Solid granular material

Abstract

To provide a novel technical means for granulating polybutadiene containing a 1,2-structure. A solid granular material containing polybutadiene with a 1,2-structure and silica with an oil absorption capacity of more than 225 mL / 100 g.

Description

[Technical Field]

[0001] This disclosure relates to solid granular materials. [Background technology]

[0002] Polybutadiene can have 1,2-structures, cis-1,4-structures, and trans-1,4-structures, and it is known that its physical properties change significantly depending on the ratio of these structures (i.e., the ratio of microstructures).

[0003] The 1,2-structure (1,2-vinyl structure) of polybutadiene is highly reactive and exhibits high crosslinking reactivity induced by heat and light. Therefore, it is used in a wide range of applications, including electronic substrates (flexible substrates), adhesives, sealants, vibration dampers, reactive crosslinking agents (in combination with acrylates), printing plate materials, and coatings (electrodeposition coatings). For this reason, polybutadiene containing the 1,2-structure is considered highly useful.

[0004] On the other hand, polybutadiene containing 1,2-structures is viscous, which makes weighing and mixing difficult during use. Therefore, improving the handling of polybutadiene containing 1,2-structures would further enhance its usability.

[0005] Patent Document 1 discloses a technique for improving handling by powdering a viscous N-alkyl-N'-phenyl-p-phenylenediamine derivative using a carrier (calcium silicate). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 08-176341 [Overview of the Initiative]

[0007] The Discloser attempted to granulate polybutadiene containing a 1,2-structure using an arbitrary carrier, referencing the method described in Patent Document 1. The Discloser's investigation revealed that polybutadiene forms aggregates. Aggregate formation is undesirable because it can significantly reduce handling and quality.

[0008] Therefore, one objective of this disclosure is to provide a novel technical means for granulating polybutadiene containing a 1,2-structure.

[0009] The Discloser, through diligent research, unexpectedly discovered that good solid granules can be obtained by mixing polybutadiene containing a 1,2-structure with silica having specific oil-absorbing properties. This disclosure is based on this finding.

[0010] According to one embodiment of the present disclosure, a solid granular material is provided comprising polybutadiene containing a 1,2-structure and silica having an oil absorption capacity of more than 225 mL / 100 g.

[0011] According to one embodiment of the present disclosure, a novel technical means can be provided for granulating polybutadiene containing a 1,2-structure. [Brief explanation of the drawing]

[0012] [Figure 1] The appearance of the solid granules obtained in Example 1-1 and Reference Example 1 (microscopic observation, magnification: 20x) is shown. [Figure 2] In Test Example 3, the results of the vulcanization test of ethylene propylene rubber using the solid granules obtained in Example 4 are shown. Detailed description of the invention

[0013] [Solid granular material of this disclosure] According to one embodiment of the present disclosure, a solid granular material (also referred to in this disclosure as "the solid granular material of the present disclosure") is provided, comprising polybutadiene containing a 1,2-structure and silica having an oil absorption capacity of more than 225 mL / 100 g. According to one embodiment of the present disclosure, since the polybutadiene containing a 1,2-structure can be granulated, it is advantageous from the viewpoint of improving the handling of the polybutadiene. The solid granular material of the present disclosure will be described in detail below.

[0014] The solid granular material of this disclosure is not particularly limited as long as it is a solid granular material, and the mass ratio of polybutadiene and silica containing the 1,2-structure described later, the average particle size, etc., may be arbitrary.

[0015] According to one embodiment of the present disclosure, the mass ratio (polybutadiene / silica) of polybutadiene containing the 1,2-structure in the solid granular material of the present disclosure to silica may be, for example, 0.3 to 2.5, preferably 1 to 2.1, more preferably 1.5 to 2.1, and even more preferably 1.8 to 2.1. According to one embodiment of the present disclosure, the solid granular material of the present disclosure is advantageous in that solid granular material can be obtained even with the above mass ratio. Furthermore, according to one embodiment of the present disclosure, the solid granular material of the present disclosure is advantageous in that the polybutadiene containing the 1,2-structure is less likely to leach out from the silica even with the above mass ratio.

[0016] The average particle size of the solid granules in this disclosure may be any value as long as it can achieve the objectives of this disclosure.

[0017] According to one embodiment of the present disclosure, the solid granules of the present disclosure may consist of at least a portion of polybutadiene containing a 1,2-structure supported on at least a portion of silica, or at least a portion of polybutadiene containing a 1,2-structure present in at least a portion of pores within the silica, or both. According to one embodiment of the present disclosure, the solid granules of the present disclosure may consist of at least a portion of polybutadiene containing a 1,2-structure present in at least a portion of pores within the silica.

[0018] According to one embodiment of the present disclosure, the solid granular material of the present disclosure may be in powder form (preferably white powder form).

[0019] (Polybutadiene containing 1,2-structure) According to one embodiment of the present disclosure, the solid granular material of the present disclosure is said to contain polybutadiene containing 1,2-structure. The "polybutadiene containing 1,2-structure" in the present disclosure means a material that contains butadiene units of the following structure (1,2-structure) within the polybutadiene molecule. Note that the 1,2-structure in the present disclosure can be used interchangeably with the 1,2-vinyl structure.

Chemical formula

[0020] The above 1,2-structure unit may be isotactic (i.e., the absolute configurations of all asymmetric carbons are the same), syndiotactic (i.e., the absolute configurations of asymmetric carbons alternate), or atactic (i.e., the absolute configurations of asymmetric carbons are irregular).

[0021] In addition to the above structural units, the polybutadiene containing 1,2-structure may also contain butadiene units such as cis-1,4 structure and trans-1,4 structure within the molecule.

Chemical formula

[0022] The proportion of the 1,2-structure contained in the polybutadiene containing 1,2-structure is not particularly limited as long as the object of the present disclosure can be achieved. According to one embodiment of the present disclosure, the polybutadiene containing 1,2-structure may contain 50 mol% or more, preferably 85 mol% or more, more preferably more than 88 mol%, and even more preferably 90 mol% or more of the 1,2-structure based on all the butadiene units in the molecule. According to one embodiment of the present disclosure, the solid granular material of the present disclosure is advantageous from the viewpoint that a solid granular material can be obtained even if it is polybutadiene containing the 1,2-structure within the above range.

[0023] The viscosity of the polybutadiene containing the 1,2-structure is not particularly limited, as long as it can achieve the purposes of this disclosure, and any viscosity may be used.

[0024] The molecular weight of the polybutadiene containing the 1,2-structure is not particularly limited as long as it can achieve the objectives of this disclosure, and any molecular weight may be used. According to one embodiment of this disclosure, the number-average molecular weight of the polybutadiene containing the 1,2-structure may be 1000 to 5000, preferably 2000 to 4000, and more preferably 2500 to 3500.

[0025] Polybutadiene containing the 1,2-structure may be commercially available or manufactured by known methods (e.g., International Publication No. 2011 / 045918).

[0026] The polybutadiene containing 1,2-structures contained in the solid granules of this disclosure may be a single type, or it may be any combination of two or more types with different proportions of 1,2-structures contained in the molecule, molecular weight, viscosity, etc.

[0027] The amount of 1,2-structure-containing polybutadiene contained in the solid granules of this disclosure is not particularly limited as long as it can achieve the objectives of this disclosure. The amount of 1,2-structure-containing polybutadiene contained in the solid granules of this disclosure may be, for example, 10 to 80% by mass, preferably 30 to 75% by mass, more preferably 50 to 70% by mass, and even more preferably 60 to 67% by mass, based on the total mass of the solid granules of this disclosure.

[0028] (silica) According to one embodiment of the present disclosure, the solid granular material of the present disclosure contains silica having an oil absorption capacity of more than 225 mL / 100 g. According to one embodiment of the present disclosure, the silica can function as a carrier. It is quite surprising that when other carriers other than silica (e.g., powdered cellulose, diatomaceous earth) or silica having an oil absorption capacity of 225 mL / 100 g or less are used, a solid granular material may not be obtained when polybutadiene containing a 1,2-structure is mixed with them.

[0029] In this disclosure, "silica" means a compound having a silicon dioxide (SiO2) content of 50% by mass or more. Therefore, silica may contain other substances (e.g., impurities) other than silicon dioxide, to the extent that it does not impair the purpose of this disclosure. The silicon dioxide content in silica may be based on information from the manufacturer selling the silica, or it may be measured by known analytical methods such as X-ray fluorescence analysis, X-ray diffraction analysis, ICP emission spectrometry, or ICP mass spectrometry. According to one embodiment of this disclosure, silica may have a silicon dioxide content of 80% by mass or more, preferably 90% by mass or more, and more preferably 93% by mass or more.

[0030] Silica may be a dry substance or may contain moisture.

[0031] Silica may be crystalline silica, amorphous silica, or a mixture thereof. According to one embodiment of the present disclosure, crystalline silica is a compound that has a characteristic X-ray diffraction pattern when analyzed by X-ray diffraction (the X-ray diffraction pattern can be confirmed from a database owned by the International Diffraction Data Center, and the crystal structure of the silica can be determined by the similarity between the X-ray diffraction pattern measured for the silica used and the X-ray diffraction pattern in the database). Examples of crystalline silica include quartz, cristobalite, tridymite, keetite, coesite, stishovite, precipitated silica, fumed silica, silica gel, etc., which may be used individually or in any combination of two or more.

[0032] According to one embodiment of the present disclosure, the silica includes amorphous silica.

[0033] The silica may be wet silica (e.g., wet precipitated silica) or dry silica (e.g., fumed silica).

[0034] According to one embodiment of the present disclosure, the silica includes wet silica (preferably wet-settled silica). According to one embodiment of the present disclosure, the silica includes amorphous wet silica (preferably amorphous wet-settled silica).

[0035] According to one embodiment of the present disclosure, the oil absorption of the silica may be 230 mL / 100g or more, preferably 235 mL / 100g or more, and more preferably 240 mL / 100g or more. According to one embodiment of the present disclosure, the oil absorption was measured in accordance with ISO 19246:2016 "Rubber compounding ingredients - Silica - Oil absorption of precipitated silica".

[0036] The specific surface area of ​​silica is not particularly limited as long as it can achieve the objectives of this disclosure. According to one embodiment of this disclosure, the BET specific surface area of ​​the silica is 1000 m². 2 Less than or equal to / g, preferably 500m 2 / g or less, more preferably 380m 2 Less than 250mg / g, more preferably 250mg 2 It may be less than or equal to / g. According to one embodiment of the present disclosure, the BET specific surface area of ​​the silica is 10 to 1000 m². 2 / g, preferably 50-500m 2 / g, more preferably 70-370m 2 / g, more preferably 100-300m 2It may also be / g. Furthermore, the silica may be pulverized using known equipment or other methods such as wet or dry methods so that it has the desired BET specific surface area. Using silica with a BET specific surface area within the above range is advantageous from the viewpoint of obtaining solid granules containing a larger amount of polybutadiene with 1,2-structures.

[0037] According to one embodiment of the present disclosure, silica may contain pores. The pore volume of the pores that may be contained in silica is not particularly limited as long as it can achieve the objectives of the present disclosure, and may be, for example, 1.40 mL / g or more, preferably 1.46 mL / g or more, and more preferably 1.50 mL / g or more. According to one embodiment of the present disclosure, the pore volume of the silica pores is measured by the BJH method.

[0038] The particle size of the silica is not particularly limited as long as it can achieve the objectives of this disclosure, and may be, for example, 0.01 to 1000 μm, preferably 0.3 to 100 μm, and more preferably 5 to 50 μm. The silica may be pulverized using wet or dry methods with known equipment or the like to obtain the desired particle size. According to one embodiment of this disclosure, the particle size of the silica is the cumulative average diameter measured by a particle size distribution analyzer (the particle size at the point where the cumulative curve reaches 50% when the total volume of the group of powders to be analyzed is taken as 100%).

[0039] The bulk density of silica is not particularly limited as long as it can achieve the objectives of this disclosure, and may be, for example, 1 to 1000 g / L, preferably 10 to 500 g / L, and more preferably 100 to 300 g / L. According to one embodiment of this disclosure, the bulk density can be measured in accordance with ISO 787-11:1981 "General methods of test for pigments and extenders Part 11: Determination of tamped volume and apparent density after tamping".

[0040] The electrical conductivity of silica is not particularly limited as long as it can achieve the objectives of this disclosure, and may be, for example, 1 to 1000 μS / cm, preferably 5 to 300 μS / cm, and more preferably 10 to 100 μS / cm. According to one embodiment of this disclosure, the electrical conductivity can be measured in accordance with ISO 787-14:2019 "General methods of test for pigments and extenders Part 14: Determination of resistivity of aqueous extract".

[0041] Silica may be partially or entirely surface-modified, to the extent that it does not impair the purposes of this disclosure. Surface-modified silica may be generally available or may have been surface-modified by known methods or other means. Compounds used for surface modification include, for example, methanesulfonic acid, ethanesulfonic acid, octanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, dimethylbenzenesulfonic acid, biphenylsulfonic acid, styrenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, naphthalenedisulfonic acid, anthracenesulfonic acid, phenanthrenesulfonic acid, tributyl phosphate, diethyl phosphate, methyl phosphate, butoxyethyl phosphate, bis(butoxyethyl) phosphate, dibutyl phosphate, dihexyl phosphate, triphenyl phosphate, phenyl phosphate, dimethylphenyl phosphate, naphthyl phosphate, and dimethylphosphonate. Phosphosphatid acid such as tributyl phosphite, triphenyl phosphite, triphenylphosphine oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphonic acids such as methylphosphonic acid, ethylphosphonic acid, octylphosphonic acid, dodecylphosphonic acid, phenylphosphonic acid, octylphenylphosphonic acid, dodecylphenylphosphonic acid, naphthalenephosphonic acid, anthracenephosphonic acid, phenanthrenephosphonic acid, methylphosphinic acid, ethylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, alkyl carboxylic acids such as acetic acid, caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, benzoic acid, toluic acid, dodecylbenzoic acid, methoxybenzoic acid, phenoxybenzoic acid, naphthalenecarboxylic acid, phthalic acid, salicylic acid, dodecylbenzoic acid, anthracenecarboxylic acid, phenanthrenecarboxylic acid, lactic acid, malic acid, adipic acid, and other organic acids;Examples include alkylalkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, and octyltrimethoxysilane; epoxyalkoxysilanes such as γ-glycidoxypropyltriethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; aminoalkoxysilanes such as aminopropyltriethoxysilane and N-phenylaminopropyltrimethoxysilane; vinylalkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; and acryloalkoxysilanes such as acryloxytrimethoxysilane and acrylomethoxytriethoxysilane; these alkoxysilane compounds may be used individually or in any combination of two or more.

[0042] According to one embodiment of the present disclosure, the silica includes silica that is not surface-modified.

[0043] The shape of silica is not particularly limited as long as it can achieve the purposes of this disclosure, and may be, for example, spherical, fusiform, rod-shaped, needle-shaped, tubular, columnar, flaky, thin, plate-shaped, or crushed.

[0044] The silica may be commercially available or manufactured by known methods (e.g., International Publication No. 2005 / 012176).

[0045] The silica contained in the solid granules of this disclosure may be a single type or any combination of two or more types.

[0046] The amount of silica contained in the solid granules of this disclosure is not particularly limited as long as it can achieve the objectives of this disclosure. The amount of silica contained in the solid granules of this disclosure may be, for example, 20 to 90% by mass, preferably 25 to 70% by mass, more preferably 30 to 50% by mass, and even more preferably 33 to 40% by mass, based on the total mass of the solid granules of this disclosure.

[0047] (Other ingredients) The solid granules of this disclosure may contain other components besides the polybutadiene and silica, to the extent that they do not impair the effects of this disclosure. Such other components include, but are not limited to, dispersants and crosslinking aids. The types and / or amounts of the other components that may be contained in the solid granules of this disclosure can be appropriately adjusted by a person skilled in the art, taking into consideration the composition of the solid granules of this disclosure, the desired use, etc.

[0048] (Application) The solid granules of this disclosure can be used for any application. For example, the solid granules of this disclosure may be used as a crosslinking agent in fields such as electronic substrates (flexible substrates), adhesives, sealants, vibration damping agents, reactive crosslinking agents (in combination with acrylates), printing plate materials, and coating agents.

[0049] According to one embodiment of the present disclosure, the solid granules of the present disclosure may be used for vulcanization of rubber (preferably ethylene propylene rubber).

[0050] [Method for producing solid granules according to this disclosure] According to one embodiment of the present disclosure, a method for producing solid granules of the present disclosure, A step of stirring heated and softened polybutadiene containing a 1,2-structure and silica in a heated mixer to obtain the above-mentioned solid granules (also referred to as the "stirring step" in this disclosure). A method (also referred to in this disclosure as the "Manufacturing Method of the Disclosure") is provided, which includes the above.

[0051] <Preparation steps for heat-softened polybutadiene containing 1,2-structures> According to one embodiment of the present disclosure, the manufacturing method of the present disclosure may include a step of preparing a heat-softened polybutadiene containing a 1,2-structure (also referred to in the present disclosure as the “preparation step”).

[0052] According to one embodiment of the present disclosure, in the preparation step described above, the polybutadiene containing the 1,2-structure may be heated until it softens. The heating method is not particularly limited and can be adjusted as appropriate by those skilled in the art.

[0053] The above heating temperature is not particularly limited as long as it is a temperature at which the polybutadiene containing the 1,2-structure can be softened, and those skilled in the art can adjust it appropriately, taking into account the physical properties of the polybutadiene containing the 1,2-structure used. According to one embodiment of this disclosure, the above heating temperature may be 70°C or higher, preferably 80°C or higher, more preferably greater than 80°C, and even more preferably 85°C or higher. According to one embodiment of this disclosure, the above heating temperature may be 70 to 160°C, preferably 80 to 140°C, more preferably greater than 80°C and 120°C or lower, and even more preferably 85 to 100°C. According to one embodiment of this disclosure, setting the upper limit of the above heating temperature to 120°C or lower is particularly advantageous from the viewpoint of suppressing the self-polymerization of the polybutadiene containing the 1,2-structure used. According to one embodiment of this disclosure, setting the lower limit of the above heating temperature to greater than 80°C is particularly advantageous from the viewpoint of improving the quantitative accuracy of the polybutadiene containing the 1,2-structure.

[0054] Although not bound by theory, further investigations by the Discloser have revealed that the solid granules of this disclosure tend to aggregate when the mass ratio of polybutadiene containing 1,2-structures to silica (polybutadiene / silica) exceeds 2.5 (preferably 2.1). Therefore, accuracy in the quantitative determination of polybutadiene containing 1,2-structures may be required. For this reason, setting the lower limit of the heating temperature in the above preparation step to 70°C or higher (preferably 80°C or higher, more preferably above 80°C, and even more preferably 85°C or higher) is particularly advantageous from the viewpoint of further preventing aggregation of the solid granules of this disclosure.

[0055] <Agitation process> According to one embodiment of the present disclosure, a stirring step is performed in the manufacturing method of the present disclosure. The stirring conditions in the stirring step (temperature, time, rotation speed, etc.) are not particularly limited as long as they are conditions under which the solid granular material of the present disclosure can be obtained, and those skilled in the art can adjust them as appropriate, taking into consideration the physical properties of the 1,2-structure-containing polybutadiene and / or silica used, the desired solid granular material, etc.

[0056] According to one embodiment of the present disclosure, stirring in the stirring step may be carried out at a rotational speed of 100 to 1000 rpm, preferably 300 to 600 rpm, and more preferably 350 to 500 rpm. Setting the stirring speed within the above range is advantageous from the viewpoint of shortening the mixing time, avoiding aggregation of solid particles, and / or reducing the load on the stirrer.

[0057] According to one embodiment of the present disclosure, stirring in the stirring step may be carried out for 0.5 to 10 minutes, preferably 1 to 6 minutes, and more preferably 1 to 5 minutes. Note that if stirring is carried out multiple times as described later, the stirring time refers to the total time of all stirring. While not bound by theory, further investigations by the discloser have revealed that when obtaining solid granules of the present disclosure with a mass ratio (polybutadiene / silica) of 1.5 or higher (preferably 1.8 or higher) of polybutadiene containing 1,2-structures to silica, the resulting solid granules tend to aggregate when stirring in the stirring step is carried out for more than 6 minutes. Therefore, carrying out stirring in the stirring step for 6 minutes or less is particularly advantageous from the viewpoint of further suppressing the aggregation of solid granules of the present disclosure with a high mass ratio.

[0058] According to one embodiment of the present disclosure, stirring in the stirring step may be performed once or multiple times. The number of times referred to in the stirring step (e.g., once, twice) does not mean the number of rotations of stirring, but rather the number of times a series of stirring operations are performed. When stirring is performed multiple times, the stirring conditions (temperature, time, rotation speed, etc.) may be the same or different. According to one embodiment of the present disclosure, stirring in the stirring step may be performed at least twice (preferably twice). Performing the stirring multiple times is advantageous from the viewpoint of obtaining a more uniform solid granular material of the present disclosure.

[0059] According to one embodiment of the present disclosure, the stirring temperature in the stirring step may be 40 to 160°C, preferably 50 to 140°C, more preferably 80 to 120°C, and even more preferably 85 to 100°C. In particular, setting the stirring temperature in the stirring step to 80 to 120°C (preferably 85 to 100°C) is advantageous from the viewpoint of improving the fluidity of polybutadiene and preventing deterioration. According to one embodiment of the present disclosure, the stirring temperature in the stirring step refers to the temperature of the inner wall surface of the mixer.

[0060] According to one embodiment of the present disclosure, the mixer used in the stirring step may be preheated to the above temperature.

[0061] The mixer used in the stirring process is not particularly limited, and any known mixer can be used.

[0062] The amounts of 1,2-structure-containing polybutadiene and silica used in the stirring step are not particularly limited and can be appropriately adjusted by those skilled in the art depending on the desired type and amount of solid granules. According to one embodiment of this disclosure, the mass ratio (polybutadiene / silica) of 1,2-structure-containing polybutadiene to silica used in the stirring step may be 0.3 to 2.5, preferably 1 to 2.1, more preferably 1.5 to 2.1, and even more preferably 1.8 to 2.1.

[0063] According to one embodiment of the present disclosure, the heating temperature of the polybutadiene containing the 1,2-structure may be 70°C or higher, preferably 80°C or higher, more preferably greater than 80°C, and even more preferably 85°C or higher. According to one embodiment of the present disclosure, the heating temperature of the polybutadiene containing the 1,2-structure may be 70 to 160°C, preferably 80 to 140°C, more preferably greater than 80°C and 120°C or lower, and even more preferably 85 to 100°C.

[0064] <Recovery Process> According to one embodiment of the present disclosure, the manufacturing method of the present disclosure may further include a step of recovering the solid granules obtained in the stirring step under non-shear stress conditions. Further investigations by the discloser have revealed that when the solid granules of the present disclosure obtained in the stirring step are recovered under normal recovery conditions, such as shear stress (for example, when recovered using a known rotary feeder), the solid granules of the present disclosure may form aggregates. Therefore, according to one embodiment of the present disclosure, recovering the obtained solid granules of the present disclosure under non-shear stress conditions is particularly advantageous from the viewpoint of further suppressing aggregate formation.

[0065] In this disclosure, "under non-shear stress" means conditions under which no shear stress occurs. Examples of methods for recovering the solid granular material of this disclosure under non-shear stress include recovering it using gravity without applying shear stress, and scooping it up directly from a mixer.

[0066] <Other processes> The manufacturing method disclosed herein may include other steps (e.g., sieving steps, purification steps) in addition to the steps described above, to the extent that they do not impair the purpose of the disclosure. Such other steps may be performed before, simultaneously with, or after each of the steps described above.

[0067] This disclosure includes the following: [1] A solid granular material containing polybutadiene with a 1,2-structure and silica having an oil absorption capacity of more than 225 mL / 100 g. [2]At least a part of the polybutadiene is supported on at least a part of the silica, at least a part of the polybutadiene is present in at least a part of the pores in the silica, or both, the solid granular material according to [1]. [3]The BET specific surface area of the silica is less than 380 m 2 / g, the solid granular material according to [1] or [2]. [4]The polybutadiene contains 85 mol% or more of 1,2-structure based on all butadiene units in the molecule, the solid granular material according to any one of [1] to [3]. [5]The polybutadiene contains more than 88 mol% of 1,2-structure based on all butadiene units in the molecule, the solid granular material according to any one of [1] to [4]. [6]The number average molecular weight of the polybutadiene is 2500 to 3500, the solid granular material according to any one of [1] to [5]. [7]The mass ratio of the polybutadiene to the silica (polybutadiene / silica) is 1 to 2.1, the solid granular material according to any one of [1] to [6]. [8]The mass ratio of the polybutadiene to the silica (polybutadiene / silica) is 1.8 to 2.1, the solid granular material according to any one of [1] to [7]. [9]The solid granular material is in powder form, the solid granular material according to any one of [1] to [8].

[10] A method for producing the solid granular material according to any one of [1] to [9], The step of stirring the heat-softened polybutadiene and the silica in a heated mixer to obtain the solid granular material including, the method.

[11] The temperature of the heat softening is above 80°C, the method according to

[10] .

[12] The stirring is carried out at a rotational speed of 300 to 600 rpm, the method according to

[10] or

[11] .

[13] The stirring is carried out for 1 to 5 minutes, the method according to any one of

[10] to

[12] .

[14] The stirring is carried out at least twice, the method according to any one of

[10] to

[13] .

[15] The method according to any one of

[10] to

[14] , wherein the mass ratio of the above polybutadiene to the above silica (polybutadiene / silica) is 1 to 2.1.

[16] A step of recovering the solid granular material obtained in the above step under non-shear stress conditions. The method described in any of

[10] to

[15] , further including the method described in any of

[10] to

[15] . [Examples]

[0068] The solid granular materials of this disclosure will be described in more detail below using examples. However, the following examples are not intended to limit the solid granular materials of this disclosure in any way. Unless otherwise specified, the percentages and ratios described herein are by mass. Unless otherwise specified, the units and measurement methods described herein are in accordance with the Japanese Industrial Standards (JIS).

[0069] [Example 1-1: Manufacturing of solid granular material 1-1] 300g of liquid polybutadiene (B-3000 (1,2-structure molar ratio of 90%), manufactured by Nippon Soda Co., Ltd.) was heated to 90°C in an oven to soften it. A 9L Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd., model: FM10C / I) was heated by circulating hot water to bring the inner wall temperature of the mixer to approximately 90°C. 150g of silica (Carplex® #80, dioctyl adipate (DOA) oil absorption 245mL / 100g (measured according to ISO19246:2016), manufactured by Evonik) and the softened liquid polybutadiene (total amount) were added to the mixer, and the mixture was mixed for 1 minute by rotating the mixer blades (rotation speed 465 rpm). Subsequently, the rotation was stopped, the deposits on the walls and blades were scraped off, and the mixer blades were rotated again (at a rotation speed of 465 rpm) for 1 minute of mixing. This series of operations was repeated three times (total mixing time: 4 minutes) to obtain the solid granular material (powdered, white) of Example 1-1. The results are shown in Table 1 and Figure 1.

[0070] [Example 1-2: Manufacturing of solid granular material 1-2] In Example 1-1, the same procedure was followed, except that the rotation was stopped, the deposits on the wall and blades were scraped off, and the mixer blades were rotated again (at a rotation speed of 465 rpm) for 1 minute of mixing. This process was repeated four times (total mixing time: 5 minutes), and the solid granular material of Example 1-2 (powdered, white) was obtained. The solid granular material of Example 1-2 was powdered and uniform, similar to the solid granular material of Example 1-1.

[0071] [Example 1-3: Manufacturing of solid granular material 1-3] In Example 1-1, the same method was followed except that liquid polybutadiene was softened by heating to 70°C, and the solid granular material (powdered, white) of Example 1-3 was obtained. The solid granular material of Example 1-3 was powdered, but was somewhat non-uniform compared to the solid granular material of Example 1-1.

[0072] [Example 1-4: Manufacturing of solid granular material 1-4] In Example 1-3, the same method was followed, except that the rotation was stopped, the deposits on the wall and blades were scraped off, and the mixer blades were rotated again (at a rotation speed of 465 rpm) for 1 minute of mixing, and this series of operations was repeated four times (total mixing time: 5 minutes), to obtain the solid granular material (powdered, white) of Example 1-4. The solid granular material of Example 1-4 was powdered, but was somewhat non-uniform compared to the solid granular material of Example 1-1.

[0073] [Example 1-5: Manufacturing of solid granular material 1-5] In Example 1-1, the same method was followed, except that the liquid polybutadiene was heated to 70°C to soften it and the temperature of the inner wall of the mixer was set to approximately 70°C, to obtain the solid granular material (powdered, white) of Example 1-5. The solid granular material of Example 1-5, although powdered, was somewhat non-uniform compared to the solid granular material of Example 1-1.

[0074] [Example 1-6: Manufacturing of solid granular material 1-6] In Example 1-5, the same method was followed, except that the rotation was stopped, the deposits on the wall and blades were scraped off, and the mixer blades were rotated again (at a rotation speed of 465 rpm) for 1 minute of mixing, and this series of operations was repeated four times (total mixing time: 5 minutes), to obtain the solid granular material (powdered, white) of Example 1-6. The solid granular material of Example 1-6 was powdered, but was somewhat non-uniform compared to the solid granular material of Example 1-1.

[0075] [Example 1-7: Manufacturing of solid granular material 1-7] In Example 1-1, the same method was followed, except that the liquid polybutadiene was heated to 50°C to soften it and the temperature of the inner wall of the mixer was set to approximately 50°C, to obtain the solid granular material (powdered, white) of Example 1-7. The solid granular material of Example 1-7 was powdered, but was somewhat non-uniform compared to the solid granular material of Example 1-1.

[0076] [Example 1-8: Manufacturing of solid granular material 1-8] In Example 1-7, the same method was followed, except that the rotation was stopped, the deposits on the wall and blades were scraped off, and the mixer blades were rotated again (at a rotation speed of 465 rpm) for 1 minute of mixing, and this series of operations was repeated four times (total mixing time: 5 minutes), to obtain the solid granular material (powdered, white) of Example 1-8. The solid granular material of Example 1-8 was powdered, but was somewhat non-uniform compared to the solid granular material of Example 1-1.

[0077] [Example 2: Manufacturing of solid granular material 2] In Example 1-1, the same method was followed except that the amount of liquid polybutadiene was changed to 225 g, and the solid granular material (powdered, white) of Example 2 was obtained. The results are shown in Table 1. The solid granular material of Example 2 was powdered and uniform, similar to the solid granular material of Example 1-1.

[0078] [Example 3: Manufacturing of solid granular material 3] In Example 1-1, the same method was followed except that the amount of liquid polybutadiene was changed to 150 g, and the solid granular material (powdered, white) of Example 3 was obtained. The results are shown in Table 1. The solid granular material of Example 3 was powdered and uniform, similar to the solid granular material of Example 1-1.

[0079] [Example 4: Manufacturing of solid granular material 4] 60 kg of liquid polybutadiene (B-3000 (1,2-structure molar ratio 90%), manufactured by Nippon Soda Co., Ltd.) was heated to 90°C in an oven to soften it. A 300L Henschel mixer (manufactured by Kawata, model: SMB-300) was heated to 140°C with steam (mixer inner wall temperature: approximately 90°C). 30 kg of silica (Carplex® #80, oil absorption 245 mL / 100 g, manufactured by Evonik) and the softened liquid polybutadiene (total amount) were added to the mixer, and the mixture was mixed for 1 minute by rotating the mixer blades (rotation speed 450 rpm). Subsequently, the rotation was stopped, the deposits on the walls and blades were scraped off, the mixer blades were rotated again (at a rotation speed of 450 rpm) and mixed for 1 minute (total mixing time: 2 minutes), and then sieved to obtain 86.8 kg of the solid granular material (powdered, white) of Example 4. The solid granular material of Example 4 was powdered and uniform, similar to the solid granular material of Example 1-1.

[0080] [Reference Example 1: Manufacturing of Solid Granules 5] In Example 1-1, the same method was followed, except that the silica used was changed to Carplex® #67 (DOA oil absorption 225 mL / 100 g (measured in accordance with ISO 19246:2016), manufactured by Evonik), to obtain the solid granular material (aggregate formation, white) of Reference Example 1. The results are shown in Table 1 and Figure 1.

[0081] [Reference Example 2: Manufacturing of Solid Granules 6] In Example 1-1, the same method was followed except that powdered cellulose (KC Floc® W-100GK, manufactured by Nippon Paper Industries Co., Ltd.) was used instead of silica, and the solid granular material (aggregate formation, white) of Reference Example 2 was obtained. The results are shown in Table 1.

[0082] [Reference Example 3: Manufacturing of Solid Granules 7] In Example 1-1, the same method was followed except that diatomaceous earth (Radiolite F, manufactured by Showa Chemical Industry Co., Ltd.) was used instead of silica, and the amount of liquid polybutadiene was changed to 150 g. This yielded the solid granular material (aggregate formation, white) shown in Reference Example 3. The results are shown in Table 1.

[0083] [Table 1]

[0084] [Test Example 1: Evaluation of Uniformity of Solid Granules] In Example 4, solid granular material immediately after production was sampled in the mixer, and the heat loss and ash content were evaluated using the following method. The results are shown in Table 2. <Heating loss> A heat loss test was conducted based on the Japanese Industrial Standard (JIS K 6220-1:2015). Three grams of the sample were accurately weighed into a flat glass container, heated in a drying oven (100-105°C) for two hours, then allowed to cool in a desiccator. The mass was then measured and the weight loss ratio was calculated. <Ash content test> Ash content loss tests were conducted in accordance with the Japanese Industrial Standard (JIS K 6220-1:2015). One g of the sample was accurately weighed into a crucible, burned to carbonize, and then ashed in an electric furnace (750 ± 25°C) for 1.5 hours. After cooling in a desiccator, the mass was measured and the residue rate was calculated.

[0085] [Table 2]

[0086] [Test Example 2: Solidification Test] The solid granular material from Example 4 was packed in 20 kg kraft paper bags lined with polyethylene bags, stacked vertically in 5 layers, and stored indoors at ambient temperature (approximately 4-40°C) for one year. As a result, the solid granular material stored in the steam paper bag placed at the bottom showed no significant change in powder fluidity.

[0087] [Test Example 3: Performance Evaluation] The crosslinking performance of the solid granules in Example 4 was evaluated using the compositions shown in Table 3 below. To 100 parts by mass of ethylene propylene rubber (EPDM) in the composition below, 15 or 30 parts by mass of the solid granules of Example 4 were mixed, and a vulcanization test (Alpha Technologies Rheometer Premier MDR, 175°C) was performed according to JIS K6296-3 (Unvulcanized rubber - Method for determining vulcanization properties - Part 3). A blank was used for EPDM with the following composition, without the solid granules of Example 4. The results are shown in Figure 2.

[0088] [Table 3]

[0089] Based on the results of Test Example 1, no variation was observed in the solid granular material of this disclosure depending on the sampling point, suggesting that the polybutadiene is uniformly dispersed on the silica. Furthermore, based on the results of Test Example 2, the solid granular material of this disclosure is considered to have excellent storage stability. Furthermore, based on the results of Test Example 3, it is considered that the solid granular material of this disclosure has good performance (e.g., crosslinking performance).

Claims

1. A solid granular material comprising polybutadiene having 85 mol% or more of 1,2-structures based on total butadiene units and a number average molecular weight of 2500 to 3500, and silica having an oil absorption capacity of more than 225 mL / 100 g, The amount of polybutadiene is 50 to 70% by mass based on the total mass of the solid granules. The mass ratio of the polybutadiene to the silica (polybutadiene / silica) is 1 to 2.

1. Solid granular material.

2. The solid granular material according to claim 1, wherein at least a portion of the polybutadiene is supported on at least a portion of the silica, or at least a portion of the polybutadiene is present in at least a portion of the pores in the silica, or both.

3. The BET specific surface area of ​​the aforementioned silica is 380 m². ２ The solid granular material according to claim 1, wherein the amount is less than / g.

4. The solid granular material according to claim 1, wherein the polybutadiene contains more than 88 mol% of 1,2-structures based on the total butadiene units in the molecule.

5. The solid granular material according to claim 1, wherein the mass ratio of polybutadiene to silica (polybutadiene / silica) is 1.8 to 2.

1.

6. The solid granular material according to claim 1, wherein the solid granular material is in the form of a powder.

7. A method for producing a solid granular material according to any one of claims 1 to 6, The process of stirring the heated and softened polybutadiene and silica in a heated mixer to obtain the solid granules. Methods that include...

8. The method according to claim 7, wherein the temperature of the heating and softening is greater than 80°C.

9. The method according to claim 7, wherein the stirring is performed at a rotational speed of 300 to 600 rpm.

10. The method according to claim 7, wherein the stirring is performed for 1 to 5 minutes.

11. The method according to claim 7, wherein the stirring is performed at least twice.

12. The method according to claim 7, wherein the mass ratio of polybutadiene to silica (polybutadiene / silica) is 1 to 2.

1.

13. A step to recover the solid granular material obtained in the above step under non-shear stress conditions. The method according to claim 7, further comprising:

Images