Methods and catalysts for hydrogen-mediated anionic copolymerization of conjugated dienes and liquid copolymers thereof

Abstract

The present disclosure relates to hydrogen-mediated anionic copolymerized conjugated diene vinyl aromatic compositions, copolymers of isoprene and / or butadiene with styrene, and methods and compositions for making the same.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This international application filed on February 28, 2023 under the Patent Cooperation Treaty claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 268,727, filed on March 1, 2022, entitled “PROCESS AND CATALYSTS FOR HYDROGEN MEDIATED ANIONIC COPOLYMERIZATION OF CONJUGATED DIENES AND LIQUID COPOLYMERS THEREO F,” the entire contents and substance of which are incorporated herein by reference as if fully set forth below. Technical Field

[0003] Various embodiments of the present disclosure generally relate to methods and compositions of conjugated diene (CD) compositions, copolymers of isoprene and / or butadiene and styrene monomers for hydrogen-mediated anionic copolymerization, and methods and compositions for preparing them. It is particularly suitable for forming hydrogen-mediated polyisoprene (HMPIP) and hydrogen-mediated polybutadiene (HMPBD) as a method and catalyst composition for liquid random copolymer distribution with polystyrene. The method can be used to form hydrogen-mediated random copolymers of styrene and butadiene, random copolymers of styrene and isoprene, and copolymers of styrene and other conjugated dienes. More generally, the method and catalyst can be used to form random copolymers (CD-VA or VA-CD copolymers) of vinyl aromatic (VA) monomers and conjugated diene (CD) monomers. The lithium alkoxide complexed saline hydride (LOXSH) catalyst disclosed herein can provide control over both regioselectivity and stereoselectivity during the copolymerization process to form a variety of hydrogen-mediated polyconjugated diene (HMPCD) copolymers with VA monomers, especially styrene monomers, and can excellently control the degree of polymerization and comonomer content. The hydrogen-mediated copolymer of polyconjugated diene and styrene (HMPCD-CoPS) ​​composition includes HMPIP-CoPS and HMPBD-CoPS product distributions. Background Art

[0004] Normally liquid butadiene-styrene random copolymers with high vinyl-1,2 content (about 70% by weight of the butadiene portion) and low vinyl-1,2 content (about 30% by weight of the butadiene portion) are commercial items with a wide range of applications, see below. The high vinyl-1,2 composition comprises 20% to 35% by weight or more styrene, has a number average molecular weight between 4500 and 5300 Daltons, a glass transition temperature (Tg) in the range of -38°C to -15°C, and a styrene content of about 1.5-2.0. g ) and a viscosity greater than 40,000 cps (45°C Brookfield). The low vinyl-1,2 content composition typically comprises 28 wt% styrene, has a number average molecular weight (M) of 3200 to 8600 Daltons n ), a glass transition temperature in the range of -65°C to -57°C, and a viscosity of 17,500 cP to 75,000 cP (25°C Brookfield). These butadiene-styrene copolymer compositions are prepared by anionic polymerization using sodium (Hsieh and Quirk Anionic Polymerization Principles and Practical Applications, page 616). Anionic polymerization using sodium requires stoichiometric levels of sodium, and although lower molecular weight compositions can be prepared, the cost increases significantly as the molecular weight decreases. It is necessary to economically produce liquid butadiene-styrene copolymers with controlled low molecular weights, which have much lower glass transition temperatures and much lower viscosities than currently available products. Such compositions should be prepared using efficient, low-cost catalysts and catalytic processes that highly control the following items: I) molecular weight distribution; II) butadiene microstructure (high, low and medium vinyl-1,2BD content); and III) styrene content.

[0005] The polymerization of dienes generally produces olefinic bonds within each polymerized unit, but the olefinic bonds can be one of several microstructural motifs, including microstructures with cis-1,4 bonds, trans-1,4 bonds, or vinyl-1,2 pendant to the polymer. (See, e.g., Figure 1 The polymer microstructure and polymer chain length distribution of conjugated dienes polymerized in this way can produce products with a range of characteristics, including glass transition temperature (T g), polymer viscosity, molecular weight, polydispersity, and asymmetry. The ability to selectively prepare copolymers of low molecular weight poly(conjugated dienes) with styrene while controlling viscosity and polymer microstructure will result in a new range of conjugated diene-styrene copolymer products. A less desirable microstructural unit formed in high vinyl polybutadiene compositions is the vinyl cyclopentane (VCP) repeat unit. This microstructure is less desirable for three reasons: 1) it reduces the number of double bonds available for derivatization; 2) it increases the glass transition temperature; and 3) it undesirably increases viscosity - relative to the composition number average molecular weight or M. n , increasing essentially exponentially. This motif is known to form under anionic polymerization conditions, where the penultimate vinyl-1,2-butadiene repeat unit of the living polybutadiene chain undergoes a cyclization reaction with the anionic lithium(polybutadienyl) anion end group. For the purpose of determining the total vinyl content, one VCP repeat unit is considered to be generated from two consecutive vinyl-1,2 motifs.

[0006] Generally speaking, high vinyl-1,2 low molecular weight polybutadiene compositions are formed under chain transfer conditions in which an aromatic hydrocarbon having one or more methyl groups (e.g., toluene) is the chain transfer agent. Effective chain transfer generally occurs when chain transfer polymerization is conducted at higher temperatures (>70°C) and / or higher ratios of polytertiary amine promoters (e.g., TMEDA) to lithium (TMEDA:Li in the range of 1.5:1 to 8:1). Therefore, in order to achieve the desired level of chain transfer - to prepare low molecular weight compositions - higher temperatures and higher promoter:Li ratios may be required. However, higher temperatures and / or higher amine to lithium ratios result in increasing levels of incorporation of the VCP microstructure of the polymer chains of the product composition. Therefore, low molecular weight compositions are not suitable for the production of polymers with the desired reduced M ratios. n The increased T g and viscosity.

[0007] According to the technical data sheet obtained from Cray Valley Ricon 100, Total brand, is a low molecular weight liquid copolymer of butadiene (80 wt%) and styrene (20 wt%), wherein the 1,2-content of the butadiene part is 70 wt%. Ricon 100 has an M of 4500 Daltons. n , -15℃ T g and a viscosity of 40,000cps at 45°C. Suggested applications for this resin include coatings, electronic laminates, tire treads, sealants, rubber, and flexographic printing plates. Similarly, Ricon 257 is a low molecular weight copolymer of butadiene (65 wt%) and styrene (35 wt%) sold as a formulation dissolved in toluene. Ricon 257 has a 1,2-content of 70 wt% of the butadiene portion, an M of 5300 Daltons, and a n , -38℃ T g and a solution viscosity of 900 cps at 25° C. Suggested applications for this resin formulation include electronics, copper clad laminates, composites, and elastomers. Ricon 181 is a low vinyl butadiene-styrene liquid copolymer comprising butadiene (72 wt%) and styrene (28 wt%), and the vinyl-1,2 content of the butadiene portion is 30 wt%. Ricon 181 has an M of 3200 Daltons. n , -65℃ T g and a viscosity of 17,500 cps at 25°C. Ricon 184 is a low vinyl butadiene-styrene liquid copolymer comprising butadiene (72 wt%) and styrene (28 wt%), and the vinyl-1,2 content of the butadiene portion is 30 wt%. Ricon 184 has an M of 8600 Daltons. n , -57℃ T g and a viscosity of 75,000 cps at 25° C. Both low vinyl grades are recommended for applications including coatings, electronics, laminating sealants, rubber and flexographic printing plates.

[0008] High vinyl-1,2 compositions can be very desirable because they are highly reactive and more easily crosslinked. However, when formed by organic chain transfer, such high vinyl-1,2 compositions have relatively high viscosities at low molecular weights, and lower molecular weights increase volatile content. Such compositions incorporate at least one organic chain transfer agent in each polymer chain that is distributed.

[0009] Thus, polybutadiene telomers (telomerization with toluene) can provide low molecular weight (900 Daltons, 1300 Daltons and 2600 Daltons, respectively) liquid butyl rubbers with low viscosity (300 cP, 700 cP and 8500 cP at 25°C Brookfield) with a vinyl content of less than about 50%. Such compositions are prepared at lower temperatures and require the addition of potassium or sodium metal alkoxides (e.g., potassium or sodium tert-butoxide). It is also understood in the art that telomerization catalysts formed from butyl lithium and TMEDA will provide BR telomers with 40% to 50% vinyl microstructure and 15% to 20% vinyl cyclopentane microstructure. n The Brookfield viscosity of such a BR telomer distribution at 25°C with a molecular weight of 1000 Daltons is 4000 cP. nThe Brookfield viscosity of the 1800 Dalton BR telomer distribution at 35° C. is 45,000 cP (in this regard, see Luxton, AR, Rubber Chem. & Tech., 1981, 54, 591).

[0010] High vinyl content may be desirable because vinyl-1,2 moieties react faster than 1,4-olefins in some chemical reactions. In addition, low viscosity, low T g and low molecular weight may be desirable physical properties and characteristics. Combining styrene as a comonomer with butadiene (or isoprene for that matter) will increase the viscosity of the composition. Low styrene content copolymer compositions may form high VCP content and therefore exhibit higher viscosity and increased glass transition temperature. It is desirable to have a copolymerization process chemistry that can provide butadiene-styrene copolymer compositions:

[0011] 1. Moderate or moderately high styrene content (10 wt% to 40 wt%), with high vinyl-1,2 content (>70% total vinyl content), low VCP content, which exhibits reduced viscosity and reduced glass transition temperature;

[0012] 2. A relatively high styrene content (25 to 40 wt %), with a moderately high vinyl-1,2 content (about 40 to about 70 wt % total vinyl content), low VCP content, which exhibits low viscosity and low glass transition temperature;

[0013] 3. Higher styrene content (25 wt% to 40 wt%), with low vinyl-1,2 content (about 30 wt% to about 40 wt% total vinyl content), low VCP content, which exhibits very low viscosity and very low glass transition temperature.

[0014] These desired compositions - which can be produced by the present disclosure - should also exhibit an iodine value / iodine number close to the theoretical value for the copolymer when adjusted for styrene content. The theoretical I2N for butadiene-styrene copolymers is given by the following equation (1):

[0015]

[0016] Where X BD is the weight fraction of butadiene repeating units. Correction of the above equation for VCP content provides the following equation (2), where X VCP It is the weight fraction of the VCP content of the total butadiene content. The VCP structural unit provides only one double bond per two butadiene units.

[0017]

[0018] Thus, it is desirable for a butadiene-styrene copolymer having a styrene content of 20 wt% to have an I2N equal to ≈80% of 456 and thus an iodine value in the range of about 350 to about 365 g I2 / 100 g copolymer.

[0019] Therefore, there remains a need for industrially efficient and cost-effective process technologies that can provide new liquid butadiene-styrene and isoprene-styrene copolymer compositions having moderately high (greater than 45 wt%) to high (up to about 80 wt%) vinyl-1,2BD content or a combined vinyl-3,4IP and vinyl-1,2IP content (as determined by proton NMR analysis). For butadiene-styrene copolymers, it is particularly desirable to maintain a high ratio of vinyl-1,2-BD to VCP and thus provide liquid polybutadiene compositions having increased reactivity (high iodine number) and low viscosity. In addition, the low molecular weight chains should consist only of polymerizable comonomers, styrene and conjugated dienes (i.e., little or no organic chain transfer agent incorporation).

[0020] By the process chemistry of the present disclosure, copolymer compositions having a whole range of relative comonomer contents of less than 100% to greater than 0% VA monomer content can be produced. And for clarity, CD monomer contents ranging from greater than 0% to less than 100% can likewise be produced. It should be noted that it is desirable that each discrete copolymer chain has at least one VA monomer. It is therefore desirable that the mole % of VA monomer should be such that the product [x VA *DP n ]≥1.0. Where x VA It has a number average degree of polymerization DP n For example, it is desirable to have a DP n =18 The weight fraction VA of the copolymer is about 11.1% and x VA =.0555%. Therefore, at lower DP n In this case, a higher VA monomer content is desirable and should be easily and accurately produced. VA *DP n ] < 1.0, it is mathematically determined that the product composition is a mixture of homopolymers and copolymers. Similar arguments can be easily made regarding the CD monomer content of high VA copolymers. Such mixtures of homopolymers and copolymers are considered to be new compositions that can be produced and are part of the present disclosure. All of these properties and characteristics of the liquid butadiene-styrene copolymer compositions cited above can be easily made by the process and catalyst of the present disclosure, via a very easily adjustable inexpensive catalyst system, and utilizing chain transfer affected by a very inexpensive chain transfer agent - hydrogen. Summary of the invention

[0021] Various embodiments of the present disclosure generally relate to methods, catalysts, compositions and polymer products for liquid conjugated diene-styrene copolymer products. One embodiment of the present disclosure may be a method for copolymerizing styrenes with conjugated diene monomers in a hydrocarbon reaction medium. The method may include chemically adding a lithium alcohol complexed salt-type hydride LOXSH reagent to a conjugated diene or styrene monomer to form a polymer initiating substance and polymerizing at least a portion of anionically polymerizable hydrocarbon monomers. Another embodiment of the present disclosure may be a method for hydrogen-mediated copolymerization of styrene monomers with conjugated diene monomers in a hydrocarbon reaction medium, wherein the method may similarly include chemically adding a lithium alcohol complexed salt-type hydride (LOXSH) reagent to a styrene monomer or a conjugated diene monomer to form a polymerization initiator, and polymerizing the copolymerized monomers in the presence of hydrogen or hydride mediation (e.g., organosilicon hydride). In each method, the LOXSH reagent comprises one or more σ-μ polar modifiers. The process may also be conducted in the presence of molecular hydrogen and may include co-feeding at least two gaseous and / or volatile compounds with at least one liquid styrenic comonomer to the reaction medium, wherein the at least two gaseous and / or volatile compounds include hydrogen and a conjugated diene.

[0022] One embodiment of the present disclosure may be the above copolymerization method, wherein the conjugated diene includes isoprene and / or butadiene. The method may include butadiene, isoprene, 2-methyl-1,3-pentadiene (E and Z isomers); piperylene; 2,3-dimethylbutadiene; 2-phenyl-1,3-butadiene; cyclohexadiene; b-myrcene; β-farnesene; and hexatriene. The random copolymerization method also requires copolymerizing the conjugated diene with a vinyl aromatic (VA) hydrocarbon monomer, which may include styrene, methyl styrene, higher C2-C10 alkyl styrene, vinyl naphthalene, α-methyl styrene, etc. Other vinyl aromatic monomers that can be used to practice the present disclosure may include 4-vinyl anisole and 6-methoxy-1-vinyl naphthalene, ortho-, para-, meta-N,N-dimethylaminostyrene and 6-N,N-dimethylamino-1-vinyl naphthalene and similar compositions, as long as the vinyl aromatic monomer does not have functional groups that will react with the catalyst, including halogens, carbonyl groups, nitriles, and other functional groups that would be expected to react with hydrides by one of ordinary skill in the art. The vinyl aromatic monomer should also have no pK a Less than 4.3 proton units lower than toluene in the reaction medium. It should be understood that the use of divinylbenzene and methylstyrene comonomers can produce HMPCD-CoPS copolymer compositions with branched polymer architectures. Such branched molecular architectures are embodiments of the present disclosure.

[0023] In one embodiment of the present disclosure, one or more σ-μ polar modifiers may be selected from one or more of structures I-IX:

[0024]

[0025] R may independently be an alkyl group, which may be further substituted by other tertiary amines or ethers. 1 R may independently be a hydrogen atom or an alkyl group, which may be further substituted by other tertiary amines or ethers. 2 It can be –(CH2) y –, where y=2, 3 or 4. Σ may include: i) O or NR for I, II, III, IV and V; ii) O or NR or CH2 for VI, VII, VIII and IX. The term n may independently be an integer equal to or greater than 0, and the term x may independently be an integer equal to or greater than 1. It should be understood and recognized that for structures V-IX above and below, when n is equal to zero, it means that the carbon atom is absent and there is a single covalent bond between two adjacent atoms of the structure. It should be understood and recognized that structures I-IX may include very complex chiral structures, such as those described in "Chart 1" (Parsons, Jr. RL et al., J. Am. Chem. Soc. 2001, 123, 9135-9143). Such chiral sm polar modifiers proposed by Parsons et al., etc., are incorporated herein by reference.

[0026] In one embodiment of the present disclosure, the reaction medium used in the method may be a A hydrocarbon solvent greater than H2. In one embodiment of the present disclosure, the reaction medium may include molecular hydrogen, and the partial pressure of the molecular hydrogen may be maintained by a set hydrogen regulator, or spontaneously maintained at a partial pressure between about 0.01 bar and about 19.0 bar by a set relative hydrogen feed rate. In one embodiment of the present disclosure, the method may include a temperature that can be maintained in the range of about 20°C to about 130°C. In one embodiment of the present disclosure, the method may include a relative feed rate of total monomer to hydrogen of about 5 moles to about 50 moles (CD+styrene monomer) / mole H2. In one embodiment of the present disclosure, the molar ratio of the total feed of monomer to the soluble salt-type hydride catalyst may be about 10:1 to about 1500:1. In one embodiment of the present disclosure, the salt-type hydride catalyst may be one or more of 1) LOXLiH reagent; 2) LOXNaH reagent; 3) LOXMgH2; and / or 4) LOXKH reagent.

[0027] In one embodiment of the present disclosure, the amino alcohol (AA) σ—μ polar modifier can be one or more of the following: N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino-2-butanol; trans-2-piperidinocyclohexan-1-ol; 1-phenyl-2-piperidin-1-ylethanol; 1-pyrrolidinoethanol; pyrrolidinylpropan-2-ol; 1-(1-pyrrolidinyl)-2-butanol; 1-phenyl- 2-(1-pyrrolidinyl)-1-ethanol; 2-pyrrolidinylcyclohexanol; 4-methyl-1-piperazineethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; 2-(4-methylpiperazino)-1-phenylethan-1-ol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol; 1-methyl-2-piperidinylmethanol; 1-methyl-2-pyrrolidinemethanol; diethylaminoethanol; N-methyl-diethanolamine; 3-dimethylamino-1-propanol; 1,3-bis(dimethylamino)-2-propanol; and 2-{[2-dimethylamino)ethyl]methylamino}ethanol;

[0028] In one embodiment of the present disclosure, the amino-ether alcohol (AEA) σ—μ polar modifier can be one or more of the following: 2-morpholinoethanol; 1-(4-morpholino)-2-propanol; 1-(4-morpholino)-2-butanol; 2-morpholino-1-phenyl-1-ethanol; trans-2-morpholin-4-ylcyclohexanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2-(2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholino)ethoxy]ethanol; 2-[2-(1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol.

[0029] In one embodiment of the present disclosure, the method may include one or more of the above-mentioned σ-μ polar modifiers, and may also include one or more of the ether-alcohol (EA) σ-μ polar modifiers 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, 2-methoxycyclohexan-1-ol, tetrahydrofurfuryl alcohol, tetrahydropyran-2-methanol, and diethylene glycol monomethyl ether.

[0030] In one embodiment of the present disclosure, the LOXSH catalyst may include between about 50 mol% and less than 100 mol% of a tertiary amino alcohol or tertiary amino-ether-alcohol σ-μ polar modifier and about 50 mol% to greater than 0 mol% of an ether-alcohol σ-μ polar modifier. The tertiary amino-alcohol σ-μ polar modifier is selected from one or more of the following: N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino-2-butanol; trans-2-piperidinocyclohexan-1-ol; 1-phenyl -2-piperidin-1-ylethanol; 1-pyrrolidinylethanol; pyrrolidinylpropan-2-ol; 1-(1-pyrrolidinyl)-2-butanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 2-pyrrolidinylcyclohexanol; 4-methyl-1-piperazineethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; 2-(4-methylpiperazinyl)-1-phenylethyl-1- alcohol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol; 2-morpholinoethanol; 1-(4-morpholino)-2-propanol; 1-(4-morpholino)-2-butanol; 2-morpholino-1-phenyl-1-ethanol; trans-2-morpholin-4-ylcyclohexanol; 1-methyl-2-piperidinylmethanol; 1-methyl-2-pyrrolidinemethanol; diethylaminoethanol, N-methyl-diethanolamine and 3-dimethylamino-1-propanol, 2-[2- [(dimethylamino)ethoxy]ethanol, 1,3-bis(dimethylamino)-2-propanol; 2-{[2-dimethylamino)ethyl]methylamino}ethanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2-(2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholinyl)ethoxy]ethanol; 2-[2-(1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol. The ether-alcohol σ-μ polar modifier can be selected from one or more of 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, trans-2-methoxycyclohexan-1-ol, 2-methoxy-1-phenylethanol, tetrahydrofurfuryl alcohol or tetrahydropyran-2-methanol or diethylene glycol monomethyl ether.

[0031] In one embodiment, the method may further include one or both of an m-type polar modifier (eg, sodium menthol, etc.) and / or an s-type polar modifier (eg, THF, TMEDA, etc.).

[0032] One embodiment of the present disclosure may include a LOXSH catalyst or reagent composition, wherein the composition may be selective for 1,4-CD monomer microstructure enchainment. The composition may include 1) at least one tertiary amino alcohol σ-μ polar modifier having a 2° or 3° alcohol functional group; 2) an organolithium compound; and 3) optionally elemental hydrogen and / or an organosilicon hydride. The polar modifier may be selected from at least one of the following structures:

[0033]

[0034] Wherein R is independently an alkyl group, and the alkyl group may be further substituted by other tertiary amines or ethers, 1 is independently a hydrogen atom or an alkyl group, which alkyl group may be further substituted with other tertiary amines or ethers, Σ may include: i) O or NR for III, IV and V; ii) and for VI, VII and IX, may include O or NR or CH2; n is independently an integer equal to or greater than 0, and x is independently an integer equal to or greater than 1. The σ—μ polar modifier may include one or more of the following: 1-dimethylamino-2-propanol, 1-piperidino-2-propanol, 1-pyrrolidinylpropan-2-ol, 1-morpholino-2-propanol, 1-(4-methyl-1-piperazinyl)-2-propanol, 1-dimethylamino-2-butanol, 1-piperidino-2-butanol, 1-pyrrolidinylbutan-2-ol, 1-morpholino-2-butanol, 1-(4-methyl-1-piperazinyl)-2-butanol, 2-dimethylaminocyclohexan-1-ol, 2-piperidinocyclohexan-1-ol, 2-pyrrolidinylcyclohexanol, 2-(4-methyl-1-piperazinyl)-cyclohexanol alcohol, 2-morpholinocyclohexan-1-ol, 2-(dimethylamino)-1-phenylethanol; 1-phenyl-2-piperidin-1-ylethanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 2-(4-methylpiperazino)-1-phenylethan-1-ol; 2-morpholino-1-phenyl-1-ethanol, 1,3-bis(dimethylamino)-2-propanol, optionally with the addition of one or more of 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, 2-methoxycyclohexan-1-ol, 2-methoxy-1-phenylethanol, tetrahydrofurfuryl alcohol or tetrahydropyran-2-methanol; or diethylene glycol monomethyl ether.

[0035] Embodiments of the present disclosure may include LOXSH catalyst or reagent compositions, wherein the compositions may be selective for 3,4-CD and / or vinyl 1,2-CD monomer microstructure attachment. The compositions may include a) at least one tertiary amino alcohol or tertiary ether alcohol σ-μ polar modifier; b) at least one separate ether-alcohol σ-μ polar modifier; c) an organolithium compound; and d) optionally elemental hydrogen and / or an organosilicon hydride. The σ-μ polar modifier may be selected from at least two of the following structures:

[0036]

[0037] Wherein R is independently an alkyl group, and the alkyl group may be further substituted by other tertiary amines or ethers, 1 are independently hydrogen atoms or alkyl groups, and the alkyl groups may be further substituted by other tertiary amines or ethers. 2 For –(CH2) y–, wherein y=2, 3 or 4, Σ may include: i) O or NR for I, II, III, IV and V; ii) and for VI, VII, VIII and IX, may include O or NR or CH2; n is independently an integer equal to or greater than 0, and x is independently an integer equal to or greater than 1. The σ-μ polar modifier of the reagent comprises between about 50 mol% and less than 100 mol% of a tertiary amino alcohol or tertiary amino ether alcohol σ-μ polar modifier selected from one or more of the following: N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino 1-(4-methyl-1-piperazinyl)-2-propanol; ... (4-Methylpiperazinyl)-1-phenylethan-1-ol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol; 2-morpholinoethanol; 1-(4-morpholino)-2-propanol; 1-(4-morpholino)-2-butanol; 2-morpholino-1-phenyl-1-ethanol; trans-2-morpholin-4-ylcyclohexanol; 1-methyl-2-piperidinylmethanol; 1-methyl-2-pyrrolidinemethanol; diethylaminoethanol, N-methyl-diethanolamine and 3-dimethylamino-1 -propanol, 2-[2-(dimethylamino)ethoxy]ethanol, 1,3-bis(dimethylamino)-2-propanol; 2-{[2-dimethylamino)ethyl]methylamino}ethanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2-(2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholinyl)ethoxy]ethanol; 2-[2-(1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol. The ether-alcohol σ-μ polar modifier can be selected from one or more of 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, trans-2-methoxycyclohexan-1-ol, 2-methoxy-1-phenylethanol, tetrahydrofurfuryl alcohol or tetrahydropyran-2-methanol or diethylene glycol monomethyl ether. In one embodiment, the ratio of total amino-alcohol (AA) and / or amino-ether-alcohol (AEA) to total individual ether-alcohol (EE) sigma-μ polar modifiers ([AA+AEA]:EA) is in the range of about 9:1 to 1:1, and preferably in the range of about 4:1 to about 2:1.

[0038] One embodiment of the present disclosure may include a hydrogen mediated anionic VA-CD copolymer distribution composition, which may be characterized as having 1) a number average degree of polymerization DP ranging from about 7 to about 50 repeating units n ; 2) a Brookfield viscosity (45°C) in the range of about 10 cP to about 300,000 cP; 3) a 1,4-CD microstructure amount in the range of 20% to about 80%; and 4) a glass transition temperature T in the range of about -110°C to about 5°C g BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 A standard polymer microstructure unit of a polyconjugated diene according to an exemplary embodiment of the present disclosure, including a microstructure of a conjugated diene-styrene copolymer composition, is shown.

[0040] Figure 2 The viscosity of HMPBD homopolymer (Y-axis, Brookfield, 45°C, cP) is shown relative to M n The XY-scatter data of (X-axis, Daltons) disclosed in the commonly owned co-pending application (WO2022051376A1) provides a lower limit for the viscosity values ​​of the butadiene-styrene copolymers of the present disclosure relative to the molecular weight.

[0041] Figure 3 The viscosity (Y-axis, Brookfield, 45° C., cP) of high vinyl 1,2-BD butadiene-styrene copolymers containing a range of styrene contents according to exemplary embodiments of the present disclosure is shown relative to M n XY-scatter data of (X-axis, Daltons).

[0042] Figure 4 The viscosity (Y-axis, Brookfield, 45° C., cP) of butadiene-styrene copolymers containing 28 wt % styrene with a range of vinyl 1,2-BD contents according to exemplary embodiments of the present disclosure is shown relative to M n XY-scatter data of (X-axis, Daltons).

[0043] Figure 5 The 1 / T ratio of the high vinyl 1,2-BD butadiene-styrene copolymer including a certain range of styrene content according to an exemplary embodiment of the present disclosure is shown. g (y-axis K -1 ) relative to 1 / M n (X axis, Dalton -1 ) of XY-scatter data.

[0044] Figure 61 / T of a butadiene-styrene copolymer containing 28 wt % styrene and containing a certain range of vinyl 1,2-BD contents according to an exemplary embodiment of the present disclosure is shown. g (y-axis K -1 ) relative to 1 / M n (X axis, Dalton -1 ) of XY-scatter data.

[0045] Figure 7 The weighted average DP of a butadiene-styrene copolymer composition according to an exemplary embodiment of the present disclosure is shown. n - (individually related, separated based on high or low vinyl content) - (after stripping of solvent and low molecular weight butadiene-styrene copolymer oligomers) as a function of the ratio of total butadiene and styrene to total hydrogen, indicating that any DP in the range of about 5 to about 45 repeating comonomer units can be produced by design n .

[0046] Figure 8 The weighted average M of the butadiene-styrene copolymer composition according to an exemplary embodiment of the present disclosure is shown. n - (individually related, separated based on high or low vinyl content) - (after stripping of solvent and low molecular weight butadiene-styrene copolymer oligomers) with the calculated weighted M derived from the ratio of total butadiene and styrene to total hydrogen n The calibration of the functional relationship of , shows that any M in the range of about 500 Daltons to about 4000 Daltons can be produced by design. n .

[0047] Fig. 9 The structure activity relationship of a preferred tertiary amino alcohol sigma-μ polar modifier for forming a catalyst according to an exemplary embodiment of the present disclosure is shown.

[0048] Fig.10 The reaction pressure and temperature profiles for Examples 7 and 8 are shown, indicating that the autogenous pressures for each Example are different, primarily due to the titanium (IV) tert-butoxide activator of Example 8.

[0049] Fig.11 The reaction pressure and temperature curve of Example 21 is shown, in which a vinyl-1,2-selective 2-piperidinoethanol σ-μ polar modifier is used to form M n The product composition was a high vinyl 1,2-BD microstructured butadiene-styrene copolymer (29.6 wt% styrene) of 1849 Daltons.

[0050] Fig.12The reaction pressure and temperature profiles of Examples 28-30 according to exemplary embodiments of the present disclosure are shown, wherein 1,4-BD selective LOXLiH is formed from 1-piperidino-2-butanol as a σ-μ polar modifier, wherein M n The low vinyl butadiene-styrene copolymer distribution compositions (28 wt% styrene) are 2004, 1318 and 2265 Daltons respectively. This comparison clearly illustrates how the autogenous pressure can be adjusted depending on the total comonomer to hydrogen ratio. DETAILED DESCRIPTION

[0051] Although the preferred embodiments of the present disclosure are explained in detail, it should be understood that other embodiments are considered. Therefore, the scope of the present disclosure is not intended to be limited to the details of the construction and arrangement of the components set forth in the following description or illustrated in the accompanying drawings. The present disclosure can have other embodiments and can be practiced or implemented in a variety of ways. In addition, when describing the preferred embodiments, specific terms will be adopted for the sake of clarity.

[0052] It must also be noted that, as used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0053] In addition, in describing the preferred embodiments, terminology will be employed for the sake of clarity. Each term is intended to encompass its broadest meaning as understood by those skilled in the art, and includes all technical equivalents that operate in a similar manner to accomplish a similar purpose.

[0054] Ranges may be expressed herein as from “about” or “approximately” one particular value and / or to “about” or “approximately” another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value.

[0055] “Comprising” or “comprising” or “including” means that at least the named compound, element, particle or method step is present in the composition or article or method, but does not exclude the presence of other compounds, materials, particles, method steps, even if other such compounds, materials, particles, method steps have the same function as the named substance.

[0056] The term "and / or" refers to either a single or a combination. For example, "A and / or B" means "A" alone, "B" alone, or a combination of A and B.

[0057] The term "with or without" means singular or in combination. For example, A with or without B means "A" alone or in combination with A and B.

[0058] It should also be understood that reference to one or more method or process steps does not exclude the presence of additional method steps or intervening method steps between those steps explicitly identified. Similarly, it should also be understood that reference to one or more components in an apparatus or system does not exclude the presence of additional components or intervening components between those components explicitly identified.

[0059] Unless otherwise specified, the term "alkyl" as used herein includes saturated monovalent hydrocarbon groups having straight or branched chain portions. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl.

[0060] As used herein, unless otherwise indicated, the term "aryl" includes organic radicals derived from aromatic hydrocarbons by removing one hydrogen, such as phenyl, naphthyl, indenyl, and fluorenyl. "Aryl" encompasses fused ring radicals in which at least one ring is aromatic.

[0061] The term "aralkyl" as used herein refers to an "aryl-alkyl-" group. Non-limiting examples of aralkyl groups are benzyl (C6H5CH2-) and methylbenzyl (CH3C6H4CH2-).

[0062] The term "alkaryl" as used herein means an "alkyl-aryl-" group. Non-limiting examples of alkaryl are methylphenyl-, dimethylphenyl-, ethylphenyl-, propylphenyl-, isopropylphenyl-, butylphenyl-, isobutylphenyl- and tert-butylphenyl-.

[0063] Unless otherwise indicated, the term "cycloalkyl" as used herein includes non-aromatic saturated cycloalkyl moieties, wherein alkyl is as defined above. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

[0064] Unless otherwise indicated, the term "polymer" as used herein refers to the term "polymer" as defined in the context of the OECD definition of "polymer", which is defined as follows:

[0065] “A chemical substance consisting of molecules characterized by a sequence of one or more types of monomeric units and in which a simple weight majority of the molecules contain at least three monomeric units covalently bonded to at least one other monomeric unit or other reactant and in which molecules less than a simple weight majority have the same molecular weight. Such molecules must be distributed over a range of molecular weights in which differences in molecular weight are primarily attributable to differences in the number of monomeric units.”

[0066] Therefore, the OECD definition is also applicable to the term copolymer. In the present disclosure, the term copolymer is applicable to any polymer comprising two or more polymerizable monomer units. Exemplary embodiments of the present disclosure are generally copolymers of two polymerizable comonomers (i.e., isoprene and styrene and butadiene and styrene), and the present disclosure also contemplates the use of three or more comonomers. It should be noted that hydrogen is a monomer of the present disclosure because it is incorporated into the composition of the present disclosure. It is not just a polymerizable monomer.

[0067] As used herein, unless otherwise specified, salt hydrides (meaning ionic hydrides) are defined as hydrogen present as the negatively charged ion H in combination with an alkali metal, including lithium, sodium, potassium, rubidium, and cesium, or an alkaline earth metal, including magnesium and calcium.

[0068] Polymer microstructure and molecular architecture: As used herein, polymer microstructure refers to the configuration of discrete polymer chains (or the distribution of chain lengths of such chains) in terms of their composition, sequence distribution, spatial configuration, geometry, and substitution isomerism. An important microstructural feature of a polymer can be its architecture and shape, which is related to the way branching points lead to deviations from simple linear chains. For anionically polymerized polybutadiene and polyisoprene, it is well known that microstructures of several compositions can be formed (see Figure 1 ).

[0069] Unless otherwise specified, the polar modifiers used in this article generally include four different cases, depending on their interaction and complexation mode with the cationic counterions of the polymerization catalyst and / or initiator. The names are σ, μ, σ+μ and σ-μ. "σ complex" refers to a polar modifier that is a Lewis base, for example, THF, TMEDA. "μ complex" refers to a polar modifier that is a Lewis acid, for example, sodium menthol (SMT). "σ+μ complex" refers to a mixture of polar modifiers containing both Lewis bases and acids. "σ-μ complex" refers to a polar modifier in which the Lewis base and the acid are on the same ligand, for example, DMEA (DMAE). Kozak and Matlengiewicz provided a comparison of the different effects of 20 individual polar modifiers or polar modifier combinations (i.e., σ+μ initiators) on the vinyl content of anionically polymerized butadiene (ranging from 10% to 90% vinyl-1,2) (Kozak, R., Matlengiewicz, M., "Influence of Polar Modifiers on Microstructure of Polybutadiene Obtained by Anionic Polymerization, Part 5: Comparison of μ, σ, σ+μ and σ—μ Complexes" Int. J. Polym. Anal. Charact. 2017, 22, 51-61).

[0070] Unless otherwise specified, LOXSH as used herein may include a lithium amine-alkoxide complex salt hydride, a lithium amine-ether-alkoxide complex salt hydride or a lithium ether-alkoxide complex salt hydride formed from: (i) molecular hydrogen; (ii) an organolithium compound with or without an organomagnesium compound; (iii) an optional polytertiary amine compound (sigma-type polar modifier); (iv) a tertiary amino alcohol and / or a tertiary amino ether alcohol and / or an ether alcohol (sigma-μ polar modifier); (v) an optional solid alkali metal or alkaline earth metal hydride or an alkali metal or alkali metal alloy; (vi) an optional aromatic hydrocarbon, at least one of which has a C—H covalent bond pK a Above the pK of toluene a 2.75pK a Units below the pK of toluene a -4.30pK a units; and (vii) pK a greater than H2 hydrocarbon solvent; wherein the aromatic hydrocarbon and the hydrocarbon solvent may be the same or different (see: Daasbjerg, K, Acta Chemica Scandinavica, 1995, 49, 878: "Estimation of the pK afor some Hydrocarbons andAldehydes and Solvation Energies of the Corresponding Anions”).

[0071] LOXLiH is a term for a monometallic form of LOXSH, wherein the catalyst / reagent is formed with a lithium reagent as the sole metal reagent. LOXNaH is a term for a bimetallic catalyst composed of lithium and sodium, wherein a portion of the active salt hydride is sodium hydride. LOXKH is a term for a bimetallic catalyst composed of lithium and potassium, wherein a portion of the active salt hydride is potassium hydride. LOXMgH2 is a term for a bimetallic catalyst composed of lithium and magnesium, wherein a portion of the active salt hydride is magnesium hydride.

[0072] A brief summary of the parameters used to describe molecular weight distribution and the equations defining them is shown in Table 1 below. (A. Rudin, The Elements of Polymer Science and Engineering, Academic Press, Orlando, 1982, pp. 54-58). Molecular weight data are determined by GPC using polystyrene hydrogen mediated anionic polystyrene (HMAPS) oligomer distribution standards, or, where appropriate, commercial polystyrene standards and commercial polybutadiene standards. The procedure is described in the Analytical Methods section of this disclosure.

[0073] Table I

[0074]

[0075] The term "molecular hydrogen", also called "elemental hydrogen", refers to H2. H2 usually refers to the common isotope 1 H2, but may also include isotopes of hydrogen 2 H2 or 3 H2, either as a mixture of isotopes or enriched in a specific isotope, either in the gaseous state in the vapor space or dissolved in the condensed phase.

[0076] The term "polar complexing agent" ([PCA] in the chemical formula) is a generic term for neutral alcohol sigma-μ polar modifiers (PMs) used to form the catalysts of the present disclosure, such as tertiary amino alcohols, tertiary amino ether-alcohols, or ether-alcohols.

[0077] The present disclosure relates to a method for copolymerizing conjugated dienes with certain vinyl aromatic monomers, particularly styrenic hydrocarbon monomers. The copolymerization method can be described in several different steps, including but not limited to initiation, polymerization, chain transfer and termination. Although it is convenient to refer to these steps as sequential steps and individual steps, the reaction mixture may undergo one or more of these steps at any time point. However, generally and without wishing to be bound by theory, the first step in the method may be an initiation step, wherein a catalyst composition, a polymerization reagent, a reactive initiator or other substance may be formed in a solution and may subsequently react with a monomer. When describing an "initiating solution" or "initiating reagent" or other initiating substance, it will be appreciated by a person of ordinary skill that the actual substance in the solution may be stoichiometrically identical or different from the components used to form it, but the reaction may still be described based on the components used to prepare the substance.

[0078] In the present disclosure, the initiation step may involve chemical addition of a salt hydride of a lithium alkoxide complexed salt hydride (LOXSH) reagent to a conjugated diene and / or a vinyl aromatic comonomer (hydrometallation reaction), and wherein the LOXSH reagent comprises one or more σ-μ polar modifiers. The present disclosure may also include a method for hydrogen-mediated copolymerization of a conjugated diene with a vinyl aromatic comonomer, wherein the initiation step may involve chemical addition of a salt hydride of a lithium alkoxide complexed salt hydride (LOXSH) reagent to a conjugated diene and / or a vinyl aromatic comonomer, and wherein: 1) the LOXSH reagent comprises one or more σ-μ polar modifiers; and 2) the method may be performed in the presence of elemental hydrogen. The initiation step may also include chemical addition of the LOXSH reagent to ethylene or any other anionically polymerizable hydrocarbon monomer (Hsieh and Quirk pp. 96-99, including only hydrocarbon monomers).

[0079] The hydrogen-mediated copolymerization of the conjugated diene and vinyl aromatic comonomer of the present disclosure can utilize a σ-μ polar modifier. These σ-μ polar modifiers can be selected from at least one of the following structures:

[0080]

[0081] Wherein R is independently an organic group, which may be further substituted by other tertiary amines or ethers, 1 are independently hydrogen atoms or organic groups, which may be further substituted by other tertiary amines or ethers, R 2 For –(CH2) y-group, wherein y=2, 3 or 4, Σ may include: i) O or NR for I, II, III, IV and V; ii) and for VI, VII, VIII and IX, may include O or NR or CH2; the index value n is independently an integer equal to or greater than 0, and the index value x is independently an integer equal to or greater than 1. Preferably, R may be an alkyl or cycloalkyl group, more preferably an alkyl group, which may be further substituted with other tertiary amines or ethers. Similarly, R1 may preferably be an alkyl or cycloalkyl group, more preferably an alkyl group, which may be further substituted with other tertiary amines or ethers.

[0082] LOXSH catalysts, also known as LOXSH reagents, LOXSH reagent catalysts or LOXSH reagent compositions, can be prepared as described in commonly owned WO2017176740 “Process and Hydrocarbon Soluble Saline Hydride Catalystfor Hydrogen Mediated Saline Hydride Initiated Anionic Chain TransferPolymerization and Polymer Distribution Compositions Produced Therefrom”, the contents of which are incorporated by reference into the present disclosure as if fully set forth herein.

[0083] The method of the present disclosure may include simultaneously feeding a vinyl aromatic comonomer and at least two gaseous and / or volatile compounds to a reaction medium, wherein the two or more gaseous and / or volatile compounds include hydrogen and a low-boiling conjugated diene. The low-boiling conjugated diene includes a conjugated diene with a low vapor pressure, which may make it difficult to maintain a standard solution phase. The low-boiling conjugated diene may have a boiling point below 200°C, or preferably below 100°C, below 80°C or below 70°C. In general, the low-boiling conjugated diene monomer is any such monomer having a boiling point lower than the desired hydrogen-mediated anionic copolymerization reaction temperature by about 15°C to 20°C (or lower), making it ineffective to run the method at a set hydrogen pressure.

[0084] Preferred conjugated dienes (CD) include isoprene (IP and PIP for polymers) and / or butadiene (BD or PBD for polymers). The method may further include styrene, styrenes, or other vinyl aromatic comonomers, which are randomly copolymerized with the conjugated diene. Other anionically polymerizable conjugated diene monomers useful in the present disclosure include 2-methyl-1,3-pentadiene (E and Z isomers); piperylene; 2,3-dimethylbutadiene; 2-phenyl-1,3-butadiene; cyclohexadiene; b-myrcene; and β-farnesene; or 2-methyl-1,3-pentadiene (E and Z isomers); piperylene; 2,3-dimethylbutadiene; 2-phenyl-1,3-butadiene; cyclohexadiene; or piperylene and 2,3-dimethylbutadiene. It is contemplated that geminally disubstituted dialkyl-cyclopentadienes may be used in the methods of the present disclosure. It should be noted that (Z)-1,3,5-hexatriene and hexatriene, although not conjugated dienes but conjugated trienes, may also be used in the present disclosure. The method may also include an amount of ethylene as an anionically polymerizable hydrocarbon monomer.

[0085] The methods of the present disclosure may be performed in a manner that includes a pK a The method may be carried out in a reaction medium of a hydrocarbon solvent having a concentration greater than H2. The method may also be characterized by a partial pressure of molecular hydrogen, wherein the partial pressure may be maintained at a pressure of about 0.01 bar to about 19.0 bar. The temperature of the method may be maintained in the range of about 20°C to about 130°C, about 30°C to about 120°C, or about 40°C to about 115°C. In the method, the molar ratio of the total feed of monomers to the initially formed soluble salt-type hydride catalyst may be from about 10:1 to about 2000:1, preferably from 20:1 to about 1500:1, and most preferably from 50:1 to about 1200:1, and the salt-type hydride catalyst may be one or more of the following: 1) LOXLiH reagent; 2) LOXNaH reagent; 3) LOXMgH2 reagent; 4) LOXKH reagent 5) LOXRbH; and / or 6) LOXCsH.

[0086] The process of the present disclosure may involve feeding low boiling point conjugated dienes, including gaseous conjugated dienes such as 1,3-butadiene, isoprene (where BP < 50°C), styrene (and / or styrenics and / or other vinyl aromatic comonomers), and hydrogen at set molar ratios throughout the feed process - allowing the reactor pressure (which may be a function of any solvent vapor pressure, partial pressures of vinyl aromatic comonomers, hydrogen, and volatile conjugated dienes) to spontaneously adjust to achieve any activity of the hydrogen and conjugated dienes in the condensed phase required to operate the process efficiently and at a relatively steady-state pressure and temperature. In some embodiments, the steady-state pressure remains constant or nearly constant. In other embodiments, where a large ratio of total monomer to added catalyst is used, especially where a more viscous product is formed, the reaction pressure may drift upward during the hydrogen-mediated anionic copolymerization process. This mode of operation may be achieved by Figures 10 to 12 The method comprises co-feeding a low boiling point conjugated diene (e.g., 1,3-butadiene) with a vinyl aromatic monomer (e.g., styrene) and hydrogen to a copolymerization reaction mixture in a preset molar ratio in a portion of the co-feed (preferably three simultaneous feeds) or preferably throughout the entire process, wherein the reactor pressure is spontaneously adjusted to the subsequent condensed phase activity of hydrogen and conjugated diene at a relatively steady-state pressure and temperature. The preset molar ratio can be changed during the process as needed. Such a method provides an accurate and reproducible product distribution composition, wherein the number average molecular weight M n It is proportional to the total amount of butadiene and styrene fed divided by the number of moles of hydrogen consumed, which is given by Figure 7 and Figure 8 The DP can be selected by adjusting the instantaneous relative feed ratio of total monomer to hydrogen into the reaction medium. n , and then select the number average molecular weight. DP n The exact feed rate is not critical; instead, when determining the desired DP n The relative feed rate is important. The weighted average of the feed monomers in terms of mole fraction (x) determines the FW of the monomers. ave The weighted average of n The product of can provide the desired M n. The exact feed rate (in terms of total monomer per unit time relative to catalyst feed) can help shape the distribution (broaden or narrow the width and affect asymmetry) as well as have an impact on the product microstructure, particularly for liquid polybutadiene copolymer compositions. Thus, the process of the present disclosure can provide a relatively narrow molecular weight distribution MWD with a polydispersity in the range of about 1.6 to about 2.5, preferably in the range of 1.6 to about 2.2, and a low asymmetry in the range of 2.0 to about 3.4, preferably in the range of 2.0 to 2.7. The spontaneously generated reaction pressure can be the result or product of some combination of: a) the relative feed rate of hydrogen relative to the total monomer; b) the reactant feed rate relative to the catalyst concentration; c) the reaction temperature; d) the activity of the particular LOXSH catalyst; and e) the vapor pressure of the reaction medium or solvent. Generally speaking, LOXLiH and LOXNaH catalyst compositions that tend to form high vinyl-1,2 content compositions also tend to be the most active catalysts and provide processes that operate at lower pressures and / or lower temperatures with set relative feeds and set relative feed rates. Figures 10 to 12 The reactor temperature and pressure curves shown in illustrate how the reactor pressure can be set spontaneously, or in other words, how the reactor pressure is "internally generated" from the reaction and reactor processes.

[0087] In the practice of the present disclosure, a crude reaction mixture may be formed by co-feeding VA and CD comonomers simultaneously with hydrogen to a reaction medium comprising a LOXSH catalyst. The relative feed of the total amount of VA and CD comonomers relative to hydrogen may be in the range of about 5 moles to about 50 moles (VA+CD) / mole H2. The relative feed rate of combined VA and CD monomers (e.g., styrene and butadiene) to hydrogen may be in the range of about 8 to about 42 moles (VA+CD) / mole H2. The relative feed may be in the range of about 14 to about 37 moles (VA+CD) / mole H2. In the range of about 15 to about 30 moles (VA+CD) / mole H2, the M of the solvent and oligomer stripping product may be in the range of about 15 to about 30 moles (VA+CD) / mole H2. n Distribution Approach Theory M n =(mol VA + mol CD) / mol H2)*[x VA FW VA +x CD FW CD ](like Figure 8 As shown), where x VA FW VA is the mole fraction of the vinyl aromatic monomer (x VA ) and chemical formula weight (FW VA ), and x CD FWCD is the mole fraction of the conjugated diene monomer (x CD ) and chemical formula weight (FWCD ). In the process of the present disclosure, the simultaneous co-feeding of VA and CD monomers with H2 can be carried out for about 20 minutes, about 40 minutes, or about 60 minutes or longer. The process of the present disclosure can be carried out intermittently for up to about 480 minutes, or for continuous operation, the time can be longer. For intermittent or semi-intermittent operation modes, the total co-feeding time can be in the range of about 60 minutes to about 240 minutes.

[0088] In the present disclosure, the relative feed rate of (VA+CD) / mole H2 / unit time can vary in the range of 0.0333 moles (VA+CD) / mole H2 / minute for the lowest molecular weight composition to 0.6667 moles (VA+CD) / mole H2 / minute for the highest molecular weight composition. Thus, the relative feed rate of (VA+CD) / H2 / unit time can vary within the following ranges: A) for the lowest molecular weights from about [8 mol (styrene+BD) / mol H2] / 240 minutes = 0.0333 mol (styrene+BD) / mol H2 / minute to about [8 mol (styrene+BD) / mol H2] / 60 minutes = 0.1333 mol (styrene+BD) / mol H2 / minute; and B) for the highest molecular weights from [40 mol (styrene+BD) / mol H2] / 240 minutes = 0.1667 mol (styrene+BD) / mol H2 / minute to about [40 mol (styrene+BD) / mol H2] / 60 minutes = 0.6667 mol (styrene+BD) / mol H2 / minute. The co-feed time of the monomers and hydrogen can be in the range of about 90 minutes to 180 minutes. The relative feed rate of (VA+CD) / H2 / unit time can vary in the range of 0.0833 mol (VA+CD) / mol H2 / minute for the lowest molecular weight composition to 0.3333 mol (VA+CD) / mol H2 / minute for the highest molecular weight composition. Thus, the relative feed rate of (VA+CD) / mol H2 / unit time may vary within the following range: A) from about [15 mol (styrene+BD) / mol H2] / 180 minutes = 0.0833 mol (styrene+BD) / mol H2 / minute for the lowest molecular weight to about [15 mol (styrene+BD) / mol H2] / 90 minutes = 0.1667 mol (styrene+BD) / mol H2 / minute; and about B) from [30 mol (styrene+BD) / mol H2] / 180 minutes = 0.1667 mol (styrene+BD) / mol H2 / minute for the highest molecular weight in the range to about [30 mol (styrene+BD) / mol H2] / 90 minutes = 0.3333 mol (styrene+BD) / mol H2 / minute. The process may be carried out at a temperature in the range of 30°C to 130°C with sufficient stirring to ensure efficient mass transfer of hydrogen to the condensed phase. In the LOXSH catalyst composition, the relative feed rate of the moles of (VA+CD) monomer to the moles of the contained salt hydride may be from about 70 to about 1500 moles (VA+CD) / mole SH; wherein the salt hydride SH may be one or more of LiH and / or NaH and / or KH and / or MgH2 and / or CsH and / or RbH.The total weight of comonomers used to form LOXSH relative to the total weight of butyl lithium can range from about 20 Kg total monomers per 1.0 Kg butyl lithium to greater than about 400 Kg total monomers per 1.0 Kg butyl lithium added. This is particularly true when the LOXSH catalyst is a LOXNaH catalyst having a Li:Na ratio of 5:1 formed with both AA and EAs-m polar modifiers.

[0089] The LOXSH catalyst used in the process of the present disclosure includes a σ-μ polar modifier, which can be one or more of the following: N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino-2-butanol; trans-2-piperidinocyclohexan-1-ol; 1-phenyl-2-piperidin- 1-methylethanol; 1-pyrrolidinylethanol; pyrrolidinylpropan-2-ol; 1-(1-pyrrolidinyl)-2-butanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 2-pyrrolidinylcyclohexanol; 4-methyl-1-piperazineethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; 2-(4-methylpiperazinyl)-1-phenylethan-1-ol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol; 2-morpholinoethanol ; 1-(4-morpholinyl)-2-propanol; 1-(4-morpholinyl)-2-butanol; 2-morpholino-1-phenyl-1-ethanol; trans-2-morpholin-4-ylcyclohexanol; 1-methyl-2-piperidinylmethanol; 1-methyl-2-pyrrolidinemethanol, diethylaminoethanol, N-methyl-diethanolamine and 3-dimethylamino-1-propanol, 2-[2-(dimethylamino)ethoxy]ethanol, 1,3-bis(dimethylamino)-2-propanol; 2-{[2-dimethylamino)ethyl]methylamino}ethanol; 2- [2-(Dimethylamino)ethoxy]ethanol; 2-(2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholinyl)ethoxy]ethanol; 2-[2-(1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol, optionally with the addition of one or more of the following: 2-methoxyethanol; 1-methoxy-2-propanol; 1-methoxy-2-butanol; trans-2-methoxycyclohexanol; tetrahydrofurfuryl alcohol; 2-tetrahydropyranylmethanol and diethylene glycol monomethyl ether.

[0090] The LOXSH catalyst used may also include a σ-μ polar modifier, which may consist of about 50 mol % to less than 100 mol % of a tertiary amino-alcohol or tertiary amino-ether-alcohol σ-μ polar modifier and about 50 mol % to greater than 0 mol % of an ether-alcohol σ-μ polar modifier. The tertiary amino-alcohol σ—μ polar modifier may be selected from one or more of the following: N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino-2-butanol; trans-2-piperidinocyclohexan-1-ol; 1-phenyl-2-piperidin-1-ylethanol; 1-pyrrolidinoethanol; pyrrolidinylpropan-2-ol; 1-(1-pyrrolidinyl)-2-butanol; 2-pyrrolidinylcyclohexanol; 1 -phenyl-2-(1-pyrrolidinyl)-1-ethanol; 4-methyl-1-piperazineethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol; 2-(4-methylpiperazino)-1-phenylethan-1-ol; 1-methyl-2-piperidinemethanol; 1-methyl-2-pyrrolidinemethanol; diethylaminoethanol, N-methyl-diethanolamine and 3-dimethylamino-1-propanol; 1,3-bis(dimethylamino)-2-propanol; 2-{[2-dimethylamino)ethyl]methylamino}-ethanol. The tertiary amino-ether-alcohol can be 2-morpholinoethanol; 1-(4-morpholinyl)-2-propanol; 1-(4-morpholinyl)-2-butanol; trans-2-morpholin-4-ylcyclohexanol; 2-morpholino-1-phenyl-1-ethanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2-(2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholinyl)ethoxy]ethanol; 2-[2-(1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol. The ether-alcohol sigma-μ polar modifier may be selected from one or more of the following: 2-methoxyethanol; 1-methoxy-2-propanol; 1-methoxy-2-butanol; 2-methoxy-1-phenylethanol; trans-2-methoxycyclohexanol; tetrahydrofurfuryl alcohol; 2-tetrahydropyranylmethanol and diethylene glycol monomethyl ether.

[0091] In general, the catalyst activity for a given alcohol functional group of a tertiary amino alcohol ligand (i.e., 1-aminoethanol, 1-amino-2-propanol, 1-amino-2-butanol, trans-2-amino-cyclohexanol, 2-amino-1-phenyl-1-ethanol) can increase from piperidinyl to dimethyl to pyrrolyl, while the selectivity can generally decrease in that order. Surprisingly, LOXLiH catalysts formed by tertiary amino alcohols with secondary alcohols (i.e., 1-amino-2-propanol, 1-amino-2-butanol, trans-2-amino-cyclohexanol), 1-dimethylamino-2-propanol are generally more selective for the formation of 1,4-CD microstructures. In contrast, amino alcohols with primary alcohols (2-aminoethanol) can have very high selectivity for vinyl addition (1,2-BD and 1,2-IP vs. 3,4-IP) of the CD portion of the copolymer product composition. In general, the piperidinyl amino functional group can be more selective than the dimethylamino group. Thus, the selectivity for vinyl microstructures decreases, and the selectivity for 1,4-CD microstructures can be increased in the following order: 2-piperidinoethanol; N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; 1-piperidino-2-propanol; 1-piperidino-2-butanol (see Fig. 9). Forming the LOXLiH catalyst with a portion of the ether alcohol generally speeds up the process (hydrogen mediated polymerization proceeds at lower temperature and / or pressure) and produces a catalyst composition that generally favors vinyl addition even when tertiary amino alcohol ligands with 2° alcohol functionality can be used. However, forming the LOXKH catalyst with a portion of the ether alcohol will hinder catalyst activity and require elevated temperatures. However, forming the LOXNaH catalyst with a portion of the ether alcohol will increase its reactivity, very similar to that of the LOXLiH catalyst. In general, catalysts formed with a portion of the ligand being an ether alcohol can provide compositions that are easier to acid wash and form less emulsions than those formed using LOXSH catalysts formed entirely with amino alcohol ligands. The same is true for amino alcohols formed from piperidine compared to dimethylamine or pyrrolidine. Addition of other polar modifiers (s-type) such as TMEDA and THF can increase some selectivity for vinyl addition, but generally retard LOXSH catalyst activity (requiring slightly higher temperatures and pressures); the exception is the LOXMgH2 catalyst. The LOXMgH2 catalyst system appears to be greatly affected by the use of TMEDA, where its addition to the catalyst system strongly promotes 1,2-PIP and 3,4-PIP microstructures (see Example 12, where 36.7 mmoles of TMEDA were added, all other examples of Table III were not added). Such s-type polar modifiers can also act as randomizers, helping to randomize the distribution and diad sequence of VA and CD monomers on any discrete copolymer chain. Potassium-based catalyst systems are much more active (operating at very low pressures and temperatures) and are generally less selective for vinyl addition. The present disclosure provides several ways to achieve the desired specific microstructure and molecular weight to produce liquid HMPCD-CoPS copolymer compositions with tailored viscosities and glass transition temperatures and specific molecular weight distributions.

[0092] One embodiment of the present disclosure can be an anionic copolymerization reagent composition formed for (1) initiation; and / or 2) hydrogen mediated LOXSH catalyst; and / or 3) organic chain transfer LOXSH catalyst, which can be selective for 1,4-CD monomer microstructure attachment in VA-CD random copolymers. The 1,4CD microstructure can be achieved with reagents that can be formed from: 1) at least one tertiary amino alcohol σ-μ polar modifier having 2° or 3° alcohol functionality; 2) an organolithium compound; and 3) optional elemental hydrogen and / or an organosilicon hydride (e.g., phenylsilane). The LOXSH catalyst composition can be further characterized as wherein the polar modifier can be selected from at least one of the following structures:

[0093]

[0094] Wherein R is independently an organic group, which may be further substituted by other tertiary amines or ethers, 1 is independently a hydrogen atom or an organic group, which may be further substituted by other tertiary amines or ethers, Σ may include: i) O or NR for III, IV and V; ii) and for VI, VII and IX, may include O or NR or CH2; the index value n is independently an integer equal to or greater than 0, and the index value x is independently an integer equal to or greater than 1.

[0095] Preferred LOXSH catalyst compositions of the present disclosure include catalyst compositions wherein the σ-μ polar modifier has a secondary alcohol functionality and includes one or more of the following: 1-dimethylamino-2-propanol, 1-piperidino-2-propanol, 1-pyrrolidinylpropan-2-ol, 1-morpholino-2-propanol, 1-(4-methyl-1-piperazinyl)-2-propanol, 1-dimethylamino-2-butanol, 1-piperidino-2-butanol, 1-pyrrolidinyl-2-butanol, 1-morpholino-2-butanol, 1-(4-methyl-1-piperazinyl)-2-butanol, 2-dimethylaminocyclohexan-1-ol, 2-piperidinocyclohexan-1-ol, 2-pyrrolidinylcyclohexanol, 2-(4-methyl-1-piperazinyl)-cyclohexanol, 2-morpholinocyclohexan-1-ol, 2-(dimethylamino)-1-phenylethanol; 1-phenyl-2-piperidin-1-ylethanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 2-(4-methylpiperazinyl)-1-phenylethyl-1-ol; 2-morpholino-1-phenyl-1-ethanol; 1,3-bis(dimethylamino)-2-propanol, optionally with the addition of one or more of the following: 2-methoxyethanol, 1-methoxy-2-propanol, 1-methoxy-2-butanol, 2-methoxy-1-cyclohexanol, 2-methoxy-1-phenylethanol, tetrahydrofurfuryl alcohol or tetrahydropyran-2-methanol; or diethylene glycol monomethyl ether.

[0096] If an aralkyl organic chain transfer agent is used, the organic chain transfer agent can be designed to compete with hydrogen mediation using LOXKH catalyst as a reagent for the aralkyl organic chain transfer agent (e.g., toluene, xylene, ethylbenzene, propylbenzene, mesitylene, etc.). Alternatively, when the organic chain transfer agent is substituted with a methyl group (e.g., one or more of toluene, -, m-, p-xylene, mesitylene, durene, etc.), the LOXLiH reagent can be used as an organic chain transfer catalyst, and under such conditions, the organic chain transfer can compete with hydrogen mediation to a certain extent. In certain special cases, VA monomers with alkyl substitutions can additionally act as chain transfer agents and provide branched molecular architectures. This is particularly true for methyl-substituted styrene monomers (i.e., 4-methylstyrene).

[0097] Another embodiment of the present disclosure may be an anionic copolymerization reagent composition formed for (1) initiation; and / or 2) hydrogen mediated LOXSH catalyst; and / or 3) organic chain transfer LOXSH catalyst, which is selective for 3,4-CD and / or 1,2-CD-vinyl monomer microstructural attachment in VA-CD copolymers. The reagent may be formed from: a) at least one tertiary amino alcohol sigma-μ polar modifier; b) at least one separate ether-alcohol sigma-μ polar modifier; c) an organolithium compound; and d) optionally elemental hydrogen and / or an organosilicon hydride.

[0098] The LOXSH of the present disclosure can be further characterized as wherein the σ-μ polar modifier can be selected from at least two of the following structures:

[0099]

[0100] Preferred LOXSHs of the present disclosure can be characterized as those wherein the σ-μ polar modifier of the reagent comprises from about 50 mol % to less than 100 mol % of a tertiary amino-alcohol σ-μ polar modifier and / or a tertiary amino-ether-alcohol σ-μ polar modifier selected from one or more of the following: I.) N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino-2-butanol; trans-2-piperidinocyclohexan-1-ol; 1-phenyl-2-piperidin-1-ylethanol; 1-pyrrolidinoethanol; pyrrolidinoethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; 2-pyrrolidinylcyclohexanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 4-methyl-1-piperazinylethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol; 2-(4-methylpiperazino)-1-phenylethan-1-ol; 1-methyl-2-piperidinylmethanol; 1-methyl-2-pyrrolidinemethanol; diethylaminoethanol, N-methyl-diethanolamine and 3-dimethylamino-1-propanol; 1,3-bis(dimethylamino)-2-propanol; 2-{[2-dimethylamino)ethyl]methylamino}-ethanol. The tertiary amino-ether-alcohol may be 2-morpholinoethanol; 1-(4-morpholino)-2-propanol; 1-(4-morpholino)-2-butanol; trans-2-morpholin-4-ylcyclohexanol; 2-morpholino-1-phenyl-1-ethanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2-(2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholino)ethoxy]ethanol; 2-[2-( 1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol; and II.) from about 50 mol % to greater than 0 mol % of an ether-alcohol σ—μ polar modifier selected from one or more of the following: 2-methoxyethanol; 1-methoxy-2-propanol; 1-methoxy-2-butanol; trans-2-methoxycyclohexanol; 2-methoxy-1-phenylethanol; tetrahydrofurfuryl alcohol; 2-tetrahydropyranylmethanol, and diethylene glycol monomethyl ether.

[0101] Preferred embodiments of the LOXSH catalyst compositions of the present disclosure can be further characterized as wherein the ratio of total amino-alcohol (AA) and / or amino-ether-alcohol (AEA) to total individual ether-alcohol (EE) σ—μ polar modifiers ([AA:EAE]:EA) can be in the range of about 9:1 to 1:1, and preferably in the range of about 4:1 to about 2:1.

[0102] The hydrogen-mediated VA-CD copolymer composition of the present disclosure comprises a polymer of hydrogen, a vinyl aromatic comonomer, and a conjugated diene comonomer without incorporating alkyl anions or solvent anions, such as toluene, which are problematic for certain process technologies. Thus, another feature of the present disclosure may be a hydrogen-mediated anionic VA-CD copolymer composition (comprising a copolymer of hydrogen, a vinyl aromatic monomer, and a conjugated diene monomer) that may be characterized as having: 1) a number average degree of polymerization DP in the range of about 7 to about 50 repeating units n ; 2) a Brookfield viscosity (45°C) in the range of about 10 cP to about 300,000 cP; 3) a 1,4-CD microstructure content in the range of 20% to about 80%; and 4) a glass transition temperature T in the range of about -110°C to about 5°C g .

[0103] Some hydrogen mediated isoprene-styrene copolymer distribution compositions may have a number average DP n In the range of about 7 to about 45, the number average molecular weight (M n ) in the range of about 500 Daltons to about 3500 Daltons, a styrene content in the range of about 10 wt % styrene to about 90 wt %, and a glass transition temperature varying in the range of -100°C at about 500 Daltons to 5°C at about 3000 Daltons, and a Brookfield viscosity (45°C) in the range of about 100 cP to about 300,000 cP. Some hydrogen mediated isoprene-styrene copolymer distribution compositions may be characterized as having a number average degree of polymerization (DP) in the range of about 7 to about 27. n ) which are further characterized as having: 1) a styrene content of 10 wt % to about 85 wt %; 2) a 1,4-PIP content between 35 wt % and 90 wt % based on the isoprene moiety; 3) a glass transition temperature T in the range of about -70°C to about -40°C g ; and a Brookfield viscosity (45° C.) ranging from about 280 cP to about 3800 cP.

[0104] Some hydrogen mediated butadiene-styrene copolymer distribution compositions may have a number average DP in the range of about 8 to about 45. n and a number average molecular weight (M) ranging from about 500 Daltons to about 3300 Daltons. n ), and having one of the following: 1) having a styrene content in the range of about 10 wt % to about 40 wt % and having a total vinyl content based on the butadiene portion of about 70 wt % to about 80 wt %, and having a Brookfield viscosity (at 45° C.) as M nand styrene content ranging from about 40 cP to about 100,000 cP; or 2) having a styrene content ranging from about 10 wt % to about 40 wt % and having a total vinyl content based on the butadiene portion of about 40 wt % to about 65 wt %, with a Brookfield viscosity (at 45° C.) as a function of M n and styrene content ranging from about 10 cP to about 10,000 cP; or 3) having a styrene content ranging from about 10 wt % to about 40 wt % and having a total vinyl content based on the butadiene portion of about 25 wt % to about 35 wt %, with a Brookfield viscosity (at 45° C.) as a function of M n The function of is varied in the range of about 10 cP to about 7,500 cP; wherein the total vinyl content of the butadiene portion is determined by 1 HNMR analysis. n =500 Daltons to M n =3300 Daltons, these compositions have a glass transition temperature in the range of less than -110°C to about -15°C, where T g The composition also has a ratio that can be in the range of about 5:1 to about 25:1 (based on 1 1H NMR analysis) of the vinyl-1,2-BD:VCP ratio.

[0105] Some hydrogen-mediated butadiene-styrene copolymer distributions of the present disclosure may have a high total vinyl content ranging from 20 wt % to 36 wt % styrene and from about 70 wt % to about 80 wt % of the butadiene portion (e.g., 1 HNMR analysis), which also exhibits a high ratio of vinyl-1,2-BD to vinyl cyclopentane (VCP) and may inherently have high reactivity and low viscosity, wherein: 1) the number average molecular weight distribution (M n ) may be in the range of about 500 Daltons to about 3000 Daltons; 2) the Brookfield viscosity (at 45°C) may be in the range of about 165 cP to about 97,000 cP; 3) the glass transition temperature (T g ) is in the range of less than about -65°C to about -18°C; 4) the molar ratio of vinyl-1,2-BD:VCP may be in the range of about 12:1 to about 25:1 (based on 1 HNMR analysis); and 5) having an iodine number of about 280 to about 395. g The range of data calculation values ​​is shown in Table X, and the equation is based on an exemplary embodiment of the present disclosure. Figure 5 and Figure 6The iodine numbers shown in Table VII are based on 1 HNMR microstructure analysis was calculated according to the above equation (2). The measured values ​​were measured by the method found in Kemp, A. and Peters, H., "Unsaturation of butadiene and related polymers as determined by iodine chloride addition" Industrial & Engineering Chemistry Analytical Edition, 1943, 15(7), pp. 453-459. 12 of the 18 examples in Table VII provide measured iodine values. It is noted that the average iodine value for the samples where both calculated and measured values ​​are reported is 329 g I2 / 100 g polymer. The standard deviation of the (calculated-measured) iodine values ​​is 9.6 - thus relying on the calculated values ​​for NMR analysis validates such spectral measurements. Therefore, it is believed that these high vinyl hydrogen mediated butadiene-styrene copolymers can be effectively halogenated (chlorine, bromine and iodine) or can be effectively chemically derivatized by other reagents.

[0106] Some hydrogen-mediated butadiene-styrene copolymer distributions of the present disclosure may have a high total vinyl content ranging from 20 wt % to 36 wt % styrene and from about 70 wt % to about 80 wt % of the butadiene portion (e.g., by 1 HNMR analysis), which also exhibits a high ratio of vinyl-1,2-BD to vinyl cyclopentane (VCP) and may inherently have high reactivity and low viscosity, wherein: 1) the number average molecular weight distribution (M n ) may be in the range of about 1000 Daltons to about 2000 Daltons; 2) the Brookfield viscosity (at 45°C) may be in the range of about 1500 cP to about 12,500 cP; 3) the glass transition temperature T g in the range of about -50°C to about -25°C; and 4) the molar ratio of vinyl-1,2-BD:VCP may be in the range of about 12:1 to about 25:1 (based on 1 1H NMR analysis).

[0107] Some hydrogen-mediated butadiene-styrene copolymer distributions of the present disclosure may have a styrene composition ranging from 25 wt % to 30 wt % of the intermediate and a total vinyl content ranging from about 40 wt % to about 65 wt % of the butadiene portion (e.g., by1 HNMR analysis), where: 1) number average molecular weight distribution (M n ) may be in the range of about 1300 Daltons to about 2000 Daltons; 2) the Brookfield viscosity (at 45°C) may be in the range of about 800 cP to about 2800 cP; 3) the glass transition temperature T g in the range of about -50°C to about -60°C; and 4) the molar ratio of vinyl-1,2-BD:VCP may be in the range of about 10:1 to about 14:1 (based on 1 1H NMR analysis).

[0108] Some hydrogen-mediated butadiene-styrene copolymer distributions of the present disclosure may have a styrene content of 25 wt % to 30 wt %, a total vinyl content ranging from about 25 wt % to about 35 wt % based on the butadiene portion (e.g., 1 HNMR analysis), where: 1) number average molecular weight distribution (M n ) may be in the range of about 1300 Daltons to about 2300 Daltons; 2) the Brookfield viscosity (at 45°C) may be in the range of about 500 cP to about 3500 cP; 3) the glass transition temperature T g in the range of about -55°C to about -70°C; and 4) the molar ratio of vinyl-1,2-BD:VCP may be in the range of about 7:1 to about 12:1.

[0109] Another notable feature of the present disclosure may be that seemingly subtle changes in the structure or organic backbone of the amino alcohol and / or any ether-alcohol ligands used to form the LOXSH catalyst composition achieve significant effects on the selectivity and activity of a particular LOXSH catalyst composition. Replacing a simple proton on the organic backbone with an alkyl group (e.g., methyl, ethyl, propyl, etc.) can change the selectivity in the styrene-butadiene copolymer distribution from greater than 80% vinyl 1,2-BD to as low as 25 wt% total vinyl 1,2-BD, and thereby change the reactivity, viscosity, and T of the resulting copolymer composition. g .

[0110] Analytical methods :

[0111] Molecular weight determination was performed by gel permeation chromatography. For Examples 1 to 3, hydrogen-mediated anionic random copolymerization of polystyrene-co-polyisoprene samples was analyzed using an OligoPore column and based on PS standards calibrated internally using a refractive index detector (for a detailed description of the method, see application number WO2017176740A1). For Examples 4 to 12 and Examples 13 to 30, M was obtained by GPC using a Viscotek TDA modular system equipped with an RI detector, an autosampler, a pump and a temperature-controlled column chamber. n 、M w 、M z and PD molecular weight distribution. The column used was an Agilent ResiPore column, 300 mm × 7.5 mm, part number 1113-6300. The solvent used was tetrahydrofuran, HPLC grade. The test procedure used involved dissolving approximately 0.06 g to 0.1 g of sample in 10 mL of THF. An aliquot of this solution was filtered and 200 μl was injected onto the column. The molecular weight determinations for Examples 4 to 12 were based on polystyrene standards. The molecular weight determinations for Examples 13 to 30 were based on polybutadiene standards with a 50% 1,4-BD microstructure and polystyrene standards. The M reported in Table VII n , DP n The values ​​of PDI and M are based on the following equations determined from the calibration curves of PBD and PS standards: n and M w The weighted average of:

[0112] M nwt. =x BD M nPBD +x sty M nPS

[0113] M wwt .=X BD M wPBD +X sty M wPS

[0114] Among them, M nwt is the weighted mean MWD; x BD is the mole fraction of butadiene in the resin; M nPBD is the number average MWD determined by BD standards; x sty is the mole fraction of styrene in the resin; and M n PS is the number average MWD determined from PS standards. wwt is the weighted average of the weighted average MWD; X BD is the weight fraction of butadiene in the resin; M wPBD is the weight average MWD determined by BD standards; X sty is the weight fraction of styrene in the resin; and M wPS is the weight average MWD determined from PS standards. Microstructure analysis for polybutadiene microstructure characterization is based on C13-NMR and 1 HNMR peak attribution is consistent with the following reports: Matlengiewcz, M., Kozak, R. International Journal of Polymer Anal. Charact. 2015, 20, 574; Fetters, L., Quack, G. Macromolecules, 1978, 11, 369. The total vinyl weight % content is based on a cyclic structure containing only vinyl cyclopentane and is generated by two vinyl units (Fetters). The weight average molecular weight distribution (MWD) and total vinyl content or equivalent as described above are determined according to Luxton, AR, Milner, R. and Young, RN Polymer, 1985, 26, 11265. FT-IR microstructure analysis of the polybutadiene portion is in accordance with: Morero, D; et al., ChemE Ind. 1959, 41 758.; Shimba, A. et al., Analytical Sciences 2001, 17, i1503.

[0115] Example

[0116] The following examples illustrate methods for in situ production of LOXSH catalysts and production of hydrogen mediated conjugated polymer and copolymer distributions according to the present disclosure. These examples are not intended to limit the present disclosure to only the procedures described therein.

[0117] The equipment used for this work was as follows: a 316 stainless steel 2 liter Parr autoclave with a thermocouple, bottom drain valve, cooling coils, hot oil jacket, four pitched blade turbine impellers, the first being 4.0", the second 6.0", the third 8", and the fourth 10" from the top of the reactor. The reactor was also equipped with a piston pump, a nitrogen purged 250 ml stainless steel addition vessel, a well calibrated high pressure metering pump, and a 1 / 16 inch OD underground monomer feed line with a 0.007" ID terminal section (as described in the Examples and / or Tables below). The magnetic drive on the agitator was connected to a high speed air driven motor and was typically operated at a near constant 1000 to 1030 RPM (gas flow and pressure were adjusted as needed as the viscosity of the reaction mixture changed). Two one liter gas flowmeters equipped with digital pressure gauges (readability 0.01 PSIG) were used. The bottle provided a wide point in the line between the reactor and the hydrogen supply. Prior to the start of the run, the bottle was pressurized to 435 PSIG to 450 PSIG hydrogen and then isolated from the hydrogen supply. Hydrogen was fed via a digital hydrogen mass flow meter with an accumulator. The copolymerized comonomers were either A) premixed into a mixture (e.g., isoprene and styrene) and fed underground via a 0.007" ID feed tip; or B) held in separate tanks but premixed (styrene and butadiene) via a static mixer in the feed line and delivered to the headspace of the reactor. Hydrogen was fed into the headspace. In all cases, unless otherwise noted, butadiene was fed as a neat liquid at a near constant rate of 4.0 g / min - styrene feed was variable between runs depending on the desired styrene:butadiene ratio. Butadiene was fed via The bottom drain valve of a lined 1000 ml sample cylinder was fed. It was fed into the feed line under positive hydrogen head pressure; this pressure was about 20 PSIG to 40 PSIG higher than the pressure on the reactor and therefore brought with it a small but insignificant amount of dissolved hydrogen.

[0118] Autoclave is passed into oil bubbler and / or 6 liters of oil jacketed pleated washing containers, which have bottom discharge port, and are used for top stirring and distillation. The bottom discharge valve and the material leg sampling port of the autoclave are all vertically connected to the washing container, for directly transferring the unquenched reaction mixture. Bulk solvent (for example, cyclohexane (CH) or methylcyclohexane (MCH) or ethylbenzene (EB) or their mixture recovered from previous operation, and therefore mainly containing butadiene or isoprene oligomer dimer, trimer at most 10 weight %) is loaded into reactor via piston pump by charging container. After diluted with solvent, catalyst component (for example polar modifier and n-butyl lithium) is loaded into reactor respectively by charging container, with the Vernier handle needle valve control flow velocity of fine metering. The metering valve was connected to the inlet valve on the reactor feed leg via a short port connection fitting and further connected to the charge vessel via an 8 inch long thick wall 1 / 8" PTFE tubing. The translucent tube served as a sight glass so that the operator could monitor the transfer of dissolved catalyst components to the reactor and thus eliminate the introduction of nitrogen by closing the shutoff valve once nitrogen was seen in the line.

[0119] The contents of the charge vessel were pressure transferred to an autoclave with a hydrogen atmosphere under minimal nitrogen back pressure. The monomer (or mixture of monomers) was fed sequentially through the following columns at a predetermined constant rate: 1) a column containing 22 grams of activated 4A molecular sieves; then 2) a basic alumina column (1 0.5" OD column with 11.0 g of 60 mesh to 325 mesh Al2O3); to remove water and remove inhibitors. For convenience, when forming the isoprene-styrene copolymers of the present disclosure, the mixture was formed, placed in a feed tank, and then fed to the underground feed system with a high pressure metering pump. When forming the butadiene-styrene copolymers of the present disclosure, styrene was fed with a metering pump, and butadiene was fed from the above The separate styrene and butadiene were fed into the same feed lines of , to a small mixing tee at a point before the molecular sieve and alumina column.

[0120] The autoclave reactor is heated with oil, the oil temperature set point is the desired reaction temperature or usually the desired reaction temperature ± 1 ° C to ± 3 ° C or so (depending on the feed rate and the desired reaction temperature), and once the reactor controller is shut down (usually no more than the first 20 minutes of monomer feed), the reaction temperature is strictly maintained at the predetermined set point. Figures 10 to 12 The reaction temperature may have brief temperature excursions, typically no more than 5°C above the desired set point temperature, particularly if the initial temperature is below the optimum temperature, thereby delaying catalyst activation, incubation and / or initial formation.

[0121] Several abbreviations for the classes of compounds used in these examples or which can be used in methods analogous to these examples are given below: i) amino alcohol (AA); II) ether-alcohol (EA) and III) amino-ether-alcohol (AEA):

[0122] AA-1.DMEA is the abbreviation of N,N-dimethylethanolamine as a neutral amino alcohol (synonyms: N,N-dimethyl-2-hydroxyethylamine, N,N-dimethylaminoethanol DMAE). The usage of the chemical formula [DMEA] herein represents N,N-dimethylethanolamine as an alkoxide, which releases a proton to become a more alkaline substance.

[0123] AA-2.DMAP is the abbreviation of 1-(dimethylamino)-2-propanol (CAS 108-16-7); synonyms are (±)-1-(N,N-dimethylamino)-2-propanol, dimethylaminopropanol, and N,N-dimethylisopropanolamine.

[0124] AA-3.DMAB is an abbreviation for 1-(dimethylamino)-2-butanol (CAS 3760-96-1); synonym 1-(dimethylamino)butan-2-ol.

[0125] AA-4.DMACH is trans-2-(dimethylamino)cyclohexanol (CAS 20431-82-7); synonyms 2-dimethylaminocyclohexan-1-ol, 2-dimethylamino-cyclohexanol.

[0126] AA-5. PipE and 2-Pip-ethanol are abbreviations for 2-piperidinoethanol (CAS 3040-44-6; synonym 1-(2-hydroxyethylpiperidine; 1-piperidinylethanol).

[0127] AA-6.Pip-2-propanol is the abbreviation for 1-piperidino-2-propanol (CAS 934-90-7; synonym a-methylpiperidin-1-ethanol).

[0128] AA-7.Pip-2-butanol is an abbreviation of 1-piperidino-2-butanol (CAS 3140-33-8); synonym 1-(piperidin-1-yl)butan-2-ol.

[0129] AA-8.2-Pip-cyclohexanol is the abbreviation for trans-2-piperidinocyclohexan-1-ol (CAS 7581-94-4; synonyms 2-(piperidin-1-yl)cyclohexan-1-ol; trans-2-piperidinylcyclohexanol).

[0130] AA-9.2-Pyr-ethanol is the abbreviation of 1-pyrrolidinoethanol (CAS 2955-88-6; N-(2-hydroxyethyl)pyrrolidine; 1-pyrrolidineethanol; Epolamine; 1-(2-hydroxyethyl)pyrrolidine).

[0131] AA-10. Pyr-2-propanol is the abbreviation for 1-pyrrolidinylpropan-2-ol (CAS 42122-41-8; 1-(pyrrolidin-1-yl)propan-2-ol; α-methylpyrrolidine-1-ethanol).

[0132] AA-11.2-Pyr-2-butanol is an abbreviation of 1-(1-pyrrolidinyl)-2-butanol (CAS 55307-73-8); synonyms 1-pyrrolidinoethanol, α-ethyl-.

[0133] AA-12.2-Pyr-cyclohexanol is the abbreviation of 2-pyrrolidinylcyclohexanol (CAS 14909-81-0; trans-2-pyrrolidinylcyclohexanol; trans-2-(pyrrolidin-1-yl)cyclohexan-1-ol; (+ / -)-trans-2-(pyrrolidin-1-yl)cyclohexanol).

[0134] AA-13.2-Piz-ethanol is an abbreviation for 4-methyl-1-piperazineethanol (CAS 5464-12-0), synonyms (1-(2-hydroxyethyl)-4-methylpiperazine; 2-(4-methylpiperazin-1-yl)ethanol; 2-(4-methyl-1-piperazinyl)ethanol).

[0135] AA-14.4-Me-Piz-2-propanol is an abbreviation of 1-(4-methyl-1-piperazinyl)-2-propanol (CAS 4223-94-3), synonym 1-(4-methylpiperazin-1-yl)propan-2-ol

[0136] AA-15.4-Me-Piz-2-butanol is an abbreviation of 1-(4-methyl-1-piperazinyl)-2-butanol (CAS 56323-03-6); synonyms 4-(4-methylpiperazin-1-yl)butan-1-ol; 1-(4-hydroxybutyl)-4-methyl-piperazine; 1-piperazinebutanol, 4-methyl-; 4-(4-methyl-1-piperazinyl)-1-butanol

[0137] AA-16.2-[4-Me-piz]-cyclohexanol is the abbreviation of trans-2-(4-methyl-1-piperazinyl)-cyclohexanol (CAS 100696-05-7, synonym trans-2-(4-methylpiperazin-1-yl)cyclohexanol; (+-)-trans-2-(4-methyl-piperazino)-cyclohexanol).

[0138] AA-17.MorE is 2-morpholinoethanol (CAS 622-40-2); synonyms 4-(2-hydroxyethyl)morpholine; 2-(morpholin-4-yl)ethanol; continuation of 2-(4-morpholinyl)ethanol.

[0139] AA-18.Mor-2-propanol is 1-(4-morpholinyl)-2-propanol (CAS 2109-66-2); synonyms N-(2-hydroxypropyl)morpholine; 1-(morpholin-4-yl)propan-2-ol; 2-morpholinoethanol, a-methyl- abbreviation.

[0140] AA-19.Mor-2-butanol is 1-(4-morpholinyl)-2-butanol (CAS 3140-35-0); synonym 1-(morpholin-4-yl)butan-2-ol; abbreviation of 2-morpholinoethanol, a-ethyl-.

[0141] AA-20.2-Mor-cyclohexanol is trans-2-morpholin-4-ylcyclohexanol (CAS 14909-79-6); synonym 2-(4-morpholinyl)cyclohexanol; abbreviation of 2-morpholin-4-ylcyclohexanol

[0142] AA-21.N-Me-Pip-2-MeOH is the abbreviation of N-methylpiperidine-2-methanol (CAS 20845-34-5, 1-methyl-2-piperidinemethanol; (1-methylpiperidin-2-yl)methanol; 1-methylpiperidine-2-methanol).

[0143] AA-22.N-Me-Pry-2-MeOH is the abbreviation of the chiral and / or racemic molecule (1-methyl-2-pyrrolidinyl)methanol (CAS 30727-24-3; 34381-71-0; synonym N-methylprolinol); 1-methyl-2-pyrrolidinemethanol.

[0144] EA-1. MeOE is the abbreviation of 2-methoxyethanol as a neutral ether-alcohol. The usage of the chemical formula [MeOE] herein represents 2-methoxyethanol as an alkoxide, which releases a proton to become a more basic substance.

[0145] EA-2.1-MeO-2-propanol is 1-methoxy-2-propanol (CAS 107-98-2); synonyms 1-methoxy-2-hydroxypropane; methoxyisopropanol; 1-methoxypropan-2-ol; Abbreviation for PM.

[0146] EA-3.1-MeO-2-butanol is an abbreviation of 1-methoxy-2-butanol (CAS 53778-73-7); synonym 1-methoxybutan-2-ol.

[0147] EA-4.2-MeO-cyclohexanol is the abbreviation of trans-2-methoxycyclohexanol (CAS 134108-68-2).

[0148] EA-5.THFA is the abbreviation of tetrahydrofurfuryl alcohol (CAS 97-99-4; synonyms (tetrahydrofuran-2-yl)methanol; tetrahydro-2-furanmethanol; THFA).

[0149] AEA-1.DMAEOE is the abbreviation of 2-N,N-dimethylaminoethoxyethanol (N(CH3)2CH2CH2O-CH2CH2OH) as a neutral aminoether-alcohol. The usage of the chemical formula [DMAEOE] herein represents N,N-dimethylaminoethoxyethanol as an alkoxide, which releases a proton to become a more basic substance.

[0150] The polar modifiers used to form the catalysts of the examples are designated in the data tables as: I) AA-#; II) EA-#; or III) AEA-#. Thus, if AA-5 is identified in the table as either AA or the polar modifier, it indicates that 2-piperidinoethanol was used in the example. Likewise, if the table indicates that AA-1 and EA-5 were used, the catalyst for that example contained N,N-dimethylethanolamine and tetrahydrofurfuryl alcohol. Additional polar modifiers (s--type) used to form the catalysts are designated as THF (tetrahydrofuran) and TMEDA (N,N,N'N'-tetramethylethylenediamine).

[0151] General procedure followed to form the catalyst

[0152] Application No. WO2017176740A1 provides a number of procedures in which catalysts useful in the practice of the present disclosure may be prepared. The following describes the general procedure followed in the present disclosure (with some variations between runs as shown):

[0153] Formation of standard [DMEA]2Li3H catalyst: Anhydrous cyclohexane (225 ml, 370 ml total) was charged to the reactor at 37.7°C under a dry hydrogen (22 PSIG H2) atmosphere. A solution previously formed of 3.908 g (0.0438 mol) N,N-dimethylethanolamine and 35 g cyclohexane was charged to the stirred solvent (≈750 RPM) through a charging vessel under positive nitrogen pressure, further combined with 50 ml of the above total amount of anhydrous solvent. Next, 33.19 ml (0.0664 mole) of 2.0 M n-butyl lithium dissolved in 23 g of anhydrous ethylbenzene and 57 g of anhydrous cyclohexane was transferred to the charging vessel and further combined with 50 ml of the above total amount of anhydrous solvent. The alkyl lithium solution was then transferred under pressure to the stirred (≈750 RPM) reaction mixture under hydrogen over a period of 9 to 15 minutes. After 3 minutes of transfer, the temperature rose to 38.4°C and the pressure rose to 23 PSIG; after 6 minutes of transfer, the temperature rose to 42.0°C and the pressure rose to 25 PSIG. At this time, the agitation was increased to 1040 RPM; and the transfer was completed in 9 minutes. At the end of the transfer, the reactor temperature was 40.8°C and the pressure dropped to 22 PSIG. At the end of the organolithium charge, the transfer line was flushed with 45 ml of anhydrous solvent from the total amount mentioned above. The reactor was then pressurized to 50 PSIG to 60 PSIG hydrogen and heated to the desired temperature (usually 68°C to 75°C) and maintained at this temperature at a pressure of (65 PSIG to 80 PSIG) for 100 to 120 minutes. At the start of the feed, the reactor pressure (hydrogen) was set to the desired initial pressure (usually vented downward) or first vented to 0 PSIG and then charged using the totalizer function of the hydrogen mass flow meter for the specific desired initial hydrogen charge - in both cases before starting the comonomer feed.

[0154] Hydrogen-mediated copolymerization of isoprene and styrene was carried out using a 2-dimethylaminoethanol-derived LOXLiH catalyst.

[0155] For Examples 1 to 3 (results reported in Table II), it was found that the hydrogen-mediated anionic copolymerization of isoprene and styrene could be achieved using the standard catalyst [DMEA]4Li6H2 formed from 4 equivalents of DMEA, 6 equivalents of n-butyllithium, and 2 equivalents of elemental hydrogen.

[0156] Example 1 is representative of these three examples. The procedure for forming [DMEA]2Li3H given above was followed, except that the catalyst was formed from: 4.008 g (0.0455 mole) DMEA; and 34.17 ml (26.530 g, 0.0683 mole) 2M n-butyllithium. At the end of the catalyst formation step, the H2 pressure was increased from 23 PSIG to 60 PSIG (39.6°C in the reactor) and the oil jacket temperature was set to 78°C and controlled at 80°C. The catalyst was aged at 71°C and 80 PSIG for 120 minutes and then vented to 10 PSIG. The hydrogen feed rate was set to 250 SCCM and the accumulator was set to 17489.5 standard cm 3 (250 standard cm 3 / min*59 minutes, monomer feed for 1 hour with 10 minutes of monomer feed line flush). Styrene-isoprene monomer feed (formed from 416 g, 4.0 moles of styrene and 68.1 g, 1.0 mole of isoprene) was started, 484 g (5.0 moles) of monomer was fed at a rate of 8.68 g / min. Therefore, the molar feed ratio of monomer to hydrogen = 8.11. Monomer was fed through an underground feed line (0.007" ID tip, 10.30 ft / s) with an initial hydrogen top pressure of 12 PSIG for the first 5 minutes, the pressure increased to 13 PSIG over the next 15 minutes, at 10 minutes, the valve from the hydrogen mass flow meter to the reactor was opened. The liquid volume of the feed line including the void volume of the molecular sieve and alumina bed was about 23.4 ml. After 50 minutes of feeding, the reactor pressure showed 1 PSIG.

[0157] At the end of the monomer feed, the monomer feed line to the reactor, including the drying tower, was flushed with 50 ml of anhydrous ethylbenzene in 10 ml increments. At the end of the flush, the monomer feed line to the reactor, including the drying tower, was flushed with a second batch of 50 ml of anhydrous ethylbenzene. When no further heat of reaction was observed (usually indicated by the permanent closure of the automatic control valve on the cooling coil), the monomer feed and reactor flush were considered complete. The unquenched polymerization mixture was transferred to a wash vessel preheated (N2 atmosphere) and pre-charged with 500 ml of deoxygenated water under positive H2 pressure.

[0158] The two-phase product mixture was heated to 65°C in the wash reactor for at least 20 minutes with thorough mixing to ensure that the organic phase was thoroughly washed with the aqueous phase, and then the phases were separated. Phase separation was readily performed at 65°C and was rapid, requiring little settling time. Water and any debris or emulsions were removed through the bottom drain valve. The reaction mixture was washed twice more: 1) 500 ml of dilute formic acid and 2) 500 ml of dilute sodium bicarbonate. The neutralized wash product mixture was stripped of cyclohexane and ethylbenzene by normal distillation in the wash reactor while gradually heating the jacket temperature of the wash reactor to 155°C. The distillation was deemed complete when the pot temperature reached a temperature above 135°C. The solution was allowed to cool and then all of the organic phase was collected. The solution was then further stripped of ethylbenzene using a wiped film evaporator (WFE, 2" glass Pope Still, operated at 50.0 mmHg vacuum, 142°C, wiper speed 65% of full speed, feed at 1.0 liter / hour). This WFE operation produced 450 g of a 93% mass yield of a hydrogen-mediated anionic copolymer formed from styrene and isoprene. The copolymer had an M n :853,M w :1403,M z :2071,PD:1.645,σ n =685, n α3 = 2.045 relative to HMAPS oligomer standard (refractive index detector). Further analytical details regarding microstructure and composition are provided in Table II below.

[0159] Examples 4 to 12 of Table III relate to the use of LOXMgH2 catalysts based on 2-piperidinoethanol further modified with triethylaluminum. Three examples (Examples 8, 10 and 11) further modified the catalyst by adding titanium (IV) tert-butoxide. For Example 12, only TMEDA (36.7 mmol) was included in the catalyst formulation.

[0160] Hydrogen-mediated copolymerization of isoprene and styrene with a 2-piperidinoethanol-derived LOXMgH2 catalyst.

[0161] Formation of the LOXMgH2 Catalyst of the Present Disclosure: The practitioner of the present disclosure may determine the amount of titanium(IV) alkoxide activator, if any, deemed appropriate for the desired hydrogen-mediated VA-CD copolymerization process when using the LOXMgH2 catalyst. For the three examples of Table III (Examples 8, 10, and 11), titanium(IV) tert-butylate (250 mg to 300 mg) was added. Modification of the LOXMgH2 by introduction of the titanium(IV) alkoxide reagent appears to reduce the autogenous pressure generated as well as shorten the incubation period of the LOXMgH2 catalyst. This Fig.10, wherein the reaction pressure and temperature profiles of Examples 7 and 8 are compared. For Example 7, the hydrogen feed was not started until after the first 40 minutes. For Example 8, when the catalyst system was clearly active, the hydrogen co-feed was started after the first 20 minutes, and a hydrogen-mediated anionic copolymerization was performed. The titanium (IV) material is preferably added after the addition of the dialkylmagnesium reagent. Similarly, practitioners of the present disclosure can determine the amount of organoaluminum or organoboron added (if any) that is considered appropriate. These can be added as separate feeds or combined with the dialkylmagnesium reagent prior to charging. Commercial grades of dialkylmagnesium [e.g., butylethylmagnesium (BEM) and di-n-butylmagnesium (DBM)] reagents are present as solutions with low or high alkylaluminum content. The presence of alkylaluminum [e.g., triethylaluminum (TEA)] is in part to reduce the viscosity of otherwise extremely viscous aluminum-free solutions of certain dialkylmagnesium reagents. Some alkyls such as sec-butyl-n-butylmagnesium do not form viscous solutions and therefore do not contain aluminum. Practitioners of the process technology of the present disclosure may add TEA or other alkyl aluminum to correct the aluminum content of the dialkyl magnesium reagent to be used. Thus, a typical low TEA BEM solution will contain 4.434 wt% magnesium (based on metal alone) and 0.1612 wt% aluminum (based on metal alone)-Mg / Al (mol / mol) = 30.54. A typical dibutyl magnesium reagent will contain 2.984 wt% magnesium metal and 0.636 wt% aluminum-Mg / Al (mol / mol) = 5.21. Additional TEA (preferably as a solution in a hydrocarbon solvent such as toluene) may be added to reduce Mg / Al (mol / mol) to about 2.9 to 4.0. Thus, when forming a LOXMgH2·TEA catalyst system, the ratio of lithium metal to magnesium metal is typically about 4:1 to about 5:1. Thus, the ratio of lithium metal to aluminum metal may be in the range of 115:1 to about 12:1. It has been found that ratios higher and lower than the specified ranges hinder hydrogen-mediated polymerization processes.

[0162] Examples 4 to 12 of Table III relate to the use of a 2-piperidinoethanol based LOXMgH2 catalyst further modified with triethylaluminium. Three examples (Examples 8, 10 and 11) further modified the catalyst by adding titanium (IV) tert-butoxide.

[0163] Example 8 represents the hydrogen-mediated anionic copolymerization of isoprene and styrene catalyzed by LOXMgH2.TEA titanium (IV) tert-butoxide. Thus, 225 ml (total 375 ml) of anhydrous recycle solvent (containing 93 wt% ethylbenzene and 6% cyclohexane and 1% isoprene oligomers) was added to the reactor at 38°C (40°C on the jacket) and under an atmosphere of dry hydrogen (23 PSIG H2). To the stirred solvent (≈890 RPM) was added a solution previously formed of 7.329 g (0.0567 mole) of 2-piperidinoethanol and 30.0 g of ethylbenzene via positive nitrogen pressure (no nitrogen was introduced into the reactor) through the charging vessel. The charging vessel and the transfer line to the reactor were rinsed with anhydrous solvent in a 25 ml portion of the total amount. Next, 21.20g (0.0579 mole) of 17.5 wt % of n-butyl lithium in cyclohexane further dissolved in 80g of ethylbenzene is transferred to the reactor by a charging vessel, and then 50ml of anhydrous solvent in the above total amount is added. Then 11.51g of 2.518 wt % n-butyl-sec-butyl magnesium solution in heptane is combined with 1.40g of 25 wt % TEA in toluene, further dissolved in 30.0g of ethylbenzene, and transferred to the reactor by a charging vessel, and then 50ml of anhydrous solvent in the above total amount is added. During the addition of organomagnesium, the stirring speed is increased to 1100RPM. Then tert-butyl titanium (IV) (0.300g, 0.88mmol) dissolved in 30g of ethylbenzene is added, and transferred to the reactor by a charging vessel, and then 25ml of anhydrous solvent in the above total amount is added. Therefore, the catalyst components are combined in a total of about 555ml of solvent under hydrogen pressure without introducing nitrogen. During the catalyst formation period, there was no evidence of hydride formation by absorption of hydrogen. The reactor was further pressurized to about 55 PSIG hydrogen and heated to the desired reaction temperature of 105°C at a pressure of 76 PSIG. The reactor was vented to 50 PSIG and a mixture containing 75 g styrene and 123 g isoprene monomer was fed at a rate of 3.44 g / min for 57.5 minutes. As the pressure began to drop and the reactor pressure began to rise, absorption of hydrogen became apparent within about 10 minutes (see Fig.10). After 20 minutes of the mixture feed, hydrogen was fed to the reactor at an average rate of 34 SCCM over about 80 minutes. Thus, styrene, isoprene and hydrogen were co-fed to the reactor for about 37 minutes. When the mixture feed was complete, the comonomer feed system was flushed into the reactor with 50 ml of anhydrous recycle solvent. After the hydrogen feed was complete, the reaction mixture was allowed to continue to react for 20 minutes, and then the entire contents were transferred to a 6-liter oil-jacketed pleated wash container. The wash container was pre-filled with 600 ml of solvent recovered from the previous round and 500 ml of water containing 6.7 g of formic acid. The contents of the wash reactor were stirred for at least 20 minutes and heated to about 70°C. Stirring was interrupted and the phases were separated. If necessary, up to 50 ml of THF was added to the organic phase to help settle any emulsion to the interface with the aqueous phase. The reaction mixture was washed twice more with 500 ml equal portions of water. The washed solution was then dried by azeotropic distillation of a 600 ml portion of the solvent. The resulting dried product solution was then further stripped using a wiped film evaporator (WFE, 2" glass Pope Still, operated at 50.0 mmHg vacuum, 142°C, wiper speed 65% of full speed, feed at 1.0 liter / hour). This WFE operation produced 183 g of a 92.4% mass yield of a hydrogen-mediated anionic copolymer formed from styrene and isoprene. The copolymer had an M n :1224,M w :2667,M z :4481,PD:2.179,σ n =1329, n α3 = 2.701, relative to PS standard (refractive index detector). Further analytical details regarding microstructure, composition and physical properties are provided in Table III below.

[0164] Examples 13-30 of Tables IV to VI relate to hydrogen-mediated anionic copolymerization of butadiene and styrene using various LOXLiH catalysts. In this series of 18 experiments, butadiene-styrene copolymers were formed in an average yield of 96.5%. The reactor system utilized a liquid feed of butadiene from the sample cylinder described above, with the butadiene feed controlled by a double-rod fine metering valve (kept as liquid, i.e., not flashing). The double-rod fine metering allowed for precise and accurate simultaneous co-feeding of butadiene and styrene into the reactor headspace.

[0165] Example 21: Representative of the preparation of LOXLiH catalyst based on 2-piperidinoethanol followed by hydrogen mediated anionic chain transfer butadiene-styrene copolymerization using constant hydrogen co-feed. This process produced a high vinyl butadiene-styrene copolymer containing 30 wt% styrene. The reaction pressure and temperature profile is shown in Fig.11 middle.

[0166] A catalyst composition having a [AA-5]2Li3H stoichiometry (wherein AA-5 is 2-piperidinoethanol) was formed following the procedure described above for forming the [DMEA]2Li3H catalyst. Thus, the catalyst was formed from the following: 6.00 g (0.04644 mole) of 2-piperidinoethanol; and 17.849 g (0.0697 mole) of 25.2 wt% n-butyllithium in cyclohexane. At the end of the initial catalyst formation step, the H2 pressure initially increased from 23 PSIG to 27 PSIG, then dropped only 1 psi to 26 PSIG, while the temperature rose from 37.5°C to 40.8°C (12.5 minutes from the start of the butyllithium feed). After the line flush was completed, the pressure was increased to 64 PSIG and heated to 80.0°C (85°C on the oil jacket) at a pressure of about 75. The piperidine-based polar modifiers of the present disclosure tend to form at a slower rate than similar dimethylamine-based PMs.

[0167] The catalyst was aged for an additional 60 minutes at 80°C and 75 PSIG and then vented to 0 PSIG. 3 The reactor was refilled with hydrogen to a pressure of 3 PSIG. Simultaneous co-feeding of butadiene (535 g, 9.891 moles, 4.0 g / min) and styrene (229.3 g, 2.205 moles, 1.729 g / min) was started, and the combined stream was fed to the head space of the reactor with 77°C hot oil on the jacket. It should be noted that at the combined feed rate, it took about 5 minutes for the comonomer to reach the reactor. During the first 15 minutes of co-feeding, the pressure increased to 14 PSIG and the temperature rose to 83.4°C. At the same time, after 2.75 minutes of comonomer feed time, the valve from the hydrogen mass flow meter (66.9 SCCM) to the reactor was opened, and the autogenous pressure was 5 PSIG to 9 PSIG in the first 100 minutes. During this period, the temperature was 81.6°C. After 132 minutes, the simultaneous co-feeding of butadiene, styrene and hydrogen was completed. The totalizer on the hydrogen mass flow meter has been set to 8826 standard cm 3 Hydrogen. Therefore, a total of 9152 standard cm 3 Hydrogen. During the last 40 minutes of co-feeding, the reactor pressure gradually drifted upward to 16 PSIG. After the co-feeding was complete, the reaction mixture was stirred (1000 RPM to 1030 RPM during the run) for about 25 minutes. During this time, the reaction temperature dropped to 77.8°C and the pressure dropped to 0 PSIG.

[0168] The unquenched polymerization reaction mixture was transferred under positive H2 pressure to a wash vessel (N2 atmosphere) previously charged with 500 ml of deoxygenated water and 5.8 g of formic acid. The quenched reaction mixture was stirred for at least 20 minutes, then allowed to settle and the aqueous phase removed. The reaction mixture was then washed twice more with 2×350 ml of water. The reaction mixture was dried by azeotropic distillation of 600 ml of solvent, and then further stripped of solvent using a wiped film evaporator (WFE, 2" glass Pope Still, operated at 12.0 mmHg vacuum, 127°C, wiper speed of 70% of full speed, fed at 1.0 liter / hour). This WFE operation produced 747 g of 97.7% yield of M n : 1849, PD: 2.10 (refractive index detector, weighted average as described above). Further analytical details on microstructure, compositional physical properties are provided in Tables VII and VIII below.

[0169] Example 29: Representative preparation of LOXLiH catalyst based on 1-piperidino-2-butanol followed by hydrogen mediated anionic chain transfer butadiene-styrene copolymerization using constant hydrogen co-feed. This process produced a high vinyl butadiene-styrene copolymer containing 30 wt% styrene. The reaction pressure and temperature profile is shown in Fig.11 and compared with Examples 28 and 30, in which 1-piperidino-2-butanol was also PM, the same molar ratio of butadiene to styrene (28 wt % styrene) was used, and the initial hydrogen charge as well as the amount of co-feed were varied during the three runs.

[0170] A catalyst composition having a [AA-7]2Li3H stoichiometry (wherein AA-7 is 1-piperidino-2-butanol) was formed following the procedure described above for forming the [DMEA]2Li3H catalyst. Thus, the catalyst was formed from 8.051 g (0.0512 moles) of 2-1-piperidino-2-butanol; and 19.697 g (0.0768 moles) of 25.2 wt% n-butyllithium in cyclohexane. At the end of the initial catalyst formation step, the H2 pressure initially increased from 24 PSIG to 27 PSIG while the temperature rose from 37.5°C to 39.3°C (19.25 minutes from the start of the butyllithium feed). After the line flush was completed, the pressure was increased to 41 PSIG, a slight increase in temperature (0.3°C) was observed and the pressure dropped to 40°C. The jacket was set to 98°C, the reaction temperature was 89.4°C, and the pressure was about 50 PSIG. As noted above, the piperidine-based polar modifiers of the present disclosure (particularly those formed to have a 2° alcohol) tend to form at a slower rate than similar dimethylamine-based PMs. Sometimes it is not clear until the monomer is introduced whether the hydride has formed.

[0171] The catalyst was aged for an additional 90 minutes at 89°C and 50 PSIG and then vented to 0 PSIG. The reactor was then charged with 539.3 standard cm 3 of hydrogen. The reactor was then heated to 97.8°C with 110°C hot oil on the jacket. The reactor pressure was now 9 PSIG. Simultaneous co-feed of butadiene (612 g, 11.314 moles, 4.0 g / min) and styrene (238.0 g, 2.288 moles, 1.568 g / min) was started, with the combined streams fed into the headspace of the reactor with 97°C hot oil on the jacket. It should be noted that at the combined feed rate, it took about 5 minutes for the comonomer to reach the reactor. During the first 15 minutes of co-feed, the pressure increased to 37 PSIG and the temperature rose to 102.2°C. At the same time, after 1.86 minutes of comonomer feed time, the valve from the hydrogen mass flow meter (110.0 SCCM) to the reactor was opened, with an autogenous pressure of 25 PSIG to 30 PSIG over the first 140 minutes. During this period, the temperature was 100.7°C. After 151.75 minutes, the simultaneous co-feed of butadiene, styrene and hydrogen was complete. The totalizer on the hydrogen mass flow meter had been set to 16615.3 standard cm 3 Hydrogen. Therefore, a total of 17154.6 standard cm 3 Hydrogen. During the last 12 minutes of the co-feed, the reactor pressure gradually drifted upward to 33 PSIG. After the co-feed was complete, the reaction mixture was stirred (1000 RPM to 1030 RPM during the run) for about 28 minutes. During this time, the reaction temperature dropped to 95.7°C and the pressure dropped to 4 PSIG.

[0172] The unquenched polymerization reaction mixture was transferred to a wash vessel (N2 atmosphere) previously charged with 500 ml of deoxygenated water and 5.9 g of formic acid under positive H2 pressure. The quenched reaction mixture was stirred for at least 20 minutes, then allowed to settle and the aqueous phase removed. The quenched reaction mixture was then washed twice more with 2×350 ml of water. The quenched reaction mixture was dried by azeotropic distillation of 600 ml of solvent, and then further stripped of solvent using a wiped film evaporator (WFE, 2" glass Pope Still, operated at 12.0 mmHg vacuum, 120°C, wiper speed of 70% of full speed, fed at 1.0 liter / hour) to produce 807 g of 94.9% yield of M n : 1318, PD: 1.99. Further analytical details on microstructure, composition and physical properties are provided in Tables VII and VIII below.

[0173] Table II

[0174]

[0175] Table III

[0176]

[0177]

[0178] Table IV

[0179]

[0180]

[0181] Table V

[0182]

[0183]

[0184] Table VI

[0185]

[0186]

[0187] Table VII

[0188]

[0189]

[0190] Table VIII

[0191]

[0192] Table IX

[0193]

[0194] Table X

[0195]

[0196] Implementation

[0197] Additionally or alternatively, the present disclosure may include one or more of the following embodiments.

[0198] Embodiment 1. A method for copolymerizing a conjugated diene with at least one vinyl aromatic comonomer in a hydrocarbon reaction medium, the method comprising chemically adding a lithium alcohol complexed salt-type hydride LOXSH catalyst to a low-boiling conjugated diene and / or the vinyl aromatic comonomer to form a polymerization initiating substance, and simultaneously co-feeding the vinyl aromatic comonomer with at least two gaseous and / or volatile compounds into the reaction medium, wherein the at least two gaseous and / or volatile compounds comprise hydrogen and the low-boiling conjugated diene, and polymerizing at least a portion of the conjugated diene, wherein the LOXSH agent comprises one or more σ-μ polar modifiers.

[0199] Embodiment 2. A method for hydrogen-mediated copolymerization of a conjugated diene with at least one vinyl aromatic comonomer in a hydrocarbon reaction medium, the method comprising chemically adding a lithium alcohol complexed salt-type hydride (LOXSH) catalyst to a low-boiling conjugated diene and / or the vinyl aromatic comonomer to form a polymerization initiating substance, and simultaneously co-feeding the vinyl aromatic comonomer and at least two gaseous and / or volatile compounds into the reaction medium, wherein the at least two gaseous and / or volatile compounds comprise hydrogen and the low-boiling conjugated diene, wherein the LOXSH catalyst comprises one or more σ-μ polar modifiers.

[0200] Embodiment 3. A LOXSH catalyst or reagent composition, wherein the composition is selective for 1,4-CD monomer microstructure attachment, and the composition comprises 1) at least one tertiary amino alcohol σ-μ polar modifier having a 2° or 3° alcohol functional group; 2) an organic lithium compound; and 3) optionally elemental hydrogen and / or an organic silicon hydride.

[0201] Embodiment 4. A LOXSH catalyst or reagent composition, wherein the composition is selective for 3,4-CD and / or 1,2-CD-vinyl monomer microstructural linkage in a (VA-CD) copolymer, and the composition comprises: a) at least one tertiary amino alcohol σ-μ or amino-ether-alcohol polar modifier; b) optionally at least one separate ether-alcohol σ-μ polar modifier; c) an organolithium compound; and d) optionally elemental hydrogen and / or an organosilicon hydride.

[0202] Embodiment 5. A hydrogen-mediated anionic VA-CD copolymer composition (a copolymer comprising hydrogen, a vinyl aromatic monomer, and a conjugated diene monomer) that can be characterized as having: 1) a number average degree of polymerization DP in the range of about 7 to about 50 repeating units n; 2) a Brookfield viscosity (45°C) in the range of about 10 cP to about 300,000 cP; 3) a 1,4-CD microstructure content in the range of 20% to about 80%; and 4) a glass transition temperature T in the range of about -110°C to about 5°C g .

[0203] Embodiment 6. A method, catalyst or composition as described in any of the preceding embodiments, comprising simultaneously co-feeding a vinyl aromatic comonomer with a low boiling point conjugated diene and hydrogen in a predetermined molar ratio to a polymerization reaction mixture during at least a portion of the entire co-feed, wherein the reactor pressure is spontaneously adjusted to the condensed phase activity of hydrogen and the conjugated diene at a relatively steady-state pressure and temperature. The reactor pressure during the process (the autogenous reaction pressure) can be the result or product of some combination of: a) the relative feed rates of hydrogen and comonomer; b) the feed rates of reactants relative to catalyst concentration; c) the reaction temperature; d) the activity of a particular LOXSH catalyst; and e) the vapor pressure of the reaction medium or solvent.

[0204] Embodiment 7. A method, catalyst or composition as described in any of the preceding embodiments, wherein the total amount of VA and CD comonomers relative to the relative feed of hydrogen can be in the range of about 5 moles to about 50 moles (VA+CD) / mole H2, and the relative feed of the conjugated diene (VA+CD) monomer relative to hydrogen can be about 5 moles to about 42 moles (VA+CD) / mole H2; or wherein the relative feed rate of (VA+CD) / H2 / unit time is from about 0.0333 moles (VA+CD) / mole H2 / minute to about 0.6667 moles CD / mole H2 / minute; or wherein the moles (VA+CD) in the LOXSH catalyst are about 1.5 to about 2.0 moles (VA+CD) / mole H2 / minute. The relative feed of monomer to molar salt hydride (SH) is from about 70 moles to about 1500 moles per mole of SH (VA+CD); wherein the salt hydride (SH) is one or more of LiH, and / or NaH, and / or KH, and / or MgH2 and / or CsH; or wherein the conjugated diene comprises one or more of butadiene, isoprene, 2-methyl-1,3-pentadiene (E and Z isomers); piperylene; 2,3-dimethylbutadiene; 2-phenyl-1,3-butadiene; cyclohexadiene; b-myrcene; β-farnesene; and hexatriene; or wherein the conjugated diene comprises one or more of butadiene and / or isoprene.

[0205] Embodiment 8. The method, catalyst, or composition of any of the preceding embodiments, wherein the one or more σ-μ polar modifiers can be selected from one or more of the following structures:

[0206]

[0207] Wherein R is independently an alkyl group, and the alkyl group can be further substituted by other tertiary amines or ethers, 1 are independently a hydrogen atom or an alkyl group, and the alkyl group can be further substituted by other tertiary amines or ethers, R 2 For –(CH2) y –, wherein y=2, 3 or 4, Σ can include: i) O or NR for I, II, III, IV and V; ii) and for VI, VII, VIII and IX, can include O or NR or CH2; n is independently an integer equal to or greater than 0, and x is independently an integer equal to or greater than 1.

[0208] Embodiment 9. A method, catalyst or composition as described in any of the preceding embodiments, wherein the hydrocarbon reaction medium can be pK a greater than H2; or wherein the hydrocarbon reaction medium can contain molecular hydrogen and the partial pressure of the molecular hydrogen can be maintained at a pressure between about 0.01 bar and about 19.0 bar; or wherein the autogenous reaction pressure can be between about 0.01 bar and about 19.0 bar; or wherein the process can include a temperature and the temperature is maintained between about 20°C and about 130°C; or wherein the molar ratio of the total feed of monomers to the salt-type hydride catalyst can be from about 10:1 to about 1000:1.

[0209] Embodiment 10. A method, catalyst or composition as described in any of the preceding embodiments, wherein the σ-μ polar modifier can be one or more of the following: N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino-2 -Butanol; trans-2-piperidinocyclohexan-1-ol; 1-phenyl-2-piperidin-1-ylethanol; 1-pyrrolidinylethanol; pyrrolidinylpropan-2-ol; 1-(1-pyrrolidinyl)-2-butanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 2-pyrrolidinylcyclohexanol; 4-methyl-1-piperazineethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; 2-(4- methylpiperazino)-1-phenylethan-1-ol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol; 2-morpholinoethanol; 1-(4-morpholino)-2-propanol; 1-(4-morpholino)-2-butanol; 2-morpholino-1-phenyl-1-ethanol; trans-2-morpholin-4-ylcyclohexanol; 1-methyl-2-piperidinylmethanol; 1-methyl-2-pyrrolidinemethanol, diethylaminoethanol, N-methyl-diethanolamine and 3-dimethylamino-1- propyl alcohol, 2-[2-(dimethylamino)ethoxy]ethanol, 1,3-bis(dimethylamino)-2-propanol; 2-{[2-dimethylamino)ethyl]methylamino}ethanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2-(2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholinyl)ethoxy]ethanol; 2-[2-(1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol. The method, catalyst or composition can also include one or more of the following: 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, trans-2-methoxycyclohexan-1-ol, 2-methoxy-1-phenylethanol, tetrahydrofurfuryl alcohol or tetrahydropyran-2-methanol or diethylene glycol monomethyl ether.

[0210] Embodiment 11. A method, catalyst or composition as described in any of the preceding embodiments, wherein the LOXSH catalyst comprises between about 50 mol% and less than 100 mol% of a tertiary amino-alcohol or tertiary amino-ether-alcohol σ—μ polar modifier selected from one or more of the following: N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino- 2-Butanol; trans-2-piperidinocyclohexan-1-ol; 1-phenyl-2-piperidin-1-ylethanol; 1-pyrrolidinylethanol; pyrrolidinylpropan-2-ol; 1-(1-pyrrolidinyl)-2-butanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 2-pyrrolidinylcyclohexanol; 4-methyl-1-piperazineethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; 2-(4-methylpiperazinyl)-1-phenylethan-1-ol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol alcohol; 2-morpholinoethanol; 1-(4-morpholino)-2-propanol; 1-(4-morpholino)-2-butanol; 2-morpholino-1-phenyl-1-ethanol; trans-2-morpholin-4-ylcyclohexanol; 1-methyl-2-piperidinylmethanol; 1-methyl-2-pyrrolidinemethanol, diethylaminoethanol, N-methyl-diethanolamine and 3-dimethylamino-1-propanol, 2-[2-(dimethylamino)ethoxy]ethanol, 1,3-bis(dimethylamino)-2-propanol; 2-{[2-dimethylamino)ethyl]methylamino}ethanol; 2-[2-(dimethylamino)ethoxy] ethanol; 2-(2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholinyl)ethoxy]ethanol; 2-[2-(1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol; and about 50 mol% to greater than 0 mol% of an ether-alcohol σ-μ polar modifier selected from one or more of the following: 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, 2-methoxycyclohexan-1-ol, 2-methoxy-1-phenylethanol; tetrahydrofurfuryl alcohol, tetrahydropyran-2-methanol, diethylene glycol monomethyl ether.

[0211] Components referred to by chemical names or chemical formulas in any position of the specification or its claims (whether referred to in the singular or in the plural) are identified as existing before contacting with another substance referred to by chemical name or chemical type (eg another component, solvent, etc.). It is not important what chemical changes, transformations and / or reactions (if any) occur in the resulting mixture or solution, because such changes, transformations and / or reactions are the natural result of putting the specified components together under the conditions required according to the present disclosure. Therefore, components are identified as ingredients that are brought together in conjunction with performing a desired operation or forming a desired composition. In addition, even though the claims below may refer to substances, components and / or ingredients in the general present tense ("including", "is", etc.), the substances, components or ingredients are referred to as existing before first contacting, blending or mixing with one or more other substances, components and / or ingredients according to the present disclosure. Therefore, the fact that substances, components or ingredients may lose their original properties through chemical reactions or transformations during the process of contacting, blending or mixing operations (if performed according to the present disclosure and according to the ordinary skills of chemists) is of no practical significance.

[0212] Each patent or publication mentioned in any part of this specification is incorporated by reference into the present disclosure in its entirety as if fully set forth herein.

[0213] The present disclosure is susceptible to considerable variation in its practice. Therefore, the foregoing description is not intended and should not be construed as limiting the present disclosure to the particular examples given above.

[0214] It should be understood that the embodiments and claims disclosed herein are not limited in their application to the details of the construction and arrangement of the components set forth in the specification and illustrated in the drawings. Rather, the specification and drawings provide examples of contemplated embodiments. The embodiments and claims disclosed herein are capable of other embodiments and can be practiced and implemented in a variety of ways. In addition, it should be understood that the words and terms used herein are for descriptive purposes and should not be considered to limit the claims.

[0215] Therefore, it should be appreciated by those skilled in the art that the concepts upon which the present application and claims are based can be readily used as a basis for designing other structures, methods and systems for carrying out the several purposes of the embodiments and claims set forth in the present application. It is therefore important that the claims be deemed to include such equivalent constructions.

Claims

1. A process for copolymerizing a conjugated diene with a vinyl aromatic comonomer in a hydrocarbon reaction medium, the process comprising a) chemically adding a lithium alcohol complex salt type hydride (LOXSH) catalyst to a low boiling point conjugated diene to form a polymerization initiating substance, b) co-feeding the vinyl aromatic comonomer simultaneously with at least two gaseous and / or volatile compounds into the reaction medium, wherein the at least two gaseous and / or volatile compounds comprise hydrogen and the low boiling point conjugated diene, and c) polymerizing at least a portion of the conjugated diene, The LOXSH reagent comprises one or more σ-μ polar modifiers.

2. A method for hydrogen-mediated copolymerization of conjugated dienes and vinyl aromatic monomers in a hydrocarbon reaction medium, the method comprising chemically adding a lithium alcohol complex salt-type hydride (LOXSH) catalyst to a low-boiling conjugated diene and / or a vinyl aromatic comonomer to form a polymerization initiating substance, and co-feeding at least two gaseous and / or volatile compounds into the reaction medium, wherein the at least two gaseous and / or volatile compounds comprise hydrogen and the low-boiling conjugated diene, wherein the LOXSH catalyst comprises one or more σ-μ polar modifiers.

3. The process of claim 1 or 2, comprising simultaneously co-feeding the low boiling point conjugated diene, the vinyl aromatic comonomer and the hydrogen into the polymerization mixture in a predetermined molar ratio during at least a portion of the entire co-feed, wherein the reactor pressure is spontaneously adjusted to the condensed phase activity of hydrogen and the conjugated diene at a relatively steady-state pressure and temperature.

4. A process as claimed in claim 1 or 2, wherein the reactor pressure (autogenous reaction pressure) during the process is the result or product of some combination of: a) the relative feed rates of hydrogen and monomer; b) the feed rates of reactants relative to catalyst concentration; c) the reaction temperature; d) the activity of the specific LOXSH catalyst; and e) the vapor pressure of the reaction medium or solvent.

5. The process of claim 1 or 2, wherein the relative feed of total (VA+CD) comonomer to hydrogen is from about 5 moles to about 50 moles CD / mole H 2 .

6. The method of claim 5, wherein (VA+CD) / H 2 The relative feed rate per unit time is about 0.0333 mol (VA+CD) / mol H 2 / min to about 0.6667 mol (VA + CD) / mol H 2 / minute.

7. The method of claim 1 or 2, wherein in the LOXSH catalyst, the relative feed of total (VA+CD) comonomer moles to salt hydride (SH) moles is from about 70 moles to about 1500 moles CD per mole SH; wherein the salt hydride (SH) is LiH, and / or NaH, and / or KH, and / or MgH 2 and / or one or more of CsH and / or RbH.

8. The method of claim 1 or 2, wherein the conjugated diene comprises one or more of the following: butadiene, isoprene, 2-methyl-1,3-pentadiene (E and Z isomers); piperylene; 2,3-dimethylbutadiene; 2-phenyl-1,3-butadiene; cyclohexadiene; b-myrcene; β-farnesene; and hexatriene.

9. The method of claim 1 or 2, wherein the conjugated diene comprises one or more of butadiene and / or isoprene, and the vinyl aromatic compound comprises styrene.

10. The method of claim 1 or 2, wherein the vinyl aromatic comonomer is one or more of the following: styrene, methyl-styrene; C 2 -C 10 Alkylstyrenes; vinyl-naphthalene; alpha-methylstyrene; 4-vinylanisole; 6-methoxy-1-vinylnaphthalene; o-, m- or p-N,N-dimethylaminostyrene; and 6-N,N-dimethylamino-1-vinylnaphthalene.

11. The method of claim 1 or 2, wherein the one or more σ-μ polar modifiers are selected from one or more of the following structures: Wherein R is independently an alkyl group, and the alkyl group can be further substituted by other tertiary amines or ethers, 1 are independently a hydrogen atom or an alkyl group, and the alkyl group can be further substituted by other tertiary amines or ethers, R 2 =CH 2 ) y –, where y = 2, 3 or 4, Σ can include: i) O or NR for I, II, III, IV and V; ii) and for VI, VII, VIII and IX, can include O or NR or CH 2 ; n is independently an integer equal to or greater than 0, and x is independently an integer equal to or greater than 1.

12. The process of claim 1 or 2, wherein the hydrocarbon reaction medium comprises a pK a Greater than H 2 of hydrocarbon solvents.

13. The process of claim 1 or 2, wherein the hydrocarbon reaction medium comprises molecular hydrogen and the partial pressure of the molecular hydrogen is maintained at a pressure between about 0.01 bar and about 19.0 bar.

14. The process of claim 3 or 4, wherein the autogenous reaction pressure is between about 0.01 bar and about 19.0 bar.

15. The method of claim 1 or 2, wherein the method comprises a temperature, and the temperature is maintained between about 20°C and about 130°C.

16. The process of claim 1 or 2, wherein the molar ratio of the total feed of monomers to the salt-type hydride catalyst is from about 10:1 to about 1500:

1.

17. The method of claim 1 or 2, wherein the salt-type hydride catalyst is one or more of the following: 1) LOXLiH reagent; 2) LOXNaH reagent; 3) LOXMgH 2 ; and / or 4) LOXKH reagent.

18. The method of claim 1 or 2, wherein the σ-μ polar modifier is one or more of the following: N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino-2-butanol; trans-2-piperidino Cyclohexanol-1-ol; 1-phenyl-2-piperidin-1-ylethanol; 1-pyrrolidinylethanol; pyrrolidinylpropan-2-ol; 1-(1-pyrrolidinyl)-2-butanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 2-pyrrolidinylcyclohexanol; 4-methyl-1-piperazineethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; 2-(4-methylpiperazinyl)-1 -phenylethan-1-ol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol; 2-morpholinoethanol; 1-(4-morpholino)-2-propanol; 1-(4-morpholino)-2-butanol; 2-morpholino-1-phenyl-1-ethanol; trans-2-morpholin-4-ylcyclohexanol; 1-methyl-2-piperidinylmethanol; 1-methyl-2-pyrrolidinemethanol, diethylaminoethanol, N-methyl-diethanolamine and 3-dimethylamino-1-propanol, 2 -[2-(dimethylamino)ethoxy]ethanol, 1,3-bis(dimethylamino)-2-propanol; 2-{[2-dimethylamino)ethyl]methylamino}ethanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2-(2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholinyl)ethoxy]ethanol; 2-[2-(1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol.

19. The method of claim 18, further comprising one or more of 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, trans-2-methoxycyclohexan-1-ol, 2-methoxy-1-phenylethanol, tetrahydrofurfuryl alcohol, tetrahydropyran-2-methanol, or diethylene glycol monomethyl ether.

20. The method of claim 1 or 2, wherein the LOXSH catalyst comprises between about 50 mol% and less than 100 mol% of a tertiary amino-alcohol or tertiary amino-ether-alcohol sigma-μ polar modifier selected from one or more of the following: N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino-2-butanol; trans-2-piperidino 1-Phenyl-2-piperidin-1-ylethanol; 1-pyrrolidinoethanol; pyrrolidinylpropan-2-ol; 1-(1-pyrrolidinyl)-2-butanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 2-pyrrolidinylcyclohexanol; 4-methyl-1-piperazineethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; 2-(4-methylpiperazinyl)-1-phenylethan-1-ol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol; 2-morpholinoethanol ; 1-(4-morpholinyl)-2-propanol; 1-(4-morpholinyl)-2-butanol; 2-morpholino-1-phenyl-1-ethanol; trans-2-morpholin-4-ylcyclohexanol; 1-methyl-2-piperidinolmethanol; 1-methyl-2-pyrrolidinemethanol, diethylaminoethanol, N-methyl-diethanolamine and 3-dimethylamino-1-propanol, 2-[2-(dimethylamino)ethoxy]ethanol, 1,3-bis(dimethylamino)-2-propanol; 2-{[2-dimethylamino)ethyl]methylamino}ethanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2-( 2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholinyl)ethoxy]ethanol; 2-[2-(1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol; and about 50 mol% to greater than 0 mol% of an ether-alcohol σ-μ polar modifier selected from one or more of the following: 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, trans-2-methoxycyclohexan-1-ol, 2-methoxy-1-phenylethanol, tetrahydrofurfuryl alcohol or tetrahydropyran-2-methanol or diethylene glycol monomethyl ether.

21. The method of claim 1 or 2, further comprising one or both of a sigma-type polar modifier and / or a μ-type polar modifier.

22. A LOXSH catalyst or reagent composition, wherein the composition is selective for 1,4-CD monomer microstructural linkage in a VA-CD copolymer composition, and the LOXSH composition comprises 1) at least one tertiary amino alcohol σ-μ polar modifier having a 2° or 3° alcohol functionality; 2) an organolithium compound; and 3) optionally elemental hydrogen and / or an organosilicon hydride.

23. The LOXSH composition according to claim 22, wherein the σ-μ polar modifier is selected from at least one of the following structures: Wherein R is independently an alkyl group, and the alkyl group can be further substituted by other tertiary amines or ethers, 1 is independently a hydrogen atom or an alkyl group, and the alkyl group can be further substituted by other tertiary amines or ethers. include: i) O or NR for III, IV and V; ii) and for VI, VII and IX, can include O or NR or CH 2 ; n is independently an integer equal to or greater than 0, and x is independently an integer equal to or greater than 1.

24. The LOXSH composition of claim 22, wherein the σ-μ polar modifier comprises one or more of the following: 1-dimethylamino-2-propanol, 1-piperidino-2-propanol, 1-pyrrolidinylpropan-2-ol, 1-morpholino-2-propanol, 1-(4-methyl-1-piperazinyl)-2-propanol, 1-dimethylamino-2-butanol, 1-piperidino-2-butanol, 1-pyrrolidinylbutan-2-ol, 1-morpholino-2-butanol, 1-(4-methyl-1-piperazinyl)-2-butanol, 2-dimethylaminocyclohexan-1-ol, 2-piperidinocyclohexan-1-ol, 2-pyrrolidinylcyclohexanol, 2-(4-methyl-1-piperazinyl)-2-butanol -1-piperazinyl)-cyclohexanol, 2-morpholinocyclohexan-1-ol, 2-(dimethylamino)-1-phenylethanol; 1-phenyl-2-piperidin-1-ylethanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 2-(4-methylpiperazino)-1-phenylethan-1-ol; 2-morpholino-1-phenyl-1-ethanol, 1,3-bis(dimethylamino)-2-propanol, optionally with the addition of one or more of the following: 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, 2-methoxycyclohexan-1-ol, 2-methoxy-1-phenylethanol, tetrahydrofurfuryl alcohol, tetrahydropyran-2-methanol, diethylene glycol monomethyl ether.

25. A LOXSH catalyst or reagent composition, wherein the composition is selective for 3,4-CD and / or 1,2-CD-vinyl monomer microstructural attachment, and the composition comprises: a) at least one tertiary amino alcohol sigma-μ or amino-ether-alcohol polar modifier; b) optionally at least one separate ether-alcohol sigma-μ polar modifier; c) an organolithium compound; and d) optionally elemental hydrogen and / or an organosilicon hydride.

26. The LOXSH composition of claim 25, wherein the σ-μ polar modifier is selected from at least two of the following structures: Wherein R is independently an alkyl group, and the alkyl group can be further substituted by other tertiary amines or ethers, 1 are independently a hydrogen atom or an alkyl group, and the alkyl group can be further substituted by other tertiary amines or ethers, R 2 =CH 2 ) y –, where y = 2, 3 or 4, Σ can include: i) O or NR for I, II, III, IV and V; ii) and for VI, VII, VIII and IX, can include O or NR or CH 2 ; n is independently an integer equal to or greater than 0, and x is independently an integer equal to or greater than 1.

27. The LOXSH composition of claim 25, wherein the σ-μ polar modifier of the reagent comprises between about 50 mol% and less than 100 mol% of a tertiary amino-alcohol or tertiary amino-ether-alcohol σ-μ polar modifier selected from one or more of the following: 1.) N,N-dimethylethanolamine; 1-(dimethylamino)-2-propanol; 1-(dimethylamino)-2-butanol; trans-2-(dimethylamino)cyclohexanol; 2-(dimethylamino)-1-phenylethanol; 2-piperidinoethanol; 1-piperidino-2-propanol; 1-piperidino-2-butanol; alcohol; trans-2-piperidinocyclohexan-1-ol; 1-phenyl-2-piperidin-1-ylethanol; 1-pyrrolidinylethanol; pyrrolidinylpropan-2-ol; 1-(1-pyrrolidinyl)-2-butanol; 1-phenyl-2-(1-pyrrolidinyl)-1-ethanol; 2-pyrrolidinylcyclohexanol; 4-methyl-1-piperazineethanol; 1-(4-methyl-1-piperazinyl)-2-propanol; 1-(4-methyl-1-piperazinyl)-2-butanol; 2-(4-methylpiperazinyl)-1-phenylethan-1-ol; trans-2-(4-methyl-1-piperazinyl)-cyclohexanol; 2- Morpholinoethanol; 1-(4-morpholino)-2-propanol; 1-(4-morpholino)-2-butanol; 2-morpholino-1-phenyl-1-ethanol; trans-2-morpholin-4-ylcyclohexanol; 1-methyl-2-piperidinolmethanol; 1-methyl-2-pyrrolidinemethanol, diethylaminoethanol, N-methyl-diethanolamine and 3-dimethylamino-1-propanol, 2-[2-(dimethylamino)ethoxy]ethanol, 1,3-bis(dimethylamino)-2-propanol; 2-{[2-dimethylamino)ethyl]methylamino}ethanol; 2-[2-(dimethylamino)ethoxy]ethanol; 2 -(2-(piperidinyl)ethoxy)ethanol; 2-[2-(4-morpholinyl)ethoxy]ethanol; 2-[2-(1-pyrrolidinyl)ethoxy]ethanol; 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol; and II.) about 50 mol% to greater than 0 mol% of an ether-alcohol σ-μ polar modifier selected from one or more of the following: 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, 2-methoxycyclohexan-1-ol, 2-methoxy-1-phenylethanol, tetrahydrofurfuryl alcohol, tetrahydropyran-2-methanol, diethylene glycol monomethyl ether.

28. The LOXSH composition of claim 25, wherein the ratio of total amino-alcohol (AA) and / or amino-ether-alcohol (AEA) to total individual ether-alcohol (EE) sigma-μ polar modifiers ([AA+AEA]:EA) is from about 9:1 to about 1:

1.

29. The LOXSH composition of claim 25, wherein the ratio of total amino-alcohol (AA) and / or amino-ether-alcohol (AEA) to total individual ether-alcohol (EE) sigma-μ polar modifiers ([AA+AEA]:EA) is from about 4:1 to about 2:

1.

30. A hydrogen-mediated anionic VA-CD copolymer composition, Features Having: 1) a number average degree of polymerization (DP) ranging from about 7 to about 50 repeating units n ); 2) a Brookfield viscosity (45°C) in the range of about 10 cP to about 300,000 cP; 3) a 1,4-CD microstructure content in the range of 20% to about 80% based on the conjugated diene portion; and 4) a glass transition temperature T in the range of about -110°C to about 5°C. g .

31. The composition of claim 30, wherein the composition is a hydrogen mediated isoprene-styrene copolymer distribution composition, the composition being capable of having a number average DP in the range of about 7 to about 45. n , and having a number average molecular weight (M) in the range of about 500 Daltons to about 3500 Daltons n ), and having a styrene content in the range of about 10 wt % to about 90 wt % styrene, and having a glass transition temperature varying in the range of -100°C at about 500 Daltons to 5°C at about 3000 Daltons, and having a Brookfield viscosity (45°C) in the range of about 100 cP to about 300,000 cP.

32. The composition of claim 31, Features Having a number average degree of polymerization (DP) in the range of about 7 to about 27 n ), further characterized by having: 1) a styrene content of 10 wt % to about 85 wt %; 2) a 1,4-PIP content of between 35 wt % and 90 wt % based on the isoprene portion; 3) a glass transition temperature T in the range of about -70°C to about -40°C g ; and a Brookfield viscosity (45° C.) ranging from about 280 cP to about 3800 cP.

33. The composition of claim 30, wherein the composition is a hydrogen mediated butadiene-styrene copolymer distribution composition having a number average DP in the range of about 8 to about 45. n and a number average molecular weight (M) ranging from about 500 Daltons to about 3300 Daltons. n ), and having one of the following: 1) having a styrene content in the range of about 10 wt % to about 40 wt %, and having a total vinyl content based on the butadiene portion of about 70 wt % to about 80 wt %, and having a Brookfield viscosity (at 45° C.) as M n % to about 100,000 cP as a function of the styrene content; or 2) having a styrene content in the range of about 10 wt % to about 40 wt % and having a total vinyl content of about 40 wt % to about 65 wt % based on the butadiene portion, and having a Brookfield viscosity (at 45° C.) as a function of the M n % to about 10,000 cP as a function of the styrene content; or 3) having a styrene content in the range of about 10 wt % to about 40 wt % and having a total vinyl content of about 25 wt % to about 35 wt % based on the butadiene portion, and having a Brookfield viscosity (at 45° C.) as a function of the M n The total vinyl content of the butadiene portion is determined by 1 HNMR analysis; the composition has n =500 Daltons to M n =3300 Daltons in the range of less than -110°C to about -15°C, wherein the T g Increases as a function of molecular weight and total vinyl content and has a ratio of vinyl-1,2-BD:VCP ranging from about 5:1 to about 25:

1.

34. The composition of claim 30, wherein the composition is a hydrogen mediated butadiene-styrene copolymer distribution composition, Its characteristics are also Having 20 wt % to 36 wt % styrene and a total vinyl content in the range of about 70 wt % to about 80 wt % based on the butadiene portion: 1) number average molecular weight distribution (M n ) in the range of about 500 Daltons to about 3000 Daltons; 2) Brookfield viscosity (at 45°C) in the range of about 165 cP to about 97,000 cP; 3) glass transition temperature (T g ) is in the range of less than about -65°C to about -18°C; 4) the molar ratio of vinyl-1,2-BD:VCP can be in the range of about 12:1 to about 25:1 (based on 1 1H NMR analysis); and 5) having an iodine number of about 280 to about 395.

35. The composition of claim 30, wherein the composition is a hydrogen mediated butadiene-styrene copolymer distribution having a styrene content of 25 wt % to 30 wt %, a total vinyl content in the range of about 40 wt % to about 65 wt % based on the butadiene portion, in: 1) Number average molecular weight distribution (M n ) can be in the range of about 1300 to about 2000 Daltons; 2) Brookfield viscosity (at 45°C) can be in the range of about 800 cP to about 2800 cP; 3) glass transition temperature T g in the range of about -50°C to about -60°C; and 4) the molar ratio of vinyl-1,2-BD:VCP can be in the range of about 10:1 to about 14:1 1 (based on 1 HNMR analysis of vinyl content).

36. The composition of claim 30, wherein the composition is a hydrogen mediated butadiene-styrene copolymer distribution having a styrene content of 25 wt % to 30 wt %, a total vinyl content in the range of about 25 wt % to about 35 wt % based on the butadiene portion, in: 1) Number average molecular weight distribution (M n ) in the range of about 1300 Daltons to about 2300 Daltons; 2) Brookfield viscosity (at 45°C) in the range of about 500 cP to about 3500 cP; 3) glass transition temperature T g in the range of about -55°C to about -70°C; and 4) the molar ratio of vinyl-1,2-BD:VCP can be in the range of about 7:1 to about 12:1 1 (based on 1 HNMR analysis of vinyl content).

37. The composition of claim 30, wherein the composition is a hydrogen mediated butadiene-styrene copolymer distribution composition, Its characteristics are also Having 20 wt % to 36 wt % styrene and a total vinyl content in the range of about 70 wt % to about 80 wt % based on the butadiene portion: 1) number average molecular weight distribution (M n ) in the range of about 500 Daltons to about 3000 Daltons; 2) Brookfield viscosity (at 45°C) in the range of about 165 cP to about 97,000 cP; 3) glass transition temperature (T g ) is in the range of less than about -65°C to about -18°C; 4) the molar ratio of vinyl-1,2-BD:VCP can be in the range of about 12:1 to about 25:1 (based on 1 1H NMR analysis); and 5) having an iodine number of about 280 to about 395.

38. A brominated conjugated diene vinyl aromatic copolymer comprising the brominated product of any of the hydrogen mediated anionic VA-CD copolymer compositions of claim 30.

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