JP2012097271A - Functionalized high cis-1,4-polybutadiene prepared using novel functionalizing agent - Google Patents

Abstract

Provided is a functionalized polymer that reacts with a polymer formed using a coordination catalyst and has a high cis microstructure and exhibits affinity for carbon black and silica.
A pseudo-living polymer is produced by polymerizing a conjugated monomer using a lanthanide-based catalyst, and the pseudo-living polymer is represented by the formula AR ¹ -Z [wherein R ¹ Is a divalent organic group having from 0 to about 20 carbon atoms, A is a substituent that will undergo an addition reaction with the pseudo-living polymer, and Z is a silica or reinforcing filler Is a substituent that will react or interact with carbon black, provided that A, R ¹ and Z are substituents that will not protonate the pseudo-living polymer]. A functionalized polymer produced using a method comprising the step of reacting with a functionalizing agent.
[Selection figure] None

Description

(Field of Invention)
The present invention relates to functionalizing agents, functionalized polymers prepared by contacting at least one functionalizing agent with a pseudo-living polymer, and such polymers. It relates to a functionalization method. The functionalizing agent generally has the formula A—R ¹ —Z, wherein A is a substituent that will undergo an addition reaction with the pseudo-living polymer, R ¹ is a divalent organic group, and Z is Are substituents that will react or interact with organic or inorganic fillers.

(Background of the Invention)
Conjugated diene polymers are commonly used in the rubber industry. Such polymers are often prepared using coordination catalyst technology because the microstructure of the resulting polymer can be controlled. When a coordination catalyst system containing a nickel, cobalt or titanium compound, an alkylating agent and a halogen source is used, polybutadiene having a 1,4-cis form of more than 90 percent of the units can be produced. A polymer having such a fine structure has a low glass transition temperature (T _g ) and thus has good low temperature characteristics. High 1,4-cis polymers also exhibit excellent wear resistance and mechanical properties, such as low cut growth.

  Designing tires that exhibit improved rolling resistance (which contributes to better fuel efficiency) has been a challenge for the tire industry. Attempts to improve rolling resistance have included designing alternative tires and using rubbers with lower hysteresis losses. There is also a tendency to use silica as a reinforcing filler. Polymers that interact with tire reinforcement fillers have been shown to exhibit low hysteresis loss.

  It has been demonstrated that it is lower than the hysteresis loss exhibited by functionalized polymers made using anionic polymerization techniques. Their functionalization can take place both at the start and at the termination. Initiating the polymerization of 1,3-butadiene using a functionalization initiator to produce polybutadiene results in a polymer that has a high affinity for carbon black or silica filler. Terminating an anionically polymerized polymer with functionalized terminators also provides a polymer with high affinity for carbon black or silica filler. Unfortunately, anionic polymerization does not provide a high 1,4-cis polymer because the microstructure of the polymer cannot be strictly controlled.

  Since coordination catalysis involves the interaction of several chemical components and also functions in a chemical mechanism that often involves a self-stopping reaction, its ability to functionalize the resulting polymer is limited. As a result, it is difficult to obtain the reaction conditions necessary to achieve functionalization.

  Terminators such as organometallic halides, heterocumulene compounds, three-membered heterocyclic compounds and other specific halogen-containing compounds may be obtained from polymers formed using lanthanide-based catalyst systems. Will react. However, as a result, the functionalized polymer does not exhibit an effective and sufficient affinity for the filler silica or carbon black.

  European Patent Application Publication No. 0 713 885 relates to a modified polymer produced by subjecting a conjugated diene polymer obtained by polymerization using a lanthanoid-containing catalyst to terminal modification with an N-substituted amino active compound in an organic solvent, This indicates a Mw of 100,000-1,000,000, a peak Mw distribution, a Mw / Mn of 1.3-5 and a terminal modification of at least 50%. The production of this modified polymer consists of (1) (i) a product formed by reacting a lanthanoid-containing compound with organoaluminum hydride and then a Lewis base and (ii) a mixture of halo compounds or (ii). The conjugated diene is polymerized using a catalyst that is either a reaction product of (i) and (ii) produced by reacting a portion of the conjugated diene monomer prior to reaction and then (2 ) The resulting living polymer is end-modified with an N-substituted amino active compound.

  European Patent Application No. 0 957 115 relates to a process for producing a conjugated diene polymer, which is obtained by reacting a compound containing a rare earth element with an atomic number of 57-71 in the periodic table or a reaction of said compound with a Lewis base. Polymerizing one or more conjugated diene compounds with a catalyst consisting essentially of: an aluminoxane; an organoaluminum compound; and a reaction product of a metal halide and a Lewis base.

EP-A-0 920 886 relates to rubber compositions, which
(A) 50 polybutadiene rubber having a 1,4-cis bond content of 80% or more, a 1,2-vinyl bond content of 2.0% or less and a ratio of the weight average molecular weight to the number average molecular weight of 3.5 or less. To 100 parts by weight,
(B) 0 to 50 parts by weight of diene rubber other than component (a),
(C) 10 to 50 parts by weight of a crosslinking monomer,
(D) 20 to 80 parts by weight of inorganic filler, and (e) an effective amount of organic peroxide,
Comprising.

  Therefore, in the present technical field, a functionalized polymer having a high cis microstructure and reacting with a polymer formed using a coordination catalyst and having an affinity for carbon black and silica is obtained. There is a need to provide functionalizing agents that provide.

(Summary of the Invention)
The present invention generally provides a functionalized polymer in which a pseudo-living polymer is formed by polymerizing a conjugated monomer using a lanthanide-based catalyst and the pseudo-polymer is formed. Living polymer is represented by the formula (I)

Wherein R ¹ is a divalent bond or divalent organic group having from 0 to about 20 carbon atoms, A is a substituent that will undergo an addition reaction with the pseudo-living polymer, and Z Is a substituent that will react or interact with the reinforcing filler silica or carbon black, provided that A, R ¹ and Z do not protonate the pseudo-living polymer. As long as they are substituents]
Prepared using a process comprising the step of reacting with a functionalizing agent as defined above.

  The present invention also includes a process for producing a functionalized polymer, wherein the process comprises producing a pseudo-living polymer by polymerizing a conjugated diene monomer using a lanthanide-based catalyst and said pseudo-living polymer. The polymer is represented by the formula (I)

Wherein R ¹ is a divalent bond or divalent organic group having from 0 to about 20 carbon atoms, A is a substituent that will undergo an addition reaction with the pseudo-living polymer, and Z Is a substituent that will react or interact with the reinforcing filler silica or carbon black, provided that A, R ¹ and Z are substituents that will not protonate the pseudo-living polymer. On condition that]
Reacting with at least one functionalizing agent as defined by

  The present invention further includes a vulcanizable composition, which produces a pseudo-living polymer by polymerizing a conjugated monomer using a lanthanide-based catalyst and formulates said pseudo-living polymer. (I)

Wherein A is a substituent that will undergo an addition reaction with the pseudo-living polymer, R ¹ is a divalent bond or a divalent organic group, and Z is a silica that is a reinforcing filler. Or a substituent that will react or interact with carbon black, provided that A, R ¹ and Z are substituents that will not protonate the pseudo-living polymer.]
A functionalized polymer produced by a process comprising the step of reacting with a functionalizing agent as defined by (the cis microstructure of the polymer is greater than about 90% and 1,2- or 3,4- Comprising a rubber component and a reinforcing filler (including inorganic filler) comprising a unit content of less than about 2% and a molecular weight distribution of less than about 4.

  The functionalizing agent of the present invention advantageously reacts with the pseudo-living polymer to produce a terminally functionalized polymer, but does not protonate the pseudo-living polymer. In particular, such reactivity produces a functionalized pseudo-living polymer by a process comprising contacting one or more functionalizing agents (including mixtures thereof) with the pseudo-living polymer. Is possible. Furthermore, the functionalized polymer so produced contains substituents that will react or interact with the filler, thereby reducing hysteresis losses. Moreover, the method of the present invention can be used to functionalize high cis 1,4-polymers, resulting in functionalized polymers that exhibit low glass transition temperatures and good low temperature properties. In addition, the functionalized polymers of the present invention can be advantageously used in the manufacture of various tire components including, but not limited to, tire treads, sidewalls, subtreads and beads. Filler is included.

(Detailed description of explanatory aspects)
The polymer to be functionalized is prepared using a coordination catalyst system based on lanthanides. Such polymers preferably have about 85% or more of the polymer having a cis microstructure, the polymer has less than about 3% of 1, 2 or 3, 4 microstructure and The molecular weight distribution of the polymer is less than about 4. Since it has been confirmed that the living properties of such polymers are to some extent, they can be referred to as pseudo-living polymers within the scope of this specification.

The present invention is not limited to the functionalization of polymers produced using specific catalysts based on lanthanides. One useful catalyst is a catalyst containing a lanthanide compound, an alkylating agent, and a halogen source. Such lanthanide compounds may include neodymium (Nd) carboxylates (including neodecanoic acid Nd). Such lanthanide compounds may also include reaction products of Nd carboxylates and Lewis bases such as acetylacetone. The alkylating agent is generally of the formula AlR ₃ wherein each R may be the same or different and is hydrogen, a hydrocarbyl group or an alkylaluminoxy group, provided that at least one R is a hydrocarbyl group. Can be defined in the above. Examples of such alkylating agents include, but are not limited to, trialkylaluminums, dialkylaluminum hydrides, alkylaluminum dihydrides, and mixtures thereof. Examples of alkylating agents where R is an alkylaluminoxy group include methylaluminoxanes. The halogen source can include an organoaluminum chloride compound. In general, catalyst systems containing a lanthanide compound and an alkylating agent definable by the formula AlR ₃ are described in US Pat. Nos. 3,297,667, 3,541,063, and 3,794,604, which are incorporated by reference. (Incorporated herein).

  Certain particularly suitable catalysts include (a) the reaction product of Nd carboxylate and acetylacetone, (b) triisobutylaluminum, diisobutylaluminum hydride, isobutylaluminum dihydride or mixtures thereof and (c) diethyl. A catalyst containing aluminum chloride, ethylaluminum dichloride or a mixture thereof. This catalyst system is disclosed in US Pat. No. 4,461,883, which is incorporated herein by reference. Another suitable catalyst is (a) neodecanoic acid Nd and (b) triisobutylaluminum, diisobutylaluminum hydride, isobutylaluminum dihydride or mixtures thereof and (c) diethylaluminum chloride, ethylaluminum dichloride or mixtures thereof. It is a catalyst containing. This catalyst system is disclosed in Canadian Patent 1,223,396 (incorporated herein by reference).

  Typically, about 0.0001 to about 1.0 mmol of lanthanide metal is used per 100 grams of monomer. More preferably, the lanthanide metal is used from about 0.001 to about 0.75, and even more preferably from about 0.005 to about 0.5 millimoles per 100 grams of monomer. The ratio of alkylating agent to lanthanide metal is from about 1: 1 to about 1: 500, more preferably from about 3: 1 to about 250: 1, and even more preferably from about 5: 1 to about 200: 1. The ratio of halogen source to lanthanide metal is about 0.1: 1 to about 30: 1, more preferably about 0.2: 1 to about 15: 1, and even more preferably about 1: 1 to about 10: 1. It is.

Monomers to be polymerized using such lanthanide-based catalysts are conjugated diene monomers such as, but not limited to, 1,3-butadiene, Isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and myrcene are included. 1,3-butadiene is most preferred. Such conjugated dienes can be used either alone or in combination. If desired, small amounts of monomers other than conjugated dienes can be added. Such other monomers include, but are not limited to, aromatic vinyl compounds such as styrene. The amount of such copolymerizable monomer is not limited, but is usually less than 10 weight percent (pbw) of the total polymer, preferably less than 5 pbw, and even more preferably less than about 3 pbw.

  Useful functionalizing agents include those of formula (I)

[Wherein A is a substituent that will undergo an addition reaction with the pseudo-living polymer, R ¹ is a divalent bond or a divalent organic group, and Z reacts with an organic or inorganic filler. Or a substituent that will interact, provided that A, R ¹ and Z are substituents that will not protonate the pseudo-living polymer.]
Includes the functionalizing agents generally defined by: A substituent that will not protonate the pseudo-living polymer refers to a substituent that will not donate protons to the polymer in a protolysis reaction.

  Substituents that will undergo an addition reaction with the pseudo-living polymer and are therefore useful as substituent A in the above formula include ketone, aldehyde, amide, ester and imidazolidinone groups, isocyanate and isothiocyanate groups. The amide group includes an isocyanurate group.

  Substituents that will react or interact with organic or inorganic fillers and are therefore useful as substituent Z in the above formula include N, N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate And amide groups.

  Divalent organic groups include hydrocarbylene groups containing from 0 to about 20 carbon atoms. More preferably, such hydrocarbylene groups contain about 1 to about 10 carbon atoms, and even more preferably about 2 to about 8 carbon atoms. When the number of carbon atoms contained in such a hydrocarbylene group is 0, the group simply represents a single bond between the group Z and the group A. Suitable hydrocarbylene groups include, but are not limited to, alkylene, cycloalkylene, substituted alkylene, substituted cycloalkylene, alkenylene, cycloalkenylene, substituted alkenylene, substituted cycloalkenylene, arylene, and substituted arylene. The term “substituted” refers to an organic group that replaces a hydrogen atom bonded to a carbon within the group, such as a hydrocarbyl group. Such hydrocarbylene groups can contain heteroatoms such as nitrogen (N), oxygen (O), sulfur (S), phosphorus (P), silicon (Si), and the like. A hydrocarbylene group containing O can be referred to as an oxo-hydrocarbylene group, or if it contains N, it can be referred to as an aza-hydrocarbyl-hydrocarbylene group.

  Some specific examples of hydrocarbylene groups include methylene, ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,4- (2-methyl) butylene, 1,5-pentylene. , Cyclopentylene and phenylene.

  An embodiment of the functionalizing agent in which A contains a ketone or aldehyde group has the formula (II)

[Wherein R ¹ and Z are as defined above, and R ² is a divalent organic group, or when R ² together with R ³ forms a cyclic group. Is a trivalent organic group and R ³ is a hydrogen atom or a monovalent organic group, or when R ³ is combined with R ² , R ³ is a divalent organic group. May be]
Can be defined.

  Monovalent organic groups include hydrocarbyl groups containing 1 to about 20 carbon atoms. Such groups more preferably contain from about 2 to about 10 carbon atoms, and even more preferably from about 3 to about 8 carbon atoms. Such hydrocarbyl groups include, but are not limited to, alkyl, cycloalkyl, substituted alkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, substituted cycloalkenyl, aryl, substituted aryl, allyl, aralkyl, alkenyl. Reel and alkynyl groups can be included, which can contain heteroatoms such as N, O, S, P and Si. If such a hydrocarbyl group contains O, it can be referred to as an oxo-hydrocarbyl group, or if it contains N, it can be referred to as an aza-hydrocarbyl-hydrocarbyl group.

  Specific examples of hydrocarbyl groups include methyl, ethyl, propyl, isopropyl, butyl, 2-methylbutyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, 2-ethylhexyl and 2-propylhexyl.

Substituent A when R ³ is an organic group contains a ketone group. Non-limiting examples of ketone groups include benzophenone and acetophenone. Non-limiting examples of ketone-containing functionalizing agents that can be defined by formula (II) include 4,4′-bis (N, N-dimethylamino) benzophenone, 4,4′-bis (N, N-diethylamino) benzophenone. 4- (N, N-dimethylamino) benzophenone, 4- (N, N-diethylamino) benzophenone, (4-N, N-dimethylaminophenyl) methyl ethyl ketone, 4,4′-bis (1-hexamethyleneiminomethyl) ) Benzophenone, 4,4′-bis (1-pyrrolidinomethyl) benzophenone, 4- (1-hexamethyleneiminomethyl) benzophenone, 4- (1-pyrrolidinomethyl) benzophenone and (4- (1-hexamethyleneimino) ) Phenyl) methyl ethyl ketone.

Substituent A when R ³ is a hydrogen atom contains an aldehyde group. Non-limiting examples of reactive aldehyde groups include benzaldehyde groups. Non-limiting examples of aldehyde-containing functionalizing agents include 4- (N, N-dimethylamino) benzaldehyde, 4- (N, N-diethylamino) benzaldehyde, 4- (1-hexamethyleneiminomethyl) benzaldehyde and 4- ( 1-pyrrolidinomethyl) benzaldehyde is included.

Certain particularly preferred ketone-containing functionalizing agents include compounds where Z is an N, N-disubstituted aminophenyl group. Such functionalizing agents are surprisingly based on lanthanides using alkylating agents trialkylaluminum, dialkylaluminum hydride, alkylaluminum hydride or alkylaluminoxane or any combination thereof and a halide source. It has been found to be extremely useful for the functionalization of pseudo-living polymers produced using different catalyst systems. This discovery is advantageous because such pseudo-living polymers can be produced in the absence of phosphorus-containing compounds and the catalyst does not need to be prepared in a special way.

  Certain aldehyde-containing functionalizing agents that are particularly suitable include compounds where Z is an N, N-disubstituted aminophenyl group. Such functionalizing agents are surprisingly produced using lanthanide-based catalyst systems using trialkylaluminum, dialkylaluminum hydride or alkylaluminum hydride or any combination thereof and a halide source. It has been found to be extremely useful for use in the functionalization of pseudo-living polymers. This discovery shows that such pseudo-living polymers can be produced in the absence of phosphorus-containing compounds and in the absence of alkylaluminoxane compounds (which are expensive) and the catalyst is prepared in a particularly specialized manner. This is advantageous because there is no need to do so.

  Another embodiment of the functionalizing agent wherein A contains an ester group is of formula (III) and (IV)

Wherein R ¹ , R ² and Z are as defined above, and R ⁴ is a monovalent organic group, or R ² or R ¹ together with R ⁴ In the case of forming a cyclic group, R ⁴ may be a divalent organic group and R ² may be a trivalent organic group]
Can be defined.

  Non-limiting examples of ester groups include α, β-unsaturated esters, methacrylic acid esters and acrylic acid esters.

  Suitable ester-containing compounds include groups that can interact with the filler, ie Z, which include N, N-disubstituted aminophenyl, imine, cyclic amino, isocyanate, isothiocyanate and amide groups. Non-limiting examples of such ester-containing functionalizing agents include t-butyl 4- (N, N-dimethylamino) benzoate, t-butyl 4- (N, N-diethylamino) benzoate, bis (maleate) ( 4- (N, N-diethylamino) benzyl, t-butyl 4- (1-hexamethyleneiminomethyl) benzoate, bis (4- (1-hexamethyleneiminomethyl) benzyl) maleate, 4-isocyanatobenzoic acid t -Butyl and bis (4-isocyanatobenzyl) maleate are included.

  Another embodiment of the functionalizing agent wherein A contains an isocyanate or isothiocyanate group is of the formula (V)

[Wherein R ¹ , R ² and Z are as defined above and E is O or S]
Can be defined.

  Non-limiting examples of isocyanate groups include (2-isocyanato) ethyl, (3-isocyanato) propyl, (4-isocyanato) butyl and (5-isocyanato) pentyl. Examples of isothiocyanate groups include isothiocyanate equivalents of the groups shown above.

  Suitable isocyanate or isothiocyanate containing groups include groups capable of interacting with the filler, ie Z, which include N, N-disubstituted aminophenyl, cyclic amino, imine and amide groups. Non-limiting examples of isocyanate-containing functionalizing agents that can be defined by formula (V) include 4- (N, N-diethylamino) phenyl-4'-isocyanatophenylmethane.

  Another embodiment of the functionalizing agent of the invention wherein A contains an amide group is represented by formulas (VI) and (VII)

[Wherein R ¹ , R ² , Z and each R ⁴ may be the same or different and are as defined above and R ² together with any R ⁴ or May be formed by combining two R ⁴ groups together]
Can be defined. In the above formulas and any other formulas shown herein, the R group is defined by the type of group that it may contain. It should be understood that whenever two or more R groups of the same general type, ie R ⁴ , appear in the formula, these R groups may be the same or different within the scope of these general definitions. It is.

  Non-limiting examples of reactive amide groups include N-alkyl isocyanurate, 3- (N, N-dialkylamido) propyl, isocyanuric acid trihydrocarbyl, 3- (N, N-dihydrocarbylamido) alkyl, N- Hydrocarbyl caprolactam and N-hydrocarbyl pyrrolidone groups are included.

  Certain particularly preferred amide-containing functionalizing agents include compounds where Z is an amide. Such functionalizing agents are surprisingly based on lanthanides using alkylating agents trialkylaluminum, dialkylaluminum hydride, alkylaluminum hydride or alkylaluminoxane or any combination thereof and a halide source. It has been found to be very useful for the functionalization of pseudo-living polymers produced using a catalyst system. This discovery is advantageous because such pseudo-living polymers can be produced in the absence of phosphorus-containing compounds and the catalyst does not need to be prepared in a special way.

  Some specific non-limiting examples of amide-containing functionalizing agents that can be defined by formula (VI) or (VII) include N-methylpyrrolidone, N-ethylpyrrolidone and N ′, N-dimethylimidazolidinone (DMI). ) Is included.

  A functionalized polymer is formed by contacting one or more of the functionalizing agents (including mixtures thereof) with a pseudo-living polymer. If a solvent is used, it is preferred to use a solvent that can dissolve both the pseudo-living polymer and the functionalizing agent or suspend both of them. Such contact is preferably effected at a temperature below 160 ° C, more preferably at a temperature from about 20 ° C to about 100 ° C. Further, the reaction time is preferably from about 0.1 to about 10 hours, more preferably from about 0.2 to about 5 hours.

  The amount of functionalizing agent used can vary. The functionalizing agent is preferably used from about 0.01 to about 200 moles per mole of lanthanide, more preferably from about 0.1 to about 150 moles per mole of lanthanide.

  When the reaction between the pseudo-living polymer and the functionalizing agent is quenched, it is quenched using reactants such as, but not limited to, isopropyl alcohol, methanol and water. A stabilizer such as 2,6-di-t-butyl-4-methylphenol (BHT) can be added during or after quenching.

  However, prior to quenching the resulting polymer, certain reactive compounds can be added that impart additional functionality to the polymer. Such reactive compounds include compounds that will undergo an addition reaction with a metal alkoxide or metal amide. It is believed that the addition of a protic quenching agent removes the metal by a substitution reaction, thereby leaving a lanthanide or aluminum amino group at the end of the polymer chain. It is believed that the reaction between the metal amide and the metal amide reactive compound prior to quenching provides additional functionality.

  Any technique commonly used in the art can be used to recover the product polymer. For example, the polymer as a product can be solidified in a hindered solvent, such as isopropyl alcohol, and then dried in a hot air oven or a hot mill. Alternatively, it is possible to recover the polymer as a product, for example, by desolvation with steam followed by hot air drying or drying with a hot mill. Processing oil may be added before finishing.

  The resulting functionalized polymer has the formula (XV)

Where R ¹ and R ³ are as defined above, and A * is the residue of the imino moiety of the functionalizing agent that has undergone an addition reaction with the pseudo-living polymer. Possible, which is a polymer having a cis microstructure of about 85% or more, a 1,2- or 3,4-unit content of less than about 3% and a molecular weight distribution of less than about 5. . More preferably, such polymers have a cis microstructure of about 90% or greater, a 1,2- or 3,4-unit content of less than about 2% and a molecular weight distribution of less than about 4. is there.

  Polymers having alkoxysilane functionality can be coupled by condensation reactions. For example, the polymer represented by the formula (XV) undergoes condensation to produce the following formula (XVI)

[Wherein A *, R ¹ and R ⁴ are as defined above]
It is possible to produce a coupled polymer represented by:

References to such functionalized polymers also include their condensation products. If any R ⁴ is OR ⁵ , it can be coupled with another functionalized polymer as well. When the functionalized polymer in which Z is a silane group undergoes coupling, the cold flow resistance (cold flow resistance) of the polymer is preferably increased.
(Resistance) is improved.

  The functionalized polymers of the present invention can be advantageously used in the manufacture of a variety of tire components including, but not limited to, tire treads, sidewalls, subtreads and beads. Filler is included. These can be used as all or part of the elastic polymer component of the tire stock. In one embodiment, the functionalized polymer comprises about 10 weight percent (pbw) or more of the elastic polymer component of the tire stock, more preferably about 20 pbw or more, and even more preferably about 30 pbw or more. The addition of the functionalized polymer to the tire stock does not change the type or amount of other materials typically included in such vulcanizable compositions. Accordingly, the practice of the present invention is not limited to any particular vulcanizable composition or tire compounding stock.

  Tire stock typically includes an elastomeric polymer component that is mixed with a reinforcing filler and at least one vulcanizing agent. Often, accelerators, oils, waxes, fatty acids and processing aids are also included. Synthetic rubber-containing vulcanizable compositions typically include anti-degradants, processing oils, zinc oxide, optional tackifying resins, optional reinforcing resins, optional peptizers, and optional scorch inhibitors. (Scorch inhibiting agents).

  It is also possible to use the functionalized polymer of the present invention with other rubbers to produce an elastic polymer component of a tire stock. Such other rubbers may include natural rubber, synthetic rubber or both. Examples of synthetic rubbers include synthetic poly (isoprene), poly (styrene-co-butadiene), poly (butadiene), poly (styrene-co-butadiene-co-isoprene) and mixtures thereof.

Reinforcing fillers can include both organic and inorganic fillers. Organic fillers include, but are not limited to, carbon black, and inorganic fillers include, but are not limited to, silica, alumina, aluminum hydroxide, and magnesium hydroxide. The reinforcing filler is typically about 1 to about 100 parts by weight per 100 parts by weight of rubber (phr), preferably about 20 to about 80 parts by weight phr, based on the total weight of the reinforcing filler used. More preferably, it is used in an amount of about 40 to about 80 parts by weight phr. When using an inorganic filler, it is typically used with an organic filler. In such an embodiment, the total amount of reinforcing filler includes from about 30 to about 99 parts by weight inorganic filler and from 1 to about 70 parts by weight organic filler, based on 100 parts by weight of the total filler. More preferably, the entire filler includes from about 50 to about 95 parts by weight inorganic filler and from about 5 to about 50 parts by weight organic filler based on 100 parts by weight filler.

The carbon black can include any commercially available carbon black, but a carbon black with a surface area (EMSA) of at least 20 m ² / g, more preferably at least 35 m ² / g to 200 m ² / g or more is preferred. . Surface area values used in this application are those measured by ASTM test D-1765 using the cetyltrimethyl-ammonium bromide (CTAB) technique.

Silica (silicon dioxide) generally refers to wet-processed hydrated silica because they are produced by chemical reactions performed in water and precipitate it as ultrafine spherical particles. Such particles are strongly bonded to form a coagulum, which together form agglomerates together to a lesser degree. The surface area as measured by the BET method is the best measure of the various reinforcing properties of silica. Useful silica is silica having a surface area of preferably about 32 to about 400 m ² / g, preferably about 100 to about 250 m ² / g, more preferably about 150 to about 220 m ² / g. The pH of the silica filler is generally from 5.5 to about 7, preferably from about 5.5 to about 6.8. Commercially available silicas include Hi-Sil ™ 215, Hi-Sil ™ 233 and Hi-Sil ™ 190 [PPG Industries; Pittsburgh, PA]. A variety of useful commercial grade silicas are also available from other sources including Rhone Poulenc.

  When using silica, a coupling agent is typically added. One type of coupling agent commonly used is bis- [3 (triethoxysilyl) propyl] -tetrasulfide, which is commercially available under the trademark SI69 (Degussa, Inc .; New York, NY). is there. Additional coupling agents include bis (3- (triethoxysilyl) propyl) trisulfide, bis (3- (triethoxysilyl) propyl) disulfide, 3-mercaptopropyltriethoxysilane, bis (3- (trimethoxysilyl) ) Propyl) tetrasulfide, bis (3- (trimethoxysilyl) propyl) trisulfide, bis (3- (trimethoxysilyl) propyl) disulfide, 3-mercaptopropyltrimethoxysilane, 3- (trimethoxysilyl) propyl) Diethylthiocarbamyl tetrasulfide and 3- (trimethoxysilyl) propyl) benzothiazyl tetrasulfide may be included. Such agents are typically used in an amount of about 1 to about 20 phr, more preferably about 3 to about 15 phr. The use of a functionalized polymer of the present invention containing silane functionality advantageously reduces the amount of coupling agent required.

The reinforced rubber compound can be cured in a conventional manner using known vulcanizing agents. For example, a curing system based on sulfur or peroxide can be used. For general disclosure of suitable vulcanizing agents, Kirk-Othmer, ENCYCLOPEDIA OF
CHEMICAL TECHNOLOGY, 3rd edition, Wiley Interscience, N.C. Y. 1982, Volume 20, pages 365-468, especially VULCANIZATION
AGENTS AND AUXILIARY MATERIALS, pages 390-402, or A. Y. Vulcanization by Coran, ENCYCLOPE
DIA OF POLYMER SCIENCE AND ENGINEERING, 2nd edition, John Wiley & Sons, Inc. 1989 can be referred to. Vulcanizing agents can be used alone or in combination. The present invention does not significantly affect the curing time. Typically, the vulcanizable composition is heated to vulcanize, for example, to about 170 ° C. Cured or crosslinked polymers can be referred to as vulcanized rubber.

  Such formulations are compounded using mixing equipment and procedures commonly used in the art. Preferably, an initial masterbatch is prepared containing an elastomeric polymer component and reinforcing filler, and other optional additives such as processing oils and antioxidants. A polyolefin additive is preferably added during the preparation of this initial masterbatch. After preparing such an initial masterbatch, the composition is mixed with a vulcanizing agent. The composition can then be processed into tire components according to conventional tire manufacturing techniques, such techniques including standard rubber curing techniques. Techniques for compounding rubber and the additives used in this technique are disclosed in "The Compounding and Vulcanization" by Stevens in "Rubber Technology Noseland Revision Company" in 1973 Van Nostrand Reinhold Company. is there. The manufacture of pneumatic tires is described in US Pat. Nos. 5,866,171, 5,876,527, 5,931,211 and 5,971,046, which are incorporated herein by reference. Can be implemented according to

  The functionalized polymers of the present invention can also be used in the manufacture of hoses, belts, shoe soles, window seals, other seals, vibration damping rubbers and other industrial products.

  For purposes of illustrating the practice of the present invention, the following examples are prepared and tested as described in the Examples section disclosed herein below. However, this example should not be considered as limiting the scope of the invention. The claims will limit the invention.

(Example)
Example 1-4
0.5 g 1,3-butadiene monomer placed in hexane in a bottle with rubber septum that was dried and purged with N ₂ , 0.32 mmol neodymium neodecanoate placed in hexane, toluene The catalyst was prepared by mixing 31.7 mmol of methylaluminoxane that had been placed in and 6.67 mmol of diisobutylaluminum hydride in hexane. The mixture was contacted for 2 minutes, after which 1.27 mmol of diethylaluminum chloride in hexane was added. The mixture was then aged for about 15 minutes at room temperature.

In a 2 gallon stainless steel reactor equipped with a stirrer and temperature control jacket, the catalyst solution prepared above and 611 g of 1,3-butadiene monomer were placed in about 3,459 g of hexane and 25 A polybutadiene polymer was produced by mixing at 0 ° C. The mixture was stirred at 24 ° C. for about 10 minutes. The jacket temperature was raised to 72 ° C and stirring was continued for 33 minutes, after which the jacket temperature was lowered to 70 ° C. The polymer cement is sampled and placed into separate bottles that have been dried and purged with N ₂ and are identified as Examples 1-4.

4,4′-Bis (N, N-diethylamino) benzophenone (DEAB) was added as a toluene solution to individual samples in the amounts and temperatures listed in Table I. This functionalizing agent is allowed to react for a specified time, and after quenching with a small amount of isopropyl alcohol in hexane and 2,6-di-t-butyl 4-methylphenol (BHT), solidification occurs in isopropyl alcohol. The polymer was isolated and then dried on a drum. When Comparative Example 4 was measured by FTIR analysis, the cis structure was 93 percent.

Table I shows Mooney viscosity (ML1 + 4 @ 100 ° C.), Mooney relaxation (T-80) for 20% torque, number average molecular weight (M _n ), weight average molecular weight (M _w ) and molecular weight distribution [based on polystyrene. The polybutadiene has been universally calibrated (measured by GPC analysis). The bound rubber was measured by immersing a finely cut uncured rubber specimen in toluene at room temperature. After 40 hours, the composition was filtered and the bonded rubber was calculated by comparing the weight of the dried sample with other insoluble materials. These samples were also tested to measure tan δ at 50 ° C. (frequency at 31.4 radians / second and 3% strain).

The percent functionality of this polymer was obtained with GPC using universal calibration for polystyrene and high cis butadiene based on the ratio of area of UV and RI chromatograms and polystyrene standards. It was obtained from the number average molecular weight (M _n ) of the polymer. The following three assumptions were made: (1) The UV absorbance of the terminal functional group of the polymer using n-butyllithium (n-BuLi) as the initiator is the terminal functionality of the polymer using the lanthanide catalyst. The same UV absorbance as the group, (2) the polymer using n-BuLi as an initiator is 100% functionalized, and (3) the area ratio of UV / RI is the M It is a linear function of the inverse of _n . In accordance with the method used, a UV / RI area ratio (A) and M _n calibration curve exhibited by a polymer started with n-BuLi and terminated with the same imine compound is represented by the following formula: A = a (1 / M _n ) + b [where A _(BuLi , _endgroup) = A _(BuLi , _polymer) −A _{(BuLi-backbone)} = (a _(polymer) −a _(backbone) ) (1 / M _n ) + (b _(polymer) -b _(backbone) )]. The parameters a and b of the GPC data indicated by the polymer initiated with n-BuLi and terminated with imine and the polymer initiated with n-BuLi and terminated with alcohol (with three different molecular weights) Obtained with a least square linear fitting. The functional percentage (F) of an unknown polymer initiated using a lanthanide catalyst is _{expressed as follows} : F = A _(unknown , _endgroup , _M) / A _(BuLi , _endgroup , _M) = (A _(unknown , _polymer , _M) -A _(unknown , _backbone , _M) ) / [(a _(polymer) -a _(backbone) ) (1 / M) + (b _(polymer) -b _(backbone) )] Obtained from GPC data of the unknown polymer and the corresponding unfunctionalized (base) polymer.

Example 5-7
0.5 g 1,3-butadiene monomer placed in hexane in a bottle with rubber septum that was dried and purged with N ₂ , 0.275 mmol neodymium neodecanoate in toluene, toluene The catalyst was prepared by mixing 27.5 mmol of methylaluminoxane in 5 and 5.77 mmol of diisobutylaluminum hydride in hexane. The mixture was contacted for 2 minutes, after which 1.10 mmol of diethylaluminum chloride in hexane was added. The mixture was then aged for about 15 minutes at room temperature.

A polybutadiene polymer was produced in the same manner as in Example 1-4 except that the temperature of the jacket was initially set to 26 ° C. and increased to 82 ° C. The polymer cement was sampled and placed in separate bottles that were dried and purged with N ₂ as shown in Examples 5-7. In Examples 6 and 7, DEAB was functionalized by charging the bottle as a toluene solution as listed in Table I. Comparative Example 5 contains DE
No functionalization with AB was performed.

Example 8-10
0.5 g 1,3-butadiene monomer placed in hexane in a bottle with a rubber septum that was dried and purged with N ₂ , 0.317 mmol neodymium neodecanoate in toluene, toluene The catalyst was prepared by mixing 31.7 mmol of methylaluminoxane in 6 and 6.67 mmol of diisobutylaluminum hydride in hexane. The mixture was contacted for 2 minutes, after which 1.27 mmol of diethylaluminum chloride in hexane was added. The mixture was then aged for about 15 minutes at room temperature.

A polybutadiene polymer was produced in the same manner as in Example 1-4, except that the jacket temperature was initially set to 27 ° C. and increased to 82 ° C. The polymer cement was sampled and placed in separate bottles that were dried and purged with N ₂ as shown in Examples 8-10. In Examples 9 and 10, DMI was functionalized by charging them into the bottles in the form of a mixture as listed in Table I. Comparative Example 8 was not functionalized with DMI.

Examples 11-18
The resulting specific polymers were individually blended with silica as filler [Nipsil VN3 ™; Nippon Silica; Japan] or carbon black (N339) to produce rubber blends. That is, the initial master batch was mixed in the internal mixer at an initial temperature of about 110 ° C. for about 3.5 minutes. The master batch was cooled and then kneaded again for about 2 minutes in the same internal mixer. The curing system was then added to the blend while continuing to process the blend at about 80 ° C. for about 1 minute in the internal mixer. The recipes used are listed in Tables II and III below.

Table II
Formulation using silica
Material Number of parts per 100 parts of rubber
Elastic polymer 100
Aromatic oil 10
Silica 50
Stearic acid 2
Antioxidant 1
Master batch total 163

Zinc oxide 2.5
Sulfur 0.03
Accelerator 2.5
Total amount 171.5

Table III
Formulation using carbon black
Material Number of parts per 100 parts of rubber
Elastic polymer 100
Aromatic oil 10
Paraffin oil 1.5
Carbon black 50
Stearic acid 2
Antioxidant 1
Total master batch 164.5

Zinc oxide 2
Sulfur 1.3
Accelerator 1.2
Total amount 169.0

  Each compound was compounded and then cured in a press at about 145 ° C. for about 33 minutes. Next, the cured sample was analyzed according to JIS-K6301 for measuring tensile strength at break and elongation at break. These samples were also tested to measure tan δ and G 'at 50 ° C (31.4 radians / second frequency and 3% strain) and Lambourne wear test.

  Table IV shows the results when the carbon black filled vulcanized rubber was tested, and Table V shows the results when the silica filled vulcanized rubber was tested. The data shown in Table IV is an index for the vulcanized rubber produced using polymer sample 1 except for Mooney viscosity (ML1 + 4 @ 100 ° C.), and the data shown in Table V excludes Mooney viscosity. The index for a vulcanized rubber produced using the polymer sample 8. The polymer sample labeled A is a weighted average between sample polymers 1 and 11 calculated so that the Mooney viscosity (ML1 + 4 @ 100 ° C.) is about 44.

  Various modifications and variations will occur to those skilled in the art without departing from the scope and spirit of the invention. Formally, the invention is not limited to the illustrative embodiments listed herein.

Claims (17)

A pseudo-living polymer is formed by polymerizing a conjugated monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (II)

[Wherein R ¹ and R ² are each a divalent organic group, or a trivalent organic group when they together with R ³ form a cyclic group, and R ³ is a hydrogen atom or a monovalent organic group, or when R ³ is combined with R ² , R ³ may be a divalent organic group, and Z is N, Selected from N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate and amide groups]
Reacting with a functionalizing agent as defined by
A functionalized polymer produced by a process comprising steps. A pseudo-living polymer is produced by polymerizing a conjugated monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (III)

[Wherein R ¹ and R ² are each a divalent organic group, or a trivalent organic group if they together with R ⁴ form a cyclic group, and R ⁴ is a hydrogen atom or a monovalent organic group, or when R ⁴ is combined with R ² , R ⁴ may be a divalent organic group, and Z is N, Selected from N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate and amide groups]
Reacting with a functionalizing agent as defined by
A functionalized polymer produced by a process comprising steps. A pseudo-living polymer is produced by polymerizing a conjugated monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (V)

Wherein R ¹ and R ² are divalent organic groups and E is O or S, Z is N, N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate And an amide group are selected]
Reacting with a functionalizing agent as defined by
A functionalized polymer produced by a process comprising steps. A pseudo-living polymer is produced by polymerizing a conjugated monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (VI), (VII)

[Wherein R ¹ and R ² are each a divalent organic group, or a trivalent organic group if they together with R ⁴ form a cyclic group, and R ⁴ is a hydrogen atom or a monovalent organic group, or when R ⁴ is combined with R ² , R ⁴ may be a divalent organic group, and Z is N, Selected from N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate and amide groups]
Reacting with a functionalizing agent as defined by
A functionalized polymer produced by a process comprising steps. A method for producing a functionalized polymer comprising:
A pseudo-living polymer is formed by polymerizing a conjugated diene monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (III)

[Wherein R ¹ and R ² are each a divalent organic group, or a trivalent organic group if they together with R ⁴ form a cyclic group, and R ⁴ is a hydrogen atom or a monovalent organic group, or when R ⁴ is combined with R ² , R ⁴ may be a divalent organic group, and Z is N, Selected from N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate and amide groups]
Reacting with at least one functionalizing agent as defined by
A method comprising the steps. A pseudo-living polymer is produced by polymerizing a conjugated diene monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (V)

Wherein R ¹ and R ² are divalent organic groups and E is O or S, Z is N, N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate And an amide group are selected]
Reacting with at least one functionalizing agent as defined by
A method comprising the steps. A pseudo-living polymer is formed by polymerizing a conjugated diene monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (VII)

[Wherein R ¹ and R ² are each a divalent organic group, or a trivalent organic group if they together with R ⁴ form a cyclic group, and R ⁴ is a hydrogen atom or a monovalent organic group, or when R ⁴ is combined with R ² , R ⁴ may be a divalent organic group, and Z is N, N -Selected from disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate and amide groups]
Reacting with at least one functionalizing agent as defined by
A method comprising the steps. A pseudo-living polymer is formed by polymerizing a conjugated monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (II)

[Wherein R ¹ and R ² are each a divalent organic group, or a trivalent organic group when they together with R ³ form a cyclic group, and R ³ is a hydrogen atom or a monovalent organic group, or when R ³ is combined with R ² , R ³ may be a divalent organic group, and Z is N, Selected from N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate and amide groups]
Reacting with a functionalizing agent as defined by
A functionalized polymer produced by a process comprising steps, having a cis microstructure of 90% or more, a 1,2- or 3,4-unit content of less than 2% and a molecular weight distribution of less than 4. And a reinforcing filler comprising 1 to 100 parts by weight (phr) of inorganic filler per 100 parts by weight of rubber. A pseudo-living polymer is produced by polymerizing a conjugated monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (III)

[Wherein R ¹ and R ² are each a divalent organic group, or a trivalent organic group if they together with R ⁴ form a cyclic group, and R ⁴ is a hydrogen atom or a monovalent organic group, or when R ⁴ is combined with R ² , R ⁴ may be a divalent organic group, and Z is N, Selected from N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate and amide groups]
Reacting with a functionalizing agent as defined by
A functionalized polymer produced by a process comprising steps, having a cis microstructure of 90% or more, a 1,2- or 3,4-unit content of less than 2% and a molecular weight distribution of less than 4. And a reinforcing filler comprising 1 to 100 parts by weight (phr) of inorganic filler per 100 parts by weight of rubber. A pseudo-living polymer is produced by polymerizing a conjugated monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (V)

Wherein R ¹ and R ² are divalent organic groups and E is O or S, Z is N, N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate And an amide group are selected]
Reacting with a functionalizing agent as defined by
A functionalized polymer produced by a process comprising steps, having a cis microstructure of 90% or more, a 1,2- or 3,4-unit content of less than 2% and a molecular weight distribution of less than 4. And a reinforcing filler comprising 1 to 100 parts by weight (phr) of inorganic filler per 100 parts by weight of rubber. A pseudo-living polymer is produced by polymerizing a conjugated monomer using a catalyst containing aluminoxane and based on a lanthanide, and the pseudo-living polymer is represented by the formula (VI), (VII)

[Wherein R ¹ and R ² are each a divalent organic group, or a trivalent organic group if they together with R ⁴ form a cyclic group, and R ⁴ is a hydrogen atom or a monovalent organic group, or when R ⁴ is combined with R ² , R ⁴ may be a divalent organic group, and Z is N, Selected from N-disubstituted aminophenyl, imine, cyclic amino, epoxy, isocyanate, isothiocyanate and amide groups]
Reacting with a functionalizing agent as defined by
A functionalized polymer produced by a process comprising steps, having a cis microstructure of 90% or more, a 1,2- or 3,4-unit content of less than 2% and a molecular weight distribution of less than 4. And a reinforcing filler comprising 1 to 100 parts by weight (phr) of inorganic filler per 100 parts by weight of rubber.   The polymer according to claim 2, wherein Z is N, N-disubstituted aminophenyl.   6. The method of claim 5, wherein Z is N, N-disubstituted aminophenyl.   The vulcanizable composition according to claim 9, wherein Z is N, N-disubstituted aminophenyl.   The polymer according to claim 4, wherein Z is an amide.   The method of claim 7, wherein Z is an amide.   The vulcanizable composition according to claim 11, wherein Z is an amide.