Method for producing a modified conjugated diene-based polymer

专利摘要:
A method of producing a modified conjugated diene-based polymer is provided with a modified conjugated diene-based polymer having a good balance between the properties of hysteresis loss and wet slip resistance, abrasion resistance and fracture resistance really sufficient, and with high processability when formed into a vulcanized product, and a modified conjugated diene-based polymer composition. A method for producing a modified conjugated diene-based polymer comprises: a polymerization step of polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound with an aromatic vinyl compound using an alkali metal compound or a metal compound alkaline earth as a polymerization initiator to obtain a conjugated diene-based polymer having a reactive end, and a modification step of reacting a compound having a specific structure with the reactive end of the conjugated diene polymer.
公开号:BR112012006333B1
申请号:R112012006333-2
申请日:2010-09-22
公开日:2019-09-17
发明作者:Junichi Yoshida；Shinichi Sekikawa；Takaaki Matsuda
申请人:Asahi Kasei Chemicals Corporation；
IPC主号:

专利说明:

TECHNICAL FIELD
The present invention relates to a method for producing a modified conjugated diene-based polymer, a modified conjugated diene-based polymer, and a modified conjugated diene-based polymer composition.
BACKGROUND ART
Recently, consideration for environmental protection as a reduction in the emission of carbon dioxide has been requested in society. Specifically, the demand for fuel efficiency in automobiles has been increased. For such a circumstance, as a material for automobile tires, particularly a material for a tire tread contacting the ground, development of a material demonstrating a low rolling resistance has been sought. On the other hand, from the point of view of safety, the development of a material exhibiting excellent skid resistance in wet conditions, fracture characteristics and abrasion resistance really sufficient has been sought.
Conventionally, they have been used, as a reinforcement charge for the tire tread, carbon black, silica and the like. The use of silica has the advantage of achieving decreased hysteresis loss properties and improved wet skid resistance. However, unlike carbon black having a hydrophobic surface, silica having a hydrophilic surface has disadvantages such as low affinity for conjugated diene rubber and lower dispersibility than carbon black. For this reason, a silane copulating agent and the like need to be additionally contained in order to improve dispersibility and bonded silica in rubber.
In addition, attempts have recently been made to reduce the
Petition 870190036187, of 16/16/2019, p. 35/83 loss by hysteresis introducing a functional group having affinity and / or reactivity with silica at a chain end of a rubber molecule having high mobility. The introduction of a functional group for the chain end can reduce the loss by hysteresis improving the dispersibility of silica in a rubber material, and also, reducing the number of free polymer ends via bonding with the charge particles. For example, patent document 1 describes a modified diene rubber obtained by reacting a modifier having a glycidyl amino group with the polymer end, and patent document 2 describes a modified diene rubber obtained by reacting glycidoxialoxysilane with the polymer end. In addition, patent documents 3 to 7 describe modified diene rubbers obtained by reacting alkoxysilanes containing an amino group with a polymer end, and compositions comprising these modified diene rubbers and silica.
PATENT DOCUMENTS
Patent document 1: International publication WO 01/23467.
Patent document 2: JP patent publicly available 07233217.
Patent document 3: Publicly available JP patent 2001158834.
Patent document 4: JP patent publicly available 2003171418.
Patent document 5: International publication WO 07/34785. Patent document 6: International publication WO 08/13090. Patent document 7: International publication WO 07/114203. EP 1942120 describes a process for producing a conjugated diene polymer. EP 2045272 describes a modified conjugated diene polymer and a method for producing it. EP 1785437 describes a
Petition 870190036187, of 16/16/2019, p. 36/83 impact resistant vinyl aromatic hydrocarbon resin.
SUMMARY OF THE INVENTION
Problems to be solved by the invention
In the event that a functional group having high reactivity with silica is introduced at the polymer end, however, the functional group tends to react with silica particles during a kneading step to increase the viscosity of the composition, leading to lower processability such as difficulties in kneading the composition and frequent occurrence of roughness on the leaf surface and leaf rupture in the leaf formation process after mixing. In addition, when the composition is formed from a vulcanized product, particularly when the composition is formed from a vulcanized product containing an inorganic filler, an improved balance between the properties of hysteresis loss and resistance to slippage in the wet is required.
The present invention has been made in consideration of such circumstances and an object of the present invention is to provide a method for producing a modified conjugated diene-based polymer, a modified conjugated diene-based polymer, and a conjugated diene-based polymer composition modified, in which the modified conjugated diene-based polymer has a good balance between the properties of hysteresis loss and wet slip resistance, abrasion resistance and fracture resistance really sufficient, and high processability when the polymer based modified conjugated diene is formed into a vulcanized product.
MEANS TO SOLVE PROBLEMS
As a result of extensive research to solve the above problems, the present inventors have found that a method for producing a modified conjugated diene-based polymer can solve the above problems, the method comprising: a step of polymerizing a
Petition 870190036187, of 16/16/2019, p. 37/83 conjugated diene compound or copolymerize a diene compound conjugated to an aromatic vinyl compound using an alkali metal compound or an alkaline earth metal compound as a polymerization initiator to obtain a conjugated diene polymer having an end reactive; and a reaction modification step of a compound having a specific structure with the reactive end of the conjugated diene-based polymer.
The present invention is as follows.
[1]
A method for producing a modified conjugated diene-based polymer, comprising:
a polymerization step of polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound with an aromatic vinyl compound using an alkali metal compound or an alkaline earth metal compound as a polymerization initiator to obtain a diene-based polymer conjugate having a reactive end, and a modification step of reacting a modifier with the reactive end of the conjugated diene-based polymer, wherein the modifier is a compound represented by formula (1):
(where R ¹ to R ⁴ each independently represents an alkyl group or an aryl group having 1 to 20 carbon atoms; R ⁵ and R ⁶ each independently represents an alkylene group having 1 to 20 carbon atoms; R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and form a ring structure of a ring of 5 or more members
Petition 870190036187, of 16/16/2019, p. 38/83 with two adjacent Ns; and m and n each, independently, represent an integer of 2 or 3).
[2]
The method for producing the conjugated diene polymer modified according to [1], wherein all the silyl groups on the modifier are each silyl group to which three alkoxy groups are attached.
[3]
The method for producing the modified conjugated diene-based polymer according to any of [1] or [2], wherein a total number of moles of the alkoxy group attached to the silyl group on the modifier is within a range of 0, 8 to 3 times the number of moles of the polymerization initiator to be added.
[4]
The method for producing the modified conjugated diene-based polymer according to any one of [1] to [3], wherein the polymerization step is continuous.
[5]
The method for producing the modified conjugated diene-based polymer according to any one of [1] to [4], wherein a polystyrene-equivalent numerical average molecular weight of the modified conjugated diene-based polymer measured by permeation chromatography on gel (GPC) is 200,000 to 600,000.
[6]
A modified conjugated diene-based polymer obtained by the method to produce the modified conjugated diene-based polymer according to any one of [1] to [5].
[7]
A conjugated diene-based polymer composition
Petition 870190036187, of 16/16/2019, p. 39/83 modified, comprising:
100 parts by weight of a rubber component containing not less than 20 parts by weight of the modified conjugated diene-based polymer according to [6], and
0.5 to 300 parts by mass of an inorganic silica-based filler.
ADVANTAGE EFFECTS OF THE INVENTION
According to the present invention, a method can be provided for producing a modified conjugated diene-based polymer, a modified conjugated diene-based polymer and a modified conjugated diene-based polymer composition, wherein the polymer based on modified conjugate diene has a good balance between the properties of hysteresis loss and wet slip resistance, really sufficient abrasion resistance and fracture resistance, and high processability when the modified conjugated diene polymer is formed into a vulcanized product .
MODES FOR CARRYING OUT THE INVENTION
Here below, an embodiment for the implementation of the present invention (hereinafter, referred to as the present embodiment) will be described in detail. The present embodiment below is just an example to describe the present invention, and the present invention will not be limited to the contents below. The present invention can be modified appropriately within the scope of its essence and implemented.
A method for producing a conjugated diene-based polymer modified according to the present embodiment comprises:
a polymerization step of polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound with a
Petition 870190036187, of 16/16/2019, p. 40/83 aromatic vinyl compound using an alkali metal compound or an alkaline earth metal compound as a polymerization initiator to obtain a conjugated diene polymer having a reactive end, and a modification step to react a modifier with reactive end of the conjugated diene-based polymer, the modifier being a compound that has one or more heterocycles comprising two or more nitrogen atoms and a hydrocarbon and which has two or more silyl groups to which two or more alkoxy groups are attached.
In a polymerization step of the modified conjugated diene-based polymer according to the present embodiment, a conjugated diene compound is polymerized or copolymerized with an aromatic vinyl compound using an alkali metal compound or an alkali metal compound earthy as a polymerization initiator to obtain a conjugated diene-based polymer having a reactive end.
The conjugated diene-based polymer that forms a modified conjugated diene-based polymer is a polymer of a single conjugated diene compound, a polymer of different types of conjugated diene compounds, that is, a copolymer of different types of compounds of conjugated diene, or a copolymer of a conjugated diene compound and an aromatic vinyl compound.
The conjugated diene compound can be any polymerizable monomer and is not particularly limited. Examples of the polymerizable monomer can include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, and 1,3hexadiene . Among these, 1,3-butadiene and isoprene are preferable from the point of view of industrial availability. One of these can be used alone, or two or more of them can be used in combination.
The aromatic vinyl compound can be a monomer
Petition 870190036187, of 16/16/2019, p. 41/83 copolymerizable with the conjugated diene compound, and it is not particularly limited. Examples of the aromatic vinyl compound can include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene. Among these, styrene is preferable from the point of view of industrial availability. One of these can be used alone, or two or more of them can be used in combination.
In the case where the conjugated diene-based polymer is a copolymer, it can be a random copolymer or a block copolymer. Examples of the random copolymer can include random butadiene-styrene copolymers, random butadiene-styrene copolymers, random isoprene-styrene copolymers, and random butadiene-styrene copolymers. Examples of composition distribution of the respective monomers in the copolymer chain can include perfect random copolymers having a composition close to a random statistical composition, or a tapered random copolymer in which the composition distribution is tapered. The composition having one form of the conjugated diene bond, i.e., 1,4-bond, 1,2-bond and another can be uniform or distributed.
Examples of the block copolymer can include diblock copolymers composed of two blocks, tri-block copolymers composed of three blocks, tetra-block copolymers composed of four blocks and others. For example, the block copolymer is expressed as a SB block copolymer, an SBS tri-block copolymer, or a SBSB tetrablock block copolymer in which S represents a block composed of an aromatic vinyl compound such as styrene, and B represents a block composed of the conjugated diene compound such as butadiene and isoprene and / or a block composed of the copolymer of the aromatic vinyl compound and the conjugated diene compound. In the formula above, the boundary between the blocks does not always need to be clearly distinguished. At the
Petition 870190036187, of 16/16/2019, p. 42/83 case where block B is the copolymer of the aromatic vinyl compound and the conjugated diene compound, the aromatic vinyl compound in block B can be uniformly distributed, or distributed in a tapered manner. Alternatively, in block B, they can co-exist in several portions in which the aromatic vinyl compound is uniformly distributed and / or several portions in which the aromatic vinyl compound is distributed in a tapered manner. Alternatively, in block B, several segments can co-exist having different contents of the aromatic vinyl compound. In the case where several S blocks or several B blocks exist in the copolymer, the molecular weight and structure, like the composition, of these blocks can be the same or different.
In the present embodiment, the conjugated diene-based polymer having a functional group is further hydrogenated in an inactive solvent. Thus, all or part of the double bonds can be converted into saturated hydrocarbons. In this case, the thermal resistance and the ability to withstand the weather can be improved to avoid the deterioration of products during processing at an elevated temperature. As a result, the products obtained demonstrate greater performance in various applications such as automotive applications.
More specifically, the rate of hydrogenation of unsaturated double bonds based on the conjugated diene compound can be arbitrarily selected according to the purpose, and is not particularly limited. In use as a vulcanized rubber, preferably, the double bonds in the partially conjugated diene portion remain. From such a point of view, the hydrogenation rate of the conjugated diene portion in the polymer is preferably 3 to 70%, more preferably 5 to 65%, and even more preferably 10 to 60%. The hydrogenation rate of the aromatic double bonds based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not
Petition 870190036187, of 16/16/2019, p. 43/83 is particularly limited, preferably not greater than 50%, more preferably not greater than 30%, and even more preferably not greater than 20%. The hydrogenation rate can be measured by a nuclear magnetic resonance (NMR) spectrometer.
A method for hydrogenation is not particularly limited and a known method can be used. Examples of a particularly suitable method for hydrogenation may include a method of blowing hydrogen gas into a polymer solution in the presence of a catalyst to carry out the hydrogenation. Examples of the catalyst may include heterogeneous catalysts as catalysts having a noble metal supported on a porous inorganic substance; and homogeneous catalysts such as catalysts obtained by making a salt like nickel and cobalt soluble and reacting the salt with organic aluminum or others, and catalysts using metallocene like titanocene. Among these, titanocene catalysts are preferred from the point of view of allowing the selection of a particularly mild hydrogenation condition. In addition, an aromatic group can be hydrogenated using a supported noble metal catalyst.
Specific examples of the hydrogenation catalyst may include (1) supported heterogeneous hydrogenation catalysts having a metal such as Ni, Pt, Pd, and Ru supported on carbon, silica, alumina, and diatomite, (2) the hydrogenation catalyst called Ziegler using an organic acid salt like Ni, Co, Fe, and Cr or a transition metal salt like acetylacetone salts and a reducing agent like organoalumin, and (3) organometallic complexes called organometallic compounds like Ti, Ru, Rh, and Zr. For example, as the hydrogenation catalyst, hydrogenation catalysts described in patent publication JP 42-8704, 43-6636, 634841, 1-37970, 1-53851, and 2-9041, and the JP patent publicly accessible 8-109219 can be used. Examples of a preferable hydrogenation catalyst
Petition 870190036187, of 16/16/2019, p. 44/83 may include a reaction mixture of a titanocene compound and a reducing organometallic compound.
The alkali metal compound used as the polymerization initiator is not particularly limited, and organolithium compounds are preferable. Examples of the organolithium compound may include lower molecule compounds, organolithium compounds of solubilized oligomers, compounds comprising carbon-lithium bonds in the form of an organic and lithium group bond, compounds comprising nitrogen lithium bonds, and compounds comprising tin-lithium bonds . Examples of the organolithium compound can include n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, and stilbene lithium. Examples of the compound comprising nitrogen-lithium bonds can include lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium di-n-hexylamide, lithium diisopropylamide, lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, and lithium morphide.
In addition to monoorganicolithium compounds, a polyfunctional organolithium compound can be used in combination to carry out the polymerization. Examples of the polyfunctional organolithium compound may include 1,4dilithiobutane, a reaction product of sec-butyl lithium and diisopropenylbenzene,
1,3,5-trilithiobenzene, a reaction product of n-butyl lithium, 1,3-butadiene, and divinylbenzene, and reaction products of n-butyl lithium and polyacetylene compounds. In addition, the organoalkaline metal compounds described in US patent 5,708,092, British patent 2,241,239, US 5,527,753, and others can also be used.
As the organolithium compound, n-butyl lithium and secbutium lithium are preferred from the point of view of industrial availability and ease of controlling a polymerization reaction.
One of these organolithium compounds can be used, or two or more
Petition 870190036187, of 16/16/2019, p. 45/83 of them can be used as a mixture.
Examples of other organoalkaline metal compounds can include organosodium compounds, organopotassium compounds, organorubidium compounds, and organocesium compounds. Specifically, examples thereof can include sodium naphthalene and potassium naphthalene. In addition, examples thereof may include alkoxides, sulfonates, carbonates, and amides of lithium, sodium and potassium. In addition, the other organoalkaline metal compounds can be used in combination with another organometallic compound.
Examples of the alkaline earth metal compound can include organomagnesium compounds, organocalcium compounds, and organoestronium compounds. Specifically, examples thereof can include dibutylmagnesium, ethylbutylmagnesium and propylbutylmagnesium. In addition, compounds such as alkoxides, sulfonates, carbonates, and alkaline earth metal amides can be used. These alkaline earth organometallic compounds can be used in combination with an alkali metal compound or another organometallic compound.
In the present embodiment, the conjugated diene-based polymer is preferably obtained by growth by an anionic polymerization reaction using the alkali metal compound and / or the alkaline earth metal compound as the polymerization initiator. Particularly, the conjugated diene-based polymer is more preferably a polymer having a reactive end and obtained by a propagation reaction by live anionic polymerization. Thus, a modified conjugated diene-based polymer having a high modification ratio can be obtained. The form of the polymerization is not particularly limited and the polymerization can be carried out in batch or continuous mode using two or more reactors connected together. In particular, a continuous polymerization step is
Petition 870190036187, of 16/16/2019, p. 46/83 is preferable, because a relatively high molecular weight polymer can be produced in a stable manner.
If the conjugated diene compound contains alenes, acetylenes, and the like as impurities, the modification reaction described below can be inhibited. For this reason, the total concentration (mass) of these impurities is preferably not greater than 200 ppm, more preferably not greater than 100 ppm, and even more preferably not greater than 50 ppm. Examples of alenes may include propadiene and 1,2-butadiene. Examples of acetylenes can include ethylacetylene and vinylacetylene.
Preferably, the polymerization reaction of the conjugated diene-based polymer is carried out in a solvent. Examples of the solvent may include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specifically, examples of hydrocarbon solvents can include aliphatic hydrocarbons such as butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene and hydrocarbons comprising a mixture thereof. Preferably, impurities such as alenes and acetylenes are treated with an organometallic compound before the conjugated diene compound is subjected to a polymerization reaction because a polymer having a reactive end at a high concentration is likely to be obtained and yet a higher modification ratio is likely to be obtained be obtained.
In the polymerization reaction of the conjugated diene-based polymer, a small amount of a polar compound can be added to randomly copolymerize an aromatic vinyl compound with a conjugated diene compound to control a microstructure of a portion of the diene conjugate of a copolymer as a vinylant, and
Petition 870190036187, of 16/16/2019, p. 47/83 in order to improve the polymerization rate.
As the polar compound, ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis (2-oxolanyl) propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, and quinuclidine; alkali metal alkoxide compounds such as potassium-t-amylate, potassium-t-butyrate, sodium-t-butyrate, and sodium amylate; phosphine compounds like triphenylphosphine, and others can be used. One of these polar compounds can be used alone, or two or more of them can be used in combination.
The amount of polar compound to be used is not particularly limited, and is selected depending on the purpose and the degree of the effect. Generally, the amount of the polar compound to be used is preferably 0.01 to 100 mol based on 1 mol of the polymerization initiator. As a polar compound (vinylant) it can be used appropriately as a regulator for the microstructure of the conjugated diene portion in the polymer depending on the desired vinyl bond content. Many polar compounds simultaneously have an effective randomizing effect on the copolymerization of the diene compound conjugated to the aromatic vinyl compound, and can be used to adjust the distribution of the aromatic vinyl compound or as an adjustment for a styrene block amount. As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, a method can be used in which part of 1,3-butadiene is intermittently added during copolymerization, as described in publicly available JP patent 59-140211.
The polymerization temperature is not particularly limited as long as it is a temperature at which the polymerization reaction as
Petition 870190036187, of 16/16/2019, p. 48/83 live anionic polymerization progresses. From the viewpoint of productivity, the temperature is preferably not lower than 0 C. From the viewpoint of ensuring a sufficient quantity of the reaction modifier to the reactive end after the polymerization is complete, the temperature is preferably not greater than 120OC.
In addition, from the point of view of preventing a cold flow of the conjugated diene-based polymer, a polyfunctional aromatic vinyl compound such as divinylbenzene can be used to control branching.
The amount of conjugated diene to be bonded to the conjugated diene-based polymer according to the present embodiment is not particularly limited, and the amount is preferably 50 to 100% by weight, and more preferably 60 to 80% by weight. pasta. The amount of aromatic vinyl to be bonded to the conjugated diene-based polymer according to the present embodiment is not particularly limited, and the amount is preferably 0 to 50% by weight, and more preferably 20 to 40% by weight. pasta. If the amount of conjugated diene to be bonded and the amount of aromatic vinyl to be bonded are within the ranges, a vulcanized product can be obtained in which the balance between the hysteresis loss properties and the skid resistance in the wet is better and abrasion resistance and fracture resistance are satisfactory. Here, the amount of aromatic vinyl to be bonded can be measured by ultraviolet absorption of a phenyl group. From this, the amount of conjugated diene to be linked can also be determined. Specifically, the amount of aromatic vinyl to be bonded can be measured by the method according to the examples described below.
In addition, the vinyl bond content in the conjugated diene bonding units is not particularly limited, preferably from 10 to
75 mol%, and more preferably 25 to 65 mol%. At a vinyl bond content within the range, a vulcanized product can be obtained in which the
Petition 870190036187, of 16/16/2019, p. 49/83 the balance between hysteresis loss and wet skid resistance properties is better and the abrasion resistance and fracture resistance are satisfactory. Here, in the case where the modified conjugated diene-based polymer is a copolymer of butadiene and styrene, the vinyl bond content (1,2-bond content) in the butadiene bonding units can be determined by a method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)).
If the microstructure (amounts of the respective bonds in the modified conjugated diene-based polymer) is within the range, and at the glass transition temperature of the copolymer within the range of -45 to -15 ^O C, a vulcanised product can be obtained in that the balance between hysteresis loss properties and wet skid resistance is much better. Like the glass transition temperature, according to ISO 22768: 2006, a DSC curve is recorded while the temperature is raised 15 in a predetermined temperature range. The peak top of the DSC differentiation curve (inflection point) is defined as the glass transition temperature.
In the case where the diene-based polymer conjugated according to the present embodiment is the vinyl diene copolymer 20 aromatic conjugate, preferably there are few or none of the poly-aromatic vinyl blocks in which no less than 30 aromatic vinyl units are chained together. Specifically, in the case where the copolymer is a butadiene-styrene copolymer, the polymer is decomposed by a Kolthoff method (a method described in IM KOLTHOFF, et al., J. Polym. Sci. 1, 2 5 429 (1946 )). In a known method for analyzing the amount of methanol-insoluble polystyrene, the proportion of the block, in which no less than 30 aromatic vinyl units are chained, is preferably not greater than 5% by mass, and more preferably not greater than 3% in
Petition 870190036187, of 16/16/2019, p. 50/83 mass, based on the amount of the polymer.
By the method described above, the conjugated diene polymer having a reactive end is obtained, and a modification step of reacting a modifier with the reactive end is carried out, the modifier being a compound having one or more heterocycles comprising two or more nitrogen atoms and a hydrocarbon and which has two or more silyl groups to which two or more alkoxy groups are attached. Thus, the modified conjugated diene-based polymer according to the present embodiment can be obtained. The compound that has one or more heterocycles comprising 10 or more nitrogen atoms and a hydrocarbon and which has two or more silyl groups to which two or more alkoxy groups are attached is used as the modifier. Thus, a bond can be formed between the terminal of the conjugated diene-based polymer and Si.
In the compound used as the modifier, all the silyl groups are each preferably one silyl group to which three alkoxy groups are attached.
If the compound is used as the modifier, the reactivity of the modifier and the interaction properties of the modifier with another compound can be further improved, and the processability of the modified conjugated diene-based polymer to be obtained can be further improved.
In accordance with the present invention, the modifier which is the compound represented by formula (1) is preferable. If the alkoxysilyl group in formula (1) efficiently reacts with the reactive end of the conjugated diene-based polymer, the bond between the terminal of the conjugated diene-based polymer and Si can be formed more efficiently.
Petition 870190036187, of 16/16/2019, p. 51/83
(where R ¹ to R ⁴ each independently represents an alkyl group or an aryl group having 1 to 20 carbon atoms; R ⁵ to R ⁶ each independently represents an alkylene group having 1 to 20 carbon atoms; R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 6 carbon atoms and form a ring structure of 5 or more ring members with two
Adjacent nodes; and m and n each, independently, represent an integer of 2 or 3).
Examples of the modifier represented by formula (1) may include 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [3- (triethoxysilyl) propyl] piperazine, 1,4-bis [3- ( dimethoxymethylsilyl) propyl] piperazine, 1,3-bis [3 (trimethoxysilyl) propyl] imidazolidine, 1,3-bis [3 - (triethoxyethyl) propyl] imidazolidine, 1,3-bis [3- (diethoxyethylsilyl) propyl] imidazolidine, 1,3-bis [3 (trimethoxysilyl) propyl] hexahydropyrimidine, 1,3-bis [3- (triethoxysilyl) propyl] hexahydropyrimidine, and 1,3-bis [3- (tributoxysilyl) propyl] -1,2,3, 4tetrahydropyrimidine. Among these, the ones in which men are 3 from the point of view of the reactivity of the modifier, the interaction properties with other compounds, for example, inorganic charge such as silica, and the processability of the modified conjugated diene polymer to be obtained are preferable. . Specifically, 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [3 (triethoxysilyl) propyl] piperazine, 1,3-bis [3- (trimethoxysilyl) propyl] imidazolidine,
1,3-bis [3- (triethoxysilyl) propyl] imidazolidine, 1,3-bis [3- (trimethoxysilyl) propyl] hexahydropyrimidine, 1,3-bis [3- (triethoxysilyl) propyl] hexahydropyrimidine, 1,3bis [3 - (tributoxysilyl) propyl] -1,2,3,4-tetrahydropyrimidine are preferable. Among these, 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, and 1,4-bis [3- (triethoxysilyl)
Petition 870190036187, of 16/16/2019, p. 52/83 propyl] piperazine are more preferable.
The modifier may contain other compounds, for example, impurities as an intermediate product during the synthesis of the modifier and a condensate of the modifier as long as these do not significantly affect the modification reaction and the like. Alternatively, other conventionally known modifiers can be used in combination within the range in which the effect of the present embodiment is obtained.
The reaction temperature and reaction time when the modifier is reacted with the reactive end are not particularly limited. The reaction is preferably carried out at 0 to 120 ° C for not less than 30 seconds.
In the modifier, the total number of moles of the alkoxy group for attachment to the silyl group in the compound is preferably within the range of 0.8 to 3 times, more preferably within the range of 1 to 2.5 times, and even more preferably within the range of 1 to 2 times the number of moles of the polymerization initiator to be added. The total number of moles of the alkoxy group is preferably 0.8 times or more from the point of view of obtaining a sufficient modification ratio in the modified conjugated diene-based polymer to be obtained, and preferably 3 times or less from the point of view modifier cost. Preferably, from the point of view of improving processability, the ends of the polymer are copulated to each other to obtain a branched polymer component.
From the point of view of further improving the effect of the present embodiment, the modified conjugated diene-based polymer is preferably produced so that the polymer preferably contains not less than 5% by weight, more preferably not less than 20% by mass, and even more preferably not less than 50% by mass of the polymer
Petition 870190036187, of 16/16/2019, p. 53/83 having a functional group component (the modified conjugated diene-based polymer being modified with the modifier). As a method for determining the polymer having a functional group component, chromatography can be used for measurement, wherein a modified component containing a functional group can be separated from an unmodified component. Examples of the method using chromatography may include a method in which the determination is carried out using a GPC column filled with a polar substance that adsorbs the functional group component, such as silica, as a filler, and using the internal standard of an unsorbed component for Comparation.
The equivalent numerical average molecular weight of polystyrene (Mn) of the modified conjugated diene-based polymer according to the present embodiment obtained by gel permeation chromatography (GPC) is preferably from 20,000 to 2,000,000, more preferably from 100,000 to 1,000,000, even more preferably 200,000 to 600,000, and even more preferably 300,000 to 400,000. At a molecular weight not less than the lower limit value, the strength when the modified conjugated diene-based polymer is formed in a vulcanized product can be further improved. With a molecular weight not above the upper limit value, processability can be further improved. From the point of view of the physical properties of the vulcanized product, a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the numerical average molecular weight (Mn) is preferably from 1.05 to 3.0, and more preferably from 1.1 to 2.5.
In the method for producing the conjugated diene polymer modified according to the present embodiment, after the modification reaction is carried out, a deactivating agent, a neutralizer and the like can be added to the copolymer solution when necessary. Examples of the deactivating agent can include water; and alcohols like methanol, ethanol, and
Petition 870190036187, of 16/16/2019, p. 54/83 isopropanol. Examples of the neutralizer can include carboxylic acids such as stearic acid, oleic acid, and versatic acid; and aqueous solutions of inorganic acids from carbon dioxide gas.
From the point of view of preventing gel formation in a finishing step after polymerization, and improving stability during processing, a rubber stabilizer is preferably added to the modified conjugated diene-based polymer according to the present form of realization. The rubber stabilizer is not particularly limited, and a known one can be used. Preferable are 2,6-di-tert-butyl-4hydroxytoluene (BHT), n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-tert-butylphenol) propionate, 2-methyl-4,6 bis [(octylthium) methyl] phenol, and the like.
In order to improve the processability of the modified conjugated diene-based polymer according to the present embodiment, an extender oil can be added to the modified conjugated diene-based polymer when necessary. The method for adding an extender oil to a modified conjugated diene-based polymer is not particularly limited. Preferable is a method in which an extender oil is added to a polymer solution, and mixed to prepare an extended copolymer solution, and the solvent is removed from the extended oil copolymer solution. Examples of extender oil may include aromatic oils, naphthenic oils, and paraffinic oils. Among these, preferable are alternative aromatic oils containing a polycyclic aromatic component (PCA) whose content determined in accordance with the IP 346 method is not greater than 3% by mass, from the point of view of environmental safety, prevention of bleeding oil and wet grip properties. Examples of alternative aromatic oils may include ADHD and MES shown in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999), and RAE. The amount of extender oil to be added is not particularly limited. Generally, the amount is 10 to
Petition 870190036187, of 16/16/2019, p. 55/83 parts by weight, and preferably 20 to 37.5 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.
As the method for obtaining the conjugated diene-based polymer modified according to the present embodiment from the polymer solution, a known method can be used. Examples of the method may include a method in which a solvent is removed by extraction with steam or the like, and a polymer is filtered, the water being removed and dried to obtain a polymer; a method in which the polymer solution is condensed using an instant distillation tank, and volatilized by an extruder with ventilation or the like; and a method in which the polymer solution is directly volatilized by a drum dryer or the like.
The conjugated diene-based polymer modified according to the present embodiment is used appropriately as a vulcanized product. For example, the vulcanized product can be obtained as follows: the conjugated diene-based polymer modified according to the present embodiment is mixed with an inorganic filler as an inorganic filler based on silica and carbon black, a rubber polymer other than the conjugated diene polymer modified according to the present embodiment, a silane copulating agent, a rubber softener, a vulcanizing agent, a vulcanizing and auxiliary accelerator, and the like, when necessary to prepare a modified conjugated diene-based polymer composition, and the modified conjugated diene-based polymer composition is heated and vulcanized. Among these, the modified conjugated diene-based polymer composition 25 comprising a rubber component containing the modified conjugated diene-based polymer according to the present embodiment, and the inorganic silica-based filler are preferable. The inorganic silica-based filler is dispersed in the modified conjugated diene-based polymer according to the present
Petition 870190036187, of 16/16/2019, p. 56/83 embodiment. Thus, the modified conjugated diene-based polymer can have a good balance between the properties of hysteresis loss and wet slip resistance and really sufficient abrasion and fracture resistance, and achieve high processability when the polymer based of modified conjugated diene is formed into a vulcanized product. Preferably, the silica-based inorganic filler is contained as a reinforcing filler also in the case where the modified conjugated diene-based polymer composition according to the present embodiment is used for automobile parts such as tires and rubber tires. 10 of vibration, and for vulcanized rubbers like shoes.
In the composition of conjugated diene-based polymer, a rubber polymer other than the modified conjugated diene-based polymer according to the present embodiment can be used in combination with the modified conjugated diene-based polymer according to present embodiment. Examples of this rubber polymer may include conjugated diene-based polymer or hydrogenated products thereof, random copolymers of a conjugated diene compound and an aromatic vinyl compound or hydrogenated products thereof, block copolymers of a conjugated diene compound and a composed of 20 aromatic vinyl or hydrogenated products thereof, non-diene-based polymers, and natural rubbers. Specifically, examples of the rubber polymer can include butadiene rubbers or hydrogenated products thereof; isoprene rubbers or hydrogenated products thereof; styrene elastomers such as styrene-butadiene rubbers or hydrogenated products thereof, styrene-butadiene copolymers in blocks or hydrogenated products thereof, and styrene-isoprene copolymers in blocks or hydrogenated products thereof; and acrylonitrile butadiene rubbers or hydrogenated products thereof.
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Examples of non-diene-based polymers may include olefin elastomers such as ethylene-propylene rubbers, ethylene-propylene-diene rubbers, ethylene-butene-diene rubbers, ethylene-butene rubbers, ethylene-hexene rubbers, ethylene-rubene rubbers ethylene-octene; butyl rubbers; brominated butyl rubbers; acrylic rubbers; fluorine rubbers; silicone rubbers; chlorinated polyethylene rubbers; epichlorohydrin rubbers; copolymerization rubbers of α, β-unsaturated nitrile-ester of acrylic acid-conjugated diene; urethane rubbers; and polysulfide rubbers.
The variety of rubber polymers above can be a modified rubber having a polar functional group such as a hydroxyl group and an amino group. From the point of view of balance between performance and processing properties, the average molecular weight is preferably 2,000 to 2,000,000, and more preferably 5,000 to 1,500,000. Alternatively, a so-called low molecular weight liquid rubber can be used. One of these rubber polymers can be used alone, or two or more of them can be used in combination.
In the case of a modified conjugated diene-based polymer composition comprising the modified conjugated diene-based polymer according to the present embodiment and the rubber polymer, a mixing ratio (mass ratio) of polymer based on modified conjugate diene / rubber polymer is preferably from 20/80 to 100/0, and more preferably from 30/70 to 90/10, and even more preferably from 50/50 to 80 / 20. In the ratio of polymer mixture to modified conjugated diene / rubber polymer base within the range, a vulcanized product can be obtained in which the balance between the properties of hysteresis loss and wet skid resistance is better, and the abrasion resistance and fracture resistance are most satisfactory.
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The inorganic charge based on silica is not particularly limited, and a known one can be used. Solid particles containing SiO2 or Si3Al are preferred as a structural unit. More preferably, SiO2 or Si3Al is the main component of the structural unit. Specifically, 5 examples of silica-based inorganic fillers can include fibrous inorganic substances such as silica, clay, talc, mica, diatomite, wollastonite, montmorillonite, zeolite, and glass fibers. Alternatively, the silica-based inorganic filler having a surface becomes hydrophobic, or a mixture of a silica-based inorganic filler and an inorganic filler other than silica 10 can be used. Among these, silica and glass fibers are preferable, and silica is more preferable from the point of view of reinforcing properties. Examples of silica can include anhydrous silica, precipitated silica, and synthetic silicate. Among these, precipitated silica is preferable from the point of view of a good balance between the effect of improving the fracture characteristics and resistance to skidding in the wet.
In the modified conjugated diene polymer composition, from the point of view of obtaining sufficiently sufficient abrasion and fracture resistance characteristics, the specific nitrogen adsorption surface area of an inorganic silica-based filler determined by the 2 0 method of BET adsorption is preferably from 100 to 300 m ² / g, and more preferably from 170 to 250 m ² / g. When necessary, the silica-based inorganic filler having a relatively small specific surface area (for example, the silica-based inorganic filler having a specific surface area of less than 200 m ² / g) and having an area of relatively large specific surface 25 (e.g., silica-based inorganic filler having a specific surface area of not less than 200 m ² / g) can be used in combination. Thus, high abrasion and fracture resistance characteristics and hysteresis loss properties can be obtained in a
Petition 870190036187, of 16/16/2019, p. 59/83 highly balanced.
As described above, the amount of silica-based inorganic filler to be mixed in the modified conjugated diene-based polymer composition is preferably 0.5 to 300 parts by weight, more preferably 5 to 200 parts by weight, and further more preferably from 20 to 100 parts by weight based on 100 parts by weight of the rubber component containing no less than 20 parts by weight of the modified conjugated diene-based polymer according to the present embodiment. The amount of silica-based inorganic filler to be mixed is preferably not less than 0.5 parts by weight in order to demonstrate the effect of the added inorganic filler, while the amount is preferably not more than 300 parts by weight from the point of view of sufficiently dispersing the inorganic filler to obtain a composition having really sufficient processability and mechanical strength.
The modified conjugated diene-based polymer composition may contain carbon black. Carbon black is not particularly limited, and, for example, carbon black of each class such as SRF, FEF, HAF, ISAF, and SAF can be used. Among these, carbon black is preferable in which the specific nitrogen adsorption surface area is not less than 50 m ² / g, and a dibutyl phthalate (DBP) adsorption number is not less than 80 mL / 100 g.
The amount of carbon black to be mixed is preferably 0.5 to 100 parts by weight, more preferably 3 to 100 parts by weight, and even more preferably 5 to 50 parts by weight based on 100 parts by weight of a rubber component containing the modified conjugated diene-based polymer according to the present embodiment. The amount of carbon black to be mixed is preferably not less than 0.5 parts by mass from the point of view of
Petition 870190036187, of 16/16/2019, p. 60/83 demonstrate dry grip performance and performance as required conductivity in application of tires and the like, and preferably no more than 100 parts by mass from the point of view of dispersibility.
In addition, the modified conjugated diene-based polymer composition may contain a metal oxide and a metal hydroxide in addition to an inorganic filler based on silica and carbon black. Metal oxide is a solid particle containing a compound represented by the formula MxOy (M represents a metal atom, and x and y each represent an integer from 1 to 6) as a major component of the structural unit. For example, alumina, titanium oxide, magnesium oxide, and zinc oxide can be used. Alternatively, a mixture of metal oxide and an inorganic charge other than metal oxide can be used. Metal hydroxide is not particularly limited, and examples thereof can include aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.
The modified conjugated diene-based polymer composition may contain a silane copulating agent. The silane copulating agent has a function of making the interaction between the rubber components and the silica-based inorganic filler close, and has an affinity group with or bondable to the rubber component and an affinity group with or bondable to an inorganic silica-based filler. Generally, a compound having a sulfur-binding portion, a silyl alkoxy group, a portion of the silanol group in a molecule is used. Specifically, examples of the silane copulating agent may include bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis [3- (triethoxysilyl) -propyl] -disulfide, and bis- [2- (triethoxysilyl) -ethyl] -tetrasulfide.
The amount of the silane copulating agent to be mixed is preferably from 0.1 to 30 parts by weight, more preferably from 0.5 to 20 parts by weight, and even more preferably from 1 to 15 parts by weight based on 100 parts by weight. mass of an inorganic silica-based filler. In a
Petition 870190036187, of 16/16/2019, p. 61/83 amount of the silane copulating agent to be mixed within the range, the effect of the added silane copulating agent may be more noticeable.
In order to improve processability, the modified conjugated diene-based polymer composition may contain a rubber softening agent. As the rubber softener, synthetic mineral oil softening agents, synthetic liquid softening agents or synthetic low molecular weight softening agents are suitable. The mineral oil rubber softener referred to as a process oil or extender oil, which is used to soften the rubber, increase volume, and improve processability, is a mixture of an aromatic ring, a naphthene ring, and paraffin chains. If the carbon atoms in the paraffin chains are not less than 50% of the total carbons, the rubber softener is referred to as a paraffinic rubber softener. If the carbon atoms in the naphthalene ring have 30 to 45% total carbons, it is referred to as a 15 naphthenic softener. If aromatic carbon atoms have more than 30% total carbons, it is referred to as an aromatic rubber softener. As the rubber softener used with the modified aromatic conjugated diene vinyl copolymer according to the present embodiment, those containing an appropriate amount of aromatics are preferable because this rubber softener tends to have an affinity for the copolymer.
The amount of the rubber softener to be mixed is preferably 0 to 100 parts by weight, more preferably 10 to 90 parts by weight, and even more preferably 30 to 90 parts by weight with 25 base in 100 parts by weight of the component. rubber containing the modified conjugated diene-based polymer according to the present embodiment. If the amount of the rubber softener to be mixed is not greater than 100 parts by weight based on 100 parts by weight of
Petition 870190036187, of 16/16/2019, p. 62/83 rubber component, bleeding and stickiness of the composition surface can be suppressed.
The method for mixing the modified conjugated diene-based polymer according to the present embodiment with the other 5 rubber polymers and additives such as the inorganic filler based on silica, carbon black, another filler, the copulating agent of silane, and the rubber softener is not particularly limited. Examples of the method may include a melt kneading method using a common mixer such as an open roller mill, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, and a multiple screw extruder, and a method in which each component is dissolved and mixed and then heated and a solvent is removed. Among these, the melting kneading method using a roller, a Banbury mixer, a kneader, or an extruder from the point of view of productivity and good kneading properties is preferable. In addition, a method of kneading the modified conjugated diene-based polymer and a variety of additives can be used at the same time, or a method of dividing the modified conjugated diene-based polymer and a variety of additives into several portions to perform the mixture.
The modified conjugated diene-based polymer composition can be a vulcanized composition obtained by vulcanization by a vulcanizing agent. As the vulcanizing agent, a radical generator such as organic peroxides and azo compounds, oxime compounds, nitrous compounds, polyamine compounds, sulfur, sulfur compounds can be used, for example. Sulfur compounds can include sulfur monochloride, sulfur dichloride, disulfide compounds, polymeric polysulfate compounds, and the like. The amount of the vulcanizing agent to be used is generally 0.01 to 20 parts by weight, and preferably 0.1 to 15 parts
Petition 870190036187, of 16/16/2019, p. 63/83 by weight based on 100 parts by weight of the rubber component containing the modified conjugated diene-based polymer according to the present embodiment. As the method for vulcanization, a conventionally known method can be used. The temperature of vulcanization is generally from 120 to 200 ^O C, and preferably from 140 to 180 ^O C.
In vulcanization, a vulcanization accelerator can be used when necessary. As the vulcanization accelerator, a conventionally known material can be used. Examples of the vulcanization accelerator may include vulcanization accelerators such as sulfenamide-based vulcanization accelerators, guanidine-based vulcanization accelerators, tiuram-based vulcanization accelerators, aldehyde-amine-based vulcanization accelerators, vulcanization accelerators with aldehyde-ammonia-based, thiazole-based vulcanization accelerators, thiourea-based vulcanization accelerators, and dithiocarbamate-based vulcanization accelerators. As the vulcanization aid, zinc oxide, stearic acid, and the like can be used. The amount of the vulcanization accelerator to be used is generally 0.01 to 20 parts by weight, and preferably 0.1 to 15 parts by weight based on 100 parts by weight of the rubber component containing the diene-based polymer. The modified conjugate according to the present embodiment.
In the modified conjugated diene polymer composition, a softening agent and filler other than those described above, and a variety of additives such as a thermal stabilizer, an antistatic agent, a weather stabilizer, an antioxidant, a coloring agent, and 2 5 a lubricant can be used within the range as long as the purpose of the present embodiment is not impaired. Like the other softening agent, a known softening agent can be used. Examples of other fillers may specifically include calcium carbonate, carbonate
Petition 870190036187, of 16/16/2019, p. 64/83 magnesium, aluminum sulfate, and barium sulfate. As the thermal stabilizer, antistatic agent, weather stabilizer, antioxidant, coloring agent, and lubricant described above, known materials can be used.
EXAMPLES
According to the examples below, the present embodiment will be described in more detail, but the present embodiment will not be limited to the examples below. The samples were analyzed according to the methods shown below.
(1) Content of bonded styrene
A chloroform solution was used as a sample. Based on UV absorption at 254 nm by a phenyl group in styrene, the content of bound styrene (mass%) was measured (UV-2450: manufactured by Shimadzu Corporation).
(2) Microstructure of the butadiene portion (1,2-vinyl bond content)
A carbon disulfide solution was used as a sample. Using a solution cell, an infrared spectrum was measured within the range of 600 to 1000 cm ^-1 , and the microstructure of a butadiene portion was determined based on the absorbance at a wave number predetermined by the expression according to the Hampton method (FT-IR230: manufactured by JASCO Corporation).
(3) Mooney viscosity
According to JIS K 6300, a sample was preheated at 100 ° C for 1 minute and the viscosity after four minutes was measured.
(4) Molecular weight and molecular weight distribution
A chromatogram was obtained by measurement using gel permeation chromatography (GPC) using a series of three columns in which a polystyrene-based gel was used as a filler. The average molecular weight
Petition 870190036187, of 16/16/2019, p. 65/83 weight (Mw) and numerical average molecular weight (Mn) were determined according to a calibration curve using standard polystyrene. From the ratio of the average molecular weight to the numerical average molecular weight (Mw / Mn), a molecular weight distribution index was calculated.
Tetrahydrofuran (THF) was used as an eluent.
The columns used were a guard column: TSKguardcolumn HHR-H from Tosoh Corporation TSK, and columns: Tosoh Corporation TSKgel G6000 HHR, TSKgel G5000 HHR, and TSKgel G4000 HHR.
In the condition of a temperature of an oven of 40 C and a THF flow rate of 1.0 ml / min, a molecular weight was measured using an RI detector HLC 8020 made by Tosoh Corporation. 10 mg of a sample was dissolved in 20 ml of THF, and 200 pL of the solution was injected into the apparatus, and measured.
(5) Glass transition temperature (Tg)
According to ISO 22768: 2006, using a DSC3200S made by Mac Science Co., Ltd., the DSC curve was recorded while the temperature was raised from -100OC at a rate of 20OC / min under a helium flow of 50 mL / min. The peak peak of the differential DSC curve (inflection point) was defined as the glass transition temperature.
[Example 1]
Two autoclaves were connected to each other in series, the autoclave having an internal volume of 10 L and a ratio of an internal height to a diameter (L / D) of 4, and having an inlet at the bottom of the autoclave and an outlet at the top , and a stirrer and a jacket to control the temperature. Of the autoclaves, the first autoclave was used as a polymerization reactor, and the second autoclave was used as a modification reactor.
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The mixing was carried out under the condition of 16.0 g / min of butadiene, 8.0 g / min of styrene, and 125.6 g / min of n-hexane from which impurities such as moisture were removed before. For impurity deactivation treatment, the mixture was further mixed with 0.075 mmol / min of n-butyl lithium (n-butyl lithium for treatment) by a static mixer just before the mixture was fed to the first reactor, and continuously fed to the bottom of the tank. first reactor. In addition, 2,2-bis (2-oxolanyl) propane was fed as a polar substance at a rate of 0.020 g / min, and n-butyl lithium was fed as a polymerization initiator at a rate of 0.150 mmol / min at bottom of the first reactor. The polymerization reaction was continued so that the internal temperature at the reactor outlet was 90 ^O C.
The temperature of the second reactor was maintained at 85 ° C, and 1,4-bis [3 (trimethoxysilyl) propyl] piperazine was added as a modifier at a rate of 0.0375 mmol / min from the bottom of the second reactor to perform a reaction modification (copulation).
An antioxidant (BHT) was continuously added to a polymer solution flowing from the top of the second reactor at 0.048 g / min (n-hexane solution) so that the flow rate was 0.2 g per 100 g of the polymer , and the modification reaction has been completed. Then, the solvent was removed to obtain a modified conjugated diene-based polymer.
In addition, 37.5 parts by weight of an S-RAE oil (NC-140, made by JX Nippon Oil & Energy Corporation) per 100 parts by weight of the polymer were added to the modified conjugated diene-based polymer solution, and the solvent was removed by a dryer drum to obtain an oil-modified modified conjugated diene-based polymer (sample A).
The Mooney viscosity at 100 OC of sample A was 80.0, the average molecular weight equivalent of polystyrene measured by GPC was
Petition 870190036187, of 16/16/2019, p. 67/83
908,000, and the numerical average molecular weight was 393,000. In addition, as a result of measuring the sample prior to extension with oil, the bonded styrene content was 33% by mass, the vinyl bond content (1,2-bond content) in butadiene bonding units was 38 mol% , and the glass transition temperature measured by DSC was -25 ^o C.
[Example 2]
An oil-modified conjugated diene-based polymer (sample B) was obtained in the same manner as in example 1 except that the amount of 1,4-bis [3- (trimethoxysilyl) propyl] piperazine to be added as the modifier was 0.0563 mmol / min.
The result of a sample B analysis was shown in table 1. [Example 3]
An oil-modified conjugated diene-based polymer (sample C) was obtained in the same way as in example 1 except that the modifier was changed from 1,4-bis [3- (trimethoxysilyl) propyl] piperazine to 1,4- bis [3- (triethoxysilyl) propyl] piperazine.
The result of a sample C analysis was shown in table 1. [Example 4]
An oil-modified modified conjugated diene-based polymer (sample D) was obtained in the same way as in example 1 except that the modifier was changed from 1,4-bis [3- (trimethoxysilyl) propyl] piperazine to 1,4- bis [3- (dimethoxymethylsilyl) propyl] piperazine, and the amount of the modifier to be added was 0.0563 mmol / min.
The result of a sample D analysis was shown in table 2. [Example 5]
An oil-modified conjugated diene-based polymer (sample E) was obtained in the same way as in example 1 except that the modifier was changed from 1,4-bis [3- (trimethoxysilyl) propyl] piperazine
Petition 870190036187, of 16/16/2019, p. 68/83 for 1,3-bis [3- (trimethoxysilyl) propyl] hexahydropyrimidine.
The result of an analysis of sample E was shown in table 2.
[Comparative example 1]
An oil-modified conjugated diene-based polymer (sample F) was obtained in the same manner as in example 1 except that the modifier was changed from 1,4-bis [3- (trimethoxysilyl) propyl] piperazine to bis [3- (trimethoxysilyl) propyl] -N-methylamine.
The result of a sample F analysis was shown in table 3.
[Comparative example 2]
An oil-modified conjugated diene-based polymer (sample G) was obtained in the same way as in example 1 except that the modifier was changed from 1,4-bis [3- (trimethoxysilyl) propyl] piperazine to 1,2- bis (3-triethoxysilyl) ethane.
The result of a sample G analysis was shown in table 3.
[Comparative example 3]
An oil-modified modified conjugated diene-based polymer (sample H) was obtained in the same way as in example 1 except that the amount of n-butyl lithium (polymerization initiator) to be added was 0.120 mmol / min, the amount of 2,2-bis (2-oxolanyl) propane to be added was 0.018 g / min, the modifier was changed from 1,4-bis [3 (trimethoxysilyl) propyl] piperazine to 1- [3- (triethoxysilyl) propyl] - 4 methylpiperazine, and the amount of the modifier to be added was 0.130 mmol / min.
The result of an analysis of sample H was shown in table 3.
[Table 1]
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Ex. 1 Ex. 2 Ex. 3 Sample No. THE B Ç OQN • c”6 Q<D ΌOQ ’-Οc o U Butadiene (g / min) 16.0 16.0 16.0 Styrene (g / min) 8.0 8.0 8.0 n-Hexane (g / min) 125.6 125.6 125.6 Polymerization temperature (° C) 90 90 90 n-butyl lithium for treatment (mmol / min) 0.075 0.075 0.075 n-butyl lithium for initiator of(mmol / min) polymerization 0.150 0.150 0.150 Amount of polar substance ^{* 1} to be added ^{p (g / mln)} 0.020 0.020 0.020 Modified r Modifier type * ² BTMSP BTMSP BTESP Quantity to be,,,. .(mmol / min) added 0.0375 0.0563 0.0375 Equivalent lithium ratio * ³ 1.0 1.5 1.0 Analysis value Bonded styrene content (% by mass) 33 33 33 Vinyl bond content (mol%) 38 38 38 Glass transition temperature (° C) -25 -25 -25 Weight average molecular weight,, (Mw) ^(thousand) 908 870 824 Numerical average molecular weight (Mn) ^(thousand) 393 399 379 Mw / Mn 2.31 2.18 2.17 Mooney viscosity after 37.5 phr extended with oil (100 ° C) 80.0 89.7 77.3 * 1 2,2-bis (2-oxolanyl) propane* 2 BTMSP: 1,4-bis [3- (trimethoxysilyl) propyl] piperazineBTESP: 1,4-bis [3- (triethoxysilyl) propyl] piperazine* 3 Molar ratio of the total amount of an alkoxy group attached to a silyl group contained in the modifier added to the total amount of n-butyl lithium to be added
[Table 21
Example 4 Example 5 Sample No. D AND Polymerization condition Butadiene (g / min) 16.0 16.0 Styrene (g / min) 8.0 8.0 n-Hexane (g / min) 125.6 125.6 Polymerization temperature (° C) 90 90 n-butyl lithium for treatment (mmol / min) 0.075 0.075 n-butyl lithium for initiator of(mmol / min) polymerization 0.150 0.150 Amount of polar substance ¹ a,,. . be added ^{(g / min)} 0.020 0.020 Modifier Modifier type * ² BDMMSP BTMSHP Quantity to be(mmol / min) added 0.0563 0.0375 Equivalent lithium ratio * ³ 1.0 1.0
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Bonded styrene content (% in large scale) 33 33 Vinyl bonding content (mol%) 38 38 Glass transition temperature (OC) -25 -25 Weight average molecular weight (Mw) (thousand) 746 888 Numerical average molecular weight (Mn) (thousand) 352 382 Mw / Mn 2.12 2.32 Mooney viscosity after 37.5 phr (100 ^O C) extended with oil 57.9 78.9
* 1 2,2-bis (2-oxolanyl) propane * 2 BDMMSP: 1,4-bis [3- (dimethoxymethylsilyl) propyl] piperazine BTMSHP: 1,3-bis [3- (trimethoxysilyl) propyl] hexahydropyrimidine * 3 molar of the total amount of an alkoxy group attached to a silyl group contained in the modifier added in the total amount of n-butyl lithium to be added [Table 3]
Ex. Comp. 1 Example comp.2 Example comp.3 Sample No. F G H Butadiene (g / min) 16.0 16.0 16.0 Polymerization conditionStyrene (g / min) 8.0 8.0 8.0n-Hexane (g / min) 125.6 125.6 125.6 Polymerization temperature (OC) 90 90 90 n-butyl lithium for treatment (mmol / min) 0.075 0.075 0.075 n-butyl lithium for polymerization initiator (mmol / min) 0.150 0.150 0.120 1 Amount of polar substance ^{* 1} to be added (g / min) 0.020 0.020 0.018Modifier type * ² BTMSA BTESE TESMP Modifies pain Quantity to be added (mmol / min) 0.0375 0.0375 0.1300 Equivalent lithium ratio * ³ 1.0 1.0 2.0Bonded styrene content (% in large scale) 33 33 33 Analysis value Vinyl bonding content (mol%) 38 38 39 Glass transition temperature (OC) -25 -25 -25 Weight average molecular weight (Mw) (thousand) 901 901 717 Numerical average molecular weight (Mn) (thousand) 384 397 372Mw / Mn 2.35 2.27 1.93Mooney viscosity after 37.5 phr (100OC) extended with oil 75.1 74.8 54.9
Petition 870190036187, of 16/16/2019, p. 71/83 * 1 2,2-bis (2-oxolanyl) propane * 2 BTMSA: bis (3-trimethoxysilylpropyl) -N-methylamine
BTESE: 1,2-bis [3- (triethoxysilyl) ethane
TESMP: 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine * 3 Molar ratio of the total amount of an alkoxy group attached to a silyl group contained in the modifier added to the total amount of n-butyl lithium to be added [Examples 6 to 10, comparative examples 4 to 6]
Each of the samples shown in tables 1 to 3 (sample A to sample H) was used as a raw material rubber to obtain a rubber composition containing the raw material rubber according to the mixture shown below.
Modified conjugated diene-based polymer extended with oil (samples A to H): 137.5 parts by mass
Silica (Ultrasil VN3, made by Evonik Industries AG): 75.0 parts by mass
Carbon black (SEAST KH (N339), made by Tokai Carbon Co., Ltd.): 5.0 parts by mass
Silane copulating agent (Si75, made by Evonik Industries AG): 6.0 parts by mass
S-RAE oil (JOMO Process NC140, made by JX Nippon Oil & Energy Corporation): 4.5 parts by mass
Zinc oxide: 2.5 parts by mass
Stearic acid: 1.5 parts by weight
Antioxidant (N-isopropyl-N'-phenill-p-phenylenediamine): 2.0 parts by weight
Sulfur: 2.2 parts by mass
Vulcanization accelerator (N-cyclohexyl-2-benzothiazil sulfinamide): 1.7 parts by mass
Vulcanization accelerator (diphenyl guanidine): 2.0 parts by mass
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Total: 240.9 pieces by mass
The rubber composition was kneaded by the following method.
A sealed kneader (the internal volume of 0.3 L) including a temperature control device was used. As a first stage of kneading, the raw material rubber (samples A to H), the fillers (silica, carbon black), the organic silane copulating agent, the process oil, zinc oxide, and stearic acid were kneaded under the condition of a filling factor of 65%, the number of rotations of a rotor of 50/57 rpm. At this time, the temperature of the sealed kneader was controlled to obtain a composition of the rubber at a discharge temperature (rubber compound) of 155 to 160 ^O C.
Then, as a second kneading stage, the rubber compound obtained was cooled to room temperature. The antioxidant was added, and the product was kneaded again to improve the dispersion of silica. In this case, the temperature of the mixer was controlled to adjust the discharge temperature (rubber compound) to 155 to 160 ° C.
After cooling, as a third kneading stage, sulfur and the vulcanization accelerator were added to the mixed product, and the product was kneaded by an open roller mill set at 70 ° C. Subsequently, the product obtained was molded, and vulcanized at 160 ° C for 20 minutes by a vulcanization press. After vulcanization, the physical properties of the rubber composition were measured. The result of the measurement of physical properties was shown in tables 4 and 5.
The physical properties of the rubber composition were measured by the following method.
(1) Mooney viscosity of compound
Using a Mooney viscometer, according to JIS K6300-1, a sample was preheated to 130 ° C for 1 minute; and the rotor was rotated 2
Petition 870190036187, of 16/16/2019, p. 73/83 rpm, and the viscosity after 4 minutes was measured. Mooney viscosity indicates that the processability is higher as the value is lower.
(2) Tensile strength
The tensile strength was measured by the tensile test method according to JIS K6251 and indexed, where comparative example 4 was 100.
(3) Viscoelasticity parameter
Using a viscoelasticity tester (ARES) made by Rheometric Scientific, Inc., the viscoelasticity parameter was measured in a torsion mode. Each of the measured values was indexed in which comparative example 4 was 100. Tan δ measured at 0 ^O C, a frequency of 10 Hz, and an effort of 1% was defined as an index of wet grip performance. This indicates that the wet grip performance is higher as the value is higher. In addition, tan δ measured at 50OC, a frequency of 10 Hz, and an effort of 3% were defined as an index of fuel efficiency properties. This indicates that the fuel efficiency performance is higher as the value is lower.
(4) Abrasion resistance
Using an AKRON abrasion tester (made by YASUDA SEIKI SEISAKUSHO, LTD.), According to JIS K6264-2, the amount of wear on a load of 44.1 N and the rotation number of 1000 were measured and indexed where comparative example 4 was 100. The abrasion resistance is higher as the index is higher.
[Table 4]
Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Styrene-butadiene copolymer extended with oil THE B Ç D AND Viscosity of Mooney compound 54 63 58 55 57 Propertyphysical product vulcanized Tensile strength index 111 111 105 104 110 Abrasion resistance index 104 115 113 114 113 0 Tan δ ^C index (1% effort) 104 106 104 101 106
Petition 870190036187, of 16/16/2019, p. 74/83
⁵⁰ tan δ ^O C index (3% effort) 92 87 93 98 91
[Table 51
Ex. Comp.4 Ex.Comp.5 Ex.Comp.6 Styrene-butadiene copolymer extended with oil F G H Viscosity of Mooney compound51 58 63 Physical properties vulcanized product Tensile strength index 100 111 110 Abrasion resistance index 100 95 101 0OC tan δ(effort 1%) index 100 98 108 50OC tan δ(3% effort) index 100 116 96
As shown in Tables 4 and 5, it was found that in the conjugated diene polymer composition modified in Examples 6 to 10, tan δ at an elevated temperature was lower, which means that the hysteresis loss was lower and the low rolling resistance of the tire was performed, tan δ at a low temperature was higher, which means the skid resistance in the wet was higher than in the compositions in comparative examples 4 and
5. It was found that the abrasion resistance and tensile strength were excellent. In addition, compared to comparative example 6, it was found that the Mooney viscosity of the compound was lower, and the balance between processability and physical properties of the vulcanized product was better.
[Example 11]
An autoclave having an internal volume of 10 L, including a stirrer and jacket, and capable of controlling the temperature was used as a reactor. 777 g of butadiene, 273 g of styrene, 4800 g of cyclohexane, and 1.30 g of 2,2-bis (2-oxolanyl) propane as the polar substance, from which impurities were removed earlier, were placed in the reactor, and the internal temperature of the reactor was maintained at 37 ^o C. As the polymerization initiator, a solution of cyclohexane containing 15.1 mmol of n-butyl lithium was fed to the reactor. After starting the polymerization reaction, the temperature inside the
Petition 870190036187, of 16/16/2019, p. 75/83 reactor started to be elevated by the heat generated by the polymerization, and finally reached 70 ^o C. After the polymerization reaction was complete, 3.39 mmol of 1,4-bis [3- (trimethoxysilyl) propyl] piperazine were added in the reactor, and the modification reaction was carried out at 69 ° C for 5 minutes. At this time, the molar ratio of the total amount of the methoxy group attached to the silyl group in the modifier added in an amount of n-butyl lithium to be added was 1.35. 2.1 g of the antioxidant agent (BHT) was added to the polymer solution, and the solvent was removed by steam extraction, and the resulting polymer solution was dried by a dryer to obtain a styrene-butadiene copolymer (sample I) having a modified component.
As an analysis result (sample I), the bonded styrene content was 26% by weight, and the bonded butadiene content was 74%.
The Mooney viscosity of the polymer was 60.
The vinyl bond content (1,2-bond content) of the microstructure of the butadiene portion determined from the measurement result using an infrared spectrophotometer by calculation according to the Hampton method was 56%.
The glass transition temperature was -23 ° C.
The equivalent weight average molecular weight of polystyrene (Mw) measured by GPC was 372,000, the numerical average molecular weight (Mn) was 318,000, and the Mw / Mn was 1.17.
[Comparative example 7]
An autoclave having an internal volume of 10 L, including a stirrer and jacket, and capable of controlling the temperature was used as a reactor. 777 g of butadiene, 273 g of styrene, 4800 g of cyclohexane, and 0.52 g of 2.2bis (2-oxolanyl) propane as the polar substance, from which impurities were removed earlier, were placed in the reactor, and the internal temperature reactor
Petition 870190036187, of 16/16/2019, p. 76/83 was maintained at 43 ^o C. As the polymerization initiator, a solution of cyclohexane containing 6.52 mmol of n-butyl lithium was fed to the reactor. After starting the polymerization reaction, the temperature inside the reactor started to be raised by the heat generated by the polymerization, and finally reached 71 ° C.
After completing the polymerization reaction, 4.35 mmol of 1 [3- (triethoxysilyl) propyl] -4-methylpiperazine was added to the reactor, and the modification reaction was carried out at 70 ° C for 5 minutes. 2.1 g of the antioxidant agent (BHT) was added to the polymer solution, and the solvent was removed by steam extraction, and the resulting polymer solution was dried by a dryer to obtain a styrene-butadiene copolymer (sample J) having a modified component.
As an analysis result (sample J), the bonded styrene content was 26% by weight, and the bonded butadiene content was 74%.
The Mooney viscosity of the polymer was 58.
The vinyl bond content (1,2-bond content) of the microstructure of the butadiene portion determined from the measurement result using an infrared spectrophotometer by calculation according to the Hampton method was 56%.
The glass transition temperature was -23 ° C.
The equivalent weight average molecular weight of polystyrene (Mw) measured by GPC was 368,000, the numerical average molecular weight (Mn) was 281,000, and the Mw / Mn was 1.31.
[Example 12, comparative example 8]
Each of the samples (samples I and J) obtained in example 11 and comparative example 7 was used as the raw material rubber to obtain a rubber composition containing the raw material rubber according to the mixture shown below.
Petition 870190036187, of 16/16/2019, p. 77/83
Modified conjugated diene-based polymer (samples I and J): 100.0 parts by mass
Silica (Ultrasil VN3, made by Evonik Industries AG): 25.0 parts by mass
Carbon black (SEAST KH (N339), made by Tokai Carbon Co., Ltd.): 20.0 parts by mass
Silane copulating agent (Si75, made by Evonik Industries AG): 2.0 parts by mass
S-RAE oil (JOMO Process NC140, made by JX Nippon Oil & Energy Corporation): 5.0 parts by mass
Zinc oxide: 3.0 parts by mass
Stearic acid: 2.0 parts by weight
Antioxidant (N-isopropyl-N'-phenill-p-phenylenediamine): 1.0 part by mass
Sulfur: 1.9 parts by mass
Vulcanization accelerator (N-cyclohexyl-2-benzothiazil sulfinamide): 1.0 part by mass
Vulcanization accelerator (diphenyl guanidine): 1.5 parts by mass
Total: 162.4 parts by mass
The rubber composition was kneaded by the same method as in examples 6 to 10 and comparative examples 4 to 6. The physical properties of the rubber composition were also measured by the same method as in examples 6 to 10 and comparative examples 4 to 6. The result measurement of physical properties was shown in table 6. The index values by which the result is expressed were determined in which comparative example 8 was 100.
[Table 6]
Petition 870190036187, of 16/16/2019, p. 78/83
Example12 Comparative example 8 Styrene-butadiene copolymer I J Viscosity and Mooney compound 64 71 Physical properties of vulcanized product Tensile strength index 99 100 Abrasion resistance index 101 100 0 ° C tan δ (effort 1%) index 103 100 _c tan δ (3% effort) index 96 100
As shown in table 6, it was found that in the conjugated diene polymer composition modified in example 12, tan δ at an elevated temperature is lower, which means that the hysteresis loss is lower and the rolling resistance is low. tire is carried out, tan δ at a low temperature is higher, which means that the skid resistance in the wet is higher than in a composition in comparative example 8. In addition, it was found that the Mooney viscosity of the compound is low, and the balance between processability and physical properties of the vulcanized product is good. Abrasion resistance and tensile strength have been found to be excellent.
As above, the conjugated diene polymer modified according to the present examples has been found to have a good balance between the properties of hysteresis loss and wet slip resistance, abrasion resistance and fracture resistance really sufficient and processability high when the modified conjugated diene-based polymer is formed into a vulcanized product.
This application was made on the basis of patent application JP 2009-230412 filed on October 2, 2009 with the Japan Patent Office, and the contents thereof.
INDUSTRIAL APPLICABILITY
According to the method for producing the modified conjugated diene-based polymer according to the present invention, the polymer based
Petition 870190036187, of 16/16/2019, p. 79/83 modified conjugated diene having the good balance between hysteresis loss properties and wet slip resistance, really sufficient abrasion resistance and fracture resistance, and high processability when formed in a vulcanized product, can be obtained and the modified conjugated diene-based polymer can be appropriately used as a material for various elements, such as tire treads, footwear, and industrial products.

权利要求:
Claims (6)
[1]
1. Method for producing a modified conjugated diene-based polymer, characterized by the fact that it comprises:
a polymerization step of polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound with an aromatic vinyl compound using an alkali metal compound or an alkaline earth metal compound as a polymerization initiator to obtain a diene-based polymer conjugate having a reactive end, and a modification step of reacting a modifier with the reactive end of the conjugated diene-based polymer, wherein the modifier is a compound represented by formula (1):
(where R ¹ to R ⁴ each independently represents an alkyl group or an aryl group having 1 to 20 carbon atoms; R ⁵ and R ⁶ each independently represents an alkylene group having 1 to 20 carbon atoms; R ⁷ and R ⁸ each, independently, represent a hydrocarbon group having 1 to 6 carbon atoms, and form a ring structure of a ring of 5 or more members with two adjacent Ns; each, independently, represents an integer of 2 or 3).
[2]
A method for producing the modified conjugated diene-based polymer according to claim 1, characterized in that all the silyl groups in the modifier are each silyl group to which three alkoxy groups are attached.
[3]
3. Method for producing the modified conjugated diene-based polymer according to claim 1 or 2, characterized by the fact that
Petition 870190036187, of 16/16/2019, p. 81/83 that a total number of moles of the alkoxy group attached to the silyl group in the modifier is within a range of 0.8 to 3 times the number of moles of the polymerization initiator to be added.
[4]
Method for producing the modified conjugated diene-based polymer 5 according to any one of claims 1 to 3, characterized in that the polymerization step is continuous.
[5]
Method for producing the modified conjugated diene-based polymer according to any one of claims 1 to 4, characterized in that an equivalent numerical average molecular weight
[6]
10 the polystyrene of the modified conjugated diene-based polymer measured by gel permeation chromatography (GPC) is 200,000 to 600,000.

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-02-19| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-07-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-09-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/09/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/09/2010, OBSERVADAS AS CONDICOES LEGAIS |

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2021-08-10| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |

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2021-11-30| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2640 DE 10-08-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2009230412|2009-10-02|

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JP2009-230412|2009-10-02|

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PCT/JP2010/066431|WO2011040312A1|2009-10-02|2010-09-22|Production method for modified conjugated diene polymer, modified conjugated diene polymer, and modified conjugated diene polymer composition|

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