阅读说明：本技术 官能化聚合物、用于制备该官能化聚合物的方法和含有该官能化聚合物的橡胶组合物 (Functionalized polymer, method for preparing the same and rubber composition containing the same ) 是由 闫远勇 秦增全 斋藤光一 丽塔·E·库克 于 2018-12-13 设计创作，主要内容包括：本文公开了一种含有第一官能化基团和第二官能化基团的含二烯单体的官能化聚合物、用于制备该官能化聚合物的方法以及含有该官能化聚合物的橡胶组合物。该官能化聚合物含有聚合物链,该聚合物链由任选地与至少一种乙烯基芳族单体组合的至少一种共轭二烯单体组成,其中每条聚合物链在其链末端至少被该第一官能化基团官能化并经由该第一官能化基团与该第二官能化基团偶联。(Disclosed herein are functionalized polymers containing diene monomers containing a first functional group and a second functional group, methods for preparing the functionalized polymers, and rubber compositions containing the functionalized polymers. The functionalized polymer contains polymer chains composed of at least one conjugated diene monomer, optionally in combination with at least one vinyl aromatic monomer, wherein each polymer chain is functionalized at its chain ends with at least the first functional group and coupled to the second functional group via the first functional group.)

1. A method for preparing a functionalized polymer comprising diene monomer, the method comprising:

a. polymerizing at least one conjugated diene monomer and optionally at least one vinyl aromatic monomer to produce a polymer chain having living ends;

b. reacting the living terminal polymer chain from (a) with a first functionalizing compound selected from:

i.

wherein n is an integer from 0to 16, or

ii.

Wherein R is¹A hydrocarbon group selected from H and C1-C20, preferably C1-C10), and R²Selected from H and C1-C20 hydrocarbon groups,

thereby producing an intermediate product comprising a polymer chain end-functionalized with the first functionalizing compound;

c. coupling the intermediate product from (b) with a second functionalizing compound selected from:

wherein B is boron and each R is⁶Independently selected from H and C1-C20 hydrocarbyl groups, and each X is halogen,

thereby forming a final product comprising a diene monomer-containing functionalized polymer having a trans bond content of no more than 60% and functionalized with both a first functionalized group produced by the first functionalizing compound and a second functionalized group produced by the second functionalizing compound.

2. The method of claim 1 wherein the functionalized polymer comprising diene monomer has a molar ratio of first functional groups to second functional groups of from 1:1 to 6:1, preferably from 2:1 to 6: 1.

3. The method of claim 1 or claim 2, wherein (a) comprises anionic polymerization comprising an initiator, and

i. utilizing said first functionalizing compound in a molar ratio of from about 0.1:1 to about 1:1 based on the amount of initiator used in (a); and is

Utilizing the second functionalizing compound in a molar ratio of about 1:1 to about 0.1:1 based on the amount of initiator used in (a).

4. The method of any one of claims 1-3, wherein the first functionalizing compound comprises (i), wherein n is an integer from 1-16.

5. The method of any one of claims 1-4, wherein the conjugated diene monomer is selected from the group consisting of 1, 3-butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene, 2, 3-dimethyl-1, 3-butadiene, 2-ethyl-1, 3-butadiene, 2-methyl-1, 3-pentadiene, 3-methyl-1, 3-pentadiene, 4-methyl-1, 3-pentadiene, 2, 4-hexadiene, and combinations thereof.

6. The method of any one of claims 1-5, wherein a majority of the living terminal polymer chains from (a) are reacted with the first functionalizing compound during (b).

7. The method of any one of claims 1-6, wherein 5% to 95% of the polymer chains end-functionalized with the first functionalizing compound from (b) are functionalized with the second functionalizing compound during (c).

8. The process of any one of claims 1-7, wherein the final product of (c) contains at least 10% of polymer functionalized with both the first functionalizing compound and the second functionalizing compound.

9. The method of any one of claims 1-8, wherein the functionalized polymer containing diene monomer comprises styrene-butadiene or polybutadiene.

10. A functionalized diene monomer-containing polymer comprising

At least one polymer chain consisting of at least one conjugated diene monomer, optionally in combination with at least one vinyl aromatic monomer,

wherein each polymer chain is functionalized at its chain ends with at least a first functional group and is coupled via said first functional group to a second functional group,

wherein the first functional group is produced from a first functional compound selected from the group consisting of:

i.

wherein n is an integer from 0to 16, or

ii.

Wherein R is¹Selected from H and C1-C20 hydrocarbyl groups, and R²Is selected from H and C1-C20 hydrocarbon groups, and

the second functionalizing group is produced by a second functionalizing compound selected from:

wherein B is boron and each R is⁶Independently selected from H and C1-C20 hydrocarbyl groups, and each X is halogen,

and the first functional group is present in a molar ratio of from 1:1 to 6:1 compared to the second functional group.

11. The polymer of claim 10, wherein the first functional group is produced from a compound selected from (i).

12. The polymer of claim 10, wherein the first functional group is produced from a compound selected from (ii).

13. The polymer of any one of claims 10-12, wherein the second functionalizing group results from a second functionalizing compound, wherein each X is chloro and each R is⁶Is methyl or ethyl.

14. The polymer of any one of claims 10-13, which has an ML1+4 at 100 ℃ of 30-100.

15. The polymer of any one of claims 10-14, having a% coupling of at least 50%.

16. The polymer of any of claims 10-15, wherein the at least one conjugated diene monomer comprises 1, 3-butadiene optionally in combination with styrene.

17. A rubber composition, comprising:

a.10 parts to 100 parts of at least one diene monomer-containing functionalized polymer according to any one of claims 10 to 16 or produced by the method of any one of claims 1 to 9;

b.0 parts to 90 parts of at least one diene monomer-containing polymer, preferably selected from the group consisting of natural rubber, polyisoprene, polybutadiene rubber, styrene-butadiene-isoprene rubber, isoprene-butadiene rubber, and combinations thereof;

c.10phr to 100phr of at least one carbon black filler and 0phr to 100phr of at least one silica filler.

18. The rubber composition of claim 17, wherein the at least one functionalized polymer containing diene monomer of (a) comprises styrene-butadiene, polybutadiene, or a combination thereof.

19. The rubber composition according to claim 17 or claim 18, wherein the at least one diene monomer-containing functionalized polymer (a) is present in an amount from 20phr to 60phr, and the at least one diene monomer-containing polymer (b) is present in an amount from 40phr to 80 phr.

20. The rubber composition of any of claims 17-19, wherein the 10phr to 100phr of the at least one carbon black filler includes 10phr to 70phr of the reinforcing carbon black, and the silica filler is present in an amount from 5phr to 70 phr.

Technical Field

The present application relates to a functionalized polymer containing a first functionalized group and a second functionalized group, a process for preparing the functionalized polymer, and a rubber composition containing the functionalized polymer.

Background

Rubber compositions utilized in various tire components, such as tire treads, are often reinforced with fillers such as carbon black and/or silica. The use of functionalized polymers can affect the dispersion of such fillers and filler-polymer interactions, and can result in improved properties in the resulting rubber composition.

Disclosure of Invention

Disclosed herein is a functionalized diene monomer-containing polymer comprising a first functional group and a second functional group. Also disclosed are methods for preparing the functionalized polymers and rubber compositions containing the functionalized polymers.

In a first embodiment, a process for preparing a functionalized polymer containing diene monomer is disclosed. The method comprises the following steps: (a) polymerizing at least one conjugated diene monomer and optionally at least one vinyl aromatic monomer to produce a polymer chain having living ends; (b) reacting the living terminal polymer chains from (a) with a first functionalizing compound selected from structure I or structure II, thereby producing an intermediate product comprising polymer chains end-functionalized with the first functionalizing compound; and (c) coupling the intermediate product from (b) with a second functionalizing compound selected from structure V, thereby forming a final product comprising a diene monomer-containing functionalized polymer having a trans-bond content of no more than 60% and functionalized with both a first functionalizing group derived from the first functionalizing compound and a second functionalizing group derived from the second functionalizing compound.

In a second embodiment, a functionalized polymer comprising a diene monomer is disclosed. The functionalized polymer comprises at least one polymer chain comprised of at least one conjugated diene monomer, optionally in combination with at least one vinyl aromatic monomer, wherein each polymer chain is functionalized at its chain ends with at least a first functional group and coupled via the first functional group to a second functional group. According to a second embodiment, the first functionalizing group is produced by a first functionalizing compound selected from structure I or structure I, and the second functionalizing group is produced by a second functionalizing compound selected from structure V. Further according to the second embodiment, the first functional group of the functionalized polymer comprising diene monomer is present in a ratio of from 1:1 to 6:1 as compared to the second functional group.

In a third embodiment, a rubber composition is disclosed that comprises (a)10 parts to 100 parts of at least one diene monomer-containing functionalized polymer according to the second embodiment or produced according to the method of the first embodiment; (b) from 0parts to 90 parts of at least one diene monomer-containing polymer, preferably selected from the group consisting of natural rubber, polyisoprene, polybutadiene rubber, styrene-butadiene-isoprene rubber, isoprene-butadiene rubber, and combinations thereof; and (c) from 10phr to 100phr of at least one carbon black filler and from 0phr to 100phr of at least one silica filler.

Detailed Description

Disclosed herein is a functionalized diene monomer-containing polymer comprising a first functional group and a second functional group. Also disclosed are methods for preparing the functionalized polymers and rubber compositions containing the functionalized polymers.

In a first embodiment, a process for preparing a functionalized polymer containing diene monomer is disclosed. The method comprises the following steps: (a) polymerizing at least one conjugated diene monomer and optionally at least one vinyl aromatic monomer to produce a polymer chain having living ends; (b) reacting the living terminal polymer chains from (a) with a first functionalizing compound selected from structure I or structure II, thereby producing an intermediate product comprising polymer chains end-functionalized with the first functionalizing compound; and (c) coupling the intermediate product from (b) with a second functionalizing compound selected from structure V, thereby forming a final product comprising a diene monomer-containing functionalized polymer having a trans-bond content of no more than 60% and functionalized with both a first functionalizing group derived from the first functionalizing compound and a second functionalizing group derived from the second functionalizing compound.

In a second embodiment, a functionalized polymer comprising a diene monomer is disclosed. The functionalized polymer comprises at least one polymer chain comprised of at least one conjugated diene monomer, optionally in combination with at least one vinyl aromatic monomer, wherein each polymer chain is functionalized at its chain ends with at least a first functional group and coupled via the first functional group to a second functional group. According to a second embodiment, the first functionalizing group is produced by a first functionalizing compound selected from structure I or structure I, and the second functionalizing group is produced by a second functionalizing compound selected from structure V. Further according to the second embodiment, the first functional group of the functionalized polymer comprising diene monomer is present in a ratio of from 1:1 to 6:1 as compared to the second functional group.

In a third embodiment, a rubber composition is disclosed that comprises (a)10 parts to 100 parts of at least one diene monomer-containing functionalized polymer according to the second embodiment or produced according to the method of the first embodiment; (b) from 0parts to 90 parts of at least one diene monomer-containing polymer, preferably selected from the group consisting of natural rubber, polyisoprene, polybutadiene rubber, styrene-butadiene-isoprene rubber, isoprene-butadiene rubber, and combinations thereof; and (c) from 10phr to 100phr of at least one carbon black filler and from 0phr to 100phr of at least one silica filler.

Definition of

The terminology described herein is for the purpose of describing embodiments only and is not to be construed as limiting the invention as a whole.

As used herein, the term "living end" (e.g., living end of a polymer chain) is used to refer to a polymeric species having a living end that has not been capped. The active end is capable of reacting with the functionalizing compound and, thus, can be described as reactive.

As used herein, the term "majority" refers to more than 50% (e.g., 50.5%, 51%, 60%, etc.) and may encompass 100%.

As used herein, the term "natural rubber" refers to naturally occurring rubbers, such as rubbers that may be harvested from sources such as the Hevea (Hevea) rubber tree and non-Hevea sources (e.g., guayule shrubs and dandelions such as TKS). In other words, the term "natural rubber" should be interpreted to exclude synthetic polyisoprene.

As used herein, the term "phr" refers to parts per hundred parts of rubber. 100 parts of rubber means 100 parts of elastomer. By way of non-limiting example, in an exemplary rubber composition according to the third embodiment, which contains 50 parts of the functionalized polymer containing diene monomer according to the second embodiment, 50 parts of polybutadiene, and 50 parts of silica filler, the amount of silica filler may be referred to as 50 phr.

As used herein, the term "polyisoprene" refers to synthetic polyisoprene. In other words, the term is used to refer to polymers made from isoprene monomers, and should not be construed to include naturally occurring rubbers (e.g., hevea natural rubber, guayule-derived natural rubber, or dandelion-derived natural rubber). However, the term "polyisoprene" should be construed to include polyisoprene made from natural sources of isoprene monomers.

As used herein, the term "polymer" is meant to encompass both polymers (i.e., containing repeat units from one monomer) and copolymers (i.e., containing repeat units from two or more monomers).

Functionalized polymers containing diene monomers

As discussed above, according to the second embodiment, a functionalized polymer containing diene monomer is provided, and similarly, a functionalized polymer containing diene monomer is produced by the method of the first embodiment. Likewise, the rubber composition of the third embodiment utilizes the functionalized diene monomer-containing polymer of the second embodiment or the functionalized diene monomer-containing polymer produced by the method of the first embodiment. According to the first to third embodiments, the functionalized polymer or polymer chain containing diene monomers has a trans bond content of no more than 60% by weight (e.g., 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less). In certain embodiments of the first to third embodiments, the functionalized polymer or polymer chain containing diene monomers has a trans bond content of 25% to 60% (e.g., 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%) by weight. The trans bond content in the butadiene portion of the polymer chain or the resulting end-functionalized polymer can be determined by H¹NMR and C¹³NMR determination (e.g. using 300MHz Gemi)ni300NMR spectrometer system (Varian)).

In certain embodiments of the first to third embodiments, the functionalized polymer comprising diene monomer comprises styrene-butadiene or polybutadiene; in certain such embodiments, the polybutadiene is a high-cis polybutadiene having a cis bond content of at least 90% or 95% or more). In certain embodiments of the first to third embodiments, the functionalized polymer containing diene monomer is a styrene-butadiene polymer.

Conjugated diene monomer

As discussed above, according to the first to third embodiments, the functionalized polymer or polymer chain containing diene monomers includes at least one conjugated diene monomer, optionally in combination with at least one vinyl aromatic monomer. Conjugated dienes are compounds having two carbon-carbon double bonds (i.e., two-C ═ C-bonds) separated by one single bond (i.e., -C-); thus, the conjugated diene will contain at least one-C-moiety. The specific structure of the conjugated diene monomer present in or contained in the functionalized polymer in the polymer chains of the first through third embodiments disclosed herein may vary. According to the first to third embodiments, one or more types of conjugated diene monomers may be utilized. Reference herein to one or more types of conjugated diene monomer means that the conjugated diene monomer may comprise all one or a mixture of each formula. As a non-limiting example, the two types of conjugated diene monomers may comprise a combination of 1, 3-butadiene and isoprene. In certain embodiments of the first through third embodiments disclosed herein, the conjugated diene monomer comprises at least one of: 1, 3-butadiene; isoprene; 1-3-pentadiene; 2, 3-dimethyl-1, 3-butadiene; 2-ethyl-1, 3-butadiene; 2-methyl-1, 3-pentadiene; 3-methyl-1, 3-pentadiene; 4-methyl-1, 3-pentadiene; 2, 4-hexadiene; 1, 3-hexadiene; 1, 3-cyclopentadiene; 1, 3-cyclohexadiene; 1, 3-cycloheptadiene; or 1, 3-cyclooctadiene. In certain preferred embodiments of the first to third embodiments, the conjugated diene monomer comprises 1, 3-butadiene. In certain embodiments of the first through third embodiments, the conjugated diene monomer comprises 1, 3-butadiene in combination with isoprene. In certain particularly preferred embodiments of the first to third embodiments, the only conjugated diene monomer utilized is 1, 3-butadiene.

Vinyl aromatic monomer

In other embodiments of the first to third embodiments, the functionalized polymer or polymer chain containing conjugated diene monomer contains at least one conjugated diene monomer, but does not contain any vinyl aromatic monomer (i.e., 0 weight percent of the polymer or polymer chain containing conjugated diene monomer contains vinyl aromatic monomer.) in certain embodiments of the first to third embodiments disclosed herein, the at least one type of vinyl aromatic monomer is present and comprises at least one of styrene, α -methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, vinylnaphthalene, p-t-butylstyrene, 4-vinylbiphenyl, 4-vinylbenzocyclobutene, 2-vinylnaphthalene, 9-vinylanthracene, 4-vinylether, or a combination of the first embodiment disclosed herein, the second embodiment disclosed herein, the third embodiment, the second embodiment disclosed herein, the third embodiment disclosed herein, or a combination of the first embodiment, the second embodiment disclosed herein, the second embodiment, the third embodiment, the second embodiment disclosed herein, the second embodiment, the use of the second embodiment, the use of the first embodiment, the secondAnd (4) utilization ratio. In certain embodiments of the first to third embodiments, wherein the functionalized polymer or polymer chain comprises a combination of 1, 3-butadiene and styrene monomers, the styrene content of the functionalized polymer or polymer chain is from about 10% to about 50% (e.g., 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%) of the total monomer content weight (i.e., 1, 3-butadiene + styrene), including 10% to 50%, about 18% to about 40%, and 18% to 40% by weight. In certain embodiments of the first to third embodiments wherein the functionalized polymer or polymer chain comprises a combination of 1, 3-butadiene and styrene, the microstructure of the functionalized polymer or polymer chain has from about 8% to about 99% by mass (e.g., 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 80%, 85%, 90%, 95%, 99%) of vinyl bonds (1, 2-vinyl groups) in the butadiene portion, including from 8% to 99%, from about 10% to about 60%, and from 10% to 60%, by weight. The vinyl bond content in the butadiene portion of the polymer chain or of the resulting end-functionalized polymer may be determined by H¹NMR and C¹³NMR measurements (e.g. using a 300MHz Gemini300NMR spectrometer System (Varian)).

First functionalized group/first functionalized compound

As discussed above, the functionalized polymers containing diene monomers of the second embodiment are functionalized at each chain end with at least a first functional group. The first functionalized group is produced from a first functionalizing compound selected from structure I or structure II. The rubber composition of the third embodiment can incorporate the functionalized diene monomer-containing polymer of the second embodiment (i.e., a polymer functionalized at each chain end with at least a first functional group resulting from a first functionalized compound having structure I or structure II). The functionalized polymer containing diene monomer resulting from the method of the first embodiment can also be described as being functionalized at each chain end with at least a first functional group, which, as discussed above, is a structure resulting from the reaction of the living terminal polymer chain with a first functionalizing compound selected from structure I or structure II.

According to the first to third embodiments, structure I is as follows:

where n is an integer from 0to 16 (e.g., 0, 1,2, 3, 4, 5,6, 7,8, 9, 10, 11, 12, 13, 14, 15, or 16). In certain embodiments of the first through third embodiments, wherein the first functionalized group is generated with or from a first functionalizing compound having structure I, n is an integer from 0to 10 or from 0to 6. Exemplary compounds having structure I include, but are not limited to: n-vinylcaprolactam, N-vinylpyrrolidone (also known as N-vinylpyrrolidone, 1-vinyl-2-pyrrolidone and N-vinylpyrrolidone), N-vinylpiperidone (also known as N-vinyl-2-piperidone or 1-vinyl-2-piperidone), N-vinyl-4-butylpyrrolidone, N-vinyl-4-propylpyrrolidone, N-vinyl-4-methylcaprolactam, N-vinyl-6-methylcaprolactam and N-vinyl-7-butylcaprolactam.

According to the first to third embodiments, structure II is as follows

Wherein R is¹A hydrocarbyl group selected from H and C1-C20 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, or C20) and R²A hydrocarbyl group selected from H and C1-C20 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, or C20). In certain embodiments of the first through third embodiments, wherein a first functionalizing compound having structure II or a second functionalizing compound having structure I is utilizedThe first functionalizing compound of I produces a first functionalizing group, R¹、R²Or both are selected from H and C1-C10 hydrocarbyl groups.

According to the first to third embodiments, the functionalization at each polymer chain end by a first functional group means that the end of the polymer is bonded to the first functional group. In those embodiments of the first through third embodiments in which the first functionalized group is generated from a first functionalizing compound having structure I, the polymer chain may be bonded to the β -carbon from the vinyl group attached to the nitrogen (in which case the α and β carbons from the vinyl group will no longer be double bonded) or to the carbon of the carbonyl group (in which case the carbon will no longer be double bonded to oxygen). The above attachment points of the polymer chains are shown below in structures I-a and I-B, where x represents the attachment point of the polymer chain to the first functionalized group produced by the first functionalized compound of structure I.

In those embodiments of the first through third embodiments in which the first functionalized group is generated from a first functionalizing compound having structure II, the polymer chain may be bonded to the β -carbon from the vinyl group attached to the nitrogen (in which case the α and β carbons from the vinyl group would no longer be double bonded) or to the carbon of the carbonyl group (in which case the carbon would no longer be double bonded to oxygen). The above attachment points of the polymer chains are shown below in structures II-a and II-B, where x represents the attachment point of the polymer chain to the first functionalized group produced by the first functionalized compound of structure II.

In certain embodiments of the second and third embodiments, at least 10% (e.g., 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or more) of the functionalized conjugated diene monomer-containing polymer (i.e., the final product polymer) will be functionalized at the chain ends with both a first functionalized group (resulting from the first functionalized compound as explained above) and a second functionalized group (resulting from the second functionalized compound as explained below). In other words, at least 1 polymer of the 10 polymers will be functionalized with both the first and second functionalizing groups. In certain embodiments of the second and third embodiments, 30% to 90% of the functionalized polymer comprising conjugated diene monomer (i.e., the final product polymer) will be functionalized at chain ends with both a first functionalizing group (resulting from the first functionalizing compound, as explained above) and a second functionalizing group (resulting from the second functionalizing compound, as explained below). The foregoing percentages may be considered as mole percent, as they refer to the relative number of polymer chains functionalized with both the first and second functionalizing groups.

Second functionalized group/second functionalized compound

As discussed above, the functionalized polymers containing diene monomers of the second embodiment are not only functionalized at each chain end with at least a first functional group, but are also coupled to a second functional group via the first functional group. The second functionalizing group is produced by a second functionalizing compound selected from structure V. The rubber composition of the third embodiment may incorporate the functionalized diene monomer-containing polymer of the second embodiment (i.e., a polymer that is not only functionalized at each chain end with at least a first functional group resulting from a first functional compound, but is also coupled to a second functional group via the first functional group). The functionalized polymer containing diene monomers produced by the method of the first embodiment may also be described as being functionalized at each chain end with at least a first functionalizing group (resulting from the reaction of the living terminal polymer chain with a first functionalizing compound selected from structure I or structure II) and coupled via the first functionalizing group with a second functionalizing group resulting from a second functionalizing compound having structure V.

According to the first to third embodiments, structure V is as follows:

wherein B is boron and each R is⁶Independently selected from H and C1-C20 hydrocarbyl groups (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, or C20), and each X is halogen. In certain embodiments of the first through third embodiments, each X of structure V is a halogen selected from chlorine or bromine. In certain preferred embodiments of the first to third embodiments, each X of structure V is chloro. In certain embodiments of the first through third embodiments, each R is independently selected from R, g⁶Independently selected from H and C1-C10 hydrocarbyl groups, preferably C1-C3 hydrocarbyl groups. In certain particularly preferred embodiments of the first through third embodiments, each R6 in structure V is selected from methyl or ethyl and each X is chloro. Non-limiting examples of compounds according to structure V that may be suitably used according to the first to third embodiments include, but are not limited to, N- (dichloroboryl) hexamethyldisilazane and N- (dichloroboryl) hexaethyldisilazane.

By stating that the polymer is coupled to the second functionalized group via the first functionalized group is meant that the polymer or polymer chain is attached directly to the first functionalized group (as discussed above), and the atoms within the first functionalized group are attached to the atoms within the second functionalized group. Typically, the coupling of the polymer or polymer chain via the first functional group to the second functional group will result from the loss of halogen from the second functional group, resulting in boron attaching the first functional group to the second functional group. When the polymer or polymer chain is bonded to a beta carbon or to an oxygen from a carbonyl group (structure I or structure II), the Si or Sn of the first functional group will bond to the beta carbon from a vinyl group (structure I or structure II) when the polymer or polymer chain is bonded to a carbon from the carbonyl group. In those embodiments of the first to third embodiments in which the second functionalizing group contains more than one halogen, more than one polymer or polymer chain may be bonded to the second functionalizing group via its respective first functionalizing group. In certain embodiments of the first to third embodiments, the molar ratio of the first functional group to the second functional group of the functionalized diene monomer-containing polymer will be from 1:1 to 6:1 (e.g., 1:1, 2:1, 3:1, 4:1, 5:1, or 6:1), and in certain embodiments from 2:1 to 6: 1. In other words, each second functionalizing group may couple from 1 to 6 polymer chains, wherein each polymer chain is end-functionalized with a first functionalizing group, and the coupling occurs via bonding of the first functionalizing group to the second functionalizing group.

It is understood that the functionalized polymer or polymer chain functionalized at least at its chain ends with a first functionalizing group and coupled via the first functionalizing compound with a second functionalizing group resulting from a second functionalizing compound of structure V has a structure corresponding to the following formula:

wherein one or both X are replaced by structure I-A, I-B, II-A, II-B or a combination thereof (as discussed above). Preferably, at least a majority of the halogen in a given amount of the second functionalizing compound having structure V is replaced by structure I-A, I-B, II-A, II-B or a combination thereof, and in certain embodiments, 51% to 95% (e.g., 51%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%) or 60% to 90% of the halogen is replaced by structure I-A, I-B, II-A, II-B or a combination thereof.

According to the first embodiment, the mooney viscosity (ML 1+4 at 100 ℃) of the functionalized polymer containing diene monomer may vary. In certain embodiments of the first embodiment, the mooney viscosity (ML 1+4 at 100 ℃) of the diene monomer-containing functionalized polymer is 15 to 100 (e.g., 15, 20, 30, 40, 50, 60, 70, 80, 90, or 100), 20 to 100 (e.g., 20, 30, 40, 50, 60, 70, 80, 90, or 100), 50 to 100 (e.g., 50, 60, 70, 80, 90, or 100), or 30 to 80(30, 40, 50, 60, 70, 80, 90, or 100). Generally, mooney viscosities in the range of 30-100 or even 50-100 can be advantageous in limiting undesirable cold flow of polymer that may otherwise occur over time during storage in low mooney polymers. According to a first embodiment, the% coupling of the functionalized polymer containing diene monomer may vary. In certain embodiments of the first embodiment, the percent coupling of the functionalized polymer containing diene monomer is at least 15% (e.g., 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or higher), at least 25%, at least 40%, preferably at least 50%.

Process for preparing functionalized polymers containing diene monomers

As discussed above, according to a first embodiment, a method for preparing a functionalized polymer containing diene monomer is disclosed. The method comprises the following steps: (a) polymerizing at least one conjugated diene monomer and optionally at least one vinyl aromatic monomer to produce a polymer chain having living ends; (b) reacting the living terminal polymer chains from (a) with a first functionalizing compound selected from structure I or structure II, thereby producing an intermediate product comprising polymer chains end-functionalized with the first functionalizing compound; and (c) reacting the intermediate product from (b) with a second functionalizing compound selected from structure V, thereby forming a final product comprising a diene monomer-containing functionalized polymer having a trans-bond content of no more than 60% and functionalized with both the first functionalizing compound and the second functionalizing compound. According to a first embodiment, a diene monomer-containing functionalized polymer produced as part of the final product and functionalized with both a first functionalizing group (produced by a first functionalizing compound) and a second functionalizing group (produced by a second functionalizing compound) compound may be more specifically described as having a polymer chain functionalized at its chain ends with at least a first functionalizing group and coupled to a second functionalizing group via the first functionalizing group.

Polymerisation

As mentioned above, the process of the first embodiment comprises polymerizing at least one conjugated diene monomer and optionally at least one vinyl aromatic monomer to produce a polymer chain having living ends. The living end of the polymer chain is reacted with a first functionalizing compound. The polymerization of the monomer or monomers can be carried out by various methods, such as by anionic polymerization.

In certain embodiments of the first embodiments disclosed herein, the polymerization is anionically initiated. In other words, in certain embodiments of the first embodiment, the polymerization of the at least one conjugated diene monomer and optionally the at least one vinyl aromatic monomer comprises an anionic polymerization comprising an initiator. Anionic polymerization of conjugated diene monomers generally involves the use of an anionic initiator in combination with the monomers and optional solvent, and such general methods (i.e., in addition to the use of the functionalizing compounds disclosed herein) are well known to those skilled in the art. Generally, the monomer or monomers are polymerized according to various suitable methods such as batch, semi-continuous, or continuous operation. The polymerization can also be carried out in a number of different polymerization reactor systems, including but not limited to bulk polymerization, gas phase polymerization, solution polymerization, suspension polymerization, and emulsion polymerization; in the solution polymerization, the concentration of the monomer in the solution is preferably in the range of 5to 50 mass%, more preferably 10 to 30 mass%. The polymerization system is not particularly limited, and may be a batch system or a continuous system. In certain embodiments of the first embodiments disclosed herein, anionic polymerization is carried out using an anionic initiator, typically an organic alkali metal compound, preferably a lithium-containing compound. Examples of lithium-containing compounds that can be used as anionic initiators include, but are not limited to, hydrocarbyl lithium compounds, aminolithium compounds, and similar sodium compounds. In certain embodiments of the first embodiments disclosed herein, the amount of lithium compound used as an anionic initiator is preferably in the range of 0.2 mmol/100 g monomer to 20 mmol/100 g monomer. In certain embodiments of the first embodiment, a functionalized initiator is utilized. Non-limiting examples of functionalized initiators include organoalkali metal compounds (e.g., organolithium compounds) that additionally include one or more heteroatoms (e.g., nitrogen, oxygen, boron, silicon, sulfur, tin, and phosphorus atoms) or heterocyclic groups containing the foregoing heteroatoms, typically one or more nitrogen atoms (e.g., substituted aldimines, ketimines, secondary amines, etc.) optionally pre-reacted with a compound such as diisopropenylbenzene. Many functional initiators are known in the art. Exemplary functionalized initiators are disclosed in U.S. Pat. Nos. 5,153,159, 5,332,810, 5,329,005, 5,578,542, 5,393,721, 5,698,464, 5,491,230, 5,521,309, 5,496,940, 5,567,815, 5,574,109, 5,786,441, 7,153,919, 7,868,110, and U.S. patent application publication No. 2011-0112263, which are incorporated herein by reference. In certain preferred embodiments, when a functional initiator is utilized, the functional group added by the initiator is different from the functional group added by the functionalizing compound disclosed herein. In certain embodiments of the first embodiment, a nitrogen-containing functional initiator is utilized; non-limiting examples include cyclic amines, particularly cyclic secondary amines, such as azetidine; a pyrrolidine; piperidine; morpholine; an N-alkyl piperazine; hexamethyleneimine; a heptamethylene imine; and dodecamethyleneimine.

Non-limiting examples of hydrocarbyl lithium compounds include the reaction products of ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyllithium, n-decyllithium, phenyllithium, 2-naphthyllithium, 2-butyl-phenyllithium, 4-phenyl-butyllithium, cyclohexyllithium, cyclopentyllithium, diisopropenylbenzene, and butyllithium, and mixtures thereof. Among them, alkyllithium compounds such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyllithium, n-decyllithium and the like are preferable, and n-butyllithium is particularly preferable. Generally, anionic polymerization is carried out using monomers in a hydrocarbon solvent that is not reactive to the polymerization reaction, examples of which include hydrocarbon solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, or alicyclic hydrocarbons. Non-limiting examples of hydrocarbon solvents that are inactive to the polymerization reaction include propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propylene, 1-butene, isobutylene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene, and mixtures thereof.

In certain embodiments of the first embodiment, the anionic polymerization process is conducted in the presence of a randomizer. The randomizer controls the microstructure of the resulting polymer and has the following effect: the 1, 2-bond content in the butadiene unit (or butadiene portion) of the polymer using, for example, 1, 3-butadiene as a monomer is controlled, and the butadiene unit and the styrene unit in the copolymer using 1, 3-butadiene and styrene as monomers are randomized, and the like. Non-limiting examples of randomizers include dimethoxybenzene, tetrahydrofuran, linear and cyclic oligomeric oxolanyl alkanes (oligomeric oxolanyl alkanes) such as 2, 2-bis (2' -tetrahydrofuryl) propane, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, bistetrahydrofuryl propane, triethylamine, pyridine, N-methylmorpholine, N, N, N ', N ' -tetramethylethylenediamine, 1, 2-dipiperidinoethane, potassium tert-butoxide, sodium tert-butoxide, and the like. The amount of the randomizer used is preferably in the range of 0.01 to 100 molar equivalents per 1 mole of the organic alkali metal compound as the polymerization initiator.

The polymerization temperature in the anionic polymerization is preferably in the range of 0 ℃ to 150 ℃, more preferably 20 ℃ to 130 ℃. The polymerization can be carried out under the generated pressure, or preferably at a pressure sufficient to maintain the reactive monomers substantially in the liquid phase. When the polymerization reaction is carried out under a pressure higher than the generated pressure, the reaction system is preferably pressurized with an inert gas. Preferably, any reaction-impeding substances, such as water, oxygen, carbon dioxide, protic compounds, etc., are removed before the polymerization reaction is started.

Reacting the living terminal polymer chain with a first functionalizing compound

As discussed above, the method of the first embodiment includes reacting the living terminal polymer chain with a first functionalizing compound selected from structure I or structure II. According to a first embodiment, one or more first functionalizing compounds may be utilized. In certain embodiments of the first embodiment, only one type of first functionalizing compound is utilized. In certain embodiments of the first embodiment, the first functionalizing compound is selected from compounds having structure I. In other embodiments of the first embodiment, the first functionalizing compound is selected from compounds having structure II. In certain embodiments of the first embodiment, the first functionalizing compound, the second functionalizing compound, or both will be diluted in one or more solvents prior to use in the process; in certain such embodiments, the solvent comprises a hydrocarbon solvent (e.g., hexane, cyclohexane).

According to the method of the first embodiment, polymerization of the monomers is allowed to proceed sufficiently to produce the desired amount of living terminal polymer chains prior to addition of the first functionalizing compound. The amount of time allowed for polymerization can be influenced by the concentration of reactants (e.g., initiator, monomer or monomers) and the reaction conditions (e.g., temperature). In certain embodiments of the first embodiment, the polymerization is allowed to proceed until a temperature peak is reached, and then (i.e., once the reaction temperature begins to decrease), the first functionalizing compound is added. In certain embodiments of the first embodiment, the polymerization is allowed to proceed for 0.2 hours to 5 hours (e.g., 0.2 hours, 0.3 hours, 0.4 hours, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours), preferably 0.5 hours to 2 hours, prior to addition of the first functionalizing compound.

The amount of first functionalizing compound used to react with the living terminal polymer chains may vary according to the method of the first embodiment. Generally, the amount of the first functionalizing compound may be described based on the amount of initiator used to polymerize the monomer. Preferably, the amount of first functionalizing compound utilized will be sufficient to functionalize a majority of the living terminal polymer chains. In certain embodiments of the first embodiment, the amount of the first functionalizing compound utilized will be sufficient to functionalize at least 60%, at least 70%, at least 80%, at least 90%, or 51% -95%, or 60% -90% of the living terminal polymer chains. The foregoing percentages may be considered as mole% because they refer to the relative number of polymer chains functionalized by the first functionalizing compound. In certain embodiments of the first embodiment, the first functionalizing compound is utilized in the following molar ratios based on the amount of initiator used to polymerize the monomer: about 0.1:1 to about 2:1 (e.g., 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1) or 0.1:1 to 1:1, preferably about 0.1:1 to about 1:1 or 0.1:1 to 1:1, even more preferably about 0.5:1 to 0.95:1 or 0.5:1 to 0.95:1 (e.g., 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 0.1).

As discussed above, the method of the first embodiment includes reacting the living terminal polymer chain (resulting from polymerization) with a first functionalizing compound selected from structure I or structure II. Structures I and II are discussed above, and such discussion should be considered applicable to the method of the first embodiment.

Coupling with a second functionalised compound

As discussed above, the method of the first embodiment includes coupling the intermediate product (i.e., the product resulting from the reaction of the living terminal polymer chain with the first functionalizing compound) with the second functionalizing compound. More specifically, the end of the polymer chain functionalized with a first functionalizing compound is coupled with a second functionalizing compound. The term coupling is used to imply the ability of the second functionalizing compound to bond to more than one end of the polymer chain functionalized with the first functionalizing compound. According to the method of the first embodiment, one or more second functionalizing compounds may be utilized. As a result of coupling with the second functionalizing compound, a final product is formed that includes a diene monomer-containing functionalized polymer having a trans bond content of no more than 60% and that is functionalized with both the first functionalizing compound and the second functionalizing compound. The final product polymer can also be described as being functionalized at the end of the polymer chain with a first functionalizing group (resulting from the first functionalizing compound) and coupled via the first functionalizing group to a second functionalizing group (resulting from the second functionalizing group).

In certain embodiments of the first embodiment, only one type of second functionalizing compound is utilized. In certain embodiments of the first embodiment, the first functionalizing compound is selected from compounds having structure V.

The method according to the first embodiment allows the reaction of the living terminal polymer chains with the first functionalizing compound to proceed sufficiently before the addition of the second functionalizing compound. The amount of time allowed to react with the first functionalizing compound may be influenced by the concentration of the reactants (e.g., living terminal polymer chain, first functionalizing compound) as well as the reaction conditions (e.g., temperature). In certain embodiments of the first embodiment, the reaction of the living terminal polymer chains with the first functionalizing compound is allowed to proceed until a majority of the living terminal polymer chains react with the first functionalizing compound. In certain embodiments of the first embodiment, at least 60%, at least 70%, at least 80%, at least 90%, or 51% to 95%, or 60% to 90% of the living terminal polymer chains will be reacted with the first functionalizing compound prior to the addition of the second functionalizing compound. The foregoing percentages may be considered as mole percent, as they refer to the relative number of polymer chains reacted with the first functionalizing compound. In certain embodiments of the first embodiment, the reaction between the living terminal polymer chain and the first functionalizing compound is allowed to proceed for 0.3 hours to 2 hours (e.g., 0.3 hours, 0.4 hours, 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, or 2 hours), preferably 0.3 hours to 1 hour, prior to addition of the first functionalizing compound.

The amount of second functionalizing compound used to react with the polymer chain ends functionalized with the first functionalizing compound may vary according to the method of the first embodiment. Generally, the amount of the second functionalizing compound may be described based on the amount of initiator used to polymerize the monomers. Preferably, the amount of the second functionalizing compound utilized will be a molar amount that is less than or equal to the molar amount of the first functionalizing compound utilized. In certain embodiments, a lesser molar amount of second functionalizing compound than first functionalizing compound may be utilized, as each second functionalizing compound has the ability to bind (couple) more than one polymer chain end functionalized with the first functionalizing compound. In certain embodiments of the first embodiment, the amount of the second functionalizing compound utilized will be sufficient to functionalize 5% to 95% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%) or 10% to 85% of the polymer chain ends functionalized with the first functionalizing compound. In certain embodiments of the first embodiment, the amount of the second functionalizing compound utilized will be sufficient to functionalize a majority of the polymer chain ends functionalized by the first functionalizing compound. The foregoing percentages may be considered as mole percent, as they refer to the relative number of polymer chain ends functionalized with a first functionalizing compound and then coupled with a second functionalizing compound. In certain embodiments of the first embodiment, the second functionalizing compound is utilized in the following molar ratios based on the amount of initiator used to polymerize the monomers: about 1:1 to about 0.1:1 (e.g., 1:1, 0.9:1, 0.8:1, 0.7:1, 0.6:1, 0.5:1, 0.4:1, 0.3:1, 0.2:1, 0.1) or 1:1 to 0.1:1, preferably about 0.5:1 to 0.1:1 or 0.5:1 to 0.1:1 (e.g., 0.5:1, 0.4:1, 0.3:1, 0.2:1, 0.1: 1). In certain embodiments of the first embodiment, the second functionalizing compound is utilized in a molar amount that is 10% to 50% (e.g., 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%) or 15% to 35% of the molar amount of the first functionalizing compound; the aforementioned relative molar amounts may also be expressed in ratios (e.g., when the second functionalizing compound is used in a molar amount that is 20% of the molar amount of the first functionalizing compound, they are used in a molar ratio of the second functionalizing compound to the first functionalizing compound of 1: 5). As a non-limiting example, if the molar amount of the first functionalizing compound used is 1:1 based on the amount of initiator used for the polymerization, and the second functionalizing compound is utilized at 20% of the molar amount of the first functionalizing compound, the amount of the second functionalizing compound will be 0.2:1 based on the amount of initiator used for the polymerization.

The mooney viscosity (ML 1+4 at 100 ℃) of the functionalized polymer comprising diene monomer produced by the process of the second embodiment may vary. In certain embodiments of the second embodiment, the mooney viscosity (ML 1+4 at 100 ℃) of the diene monomer-containing functionalized polymer is 15 to 100 (e.g., 15, 20, 30, 40, 50, 60, 70, 80, 90, or 100), 20 to 100 (e.g., 20, 30, 40, 50, 60, 70, 80, 90, or 100), 50 to 100 (e.g., 50, 60, 70, 80, 90, or 100), or 30 to 80(30, 40, 50, 60, 70, 80, 90, or 100). Generally, mooney viscosities in the range of 30-100 or even 50-100 can be advantageous in limiting undesirable cold flow of polymer that may otherwise occur over time during storage in low mooney polymers. The% coupling of the functionalized diene monomer-containing polymer produced by the process of the second embodiment may vary. In certain embodiments of the second embodiment, the percent coupling of the functionalized polymer containing diene monomer is at least 15% (e.g., 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or higher), at least 25%, at least 40%, preferably at least 50%.

Rubber composition

As discussed above, according to a third embodiment, a rubber composition is provided that comprises (a)10 parts to 100 parts of at least one diene monomer-containing functionalized polymer according to the second embodiment or produced according to the method of the first embodiment; (b) from 0parts to 90 parts of at least one diene monomer-containing polymer, preferably selected from the group consisting of natural rubber, polyisoprene, polybutadiene rubber, styrene-butadiene-isoprene rubber, isoprene-butadiene rubber, and combinations thereof; and (c) from 10phr to 100phr of at least one carbon black filler and from 0phr to 100phr of at least one silica filler. According to a third embodiment, the total amount of (a) and (b) is 100 parts.

As mentioned above, the functionalized polymer containing diene monomer according to the second embodiment or produced according to the method of the first embodiment may be used in a rubber composition along with other ingredients. According to a third embodiment, the rubber composition comprises 10 parts to 100 parts (e.g., 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, or 100 parts), 20 parts to 100 parts, 10 parts to 60 parts, or 20 parts to 60 parts of the functionalized polymer comprising diene monomer. In other preferred embodiments of the third embodiment, the rubber composition comprises from 50 parts to 100 parts (e.g., 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, or 100 parts) of a functionalized polymer comprising a diene monomer.

In the rubber composition according to the third embodiment, the one or more additional rubbery polymers may be present in an amount of 0parts to 90 parts (e.g., 0parts, 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts). In those embodiments of the third embodiment, when at least one diene monomer-containing polymer (b) is present, it may be selected from: natural rubber, polyisoprene, polybutadiene rubber, styrene-butadiene-isoprene rubber, isoprene-butadiene rubber, and combinations thereof. In certain embodiments of the third embodiment, the amount of the at least one diene monomer-containing polymer (b) is from 40phr to 80phr, and the amount of the at least one diene monomer-containing functionalized polymer (a) is from 20phr to 60 phr.

The rubber composition according to the third embodiment is considered to be particularly suitable for use in the manufacture of tire components, in particular tire treads. Accordingly, it should be considered that the tire component comprising the rubber composition according to the third embodiment is fully disclosed herein; in certain such embodiments, the tire component is a tire tread.

In certain embodiments of the third embodiment, the use of the conjugated diene monomer-containing functionalized polymer of the second embodiment or the conjugated diene monomer-containing functionalized polymer made by the method of the first embodiment will result in improved properties of the rubber composition as compared to the use of a non-functionalized version of the conjugated diene monomer-containing polymer (preferably having the same monomer content for comparison purposes). In certain such embodiments, the improved performance includes a reduction in rolling resistance of at least 10%, at least 15%, at least 20%, or more (e.g., a reduction of 100% or more in certain instances) (e.g., as measured by tan at 60C); in certain such embodiments, the rolling resistance is reduced by 10% to 50%, 10% to 100%, 50% to 100%, or 50 to 150%. In certain embodiments, the improved properties include an increase in bound rubber of at least 10 percent units, at least 15 percent units, at least 20 percent units, or more; in certain such embodiments, the bound rubber increases by 10 percent units to 50 percent units, 10 percent units to 40 percent units, or 10 percent units to 30 percent units. Rolling resistance and bound rubber can be measured according to the procedure described in the working examples.

Filler material

According to a third embodiment, the rubber composition comprises (includes) from 10phr to 100phr (e.g., 10phr, 20phr, 30phr, 40phr, 50phr, 60phr, 70phr, 80phr, 90phr, 100phr) of at least one carbon black filler and from 0phr to 100phr (e.g., 5phr, 10phr, 20phr, 30phr, 40phr, 50phr, 60phr, 70phr, 80phr, 90phr, 100phr) of at least one silica filler. Thus, in certain embodiments, the rubber composition of the third embodiment may be free of silica filler. In other embodiments, the rubber composition of the third embodiment includes from 10phr to 100phr of the at least one carbon black filler and from 5phr to 100phr of the at least one silica filler. According to a third embodiment, in the rubber composition, one more or more carbon black fillers may be utilized, no silica filler, with limited silica fillers (e.g., less than 50phr, less than 40phr, less than 30phr, less than 20phr, less than 15phr, less than 10phr, or less than 5phr), one silica filler or more than one silica filler may be utilized. In certain embodiments of the third embodiment, the total amount of carbon black filler is from 10phr to 90phr, from 10phr to 80phr, from 10phr to 70phr, from 10phr to 60phr, from 10phr to 50phr, from 20phr to 90phr, from 20phr to 80phr, from 20phr to 70phr, from 20phr to 60phr, from 20phr to 50phr, from 30phr to 90phr, from 30phr to 80phr, from 30phr to 70phr, from 30phr to 60phr, or from 30phr to 50 phr. In certain embodiments of the third embodiment, the total amount of silica filler is from 10phr to 90phr, from 10phr to 80phr, from 10phr to 70phr, from 10phr to 60phr, from 10phr to 50phr, from 20phr to 90phr, from 20phr to 80phr, from 20phr to 70phr, from 20phr to 60phr, from 20phr to 50phr, from 30phr to 90phr, from 30phr to 80phr, from 30phr to 70phr, from 30phr to 60phr or from 30phr to 50 phr.

In certain embodiments of the third embodiment, the rubber composition comprises at least one reinforcing filler. In other words, in such embodiments, at least one of the at least one carbon black filler or the at least one silica filler is a reinforcing filler. The term "reinforcing filler" as used herein refers to particulate materials: nitrogen absorption specific surface area (N) thereof₂SA) of about 20m²A,/g or more, including 20m²A/g or greater of greater than about 50m²A/g of more than 50m²A/g of greater than about 100m²A/g of more than 100m²A/g of greater than about 125m²A,/g, and greater than 125m²(ii) in terms of/g. In certain embodiments, the term "reinforcing filler" may alternatively or additionally be used to refer to particulate materials that: the particle size is from about 10nm up to about 1000nm, including 10nm up to 1000nm, about 10nm up to about 50nm, and 10nm up to 50 nm. In certain embodiments of the third embodiment, the total amount of the at least one reinforcing filler is (includes) from about 10phr to about 200phr, from 10phr to 200phr, from about 10phr to about 175phr, from 10phr to 175phr, from about 25phr to about 150phr, from 25phr to 150phr, from 35phr to about 150phr, from 35phr to 150phr, from 25phr to about 125phr, from 25phr to 125phr, from about 25phr to about 100phr, from 25phr to 100phr, from about 25phr to about 80phr, from 25phr to 80phr, from about 35phr to about 125phr, from 35phr to 125phr, from about 35phr to about 100phr, from 35phr to 100phr, from about 35phr to about 80phr, or from 35phr to 80 phr.

In certain embodiments of the third embodiment, the rubber composition comprises at least one non-reinforcing filler. The non-reinforcing filler may be a non-reinforcing carbon black, a non-carbon black non-reinforcing filler, or a combination thereof. As used herein, the phrase "non-reinforcing filler" refers to a filler having a thickness of less than about 20m²(including less than 20 m)²/g) and in certain embodiments less thanAbout 10m²(including less than 10 m)²A nitrogen surface area of per gram); the reinforcing extender will have a surface area higher than the aforementioned values. The nitrogen surface area of the particulate extender material may be determined according to various standard methods, including ASTM D6556 or D3037. In certain embodiments of the third embodiment, the term non-reinforcing extender is additionally or alternatively used to refer to particulate materials having a particle size greater than about 1000nm (including greater than 1000 nm); the reinforcing extender will have a particle size less than the foregoing values. In certain embodiments of the third embodiment, the rubber composition comprises (includes) one or more of the following non-reinforcing fillers: graphite, clay, titanium dioxide, magnesium dioxide, alumina, starch, boron nitride, silicon nitride, aluminum nitride, calcium silicate, or silicon carbide.

Silica fillers suitable for use in the rubber compositions of certain embodiments of the third embodiment disclosed herein are well known. Non-limiting examples of silica fillers suitable for use in the rubber composition include, but are not limited to, precipitated amorphous silica, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), fumed silica, calcium silicate, and the like. Other silica fillers suitable for use in the rubber compositions of certain embodiments of the third embodiment disclosed herein include, but are not limited to, aluminum silicate, magnesium silicate (Mg)₂SiO₄、MgSiO₃Etc.), calcium magnesium silicate (CaMgSiO)₄) Calcium silicate (Ca)₂SiO₄Etc.), aluminum silicate (Al)₂SiO₅、Al₄.3SiO₄.5H₂O, etc.), calcium aluminum silicate (Al)₂O₃.CaO₂SiO₂Etc.) and the like. Among the silica fillers listed, precipitated amorphous wet process, hydrated silica fillers are preferred. Such silica fillers are produced by a chemical reaction in water, whereby the silica filler precipitates as ultrafine spherical particles, with the primary particles strongly associated into aggregates which in turn are less strongly associated into agglomerates. The surface area, measured by the BET method, is the preferred measure for characterizing the reinforcing properties of the different silica fillers. Third disclosure hereinIn certain of the embodiments, the rubber composition comprises a rubber having a thickness of about 32m²G to about 400m²(including 32 m)²G to 400m²A silica filler having a surface area (as measured by BET method) of about 100m is preferred²G to about 300m²(including 100 m)/g²G to 300m²A,/g) and including about 150m²G to about 220m²G (including 150 m)²G to 220m²A range of/g). In certain embodiments of the third embodiment disclosed herein, the rubber composition comprises a silica filler having a pH of from about 5.5 to about 7 or slightly above 7, preferably from about 5.5 to about 6.8. Some commercially available silica fillers that may be used in the rubber composition include, but are not limited to, those produced by PPG Industries (PPG Industries, Pittsburgh, Pa.)

190、

210、215、233、243, etc. In addition, it is also available from Degussa Corporation (Degussa Corporation) (e.g., VN2, VN3), Rhone Poulenc (e.g., Zeosil)^TM1165MP) and j.m. churu Corporation (j.m. huber Corporation) have available a variety of different silica fillers of commercial grades.

In certain embodiments of the third embodiments disclosed herein, the silica filler comprises silica that has been pre-reacted with a silica coupling agent; preferably, the pretreated silica comprises silica that has been pretreated with a silane-containing silica coupling agent. In other embodiments of the third embodiment, the rubber composition comprises a silica filler and a separate silica coupling agent (suitable silica coupling agents are discussed in more detail below).

As discussed above, according to the third embodiment disclosed herein, a carbon black filler is utilized in the rubber composition. Most (but not all) carbon blacks are reinforcing fillers. In certain embodiments of the third embodiments disclosed herein, the rubber composition comprises from 10phr to 100phr (e.g., 10phr, 20phr, 30phr, 40phr, 50phr, 60phr, 70phr, 80phr, 90phr, 100phr) of at least one reinforcing carbon black filler²Per g (including at least 20 m)²Per gram), and more preferably at least about 35m²Per gram of up to about 200m²(including 35 m) or more²G up to 200m²In terms of/g). The surface area values used in this application were measured by ASTM D-1765 using the cetyltrimethylammonium bromide (CTAB) method. Among the carbon blacks that can be used are furnace black, channel black, and lamp black. More specifically, examples of usable carbon blacks include Super Abrasion Furnace (SAF) black, High Abrasion Furnace (HAF) black, Fast Extrusion Furnace (FEF) black, Fine Furnace (FF) black, medium super abrasion furnace (ISAF) black, semi-reinforcing furnace (SRF) black, medium process channel black, difficult process channel black, and conductive channel black. Other carbon blacks that may be utilized include acetylene blacks. In certain embodiments of the third embodiment disclosed herein, the rubber composition comprises a mixture of two or more of the above carbon blacks. Typical reinforcing carbon blacks suitable for use in certain embodiments of the third embodiment disclosed herein are N-110, N-220, N-339, N-330, N-351, N-550, and N-660 as specified by ASTM D-1765-82 a. The carbon black used may be in granular form or as a non-granular flocculated mass. Preferably, non-particulate carbon black is preferred for more uniform mixing. In the rubber composition suitable for certain embodiments of the third embodimentNon-limiting examples of non-reinforcing carbon blacks include, but are not limited to, thermal carbon blacks or N9 series carbon blacks (also referred to as the N-900 series), such as the carbon blacks with ASTM designations N-907, N-908, N-990, and N-991. Various carbon blacks meeting the foregoing requirements are commercially available, including but not Limited to those available from Cancarb Limited (Medicine Hat, Alberta, Canada, Alberta, Adam, Cancarb, Inc.)N990 carbon black.

In certain embodiments of the third embodiment, the rubber composition comprises at least one filler in addition to carbon black (and in addition to the silica filler, when present). Non-limiting examples of suitable additional fillers include, but are not limited to, alumina, aluminum hydroxide, clay, magnesium hydroxide, boron nitride, aluminum nitride, titanium dioxide, reinforced zinc oxide, aluminum hydroxide, talc, clay, alumina (Al)₂O₃) Aluminum hydrate (Al)₂O₃H₂O), aluminum hydroxide (Al (OH)₃) Aluminum carbonate (Al)₂(CO₃)₂) Aluminum nitride, aluminum magnesium oxide (MgOAl)₂O₃) Valance rock soil (Al)₂O₃4SiO₂.H₂O), bentonite (Al)₂O₃.4SiO₂.2H₂O), boron nitride, mica, kaolin, glass spheres, glass beads, calcium oxide (CaO), calcium hydroxide (Ca (OH)₂) Calcium carbonate (CaCO)₃) Magnesium carbonate, magnesium hydroxide (MH (OH))₂) Magnesium oxide (MgO), magnesium carbonate (MgCO)₃) Titanium oxide, titanium dioxide, potassium titanate, barium sulfate, zirconium oxide (ZrO)₂) Zirconium hydroxide [ Zr (OH) ]₂.nH₂O]Zirconium carbonate [ Zr (CO) ]₃)₂]Crystalline aluminosilicates, enhanced grades of zinc oxide (i.e., enhanced zinc oxide), and combinations thereof.

Silica coupling agent

In certain embodiments of the third embodiment disclosed herein (particularly those embodiments in which at least one silica filler is utilized), one or more silica coupling agents are utilized in the rubber composition. Silica coupling agents may be used to prevent or reduce aggregation of the silica filler in the rubber composition. It is believed that the aggregates of silica filler particles increase the viscosity of the rubber composition, and therefore, preventing such aggregates reduces the viscosity and improves the processability and blendability of the rubber composition.

In general, any conventional type of silica coupling agent may be used, such as those having a silane and a constituent component or moiety that is reactive with a polymer, particularly a vulcanizable polymer. The silica coupling agent acts as a connecting bridge between the silica and the polymer. Silica coupling agents suitable for use in certain embodiments of the third embodiment disclosed herein include those comprising: such as alkylalkoxy, mercapto, blocked mercapto, sulfide-containing groups (e.g., monosulfide-based alkoxy, disulfide-based alkoxy, tetrasulfide-based alkoxy), amino, vinyl, epoxy, and combinations thereof. In certain embodiments of the third embodiment, the silica coupling agent may be added to the rubber composition as pretreated silica; the pretreated silica has been surface pretreated with a silane prior to addition to the rubber composition. The use of pretreated silica allows the two ingredients (i.e., silica and silica coupling agent) to be added in one ingredient, which generally makes the rubber easier to compound.

The alkylalkoxysilane has the general formula R¹ _pSi(OR²)_4-pWherein each R is²Independently a monovalent organic group, and p is an integer of 1 to 3, with the proviso that at least one R is¹Is an alkyl group. Preferably p is 1. In general, each R¹Independently contain C₁To C₂₀Aliphatic radical, C₅To C₂₀Cycloaliphatic radical or C₆To C₂₀An aromatic group; and each R²Independently contain C₁To C₆An aliphatic group. In certain exemplary embodiments, each R is¹Independently contain C₆To C₁₅Aliphatic radical, and in other embodiments, each R¹Independently contain C₈To C₁₄An aliphatic group. The mercaptosilanes have the general formula HS-R³-Si(R⁴)(R⁵)₂Wherein R is³Is a divalent organic radical, R⁴Is a halogen atom or an alkoxy group, each R⁵Independently a halogen, an alkoxy group or a monovalent organic group. Halogen is chlorine, bromine, fluorine or iodine. The alkoxy group preferably has 1 to 3 carbon atoms. The blocked mercaptosilanes have the general formula Bl-S-R⁶-Si-X₃Having available silyl groups for reaction with silica in a silica-silane reaction, and a blocking group B replacing a mercapto hydrogen atom to block the reaction of the sulfur atom with the polymer. In the above formula, Bl is a capping group which may be in the form of an unsaturated heteroatom or a carbon directly bonded to sulfur via a single bond; r⁶Is C₁To C₆Linear or branched alkylene, and each X is independently selected from C₁To C₄Alkyl or C₁To C₄An alkoxy group.

Non-limiting examples of alkylalkoxysilanes suitable for use in certain embodiments of the third embodiment disclosed herein include, but are not limited to, octyltriethoxysilane, octyltrimethoxysilane, trimethylethoxysilane, cyclohexyltriethoxysilane, isobutyltriethoxysilane, ethyltrimethoxysilane, cyclohexyltributoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, propyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, tetradecyltriethoxysilane, octadecyltriethoxysilane, methyloctyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, Nonyl trimethoxysilane, decyl trimethoxysilane, dodecyl trimethoxysilane, tetradecyl trimethoxysilane, octadecyl-trimethoxysilane, methyl octyl dimethoxysilane, and mixtures thereof.

Non-limiting examples of bis (trialkoxysilylorgano) polysulfides suitable for use in certain embodiments of the third embodiment disclosed herein include bis (trialkoxysilylorgano) disulfide and bis (trialkoxysilylorgano) tetrasulfide. Specific non-limiting examples of bis (trialkoxysilylorgano) disulfides suitable for use in certain exemplary embodiments of the second and fourth embodiments disclosed herein include, but are not limited to: 3,3 '-bis (triethoxysilylpropyl) disulfide, 3' -bis (trimethoxysilylpropyl) disulfide, 3 '-bis (tributoxysilylpropyl) disulfide, 3' -bis (tri-tert-butoxysilylpropyl) disulfide, 3 '-bis (trihexyloxysilylpropyl) disulfide, 2' -bis (dimethylmethoxysilylethyl) disulfide, 3 '-bis (diphenylcyclohexyloxysilylpropyl) disulfide, 3' -bis (ethyldi-sec-butoxysilylpropyl) disulfide, 3 '-bis (propyldiethoxysilylpropyl) disulfide, 12' -bis (triisopropoxysilylpropyl) disulfide, sodium hydrogen sulfide, 3,3' -bis (dimethoxyphenylsilyl-2-methylpropyl) disulfide and mixtures thereof. Non-limiting examples of bis (trialkoxysilylorgano) tetrasulfide silica coupling agents suitable for use in certain of the third embodiments disclosed herein include, but are not limited to, bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, silicon dioxide coupling agents, 3-triethoxysilylpropylbenzothiazole tetrasulfide and mixtures thereof. Bis (3-triethoxysilylpropyl) tetrasulfide is available under the trade name Evonik Degussa Corporation

And (5) selling.

Non-limiting examples of mercaptosilanes suitable for use in certain of the third embodiments disclosed herein include, but are not limited to, 1-mercaptomethyltriethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 2-mercaptoethyltripropoxysilane, 18-mercaptooctadecyldiethoxychlorosilane, and mixtures thereof.

Non-limiting examples of blocked mercaptosilanes suitable for use in certain embodiments of the third embodiment disclosed herein include, but are not limited to, those described in U.S. Pat. Nos. 6,127,468, 6,204,339, 6,528,673, 6,635,700, 6,649,684, and 6,683,135, the disclosures of which are hereby incorporated by reference. Representative examples of blocked mercaptosilanes for use in certain exemplary embodiments disclosed herein include, but are not limited to, 2-triethoxysilyl-1-ethylthioacetate, 2-trimethoxysilyl-1-ethylthioacetate, 2- (methyldimethoxysilyl) -1-ethylthioacetate, 3-trimethoxysilyl-1-propylthioacetate, triethoxysilylmethyl-thioacetate, trimethoxysilylmethylthioacetate, triisopropoxysilylmethylthioacetate, methyldiethoxysilylmethylthioacetate, methyldimethoxysilylmethylthioacetate, methyldiisopropyloxysilylmethylthioacetate, mixtures thereof, and mixtures thereof, Dimethylethoxysilylmethyl thioacetate, dimethylmethoxysilylmethyl thioacetate, dimethylisopropoxysilylmethyl thioacetate, 2-triisopropoxysilyl-1-ethylthioacetate, 2- (methyldiethoxysilyl) -1-ethylthioacetate, 2- (methyldiisopropyloxysilyl) -1-ethylthioacetate, 2- (dimethylethoxysilyl-1-ethylthioacetate, 2- (dimethylmethoxysilyl) -1-ethylthioacetate, 2- (dimethylisopropoxysilyl) -1-ethylthioacetate, 3-triethoxysilylSilyl-1-propylthioacetate, 3-triisopropoxysilyl-1-propylthioacetate, 3-methyldiethoxysilyl-1-propyl-thioacetate, 3-methyldimethoxysilyl-1-propylthioacetate, 3-methyldiisopropyloxysilyl-1-propylthioacetate, 1- (2-triethoxysilyl-1-ethyl) -4-thioacetylcyclohexane, 1- (2-triethoxysilyl-1-ethyl) -3-thioacetylcyclohexane, 2-triethoxysilyl-5-thioacetylnorbornene, 2-triethoxysilyl-4-thioacetylnorbornene, and a salt thereof, 2- (2-triethoxysilyl-1-ethyl) -5-thioacetyl norbornene, 2- (2-triethoxysilyl-1-ethyl) -4-thioacetyl norbornene, 1- (1-oxo-2-thia-5-triethoxysilylphenyl) benzoic acid, 6-triethoxysilyl-1-hexylthioacetate, 1-triethoxysilyl-5-hexylthioacetate, 8-triethoxysilyl-1-octylthioacetate, 1-triethoxysilyl-7-octylthioacetate, 6-triethoxysilyl-1-hexylthioacetate, 1-triethoxysilyl-5-octylthioacetate, 8-trimethoxysilyl-1-octylthioacetate, 1-trimethoxysilyl-7-octylthioacetate, 10-triethoxysilyl-1-decylthioacetate, 1-triethoxysilyl-9-decylthioacetate, 1-triethoxysilyl-2-butylthioacetate, 1-triethoxysilyl-3-methyl-2-butylthioacetate, 1-triethoxysilyl-3-methyl-3-butylthioacetate, 3-trimethoxysilyl-1-propylthiooctanoate, 3-triethoxysilyl-1-propyl-1-propylthiopalmitate, 3-triethoxysilyl-1-propylthiooctanoate, 3-triethoxysilyl-1-propylthiobenzoate, 3-triethoxysilyl-1-propylthio-2-ethylhexanoate, 3-methyldiethoxysilyl-1-propylthioacetate, 3-triacetoxysilyl-1-propylthioacetate, 2-methyldiethoxysilyl-1-ethylthioacetate, 2-triacetoxysilyl-1-ethylthioacetate, 1-methyldiethoxymethylSilyl-1-ethylthioacetate, 1-triacetoxysilyl-1-ethyl-thioacetate, tris- (3-triethoxysilyl-1-propyl) trithiophosphate, bis- (3-triethoxysilyl-1-propyl) methyldithiophosphonate, bis- (3-triethoxysilyl-1-propyl) ethyldithiophosphonate, 3-triethoxysilyl-1-propyldimethylthiophosphinate, 3-triethoxysilyl-1-propyldiethylthiophosphinate, tris- (3-triethoxysilyl-1-propyl) tetrathiophosphate, bis- (3-triethoxysilyl-1-propyl) methyltrithiophosphonate, N-ethyl-1-propylthiophosphonate, N-ethyl-1-thiophosphonate, N-ethyl-1-propylthiophosphonate, Bis- (3-triethoxysilyl-1-propyl) ethyl trithiophosphonite, 3-triethoxysilyl-1-propyl dimethyldithiophosphonite, 3-triethoxysilyl-1-propyl diethyldithiophosphonite, tris- (3-methyldimethoxysilyl-1-propyl) trithiophosphonite, bis- (3-methyldimethoxysilyl-1-propyl) methyldithiophosphonite, bis- (3-methyldimethoxysilyl-1-propyl) -ethyldithiophosphonite, 3-methyldimethoxysilyl-1-propyl dimethylthiophosphite, 3-methyldimethoxysilyl-1-propyl diethylthiophosphite, bis- (3-triethoxysilyl-1-propyl) thiophosphonite, bis- (3-methyldimethoxysilyl-1-propyl) dimethylthiophosphite, bis- (3-methyldimethoxysilyl-1-propyl) dimethylthiophosph, 3-triethoxysilyl-1-propylmethylthiosulfate, 3-triethoxysilyl-1-propylmethanethiosulfonate, 3-triethoxysilyl-1-propylethanethiosulfonate, 3-triethoxysilyl-1-propylbenzenethiosulfonate, 3-triethoxysilyl-1-propyltoluenesulfonothionate, 3-triethoxysilyl-1-propylnaphthalenesthiosulfonate, 3-triethoxysilyl-1-propylxylenethiosulfonate, triethoxysilylmethyl methylthiosulfate, triethoxysilylmethylmethylmethylmethylmethylmethanesulfonato, triethoxysilylmethylethanesulfoxato thiosulfonate, triethoxysilylmethylthiomethylsulfanylsulfonate, triethoxysilylmethylthiosulfonate, thiobenzosulfonate, thiosulfonate, triethoxysilylmethyl tosylate, triethoxysilylmethyl naphthalene thiosulfonate, triethoxysilylmethyl xylene thiosulfonate, and the like. Mixtures of various blocked mercaptosilanes can be used. Another example of a blocked mercaptosilane suitable for use in certain exemplary embodiments is NXT^TMSilane (3-octanoylthio-1-propyltriethoxysilane), commercially available from Momentive Performance Materials Inc., Albany, NY, of Albany, N.Y..

Non-limiting examples of pretreated silica (i.e., silica that has been surface pretreated with silane) suitable for use in certain embodiments of the third embodiment disclosed herein include, but are not limited to, silica that has been pretreated with mercaptosilane255LD and

LP (PPG Industries) silica; and

8113 (Degussa) which is an organosilane bis (triethoxysilylpropyl) polysulfide (Si69) andVN3 product of the reaction between silica. Couppsil 6508, Agilon 400 from PPG Industries, Inc. (PPG Industries)^TMSilicon dioxide; agilon from PPG Industries (PPG Industries)Silicon dioxide; and from PPG Industries, Inc. (PPG Industries)Silicon dioxide. In those embodiments in which the silica comprises pretreated silica, the pretreated silica is used in an amount as previously disclosed for the silica filler (i.e., 5phr to 100phr, etc.).

When a silica coupling agent is utilized in a rubber composition according to the second or fourth embodiments disclosed herein, the amount may vary. In certain embodiments of the third embodiments disclosed herein, the silica coupling agent is present in an amount sufficient to provide a ratio of silica coupling agent to total amount of silica filler of from about 1:100 to about 1:5 (i.e., from about 0.01 to about 20 parts by weight per 100 parts silica), including from 1:100 to 1:5, from about 1:100 to about 1:10, from 1:100 to 1:10, from about 1:100 to about 1:20, from 1:100 to 1:20, from about 1:100 to about 1:25 and from 1:100 to 1:25 and from about 1:100 to about 0:100 and from 1:100 to 0: 100. In certain embodiments according to the second and fourth embodiments disclosed herein, the rubber composition comprises from about 0.01phr to about 10phr (including from 0.01phr to 10phr, from about 0.01phr to about 5phr, from 0.01phr to 5phr, from about 0.01phr to about 3phr, and from 0.01phr to 3phr) of the silica coupling agent.

Curing bag

In certain embodiments of the third embodiments disclosed herein, the rubber composition comprises (further comprises) a cure package. Typically, the cure package comprises at least one of the following components: vulcanizing agents, vulcanization accelerators, vulcanization activators (e.g., zinc oxide, stearic acid, and the like), vulcanization inhibitors, and scorch retarders. In certain embodiments of the third embodiment, the curative package comprises at least one vulcanization agent, at least one vulcanization accelerator, at least one vulcanization activator, and optionally a vulcanization inhibitor and/or scorch retarder. Vulcanization accelerators and vulcanization activators are used as catalysts for the vulcanizing agents. Vulcanization inhibitors and scorch retarders are known in the art and can be selected by one skilled in the art based on the desired vulcanization properties.

Examples of suitable types of curing agents for use in certain embodiments of the third embodiment include, but are not limited to, sulfur-based curing components or peroxide-based curing components. Thus, in certain such embodiments, the curative component includes a sulfur-based curative or a peroxide-based curative. Examples of specific suitable sulfur-based vulcanizing agents include "rubber-specific (rubber maker)" soluble sulfur; sulfur-donating curing agents such as dithioamines, polymeric polysulfides, or sulfur olefin adducts; and insoluble polymeric sulfur. Preferably, the sulfur-based vulcanizing agent is soluble sulfur or a mixture of soluble and insoluble polymeric sulfur. For a general disclosure of suitable curatives and other components for curing, such as cure inhibitors and scorch retarders, reference may be made to Kirk-Othmer, Encyclopedia of Chemical Technology,3rd ed., Wiley Interscience, N.Y.1982, Vol.20, pp.365to 468(Kirk-Othmer, Encyclopedia of Chemical Technology, third Edition, West national Science, New York, 1982, Vol.20, pp.365to 468), in particular Vulcanization Agents and Autoliary Materials, pp.390402 ("curatives and Auxiliary Materials", pp.390to 402), or Vulcanization by A.Y. Coran, Encyclopedia of Polymer Science and Engineering, Second Edition John Wiley & Sons, Softy, Inc., incorporated by reference, the Second Edition of Engineering, Inc. of Japan, Inc. and Cork.1982. The vulcanizing agents may be used alone or in combination. Typically, the vulcanizing agent is used in an amount within the range of 0.1phr to 10phr, including 1phr to 7.5phr, including 1phr to 5phr, and preferably 1phr to 3.5 phr.

Vulcanization accelerators are used to control the time and/or temperature required for vulcanization and to improve the properties of the vulcanizate. Examples of vulcanization accelerators suitable for use in certain embodiments of the third embodiment disclosed herein include, but are not limited to, thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, 2' -dithiobis (benzothiazole) (MBTS), N-cyclohexyl-2-benzothiazole-sulfenamide (CBS), N-tert-butyl-2-benzothiazole-sulfenamide (TBBS), and the like; guanidine vulcanization accelerators such as Diphenylguanidine (DPG) and the like; a thiuram vulcanization accelerator; a urethane vulcanization accelerator; and the like. In general, the vulcanization accelerators are used in an amount in the range from 0.1phr to 10phr, preferably from 0.5phr to 5 phr.

Vulcanization activators are additives used to support vulcanization. Typically, the vulcanization activator comprises both an inorganic component and an organic component. Zinc oxide is the most widely used inorganic vulcanization activator. Various organic vulcanization activators are commonly used, including stearic acid, palmitic acid, lauric acid, and zinc salts of the foregoing. In general, the vulcanization activators are used in an amount ranging from 0.1phr to 6phr, preferably from 0.5phr to 4 phr.

Vulcanization inhibitors are used to control the vulcanization process and generally delay or inhibit vulcanization until the desired time and/or temperature is reached. Common vulcanization inhibitors include, but are not limited to, PVI (cyclohexyl thiophthalimide) available from Santogard. In general, the amount of vulcanization inhibitor is from 0.1phr to 3phr, preferably from 0.5phr to 2 phr.

Other ingredients

Various other ingredients that may optionally be added to the rubber compositions of the third embodiment disclosed herein include processing oils, waxes, processing aids, tackifying resins, plasticizing resins, reinforcing resins, and peptizers.

Various types of process oils and extender oils may be utilized including, but not limited to, aromatic oils, naphthenic oils, and low PCA oils as discussed above. Suitable low PCA oils include those having a polycyclic aromatic content of less than 3 weight percent as determined by the IP346 method. Procedures for the IP346 method can be found in Standard Methods for Analysis & Testing of Petroleum and related products published in 2003 by the Institute of Petroleum, United Kingdom and the Institute of United Kingdom, Standard 2000Parts, 62 nd edition, British Standard 2000 Parts. Suitable low PCA oils include Mild Extraction Solvates (MES), Treated Distillate Aromatic Extract (TDAE), TRAE, and heavy naphthenes. Suitable MES oils are commercially available as CATENEX SNR from Shell (SHELL), PROREX 15 and FLEXON 683 from Exxonmobil (EXXONMOBIL), VIVATEC200 from British oil company (BP), PLAAXOLENE MS from Dodar Philadelphia ELF (TOTAL FINA ELF), TUDALEN4160/4225 from DAHLEKE, MES-H from Repesol (REPSOL), MES from Z8 and OLIOMES 201 from AgIP. Suitable TDAE oils are available from EXXONMOBIL as TYREX 20, from British Petroleum (BP) as VIVATEC 500, VIVATEC 180 and ENERTHENE 1849, and from REPSOL as extrusiol 1996. Suitable heavy naphthenic OILs are available as SHELFLEX 794, ERGON BLACK OIL, ERGONH2000, CROSS C2400 and SAN JOAQUIN 2000L. Suitable low PCA oils also include oils of various vegetable origin, such as those harvestable from vegetables, nuts, and seeds. Non-limiting examples include, but are not limited to, soybean or soybean oil, sunflower oil (including high oleic sunflower oil with an oleic acid content of at least 60%, at least 70%, or at least 80%), safflower oil, corn oil, linseed oil, cottonseed oil, rapeseed oil, cashew nut oil, sesame oil, camellia oil, jojoba oil, macadamia nut oil, coconut oil, and palm oil. Generally, for most applications, the total amount of oil (processing oil and any extender oil) used in the rubber compositions disclosed herein ranges from about 1phr to about 70phr, including from 1phr to 70phr, from about 2phr to about 60phr, from 2phr to 60phr, from about 3phr to about 50phr, and from 3phr to 50 phr. However, in certain applications, the total amount of oil (processing oil and any extender oil) used in the rubber compositions and methods disclosed herein is much higher and ranges up to about 175phr, including up to 175phr, up to about 150phr, up to about 100phr, and up to 100 phr.

In certain embodiments of the third embodiment, the rubber composition comprises from about 5phr to about 60phr (e.g., 5phr, 10phr, 15phr, 20phr, 25phr, 30phr, 35phr, 40phr, 45phr, 50phr, 55phr, or 60phr), from 5phr to 60phr, from 5phr to 20phr, from about 25phr to about 60phr, from 25phr to 60phr, or from 30phr to 50phr of the at least one resin; in certain such embodiments, the at least one resin is a plasticizing resin. As used herein, the term plasticizing resin refers to a compound that is solid at room temperature (23 ℃) and miscible in the rubber composition in an amount that is typically at least 5 phr. Generally, the plasticizing resin will act as a diluent and may contrast with the normally immiscible tackifying resin and may migrate to the surface of the rubber composition providing tackiness. In certain embodiments of the third embodiment, wherein a plasticizing resin is utilized, it comprises a hydrocarbon resin and may be aliphatic, aromatic or aliphatic/aromatic depending on the monomers contained therein. Examples of the plasticizing resin suitable for the rubber composition of the third embodiment include, but are not limited to, cyclopentadiene (abbreviated as CPD) or dicyclopentadiene (abbreviated as DCPD) homopolymer or copolymer resins, terpene homopolymer or copolymer resins, and C5 fraction homopolymer or copolymer resins. Such resins may be used, for example, singly or in combination. In certain embodiments of the third embodiment, a plasticizing resin satisfying at least one of the following may be used: tg greater than 30 ℃ (preferably greater than 40 ℃ and/or not greater than 120 ℃ or not greater than 100 ℃), a number average molecular weight (Mn) between 400 and 2000 grams/mole (preferably 500-2000 grams/mole), and a Polydispersity Index (PI) less than 3 (preferably less than 2), where PI is Mvv/Mn, and Mvv is the weight average molecular weight of the resin. The Tg of the resin can be measured by DSC (differential scanning calorimetry) according to ASTM D3418 (1999). The Mw, Mn and PI of the resin can be determined by Size Exclusion Chromatography (SEC) using THF (35 ℃; concentration 1 g/1; flow rate 1 ml/min; filtration of the solution through a filter with 0.45 μm porosity prior to injection; molar calibration using polystyrene standards; 3 "Waters" column sets ("Styragel" HR4E, HR1 and HR0.5) in series; detected by differential reflectometry ("Waters 2410") and its associated operating software ("Waters Empower").

In certain embodiments of the third embodiment, using a diene monomer-containing functionalized polymer having a first functionalized group of formula (I) or formula (II) and a second functionalized group of formula (V) (i.e., the polymer prepared by the method of the first embodiment and/or the polymer according to the second embodiment), a rubber composition having a higher mooney viscosity, improved tan numbers at 60 ℃ and 0 ℃, and higher percent bound rubber can be produced as compared to a control rubber composition having a difunctional polymer replaced with a non-functionalized polymer (prepared under the same polymerization conditions using the same monomers and except lacking functionalization). In certain embodiments, at least one of the following is satisfied: (i) the mooney viscosity ML1+4 at 130 ℃ is at least 25% (e.g., at least 25%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90% or at least 100%) higher than the mooney viscosity of a control rubber composition having a bifunctional polymer (as discussed above) substituted for the bifunctional polymer, (e.g., at least 50%, at least 60%, at least 70%, at least 80%, at least 90% or at least 100% higher), at least 60%, at least 70%, at least 80%, 50% -100% higher or 50% -80% higher, (ii) the tan number at 60 ℃ is at least 5 indicator units (e.g., 5 indicator units, b) higher than the tan number at 60 ℃ of a control rubber composition having a nonfunctionalized polymer (as discussed above) substituted for the bifunctional polymer, 10 index units, 20 index units, 30 index units, 40 index units, 50 index units, 60 index units or higher), at least 10 index units higher (e.g., 10 index units, 20 index units, 30 index units, 40 index units, 50 index units, 60 index units or higher), at least 20 index units higher, at least 30 index units higher, at least 40 index units higher, at least 50 index units higher, at least 60 index units higher, 10-60 index units higher, or 10-50 index units higher; (iii) a tan value at 0 ℃ that is at least 5 index units (e.g., 5 index units, 10 index units, 15 index units, 20 index units, 30 index units, or higher), at least 10 index units higher, at least 20 index units higher, at least 30 index units higher, 5to 30 index units higher, or 5to 15 index units higher than a control rubber composition having a difunctional polymer (as discussed above) substituted for the difunctional polymer at 0 ℃; (iv) the% bound rubber is at least 400% (e.g., 400%, 500%, 600%, 700%, 800%, 900%, 1000%, 1100%, 1200%, or more), at least 500% higher, at least 700% higher, at least 900% higher, at least 1000% higher, at least 1200% higher, 500% -1200%, or 500% -1100% higher than the% bound rubber of a control rubber composition having a difunctional polymer (as discussed above) replaced with a non-functional polymer. In certain preferred embodiments, the mooney viscosity ML1+4 at 130 ℃ is at least 50% higher than the control rubber composition, the tan number at 60 ℃ is at least 30 indicator units (even more preferably, at least 40 indicator units) higher than the control rubber composition, and the bound rubber% is at least 500% higher than the control rubber composition. In certain embodiments, each of (i) - (iv) is satisfied.

Process for producing rubber composition

The rubber composition according to the third embodiment disclosed herein may be generally formed by: the ingredients of the rubber composition (as disclosed above) are mixed together by methods known in the art, such as, for example, by kneading the ingredients together in a banbury mixer or on grinding rolls. These processes typically include at least one non-productive masterbatch mixing stage and a final productive mixing stage. The term "non-productive masterbatch stage" is known to the person skilled in the art and is generally understood to mean a mixing stage in which no vulcanizing agent or vulcanization accelerator is added. The term final productive mixing stage is also known to those skilled in the art and is generally understood to be a mixing stage in which vulcanizing agents and vulcanization accelerators are added to the rubber composition. In certain embodiments of the third embodiment, a non-productive masterbatch mixing stage may be used in preparing the rubber composition. In certain embodiments of the third embodiment, more than one non-productive mother stock mixing stage is used. In certain embodiments of the third embodiment utilizing silica and a silica coupling agent, more than one non-productive masterbatch mixing stage is used, and at least a portion of the silica filler is added to the second non-productive masterbatch mixing stage (also referred to as the regrind stage); in certain such embodiments, all of the silica coupling agent (along with at least a portion of the silica filler) is added only in the second non-productive masterbatch mixing stage, and no silica coupling agent is added in the initial non-productive masterbatch mixing stage.

In certain embodiments of the third embodiment, the masterbatch mixing stage comprises at least one of serial mixing or intermeshing mixing. Inline mixing is understood to include the use of a mixer having two mixing chambers, wherein each chamber has a set of mixing rotors; typically, two mixing chambers are stacked together, with the upper mixing being the main mixer and the lower mixer receiving batch material from either the upper or main mixer. In certain embodiments, the main mixer utilizes intermeshing-type rotors, and in other embodiments, the main mixer utilizes tangential-type rotors. Preferably, the lower mixer utilizes a meshing type rotor. Intermeshing mixing is understood to include the use of mixers with intermeshing rotors. Intermeshing rotors refer to a set of rotors in which the major diameter of one rotor in the set interacts with the minor diameter of the opposing rotor in the set such that the rotors intermesh with each other. Due to the interaction between the rotors, the intermeshing type rotors must be driven at a uniform speed. By tangential type rotor is meant, in contrast to the meshed type rotor, a group of rotors: where each rotor rotates independently of the other in a cavity (which may be referred to as a side). Typically, a mixer with a tangential type rotor will include a plunger, whereas a plunger is not necessary in a mixer with a meshing type rotor.

In certain embodiments of the third embodiment, the rubber composition is prepared by performing the process with a non-productive masterbatch mixing stage at a temperature of about 130 ℃ to about 200 ℃. In certain embodiments of the third embodiment, the rubber composition is prepared by a process of a final productive mixing stage conducted at a temperature below the vulcanization temperature in order to avoid undesired pre-curing of the rubber composition. Thus, the temperature of the productive mixing stage should not exceed about 120 ℃, and typically is about 40 ℃ to about 120 ℃, or about 60 ℃ to about 110 ℃, and especially about 75 ℃ to about 100 ℃.