WO2013118496A1 - 変性ポリマーの製造方法、並びにジエン系ポリマー、ゴム組成物及び空気入りタイヤ - Google Patents
変性ポリマーの製造方法、並びにジエン系ポリマー、ゴム組成物及び空気入りタイヤ Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/08—Depolymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
- C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
Definitions
- the present invention relates to a method for producing a modified polymer, a diene polymer, a rubber composition using the diene polymer, and a pneumatic tire.
- Polymer modification techniques are known as techniques for changing the properties of natural polymers such as natural rubber and synthesized polymers themselves.
- terminal structure modification to synthetic rubber such as styrene-butadiene rubber
- addition modification on the main chain, or modification method in the polymerization stage has been proposed (see Patent Documents 1 to 7 below).
- modification methods such as adding a functional group directly to a side chain or grafting a polymer to add a functional group have been proposed (See Patent Documents 8 to 12 below).
- Such a modified polymer is used, for example, as a rubber component in a rubber composition.
- diene rubber is used as a rubber component in a rubber composition, and a filler such as carbon black or silica is blended therein.
- the modified polymer is used as a rubber component.
- Patent Document 13 discloses depolymerized natural rubber useful as an adhesive, a pressure-sensitive adhesive, a sealing agent, a caulking agent, a plasticizer, and the like.
- a deproteinized natural rubber dissolved in an organic solvent is depolymerized by air oxidation in the presence of a metal catalyst to produce a liquid depolymerized natural rubber having a number average molecular weight of 2000 to 50000.
- the main chain is decomposed by air oxidation to form a molecular chain having a carbonyl group at one end and a formyl group at the other end, and then the formyl group is recombined by aldol condensation. Has been.
- depolymerization is performed in a solution of an organic solvent, and it is disclosed that a system containing a decomposed polymer is recombined by changing from acidic to basic or from basic to acidic. Absent.
- This document is intended to obtain a telechelic liquid rubber having carbonyl groups at both ends, and is intended only to obtain a liquid rubber obtained by reducing the molecular weight of natural rubber. Therefore, the polymer is not modified by rearranging the main chain structure while controlling the molecular weight without drastically decreasing.
- Non-Patent Document 1 discloses that a polyester having a carbon-carbon double bond in the main chain and polyisoprene derived from natural rubber are combined by a main chain exchange reaction.
- the technique disclosed in this document is based on an olefin cross-metathesis reaction, requires a metal catalyst such as a Grubbs catalyst, and is generally not easy to control the reaction system.
- an object is to provide a novel method for modifying a polymer. More specifically, the present invention provides a method for producing a modified polymer capable of simply introducing a functional group into the main chain structure. Moreover, in another embodiment, it aims at providing the novel diene type polymer in which the functional group was introduce
- a polymer having a carbon-carbon double bond in the main chain is decomposed by oxidative cleavage of the carbon-carbon double bond to reduce the molecular weight.
- the acid-basicity so that the system containing the base is acidic (ie, alkaline) in the case of acidity and acidic in the case of the basicity, the polymer chains of the decomposed polymer are bonded to form a structure.
- a modified modified polymer is obtained.
- the decomposed polymer may include a structure represented by the following formula (1) at the terminal.
- R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen group.
- the diene polymer according to the embodiment has in the molecule at least one linking group selected from the group of linking groups represented by the following formulas (2) to (5), and the diene polymer chain is the linking group. It has a structure connected through a group.
- the rubber composition according to the embodiment contains 5 to 150 parts by mass of filler with respect to 100 parts by mass of the rubber component containing the diene polymer.
- the pneumatic tire according to the embodiment is formed using the rubber composition.
- the polymer is decomposed by oxidative cleavage of the double bond of the main chain to reduce the molecular weight, and then the system containing the polymer is made acidic or basic.
- the system containing the polymer is made acidic or basic.
- the method for producing a modified polymer according to an embodiment includes a system comprising a polymer having a carbon-carbon double bond as a main chain that is decomposed by oxidative cleavage of the double bond to reduce the molecular weight, A modified polymer in which the structure is changed by recombination by making them acidic or basic is prepared.
- a polymer having a carbon-carbon double bond in the repeating unit of the main chain can be used as the polymer to be modified.
- examples of such polymers include various diene polymers, preferably diene rubber polymers, and other examples include unsaturated polyesters, unsaturated polyols, unsaturated polyurethanes, polyalkyne compounds, and unsaturated fatty acids.
- the diene polymer is a conjugated diene compound such as butadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, or 1,3-hexadiene. It is a polymer obtained by using as a part.
- conjugated diene compounds may be used alone or in combination of two or more.
- the diene polymer includes a copolymer of a conjugated diene compound and a monomer other than the conjugated diene compound.
- Other monomers include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, ethylene, propylene, isobutylene, acrylonitrile, or And various vinyl compounds such as acrylic acid esters. These vinyl compounds may be used alone or in combination of two or more.
- diene rubber polymer examples include various rubber polymers having at least one selected from the group consisting of isoprene units, butadiene units and chloroprene units (preferably isoprene units and / or butadiene units) in the molecule.
- NR Natural rubber
- IR synthetic isoprene rubber
- BR butadiene rubber
- SBR styrene butadiene rubber
- NBR nitrile rubber
- chloroprene rubber CR
- butyl rubber (IIR) butyl rubber
- styrene-isoprene copolymer examples thereof include rubber, butadiene-isoprene copolymer rubber, and styrene-isoprene-butadiene copolymer rubber.
- Only one type of polymer to be modified may be used, or two or more types may be used.
- a main chain exchange reaction can be performed between the two or more kinds of polymers, and a composite polymer including different polymer chains is obtained.
- the combination of the polymers in this case is not particularly limited, but at least one is preferably a diene polymer, more preferably at least one is a diene rubber polymer, and more preferably at least one is styrene.
- Two or more diene polymers may be used, and two or more diene rubber polymers may be used.
- styrene butadiene rubber may be combined with natural rubber and / or synthetic isoprene rubber.
- the polymer to be modified it is preferable to use a polymer having a number average molecular weight of 60,000 or more.
- a preferred embodiment is a solid polymer at normal temperature (23 ° C.).
- the number average molecular weight is 60,000 or more in order to prevent plastic deformation without applying force at room temperature, and if it is smaller than this, the viscosity is low. It becomes difficult to mold as a product.
- the solid state is a state without fluidity.
- the number average molecular weight of the polymer is preferably 60,000 to 1,000,000, more preferably 80,000 to 800,000, still more preferably 100,000 to 600,000, and even if it is 100,000 to 500,000 Good.
- a polymer dissolved in a solvent can be used. It is preferable to use a water-based emulsion, that is, a latex, which is micellar in water, which is a protic solvent.
- a water-based emulsion that is, a latex, which is micellar in water, which is a protic solvent.
- concentration of the aqueous emulsion is not particularly limited, but is preferably 5 to 70% by mass, more preferably 10 to 50% by mass. By setting it as such solid content concentration, it can suppress that a micelle breaks easily with respect to pH fluctuation of a reaction field, can improve stability of an emulsion, and can secure a practical reaction rate. it can.
- an oxidant can be used.
- the oxidative cleavage can be performed by adding an oxidant to the aqueous emulsion of the polymer and stirring.
- the oxidizing agent include manganese compounds such as potassium permanganate and manganese oxide, chromium compounds such as chromic acid and chromium trioxide, peroxides such as hydrogen peroxide, perhalogen acids such as periodic acid, or Examples include oxygen such as ozone and oxygen. Among these, it is preferable to use periodic acid. Periodic acid makes it easy to control the reaction system, and a water-soluble salt is produced.
- a metal-based oxidation catalyst such as a salt or complex of a metal such as cobalt, copper, or iron with a chloride or an organic compound may be used in combination, for example, the presence of the metal-based oxidation catalyst. Air oxidation may be performed underneath.
- each polymer may be oxidatively cleaved by adding an oxidant in separate systems, or alternatively, two or more kinds of polymers may be mixed in advance before the oxidant is added to the mixed system. May be oxidatively cleaved together by adding
- the polymer is decomposed by the oxidative cleavage, and a polymer having a carbonyl group (> C ⁇ O) or a formyl group (—CHO) at the terminal (hereinafter sometimes referred to as a polymer fragment) is obtained.
- a polymer fragment has a structure represented by the above formula (1) at the terminal.
- R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen group, and more preferably a hydrogen atom, a methyl group, or a chloro group.
- R 1 is a methyl group at one cleavage end and R 1 is a hydrogen atom at the other cleavage end.
- R 1 is a hydrogen atom at both cleavage ends.
- R 1 becomes a chloro group at one cleavage end and R 1 becomes a hydrogen atom at the other cleavage end.
- the decomposed polymer (that is, polymer fragment) has a structure represented by the above formula (1) at at least one end of its molecular chain. That is, as shown in the following formulas (6) and (7), a polymer in which a group represented by the formula (1) is directly bonded to one end or both ends of a diene polymer chain is generated.
- R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen group
- the portion represented by a wavy line is a diene polymer chain.
- the portion represented by a wavy line is a polyisoprene chain composed of a repeating structure of isoprene units.
- the portion indicated by a wavy line is a random copolymer chain including a styrene unit and a butadiene unit.
- the molecular weight is decreased by decomposing the polymer by the above oxidative cleavage.
- the number average molecular weight of the polymer after decomposition is not particularly limited, but is preferably 3 to 500,000, more preferably 5 to 100,000, and still more preferably 1,000 to 50,000.
- the amount of the functional group after recombination can be adjusted by the size of the molecular weight after decomposition, but if the molecular weight at the time of decomposition is too small, a binding reaction within the same molecule tends to occur.
- the binding reaction that is the reverse reaction to cleavage proceeds preferentially. That is, the oxidative cleavage is a reversible reaction, and the cleavage reaction proceeds preferentially over the binding reaction, which is the reverse reaction, so the molecular weight decreases until equilibrium is reached.
- the binding reaction now proceeds preferentially, so that the molecular weight once decreased starts to increase, and the molecular weight increases until equilibrium is reached. Therefore, a modified polymer having a desired molecular weight can be obtained.
- the structure of the above formula (1) has two types of tautomerism and is bonded to the original carbon-carbon double bond structure and a linking group represented by the above formulas (2) to (5). Divided into what forms.
- a polymer containing at least one linking group of any one of formulas (2) to (5) can be generated with priority on the aldol condensation reaction.
- some reaction systems, especially aqueous emulsions have pH adjusted for stabilization.
- the pH during decomposition is either acidic or basic. Stop by either. Therefore, when the reaction system at the time of decomposition is acidic, the reaction system is made basic. Conversely, if the reaction system at the time of decomposition is basic, the reaction system is made acidic.
- the pH of the reaction system for the binding reaction may be larger than 7, preferably 7.5 to 13, and more preferably 8 to 10.
- the pH should be lower than 7, preferably 4 to 6.8, more preferably 5 to 6.
- the pH can be adjusted by adding an acid or a base to the reaction system.
- the acid includes hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid
- the base includes sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium bicarbonate. Is mentioned.
- an acid or base for adjusting the pH serves as a catalyst for the binding reaction
- pyrrolidine-2-carboxylic acid may be used as a catalyst for controlling the reaction.
- the water-based emulsion is coagulated and dried to obtain a solid modified polymer at room temperature.
- the linking group represented by the above formulas (2) to (5) is introduced into the main chain, and a modified polymer having a changed structure is obtained.
- the modified polymer according to the embodiment has in the molecule at least one linking group of the linking groups represented by the above formulas (2) to (5), and the polymer chain passes through the linking group. It has a directly connected structure.
- any one of the linking groups represented by the formulas (2) to (5) is represented by X
- the polymer chain preferably a diene polymer chain
- Y—XY— The structure represented is contained in the molecule, and usually has a structure in which the linking group X and the polymer chain Y are alternately repeated.
- the polymer chains Y on both sides of X may be the same or different.
- the (diene-based) polymer chain is a part of the molecular chain of the (diene-based) polymer to be modified.
- the diene polymer chain is a repeating structure of A 1 represented by-(A 1 ) n- , where A 1 is a structural unit composed of the conjugated diene compound ( n is an integer of 1 or more, preferably 10 to 10,000, and more preferably 50 to 1,000.
- the diene-based polymer chain has each constituent unit as A 1 and A 2 (at least one of A 1 and A 2 is a unit composed of a conjugated diene compound, and other units as Is a unit composed of the above-mentioned vinyl compound.),
- a repeating structure of A 1 and A 2 represented by- (A 1 ) n- (A 2 ) m- (these may be random type or block type) N and m are each an integer of 1 or more, preferably 10 to 10,000, and more preferably 50 to 1,000.
- the diene-based polymer chain is composed of A 1 , A 2 and A 3 as constituent units (at least one of A 1 , A 2 and A 3 is a unit composed of a conjugated diene compound. And other units include units composed of the above vinyl compounds.),
- a 1 , A 2 and A represented by — (A 1 ) n — (A 2 ) m — (A 3 ) p — 3 is a repeating structure of (these may be of a block type in a random type .n, m, p are each an integer of 1 or more, preferably from 10 to 10,000, further preferably from 50 to 1000). The same applies to quaternary copolymers or more.
- the modified polymer has at least one linking group selected from the group of linking groups represented by the above formulas (2) to (5) in the molecule, represented by the following formula (8). It may be a modified isoprene rubber in which the polyisoprene chain is linked via the linking group.
- the modified isoprene rubber is a case where natural rubber or synthetic isoprene rubber is used as a modification target, and has the polyisoprene chain composed of a repeating structure of isoprene units as a diene polymer chain.
- n is an integer of 1 or more, preferably 10 to 10000, more preferably 50 to 1000.
- the modified polymer has at least one linking group selected from the group of linking groups represented by the above formulas (4) and (5) in the molecule, and is represented by the following formula (9). It may be a modified styrene butadiene rubber in which the random copolymer chains to be linked are linked via the linking group.
- the modified styrene butadiene rubber is a case where styrene butadiene rubber is used as a modification target, and has a styrene butadiene copolymer chain represented by the formula (9) including a styrene unit and a butadiene unit as a diene polymer chain.
- n and m are each independently an integer of 1 or more, preferably 10 to 10,000, and more preferably 50 to 1000.
- the diene polymer chain contained in the modified polymer may be a polybutadiene chain represented by the following formula (10) in addition to the polyisoprene chain and the styrene butadiene copolymer chain. That is, when polybutadiene rubber is used as a modification target, the polybutadiene chain has at least one linking group selected from the group of linking groups represented by the above formulas (4) and (5) in the molecule. A modified butadiene rubber connected through the connecting group is obtained.
- n is an integer of 1 or more, preferably 10 to 10000, more preferably 50 to 1000.
- the diene polymer chains are preferably diene rubber polymer chains such as these polyisoprene chains, styrene butadiene copolymer chains, and polybutadiene chains.
- the modified polymer has a structure in which polymer chains derived from different types of polymers are linked via the linking group. That is, the modified polymer is a composite polymer including polymer chains derived from two or more kinds of polymers.
- the modified polymer since the coupling reaction occurs not only between different polymer fragments, but also between the same kind of polymer fragments, the modified polymer usually has a structure in which the same kind of polymer chains are linked via the linking group, Therefore, it has a structure in which a connection structure between the same kind of polymer chains and a connection structure between different kinds of polymer chains are mixed.
- the heterogeneous diene polymer chain includes a polyisoprene chain represented by formula (8), a random copolymer chain represented by formula (9), and a polybutadiene chain represented by formula (10). It is preferable that at least one of these is included. That is, a combination of the polyisoprene chain and another diene polymer chain, a combination of the random copolymer chain and another diene polymer chain, a combination of the polybutadiene chain and another diene polymer chain, and A combination of two or more of the polyisoprene chain, the random copolymer chain, and the polybutadiene chain is included.
- two or more kinds of diene polymers including at least one of natural rubber and / or synthetic isoprene rubber, styrene butadiene rubber and butadiene rubber may be used as the modification target.
- the modified polymer has a structure in which at least two kinds selected from the group consisting of the polyisoprene chain, the random copolymer chain, and the polybutadiene chain are linked via the linking group.
- two or more kinds selected from the group consisting of isoprene rubber that is, natural rubber or synthetic isoprene rubber
- styrene butadiene rubber, and butadiene rubber are combined as two or more kinds of diene rubber polymers to be modified. More preferably, it is a combination of isoprene rubber and styrene butadiene rubber, or a combination of isoprene rubber and butadiene rubber.
- One or more of the above linking groups are contained in one molecule of the modified polymer, and usually a plurality of linking groups are contained in one molecule. When two or more are included, a plurality of any one of the linking groups represented by the above formulas (2) to (5) may be included, or two or more of them may be included.
- the content of the linking group is not particularly limited, but is preferably 0.001 to 25 mol%, more preferably 0.1 to 15 mol% in total of the linking groups of the formulas (2) to (5). More preferably, it is 0.5 to 10 mol%.
- the content (modification rate) of the linking group is a ratio of the number of moles of the linking group to the number of moles of all the structural units constituting the modified polymer.
- the ratio of the number of moles of linking groups to the total number of moles of all isoprene units and linking groups of the modified polymer In the case of styrene butadiene rubber, it is the ratio of the number of moles of linking groups to the total number of moles of butadiene units, styrene units and linking groups in the modified polymer. In the case of a composite polymer of natural rubber and styrene-butadiene rubber, it is the ratio of the number of moles of linking groups to the total number of moles of isoprene units, butadiene units, styrene units, and linking groups in the modified polymer.
- each linking group represented by formulas (2) to (5) is not particularly limited, but is preferably 25 mol% or less (that is, 0 to 25 mol%).
- all of the linking groups represented by the formulas (2) to (5) can usually be included.
- 2) is mainly included, in which case the content of the linking group represented by the formula (2) is preferably 0.001 to 20 mol%, more preferably 0.05 to It is 10 mol%, more preferably 0.5 to 5 mol%.
- the linking group represented by the formulas (4) and (5) is usually included.
- the content of the linking group represented by the formula (5) is preferably 0.001 to 20 mol%, more preferably 0.05 to It is 10 mol%, more preferably 0.5 to 5 mol%.
- the modified polymer according to the embodiment is preferably solid at normal temperature (23 ° C.). Therefore, the number average molecular weight of the modified polymer is not particularly limited, but is preferably 60,000 or more, more preferably 60,000 to 1,000,000, still more preferably 80,000 to 800,000, and even more preferably 10 It may range from 100,000 to 600,000, and may be 100,000 to 500,000. Thus, the molecular weight of the modified polymer is preferably set to be equivalent to that of the original polymer by recombination as described above. This allows functional groups to be introduced into the main chain of the polymer without lowering the molecular weight and thus avoiding adverse effects on physical properties. Of course, a polymer having a molecular weight smaller than that of the original polymer may be obtained.
- the weight average molecular weight of the modified polymer is not particularly limited, but is preferably 70,000 or more, more preferably 100,000 to 2,000,000, still more preferably 100,000 to 1,500,000, and particularly preferably 30. 10,000 to 1,000,000.
- the double bond of the main chain is oxidatively cleaved to decompose the polymer to reduce the molecular weight, and then recombine by changing the acid basicity of the reaction system.
- the reaction for oxidative cleavage can be controlled by adjusting the kind and amount of the oxidizing agent that is an agent that dissociates the double bond, the reaction time, and the like.
- the binding reaction can be controlled by adjusting the pH, catalyst, reaction time, etc. during recombination.
- the molecular weight of the modified polymer can be controlled by these controls. Therefore, the number average molecular weight of the modified polymer can be set equal to that of the original polymer, and can be set lower than that of the original polymer.
- the above linking group is inserted as a structure different from that of the main chain, and the bonding point of the segment of the main chain structure is functionalized. That is, a highly reactive structure or a structure that easily changes the polymer structure parameters is introduced into the molecular main chain.
- the method of the present embodiment changes the main chain structure of a polymer that is neither grafted nor directly added nor ring-opened, and is clearly different from the conventional modification method, and the main chain structure is simplified. Functional groups can be introduced into the.
- a modified polymer having a novel structure can be produced by modifying the main chain structure of a natural polymer such as natural rubber, and the characteristics of the polymer can be changed.
- a modified polymer having a recombined structure can be obtained by exchanging the polymer chains between different types of polymers.
- the main chain exchange reaction of the high molecular weight can be performed without using a metal catalyst.
- two or more polymers to be modified have different molecular weights, they can be monodispersed by decomposing and recombining them to obtain a modified polymer with a certain length. Can do. In this way, modified polymers having a block-like arrangement in which main chains are exchanged between different polymers can be obtained in a certain length.
- the obtained phase structure is not a structure separated into a matrix phase and a dispersed phase like the sea-island phase obtained by polymer blending, but can have the same phase structure as a block copolymer, and has various characteristics. Can be demonstrated.
- the modified polymer according to this embodiment can be used as a polymer component in various polymer compositions, and is not particularly limited.
- a modified diene rubber obtained by modifying a diene rubber is obtained, and the modified diene rubber is used in various ways. It is preferable to use it as a rubber component in the rubber composition.
- it does not specifically limit as a use of a rubber composition, It can use for various rubber members, such as an object for tires, a vibration proof rubber, and a conveyor belt.
- the modified diene rubber is compatible with the filler by changing the interaction (intermolecular force, polarity and reactivity) between the polymer and the filler, or by changing the composition of the polymer. Or dispersibility is improved. Due to this effect, for example, when used in tire rubber compositions, improvements in fuel economy and tensile properties are seen, especially in tire tread formulations, which are important for reinforcement, wet skid performance, rolling resistance performance. Can be achieved at a high level.
- the physical properties can be improved with a uniform structure by selecting two or more types of polymers as the modification target. That is, in the conventional polymer blend, the macro phase separation due to the difference in polarity between the polymers and the localization of the filler results in a non-uniform structure.
- the physical properties are improved with a uniform structure. It becomes possible. For this reason, it can be used for viscoelastic effect, adjustment of relaxation with respect to load (subtraction of noise), and rigidity control of a non-pneumatic tire or the like. It can also be used for rubber regeneration.
- the rubber component may be the above-mentioned modified diene rubber alone or a blend of the modified diene rubber and another rubber.
- Other rubbers are not particularly limited.
- natural rubber NR
- synthetic isoprene rubber IR
- butadiene rubber BR
- styrene butadiene rubber SBR
- nitrile rubber NBR
- butyl rubber IIR
- various diene rubbers such as halogenated butyl rubber, are mentioned. These can be used alone or in combination of two or more.
- the content of the modified diene rubber in the rubber component is not particularly limited, but is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 50 parts by mass in 100 parts by mass of the rubber component. More than a part.
- a filler can be mix
- various inorganic fillers such as silica, carbon black, titanium oxide, aluminum silicate, clay, or talc can be used, and these can be used alone or in combination of two or more. .
- silica and / or carbon black is preferably used.
- the silica is not particularly limited and includes wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), etc. Among them, wet silica is preferable.
- the colloidal characteristics of silica are not particularly limited, but those having a nitrogen adsorption specific surface area (BET) of 150 to 250 m 2 / g by the BET method are preferably used, and more preferably 180 to 230 m 2 / g.
- BET nitrogen adsorption specific surface area
- the carbon black is not particularly limited, and various grades of furnace carbon black such as SAF, ISAF, HAF, or FEF, which are used as rubber reinforcing agents, can be used alone or in combination of two or more. .
- the amount of the filler is 5 to 150 parts by weight, preferably 20 to 120 parts by weight, and more preferably 30 to 100 parts by weight with respect to 100 parts by weight of the rubber component.
- the modified isoprene rubber when used as the modified diene rubber, it is preferable to blend carbon black as a filler.
- the filler is preferably carbon black alone or a combination of carbon black and silica. Carbon black is preferably blended in an amount of 5 to 80 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the rubber component.
- the modified styrene butadiene rubber when used as the modified diene rubber, it is preferable to blend silica as a filler. This is because in the case of the modified styrene butadiene rubber, the use of silica as the filler exhibits a greater effect in terms of improving compatibility than when carbon black is used. Therefore, when a modified styrene butadiene rubber is used, the filler is preferably silica alone or a combination of silica and carbon black. Silica is preferably blended in an amount of 5 to 80 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the rubber component.
- silane coupling agent such as sulfide silane or mercaptosilane may be added to the rubber composition in order to further improve the dispersibility of silica.
- the compounding amount of the silane coupling agent is not particularly limited, but is preferably 2 to 20% by mass with respect to the silica compounding amount.
- the rubber composition contains various additives commonly used in rubber compositions such as oil, zinc white, stearic acid, anti-aging agent, wax, vulcanizing agent, vulcanization accelerator, etc. Can be blended.
- the vulcanizing agent examples include sulfur or a sulfur-containing compound (for example, sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide, and alkylphenol disulfide). Or it can use in combination of 2 or more types.
- the compounding amount of the vulcanizing agent is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. .
- various vulcanization accelerators such as a sulfenamide type
- the blending amount of the vulcanization accelerator is not particularly limited, but is preferably 0.1 to 7 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. is there.
- the rubber composition according to the embodiment can be prepared by kneading according to a conventional method using a commonly used Banbury mixer, kneader, roll, or other mixer. That is, in the first mixing stage, other additives except the vulcanizing agent and the vulcanization accelerator are added and mixed with the rubber component in the first mixing stage, and then the vulcanizing agent is added to the obtained mixture in the final mixing stage. And a rubber composition can be prepared by adding and mixing a vulcanization accelerator.
- the rubber composition thus obtained can be used in various applications such as passenger cars, large tires for trucks and buses, tread parts, side wall parts, bead parts, tire cord covering rubbers, etc. Can be applied to the site. That is, the rubber composition is molded into a predetermined shape by, for example, extrusion processing according to a conventional method, and combined with other components, and then vulcanized at, for example, 140 to 180 ° C. to produce a pneumatic tire. can do. Among these, it is particularly preferable to use as a tire tread formulation.
- modified polymer according to the present embodiment is not limited to the rubber composition, and for example, it can be used as a material in various fields including a device material such as an electronic circuit element.
- Mn Numberer average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)] Mn, Mw and Mw / Mn in terms of polystyrene were determined by measurement with gel permeation chromatography (GPC). Specifically, the measurement sample used was 0.2 mg dissolved in 1 mL of THF. “LC-20DA” manufactured by Shimadzu Corporation was used, and the sample was filtered and passed through a column (“PL Gel 3 ⁇ m Guard ⁇ 2” manufactured by Polymer Laboratories) at a temperature of 40 ° C. and a flow rate of 0.7 mL / min. Detection was performed by “RI Detector” manufactured by System.
- GPC gel permeation chromatography
- [Content of linking group] The content of the linking group was measured by NMR.
- the NMR spectrum was measured using “400ULTRASHIELDTM PLUS” manufactured by BRUKER, with TMS as a standard. 1 g of the polymer was dissolved in 5 mL of deuterated chloroform, 87 mg of acetylacetone chromium salt was added as a relaxation reagent, and the measurement was performed with an NMR 10 mm tube.
- the peak of carbon with a ketone group is at 195 ppm in 13 C-NMR.
- the peak of carbon with a ketone group is at 205 ppm in 13 C-NMR.
- the peak of carbon with a ketone group is at 200 ppm in 13 C-NMR.
- the peak of carbon with a ketone group is at 185 ppm in 13 C-NMR. Therefore, the structural amount (number of moles) of each peak was determined by the ratio with the base polymer component.
- Example 1 Synthesis of modified polymer A
- the molecular weight of the unmodified natural rubber contained in the natural rubber latex was measured, and it was found that the weight average molecular weight was 15.1 million, the number average molecular weight was 26.90,000, and the molecular weight distribution was 5.6.
- the obtained modified polymer A has a weight average molecular weight Mw of 790,000, a number average molecular weight Mn of 304,000, a molecular weight distribution Mw / Mn of 2.6, and a content of the above linking group.
- Mw weight average molecular weight
- Mn number average molecular weight
- Mw / Mn molecular weight distribution
- a content of the above linking group 1.03 mol%
- the modified polymer A had a number average molecular weight substantially equal to that of the unmodified natural rubber.
- the molecular weight distribution was smaller than that of the unmodified natural rubber, and the uniformity was excellent.
- Examples 2 to 4 Synthesis of modified polymers B to D
- the reaction time during oxidative decomposition, the amount of periodic acid added, the pH adjuster and pH added during the recombination reaction, and the amount of catalyst were changed as shown in Table 1 below, and the others were the same as in Example 1.
- Solid modified polymers B to D were synthesized. Table 1 shows the contents of Mw, Mn, Mw / Mn and each linking group in the obtained modified polymers B to D.
- the linking group having a functional group was introduced into the main chain, and the molecular weight distribution was smaller than that of the unmodified natural rubber, and the uniformity was excellent.
- the molecular weight could be controlled by changing the above conditions.
- the weight average molecular weight was 680,000, the number average molecular weight was 324,000, and the molecular weight distribution was 2.1 Using this styrene butadiene rubber latex, according to the conditions described in Table 1, other examples and Similarly, solid modified polymers E to H were synthesized, and the contents of Mw, Mn, Mw / Mn and each linking group in the obtained modified polymers E to H were as shown in Table 1. In the polymers E to H, only the formulas (4) and (5) were introduced as linking groups, and the modified polymers E to H also had no molecular weight distribution. Smaller than sexual styrene-butadiene rubber was excellent in uniformity. Also, by changing the conditions, it was possible to control the molecular weight.
- Comparative Example 2 in Table 1 is an unmodified styrene butadiene rubber obtained by coagulating and drying the styrene butadiene rubber latex without modification.
- Example 9 to 13 Synthesis of modified polymers I to M
- the molecular weight of the unmodified synthetic isoprene rubber contained in the rubber latex was measured. The weight average molecular weight was 83,000, the number average molecular weight was 66,000, and the molecular weight distribution was 1.3.
- solid modified polymers I to M were synthesized in the same manner as in Example 1 except for the conditions described in Table 1.
- Table 1 shows the contents of Mw, Mn, Mw / Mn and each linking group of the modified polymers I to M obtained.
- a linking group having a functional group could be easily introduced into the main chain.
- the molecular weight could be controlled by changing the conditions.
- Comparative Example 3 in Table 1 is an unmodified synthetic isoprene rubber obtained by coagulating and drying the above synthetic isoprene rubber latex without modification.
- Examples 14 to 38 and Comparative Examples 4 to 16 Rubber compositions
- Silane coupling agent bis (3-triethoxysilylpropyl) tetrasulfide, “Si69” manufactured by Evonik Degussa ⁇
- Zinc flower “Zinc flower 1” manufactured by Mitsui Mining & Smelting Co., Ltd.
- Anti-aging agent “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
- Each rubber composition obtained was vulcanized at 160 ° C. for 20 minutes to prepare a test piece having a predetermined shape, and a dynamic viscoelasticity test was performed using the obtained test piece to obtain wet skid performance (tan ⁇ (0 ° C.)) and low fuel consumption performance (tan ⁇ (60 ° C.)) were evaluated, and a tensile test was performed to evaluate the elastic modulus M300 and the tensile strength.
- Each evaluation method is as follows.
- -Modulus of elasticity M300 A tensile test (dumbbell-shaped No. 3 type) based on JIS K6251 was performed to measure the 300% modulus, and the value was expressed as an index with the value of each corresponding comparative example being 100. The larger the index, the larger M300 and the higher the rigidity.
- Tensile test (dumbbell-shaped No. 3 type) based on JIS K6251 was performed to measure the strength at break, and displayed as an index with the value of each corresponding comparative example as 100. The larger the index, the higher the tensile strength and the better.
- Example 39 Synthesis of modified polymer N
- SBR Latex LX110, DRC manufactured by Nippon Zeon Co., Ltd. SBR Latex LX110, DRC manufactured by Nippon Zeon Co., Ltd.
- Natural rubber latex and styrene butadiene rubber latex are mixed so that the polymer mass ratio is 1: 1, and 3.3 g of periodic acid (H 5 IO 6 ) with respect to 100 g of polymer mass contained in the mixed latex. And the polymer was decomposed by stirring at 23 ° C. for 3 hours.
- the obtained decomposition polymer had a weight average molecular weight of 21,300, a number average molecular weight of 9,100, a molecular weight distribution of 2.3, and the pH of the reaction solution after decomposition was 6.2.
- the obtained modified polymer N has a linking group represented by the above formulas (2) to (5) in the molecule, and is represented by the polyisoprene chain represented by the formula (8) and the formula (9).
- This is a modified diene rubber in which styrene-butadiene copolymer chains are linked through the linking group.
- the modified polymer N has a weight average molecular weight Mw of 16.2 million, a number average molecular weight Mn of 500,000, a molecular weight distribution Mw / Mn of 3.2, and the content of the linking group represented by the formula (2 ) Is 1.3 mol%, formula (3) is 0.4 mol%, formula (4) is 0.2 mol%, formula (5) is 0.4 mol%, and 2.3 mol% in total. Met.
- the peak of the linking group was confirmed by NMR, and it was copolymerized because the glass transition temperature was unified by ⁇ DSC-822e '' differential scanning calorimetry (DSC) manufactured by METTLER. That is, it is clear that the main chain is exchanged (the same applies to the modified polymers O to S described below).
- Example 40 Synthesis of modified polymer O
- the natural rubber latex and styrene butadiene rubber latex used in Example 39 were separately subjected to an oxidative decomposition reaction and then mixed to perform a recombination reaction. Specifically, 1.65 g of periodic acid was added to 50 g of polymer mass in the natural rubber latex, and the mixture was stirred at 23 ° C. for 3 hours.
- the obtained decomposition polymer had a weight average molecular weight of 13,500, a number average molecular weight of 5,300, a molecular weight distribution of 2.6, and the pH of the reaction solution after decomposition was 6.4.
- the obtained decomposed polymer had a weight average molecular weight of 3630, a number average molecular weight of 2400, a molecular weight distribution of 1.5, and the pH of the reaction solution after decomposition was 6.1.
- Both latexes after the decomposition reaction were mixed so that the polymer mass ratio was 1: 1.
- the pH of the mixed solution was 6.2.
- 0.1 g of pyrrolidine-2-carboxylic acid is added as a catalyst to 100 g of polymer mass, and 1N sodium hydroxide is added so that the pH of the reaction solution becomes 8, and the mixture is stirred for 24 hours at 23 ° C.
- Binding reaction was performed. Thereafter, in the same manner as in Example 39, precipitation, washing and drying were performed to obtain a modified polymer O solid at room temperature.
- the resulting modified polymer O like the modified polymer N, has a linking group represented by the above formulas (2) to (5) in the molecule, a polyisoprene chain represented by the formula (8) and a formula ( 9) is a modified diene rubber in which the styrene butadiene copolymer chain represented by 9) is linked through the linking group, and as shown in Table 7 below, the weight average molecular weight Mw is 15.1 million and the number average molecular weight Mn is 490,000, the molecular weight distribution Mw / Mn is 3.1, the content of the linking group is 1.0 mol% in the formula (2), 0.3 mol% in the formula (3), and 0.3 mol% in the formula (4). It was 2 mol%, 0.5 mol% in the formula (5), and 2.0 mol% in total.
- Example 41 Preparation of modified polymer blend 1
- the natural rubber latex and styrene butadiene rubber latex used in Example 39 were separately mixed after the oxidative decomposition reaction and the recombination reaction.
- periodic acid was added to natural rubber latex and styrene butadiene rubber latex, respectively, to conduct an oxidative decomposition reaction.
- 0.05 g of pyrrolidine-2-carboxylic acid is added to each of the natural rubber latex and the styrene butadiene rubber latex, 1N sodium hydroxide is added so that the pH of the reaction solution becomes 8, and the mixture is stirred at 23 ° C. for 24 hours. And recombined with each other.
- the natural rubber after recombination had a weight average molecular weight Mw of 1.85 million, a number average molecular weight Mn of 498,000 and a molecular weight distribution Mw / Mn of 3.71.
- the styrene-butadiene rubber after recombination had a weight average molecular weight Mw of 490,000, a number average molecular weight Mn of 279,000, and a molecular weight distribution Mw / Mn of 1.73.
- both latexes were mixed so that the mass ratio of the polymer was 1: 1, precipitated in methanol, washed with water, and then dried at 30 ° C. for 24 hours with a hot air circulating dryer. Polymer blend 1 was obtained.
- the formula (2) was 1.0 mol%
- the formula (3) was 0.3 mol%
- the formula (4) was 0.3 mol%.
- the formula (5) was 0.6 mol%, and the total amount was 2.2 mol%.
- Example 42 Synthesis of modified polymer P
- the polymer mass ratio when mixing the natural rubber latex and the styrene butadiene rubber latex was 2: 1, and the others were the same as in Example 39 to obtain a modified polymer P solid at room temperature.
- Example 43 Synthesis of modified polymer Q
- the polymer mass ratio when the natural rubber latex and the styrene butadiene rubber latex were mixed after the oxidative degradation reaction was 2: 1, and the others were the same as in Example 40 to obtain a modified polymer Q solid at room temperature.
- Example 44 Preparation of modified polymer blend 2 A modified polymer blend 2 was obtained in the same manner as in Example 41 except that the polymer mass ratio when the natural rubber latex and the styrene butadiene rubber latex were mixed after the recombination reaction was 2: 1. The content of each linking group in the modified polymer blend 2 obtained is as shown in Table 7.
- Example 45 Synthesis of modified polymer R
- the amount of periodic acid added during the oxidative decomposition reaction, the pH adjuster and pH added during the recombination reaction were changed as shown in Table 7, and the others were modified in a solid state at room temperature in the same manner as in Example 39. Polymer R was obtained.
- Example 46 Synthesis of modified polymer S
- the amount of periodic acid added during the oxidative decomposition reaction, the pH adjuster and pH added during the recombination reaction were changed as shown in Table 7, and the others were modified in a solid state at room temperature in the same manner as in Example 40. Polymer S was obtained.
- Example 47 Preparation of modified polymer blend 3
- the amount of periodic acid added during the oxidative decomposition reaction, the pH adjuster and the pH added during the recombination reaction were changed as shown in Table 7, and the others were modified in a solid state at room temperature in the same manner as in Example 41.
- Polymer blend 3 was obtained.
- the content of each linking group in the modified polymer blend 3 obtained is as shown in Table 7.
- the modified polymers P, Q, R and S like the modified polymer N, have a linking group represented by the above formulas (2) to (5) in the molecule, and are polyisoprene represented by the formula (8).
- Examples 48 to 56 and Comparative Examples 19 to 21 Rubber compositions
- Each rubber composition obtained was vulcanized at 160 ° C. for 20 minutes to prepare a test piece having a predetermined shape, and the obtained test piece was used to obtain dynamic viscoelasticity in the same manner as in the first example.
- a test was conducted to evaluate wet skid performance (tan ⁇ (0 ° C.)) and low fuel consumption performance (tan ⁇ (60 ° C.)), and a tensile test was conducted to evaluate the elastic modulus M300 and tensile strength.
- the measured values in each evaluation method are shown as indices in Table 8 with the value of Comparative Example 19, Table 9 with the value of Comparative Example 20, and Table 10 with the value of Comparative Example 21.
- Examples 48, 51, and 54 are obtained by blending modified polymers obtained by recombining natural rubber and styrene butadiene rubber after oxidative cleavage, and each modified polymer is the above-described one. It has a linking group represented by formulas (2) to (5). Therefore, compared with Comparative Examples 19 to 21 using a blend of unmodified rubbers having no linking group, the fuel economy and wet skid performance were excellent.
- Examples 49, 50, 52, 53, 55 and 56 a modified diene rubber having such a linking group and having a different diene polymer chain recombined by a main chain exchange reaction was used.
- the modified polymer according to the present invention can be used as a polymer component to be blended in various polymer compositions including a rubber composition.
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Abstract
Description
ゲルパーミエーションクロマトグラフィ(GPC)での測定により、ポリスチレン換算のMn、Mw及びMw/Mnを求めた。詳細には、測定試料は0.2mgをTHF1mLに溶解させたものを用いた。(株)島津製作所製「LC-20DA」を使用し、試料をフィルター透過後、温度40℃、流量0.7mL/分でカラム(Polymer Laboratories社製「PL Gel3μm Guard×2」)を通し、Spectra System社製「RI Detector」で検出した。
NMRにより、連結基の含有率を測定した。NMRスペクトルは、BRUKER社製「400ULTRASHIELDTM PLUS」によりTMSを標準とし測定した。ポリマー1gを重クロロホルム5mLに溶解し、緩和試薬としてアセチルアセトンクロム塩87mgを加え、NMR10mm管にて測定した。
東亜ディ-ケーケー(株)製のポータブルpH計「HM-30P型」を用いて測定した。
[実施例1:変性ポリマーAの合成]
変性対象のポリマーとして、天然ゴムラテックス(レヂテックス社製「LA-NR」、DRC(Dry Rubber Content)=60質量%)を用いた。この天然ゴムラテックスに含まれる未変性の天然ゴムについて、分子量を測定したところ、重量平均分子量が151万、数平均分子量が26.9万、分子量分布が5.6であった。
酸化分解時の反応時間、過ヨウ素酸の添加量、再結合反応時に添加するpH調整剤及びpH、触媒の量を下記表1に示す通りに変更し、その他は実施例1と同様にして、固形状の変性ポリマーB~Dを合成した。得られた変性ポリマーB~DのMw,Mn,Mw/Mn及び各連結基の含有量は表1に示す通りであった。変性ポリマーB~Dについても、官能基を持つ上記連結基が主鎖中に導入され、また、分子量分布が未変性天然ゴムよりも小さく、均一性に優れていた。また、上記条件を変更することにより、分子量を制御することができた。
変性対象のポリマーとして、スチレンブタジエンゴムラテックス(日本ゼオン(株)製「SBRラテックスLX110、DRC=50質量%)を用いた。このゴムラテックスに含まれる未変性のスチレンブタジエンゴムについて、分子量を測定したところ、重量平均分子量が68万、数平均分子量が32.4万、分子量分布が2.1であった。このスチレンブタジエンゴムラテックスを用い、表1に記載した条件に従って、その他は実施例1と同様にして、固形状の変性ポリマーE~Hを合成した。得られた変性ポリマーE~HのMw,Mn,Mw/Mn及び各連結基の含有量は表1に示す通りであった。変性ポリマーE~Hでは、連結基として式(4)及び(5)のみが導入された。また、変性ポリマーE~Hについても、分子量分布が未変性のスチレンブタジエンゴムよりも小さく、均一性に優れていた。また、条件を変更することにより、分子量を制御することができた。
変性対象のポリマーとして、合成イソプレンゴムラテックス(住友精化(株)製「セポレックスIR-100」、DRC=65質量%)を用いた。このゴムラテックスに含まれる未変性の合成イソプレンゴムについて、分子量を測定したところ、重量平均分子量が8.3万、数平均分子量が6.6万、分子量分布が1.3であった。この合成イソプレンゴムラテックスを用い、表1に記載した条件に従って、その他は実施例1と同様にして、固形状の変性ポリマーI~Mを合成した。得られた変性ポリマーI~MのMw,Mn,Mw/Mn及び各連結基の含有量は表1に示す通りであった。変性ポリマーI~Mについても、官能基を持つ連結基を主鎖中に簡単に導入することができた。また、条件を変更することにより、分子量を制御することができた。
上記で合成した変性ポリマーA,B,E,Fを、変性ジエン系ゴムとして用いてゴム組成物の評価を行った。詳細には、バンバリーミキサーを使用し、下記表2~6に示す配合(質量部)に従って、まず、第一混合段階で、ゴム成分に対し硫黄及び加硫促進剤を除く他の配合剤を添加し混練し(排出温度=160℃)、次いで、得られた混練物に、最終混合段階で、硫黄と加硫促進剤を添加し混練して(排出温度=90℃)、ゴム組成物を調製した。ゴム成分を除く、表2~6中の各成分の詳細は、以下の通りである。
・カーボンブラック:東海カーボン(株)製「シースト3」
・シランカップリング剤:ビス(3-トリエトキシシリルプロピル)テトラスルフィド、エボニック・デグサ社製「Si69」
・亜鉛華:三井金属鉱業(株)製「亜鉛華1種」
・老化防止剤:大内新興化学工業(株)製「ノクラック6C」
・ステアリン酸:花王(株)製「ルナックS-20」
・プロセスオイル:株式会社ジャパンエナジー製「X-140」
・硫黄:細井化学工業(株)製「ゴム用粉末硫黄150メッシュ」
・加硫促進剤:大内新興化学工業(株)製「ノクセラーCZ」
[実施例39:変性ポリマーNの合成]
変性対象のポリマーとして、天然ゴムラテックス(レヂテックス社製「HA-NR」、DRC=60質量%)と、実施例5で用いたスチレンブタジエンゴムラテックス(日本ゼオン(株)製「SBRラテックスLX110、DRC=50質量%)を用いた。天然ゴムラテックスに含まれる未変性の天然ゴムについて、分子量を測定したところ、重量平均分子量が202万、数平均分子量が51万、分子量分布が4.0であった。
実施例39で用いた天然ゴムラテックスとスチレンブタジエンゴムラテックスを、それぞれ別々に酸化分解反応を行った後、混合して再結合反応を行った。詳細には、天然ゴムラテックス中のポリマー質量50gに対して、過ヨウ素酸1.65gを加え、23℃で3時間攪拌した。得られた分解ポリマーは、重量平均分子量が13500、数平均分子量が5300、分子量分布が2.6であり、また分解後の反応液のpHは6.4であった。また、スチレンブタジエンゴムラテックス中のポリマー質量50gに対して、過ヨウ素酸1.65gを加え、23℃で3時間攪拌した。得られた分解ポリマーは、重量平均分子量が3630、数平均分子量が2400、分子量分布が1.5であり、また分解後の反応液のpHは6.1であった。
実施例39で用いた天然ゴムラテックスとスチレンブタジエンゴムラテックスを、ポリマー質量比が1:1となるように混合した後、混合液をメタノール中に沈殿させ、水で洗浄後、熱風循環乾燥機により30℃で24時間乾燥させて、未変性ポリマーブレンド1を得た。
実施例39で用いた天然ゴムラテックスとスチレンブタジエンゴムラテックスを、それぞれ別々に酸化分解反応及び再結合反応を行った後に混合した。詳細には、実施例40と同様に、天然ゴムラテックスとスチレンブタジエンゴムラテックスにそれぞれ過ヨウ素酸を加えて酸化分解反応を行った。その後、天然ゴムラテックスとスチレンブタジエンゴムラテックスのそれぞれに、ピロリジン-2-カルボン酸0.05g加え、1規定の水酸化ナトリウムを反応液のpHが8になるように加え、23℃で24時間攪拌してそれぞれ再結合反応させた。再結合後の天然ゴムは、重量平均分子量Mwが185万、数平均分子量Mnが49.8万、分子量分布Mw/Mnが3.71であった。再結合後のスチレンブタジエンゴムは、重量平均分子量Mwが49万、数平均分子量Mnが27.9万、分子量分布Mw/Mnが1.73であった。再結合反応後、両ラテックスをポリマー質量比が1:1となるように混合してから、メタノール中に沈殿させ、水で洗浄後、熱風循環乾燥機により30℃で24時間乾燥させて、変性ポリマーブレンド1を得た。
天然ゴムラテックスとスチレンブタジエンゴムラテックスを混合する際のポリマー質量比を2:1とし、その他は実施例39と同様にして、常温で固形状の変性ポリマーPを得た。
酸化分解反応後に天然ゴムラテックスとスチレンブタジエンゴムラテックスを混合する際のポリマー質量比を2:1とし、その他は実施例40と同様にして、常温で固形状の変性ポリマーQを得た。
天然ゴムラテックスとスチレンブタジエンゴムラテックスを混合する際のポリマー質量比を2:1とし、その他は比較例17と同様にして、未変性ポリマーブレンド2を得た。
再結合反応後に天然ゴムラテックスとスチレンブタジエンゴムラテックスを混合する際のポリマー質量比を2:1とし、その他は実施例41と同様にして、変性ポリマーブレンド2を得た。得られた変性ポリマーブレンド2についての各連結基の含有率は表7に示す通りである。
酸化分解反応時の過ヨウ素酸の添加量、再結合反応時に添加するpH調整剤及びpHを、表7に示す通りに変更し、その他は実施例39と同様にして、常温で固形状の変性ポリマーRを得た。
酸化分解反応時の過ヨウ素酸の添加量、再結合反応時に添加するpH調整剤及びpHを、表7に示す通りに変更し、その他は実施例40と同様にして、常温で固形状の変性ポリマーSを得た。
酸化分解反応時の過ヨウ素酸の添加量、再結合反応時に添加するpH調整剤及びpHを、表7に示す通りに変更し、その他は実施例41と同様にして、常温で固形状の変性ポリマーブレンド3を得た。得られた変性ポリマーブレンド3についての各連結基の含有率は表7に示す通りである。
バンバリーミキサーを使用し、下記表8~表10に示す配合(質量部)に従って、まず、第一混合段階で、ゴム成分に対し硫黄及び加硫促進剤を除く他の配合剤を添加し混練し、次いで、得られた混練物に、最終混合段階で、硫黄と加硫促進剤を添加し混練して、ゴム組成物を調製した。ゴム成分を除く、表8~表10中の各成分の詳細は、上記第1実施例と同じである。
Claims (20)
- 炭素-炭素二重結合を主鎖に持つポリマーを、前記炭素-炭素二重結合を酸化開裂させることで分解して分子量を低下させ、
分解したポリマーを含む系を、酸性の場合は塩基性に、塩基性の場合は酸性になるように酸塩基性を変化させることにより、前記分解したポリマーのポリマー鎖を結合させて、構造を変化させた変性ポリマーを得る、
変性ポリマーの製造方法。 - 炭素-炭素二重結合を主鎖に持つ分解前の前記ポリマーは数平均分子量が6万以上であり、かつ結合後の前記変性ポリマーは数平均分子量が6万以上である、
請求項1記載の変性ポリマーの製造方法。 - 炭素-炭素二重結合を主鎖に持つ2種以上のポリマーを、前記酸化開裂により分解して分子量を低下させる、
請求項1又は2記載の変性ポリマーの製造方法。 - 前記変性ポリマーが、前記2種以上のポリマー由来のポリマー鎖を含む複合化ポリマーである、
請求項3記載の変性ポリマーの製造方法。 - 前記炭素-炭素二重結合を、過ヨウ素酸を用いて酸化開裂させる、
請求項1~6のいずれか1項に記載の変性ポリマーの製造方法。 - 反応系が水系エマルションである、
請求項1~7のいずれか1項に記載の変性ポリマーの製造方法。 - 炭素-炭素二重結合を主鎖に持つ前記ポリマーがジエン系ゴムポリマーである、
請求項1~8のいずれか1項に記載の変性ポリマーの製造方法。 - 前記ジエン系ゴムポリマーが、スチレンブタジエンゴム、天然ゴム及び合成イソプレンゴムからなる群から選択される少なくとも1種である、
請求項9記載の変性ポリマーの製造方法。 - 請求項1~10のいずれか1項に記載の製造方法により得られた変性ポリマー。
- 異種のジエン系ポリマー鎖が前記連結基を介して連結された構造を持つ、
請求項12記載のジエン系ポリマー。 - 前記ポリイソプレン鎖と前記ランダム共重合体鎖と前記ポリブタジエン鎖からなる群から選択される少なくとも2種が前記連結基を介して連結された構造を持つ、
請求項16記載のジエン系ポリマー。 - 請求項12~17のいずれか1項に記載のジエン系ポリマーを含むゴム成分100質量部に対し、フィラーを5~150質量部含有する、ゴム組成物。
- 請求項18記載のゴム組成物を用いてなる空気入りタイヤ。
- 請求項18記載のゴム組成物をトレッドに用いてなる空気入りタイヤ。
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FR3015487A1 (fr) * | 2013-12-23 | 2015-06-26 | Michelin & Cie | Procede de depolymerisation controlee d'un caoutchouc synthetique en solution par metathese |
FR3015486A1 (fr) * | 2013-12-23 | 2015-06-26 | Michelin & Cie | Procede de depolymerisation du caoutchouc naturel en solution par metathese |
FR3015485A1 (fr) * | 2013-12-23 | 2015-06-26 | Michelin & Cie | Procede de depolymerisation controlee du caoutchouc naturel par metathese a partir d'un latex de caoutchouc naturel |
JP2016060807A (ja) * | 2014-09-17 | 2016-04-25 | 東洋ゴム工業株式会社 | 変性ジエン系ゴムの製造方法、並びにそれを用いたゴム組成物及び空気入りタイヤ |
JP7365852B2 (ja) | 2019-10-24 | 2023-10-20 | Toyo Tire株式会社 | 末端変性ジエン系ポリマー、及びその製造方法 |
CN113801382A (zh) * | 2021-10-15 | 2021-12-17 | 中国科学技术大学 | 一种高性能橡胶组合物及其制备方法 |
CN113801382B (zh) * | 2021-10-15 | 2022-05-13 | 中国科学技术大学 | 一种高性能橡胶组合物及其制备方法 |
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DE112013000646B4 (de) | 2022-01-05 |
CN104105719B (zh) | 2017-05-24 |
DE112013000646T5 (de) | 2015-04-16 |
US9365656B2 (en) | 2016-06-14 |
US20140364536A1 (en) | 2014-12-11 |
CN104105719A (zh) | 2014-10-15 |
CN106146690A (zh) | 2016-11-23 |
CN106146690B (zh) | 2018-10-02 |
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