals are substituted at one end of butadiene and within the polybutadiene can be produced.

[0210] In addition, silane coupling radicals may additionally bind to double bonds present within the modified polybutadiene. In this case, modified polybutadiene with a structure substituted with more than 2 silane coupling radicals is produced.

[0211]

[0212] According to one embodiment of the present invention, the number of Si substituted in modified polybutadiene can be measured by the following Formula 1.

[0213] [Equation 1]

[0214] {b / (a + b / 2)}×D×cM×(2 / 6)

[0215]

[0216] The above 'a' is Cis / Trans H contained in polybutadiene as shown in the following chemical formulas 6-1 to 6-3. a and H present in the vinyl location a It refers to the total sum of, and the above b is H present at the terminal vinyl position as shown in Chemical Formula 6-3 below. b It refers to the total sum of, and the above c is H bonded to a carbon adjacent to oxygen in an alkoxy group having 2 to 5 carbon atoms, as shown in Chemical Formula 6-4 below. c It means the total sum of,

[0217]

[0218] The above D represents the number of butadiene (BD) chains, and D is calculated by the following Equation 2, and

[0219] [Equation 2]

[0220] Number of BD chains (D) =

[0221] The above Mn is the number average molecular weight of the modified polybutadiene, and

[0222] The above M(s) is the molecular weight of the silane coupling agent, and

[0223] The above M(b) is the molecular weight of butadiene, and

[0224] The above M is the mole fraction of the Product, calculated by the following Equation 3, and

[0225] [Equation 3]

[0226] Mole fraction of the product (M) =

[0227] The above Mn is the number average molecular weight of the modified polybutadiene, and

[0228] The above M(s) is the molecular weight of the silane coupling agent, and

[0229] x is the remaining amount of silane coupling agent in the modified polybutadiene.

[0230] In the above equation, a, b, and c are H a , H b and H c It refers to the total sum of hydrogens at the positions, and these 1 It can be measured as H-NMR. The above H a of 1 The H-NMR value is δ6.0-5.3, and the above H b of 1 The H-NMR value is δ5.1-4.8, and the above H c of 1 The H-NMR values ​​are δ3.9-3.7.

[0231] According to one embodiment of the present invention, the average number of Si substituted in the modified polybutadiene may be 1.3 to 3.5. The lower limit of the average number of Si may preferably be 1.5, more preferably 2.1, even more preferably 2.3, even more preferably 2.4, and most preferably 2.6, but is not limited thereto. For example, if necessary, the lower limit of the average number of Si may be 2.9, 3.0, or 3.1. The upper limit of the average number of Si may preferably be 3.4, more preferably 3.3, even more preferably 3.2, even more preferably 3.1, and most preferably 2.8, but is not limited thereto. For example, the above average number of Si may be 1.5 to 3.5, 2.1 to 3.5, 2.3 to 3.5, 2.4 to 3.5, 2.6 to 3.5, 2.1 to 3.3, 2.3 to 3.3, 2.4 to 3.3, 2.6 to 3.3, 2.1 to 3.1, 2.3 to 3.1, 2.4 to 3.1, 2.6 to 3.1, 2.1 to 2.8, 2.3 to 2.8, 2.4 to 2.8, 2.6 to 2.8, 3.1 to 3.5, and 3.1 to 3.4, but is not limited thereto. When the above range is satisfied, there is an excellent effect on silica dispersion performance, and physical properties (Moony viscosity, Payne effect, wear resistance, reduction in extraction weight, crosslinking density, DMTS, etc.) are improved.

[0232]

[0233] Hereinafter, embodiments of the present invention will be described in detail.

[0234]

[0235] Examples

[0236]

[0237] Preparation of modified polybutadiene compounds A to E

[0238] Bis[3-triethoxysilyl]propyl]tetrasulfide (Compound 1), di-t-butyl peroxide, and cyclohexane were each introduced into a high-temperature, high-pressure stirred reactor at room temperature and then purged with nitrogen. Butadiene was injected through the gas line of the reactor. Subsequently, the mixture was heated to 135°C and pressurized to proceed with polymerization. The reaction was then terminated by lowering the temperature to 15°C, and unreacted butadiene was removed through the vent line after reaching 15°C. Cyclohexane was removed by vacuum distillation. The remaining initiator and silane coupling agent were removed by precipitating the polymer in ethanol and then centrifuging.

[0239] [Compound 1]

[0240]

[0241]

[0242] The specific manufacturing conditions for compounds A to E are shown in Table 1 below.

[0243] ABCDE Compound 1 (parts by weight) 913.7 16.8 19.6 30.2 Di-t-butyl peroxide (parts by weight) 4.6 4.6 4.6 4.6 4.6 Butadiene (parts by weight) 100 100 100 100 100 Molecular weight 3.42 13.21 73.03 72.96 72.432 Pressure (bar) 20 20 20 20 20 Pressure time 3h 3h 3h 3h 3h Number of substituents 0.5 1.8 6 2.1 72.6 23.21

[0244]

[0245] Analysis of Physical Properties of Modified Polybutadiene

[0246]

[0247] 1. Molecular weight analysis

[0248] Molecular weight correction was performed using a polybutadiene standard sample (Waters Corp., Germany) with size exclusion chromatography (SEC) consisting of a solvent delivery unit, a refractive index detector, and three types of styragel columns [HT 6E (10 μm, 7.8 mm × 300 mm), HMW 7 column (15-20 μm, 7.8 mm × 300 mm), HMW 6E column (15-20 μm, 7.8 mm × 300 mm)].

[0249]

[0250] 2. Analysis of Vinyl (%) Content in Polybutadiene

[0251] Proton nuclear magnetic resonance 1 The vinyl content in the above compound was confirmed using 1H NMR (Varian, Unity Plus 300 spectrometer, Garden State Scientific, Morristown, NJ, USA). The above compound was dissolved in a 5 mm NMR tube at a concentration of 15 mg / mL using dichloroform (CDCl3, Cambridge Isotope Laboratories, Inc., Andover, MA, USA) as a solvent.

[0252]

[0253] 3. Analysis of the average number of substituted Si

[0254] The average number of Si substituted in modified polybutadiene was measured according to Equation 1.

[0255] [Equation 1]

[0256] {b / (a + b / 2)}×D×cM×(2 / 6)

[0257]

[0258] In addition, M(s) (molecular weight of silane coupling agent) was used at 538.9 g / mol (molecular weight of compound 1), and M(b) (molecular weight of butadiene) was used at 54.1 g / mol.

[0259]

[0260] The results are shown in Table 2 below.

[0261] ABCDEMn(g / mol)3,4213,2173,0372,9672,432 PDI(Mw / Mn)2.712.462.552.342.53 Vinyl(%) in BD 19.721.318.619.320.8 Si Number of substituents 0.51.862.172.623.21

[0262]

[0263] Preparation of rubber composition

[0264] A rubber composition was prepared with the composition shown in Table 3 below.

[0265]

[0266] C1C2E1E2E3E4TDAE Oil 403030303030 Polymer-10 (A)10 (B)10 (C)10 (D)10 (E)SSBR808080808080BR202020202020 Silica(195MP)120120120120120120120 Silane Coupling Agent 202020202020DPG222222 Wax 111111TMQ 111111ZnO 333333 Stearic Acid 111111 Antioxidant 222222 Sulfur 1.31.31.31.31.31.3CBS 1.61.61.61.61.61.6ZBEC 0.10.10.10.10.10.1

[0267] C1, C2: Comparative Examples 1 and 2

[0268] E1 to E4: Examples 1 to 4

[0269]

[0270] - TDAE (treated distilled aromatic extracted) oil: Vivatec 500, Kukdong Oil & Chemicals Co., Yangsan, Korea

[0271] - SSBR: 5220M, Kumho Petrochemical Co., Ltd., Korea

[0272] - BR: CB24, Lanxess Chemical Industry Co., Ltd., Cologne, Germany

[0273] - Silica: ZEOSIL 195MP, Solvay Silica Korea Co., Ltd., Gunsan, Korea

[0274] - Silane coupling agent: Coupling agent comprising 50 wt% bis-[3-(triethoxysilyl)propyl]tetrasulfide and 50 wt% carbon black N330 (X50S, Evonik Industries AG, Essen, Germany)

[0275] - DPG: 1,3-Diphenylguanidine, 98%, Tokyo Chemical Industry Co. Ltd., Tokyo, Japan

[0276] - Wax: Paraffinic wax

[0277] - TMQ : 2,2,4-trimethyl-1,2-dihydroquinoline [2,2,4-trimethyl-1,2-dihydroquinoline, TMQ, Sinopec corp., Beijing, China]

[0278] - ZnO: Zinc oxide No. 2 (Sigma-Aldrich Corp., Seoul, Korea)

[0279] - Stearic acid: Sigma-Aldrich Corp., Seoul, Korea

[0280] - Antioxidant: N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine [N-(1,3-dimethylbutyl)-N'-phenyl-pphenylenediamine, 6PPD, Kumho Petrochemical Co., Daejeon, Korea]

[0281] - Sulfur: Sulfur powder (elemental sulfur, Daejung Chemicals & Metals Co., Siheung, Korea)

[0282] - CBS : [N-cyclohexyl-2-benzothiazolylsulfenamide (98%, Tokyo Chemical Industry Co. Ltd., Tokyo, Japan)]

[0283] - ZBEC: zinc dibenzyl dithiocarbamate (ZBEC; Sigma-Aldrich Corp., Seoul, Korea)

[0284]

[0285] Evaluation of rubber compositions containing modified polybutadiene

[0286]

[0287] 1. Mooney viscosity (FMB, ML) 1+4 @100℃)

[0288] It was measured using a Mooney viscometer (Vluchem IND Co., Korea) in accordance with ASTM D-1646.

[0289] 2) Mechanical properties

[0290] Universal testing machine (UTM) in accordance with ASTM D412

[0291] The modulus (M100%) at 100% elongation, the modulus (M300%) at 300% elongation, and the elongation were measured using KSU-05M-C, KSU Co., Korea.

[0292]

[0293] 2. Payne effect (G' at 0.28% - G' at 40%)

[0294] Measurements were taken using a rubber processing analyzer (RPA2000, Alpha Technologies, Hudson, OH, USA) according to the standard procedure specified in ASTM D8059. After the first mixing step, the storage modulus (G') of the compound was measured at 60°C within a deformation range of 0.01% to 40.04%. The change in storage modulus (ΔG') was calculated by subtracting the value at 0.28% deformation from the value at 40.04% deformation.

[0295]

[0296] 3. Wear resistance (DIN abrasion loss)

[0297] A cylindrical specimen with a diameter of 16 mm and a thickness of 8 mm was prepared in accordance with DIN 53516. The specimen was ground for 40 m at a speed of 40 rpm using a Deutsche Industrie Normen (DIN) wear tester to measure the mass loss.

[0298]

[0299] 4. Extraction weight loss (%)

[0300] The extraction weight loss value is an experimental result that can predict the migration of processing aids from the vulcanized material; it involves adding the crosslinker to a solvent to extract additives and comparing the weight before and after. A lower value indicates higher extraction resistance.

[0301]

[0302] 5. Total crosslinking density (10 -4 mol / g)

[0303] It is defined by the number of crosslink points in a vulcanized material. A high crosslink density means that the molecular weight between crosslink points decreases and the number of crosslink points increases. In a swelling test, the higher the crosslink density, the fewer solvent molecules can penetrate between the crosslinked rubber chains, resulting in less swelling.

[0304]

[0305] 6. Dynamic viscoelasticity

[0306] The temperature sweep was measured using an ARES meter for the storage modulus (G'), loss modulus (G"), and tan δ in torsion mode from -60 ℃ to 60 ℃ at a strain of 0.5% and a frequency of 10 Hz.

[0307] Strain sweeps were measured in tension mode from 0.5% to 10% dynamic strain at a temperature of 60 ℃ and a frequency of 10 Hz using a dynamic material thermal spectrometer (DMTS, Eplexor 500N, GABO GmbH & Co. KG, Germany).

[0308]

[0309] C1 C2 E1 E2 E3 E4 Mooney Viscosity 15 9 15 11 37 13 0 11 8 120 Payne effect (G' at 0.28% - G' at 40%) 7.2 7 7.0 9 5.3 4.3 2 2.8 4 3.11 Abrasion performance (DIN abrasion loss (mg)) 10 8 10 0 9 39 28 49 3 Weight loss during extraction (%) 10 0 7 9 9.5 7.5 2.5 6 Total crosslinking density (10 -4 mol / g)1.49 1.36 1.64 1.72 1.8 1.81 DMTS(5% strain)(Tan δ at 60℃)0.20 70.2 140.18 60.173 0.15 60.167 G'(MPa) at -30℃ 187 172 171 15 114 2160 G"MPa at -0℃ 11.4 11.1 11.29.69 39.860℃ Tanδ 0.14 60.14 90.14 0.13 70.13 50.141

[0310] C1, C2: Comparative Examples 1 and 2

[0311] E1 to E4: Examples 1 to 4

[0312]

[0313] As shown in Table 4 above, the overall physical properties of the embodiments of the present invention, considering Mooney viscosity, Payne effect, wear resistance, extraction weight reduction, total crosslinking density, and DMTS (5% strain), were improved compared to the comparative examples. Among these, Examples 2 and 3 showed excellent results in extraction weight reduction and DMTS (5% strain) (G' at -30℃, 0℃, and 60℃), and in particular, Example 3 showed significantly excellent results in Payne effect, wear resistance, extraction weight reduction, and DMTS (5% strain) (G' at -60℃, -30℃, 0℃, and 60℃).

[0314] Although embodiments of the present invention have been described above, those skilled in the art will understand that the present invention may be implemented in other specific forms without altering its technical concept or essential features. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. A composition comprising modified polybutadiene, A composition wherein the modified polybutadiene is polybutadiene substituted with 1 to 4 substituents of the following chemical formula 1: [Chemical Formula 1] In the above formula, * is the substitution position, and R 1 Each is independently hydrogen, deuterium, a halogen, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 1 One or more of them are alkoxy groups having 1 to 5 carbon atoms, and L is each independently an alkylene group having 1 to 5 carbon atoms, and m is an integer from 1 to 6, each independently.

2. In Paragraph 1, A composition characterized in that the above polybutadiene comprises one or more units of the following chemical formulas 2-1 to 2-3. [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] 3. In Paragraph 2, A composition characterized in that the above polybutadiene comprises 40 to 90 mol% of a unit represented by Chemical Formula 2-1 and a unit represented by Chemical Formula 2-2, and 10 to 60 mol% of a unit represented by Chemical Formula 2-3.

4. In Paragraph 2, A composition characterized in that the above polybutadiene has a number average molecular weight (Mn) of 1,000 to 60,000 g / mol and a molecular weight distribution expressed as Mw / Mn of 1.5 to 8.

5. In Paragraph 1, A composition characterized in that the above L is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-.

6. In Paragraph 1, A composition characterized in that the above m is an integer from 1 to 3.

7. In Paragraph 1, A composition characterized in that the above-mentioned modified polybutadiene is of the following chemical formula 3: [Chemical Formula 3] In the above formula, A 1 and A 2 Each is independently any one of the following chemical formulas 4-1 to 4-3, and [Chemical Formula 4-1] [Chemical Formula 4-2] [Chemical Formula 4-3] n and o are each independently integers from 0 to 2, and when n is 0, A 1 is a single bond, and if o is 0, then A 2 is a single bond, and Above A 3 To A 5 is a substituent represented by the above chemical formula 1, and The above p and q are integers of 0 or 1, at least one of p and q is 1, and if p is 0, A 3 is hydrogen, and when q is 0, A 4 is hydrogen, and the sum of n, o, p, and q is 1 to 4, and Above B 1 To B 3 Each is independently of the following chemical formula 2-1, 2-2, or 2-3, and [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] r, s, and t are each independently greater than or equal to 0, and if r is 0, then B 1 is a single bond, and when s is 0, B 2 is a single bond, and when t is 0, B 3 is a single bond.

8. In Paragraph 7, A composition characterized in that the sum of n and o is 1 or 2.

9. In Paragraph 7, Above A 1 and A 2 A composition characterized by each independently containing 50 mol% or more of a unit represented by Chemical Formula 4-3.

10. In Paragraph 1, A composition characterized in that the average number of substituents of Formula 1 substituted in the modified polybutadiene is 1.3 to 3.

5.

11. In Paragraph 1, The above modified polybutadiene is prepared by reacting a radical initiator, a silane coupling agent, and butadiene, and The above silane coupling agent is a compound shown in Chemical Formula 5 below, and [Chemical Formula 5] R 2 and R 3 Each is independently an alkoxy group having 2 to 5 carbon atoms, and L 1 and L 2 Each is independently an alkylene group having 1 to 5 carbon atoms, and A composition characterized in that u is independently an integer from 2 to 12.

12. In Paragraph 11, A composition characterized in that the average number of Si substituted in the modified polybutadiene is calculated by the following Formula 1. [Equation 1] {b / (a + b / 2)}×D×cM×(2 / 6) The above 'a' is Cis / Trans H contained in polybutadiene as shown in the following chemical formulas 6-1 to 6-3. a and H present in the vinyl location a It refers to the total sum of, and the above b is H present at the terminal vinyl position as shown in Chemical Formula 6-3 below. b It refers to the total sum of, and the above c is H bonded to a carbon adjacent to oxygen in an alkoxy group having 2 to 5 carbon atoms, as shown in Chemical Formula 6-4 below. c It means the total sum of, The above D represents the number of butadiene (BD) chains, and D is calculated by the following Equation 2, and [Equation 2] Number of BD chains (D) = The above Mn is the number average molecular weight of the modified polybutadiene, and The above M(s) is the molecular weight of the silane coupling agent, and The above M(b) is the molecular weight of butadiene, and The above M is the mole fraction of the Product, calculated by the following Equation 3, and [Equation 3] Mole fraction of the product (M) = The above Mn is the number average molecular weight of the modified polybutadiene, and The above M(s) is the molecular weight of the silane coupling agent, and x is the remaining amount of silane coupling agent in the modified polybutadiene.

13. In Paragraph 12, A composition characterized in that the average number of Si groups substituted in the modified polybutadiene is 1.3 to 3.

5.

14. A method for preparing a composition comprising modified polybutadiene according to claim 1, A step of obtaining a silane coupling agent radical by reacting a radical initiator and a silane coupling agent; A step of obtaining a polymer radical by polymerizing a silane coupling agent radical and butadiene; and The method includes the step of obtaining modified polybutadiene by reacting a silane coupling agent with the above polymer radicals, and The above silane coupling agent is a compound shown in Chemical Formula 5 below, and [Chemical Formula 5] R 2 and R 3 Each is independently an alkoxy group having 2 to 5 carbon atoms, and L 1 and L 2 Each is independently an alkylene group having 1 to 5 carbon atoms, and u is an integer from 2 to 12, each independently, in a method.

15. In Paragraph 14, A method characterized in that the average number of Si substituted in the modified polybutadiene is measured by the following Formula 1: [Equation 1] {b / (a + b / 2)}×D×cM×(2 / 6) The above 'a' is Cis / Trans H contained in polybutadiene as shown in the following chemical formulas 6-1 to 6-3. a and H present in the vinyl location a It refers to the total sum of, and the above b is H present at the terminal vinyl position as shown in Chemical Formula 6-3 below. b It refers to the total sum of, and the above c is H bonded to a carbon adjacent to oxygen in an alkoxy group having 2 to 5 carbon atoms, as shown in Chemical Formula 6-4 below. c It means the total sum of, The above D represents the number of butadiene (BD) chains, and D is calculated by the following Equation 2, and [Equation 2] Number of BD chains (D) = The above Mn is the number average molecular weight of the modified polybutadiene, and The above M(s) is the molecular weight of the silane coupling agent, and The above M(b) is the molecular weight of butadiene, and The above M is the mole fraction of the Product, calculated by the following Equation 3, and [Equation 3] Mole fraction of the product (M) = The above Mn is the number average molecular weight of the modified polybutadiene, and The above M(s) is the molecular weight of the silane coupling agent, and x is the remaining amount of silane coupling agent in the modified polybutadiene.

16. In Paragraph 15, A method characterized in that the average number of Si substituted in the modified polybutadiene is 1.3 to 3.5.

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