Shelf-stable loxsh catalyst solution compositions comprising soluble high hydride concentrations and the processes for preparing them

Abstract

The various embodiments of the disclosure relate generally to compositions of shelf-stable LOXSH catalyst solution compositions comprising from about 120 ppm to about 1200 ppm hydride ion concentration (from about 950 to about 9600 ppm as lithium hydride) as a homogenous hydrocarbon solution. The various embodiments of the disclosure also relate generally to processes, methods, and systems, that enable the formation and hence utilization such shelf-stable LOXSH catalyst and reagent solutions.

Description

SHELF-STABLE LOXSH CATALYST SOLUTION COMPOSITIONS COMPRISING SOLUBLE HIGH HYDRIDE CONCENTRATIONS AND THE PROCESSES FOR PREPARING THEMTECHNICAL FIELD

[0001] The various embodiments of the disclosure relate generally to compositions of, manufacturing processes for, and methods that enable the formation of novel commercially practical shelf-stable concentrates of hydrocarbon soluble lithium hydride reagents and hydrogen mediated anionic polymerization catalysts. Such composition comprising 120 ppm to 1200 ppm hydride content, from about 950 ppm to about 9600 ppm lithium hydride concentration. The disclosure also relates to methods wherein said concentrates of hydrocarbon soluble lithium hydride catalyst and reagent solutions are used to form polymerization reaction mixtures as well as used as carbonyl reducing agents.BACKGROUND

[0002] Lithium Alkoxide Complexed Saline Hydride (LOXSH) catalysts have been previously described in WO2017176740A1, WO2022051376 and WO2023168218A2 for the hydrogen mediated anionic polymerization of vinyl aromatic monomers such as styrene, conjugated diene monomers such as butadiene and isoprene, and copolymers thereof. Accordingly, the LOXSH catalyst formed from the |3-aminoalcohol dimethylethanolamine, DMEA (or in some text dimethylaminoethanol, DMAE) can be used to form low molecular weight hydrogen mediated anionic polystyrene (HMAPS) compositions wherein the polymer chains are comprised of >99% of the head to tail microstructure. Equally important to HMAPS production, the LOXSH catalyst formed from DMEA are effective to achieve high vinyl LOXSH (HV-LOXSH) catalyst formulations used in the hydrogen mediated anionic polymerization of butadiene. Accordingly, such catalysts are useful in forming high vinyl content hydrogen mediated poly butadiene compositions, HV-HMPBD. Alternatively, the -aminoalcohols 1-piperidino-Ao-propanol (PiP, also l-piperidino-2 -propanol CAS 934-90-7)) and l-piperidino-sec-butanol (PsB also l-piperidino-2-butanol. CAS 3140-33-8) are effective for low vinyl LOXSH (LV-LOXSH) catalyst formulations used to produce low vinyl contentpolymers from conjugated diene monomers - low vinyl content hydrogen mediated polybutadiene compositions, LV-HMPBD. Selection of polar modifiers, such as p-aminoalcohols, in the LOXSH catalyst system allows for tailoring the vinyl content of the polymers from conjugated diene monomers.

[0003] All of the LOXSH catalyst formulations of WO2017176740A1, WO2022051376 and WO2023168218A2 were formed in situ in the hydrogen mediated polymerization reactor within 1 to 4 hours prior to their use. The catalyst composition thus produced in WO2017176740A1 were typically in the range of about 280 ppm lithium hydride (35 ppm as hydride ion concentration) when formed. The highest concentration of a LOXSH catalyst reported was 896 ppm LiH (114 ppm hydride ion concentration). Equation 1 can be used to convert lithium hydride concentration [LiH] to hy dride ion concentration [H_].[H-] = * 1.008 Equation 1

[0004] Although hydrogen mediated polymerization processes that entail forming the LOXSH catalyst in situ have proven to be ven’ convenient and. in many cases, quite advantageous, it would be desirable to prepare the various LOXSH catalysts as concentrated solutions. Formation of the LOXSH catalyst as a concentrate in a vessel exterior to a continuous polymerization reactor would facilitate such continuous processes. Equally important, forming the LOXSH catalyst as a concentrate in a vessel exterior to a polymerization reactor, would save invaluable time in the polymerization reactor for batch and semi-batch operations.

[0005] LOXSH Catalyst are formed at least in part from pyrophoric alkyllithium solutions (e.g. w-butyllithium, BuLi) which require extra care and expertise when handling them especially on an industrial scale. The process for forming a LOXSH catalyst entails hydrogenolysis under a hydrogen atmosphere of an intermediate lithium alkoxide complexed alkyllithium reagent (BuLi / lithium aminoalkoxide aggregates). The mixing used in the hydrogenolysis requires very effective mass transfer of hydrogen gas from the vapor phase to the condensed phase. Consequently, adoption of this new technology in the industry would be facilitated by a new production process for LOXSH as well as finding conditions under which the LOXSH catalyst and reagent can be stored for extended periods of time. However, such an achievement and effort would seem a priori futile in the light of the teachings regarding the SchenckEquilibrium. (In this connection, please see Harder, Sjoerd. " From limestone to catalysis: application of calcium compounds as homogeneous catalysts." Chemical reviews 110, no. 7 (2010): 3852-3876. Harder. Sjoerd. and Florian Fed. " Dimeric benzylcalcium complexes: influence of THF in stereoselective styrene polymerization " Organometallics 21, no. 11 (2002): 2268-2274. Harder, Sjoerd. " Molecular early main group metal hydrides: synthetic challenge, structures and applications." Chemical Communications 48, no, 91 (2012): 11165-11177.)

[0006] The following chemical equation provides what is known as the Schlenk Equilibrium as written for Group I metals:2M3L1L1L2< *■ 2 M2L1L1+ M2L2L2| Accordingly, the equation shows a group I (alkali metal) metal M that is complexed by three (or more) Ligands (Li; L2; etc.) to form a soluble heteroleptic metal complex(es) M3L1L1L2 or aggregates. Ligand exchange reactions (dismutation) will lead to formation of homoleptic metal complexes M2L1L1 and M2L2L2. When M2L2L2 is insoluble, precipitation of M2L2L2 will shift the equilibrium from the heteroleptic complex to the homoleptic complexes in and out of solution. For M = Li, [PM] = Li and H = L2; higher ratios of [PM]Li to LiH would appear to suppress the Schlenk Equilibrium and keep the LiH of the catalyst in solution at least long enough for the processes of the abovementioned patent applications. Open literature teachings of Fohlmeister and Stasch would support the thought that formation of concentrated and thermally stable LOXSH catalyst solutions is not likely to be a successful endeavor (please see Fohlmeister, Lea, and Andreas Stasch. " Alkali metal hydride complexes: well-defined molecular species of saline hydrides." Australian Journal of Chemistry 68, no. 8 (2015): 1190-1201.) Accordingly, Fohlmeister and Stasch teach the following with regard to their LiH complex (DipNPPhityLisHi:‘'The strongest lattice is formed by hydrides and Li cations, which have the most compatible ion sizes. This trend explains why the reactivity of MH can increase from NaH to CsH, whereas LiH is more inert. The high lattice energies also offer an explanation for why well-defined alkali metal hydride complexesgenerally cannot be synthesized from their parent metal hydrides, because their lattices are far too stable.. ”“.. 'Illis complex can be rapidly and conveniently converted to the hydride complex [(DipNPPha LisHd] with commercially available phenylsilane in an aromatic solvent.. Above. 60°C, slow irreversible decomposition of [(DipNPPhfsLisHsj to presumably polymeric and largely insoluble [(DipNPPhi Li] and, by implication, LiH occurs..

[0007] In contrast to Fohlmeister’s and Stasch’s teachings that the high lattice energy7of LiH (920 kJ / mol). enthalpy of formation (90.5 kJ / mol) and Tdecomposition (720 to 972 K) would ensure the formation of LiH as a precipitate upon standing, the inventors have discovered that unlike (DipNPPh2) iLixH i the family of LOXSH catalysts solutions having up to 1000 ppm hydride ion (7900 ppm soluble LiH) contents can be stored in hydrocarbon solvents under an inert atmosphere (e.g. nitrogen, argon, helium) for long periods of time even at slightly elevated temperatures without formation of substantial quantities of insoluble lithium hydride precipitate. What’s more, the inventors have discovered that the family of LOXSH catalysts solutions are not pyrophoric by the UN Division 4.2 Test N.3 for pyrophoricity at or below ~ I ()()() ppm hydride content. Therefore, these novel concentrated LOXSH solutions can be prepared commercially and sold as an item of commerce. This allows the potential user of a LOXSH catalyst or reagent to simply obtain the preformed solutions, and thus avoid any hazards in its production, and to use the non-pyrophoric material in their process.BRIEF SUMMARY

[0008] The various embodiments of the disclosure relate generally to compositions of shelfstable LOXSH catalyst solution compositions comprising from about 120 ppm to about 1200 ppm hydride ion concentration (from about 950 to about 9600 ppm as lithium hydride) as a homogenous hydrocarbon solution. The various embodiments of the disclosure also relate generally to processes, methods, and systems, that enable the formation and hence utilization such shelf-stable LOXSH catalyst and reagent solutions.

[0009] Additionally or alternatively, the disclosure can include one of more of the following embodiments.

[0010] Embodiment 1. A shelf-stable LOXSH catalyst solution composition comprising from about 120 ppm to about 1200 ppm hydride ion concentration (from about 950 to about 9600 ppm as lithium hydride) as a homogenous hydrocarbon solvent solution formed from at least one o-. polar modifier (PM) lithium alkoxide, an alkyl lithium reagent, molecular hydrogen, and a hydrocarbon solvent wherein the stoichiometric formula of the catalyst is represented by [PM]xLiyHz wherein PM is a c-p polar modifier, z = y - x, x and y are independently whole or fractional numbers greater than zero, and y>x; and wherein the stable LOXSH catalyst solution retains its catalytic activity, selectivity and lithium hydride titer for a period of at least two months.

[0011] Embodiment 2. The composition of any one or more of the previous embodiments, wherein the a- polar modifier (PM) lithium alkoxylate is formed from at least one |3-aminoalcohol and one or more of an alkyllithium reagent, lithium hydride, or lithium metal in a hydrocarbon solvent.

[0012] Embodiment 3. The composition of any one or more of the previous embodiments wherein the hydrocarbon soluble LOXSH catalyst concentration is in the range of about 175 ppm to about 1075 ppm hydride ion, 1380 ppm to about 8500 ppm lithium hydride concentration.

[0013] Embodiment 4. The composition of any one or more of the previous embodiments wherein the hydrocarbon soluble LOXSH catalyst concentration is in the range of about 200 ppm to about 1050 ppm hydride ion, 1800 ppm to about 8300 ppm lithium hydride concentration and wherein the ratio of y:x is in the range of about 1.3:1 to about 3.5:1.

[0014] Embodiment 5. The composition of any one or more of the previous embodiments wherein the hydrocarbon soluble LOXSH catalyst concentration is in the range of about 200 ppm to about 1050 ppm hydride ion, 1800 ppm to about 8300 ppm lithium hydride concentration, andwherein the ratio of y:x is in the range of about 1.4:1 to about 3.0:1 or wherein the LOXSH catalyst composition for [PM]xLiyHzthe ratio ofy:x from about 1.45:1 to about 1.70:1.

[0015] Embodiment 6. The composition of any one or more of the previous embodiments wherein the hydrocarbon solvent comprises one or more of but is not limited to a C4 to C8hydrocarbon, butanes, pentanes, hexanes, heptanes, cyclopentane, cyclohexane, methylcyclohexane, and / or ethylbenzene.

[0016] Embodiment 7. The composition of any one or more of the previous embodiments wherein the c-p polar modifier (PM) lithium alkoxylate comprises the lithium alkoxylate of one or more of / V,jV-dimethylethanolamine, l-(dimethylamino)-2-propanol, 1- (dimethylamino)-2-butanol, tra«s-2-(dimethylamino) cyclohexanol; 2-piperidinoethanol; 1-piperidino-2-propanol; l-piperidino-2-butanol, / ram-2-piperidmocyclohexan-l-ol. 1-pyrrolidinoethanol, pyrrolidinylpropan-2-ol, l-(l-pyrolidinyl)-2-butanol, 2-pyrolidinocyclohexanol, 4-methyl-l -piperazineethanol, l-(4-methyl-l-piperazinyl)-2-propanol; l-(4-methyl-l -piperazinyl)-2 -butanol; / ra / 7.s-2-(4-methy I- 1 -piperazmyl)-cyclohexanol, 2-morpholinoethanol, 1 -(4-morpholinyl)-2 -propanol, 1 -(4-morpholinyl)-2-butanoL fra / ?s-2-morpholin-4-ylcyclohexanoL l-methyl-2-piperidinemethanol, l-methyl-2-pyrrolidinemethanol, / V-methyl-diethanolamine, 3-dimethylamino-l-propanol, 1,3-bis(dimethylamino)-2-propanol, 2- { [2-dimethylamino)ethyl] methylamino (ethanol, 2-[2-(dimethylamino)ethoxy] ethanol. 2-(2-(piperidyl)ethoxy)ethanol, 2-[2-(4-morpholinyl)ethoxy]ethanol, 2- [2-( 1 -pyrrolidinyl)ethoxy] ethanol, 2-[2-(4-methyl- 1 -piperazinyl)ethoxy] ethanol; and optionally from about 50 mole% to greater than 0 mole% of an ether-alcohol G — p polar modifier selected from one or more of 2-methoxy ethanol, 1-methoxypropan-2-ol, l-methoxybutan-2-ol, 2-methoxycyclohexan-l-ol, tetrahydrofurfuryl alcohol, tetrahydropyran-2-methanol, diethylene glycol monomethyl ether.

[0017] Embodiment 8. The composition of any one or more of the previous embodiments wherein the a-p polar modifier (PM) lithium alkoxylate comprises the lithium alkoxylate of one or more of / V V-dimethylethanolamme. l-(dimethylamino)-2-propanol. 1-(dimethylamino)-2-butanol, 2-piperidinoethanol; l-piperidino-2-propanol; l-piperidino-2-butanol; and optionally from about 50 mole% to greater than 0 mole% of an lithium alkoxylate formed from an ether-alcohol c— p polar modifier selected from one or more of 2-methoxyethanol, 1 -methoxypropan-2-ol, 1 -methoxy butan-2-ol, 2-methoxycyclohexan-l-ol, tetrahydrofurfuryl alcohol.

[0018] Embodiment 9. The method for forming any of previous compositional embodiments wherein a hydrocarbon solvent solution comprising at least one < J-p polar modifier (PM)lithium alkoxylate [PM]Li, is combined with an alkyl lithium reagent, and molecular hydrogen in a hydrogenolysis reactor, wherein the relative molar amount of molecular hydrogen consumed in forming the LOXSH catalyst is given byof the stoichiometric formula [PM]xLiyHz and wherein the catalyst solution is kept isolated and is transferred from the hydrogenolysis reactor to a storage vessel under hydrogen or an inert atmosphere or fed under a hydrogen atmosphere to another reactor continuously or in portions for use as a hydrogen mediated anionic polymerization catalyst.

[0019] Embodiment 10. The method of any one or more of the previous methods wherein the alkyllithium reagent, is reacted with the polar modifier to form the c— p polar modifier (PM) lithium alkoxylate and a volatile hydrocarbon gas and wherein the feed of the alkyllithium is interrupted once the [PM]Li is fully formed and wherein for the hydrogenolysis reactor: a) is established the desired hydrogenolysis reactor temperature, b) all or a portion of the co-product lite hydrocarbon gas is vented from the hydrogenolysis reactor to about 0 psig; c) to it is optionally charged with a known quantity of molecular hydrogen; d) is fed the balance of the alkyllithium at a controlled rate; and e) is cofed hydrogen gas while maintaining efficient gas dispersion into the condensed phase reaction mixture wherein the total amount of hydrogen fed of steps c) and e) is the molar quantity z wherein z = y - x, where y is the total mole of alkyllithium used and x is the total mole of the polar modifier used to prepare the formulation [PM]xLiyHz.

[0020] Embodiment 11. The method of any one or more of the previous methods wherein a preformed G-p polar modifier lithium alkoxylate, [PM]Li, is charged to the hydrogenolysis reactor under a hydrogen atmosphere and then for the hydrogenolysis reactor: a) is establish the desired hydrogenolysis reaction temperature, b) the headspace hydrogen gas is vented from the hydrogenolysis reactor to about 0 psig; c) to it is optionally charged a known quantity7of molecular hydrogen; d) to it is fed the molar amount of the alkyllithium, z, at a controlled rate; and e) to it is cofed hydrogen gas while maintaining efficient gas dispersion into the condensed phase reaction mixture wherein the total amount of hydrogen fed of steps c) and e) is also at least the molar quantity z wherein z = y - x, where y is total lithium atoms used and x is the total mole of the polar modifier used to prepare the LOXSH formulation [PM]xLiyHz.

[0021] Embodiment 12. The method of any one or more of the previous methods wherein the G-p polar modifier (PM) lithium alkoxylates are formed from the PM and an alky lithium reagent, orwherein the o-p polar modifier (PM) lithium alkoxylates are formed from the PM and one or more of lithium metal or lithium hydride.

[0022] Embodiment 13. The method of any one or more of the previous methods wherein to the hydrocarbon solvent solution of G-p polar modifier (PM) lithium alkoxylates is co-fed hydrogen gas and an alkyllithium reagent wherein the hydrogen feed is controlled externally by a regulated hydrogen pressure in the range of -4 to about 100 psig.

[0023] Embodiment 14. The method of any one or more of the previous methods wherein hydrogenolysis reactor’s pressure is maintained in the range of about -4 psig to about 35 psig.

[0024] Embodiment 15. The method of any one or more of the previous methods wherein to the G— polar modifier (PM) lithium alkoxylates is co-fed hydrogen gas and a alkyllithium reagent wherein the hydrogenolysis reactor's pressure is either: 1) held constant or near constant; or 2) is allowed to vary; wherein the relative hydrogen feed rate to the reactor is controlled external to the reactor and the total molar amount of hydrogen charged to the reactor is limited to at least the amount ‘"z”.

[0025] Embodiment 16. The method of any one or more of the previous methods wherein the pressure of the hydrogenolysis reactor is controlled externally by maintaining a regulated pressure in the range of 1 to 35 psig of a demand regulator that feeds hydrogen to the reactor such that the hydrogen pressure is kept constant or near constant and wherein the hydrogenolysis reactor progress is monitored thermally.

[0026] Embodiment 17. The method of any one or more of the previous methods wherein the hydrogenolysis reactor pressure is maintained over the range of -4 to 35 psig and is controlled externally by regulating the hydrogen feed rate as a function of time and wherein the total molar quantity of hydrogen charged is at least equal to the theoretical molar amount of hydrogen “z” of the equation z = y - x related to the stoichiometry [PM]xLiyHz wherein x mole of the polar modifier lithium alkoxylate are combined with z mole of an alkyllithium such that y = x + z.

[0027] Embodiment 18. The method of any one or more of the previous methods wherein the reactor pressure is maintained in the range of -4 to 35 psig and controlled internally by regulating a variable hydrogen feed rate such that the pressure in the reactor either: 1) does not substantially change; or 2) is varied based on a planned program rate, wherein the total molar quantity of hydrogen charged is at least equal to the theoretical molar amount of hydrogen “z” of the equation z = y-x related to the stoichiometry [PM]xLiyHzwherein x mole of the polar modifier lithium alkoxylate are combined with z mole of a alkyllithium such that y = x + z.

[0028] Embodiment 19. The method of any one or more of the previous methods wherein the PM lithium alkoxylate is pre-formed in a separate reactor and then charged to the hydrogenolysis reactor to which is then co-fed an alky 11 ithi um reagent and molecular hydrogen.

[0029] Embodiment 20. The method of any one or more of the previous methods wherein the PM lithium alkoxylate is formed in the hydrogenolysis reactor and then to which is co-fed an alkyllithium reagent and molecular hydrogen.

[0030] Embodiment 21. The method of any one or more of the previous methods wherein both a steady state pressure and a steady state activity of the alkyllithium reagent are achieved wherein the relative feed rates of hydrogen and of the alkyllithium reagent are balanced such that both components are consumed at or about the same rate.

[0031] Embodiment 22. The method of any one or more of the previous methods wherein the hydrogenolysis reactor is maintained at a temperature in the range of about 10°C to about 60°C during the cofeed of hydrogen and the alkyllithium reagent and undesired decomposition side reactions are suppressed by efficient mass transfer of hydrogen via agitation impellers designed for gas dispersion during the catalyst forming steps, such side reactions involving autodecomposition of the complexed alkyllithium superbase upon the concentrate of the polar modifier alkoxylate from which the LOXSH catalyst is formed.

[0032] Embodiment 23. The method for forming a hydrogen mediated anionically polymerized hydrocarbon monomer polymer product distribution which entails: 1) pre-forming a shelf-stable concentrated LOXSH catalysts solution in a separate operation; 2) forming a reaction mixture under a hydrogen atmosphere with the preformed LOXSH catalysts and optionally additional hydrocarbon solvent; 3) co-feeding at least one anionically polymerizablehydrocarbon monomer with hydrogen gas in a specified relative feed ratio; 4) allowing the reaction to go to completion; and 5) quenching the reaction mixture.

[0033] Embodiment 24. The method of any one or more of the previous methods for forming a hydrogen mediated anionically polymerized hydrocarbon monomer polymer product distribution which entails: 1) pre-forming a shelf-stable concentrated LOXSH catalysts solution in a separate operation; 2) forming a reaction mixture under a hydrogen atmosphere by feeding with time the preformed LOXSH catalysts and optionally additional hydrocarbon solvent; 3) co-feeding with the preformed LOXSH catalysts at least one anionically polymerizable hydrocarbon monomer with hydrogen gas in a specified relative feed ratio; 4) allowing the reaction to go to completion; and 5) quenching the reaction mixture.

[0034] Embodiment 25. The method of any one or more of the previous methods for forming a hydrogen mediated anionically polymerized hydrocarbon monomer polymer product distribution wherein the hydrocarbon monomer is one or more of a conjugated diene and / or a vinyl aromatic hydrocarbon monomer.

[0035] Embodiment 26. The method for hydride reduction of carbonyl compounds which entails forming a reaction mixture of one or more carbonyl compound with a concentrated LOXSH reducing agent solution composition optionally in an ethereal solvent.

[0036] It is to be understood that the embodiments and claims disclosed herein are not limited in their application to the details of construction and arrangement of the components set forth in the description and illustrated in the drawings. Rather, the description and the drawings provide examples of the embodiments envisioned. The embodiments and claims disclosed herein are further capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purposes of description and should not be regarded as limiting the claims.

[0037] Accordingly, those skilled in the art will appreciate that the conception upon which the application and claims are based can be readily utilized as a basis for the design of other structures, methods, and sy stems for carrying out the several purposes of the embodiments and claims presented in this application. It is important, therefore, that the claims be regarded as including such equivalent constructions.BRIEF DESCRIPTION OF THE DRAWINGS'

[0038] The following Figures illustrate, compositions, methods, reaction conditions and physical properties in accordance with exemplary embodiments of the disclosure.Figure 1: Crystal structure of LiDAME ([DMEAJsLis) that crystallized while atempting to crystallize [DMEAJzLisH from heptane. Identical to open literature crystal structure for | DMEA]sLis formed from DMEA and BuLi.Figure 2: DSC Trace of [PsB]xLixcrystallized from a LOXSH formulation having the stoichiometric formula [PsB^LisH, showing three slightly broad melting points.Figure 3: Proton NMR determination of hydride content of LOXSH catalyst solution concentrates.Figure 4: [DMEA] Li concentration m LOXSH Catalyst solution as a function of initial concentration and of time.Figure 5: Hydrogen mediated anionic polymerization of styrene using various 2 months aged DMEA based LOXSH catalysts solutions.Figure 6: Example 20 Hydrogenolysis reaction pressure / temperature profile, initial hydrogen charge 428 std. cm3with 1428 std. cm3fed, theoretical hy drogen 1428 std. cm3.Figure 7. Example 21 Hydrogenolysis reaction pressure / temperature profile, initial hydrogen charge 822 std. cm3with 4490 std. cm3fed, theoretical hydrogen 4490 std. cm3.Figure 8: Example 22 Hydrogenolysis reaction pressure / temperature profile, initial hydrogen charge 592 std. cm3with 4490 std. cm3fed of 7200 std. cm3intended, theoretical hydrogen 7592 std. cm3.Figure 9: Example 23 Hydrogenolysis reaction pressure / temperature profile, initial hydrogen charge 700 std. cm’ with 7000 std. cm3fed, theoretical hy drogen 7660 std. cm3.Figure 10: Example 24 Hydrogenolysis reaction pressure / temperature profile, initial hydrogen charge 900 std. cm3with 7500 std. cm3fed, theoretical hydrogen 7946 std. cm3.Figure II: Example 25 Hydrogenolysis reaction pressure / temperature profile, initial hydrogen charge 800 std. cm3with 8000 std. cm3fed, theoretical hydrogen 8412 std. cm3.Figure 12: Example 27 Hydrogenolysis reaction to form [DMEA]2Li4H2 pressure / temperature profile, initial hydrogen charge 1600 std. cm3with 5871 std. cm3fed, theoretical hydrogen 5871 std. cm3.Figure 13: Example 27 Hydrogenolysis reaction to form [DMEA^LieHj pressure / temperature profile, initial hydrogen charge 1600 std. cm3with 11190 std. cm3fed, theoretical hydrogen 11188 std. cm3.Figure 14: Comparison of vinyl -di methyl amine (VDMA) contents of Ex. 22-25 (wt.% relative to LOXSH), diagnostic resonances at 6 and 3.7 ppm.Figure 15: Comparison of Ex. 22-25 Li-7 NMR showing similarities of Ex. 23-25 and their difference with Ex.-22 wherein Li2O as a coproduct with VDMA.Figure 16: Hydrogen mediated anionic polymerization of butadiene reaction pressure temperature profiles, using a freshly prepared [DMEA]₂Li₃H LOXSH catalysts solutions; a) the solution of Ex. 22; and b) the blend Ex. 26 formed from solutions of Ex. 24 and 25 Figure 17: Viscosity as function of Mn of HV-HMPBD (on average 78.6% vinyl) compositions prepared in cyclic non-aromatic hydrocarbon solvent from in situ prepared as well as fresh and aged concentrated [DMEAJ LijH LOXSH catalyst solutions showing no difference in viscosity properties over the range of molecular weights.Figure 18: Glass transition temperature as function of Mnof HV-HMPBD (on average 78.6% vinyl) compositions prepared in cyclic non-aromatic hydrocarbon solvent from m situ prepared as well as fresh and concentrated aged [DMEAJsLisH LOXSH catalyst solutions showing’ no difference in Tgproperties over the range of molecular weights.Figure 19: Example 45 Hydrogenolysis reaction pressure / temperature profile, initial hydrogen charge 200 std. cm3with 5000 std. cm3fed, theoretical hydrogen 5444 std. cm3. Figure 20: Example 50 Hydrogenolysis reaction pressure / temperature profile, initial hydrogen charge 500 std. cm3with 7400 std. cm3fed, theoretical hydrogen 7418 std. cm3.Figure 21: Example 51 Hydrogenolysis reaction pressure / temperature profile, initial hydrogen charge 300 std. cm3with 7300 std. cm3fed, theoretical hydrogen 6822 std. cm3.Figure 22: Example 55 Hydrogenolysis reaction pressure / temperature profile LOXSH formed from [PsB]Li, initial hydrogen charge 600 std. cm3with 2250 std. cm’ fed, theoretical hydrogen 2727 std cm3.Figure 23: Hydrogen mediated anionic polymerization of butadiene reaction pressure temperature profiles, using a freshly prepared and aged [PsB^LisH LOXSH catalysts solutions.DETAILED DESCRIPTION

[0039] The term "alky l", as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight or branched moieties. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl and hexyl.

[0040] The term "alkenyl", as used herein, unless otherwise indicated, includes alkyl moieties having at least one carbon-carbon double bond wherein alkyl is as defined above. Examples of alkenyl include, but are not limited to, ethenyl and propenyl.

[0041] The term "alkynyl", as used herein, unless otherwise indicated, includes alkyl moieties having at least one carbon-carbon triple bond wherein alkyl is as defined above. Examples of alkynyl include, but are not limited to. ethynyl, propynyl, and butynyl.

[0042] The term “alkoxy’', as used herein, unless otherwise indicated, includes an -O-alkyl group, wherein alkyl is as defined above. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentoxy and hexoxy.

[0043] The term “alkylhydroxyl”, as used herein, unless otherwise indicated, includes an alkyl-OH group, wherein the alkyl is as defined above. The -OH is the alkylhydroxyl can be any of the carbons of the alkyl, producing primary secondary and tertiary hydroxyls, and can also include more than one hydroxyl in the alkylhydroxyl. Examples of alkylhydroxyl include, but are not limited to, -CH2CH2OH, -CH2CH2CH2OH, -CH2CH(OH)CH3, -CH(OH)CH2CH3, and -CH2C(CH3)2(OH)

[0044] The term "cycloalkyl", as used herein, unless otherwise indicated, includes nonaromatic saturated cyclic alkyl moieties wherein alkyl is as defined above. Examples of cy cloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0045] The term "cycloalkenyl", as used herein, unless otherwise indicated, includes nonaromatic cyclic alkenyl moieties wherein alkenyl is as defined above. Examples of cycloalkyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and cyclooctenyl.

[0046] The term "aryl", as used herein, unless otherwise indicated, includes an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, such as phenyl, naphthyl, indenyl, and fluorenyl. " Aryl" encompasses fused ring groups wherein at least one ring is aromatic.

[0047] The term “carbonyl’; as used herein, unless otherwise indicated, includes saturated aliphatic and cycloaliphatic, unsaturated and aliphatic and cycloaliphatic, and aromatic organic compounds processing at least one carbon oxygen double bond moiety (e.g. aldehydes, ketones, carboxylates, esters, amides and the like).

[0048] The term polar modifiers, as used herein, unless otherwise indicated, generally includes four different cases based on how they interact, moreover, complex with the cationic counter! on(s) of the polymerization catalyst and / or initiator. The designations are a, p, o + p and o— p. A “c> complex” denotes a polar modifier that is a Lewis base, e.g. THF, TMEDA. A “p complex” denotes a polar modifier that is a Lewis acid e.g. sodium mentholate (SMT). A “o + p complex” denotes a mixture of polar modifiers that contains both a Lewis base and an acid. A "o— p complex” denotes a polar modifier wherein both the Lewis base and acid are on the same ligand e.g. DMEA (DMAE). For the purpose of shortness, the abbreviation PM within the text, chemical formulae, or in chemical equations, unless otherwise specified, is restricted to mean a o— p type polar modifier. When used as [PM] it is meant that the polar modifier exists as its alkoxylate anion. When used as [PM]Li it is meant that the polar modifier alkoxylate is in solution and is associated with at least one lithium ion to balance the charge. When it is used as [PM]xLix it is meant that the polar modifier lithium alkoxylate is a solid crystalline aggregate comprising x mole of [PM] and x mole of lithium ions or is a dissolved aggregate comprising x mole of [PM] and x mole of lithium ions such that it is a neutral aggregate.

[0049] For the term “shelf-stable” in the context of chemical catalysts and reagents, "shelf stable" means that a substance can be stored at room temperature for a long period of time without significantly degrading in quality or composition, essentially remaining usable for its intended purpose without the need for special refrigeration or storage conditions. The shelflife of such chemicals can be affected by storage conditions and monitoring of those conditionsduring the discovery’ process is important to define the maximum shelf life and conditions which do not adversely affect their utility.

[0050] For the term “free of’ means with regards to a contaminants concentration if a reagent, intermediate or product: (i) from below the detection limit for the species to 50 ppm above the detection limit; or (ii) from below the detection limit of the species to about 100 ppm; (iii) from below the detection limit of the species to about 150 ppm above the detection limit; or (iv) from below the detection limit to about 500 ppm of the species.

[0051] Although preferred embodiments of the disclosure are explained in detail, it is to be understood that other embodiments are contemplated. Accordingly, it is not intended that the disclosure is limited in its scope to the details of construction and arrangement of components set forth in the following description or illustrated in the drawings. The disclosure is capable of other embodiments and of being practiced or carried out in various ways. Also, in describing the preferred embodiments, specific terminology7will be resorted to for the sake of clarity7.

[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] Also, in describing the preferred embodiments, terminology will be resorted to for the sake of clarity. It is intended that each term contemplates its broadest meaning as understood by those skilled in the art and includes all technical equivalents which operate in a similar manner to accomplish a similar purpose.

[0054] Ranges can 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] By “comprising” or “including” is meant 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 the other such compounds, material, particles, method steps have the same function as what is named.

[0056] It is also to be understood that the mention of one or more method steps does not preclude the presence of additional method steps or intervening method steps between those steps expressly identified. Similarly, it is also to be understood that the mention of one or more components in a device or system does not preclude the presence of additional components or intervening components between those components expressly identified.

[0057] The disclosure includes an industrial scale method for preparing concentrated LOXSH catalyst solutions in hydrocarbon solvents as stable, non-pyrophoric and selective catalyst solutions useful in hydrogen mediated anionic polymerizations and also as reducing agents.

[0058] The disclosure also includes shelf-stable LOXSH catalyst solutions composition comprising from about 120 ppm to about 1200 ppm hydride ion concentration which is from about 950 to about 9600 ppm lithium hydride as a homogenous hydrocarbon soluble solution formed from at least one o— p polar modifier (PM) lithium alkoxylate, an al ky I lithium reagent, molecular hydrogen, and a hydrocarbon solvent wherein the stoichiometric formula of the catalyst is represented by [PM]xLiyHzby [PM]xLiyHz wherein PM is a c>-p polar modifier, z = y - x, x and y are independently whole or fractional numbers greater than zero, and y>x, and wherein the stable LOXSH catalyst solution substantially retains its catalytic activity and lithium hydride titer for a period of at least two months to a period of greater than one full year.

[0059] For the shelf-stable LOXSH catalyst solutions composition, the o— p polar modifier (PM) lithium alkoxylate is formed in part from at least one P-ammoalcohol and one or more of an alkyllithium, lithium hydride, or lithium metal in a hydrocarbon solvent. Depending on the above-mentioned values of x, y and z and the nature of the polar modifier, preferred hydrocarbon soluble LOXSH catalyst composition can have a hydride concentration is in the range of about 175 ppm to about 1075 ppm hydride ion, corresponding to a 1380 ppm to about 8500 ppm lithium hydride concentration. Similarly, the hydrocarbon soluble LOXSH catalyst composition can have a hydride concentration in the range of about 200 ppm to about 1050 ppm hydride ion, corresponding to a 1800 ppm to about 8300 ppm lithium hydride concentration.

[0060] Accordingly, the concentrated hydrocarbon soluble LOXSH catalyst composition [PM]xLiyHz, the ratio ofy:x can be in the range of about 1.3:1 to about 3.5:1. It is preferredthat the ratio of y:x is in the range of about 1.4:1 to about 3.0:1. The most preferred LOXSH catalyst composition for [PM]xLiyHzthe ratio of y:x from about 1.45:1 to about 1.70:1.

[0061] The shelf-stable concentrated LOXSH cataly st solution compositions are formed in hydrocarbon solvents which comprises one or more of a C4 to C8 hydrocarbon, cyclohexane, methylcyclohexane, and / or ethylbenzene. Other solvents may be employed alone or in combination with the above-mentioned solvents. These include solvents such as benzene, toluene, isomers of xylene, trimethylated benzene such as mesitylene, tetramethyl benzene such as durene, higher alkylbenzene such as / ?-propylben / ene and Ao-butylbenzene and the like as well as C9 and higher hydrocarbons. Benzene, if not for its toxicological and consequent environmental complications, then it would be an ideal solvent. The methylated aromatic solvents present a problem in acting as a chain transfer agent during their use, when the LOXSH catalyst solution is used as a hydrogen mediated anionic polymerization catalyst. When hydrocarbon monomer is a conjugated diene, solvents with a boiling point greater than that of ethylbenzene may be a challenge to remove when the hydrogen mediated anionically polymerized conjugated diene polymers are isolated. When forming the catalyst concentrate for immediate use (hours to days) recycle solvent comprising oligomers (dimers, trimers, tetramers, pentamers, etc. of styrene and / or butadiene and / or isoprene) can be utilized. Other additional polar modifiers either o type (e.g. THF, TMEDA, and the like) and / or p type (e.g. sodium / c / 7-butoxide. sodium mentholate, and the like) polar modifiers can be added to the hydrocarbon solutions of the LOXSH catalyst concentrates. For Example, the addition of stoichiometric quantities of THF (as little as a Li: THF ratio of about 1:0.3 to about 1:2) to LV-LOXSH catalyst formulations will increase the vinyl content of LV-HMPBD compositions when used in hydrogen mediated anionic polymerization of butadiene. Accordingly, the addition of these stoichiometric quantities of THF will increase the vinyl contents from the range of 30 wt.% to 35 wt.% 1,2-vinyl content to the range of 38 wt.% to 45 wt.% 1.2-vinyl content if so desired (see Application Examples 31 and 32).

[0062] The concentrated LOXSH catalyst solutions comprise a-p polar modifier (PM) lithium alkoxylate which can include the lithium alkoxylate of one or more of N, N-dimethylethanolamine, l-(dimethylamino)-2-propanol, l-(dimethylamino)-2-butanol, trans-2-(dimethylamino) cyclohexanol; 2-piperidinoethanol; l-piperidino-2-propanol; 1 -piperidino-2-butanol, trans-2-piperidinocyclohexan-l-ol, 1-pyrrolidinoethanol, pyrrolidinylpropan-2-ol, 1-(l-pyrolidinyl)-2-butanol, 2-pyrolidinocyclohexanol, 4-methyl-l -piperazineethanol. l-(4-methyl-l-piperazinyl)-2-propanol; l-(4-methyl-l-piperazinyl)-2-butanol; trans-2-(4-methyl-l-piperazinyl)-cyclohexanol, 2-morpholinoethanol, l-(4-morpholinyl)-2-propanol, l-(4-morpholinyl)-2-butanol, trans-2-morpholin-4-ylcyclohexanol, 1 -methyl-2-piperidinemethanol, 1 -methyl-2-pyrrolidinemethanol, methyl-diethanolamine. 3-dimethy 1 amino- 1 -propanol, l,3-bis(dimethylamino)-2-propanol, 2-{[2-dimethylamino)ethyl]methylamino} ethanol, 2-[2-(dimethy lamino)ethoxy] ethanol, 2-(2-(piperidyl)ethoxy)ethanol, 2-[2-(4-morpholinyl)ethoxy]ethanol, 2-[2-(l -pyrrolidinyl)ethoxy] ethanol, 2-[2-(4-methyl-l-piperazinyl)ethoxy] ethanol; and optionally from about 50 mole% to greater than 0 mole% of an ether-alcohol G— p polar modifier selected from one or more of 2 -methoxy ethanol, l-methoxypropan-2-ol, 1 -methoxy butan-2-ol, 2-methoxycyclohexan-l-ol, tetrahydrofurfuryl alcohol, tetrahydropyran-2-methanol, diethylene glycol monomethyl ether.

[0063] For preferred shelf-stable concentrated LOXSH catalyst solution compositions, the o-p polar modifier (PM) lithium alkoxylate, [PM] Li. comprise the lithium alkoxy late of one or more of jV.jV-dimethylethanolamine, 1 -(dimethylamino)-2-propanoL l-(dimethylamino)-2-butanol, 2-piperidinoethanol; l-piperidino-2-propanol; l-piperidino-2-butanol; and optionally from about 50 mole% to greater than 0 mole% of an lithium alkoxylate formed from an etheralcohol G— p polar modifier selected from one or more of 2-methoxy ethanol, 1-methoxypropan-2-ol, 1 -meth oxy butan-2-ol, 2-methoxycyclohexan-l-ol, tetrahydrofurfuryl alcohol and the like.

[0064] The process for forming the shelf-stable concentrated LOXSH catalyst solution compositions entails forming a hydrocarbon solution comprising at least one o-p polar modifier (PM) lithium alkoxylate, [PM]Li, combining the solutions with an alkyl lithium reagent, and molecular hydrogen in a hydrogenolysis reactor, wherein the relative molar amount of molecular hydrogen consumed in forming the LOXSH catalyst is given by “z” of the stoichiometric formula [PM]xLiyHz, wherein z = y - x, and feeding. The process for forming the shelf-stable concentrated LOXSH catalyst solution compositions can include isolating the solution by transferring it from the hydrogenolysis reactor to a storage vesselAS-FI-8I6I-WO under hydrogen or an inert atmosphere. Alternatively, the shelf-stable concentrated LOXSH catalyst solution compositions can be fed under a hydrogen or an inert atmosphere to another reactor either continuously or in portions for use as a hydrogen mediated anionic polymerization catalyst or as a reducing agent (hydro lithiation reaction of a carbonyl compound).

[0065] The process for forming the shelf-stable concentrated LOXSH catalyst solution can entail forming the o-. polar modifier (PM) lithium alkoxylate ([PM]Li) from the PM and an alky lithium reagent in one operation (one pot). When the process entails forming the o-p polar modifier alkoxylates from an alkyllithium reagent in one pot, the process entails maintaining a hydrogen atmosphere preferably with sufficient hydrogen gas dispersion mixing as the alkyllithium reagent is fed. When the alkyllithium reagent is a butyllithium reagent, the pressure in the hydrogenolysis reactor will build as butane is formed and the condensed phase becomes saturated with this gas. It is preferred to stop the alkyllithium feed once the [PM]Li is fully formed (no unreacted PM as the aminoalcohol with or without an etheralcohol). At this point it is preferred to: a) establish the desired hydrogenolysis reactor temperature, b) vent all or a portion of the co-product butane gas from the hydrogenolysis reactor to about 0 psig; c) optionally charge a known quantity of molecular hydrogen to the reactor; d) begin feeding the BuLi at a controlled rate; and e) begin cofeeding hydrogen gas while maintaining efficient gas dispersion into the condense phase reaction mixture wherein the total amount of hydrogen fed of steps c) and e) is the molar quantity z wherein z = y - x, where y is total mole of alkyllithium used and x is the total mole of the polar modifier used to prepare the formulation [PM]xLiyHz. Accordingly, for the value z when forming a LOXSH catalyst solution that is formulated with the molar ratio [PM]xLiyHzwhen x = 2 and y = 3, then z = 1. For the formulation with molar ratio [PM]xLiyHz when x = 1 and y = 2, then z = 1. And for the formulation with the molar ratio [PM]xLiyHz when x = 1. y = 3, then z = 2. It should be understood and appreciated that for such a process, z is the total amount of BuLi charged to the hydrogenolysis reactor during the hydrogenolysis reaction and should be the minimum amount of hydrogen charged to the hydrogenolysis reactor. One of ordinary skill in the art would understand and appreciate that one mole of hydrogen (taken as an ideal gas) is 22.4 liters at STP. Accordingly, if the chargeswere such that z = 1.3 mole of hydrogen, then 29.12 std. liters of hydrogen gas would be required.

[0066] The process for forming the shelf-stable concentrated LOXSH catalyst solution may¬ otherwise entail a two-pot process which features preforming the o-p polar modifier (PM) lithium alkoxy late ([PM] Li) from the PM in a separate reactor and at a separate time. Such preformed [PM]Li solutions are formed by charging the PM to the hydrocarbon solvent and then reaction of the PM with an alkyllithium reagent and / or lithium metal and / or lithium hydride. When an alkyllithium reagent is employed, it is desired that the reaction to form [PM]Li be conducted under a hydrogen atmosphere with effective gas dispersion type mixing to maintain hydrogen mass transfer to the condensed phase reaction mixture. This has the potential of suppressing side reactions by reversing via hydrogenolysis any undesired metalation reactions involving the polar modifier alkoxylate.

[0067] When the process to form the concentrated LOXSH catalyst solution entails preformed G-p polar modifier alkoxylates, [PM]Li, the hydrogenolysis process entails charging the preformed G-p polar modifier alkoxylate(s) to the hydrogenolysis reactor under a hydrogen atmosphere and then to: a) establish the desired hydrogenolysis reactor temperature, b) venting or otherwise adjusting the hydrogenolysis reactor pressure to about 0 psig; c) optionally charging a known quantity' of molecular hydrogen to the reactor; d) feeding the alkyllithium reagent at a controlled rate; and e) cofeeding hydrogen gas while maintaining efficient gas dispersion into the condense phase reaction mixture wherein the total amount of hydrogen fed of steps c) and e) is the molar quantity- z wherein z = y - x wherein y is total mole of lithium atoms and x is the total mole of the polar modifier in the formulation [PM]xLiyHz. The value z when forming a LOXSH catalyst solution that is formulated with the molar ratio [PM]xLiyHz when x = 2 and y = 3, from preformed [PM]Li, then z = y / 3 = 1. For the formulation with the molar ratio [PM]xLiyHzwhen x = 1 and y = 2, then z = y / 2 = 1. And for the formulation with the molar ratio |PM|xLivHzwhen x = 1, y = 3, then z = 2y / 3 = 2. It should be understood and appreciated that for such processes wherein preformed [PM]Li is utilized, z is the total amount of BuLi charged to the hydrogenolysis reactor and should be the minimum amount of hydrogen charged to the hydrogenolysis reactor including the atmosphere in the reactor at 0 psig before pressuring up.

[0068] The initial charge of hydrogen in step c above can be from about 0% to about 50% of the desired total hydrogen charge. It is preferred to charge between 5% and 20% of the total molar amount of hydrogen x. During step e) above, the hydrogen co-feed, the partial pressure of hydrogen in the hydrogenolysis reactor is maintained in the range of about -4 to about 100 psig and preferably between -2 psig to 50 psig. Although unnecessary’, higher hydrogen pressures (>100 psig) can be used and are well within the scope of the disclosure. The hydrogen feed rate can be controlled externally to the hydrogenolysis reactor by’ a regulated hydrogen pressure which can be varied as needed to maintain the hydrogen activity (reactor pressure) in the hydrogenolysis reactor within the desired range. In the most preferred processes, the hydrogenolysis reactor’s pressure is maintained in the range of about -1 psig to about 35 psig hydrogen. Hydrogen can be fed above or below the surface of the condensed phase of the reaction medium in the hydrogenolysis reactor. Either method, above the surface or subsurface feeding of hydrogen, the feeding is best coupled with efficient gas dispersion ty pe mixing in order to maintain mass transfer of hydrogen. When feeding subsurface hydrogen, the hydrogen gas feed velocity of approximately 10 to about 750 ft / sec (from about 3 m / sec to about 225 m / sec) or more can be effectively employed. This type of mixing and gas dispersion helps to ensure completion of the LOXSH catalyst formation (complete hydrogenolysis) and to safeguard against significant impurity formation.

[0069] It is conceivable to charge the entire molar quantity' of hydrogen, z, of the formula [PM]xLiyHz as is generally done when forming the LOXSH catalyst in situ for immediate use in a hydrogen mediated anionic polymerization. However, such a process would be cumbersome at best when making a concentrated LOXSH catalyst solution for later use. For example, a 200-liter reactor wherein 50 mole (1120 liters) of hydrogen are to be charged and wherein the reactor has been formed a 98-liter reaction mixture of [PM] Li in the hydrocarbon solvent. The head space volume is 112 liters. Charging all 1120 liters at STP requires 10 times the volume of the headspace available at the start and hence 10 atmospheres. Consequently, the pressure at 25°C is about 150 psig. As the head space is compressed by the BuLi feed it becomes difficult to determine how far the hydrogenolysis process has progressed. Accordingly, an improved and novel process entails co-feeding the theoretical amount of hydrogen with the BuLi. This enables monitoring the progress of the hydrogenolysis reactionthermally by the heat evolution as well as by the consumption of hydrogen. Hydrogen can be fed such that a constant or near constant convenient hydrogen pressure is maintained in the reactor. When the BuLi feed is complete, when the reactor stops producing heat and when the total theoretical molar quantity of hydrogen, z, has been fed (reactor pressure no longer changes), the practitioner of this disclosure will know that the LOXSH catalyst was formed completely and successfully. The most convenient and perhaps safest method of feeding the BuLi to the hydrogenolysis reactor is a pressure transfer using an inert gas (e.g. helium, nitrogen, argon). A hydrogenolysis reactor at 100 to 150 psig can require a back pressure on the BuLi solution in the range of about 120 to 190 psig, depending upon the pressure drop from the BuLi tank to the hydrogenolysis reactor. Such high pressures will result in significant quantities of dissolved gas in the BuLi which at the very least complicates monitoring the hydrogenolysis reactor.

[0070] Accordingly, the process for forming the shelf-stable concentrated LOXSH catalyst solution can entail co-feeding hydrogen gas and an alkyllithium reagent to a hydrocarbon solution of the c-p polar modifier (PM) lithium alkoxylate, [PM]Li, in the hydrogenolysis reactor. The hydrogen activity (partial pressure) in the hydrogenolysis reactor is either: 1) held constant or near constant; or 2) is allowed to vary over some range. During the process the hydrogen feed rate relative to the feed rate of the alkyllithium reagent to the hydrogenolysis reactor is controlled externally and the total molar amount of hydrogen charged to the reactor is limited to at least about the amount “z”, such that all of the alkyllithium reagent undergoes hydrogenolysis or is otherwise consumed.

[0071] The process for forming the shelf-stable concentrated LOXSH catalyst solution can entail maintaining the pressure of the hydrogenolysis reactor in the range of about -4 psig to about 35 psig hydrogen or higher. The process entails externally controlling the hydrogenolysis reactor’s pressure by maintaining an externally regulated pressure in the range of about 1 to about 40 psig or higher of a demand regulator that feeds hydrogen on demand to the reactor such that the hydrogen pressure is kept constant or near constant and wherein the hydrogenolysis reactor progress is monitored thermally. Additionally, the practitioner of this disclosure can employ a hydrogen mass flow meter equipped with a totalizer / integrator andthereby know that the hydrogenolysis process is complete when the totalizer registers that the total theoretical amount of hydrogen has been fed.

[0072] The process for forming the shelf-stable concentrated LOXSH cataly st solution, can entail maintaining the pressure of the hydrogenolysis reactor at a constant or near constant amount over the range of -4 to 35 psig or more which is controlled externally by controlling the hydrogen feed rate as a function of time (i.e. with a mass flow controller) wherein the feed rate is kept constant or is adjusted as needed such that the hydrogenolysis reactor pressure is kept at the desired amount or in a desired range. The total molar quantity of hydrogen charged to the hydrogenolysis reactor is at least equal to the theoretical molar amount of hydrogen “z” of the equation z = y - x related to the stoichiometry [PM]xLiyHzwherein x mole of the polar modifier lithium alkoxylate are combined with z mole of an alkyllithium such that y = x + z.

[0073] Alternatively the process for forming the shelf-stable concentrated LOXSH catalyst solution can entail maintaining the reactor hydrogen pressure at a constant or near constant amount in the range of about -4 to about 35 psig or higher by controlling the hydrogen pressure internally to the reactor. For such processes the hydrogen pressure in the hydrogenolysis reactor is controlled internally by regulating a variable hydrogen feed rate such that the pressure in the reactor either: 1) does not substantially change; or 2) is varied based on a planned programed rate, wherein the total molar quantity of hydrogen charged is at least equal to the theoretical molar amount of hydrogen wherein the total molar quantity of hydrogen charged is at least equal to the theoretical molar amount of hydrogen “z” of the equation z = y - x related to the stoichiometry [PM]xLiyHz. Thus, z mole of an alkyllithium is fed to x mole of the polar modifier lithium alkoxylate, such that such that the total atoms of lithium present, y, is then x + z (i.e.[PM]xLi(x+Z)Hz).

[0074] For the process for forming the shelf-stable concentrated LOXSH catalyst solution, the PM lithium alkoxylate, [PM]Li can be pre-formed in a separate reactor (either as a isolated solid, slurry or as a homogeneous solution) and then charged to the hydrogenolysis reactor to which is then co-fed an alkyllithium reagent and molecular hydrogen. A tri-feed of the: a) [PM]Li (solution or solid); b) the alkyllithium reagent; and molecular hydrogen to a heel comprising the hydrocarbon solvent can also be conducted but appears overly and unnecessarily complicated. However, in some cases like when forming the [DMEA]xLiyHzfamily of LOXSH catalysts, the hydrogenolysis reaction of the intermediate | DMEA IzLi biit l is so rapid, that a continuous process in which in-line static mixers capable of dispersive mixing of hydrogen gas can be envisioned. In such a continuous process, [DMEA]Li in the hydrocarbon solvent, and BuLi in the hydrocarbon solvent are co-fed to the static mixer system in which hydrogen is fed counter current to the condensed phase materials. In such a set up an excess of hydrogen gas may be desired.

[0075] Because the solubility of the [PM]Li at room temperature in a hydrocarbon solvent tends to be in the range of that of the [PM]2LiaH, it may be necessary to keep the [PM]Li solution at an elevated temperature if it is prepared externally to the hydrogenolysis reactor as a solution. Accordingly, preferred processes for forming the shelf-stable concentrated LOXSH catalyst solution entail forming the PM lithium alkoxylate in the hydrogenolysis reactor and then co-feeding an alkyllithium reagent and molecular hydrogen to the PM lithium alkoxylate. Again, a tri-feed or the: a) o-p polar modifier (PM); b) the alkyllithium reagent; and c) molecular hydrogen to a heel comprising the hydrocarbon solvent can also be conducted but appears overly and unnecessarily complicated. Such a process could be extended to a continuous process as well, whether in an in-line hydrogenolysis reactor or in a back-mixed hydrogenolysis reactor with an overflow line to a receiving tank.

[0076] In order to safeguard against significant impurity formation (e.g. vinyl dimethylamine, VDMA) during the processes for forming some of the shelf-stable concentrated LOXSH catalyst solution (e.g. IDMEAI2L13H) it is best that a steady state pressure and a steady state activity of the alkyllithium reagent are maintained. This is accomplished by keeping the relative feed rates of hydrogen and of the alkyllithium reagent well balanced such that both components are consumed at about the same rate and the steady state concentration of the transient intermediate [DMEAtyLia-butyl is kept at a very small minimum.

[0077] Accordingly, during the process of forming the LOXSH catalyst, the hydrogenolysis reactor is maintained at a temperature in the range of about 10°C to about 60°C during the cofeed of hydrogen with the alkyllithium reagent to the solution of the c>-p polar modifier alkoxylate. [PM]Li the undesired decomposition side reactions are suppressed by efficient mass transfer of hydrogen via mixing impellers designed for gas dispersion during the catalystforming steps. As further described below, such side reactions entail the attack of the complexed alkyllithium superbase [PM]2Lis-butyl upon the concentrate of the polar modifier alkoxylate.FURTHER DETAILED DISCRIPTION

[0078] The following discussion regarding the discoveries resulting from the extensive experimentation leading to this disclosure should make clear the lack of obviousness and hence the inventiveness of this disclosure. This disclosure entails embodiments wherein novel shelfstable LOXSH catalyst and reagent composed of relatively concentrated hydrocarbon solutions are formed, then aged under various conditions and then tested periodically in hydrogen mediated anionic polymerization reactions. These compositions are characterized by the polar modifier(s) used in forming the LOXSH catalyst, the ratio of polar modifier to lithium, hydride ion concentration (as H-, and as LiH) as well as the concentration as wt.% in the hydrocarbon solvent. In the context of chemicals, especially catalysts and reagents, "shelf stable" means that a substance can be stored at room temperature for a long period of time without significantly degrading in quality or composition, essentially remaining usable for its intended purpose without the need for special refrigeration or storage conditions. The shelflife of such chemicals can be affected by storage conditions and monitoring of those conditions during the disco very / inv ention process is important to define a reasonable shelflife and conditions which do not adversely affect their utility. More important than just room temperature storage, a chemical for sale as an item of commerce should be stable under the shipping and warehouse storage conditions for extended periods at temperatures above as well as below room temperature. The inventors have found that the inventive LOXSH solutions can be formulated to remain homogenous at temperatures in the range of from about 5° to about 42 °C for extended periods of time, (i.e. Days to Months). It has also been found that at temperatures in the range of from about -20°C to about 5°, a portion of the catalyst formulation can phase separate, and a portion of the solvent can partially freeze. How ever, it has been found that the catalyst solution can be restored to its original activity by gently warming of the solution.

[0079] This disclosure also includes unique and novel processes and process conditions necessary’ to provide the shelf-stable concentrated LOXSH catalyst and reagent solution compositions. First and foremost, it is important to use a very high purity butyllithium reagent.Although lower quality grades of BuLi can be used in the inventive in situ generated applications of WO2017176740A1, WO2022051376 and WO2023168218A2, to create a shelf-stable composition the BuLi should have minimal levels of typical contaminants characteristic of BuLi solutions. These contaminants can include, alkali metal chlorides, alkali metal hydrides, butyl chlorides, and mineral oil. Albemarle Corporation’s Langelsheim Germany plant manufactures and provides such high grade BuLi solutions routinely. Similarly, the other reagents used in forming the shelf-stable concentrated LOXSH catalyst and reagent solution compositions should be formed from components that are 1) free of moisture (anhydrous grade); 2) free of reactive gases whether as dissolved gases in solvents or contaminant gases in the hydrogen (carbon dioxide and oxygen); 3) free of primary or secondary amine contaminants or any other components that could arise in the manufacture of the P-aminoalcohol employed. In this context “free of’ means: (i) from below the detection limit for the species to 50 ppm above the detection limit; or (ii) from below the detection limit of the species to about 100 ppm; (iii) from below the detection limit of the species to about 150 ppm above the detection limit; or (iv) from below the detection limit to about 500 ppm of the species.

[0080] In terms of the utility of the catalyst systems it is important to have very low levels of any secondary or primary amine contaminant. Levels above ca. 400 ppm can contribute to, if not be the sole cause of, emulsions formed during the quenching step of a hydrogen mediated anionic polymerization in which the LOXSH catalyst is employed. At the right pH conditions such emulsions can be overcome, however it is best to avoid their formation altogether. It is also very important to avoid forming any reactive amine impurities during the formation of the shelf-stable concentrated LOXSH catalyst and reagent solution compositions. The unique methods that achieve extremely efficient hydrogen mass transfer during the hydrogenolysis reaction that forms the LOXSH catalyst enable the formation of the shelf-stable catalyst solutions. The hydrogen gas dispersion methodologies of this disclosure enable formation of the LOXSH over commercially viable temperature ranges (from about 15°C to about 60 °C or higher) well above the cryogenic temperatures commonly used to form the transient intermediate n-BuLi / lithium aminoalkoxide aggregates such as [DMEAJeLis -butyl. As is evidenced in Figure 13, in the absence of sufficient hydrogen mass transfer, significantunwanted quantities of undesired vinyl amines (enamines) are formed. The undesired side reaction leading to such impurities is especially problematic when forming the LOXSH catalyst solution as a concentrate, especially when the polar modifier is DMEA.

[0081] The excerpt below is from Reich’s review: “Role of organolithium aggregates and mixed aggregates in organolithium mechanisms” (Hans J. Reich Chem. Rev. 2013, 113, 7130-7178). Reich’s review makes clear that lithium reagents generally if not exclusively exist as aggregates... mam’ hundreds of solid-state organolithium structures have been reported, with aggregation states ranging from monomeric to polymeric. The information about structures in solution is inherently less precise hut does closely follow the trends established for the solid state... Emphasis added.Mulvey has shown that lithium dimethylamino-ethoxide (LiDAME), [DMEA]Li, is really |DMEA|sLix a highly aggregated octameric cage structure formed from eight mole of DMEA and eight mole of n-butyllithium (see Robert E. Mulvey, et al. J. Chem. Soc., Dalton Trans., 2002, 1651-1655). Mulvey’s crystal structure suggests that [DMEA]Li in solution likely exists as a structure similar to the aggregated octamer [DMEA]sLis. The teachings of Reich cited above would indicate that the solid-state structure [DMEA]sLi8 closely represents the structure of [DMEA]Li in solution.[DMEA]2Li3H Scheme I

[0082] Among the most preferred HV-LOXSH formulations are the ones with the stoichiometric formula [DMEA]2Li3H. This composition can be formed according to the sequential chemical reaction above presented in Scheme 1. It is critically important to understand and appreciate that the chemical equations of Scheme 1 are not intended torepresent the structure, nor the total composition (molecular formula) of the catalyst and transient intermediates formed. The chemical equation is intended only to convey the relative stoichiometry and the concepts behind forming the hydrocarbon soluble lithium hydride catalyst from the reagents employed. When attempts were made to crystallize the HV-LOXSH catalyst having the stoichiometry | DMEA^LisH. surprisingly the inventors found, and have proven by X-ray crystallography, that LiDAME, [DMEA]sLis, crystallizes from solution in lieu of crystallization of the hydride catalyst. In Figure 1 the crystal structure is presented of the crystalline solid obtained from the attempted crystallization of [DMEA]₂Li₃H and is identical to Mulvey’s published crystal structure for [DMEAJsLis. The inventors have found through extensive experimentation that at certain concentrations, both HV-LOXSH and LV-LOXSH catalyst solutions resulted in crystallization of the polar modifier lithium alkoxylate [PM]Li and formation of a higher hydride content aggregate in solution. In Figure 2 is presented the DSC trace of solid crystalline [PsB]xLixshowing three points albeit slightly broad melting points, 1) 131.28 to 167.10 °C; 2) 246.68 to 252.94 °C; and 288.51 to 296.07 °C. Surprisingly therefore, despite the literature teachings mentioned above, the Schlenk equilibrium does not result in formation of insoluble lithium hydride but rather leads to precipitation of aggregates of [PM]xLixand formation of a hydride enriched catalyst formulation [PM]Li2H according to the equation:([PM]2Li3H)x[PM]xLix+ ([PM]Li2H)x.wherein PM = DMEA, PiP and PsB polar modifiers. This unpredictable and unanticipated result helps to enable this disclosure.

[0083] The formation and isolation of well-defined molecular saline hydride compounds has been reviewed, (see Fohlmeister Lea, Stasch Andreas (2015) Alkali Metal Hydride Complexes: Well-Defined Molecular Species of Saline Hydrides. Australian Journal of Chemistry 68, 1190-1201. Also see Molecular Main Group Metal Hydrides Matthew M. D. Roy, Alvaro A. Omaha, Andrew S. S. Wilson, Michael S. Hill, Simon Aldridge, and Eric Rivard Chemical Reviews 2021 121 (20), 12784-12965). Accordingly, three higher hydride content low solubility lithium hydride complexes have been isolated and X-ray crystal structures determined. These include (DipNPPh2)4LisH4 (Dip = 2,6-iPr2C6H3) having the formulaAS-FI-816I-WO [PM]L12H wherein PM = DipNPPh2 as well as [(pz)ioLi22Hi2], and [(pz)i2Li3? H25] (pzH=3,5-di-tert-butyl-lH-pyrazole) having the formulae [PMJjLinHe and [PM] 12I 37H25 respectively wherein PM = 3, 5-di -tert-butyl- IH-pyrazolate. It is important to understand and appreciate that these hydride rich compositions crystallize from solution as the well-defined molecular lithium hydride species whereas surprisingly thus far the hydride rich LOXSH compositions do not even with the addition of stoichiometric THF.

[0084] The desired stoichiometry of the LOXSH catalyst is in the range of [PM]xLiyHz, wherein the ratio of y:x is from about 1.4 to about 1.8 and preferably in the range of from about 1.45 to about 1.70. The stoichiometric ratios of x:y outside the ratio of about 1.45 to about 1.70 (whether above or below, but especially below) leads to catalyst of less activity and in some cases lower selectivity'. The inventors have discovered through extensive experimentation (as evidenced by the 55 representative Examples, and 56 representative Application Examples as well as 23 exemplary Figures) that the solubility of [PM]2Li3H in cyclohexane (a preferred solvent) is close to solubility of the corresponding lithium alkoxylate aggregate [PM]xLix. For example, as is evidenced in Figure 4 and Tables 1, 2, 4 and 5, the solubility at room temperature of [DMEAtyLisH in cyclohexane is about 5.0 wt.% which is close to the solubility [DMEA]sLis (5.3 wt.%) in cyclohexane at room temperature. At higher concentrations of [DMEAtyLisH, [DMEAJsLis crystallizes from solution leaving behind a higher hydride LOXSH formulation. These higher hydride formulations comprise the very soluble [DMEA]Li2H and [DMEA]Li3H2 LOXSH formulations each having a solubility of at least about 5 wt.% (prepared as Example 27 and 28). As can been seen in the exemplary embodiments in the Tables, a 5 wt.% [DMEAtyLisH solution comprises 250 to 280 ppm hydride. The higher hydride species [DMEA]Li2H and [DMEA]Li3H2 can comprise >590 ppm and >960 ppm hydride at 5 wt.% respectively. It is important to note that these hydride rich catalyst solutions were found to be “not pyrophoric” by the UN Division 4.2 Test N.3 for pyrophoricity. However it is strongly recommended that they be handled only under inert atmospheres and kept away from oxygen and / or water.

[0085] The inventors also discovered that replacing a portion of [DMEA] with the same molar portion of l-methoxy-2-propanol (MeOP) to form [DMEA]3[MeOP]LieH2 provides a HV-LOXSH catalyst solution having a 7 wt.% concentration at room temperature in cyclohexanecorresponding to 342 ppm hydride (Example 19). It is pointed out that a one-liter solution (780 g) of these HV-LOXSH formulations (5.0 wt.% [DMEAJLisH and 7.0 wt.% [DMEA]3[MeOP]LieH2) is sufficient catalyst to polymerize 7.0 Kg to >10.0 Kg of butadiene to form a HV-HMPBD composition as well as 12.8 Kg to >18.0 Kg of styrene to form HMAPS.

[0086] In a like fashion, the inventors discovered that the solubility of [PiP]2Li3H is about 5 wt.% corresponding to a hydride content of 167.3 ppm (Table 9, Ex. 29), and dropped only to 165.9 ppm after one year at room temperature. LV-LOXSH catalyst solutions formulated at 7.0, 9.0 and 6.0 wt.% [PiP]2Li3H (Table 9 Ex. 30 - 32) all deposited [PiP]xLixwithin days of formation. It is pointed out that after precipitation of crystalline [PiP]xLix. the catalyst solutions hydride contents only changed incrementally even after one year at room temperature. Accordingly. Examples 30, 31 and 32 were initially formulated to have hydride contents of 236.5, 293.3 and 197.0 ppm respectively. After crystallization and hence separation of [PiP]xLix, the hydride contents for Examples 30, 31 and 32 were 241.0, 312.5 and 208.8 ppm respectively. The incremental increase in the concentration of hydride in these samples is the result of an increase in catalyst wt.% due to the loss of the mass attributable to [PiP]xLixas it separated. The important point is that the hydride content did not decrease over one year of aging due to precipitation of LiH. The hydride content remained essentially constant and hence shelf-stable, notwithstanding the initial separation of [PiP]xLix. In the course of this work, a 9.97 wt.% [PiP]xLixsolution in cyclohexane was prepared. Upon standing, nearly half of the [PiP]xLixcry stallized leaving behind a 4.98 wt.% [PiP]xLixsolution.

[0087] The inventors also prepared a 14.4 wt.% [PsB]xLixsolution in cyclohexane that on standing deposited crystalline [PsB]xLixyielding a 10.4 wt.% [PsB]xLixsolution. A portion of this solution was used to prepare [PsB]2Li3H in situ to polymerize butadiene to form a LV-HMPBD composition. The chemical and physical properties of this LV-HMPBD composition included Mn= 1039, PDI = 1.84, total 1,2-vinyl content of 29.8 wt.% (1HNMR) and 32.8 wt.% (13CNMR), iodine number of 449 g I2 / IOO g of polymer, Viscosity @ 25°C of 278 cP, and Tg= 98.88.

[0088] Much like the DMEA and PiP based LOXSH catalyst solutions, the wt.% of [PsB^LisH in cyclohexane at room temperature, is about 10.5 wt.% (12.0 wt.% when fresh and 10.5 wt.% after aging for several months) which is equivalent to the solubility in weight % of [PsB]xLix.During the discovery phase, LV-LOXSH catalyst solutions comprising the formula [PsB^LisH were formulated from 10.0 wt.% to 14.0 wt.% in cyclohexane. The 14.0 wt.% solutions deposited crystalline [PsB]xLixrelatively quickly upon standing. The 12 wt.% [PsB]2Li3H solutions took months to deposit [PsB]xLixat room temperature, but formed [PsB]xLixin a freezer (-5°C) as a solid which redissolved upon warming to 42°C. A portion of the 10.5 wt.% solution of [PsB]2Li3H (Example 36, after aging 9 weeks) deposited [PsB]xLixwhen placed in a freezer (-17°C, 40 hours) as well as forming a slushy / icy heterogenous cyclohexane suspension in cyclohexane. Upon warming the cyclohexane portion thawed and became homogenous leaving behind some cry stalline [PsB]xLix. Warming the solution to 42°C resulted in a completely homogenous solution. This [PsB^LisH solution (Example 36) was used in Application Example 32 of Table 13. This catalyst solution. Example 36. was tested at two month, four months and 7 months and was found to have retained its activity over the entire period of time (see Application Examples 30, 33 and 40 of Table 13).

[0089] The 12 wt.% [PsB]2Li3H catalyst solutions Examples 35 and 38 remained homogeneous for a period of time before depositing [PsB]xLix. Accordingly, these solutions were allowed to age for 8 weeks at room temperature during which time no [PsB]xLixseparated. They were tested as LV-HMPBD catalyst. The results are presented as Application Examples 29 and 31. After 5 months at room temperature it was observed that Examples 35 and 38 had deposited some amount of [PsB]xLix. The solutions were made homogenous by warming in an oven at 42°C for a week and then tested. The results of the application test are presented as Application Examples 36 - 38.

[0090] The 14 wt.% [PsB^LisH catalyst solutions Examples 37 and 39 did not remain homogeneous and in a short period of time (days) deposited [PsB]xLix. These heterogenous solutions were aged for five months at room temperature and then for one week at 42°C to make homogenous. The homogenous solutions were then tested as LV-HMPBD catalyst. The results are presented as Application Examples 39 and 40. Example 39 was then aged an additional 2 months at 42°C and tested (see results for Application Example 42) and found to have retained its activity.

[0091] The foregoing discussion regarding the stability and stability testing of the shelf-stable concentrated LOXSH catalyst and reagent solution compositions speaks to their novelty andinventiveness and how their behavior in solutions defies conventional wisdom regarding the Schlenk Equilibrium. It is important to understand and appreciate that the shelf life of the catalyst is not a matter of inherency. It is rather a matter of great care in selection / preparation of the raw materials, the manufacturing technique and the chemical engineering methods that define the process conditions used in the manufacture of the LOXSH catalyst and reagent solution compositions. The LOXSH catalysts are formed by hydrogenolysis of BuLi / lithium aminoalkoxide aggregates. Under the process conditions of this disclosure, these aggregates are only present as transient intermediates of reduced concentration and hence undesired side reactions, especially degradation reactions that involve second order reaction kinetics are suppressed. These BuLi / lithium aminoalkoxide aggregates are powerful super bases used to selectively metalate organic amines at a position a to the nitrogen atom, (in this connection see Chartoire, Anthony, Corinne Comoy, and Yves Fort. " Toolbox for Regioselective Lithiations of Furo [2, 3-c] pyridine." The Journal of Organic Chemistry 75, no. 7 (2010): 2227-2235. Khartabil, Hassan K., Philippe C. Gros, Yves Fort, and Manuel F. Ruiz-Lopez. " Metalation of Pyridines with «BuLi-Li-Aminoalkoxide Mixed Aggregates: The Origin of Chemoselectivity. " Journal of the American Chemical Society 132, no. 7 (2010): 2410-2416. and Khartabil, Hassan K., Philippe C. Gros, Yves Fort, and Manuel F. Ruiz-Lopez. " A Theoretical Study on n BuLi / Lithium Aminoalkoxide Aggregation in Hexane and THF." The Journal of Organic Chemistry 73, no. 23 (2008): 9393-9402.) These BuLi / lithium aminoalkoxide aggregates are generally formed and used as reagents under cryogenic conditions, -40°C to -78°C, such conditions are a challenge to deal with on a large industrial scale, require specialized equipment and have a large carbon footprint associated with refrigeration.

[0092] In the course of inventing a commercially feasible process for forming the shelf-stable concentrated LOXSH catalyst and reagent solution compositions the inventors discovered that the BuLi / lithium aminoalkoxide aggregates undergo auto-decomposition reactions according to the equation below (shown for the DMEA based LOXSH):N. 44"C,,!J (4 1 Scheme 2EquatiRcitCy^^^ ^decamp. MM on 2 Wherein: x = [DMEA]Li, andy = [DMEA]Li»BuLiThe chemical mechanism above (Scheme 2) shows the bi-molecular (second order kinetics, Equation 2) auto-decomposition reaction of BuLi / lithium complexed dimethylaminoethoxide ([DMEA]2Li3-butyl = [DMEA]2Li2»BuLi) leading to the formation of butane, undesired lithium oxide and very undesired vinyl dimethyl amine (VDMA) contaminants. Figure 14 compares the VDMA contents of four catalyst [DMEAJzLisH LOXSH catalyst solutions, Examples 22-25. The highest VDMA content is exhibited by Example 22 at 5.5 wt.% relative to [DMEA]2Li3H. How this relatively high level of VDMA formed is easily rationalized based on comparison of Figures 6-11. The VDMA content of Example 20 (a more dilute solution) of Figure 6 was only 0.5 wt.% relative to [DMEA]₂Li₃H. The VDMA content of Example 21 of Figure 7 was only 1.8 wt.% relative to [DMEA]2Li3H. Figure 15 shows how the composition of Example 22 differs from compositions of Examples 23-25 and the apparent effect that the impurity Li2O has on the Li-7 NMR spectra. This high Li2O content along with a high VDMA content resulted in failure of mass transfer of hydrogen when forming the composition of Example 22 as Evidenced by the reactor pressure temperature profile of Figure 8. Figures 6-11 are the hydrogenolysis reaction pressure and temperature profiles. That is they provide the hydrogenolysis reaction pressure and temperature as a function of the BuLi feed over the time of the co-feed of BuLi with the feed of hydrogen.

[0093] Example 20 with its dilute reagent concentration and consequentially very slow BuLi feed ran very smoothly at only 1.0 psig hydrogen pressure at about 18°C feeding hydrogen at 40 SCCM. As a consequence, the concentration of [DMEA]2Li3-butyl (a function of BuLi feed rate) at any point in time was relatively low. This is achieved by rapid hydrogenolysis of [DMEA]2Li3-butyl to form [DMEA]2Li3H which requires very efficient mass transfer ofAS-FI-816I-WO hydrogen gas from the vapor phase to the condensed phase - this requires mixing designed to achieve dispersion of the molecular hydrogen. This Example would imply that the prior art very dilute LOXSH compositions formed in situ are not as susceptible to such degradation reactions and thus do not and cannot anticipate the compositions or processes of this disclosure.

[0094] Examples 21-25 were all formulated at twice the concentration of Example 20 consequentially the BuLi fed during the hydrogenolysis step was twice as concentrated and so was the [DMEA]Li to which it was fed. Inspection of Figure 7 shows that during the co-feed of hydrogen and BuLi. the relative feed rate of hydrogen had to be increased from 100 SCCM to 120 SCCM, still there was a point in time that the pressure within the reactor reached 0 psig. It is deemed that during the period from 25 minutes through the end of the feed at 35 minutes to the end of the hydrogen feed at 48 minutes, most of the undesired VDMA (1.8 wt.% relative to [DMEA]2Li3H) formed. Higher concentrations of [DMEA]Li appears to facilitate its decomposition reaction which is easily understood by those of skill in the art as is predicted by the rate expression of Equation 2 above.

[0095] Example 22 with its 5.5 wt.% VDMA relative to [DMEA]2Li3H clearly demonstrates what happens to the quality of the LOXSH catalyst solution if hydrogen mass transfer becomes inefficient and hence inadequate. As is described more fully within the Examples, the hydrogenolysis reactor is a two-liter Parr Autoclave. The reactor’s cylinder height is 10 inches. Each inch of height represents 200 ml. The hydrogenolysis reactor is equipped with 4 pitched blade impellers: the first at the very bottom (0 ml); the second at 2 inches (400 ml); the third at 4 inches (800 ml); and the fourth at 6 inches (1200 ml) from the bottom. As the BuLi is fed to the reactor the volume of the reaction mixture increases and the work of transporting hydrogen from the head space to the condensed phase is transferred from one impeller to the next higher one. It is evidenced in Figure 8 that once 83% (25 out of 30 minutes) of the BuLi had been fed, reaction mixture volume of 1470 ml, hydrogen mass transfer became impeded by the reactor geometry and hence became inefficient and inadequate. This loss of hydrogen mass transfer allowed the auto-decomposition reaction of BuLi / lithium complexed dimethylaminoethoxide and an undesired amount of VDMA to form. It was found however, that the hydrogenolysis reaction could be forced to go to completion by switching to a subsurface hydrogen feed.

[0096] Examples 23-25 as evidenced by Figures 9-11 were all run at concentrations greater than that of Example 22 while forming acceptably low levels of VDMA. Samples 24 and 25 were combined and diluted to a 5.0 wt.% [DMEA]2Li3H and tested as HV-FIMPBD catalyst in Application Examples 23-26 and are compared to Example 21 used in Application Example 22. The inventive solution discovered was to run with even more concentrated [DMEA]Li solutions while keeping the volume of the reactor below 1400 ml during the hydrogenolysis and additionally to feed hydrogen subsurface as needed through a narrow internal diameter feed tip (i.d. = 0.02 inches). It is important to note that part of the solution to the problem of increased throughput (more catalyst per unit time per unit reactor volume) was to run the process with even more concentrated [DMEA]Li solutions. This speaks to the inventiveness of the use and methods employed to provide effective hydrogen mass transfer during the catalyst forming steps of this disclosure. Accordingly, after hydrogenolysis of the more concentrated catalyst solutions is completed, the appropriate amount of solvent is then combined with the LOXSH catalyst solution to make it shelf-stable (prevent separation of crystalline LiDAME). One of ordinary skill in the art can apply these discoveries and now design a commercial scale hydrogenolysis reactor with the appropriate geometry (gas dispersive mixing, and high velocity hydrogen subsurface feeding), reagent concentrations, and co-feeding conditions, to form the shelf-stable concentrated LOXSFI catalyst and reagent solution compositions of this disclosure.

[0097] Figure 15 demonstrates the utility of the shelf-stable concentrated LOXSH catalyst and reagent solutions of Examples 22 and the blend Example 26 formed from Examples 24 and 25. Figure 15 provides the pressure and temperature profiles of the hydrogen mediated anionic polymerization of butadiene. The process technology of this applications test is that of WO2022051376 except for the fact that the [ DMEAtyLisH LOXSH catalyst was prepared 25 days in advance of the test as concentrated solutions relative to the in situ prepared catalyst of WO2022051376. In Application Examples (22-26), the HV-HMPBD distributions were formed over a range of slightly different temperatures (71°C to 74°C), over slightly different [BD] / [H2], and over slightly different at [DMEAtyLisH loadings. These differences result in the slight differences in the average pressure of each test run. The details of the applicationexperiments are in Table 7 and the chemical and physical properties of the resulting HV-HMPBD compositions are presented in Table 8.

[0098] Figure 17 and Figure 18 graphically compare the viscosity and the glass transition temperature respectively, as a function of the number average molecular weight, Mn, of 18 HV-HMPBD distributions. Six of these 18 HV-HMPBD distributions were formed using HV-LOXSH catalyst formulations formed in situ. Twelve of these 18 HV-HMPBD distributions were formed from either freshly prepared (5 total aged less than 2 weeks) or aged (7 total aged >9 months) concentrated HV-LOXSH catalyst formulations. The 18 HV-HMPBD compositions were formed using different constant [BD] / [H2] relative feed rates and total relative charges. The correlations of the graphs of Figures 17 and 18 over the range of Mnvalues have an R2value > 0.961. This excellent correlation demonstrates that whether freshly made in situ, or whether freshly prepared as a concentrate and used within weeks, or whether made as a concentrate and aged for 9 months, the microstructure and molecular architecture of the resulting HV-HMPBD compositions are the same over a range of polymerization conditions and molecular weights.

[0099] Figures 19-22 present the pressure and temperature profiles for the formation of [PsB]2Li3H for Examples 45, 50, 1 and 55. Notable from the graphs is that completion of the hydrogenolysis process, as evidenced by the ongoing uptake of the hydrogen fed, lags the BuLi feed. It is also notable that hydrogenolysis requires a higher temperature for the PsB polar-modifier-based ligand as compared to the one formed from DMEA. Small scale (NMR tube) experiments demonstrate that the PsB system is subject to formation of vinyl piperidine analogous to the auto decomposition reaction of the DMEA system (Scheme 2 above). However, the rate of decomposition of [PsB]Li is slower than that of [DMEA]Li and is suppressed if not completelyScheme 3eliminated by hydrogen with sufficient mass transfer to the condensed phase. Though the inventors wish to not be bound by theory, the mechanism for such suppression of undesired metalation reactions is provided in Scheme 3 above. Consequently. PsB based LV-LOXSH compositions having hydride contents of 300 to 400 ppm are easily produced. What is remarkable about Example 45 of Figure 19 is that the sample was produced wherein the pressure in the hydrogenolysis reactor was between -1 and 0 psig. Example 45 was tested in Application Example 46 and was found to be an excellent LV-LOXSH catalyst formulation.

[0100] Examples 42 and 43 are very instructive with regard to the flexibility and manufacturefriendliness of the processes for forming the shelf-stable concentrated LOXSH catalyst and reagent solutions. When forming Example 42 (details in Table 11), an under charge of BuLi was intentionally used such that the ratio of Li / PsB was only 1.375 vs. the standard 1.500. As can be seen in Table 14 (Ap-52) this deficiency of hydride in the catalyst resulted in an average hydrogen mediated polymerization pressure of 50 psig at the elevated temperature of 106°C. When forming Example 43 (details in Table 11). an over charge of BuLi was intentionally used such that the ratio of Li / PsB was 1.659 vs. the standard 1.500. As can be seen in Table 14 (Ap-50 and -51) the excess hydride in the catalyst had no negative effect on the applications test. In Application Example 50 the amount of catalyst used was based on an equal PsB content to the other runs - hence a deficiency in LiH. In Application Example 51 the amount of catalyst used was based on an equal lithium content to the other runs - hence a reduced and perhaps thereby an economically advantageous amount of PsB. Both test runs (Ap-50 and -51) ran at 40 psig at the standard temperature of 101 °C. A blend, Example 44, was formed from Examples 42 and 43 such that the Li / PsB was 1.496. This blend was tested after aging a totalof 4 weeks and then at 13 weeks, Ap-53 and -54 respectively. In both test runs (Ap-53 and -54) ran at 39 psig at the standard temperature of 101°C. In all cases the LV-LOXSH catalyst formulations made excellent quality LV-HMPBD compositions.

[0101] Examples 51 and 52 were formed along with Examples 49 and 50 in order to prepare the blends Examples 53 and 54. During the hydrogenolysis step of the formation of Example 51, it was immediately apparent from the hydrogenolysis reactor pressure temperature profile (Figure 21) that there was an undercharge of BuLi during the formation of [PsB]Li. This was evidenced by the fact that the pressure rise was too fast during the first part of the hydrogen / BuLi cofeed. Analysis later revealed that the BuLi sample used to form that solution was only 97% of the expected concentration. As a consequence, for Example 51, the Li / PsB ratio was 1.465. Based on the blending studies of Examples 42-44, Example 52 was made with a slight over charge of BuLi such that the Li / PsB was 1.606. Blending of Examples 49-52 resulted in Examples 53 and 54 which were tested in the application tests (Ap-55 and -56). Both test runs (Ap-55 and -56) were conducted at the standard temperature of 101°C running at 41 and 42 psig respectively.

[0102] Figure 23 presents reaction pressure temperature profiles of the hydrogen mediated anionic polymerization of butadiene application test for Application Examples 43-47 and 54-55. It should be apparent from these Application Examples and from the analyses data provided in Tables 13 and 14 along with comparative analyses data of Table 15 (compositions made according to the process technology of WO2022051376) that the LV-LOXSH catalyst [PsB]xLiyHz can be prepared as concentrates having hydride contents in the range of 270 to 430 ppm wherein the catalyst concentration is in the range of 9 wt.% to 12 wt.% and preferably in the range of 10.0 to 10.5 wt.%. What’s more, these LV-LOXSH catalyst are in fact shelf-stable with a shelf life of at least two months and likely greater than one year (Ap-57), even when stored for extended periods of time at elevated temperatures (ca. 42°C).

[0103] In general the shelf-stable LOXSH catalyst solution compositions of this disclosure comprise Li / PM molar ratios in the range of from about 1.4 to about 1.7, and preferably of about 1.5 are generally prepared, higher Li / PM molar ratio are also embodiments of this disclosure. As was discussed above LOXSH catalyst solution compositions [DMEA]Li2H and [DMEAJLisH2 Example 27 and 28 were prepared. The Li / PM molar ratio of these Examplesare 2.0 and 3.0 respectively. These compositions were formulated to have 571.2 ppm and 956.2 ppm hydride contents - 4500 and 7300 ppm hydrocarbon soluble lithium hydride. The hydride analysis test results showed 588.7 ppm and 958.9 ppm hydride ion contents. Accordingly, these shelf-stable hydride rich LOXSH catalyst solutions have the potential to deliver more catalyst per unit volume than the standard formulations. One embodiment of using such hydride rich solutions is as a precursor catalyst solution. Accordingly this embodiment entails forming a reaction medium of the hydride rich solution under a hydrogen atmosphere by: 1) charging the desired amount of hydride rich solution on a lithium basis to the hydrogen mediated anionic polymerization reactor; 2) then charging either neat or preferably as a diluted hydrocarbons solution supplementary polar modifier such that the Li / PM molar ratio for the total amount of PM present is about 1.5; 3) co-feeding an anionically polymerizable monomer with molecular hydrogen; and 4) quenching the reaction medium once the cofeed and any extended reaction time (i.e. ride at the end of the run) are complete. Preferred embodiments are when the supplemental polar modifier is one or more of DMEA, 1 -piperidinoethanol, 1-methoxyethanol, 1 -methoxy -2-propanol, tetrahydrofurfuryl alcohol, l-methoxy-2-butanol and trans-2-methoxy cyclohexanol.ANALYTICAL METHODS

[0104] Analytical methods used in the analysis of the HMAPS, HMPBD and hydrogen mediated copolymers of styrene and butadiene have been reported in WO2017176740A1, WO2022051376 and WO2023168218A2 and need not be reproduced here. The concentration of the LOXSH catalyst can be determined by1HNMR (normalization of components), by LC and / or by GC with an added internal standard. For LOXSH catalysts wherein the polar modifier is an aminoalcohol, such compositions' catalyst content can be determined by acid base titration in combination with hydride analysis.

[0105] The hydride analysis method is based on and adapted from the open literature report by Hoye et al. (see Hoye, Thomas R., Andrew W. Aspaas, Brian M. Eklov, and Troy D. Ry ba. " Reaction titration: A convenient method for titering reactive hydride agents (red-AL LiAlH4, DIBALH, L-selectride, NaH, and KH) by No-D NMR spectroscopy." Organic Letters 7, no.11 (2005): 2205-2208.) Figure 3 presents the 'HMNR spectra of the reaction mixture formed from a DMEA based LOXSH catalyst solution and 4-anisaldhyde ( -methoxybenzaldeyde)after quenching with acetic acid. This methodology relies on the ability of the various LOXSH catalyst solutions to rapidly hydro-lithiate (reduce) the aldehyde functional group to form the reduction product p-methoxybenzyl alcohol lithium alkoxide in perdeuterated tetrahydrofuran (THF- y). Acidification of the reduction product with acetic acid provides the free p-methoxybenzyl alcohol. The difference in the starting molar amount of the aldehyde and the reduction product alcohol provides molar content of the hydride content of the LOXSH catalyst solution. Surprisingly 100% of the hydride present whether formulated as [PM]sLi4H, [PM]2Li? H, [PM]Li2H or [PM]LisH2 (and blends thereof) is transferred to 4-anisaldhyde. The hydride content is determined according to the equation:H~ wt. % = 1.008 X x 100% Equation 3Wherein a = p-anisaldehyde, 5 = sample, I, = integral reduced, Iu= integral un-reduced. And wherein, the FWa=136.15 g / mole, PEais the amount of 4-anisaldhyde (Std. weight), and Wsis the weight of the LOXSH catalyst solution (Sample weight) added to the THF-cL solution of 4-anisaldhyde. Accordingly, for the data presented in Figure 3 the sample comprised 0.0244 wt.% 244 ppm) hydride (1924 ppm LiH):[1.00 / 1 H~ wt. % = 1.008 X (°-1043 / o,. c) X - - ^^ o ^3'53^x 100%= 0-0244 wt. %V! 136.15 / 0.6849 Hoye’s method employed a No D NMR technique, however the following method for obtaining the spectra w as found more convenient. Accordingly, the instrument conditions are as follows:a. Frequency 500.13 MHzb. Zgig30, pulse program with 30-degree flip angle, and inverse-gated C-13 decoupling c. Pulse delay 60 seconds.d. Sweep width 8503.401 Hze. Data points collected 128kf. Real data point after FT 128kg. Number of scans 8EXAMPLES

[0106] The following Examples illustrate methods of production of the LOXSH catalyst solution concentrates as well as methods for testing said catalyst solutions. The application tests include hydrogen mediated anionic polymerization of styrene and of butadiene pursuant to this disclosure. These Examples are not intended to limit the disclosure to only the procedures described therein.Equipment

[0107] The hydrogenolysis reactor used for this work is as follows: 316 stainless steel 2-liter Parr autoclave having, temperature controller, thermal couple, bottom drain valve, cooling coils, hot oil jacket, four pitched blade turbine impellers with the first 4.0”, the second 6.0”, the third 8” and the fourth 10” from the top head of the reactor. The reactor was further equipped with a piston pump, nitrogen purged 300 ml stainless charge vessel, a 2-liter styrene monomer feed tank on a weigh scale, a well calibrated high-pressure metering pump with a 1 / 16 inch O. D. subsurface monomer feed line having a 0.01” i.d. terminal section (as noted in the Examples below), a solvent feed tank, and a one-liter PTFE-lined butadiene charging tank on a weighing scale. The magnetic drive on the agitator shaft is connected to a high-speed air driven motor and generally operated at a near constant 1025 ± 25 RPMs (adjusting the air flow and pressure to the air motor as needed as the reaction mixture viscosity and volume changes). A hydrogen head tank comprising two one-liter gas cylinders outfitted with a digital pressure gauge (readability of 0.01 psig) provides a wide spot in the line between the reactor and the hydrogen gas supply. The pressure in the hydrogen head tank is regulated down to 20 to 70 psig as needed depending on the application, to supply hydrogen to the mass flow meter as well as the butadiene feed tank. Prior to the start of a run the hydrogen head tank is pressured 400 to 435 psig hydrogen and then isolated from the hydrogen supply located outside of the lab. The amount and rate of hydrogen feed is controlled with a digital hydrogen mass flow meter with a totalizer. For hydrogen mediated anionic styrene polymerizations, hydrogen was fed subsurface through a 0.01” I. D. feed tip. For LOXSH catalyst formation and for diene polymerizations hydrogen was either fed to the headspace or subsurface through a 0.02” I. D. terminal section, (as noted in the Examples below). Bulk solvent (e.g., cyclohexane (CH) or methylcyclohexane (MCH) or ethylbenzene (EB) or mixtures thereof recovered from a previous run) is charged to the reactor from the solvent tank via peristaltic pump (Masterflex®PFTE tubing pump head 77390-00 w777390-60 6 mm), either directly through the dip-leg or indirectly first passing through the charge vessel.

[0108] The autoclave is vented via 3-way ball valve either to an oil bubbler or to a 6-liter oil jacketed grease wash vessel having a bottom drain and outfitted for overhead stirring and distillation. When forming hydrogen mediated anionically polymerized polymer compositions, the bottom drain valve of the autoclave is plumbed to the wash vessel for direct transfer of the unquenched polymerization reaction mixtures. When forming concentrated LOXSH catalyst solutions, the bottom drain valve is plumbed to a receiving vessel comprising a nitrogen purged 1000 or 2000 ml. oven-dried, single neck (24 / 40 standard taper) round bottom flask equipped with a wired-down rubber septum and is vented to a mineral oil bubbler. The catalyst transfer is carefully executed with minimum hydrogen back pressure through an eighth inch stainless steel line outfitted with an 11 -gauge stainless steel, 4-inch-long needle, with 1 / 8-inch ferrule lock (Aldrich cat. # Z117765). Upon collection of the LOXSH catalyst solution, the collection vessel is removed and then transferred to a nitrogen purged glove box. The LOXSH catalyst solution is then transferred to clean, oven-dried amber Aldrich Sure / Seal™ bottle and capped with a steel crown cap with a PTFE liner for storage and later use.General Procedure for Concentrated LOXSH Catalyst FormationForming the concentrated [PM] Li solution from BuLi

[0109] When forming the most concentrated LOXSH catalyst solutions on a hydride bases in one pot, a heel of cyclohexane is charged to the reactor and the reactor temperature is controlled between 8°C to 15°C by applying 8°C oil to the reactor jacket and ice water (2°C to 8°C) to the cooling coils, though higher temperatures have been used for lower concentrations. A reaction medium comprising the polar modifier and solvent is then formed by introducing a diluted cyclohexane solution of the polar modifier(s). The hydrogen pressure is adjusted to about 20 psig to 25 psig, the agitator is set to 1025 ± 25 RPM and the mixture is allowed to cool to 8°C to 10°C. An equivalent molar amount of BuLi to the polar modifier(s) is charged to the charging vessel to form the [PM]Li reaction mixture for the next step. Whether the BuLi solution is fed in one or two portions and any amount of dilution with cyclohexane will dependon the ultimate concentration of the LOXSH catalyst solution and the volume to be formed in the hydrogenolysis reactor. The BuLi is then fed to the reactor from the charging vessel with nitrogen back pressure through the metering valve. A typical run wherein 1.5 liter of catalyst is formed requires two charges to and then from the charge vessel over a period of 60 minutes (each feed requiring 30 minutes). Recharging the charge vessel can take 10 minutes so the total operation is conducted in approximately 70 minutes from the start of the feed. The BuLi feed rate is such that the reaction temperature is maintained in the range of 12°C to 15°C, slower or faster feeds can be utilized. During this BuLi feed the reactor pressure will generally build to 11 ± 2 psig above the initial pressure, this pressure is vented between charges to 0 psig and the pressure is adjusted back to 20 psig to 25 psig. When this initial molar equivalent BuLi feed is finished and the [PM]Li is completely formed, the hydrogenolysis reactor is vented to the oil bubbler to 0 psig and a specified initial charge of hydrogen gas is then made using the mass flow meter.Forming the concentrated LOXSH catalyst from [PM]Li

[0110] The concentrated LOXSH catalyst solution can be formed either in one pot or in two. Whether formed in a one-pot operation or a two-pot operation, the process from this point is the same. In a one-pot operation [PM] Li as formed above is already present in the hydrogenolysis reactor. For a two-pot operation, the preformed [PM]Li is charged to the reactor as a hydrocarbon solvent solution, or is formed into a hydrocarbon solvent solution by cofeeding the PM in solvent and BuLi solution through a static mixer to the reactor. The reaction temperature of the concentrated [PM]Li hydrocarbon solution is adjusted to the desired temperature by adjusting the hydrogenolysis reactor jacket temperature. The hydrogen regulator on the two-liter hydrogen head tank is set to the desired pressure. If the hydrolysis reaction pressure is to be run at a near constant pressure controlled by the regulator, then the hydrogen mass flow meter is bypassed. Alternatively, if it is to be controlled by the hydrogen feed rate then the mass flow meter is set to deliver hydrogen at the desired initial flow rate. The totalizer is programed to shut off the hydrogen feed once the total amount of hydrogen desired has been fed. The initial pressure of the hydrogenolysis reactor is then set by charging hydrogen to a desired pressure or by charging the specific desired initial amount of hydrogen.AS-FI-8I6I-WO

[0111] The total amount of BuLi desired to form the targeted hydride content is charged to the charge vessel. The agitator motor is set for 1025 ± 25 RPM and BuLi is then pressure transferred to the reactor through the metering valve with about 15 to 30 psi nitrogen back pressure over the reactor pressure. After about 5 minutes of feeding the BuLi, the hydrogen co-feed is initiated. The flow rate of hydrogen is adjusted during the co-feed up or down to attempt to run at a constant or near constant hydrogenolysis reactor pressure. Temperature is generally kept at a constant value unless the hydrogenolysis reaction entails forming high hydride LOXSH catalyst compositions. Upon completion of the BuLi feed the transfer line is flushed with cyclohexane to adjust the concentration of the LOXSH catalyst composition. Upon completion of the run, which is generally indicated by achieving a relatively steady, if not constant, reactor pressure and generally a drop in temperature, the reaction mixture is then heated to 70°C to 74°C. Upon reaching that temperature range, the hydrogenolysis reactor is vented to the wash kettle. During which time an azeotrope of butane and cyclohexane will generally distill over into the wash kettle; especially when a one-pot operation is conducted. At this temperature the hydrogenolysis reactor pressure generally does not drop below 2 psig due to the vapor pressure of cyclohexane with butane. The reaction mixture is then cooled to about 60°C and the pressure adjusted to 5 psig with hydrogen. Agitation is interrupted and the concentrated LOXSH catalyst solution is carefully transferred to the previously weighed, clean, oven-dried and nitrogen purged glass receiver described above.EXAMPLES FOR FORMING CATALYST SOLUTIONS AND BLENDS OF SOUTIONS:

[0112] Unless otherwise indicated all solvents employed for forming the concentrated catalyst solutions and subsequent use are anhydrous grade or made anhydrous by drying over 4A molecular sieves. The polar modifier DMEA (99+%) was obtained from Aldrich Chemical company. The polar modifiers PiP and PsB were prepared by the inventors from piperidine and propylene oxide and 1,2-epoxybutane respectively. The preparation is described elsewhere. The purity of both PiP and PsB are >99%, and both comprise about 98 wt.% of the 1,2-isomer and about 2 wt.% of the 2,1-isomer. Hydrogen grade was generally high purity. Molecular sieves are activated under a stream of nitrogen at 280 °C. Alumina is used as received from the Aldrich Chemical company. For Examples 1-4, 10, and 11 two different composite samples comprising retain samples of 25 wt.% BuLi (~ 3 molar) in cyclohexaneoriginally obtained from Albemarle Corporation’s New Johnsonville, TN facility were used. For Examples 5-8. 12 and 13, these catalyst solutions utilized freshly obtained (Aldrich) 2 molar 16.5 wt.%) solutions in cyclohexane. In Example 9, a 21 wt.% blend of the New Johnsonville and Aldrich BuLi solutions was used. The rest of the Examples and all of the comparative application Examples utilized 20 wt.%2.5 molar) BuLi in cyclohexane obtained from Albemarle Corporation’s Langelsheim Germany facility.

[0113] When forming the LOXSH catalyst solutions of Examples 1-19 and 29-42 the hydrogen pressure was controlled externally by the hydrogen regulator on the hydrogen feedline bypassing the mass flow meter. The exact uptake of hydrogen was not monitored but in many cases was estimated by the pressure drop in the two-liter hydrogen head tank. When forming the LOXSH catalyst solutions of Examples 20-25, 27, 28, 43, 45-52 and 55 the mass flow meter and totalizer were used to control both the hydrogen feed rate and total amount of hydrogen fed, notwithstanding the amount of hydrogen in the hydrogenolysis reactor at 0 psig at the reaction temperature. Figures 6-13 provide the initial charge and total charge of hydrogen as well as feed rates employed for Examples 20-25, 27 and 28. Figures 19-22 provide the initial charge and total charge of hydrogen as well as feed rates employed for Examples 45, 50, 51 and 55. For Examples 43. 46-49, and 52 the amount of hydrogen initially charged and fed is listed below. Examples 26, 44, 53 and 54 are blends and are described further below.Initial H2 Initial Final average H2 Required amount H2Ex. charge Pressure Pressure feed rate Theoretical fed std. cm3std. cm3psig psig SCCM H2 std. cm343 1100 15 2963 12 64.0 3537 46 1150 16 5200 12 86.0 5480 47 1220 17 5000 17 129 4939 48 1000 14 7290 11 118 7318 49 1000 14 7090 11 108 7345 52 400 5 8900 6 119 8936

[0114] Example 14 is representative of the process technology of Examples 1-19 and entails the formation of 5 wt.% [DMEA]2Li3H in cyclohexane via regulation of the hydrogen pressure external to the hydrogenolysis reactor.

[0115] The solvent feed tank was charged with 550 ml of cyclohexane. The hydrogenolysis reactor was charged with 450 ml of the cyclohexane and warmed to 38.4°C by applying 40.0°C oil to the jacket. To the reactor was charged 33.00 g (0.370 mole) of DMEA further diluted wi th 40 g of cyclohexane via the charge vessel. The charge vessel and feed line were flushed wi th 40 ml of the cyclohexane. The hydrogen regulator external to the reactor was set to deliver at 25 psig. The hydrogenolysis reactor was pressured to 19 psig and then isolated from the hydrogen line. The agitator stir rate was adjusted to 1020 RPM. Meanwhile, two separate equal portions of BuLi were prepared in anitrogen purged glove box, each comprising 88.94 g (0.277 mole each, 0.555 mole total) of 20.0 wt.% BuLi further diluted with 40 g of cyclohexane. The first portion of BuLi was fed to the reactor from the charge vessel over a period of 20 minutes. During which time the temperature lined out at 41.9°C and the pressure built from 19 psig to 26 psig. The reactor temperature dropped to 37.7°C and the reactor was vented to 0 psig and then recharged with hydrogen to 26 psig. The second portion of BuLi was then fed to the reactor over a 32-minute period. After 11 minutes of feeding, the 2ndportion of BuLi wherein the reactor pressure increased from 26 psig to 29 psig and the temperature reached 41.3°C, the pressure began to drop and the valve to the hydrogen regulator was opened. Over the next 22 minutes of feeding the pressure in the hydrogenolysis reactor lined out at about 24 psig and the temperature lined out at about 40.5°C. During this time the pressure in the two-liter hydrogen head tank reserve dropped a total of 29.28 psig (0.179 mole of hydrogen of 0.185 theoretical). The feedlines were flushed with 40 ml cyclohexane. The reactor jacket was increased to 79° and the pressure increased to 57 psig. The total feed time required 58 minutes. At 92 minutes after the start of the feed the hydrogenolysis reactor was 70.3 °C and had a pressure of 72 psig. The reactor was vented, cooled to 60°C and the contents transferred to a 2000 ml receiver flask to yield 744 g of the concentrated catalyst solution.

[0116] Example 25 is representative of the process technology of Examples 21-25 and entails formation of 5.47 wt.% [DMEA]₂Li₃H in cyclohexane with controlled hydrogen feed rates and with high velocity subsurface hydrogen feed.

[0117] The solvent feed tank was charged with 520 ml of cyclohexane. The hydrogenolysis reactor was charged with 480 ml of the cyclohexane and cooled to 10.5°C by applying 8.0°C oil to the jacket. To the reactor was charged 66.047 g (0.741 mole) of DMEA further dilutedwith 42 g of cyclohexane via the charge vessel. The charge vessel and feed line were flushed with 20 ml of the cyclohexane. The hydrogen regulator external to the reactor was set to deliver at 32 psig. The hydrogenolysis reactor was pressured to 20 psig and then isolated from the hydrogen line. The agitator stir rate was adjusted to 1020 RPM. Meanwhile, three separate nearly equal portions of BuLi were prepared in a nitrogen purged glove box, each comprising on average 119.20 g (0.372 mole each, 1.077 mole total) of 20.0 wt.% BuLi further diluted with 67 g of cyclohexane. The actual individual 20 wt.% BuLi charges were 1st118.088 g. 2nd119.269 g and 3rd120.255 g. The first portion of BuLi comprising 23.6 g of BuLi (neat) was fed to the reactor from the charge vessel over a period of 30 minutes. During which time the temperature lined out at about 13.4°C but had reached a peak temperature of 13.9°C and the pressure built from 20 psig to 28 psig before venting to 0 psig and pressuring back to 21 psig. The second portion of BuLi comprising 23.9 g of BuLi (neat) was charged to the charge vessel and fed over another period of 34 minutes, during which time the pressure built to 31 psig, running at about 14.4°C. Upon completion of the feed, the feedline was rinsed with 20 ml of cyclohexane. During which time (4 minutes) the pressure dropped from 31 psig to 25 psig and the temperature dropped to 12.7°C this indicated that the [DMEA]Li had fully formed and that a portion of the catalyst had formed as result of the slightly unequal division of BuLi charges. The combined feeds required a total of 76 minutes. The estimated volume in the reactor at this point was 1030 ml and the LiDAME formed was about 8.54 wt.%.

[0118] The reactor was w armed to 18.3°C w ith 22 °C on the jacket. The third portion of BuLi comprising 24.1 g of BuLi (neat) was transferred to the charge vessel. The reactor was vented to 0 psig and then charged with 800 std. cm3of hydrogen. The third portion of BuLi was then fed to the reactor over a 42-minute period. Hydrogen was fed subsurface in 39 minutes, with the hydrogen feed starting and ending approximately 5 minutes before and after the third BuLi feed. When the feed w as completed, the feedlines were flushed with 20 ml cyclohexane. The estimated volume in the reactor at this point was 1275 ml and the [DMEA]₂Li₃H formed was about 7.72 wt.%. Figure 11 presents the pressure / temperature hydrogenolysis reaction profile. It also indicated how the hydrogen feed rate was adjusted over the course of the run. The reactor was then pressured to 15 psig and heated. For this run a variable hydrogen feed rate of 150 SCCM to as high as 275 SCCM, on average 205 SCCM was used. Correspondingly, thefeed velocity ranged from 40 ft / sec (12 m / sec) to 74 ft / sec (23 m / sec) and on average 55 ft / sec (17 m / sec). When the reactor temperature reached 74.7 °C the pressure was 27 psig. The reactor was vented, and the reaction mixture was further diluted with 300 ml of cyclohexane. The cooled reaction mixture (60°C) was transferred to a 2000 ml receiver flask. The reactor was further rinsed with 200 ml of cyclohexane. The combined reaction mixture and reactor rinse yielded 1340 g of the concentrated catalyst solution which was transferred to the nitrogen purged glove box. In the glove box the contents were transferred to a 2000 ml bottle and left to stir (magnetic stirring bar with PTFE coating removed) for 30 minutes to assure homogeneity. The entire operation was completed in about 4 hours.

[0119] Example 27 entails the formation of 5.51 wt.% high hydride content [DMEA]Li2H in cyclohexane with controlled hydrogen feed rates and with high velocity subsurface hydrogen feed.

[0120] The solvent feed tank was charged with 300 ml of cyclohexane. The hydrogenolysis reactor was charged with 200 ml of the cyclohexane and cooled to 10.6°C by applying 8.0°C oil to the jacket. To the reactor was charged 22.06 g (0.247 mole) of DMEA further diluted with 25 g of cyclohexane via the charge vessel. The charge vessel and feed line were flushed with 50 ml of the cyclohexane. The hydrogen regulator external to the reactor was set to deliver at 32 psig. The hydrogenolysis reactor was pressured to 25 psig and then isolated from the hydrogen line. The agitator stir rate was adjusted to 1050 RPM. Meanwhile, two separate nearly equal portions of BuLi were prepared from each comprising on average 81.61 g (0.255 mole each, 0.510 mole total) of 20.0 wt.% BuLi. The first portion of BuLi comprising 16.34 g of BuLi (neat) was fed without further dilution to the reactor from the charge vessel over a period of 19.0 minutes. During which time the temperature lined out at about 12°C but had reached a peak temperature of 13.1°C and the pressure built from 25 psig to 30 psig. Upon completion of the feed the feed line was rinsed with 20 ml of cyclohexane. During which time (4 minutes) the pressure dropped from 30 psig to 27 psig and the temperature dropped to 10.5°C this indicated that the [DMEA]Li had fully formed and that a portion of the catalyst had formed.

[0121] The reactor w as warmed to 18.3°C with 22.5°C on the jacket. The second portion of BuLi comprising 16.58 g of BuLi (neat) w as further diluted w ith 67g of cyclohexane and then transferred to the charge vessel. The reactor was vented to 0 psig and then charged with 1600std. cm3of hydrogen and the jacket temperature set to 20°C. The second portion of BuLi was then fed to the reactor over a 42-minute period. Hydrogen was fed subsurface in 39 minutes, with the hydrogen feed starting and ending approximately 5 minutes before and after the second BuLi feed. After half of the BuLi had been fed the jacket and temperature controller were adjusted to higher temperatures such that the reaction temperature gradually allowed to increase. The peak temperature in the reactor was 25.6°C. When the feed was completed, the feedline was flushed with 60 ml cyclohexane. Figure 12 presents the pressure / temperature hydrogenolysis reaction profile. For this run a constant feed rate of 175 SCCM was maintained corresponding to 40 ft / sec (12 m / sec) feed velocity. It also indicated how- the hydrogen feed rate and reaction temperature was adjusted over the course of the run. The reactor was heated to 74°C, vented, cooled to 60°C, and then transferred to a 1000 ml receiver flask to yield 463 grams of the high hydride LOXSH catalyst concentrate.

[0122] Example 28 entails the formation of 4.87 wt.% of the very high hydride content [DMEA]Li3H2 in cyclohexane with controlled hydrogen feed rates and with high velocity subsurface hydrogen feed.

[0123] The solvent feed tank was charged with 250 ml of cyclohexane. The hydrogenolysis reactor was charged with 200 ml of the cyclohexane and cooled to 10.6°C by applying 8.0°C oil to the jacket. To the reactor w-as charged 22.04 g (0.247 mole) of DMEA further diluted with 30 g of cyclohexane via the charge vessel. The charge vessel and feed line were flushed with 20 ml of the cyclohexane. The hydrogen regulator external to the reactor was set to deliver at 32 psig. The hydrogenolysis reactor was pressured to 23 psig and then isolated from the hydrogen line. The agitator stir rate was adjusted to 1050 RPM. Meanwhile, two separate portions of BuLi were prepared. The first portion of BuLi comprising 79.988 g (16.00 g neat, 0.249 mole) of 20 wt.% BuLi further diluted with 41 g of cyclohexane. This solution was fed to the reactor from the charge vessel over a period of 21.0 minutes. During which time the temperature lined out at about 12.5°C but had reached a peak temperature of 13.0°C and the pressure built from 23 psig to 29 psig. Upon completion of the feed the feed line w as rinsed with 10 ml of cyclohexane. During which time (4 minutes) the pressure dropped from 29 psig to 27 psig and the temperature dropped to 10.5°C this indicated that the [DMEA]Li had fully formed and that a portion of the catalyst had formed.

[0124] The reactor was warmed to 18.3°C with 22.5°C on the jacket. The second portion of BuLi formed from 159.161 g (31.83 g neat, 0.497 mole) was further diluted with 27 of cyclohexane and then transferred to the charge vessel. The reactor was vented to 0 psig and then charged with 1600 std. cm3of hydrogen and the jacket temperature set to 20°C. The second portion of BuLi was then fed to the reactor over a 62-minute period. Hydrogen was fed subsurface in 64 minutes, with the hydrogen feed starting and ending approximately 5 minutes before and after the second BuLi feed. After one third and after two thirds of the BuLi had been fed the jacket temperature as well reaction temperature was gradually increased. The peak temperature in the reactor was 26.7°C during the co-feed. When the feed was completed, the feedline was flushed with 20 ml cyclohexane. Figure 13 presents the pressure / temperature hydrogenolysis reaction profile. It also indicated how the hydrogen feed rate and reaction temperature were adjusted over the course of the run. For this run a constant feed rate of 175 SCCM was maintained corresponding to 47 ft / sec (14 m / sec) feed velocity. The reactor was heated to 32°C and then to 74°C, vented, cooled to 60°C, and then transferred to a 1000 ml receiver flask to yield 544 grams of the very high hydride LOXSH catalyst concentrate.

[0125] Example 36 is representative of the process technology of Examples 29-42 and entails formation of 9.83 wt.% [PsB^LisH in cyclohexane via regulation of the hydrogen pressure external to the hydrogenolysis reactor.

[0126] The solvent feed tank was charged with 800 ml of cyclohexane. The hydrogenolysis reactor was charged with 600 ml of the cyclohexane and cooled to 9.8°C by applying 8.0°C oil to the jacket. To the reactor was charged 113.17 g (0.720 mole) of PsB further diluted with 50 g of cyclohexane via the charge vessel. The charge vessel and feed line were flushed with 50 ml of the cyclohexane. The hydrogen regulator external to the reactor was set to deliver at 32 psig. The hydrogenolysis reactor was pressured to 21 psig and then isolated from the hydrogen line. The agitator stir rate was adjusted to 1020 RPM. Meanwhile, three separate nearly equal portions of BuLi were prepared in a nitrogen purged glove box, each comprising on average 114.96 g (0.239 mole each, 1.077 mole total) of 20.0 wt.% BuLi further diluted with 50 g of cyclohexane. The actual individual 20 wt.% BuLi charges were 1st115.373 g, 2nd115.260 g and 3rd114.255 g. The first portion of BuLi comprising 23.1 g of BuLi (neat) was fed to the reactor from the charge vessel over a period of 32 minutes. During which time the temperaturelined out at about 15°C but had reached a peak temperature of 17.9°C and the pressure built from 21 psig to 28 psig before venting to 10 psig and pressuring back to 19 psig. The second portion of BuLi comprising 23.0 g of BuLi (neat) was charged to the charge vessel and fed over another period of 20 minutes, during which time the pressure built to 28 psig, running at about 16°C with a peak temperature of 18.5°C. The reactor was vented to 0 psig and repressured to 20 psig after 6 minutes into the second feed. The balance of the feed was made over 14 minutes during which time the pressure increased to 25 psig and the temperature lined out at 15.7°C. Upon completion of the 2ndfeed, the jacket temperature was increased to 44°C. The combined feeds required a total of 64 minutes.

[0127] As the reactor was warmed to 42.2°C over a 32-minute period, the third portion of the BuLi was transferred to the charge vessel. During the warming the pressure the hydrogen pressure did not build but remained constant at 25 psig except when it dropped to 24 psig when the temperature reached 37.1°C. Further warming to 42.1°C restored the pressure to 25 psig -this indicated that the [PsB]Li had fully formed and that a portion of the catalyst had formed at or around 37 °C as result of the slightly unequal division of BuLi. When the reactor temperature reached 42.6°C in the hydrogenolysis reactor, 72 minutes from the start of the feed, the reactor was vented to 0 psig and then pressured up to 31 psig hydrogen leaving the hydrogen line open to the reactor. The third portion of BuLi was then fed to the reactor over a 36-minute period. After 6 minutes of feeding the third portion of BuLi, the reactor pressure decreased from 31 psig to 26 psig and the temperature reached 43.2°C. Over the next 30 minutes of feeding the pressure in the hydrogenolysis reactor lined out at about 26 psig and the temperature lined out at about 44.0°C (the regulator setting of 31 psig could only maintain a pressure of 26 psig with the rate of catalyst formation). After 32 minutes of feeding the pressure began to increase reaching 27 psig with a temperature of 44.5°C as the rate of catalyst formation slowed. When the feed was complete the pressure had returned to 31 psig and the temperature was 43.8 psig. The feedlines were flushed with 200 ml cyclohexane during which time the pressure in the hydrogen feed tank continued to drop as the hydrogenolysis reaction continued. The reactor jacket was increased to 79° and the pressure increased to 57 psig and isolated from the hydrogen tanks. The total feed and line flush time required 45 minutes. At about 70 minutes after the start of the third feed the hydrogenolysis reactor was 70.3 °C and had apressure of about 70 psig. The reactor was vented, cooled to 60°C and the contents transferred to a 2000 ml receiver flask to yield 1224 g of the concentrated catalyst solution.

[0128] Example 45 is representative of the process technology of Examples 43, 45-52 and 55 and entails formation of 10.9 wt.% [PsB^LisH in cyclohexane wherein for this Example a controlled hydrogen feed rate with a deficiency of total hydrogen fed was utilized - the ending reactor pressure was -1 psig.

[0129] The solvent feed tank was charged with 430 ml of cyclohexane. The hydrogenolysis reactor was charged with 350 ml of the cyclohexane and cooled to 10.4°C by applying 8.0°C oil to the jacket. To the reactor w as charged 76.428 g (0.486 mole) of PsB further diluted with 38 g of cyclohexane via the charge vessel. The charge vessel and feed line were flushed with 20 ml of the cyclohexane. The hydrogen regulator external to the reactor was set to deliver at 30 psig. The hydrogenolysis reactor was pressured to 15 psig and then isolated from the hydrogen line. The agitator stir rate was adjusted to 1020 RPM. Meanwhile, two separate portions of BuLi were prepared. The first was prepared with 155.67 g (31.135 g neat, 0.486 mole) further diluted with 40 g cyclohexane. The second was prepared with 77.837 g (15.570 g neat, 0.243 mole) further diluted with 72 g cyclohexane. The first portion of BuLi was fed to the reactor from the charge vessel over a period of 50 minutes. During which time the temperature lined out at about 15.5°C but had reached a peak temperature of 16.0°C and the pressure built from 15 psig to 23 psig. The feedline was flushed with 30 ml cyclohexane.

[0130] As the reactor was warmed to 44-4 43 °C, 72 minutes since the start of the feed, the reactor was vented to 0 psig and then charged with 200 std. cm3of hydrogen. The second portion of BuLi was then fed to the reactor over a 35-minute period. The feedlines w ere flushed with 40 ml cyclohexane. Figure 19 presents the pressure / temperature hydrogenolysis reaction profile. It also indicates how the hydrogen feed rate was adjusted over the course of the run. All total deficiency of hydrogen was charged hence at the end of the run the reactor pressure w as negative (-1 psig) despite the volume of solvent and reagent added to the condensed phase during the 3rdBuLi feed. The reactor was then pressured to 15 psig and heated. When the reactor temperature reached 74.7 °C the pressure was 27 psig. The reactor was vented, cooled to 60°C and the contents transferred to a 2000 ml receiver flask to yield 747 g of the concentrated catalyst solution. The entire operation was completed in about 3 hours.

[0131] Example 55 is representative of the process technology7of forming a 9.06 wt.% [PsB]2Li3H in cyclohexane from a preformed 10.0 wt.% [PsB]Li solution with a controlled hydrogen feed rate.

[0132] The hydrogenolysis reactor was charged via the charge vessel with 382.36 g of a cyclohexane solution of [PsBJLi comprising 39.5 g (0.242 mole) [PsBJLi previously formed from PsB and lithium metal. The line was flushed with 10 ml of cyclohexane. The hydrogenolysis reactor was warmed to 43.1°C, vented to 0 psig and then charged with 600 std. cm3of hydrogen. A solution of BuLi comprising 38.993 g (7.80 g neat, 0.121 mole) was then fed to the reactor over a 10-minute period. The feedlines were flushed with 10 ml cyclohexane. Figure 22 presents the pressure / temperature hydrogenolysis reaction profile showing the hydrogenolysis reactor pressure as 2250 std. cm3was fed at a rate of 75 SCCM. A slight excess of hydrogen was charged, 2850 std. cm3vs. the theoretical portion of 2727 std. cm3. Upon completion of the feed and ride the pressure in the reactor was 6 psig vs. the starting pressure of 5 psig. The reactor was then pressured to 15 psig and heated. When the reactor temperature reached 74.7 °C the pressure was 27 psig. The reactor was vented however no solvent distilled due to the low butane content. The solution was cooled to 60°C and the contents transferred to a 1000 ml receiver flask to yield 446 g of the concentrated catalyst solution. The entire operation was completed in about 1.5 hours.

[0133] Examples 26, 44. 53 and 54 are blends.

[0134] Example 26 comprising 5.04 wt.% [DMEA]2Li3H (257.8 ppm hydride ion NMR titration vs. 258.7 calculated) was formed by blending in a nitrogen purged glove box 1320 g of Example 25 with 1272 g of Example 24 and further dilution with 255 g of cyclohexane.

[0135] Example 44 comprising 10.02 wt.% [PsB]2Li3H (280.6 ppm hydride ion NMR titration vs. 299.7 ppm calculated) was formed by blending in a nitrogen purged glove box 291.0 g of Example 42 (226.6 ppm hydride ion NMR titration vs. 229.3 calculated) and 223.2 g of Example 43 (400.4 ppm hydride ion NMR titration vs. 392.04 calculated) into a one-liter bottle.

[0136] Examples 53 and 54 comprising 10.14 % [PsB]2Li H (on average 314.8 ppm hydride ion NMR titration vs. 318.0 ppm calculated) were each formed from 500 ml of Examples 49-52. Example 53 comprises 322.0 ppm hydride (NMR titration) and Example 54 comprises 307.5 ppm hydride (NMR titration). The difference between the two blends is the result of the inexactness of the volumetric measurements of the portions of the samples blended.General Procedure for Testing the Concentrated LOXSH Catalyst as Hydrogen Mediated Anionic Polymerization Catalyst

[0137] For hydrogen mediated polymerizations, a heel of anhydrous solvent is formed in the reactor to which the catalyst solution is charged. A predetermined amount of the preformed LOXSH catalyst solution is charged to the charging vessel which is maintained under a nitrogen blanket via cannula by means of positive nitrogen pressure. The LOXSH catalyst solution is then transferred to the polymerization reactor through a fine metering Vernier handle single pattern needle valve. The metering valve is coupled to the inlet valve on the reactor’s dip-leg by means of a short port connect fitting and further connected to the charge vessel via an 8-inch length of thick walled 1 / 8” PTFE tubing. The translucent tubing acts as a sight glass such that the operator can monitor the transfer of the catalyst solution to the reactor and thereby eliminate the introduction of nitrogen by closing a block valve once nitrogen is seen in the line.

[0138] In order to remove any water and to remove the tert-butyl catechol inhibitor present in the monomer, the monomer is fed at predetermined constant rates sequentially through 1) a column containing activated 4A molecular sieves; and then 2) basic alumina column (0.5” O. D columns with 60-325 mesh AI2O3). The autoclave reactor is heated with oil having a temperature set point at or generally just around ± 1°C to ± 5°C of the desired reaction temperature (depending on the feed rate) and the reaction temperature was tightly maintained at the predetermined set point once the reactor temperature controller lined out (generally for a period no longer than the first 10 to 20 minutes of the monomer feed depending on the monomer and the monomer feed rate). At the outset, the reaction temperature might have brief excursions in temperature generally no more than 5°C above the desired set-point temperature.

[0139] For the purpose of the application tests, styrene (1040 g, 10 mole) is fed via high pressure metering pump at a rate of 10.00 ml / min from a tank under a nitrogen blanket on a weigh scale sequentially through 1) a column containing activated 22 g 4A molecular sieves; and then 2) basic activated Brockman I alumina column (0.5” O. D columns with 14 g of 60-325 mesh AI2O3. The feed is delivered to the polymerization reactor subsurface and is delivered by a 1 / 16-inch O. D. subsurface monomer feed line having a 0.01” i.d. terminal section directed at the bottom impeller. Hydrogen is co-fed through a 1 / 16-inch O. D. subsurface hydrogen feed line having a 0.01” i d. terminal section directed at the bottom impeller.

[0140] For the purpose of the application tests butadiene is fed at a rate of 3.0 g / min. Accordingly, liquid butadiene 550 g to 610 g is charged to the PTFE-lined charging tank on a weigh scale. The tank is then further pressured with hydrogen. The pressure in the tank is maintained at 30 to 70 psig depending on the hydrogen / butadiene combined pressure in the polymerization reactor; the back pressure is adjusted as needed to feed butadiene at a constant rate to the reactor wherein the autogenous pressure of the reaction mixture has developed. Ideally the pressure drop across the feed system from the tank to the reactor at steady state is about 20 psi. The liquid butadiene is transferred from the charge tank to the reactor though 1 / 16-inch O. D. stainless steel tubing. During the transfer the butadiene is passed sequentially through a column of activated 4A molecular sieves (16 g) and then through a column of basic activated Brockman I alumina (10.5 g) and fed to the headspace of the polymerization reactor through a 4-inch 1 / 16-inch O. D., 0.01-inch I. D. stainless steel tube, this back pressure that prevents flashing / vaponzation of the butadiene through the metering valve. The butadiene feed rate of 3.0 grams / minute and is controlled with a stainless-steel low flow double pattern metering valve (Swagelok part number SS-SS2-D). Hydrogen is fed either to the headspace or through a 1 / 16-inch O. D. subsurface monomer feed line having a 0.02” i.d. terminal section directed at the bottom impeller.Application Example 14: representative of Application Examples 1-14 wherein DMEA based concentrated LOXSH catalyst solutions are tested as HMAPS catalyst.

[0141] The autoclave (polymerization reactor) is charged with 150 ml of a blend of ethylbenzene 13.2 wt.% and cyclohexane 86.8 wt.% from the solvent tank. The reactor is heated to 35.1°C by means of 40°C oil on the jacket and the hydrogen pressure adjusted to 18 psig. The LOXSH catalyst solution of Example 19 (57.582 g) comprising 6.73 wt.% LOXSH catalyst as [DMEA]3[MeOP]LieH2 in cyclohexane is weighed in a nitrogen purged glove box into a 250 ml pear-shaped glass flask. The solution is further diluted with 100 g ofethylbenzene. The pear-shaped flask is sealed with a rubber septum and transported to the reactor. The LOXSH catalyst solution is transferred (double tipped needle) to the nitrogen blanketed charging vessel via positive nitrogen pressure. With the reactor solution stirring at 1020 RPMs, the catalyst solution is transferred to the polymerization reactor with 60 psig nitrogen back pressure. During this period of time the reactor pressure will generally increase 2 PSI due to the added condensed phase volume. The charging line is then flushed with 50 ml of methylcyclohexane to assure all of the catalyst solution is in the reactor. Care is taken to exclude as much nitrogen as is practical from the reactor during the transfer from, and rinse of the catalyst charge vessel. The jacket temperature is changed to 84°C and the reactor is pressured with hydrogen to 53 psig. Upon reaching 78.4°C, about 60 minutes, the pressure is typically 70 psig within the polymerization reactor. The reactor is vented to atmospheric pressure and then charged with 1300 standard cubic centimeters of hydrogen gas, 12 psig. The polymerization reactor’s oil jacket temperature is then set to 80°C.

[0142] Meanwhile styrene (1040.0 g, 10.0 mole) is charged to the monomer feed tank. The line from the tank, through the molecular sieve and alumina column is flushed with cyclohexane to remove all gases. The mass flow meter hydrogen flow rate is set to 330.4 SCCM with atotal charge of hydrogen to be fed set for 38,300 standard cubic centimeters. The hydrogen feed velocity is 356 ft / sec (109 m / sec). Styrene is fed to the reactor at a rate of 9.09 g / min (10.00 ml / min) with a feed velocity of 11 ft / sec (3 m / sec). At the start of the run the temperature, pressure, line-pressure on the butadiene feed, scale reading, and reactor agitator RPMs are recorded. These values are constantly monitored throughout the course of the hydrogen mediated polymerization reaction. Data is collected every 5 minutes for the first 50 minutes, then every 10 minutes between 50 minutes and 100 minutes of feeding and again every' 5 minutes until the polymerization reaction is deemed complete (typically 130 minutes from start of feed). Figure 5 presents the polymerization reaction pressure / temperature profiles for Application Ex. 9-14.

[0143] At the end of the styrene feed, the monomer feed line to the reactor, including the mole sieves and alumina columns, were flushed with 50 ml of anhydrous solvent. The styrene feed and flush to the reactor was deemed complete when no further heat of reaction was observed generally signified by the permanent closing of the automated control valve on the coiling coils.The unquenched polymerization reaction mixture was transferred with positive H2 pressure to the wash vessel previously heated (N2 atmosphere) and previously charged with 4.67 g H2SO4 dissolved in 400 g H2O water and 400 ml of recovered solvent. The stirring during the quench is kept at a slow rate such that the phases do not mix during the transfer. Upon completion of the transfer and a 200 ml rinse of the reactor, the agitation rate is increased to ensure intimate contact of the two phases as the mixture is warmed to 70°C. The phases are separated, and the product mixture is washed a second time with 400 ml of fresh water.

[0144] The water washed product mixture was stripped in the wash reactor of cyclohexane and some of the ethylbenzene by normal distillation while gradually heating the wash reactor’s jacket temperature to 165°C. The distillation was deemed complete when the pot temperature reached a temperature above 140°C. The HMAPS product solution was allowed to cool before collecting the HMAPS solution. The HMAPS solution was then further stripped of ethylbenzene with the use of a wiped film evaporator (WFE, 2” glass Pope Still, operated at 50.0 mmHg vacuum, 140°C, wiper speed 60% of full rate, feeding at 1.0 liters / hr). The WFE operation produced 1010 g (97.1%) HMAPS distribution having GPC MWD including dimer of Mn: 706, Mw: 1149, Mz: 1700, PD: 1.627, an= 559, an3= 2.085.Application Example 24: representative of Application Examples 15-26 wherein DMEA based concentrated LOXSH catalyst solutions are tested as HV-HMPBD catalyst.

[0145] The autoclave (polymerization reactor) is charged with 250 ml of methylcyclohexane and placed under 26 psig hydrogen atmosphere and 42°C by means of 44°C oil on the jacket. The LOXSH catalyst solution (70.818 g) comprising 5.04 wt.% [DMEA]2Li3H LOXSH catalyst in cyclohexane is weighed in a nitrogen purged glove box into a 250 ml pear-shaped glass flask. The solution is further diluted with 45 g of cyclohexane. The pear-shaped flask is sealed with a rubber septum and transported to the reactor. The LOXSH catalyst solution is transferred (double tipped needle) to the charging vessel via positive nitrogen pressure. With the reactor solution stirring at 1000 RPMs, the catalyst solution is transferred to the polymerization reactor with 60 psig nitrogen back pressure. During this period of time the reactor pressure will generally increase 2-4 PSI due to the added condensed phase volume. The charging line is then flushed with 50 ml of methylcyclohexane to assure all of the catalystsolution is in the reactor. Care is taken to exclude as much nitrogen as is practical from the reactor during the transfer from, and the rinse of, the catalyst charge vessel. The jacket temperature is changed to 78°C. Upon reaching 72.2°C the reactor pressure is typically 48 psig. The reactor is vented to atmospheric pressure and then charged with 325 standard cubic centimeters of hydrogen gas, resulting in a hydrogen atmosphere of 2 psig.

[0146] Meanwhile butadiene (599.0 g, 11.07 mole) is charged to the butadiene feed tank. The line from the tank, through the molecular sieve and alumina column is flushed with cyclohexane to remove all gases. The mass flow meter hydrogen flow rate is set to 68.95 SCCM with a total charge of hydrogen to be fed set for 13,125 standard cubic centimeters. At the start of the run the temperature, pressure, line-pressure on the butadiene feed, scale reading, and reactor agitator RPMs are recorded. These values are constantly monitored throughout the course of the hydrogen mediated polymerization reaction. Data is collected every 5 minutes for the first 40 minutes, then every 10 minutes between 50 minutes and 190 minutes of feeding and again every 5 minutes until the polymerization reaction is deemed complete (typically 220 minutes from start).

[0147] At time equals zero, the butadiene (back pressure 40 psig) is transferred to the polymerization reactor through the dry ing columns to the headspace of the reactor. The targeted flow- rate is 3.0 grams / min. This flow rate is controlled with the double pattern metering valve. At about 4 minutes of feeding (12.0 grams of butadiene out of the feed tank), butadiene has reached the reactor. This is signified with a slight increase in both pressure and temperature. After 10 minutes of feeding the hydrogen mass flow meter is set such that the flow7of hydrogen (68.95 SCCM) begins which will not end until 13,125 std. cm3is fed. The molar ratio of butadiene to hydrogen (initial charge and total fed) is 18.45. The total feed time of butadiene is 199.67 minutes, and the feed time of the hydrogen is 190.3 minutes. During which the autogenous pressure is typically 14-17 psig, 16 psig on average, and the temperature is 72°C. Upon completion of the butadiene feed, the valve on the bottom of the butadiene feed tank is closed and the feed line including the columns are flushed with 50 mis of cyclohexane (4.0 ml / min) into the reactor. The reactor pressure and temperature are monitored until the reaction is deemed complete. See Figure 16 for comparison of pressure temperature polymerization reaction profiles.

[0148] The polymerization reactor is then charged with hydrogen to 25 psig to reduce any living butadiene chains and to provide pressure for the transfer to the quench / wash reactor. The wash reactor is previously charged with 600 mis of recovered solvent from a previous run and 400 mis of fresh tap water containing 3.89 g formic acid at room temperature. The transfer the hot reaction mixture (72 °C) warms the gently stirred quench / wash solution. Upon completion of the transfer and quench the polymerization reactor and transfer line to the wash reactor, are flushed with 100 ml of cyclohexane. The temperature of the wash reactor jacket is increased to 90°C and the rate of mixing is increased such that there is intimate contact between the quenched reaction mixture and the acidic wash solution. The mixing is continued for 20 to 30 minutes as the two-phase solution warms to 70°C. Mixing is interrupted and 400 ml of pH = 7 wash water is removed. Agitation is returned while 400 ml of fresh tap water is introduced to the wash vessel. After a 15-minute contact time mixing is again stopped and 400 ml of pH = 7 wash water is removed.

[0149] The jacket temperature is increased to 120°C, then to 135°C and finally 150°C as a mixture comprising cyclohexane and methylcyclohexane as well as some dimers and trimers of polybutadiene is distilled from the product mixture at atmospheric pressure. The ending pot temperature is 130°C. The product mixture (typically 730 ± 20 g) is further stripped in a 2” wiped film evaporator (Pope Still, feed rate of 1000 ml / hour, with conditions of 70% of full speed wiper rotation. 135°C jacket temperature, and 100 mmHg vacuum). A total of about 150 g of solvent and other light ends are taken overhead leaving 575.03 g (96% yield) of high vinyl hydrogen mediated polybutadiene (HMPBD) productApplication Example 43: representative of Application Examples 27-57 wherein PsB based concentrated LOXSH catalyst solutions are tested as LV -HMPBD catalyst.

[0150] The autoclave (polymerization reactor) is charged with 200 ml of methylcyclohexane and placed under 38 psig hydrogen atmosphere and 40-42°C by means of 44°C oil on the jacket. The LOXSH catalyst solution (72.5 g) comprising 9.8 wt.% LOXSH catalyst in cyclohexane is weighed in a nitrogen purged glove box into a 250 ml pear-shaped glass flask. The solution is further diluted with 38 g of cyclohexane. The pear-shaped flask is sealed with a rubberseptum and transported to the reactor. The LOXSH catalyst solution is transferred (double tipped needle) to the charging vessel via positive nitrogen pressure. With the reactor solution stirring at 1000 RPMs. the catalyst solution is transferred to the polymerization reactor with 60 psig nitrogen back pressure. During this period of time the reactor pressure will generally increase 2 PSI due to the added condensed phase volume. The charging line is then flushed with 50 ml of methylcyclohexane to assure all of the catalyst solution is in the reactor. Care is taken to exclude as much nitrogen as is practical from the reactor during the transfer from, and rinse of, the catalyst charge vessel. The jacket temperature is changed to 90°C and the reactor is pressured with hydrogen to 48 psig. Upon reaching 84°C the reactor pressure is typically 62 psig. The reactor is vented to atmospheric pressure and then charged with 425 standard cubic centimeters of hydrogen gas. The polymerization reactor's oil jacket temperature is then set to 104°C and heated to a temperature of 95°C. The reactor pressure is typically 6 psig.

[0151] Meanwhile butadiene (606.5 g, 11.2 mole) is charged to the butadiene feed tank. The line from the tank, through the molecular sieve and alumina column is flushed with cyclohexane to remove all gases. The mass flow meter hydrogen flow rate is set to 68.7 SCCM with a total charge of hydrogen to be fed set for 13,425 standard cubic centimeters. At the start of the run the temperature, pressure, line-pressure on the butadiene feed, scale reading, and reactor agitator RPMs are recorded. These values are constantly monitored throughout the course of the hydrogen mediated polymerization reaction. Data is collected every 5 minutes for the first 40 minutes, then every 10 minutes between 50 minutes and 200 minutes of feeding and again every’ 5 minutes until the polymerization reaction is deemed complete (typically 235 minutes from start).

[0152] At time equals zero, the butadiene (back pressure 50 psig) is transferred to the polymerization reactor through the dry ing columns to the headspace of the reactor. The targeted flow rate is 3.0 grams / min. This flow rate is controlled with the double pattern metering valve. At about 4 minutes of feeding (12.0 grams of butadiene out of the feed tank), butadiene has reached the reactor. This is signified with a slight increase in both pressure and temperature (see reactor temperature and pressure profile above). After 6 minutes of feeding the hydrogen mass flow meter is reset such that the flow of hydrogen (68.7 SCCM) begins. The molar ratio of butadiene to hydrogen (initial charge and total fed) is 18.14. The total feedtime of butadiene is 202 minutes, and the feed time of the hydrogen is 195.4 minutes. During which time the autogenous pressure is typically 39-41 psig and the temperature is 101°C (see Figure 23 for reaction temperature pressure profile). Upon completion of the butadiene feed, the valve on the bottom of the butadiene feed tank is closed and the feed line including the columns are flushed with 50 mis of cyclohexane (4.0 ml / min) into the reactor. The reactor pressure and temperature are monitored until the reaction is deemed complete. See Figure 23 for comparison of pressure temperature polymerization reaction profiles.

[0153] The polymerization reactor is then charged with hydrogen to 25 psig to reduce any living butadiene chains and to provide pressure for the transfer to the quench / wash reactor. The wash reactor is previously charged with 200 mis of recovered solvent from a previous run and 400 mis of fresh tap water containing 5.85 g of 98% sulfuric acid at room temperature (1.5 wt.% H2SO4). During the transfer the hot reaction mixture (100 °C) warms the gently stirred quench / wash solution. Upon completion of the transfer and quench the polymerization reactor and transfer line to the wash reactor, are flushed with 100 ml of cyclohexane. The temperature of the wash reactor jacket is increased to 90°C and the rate of mixing is increased such that there is intimate contact between the quenched reaction mixture and the acidic wash solution. The mixing is continued for 20 to 30 minutes as the two-phase solution warms to 70°C. Mixing is interrupted and 400 ml of pH = 4 wash water is removed. Agitation is returned while 400 ml of fresh tap water is introduced to the wash vessel. After a 15-minute contact time mixing is again stopped and 400 ml of pH = 7 wash water is removed.

[0154] The jacket temperature is increased to 120°C, then to 135°C and finally 145°C as a mixture comprising cyclohexane and methylcyclohexane as well as some dimers and trimers of poly butadiene is distilled from the product mixture at atmospheric pressure. The ending pot temperature is 130°C. For the sake of convenience, the product mixture (740 g) is further stripped in a 2” wiped film evaporator (Pope Still, feed rate of 1000 ml / hour, with conditions of 70% of full speed wiper rotation, 135°C jacket temperature, and 100 mmHg vacuum). A total of 150 g of solvent and other light ends are taken overhead leaving 588 g (97% yield) of hydrogen mediated polybutadiene (HMPBD) product.

[0155] Components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another component, a solvent, or etc ). It matters not what chemical changes, transformations and / or reactions, if any, take place in the resulting mixture or solution as such changes, transformations, and / or reactions are the natural result of bringing the specified components together under the conditions called for pursuant to this disclosure. Thus, the components are identified as ingredients to be brought together in connection with performing a desired operation or in forming a desired composition. Also, even though the claims hereinafter may refer to substances, components and / or ingredients in the present tense ("comprises", "is", etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, blended or mixed with one or more other substances, components and / or ingredients in accordance with the present disclosure. The fact that a substance, component or ingredient may have lost its original identity through a chemical reaction or transformation during the course of contacting, blending or mixing operations, if conducted in accordance with this disclosure and with ordinary skill of a chemist, is thus of no practical concern.

[0156] Each and every patent or publication referred to in any portion of this specification is incorporated in toto into this disclosure by reference, as if fully set forth herein.

[0157] This disclosure is susceptible to considerable variation in its practice. Therefore, the foregoing description is not intended to limit, and should not be construed as limiting, the disclosure to the particular exemplifications presented hereinabove.

[0158] It is to be understood that the embodiments and claims disclosed herein are not limited in their application to the details of construction and arrangement of the components set forth in the description and illustrated in the drawings. Rather, the description and the drawings provide examples of the embodiments envisioned. The embodiments and claims disclosed herein are further capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purposes of description and should not be regarded as limiting the claims.

[0159] Accordingly, those skilled in the art will appreciate that the conception upon which the application and claims are based can be readily utilized as a basis for the design of other structures, methods, and systems for carrying out the several purposes of the embodiments and claims presented in this application. It is important, therefore, that the claims be regarded as including such equivalent constructions.Table 1: Intial screening Examples to determine DMEA based LOXSH catalyst solubility and stability.Example 1 2 3 4 5 6 7 wt.% n-BuLi 248% 248% 248% 248% 165% 165% 165% Press. Cat. Formed24 to 28 to 20 5 to 10 Venting as needed (psig)Temperature 38-42 38-42 38-42 15-22 15-24 17-24 17-24 Post Reactionheat to 75 °C 55 psig H2transfer transfer transfer transfer ConditionsHydride content (ppm) 89.5 131 2 168.5 165.0 212.5 254.6 327.5 LiH content (ppm) 706 1034 1329 1301 1676 2008 2583 wt of all solv. to415 306 302 305 275 284 246 reactor (g)Volume (ml) of CH* 532 392 387 391 352 364 315 Calculated total wt445 338 345 348 357 400 394 (g)Weight out 450 331 349 358 352 399 398 Reactor at Start (ml) 300 250 250 250 250 299 280 Flush of lines (ml) 100 50 60 50 50 50 25 DMEA (CH) g 25 12 10 10 16 7 4 Butyllithium added100 77 64 78 32 6 5 CH mlTarget Wt.% DMEA 1.59% 2.23% 2.91% 2.88% 3.53% 4.51% 5.85% DMEA (g) 7.050 7.520 10.017 10.035 12.600 18.023 23.050 DMEA (mole) 0079 0084 0 112 0 113 0141 0202 0259 wt.% [DMEA] Li 1.69% 2.37% 3.10% 3.08% 377% 4.81% 6.24% wt % as1 761% 2.472% 3.23% 3.20% 3.92% 5.01% 6.49% [DMEA]2Li3Hmole Alkali Metal / 1.505 1.510 1.519 1.521 1.525 1.499 1.500 mole PMn-Butyllithium vol, ml 3968 42.47 56.90 57.06 107.78 151.53 193.95 BuLi mole 0.1190 0.1274 0.1707 0.1712 0.2156 0.3031 0.3879 Mass of BuLi solution30.750 32.910 44.090 44.217 83.690 117.662 150.598 gBuLi neat mass, g 7.63 8.16 10.93 10.97 13.81 19.41 24.85 * Not including CH in BuLiTable 2: Intial screening Examples to determine DMEA based LOXSH catalyst solubility and stability.Example 8 9 10 11 12 13 wt% n-Butyllithium 16.5% 21.0% 24.5% 24.5% 16.5% 16.5% Pressure range Catalyst 5 to 10 Venting as _..., „ _,.,,hRegulator at 10 Regulator at 14 to 20 formed neededTemperature 11-19 11-30 10-30-22 10-30-17 10-25-36 10-25-43 Hydride content (ppm) 390.7 455.3 522.2 587.8 491.5 960.1 LiH content (ppm) 3082 3591 4119 4636 3876 7572 wt of all solv. to reactor209 250 444 612 244 171 (g)Volume (ml) of CH* 268 321 570 786 313 220 Calculated total wt (g) 377 407 701 917 419 412 Weight out 377 385 706 913 416 402 Reactor at Start (ml) 210 200 340 300 250 200 Flush of lines (ml) 45 25 70 300 50 20 DMEA (CH) g 5 0 25 25 0 0 Butyllithium added CH ml 6 96 128 154 13 0 Butyllithium CH (g) 5 75 100 120 10 0 volume total solution (ml) 465 503 866 1132 518 508 Target Wt.% DMEA 6.909% 8.15% 8.20% 4.79%** 4.316% 4.154% DMEA (g) 26.046 31.000 57.520 43.890 18.100 17.100 DMEA (mole) 0292 0348 0645 0492 0203 0 192 wt. as [DMEA]Li 27.80 33.09 61.39 46.84 19.32 18.25 wt% DMEA-Li 7.37% 8.59% 8.75% 5.11%** 4.61% 4.43% wt % as Catalyst 7.68% 8.95% 9.11% 7.25%** 4.99% 5.17% mole Alkali Metal / mole1.500 1.500 1.567 1.531 1.999 2.996 PMw-Butyllithium vol, ml 219.15 173.89 336.99 341.61 202.95 28736 BuLi mole 0.4383 0.5217 1.0110 1 0248 04059 05747 Mass of BuLi solution g 170.168 159.181 264.340 267.958 157.590 223.130BuLi neat mass, g 28.08 33.42 64.76 65.65 26.00 36.82 * Not including CH in BuLi **Catalyst also comprised 15.94 g 1 -methoxy -2-propanol (26.4 % of the polar modifier) 1.75 wt.%, 1.88 wt.% [MeOP]Li of the final catalyst solution.Table 3: Applications test of three-month aged DMEA based LOXSH catalyst solutions for making HMAPS.Application Test 3 Months An 1 An 9Ap- Ap- Ap- Ap- Ap- Ap- Aging (HMAPS)P P3 4 5 6 7 8 Combined Examples / Example1+2 3+4 5+7 8+9 6 10 12 13 AnalysesHydride ppm (NMR hydride 275 436 241 480 484 92295.3 163.2test).4.3.9.1.3.3 ppm as Hydride (Material 274 438 254 494 494 939106.9 170.2Balance Calc.).4.8.7.5.5.4218 348 202 393 393 746 ppm as LiH 850 13531 8 5 2 2 8 4.3 4.7 4.4 4.6 4.5 4.0 DMEA wt.% (NMR) 1.888 2.77299 13 84 28 2 23 mole Li / mole DMEA (NMR 1.5 1.8 1.4 1.9 1.9 3.01.45 1.52Analyses) 5 2 8 2 5 3 Material Balance Calculated 1.5 1.8 1.5 1.9 2.0 3.01.51 1.52Value (Li / DMEA) 6 3 0 4 0 0 wt.% Catalyst (From NMR 4.9 5.3 4.9 5.3 5.2 5.02.09% 3.09%Analysis) 1% 8% 8% 2% 1% 3% Material Balance wt. % as 4.8 5.1 5.0 5.1 4.9 5.12.07% 3.22%Catalyst 2% 7 1% 8 9% 7% Aged Catalyst testing for 3 and 3 and3 3 3 3 3 3** HMAPS (Months) 10 10Average Reactor Pressure4 / 5 6 / 5 23 21 28 22 28 26 During Polymerization****Mn 685 / 71 703 / 72 728 733 736 719 737 7299 1Mw 1105 / 1 1162 / 1 138 135 137 125 145 155160 179 8 0 9 5 9 2 Mz1645 / 1 1799 / 1 303 286 288 243 372 420694 785 3 5 1 5 7 5 PDI 1.613 / 1 1.653 / 1 1.9 1.8 1.8 1.7 1.9 2.1.635 07 42 74 45 80 29 * Styrene 1040 g. Hydrogen 330 SCCM [sty] / [H2] = 5.87.** Combined with added DMEA to adjust Li / DMEA to 1.500 prior to hydrogen mediated anionic styrene polymerization. *** Styrene dimer and above included in distribution.Table 4: Examples of DMEA b< se LOXSH cataly st formed from high quality BuLi.Example 14 15 16 17 18 19 Pressure range Catalyst28-23 30-24 15-18 25-29 25-29 28-35 formedTemperature 38-42 38-42 41-40 41-40 40250.69 251.57 241.39Hydride content (ppm)246 05 247 14 341 nLiH content (ppm) 1977 1984 1904 1940 1949 2695286**wt. of solvent to reactor (g) 548 279 279 284 * 253*** Volume (ml) of CH** 704 358 358 364 367 324 Calculated total weight (g) 724 366 366 371 374 381 Weight out 744 371 382 379 378 400 Reactor at Start (ml) 450 250 250 250 240 240 Flush of lines 100 50 50 50 50 20 Flush lines g 78 39 39 39 39 16 DMEA (CH) ml 51 26 26 32 45 64 Butyllithium added CH ml 103 32 32 32 32 0 Butyllithium CH (g) 80 25 25 25 25 0 volume total solution (ml) 894 452 452 458 461 4704 352 4371Target Wt.% DMEA 4.434% 4.449% 4.325% % % 4.538% DMEA (g) 33.000 16.500 16.540 16.500 16.500 18.130 DMEA (mole) 0.370 0.185 0.186 0.185 0.185 0.203 wt. as DMEA-Li 35.22 17.61 17.65 17.61 17.61 19.354 84%*** wt.% DMEA-Li 4.73% 4.75% 4.62% 4.64% 4.67% * wt. % as Catalyst 4.94% 4.96% 4.82% 4.85% 4.87% 6.73% mole Alkali Metal / mole PM 1.500 1.500 1.494 1.500 1.500 1.5000 w-Buty llithium vol, ml 222.13 111.07 110.86 111.07 111.07 162.52 BuLi mole 0.5553 0.2777 0.2771 0.2777 0.2777 0.4063177 R7Mass of BuLi solution g388.936 88.770 88.936 88.936 130.136BuLi neat mass, g 35.57 17.79 17.75 17.79 17.79 26.03 * Hydride content of 185.7 ppm after aging 9 months at 20°C, then 3 months at 45°, combining and filtering LiH. **Not including CH in BuLi ***THF added to solvent.****Catalyst also comprised 6.08 g 1 -methoxy -2-propanol (24.9 % of the polar modifier) 1.75 wt.%, 1.64 wt.% [MeOP]Li of the final catalyst solution. ApplicationTable 5: Larger scale process for preparation of DMEA based LOXSH catalyst solutions and blends.Example 20 21 22 23 24 25*1133 ppm LiH 2049.6 2009.6 2060.3 2184.4 2228.5143 7 ppmH 0 259.91 254.83 261.26 277.00 282.60 Hydride ppm (hydride test) 148.5 262.8 277.5 260.0 290.00 305.30 Wt. of solvent to reactor (g) 399 581 920 735 739 646 Volume (ml) 0% of BuLi 512 745 1181 944 949 829 Volume with 66.7% BuLi (ml) 560 904 1451 1214 1232 1127 Volume with 100% BuLi (ml) 585 983 1586 1350 1373 1276 approximate total wt. of final 456 768 1317 1281 1269 1388 solution (g) Weight out 448 778 1342 1320 1292 1340 Reactor at Start (ml) 250 350 780 550 550 480 Flush of lines (ml) 50 100 20 60 60 40 Flush lines (g) 39 78 16 47 47 31 Reactor rinse (ml) 0 0 100 290 250 500 Flush lines g 0 0 78 226 195 390 DMEA (CH) ml 32 64 60 68 51 54 DMEA (CH) g 25 50 47 53 40 42 Butyllithium added CH ml 180 231 321 266 288 255 Butyllithium CH (g) 140 180 250 207 224 199235 Target Wt.% DMEA 4.51% 4.47% 4.55% 4.88% 4.93% DMEA (g)1035235.104 60.001 60.016 63.000 66.047 DMEA (mole) 0.118 0.394 0.673 0.673 0.707 0.741 wt. as [DMEA] Li 11.23 37.47 64.04 64.06 67.24 70.49251wt.% [DMEA] Li%4.82% 4.77% 4.85% 5.21% 5.26% wt. % as Catalyst2% 5.01% 4.97% 5.05% 5.42% 5.47% mole Alkali Metal / mole PM I.540 1.509 1.503 1.508 1.502 1.507 vol, ml 72.73 237.72 404.82 406.11 424.60 446.60 mole0 1o810.5943 1.0121 1.0153 1.0615 1.1165 o58.24 190.35 324.16 325.18 339.99 357.61 Mass of solution g0 3 2 9 8 2 neat mass, g II.65 38.07 64.83 65.04 68.00 71.52 *Ex. 24 and 25 were blended and diluted with cyclohexane to form Ex. 26 having 5.02 wt.% [DMEAJrLisH with 257.8 wt.% hydrideTable 6: Applications test of two-month aged DMEA based LOXSH catalyst solutions for making HMAPS.Application Test 2 MonthsAp-9 Ap-10 Ap-11 Ap-12 Ap-13 Ap-14 Aging (HMAPS)LOXSH Cat. Sol. Example 14 15 16 17 18 19* DMEAwt.% 4.560% 4.504% 4.516% 4.443% 4.417% 4.76% Wt. Catalyst solution 89.42 83.452 78.392 83.082 81.836 57.582 Volume Catalyst solution115 107 101 107 105 74 Hydrogen Feed Rate (SCCM) 330.4 330.4 330.4 330.4 330.4 330.4 Initial Hydrogen Charged std.1350 1350 1350 1300 1300 1300 cm3Hydrogen Feed time (min.) 113.0 113.0 113.0 115.9 115.9 115.9 Total Hydrogen std. cm338700 38700 38700 39600 39600 39600 hydrogen fed std. cm337350 37350 37350 38300 38300 38300 Temperature, °C 86 84 84 84 84 84 Hydrogen, mole 1.73 1.73 1.73 1.77 1.77 1.70 Styrene mole 10.01 10.00 10.02 9.99 9.99 9.99 mole sty rene / mole hydrogen 5.80 5.79 5.80 5.65 5.65 5.65 Mn calc 45,537 49,341 53,098 50,193 51,257 49,765 Mn 716 719 719 706 706 706 Mw 1213 1206 1206 1183 1154 1149 Mz 1946 1922 1922 1869 1720 1700 PDn 1.694 1.677 1.677 1.676 1.635 1.627 * Also comprises 1.75 wt.% MeOPTable 7: Applications test of DMEA based LOXSH catalyst solutions for making HV-HMPBD. Application Ex. 22 23 24 25 26 Catalyst solution Ex. 21 26 26 26 26 PM wt.% 4.512% 4.536% 4.536% 4.536% 4.536% wt. Catalyst solution 75.475 75.375 70.818 67.943 66.278 DMEA (g) 3.41 3.42 3.21 3.08 3.010.03582 0.03596 0.03379 0.03241 0.03162 mole 1 5 1 9 4 wt. as [DMEA]2LisH 3.781 3.784 3.555 3.411 3.327 Temperature, °C 74 74 72 71 73Time of Monomer Feed (min.) 198.20 198.20 199.67 199.67 199.67 Initial Hydrogen Charge (std. cm3) 375 375 325 345 345 Time of Hydrogen co-feed (min.) 190.0 190.0 190.3 190.3 190.3 Hydrogen Feed Rate (SCCM) 70.40 70.40 68.95 66.95 66.95 Std. cm3Hydrogen 13750 13750 13450 13090 13090 mole Hydrogen 0.614 0.614 0.600 0.584 0.584 mole monomer / Hydrogen 17.94 17.93 18.45 18.93 18.93 Theoretical Mn 969 968 996 1022 1022 Butadiene (g) 595.5 595.0 599.0 598.0 594.5 mole 11.009 11.000 11.074 11.056 10.991 Theoretical Mn969 968 996 1,022 1,016 Mn cak (no chain transfer) 32.609 32.746 35,088 36,511 37,209 g BD / g BuLi 171.977 171.666 183.941 191.404 195.064 polymer yield, g 565.0 564.31 575.03 562.20 571.31 Kg HMPBD / Kg Butyllithium 163.15 162.81 176.58 179.95 187.46 Kg BuLi / 1000 Kg PBD 6.13 6.14 5.66 5.56 5.33 Kg HMPBD / Kg Butvllithium / 49.39 49.29 53.06 54.07 56.33 hr.yield % on monomer 94.9% 94.8% 96.0% 94.0% 96.1%Table 8: Applications test of nine-month aged and freshly prepared / blended DMEA based LOXSH catalyst solutions for making High Vinyl EI1 IPBD.Applicat _, total total 1,2-TBrookfieionsCa alT pVinyl Vinyl Vinyl / IodmIdTestSolut ( -'!’leSS>wt % wt° / o VCPweViscosit J?,’ Mn PDI V°C)? ( VpPsig 5)7 ^1J I8T (,n13C„N, I, INM, N,um v c _P, & °C HV- ion her * —HMPBD MR) MR) R 25 °CAp-15 19 75 14 70.9% 77.2% 8.99 425 812 ’ 881 1.8566.93Ap-16 16 73 11 72.3% 78.2% 7.54 418 579 ~n769 1.9169.49Ap-17 15 72 13 72.5% 76.8% 7.36 425 442720 1.9814 72 12 72.3% 78.8% 8.63 420 918 ’ „ 889 1.89 Ap-1866.32Ap-19 17 72 12 71.9% 79.0% 9.14 415 786 862 1.846 / .49Ap-20 18 72 14 71.7% 78.1% 9.10 426 816 885 1.8567.0915 74 13 71.5% 78.7% 9.72 425 974 883 1.89 Ap-21 66.48Ap-22 21 74 14 743% 786% 908 410 986 ’, 927 1 8363.23Ap-23 26 74 13 74.4% 80.4% 9.66 411 1078 ’. 928 1.8863.54Ap-24 26 72 16 74.9% 79.8% 9.31 411 1092 931 1.8764.45Ap-25 26 71 18 75.0% 79.6% 9.94 402 1236 951 1.84. / oAp-26 26 73 16 74.9% 81.2% 9.72 407 1128 63.7 967 1.881Table 9: Intial screening Examples to determine l-piperidino-zso-propanol (PiP) base LOXSH catalyst solubility and stability.Example 29 30 31 32 Pressure range Catalyst formed 29-25 25-30 25-31 18-25 Temperature 40° 40° 43° 43° Hydride content (ppm) 167.3 236.5 293.3 197.0LiH content (ppm) 1319.5 1865.0 2312.9 1553.9[PiP] Li after filtration (1 month) 4.92* 5.80 6.85 5.08 Hydride ppm (hydride test 12 months) ** 165.9 241.0 312.5 208.8wt. of charged solvent to reactor (g) 289 250 255 586 Volume (ml) of CH*** 371 321 328 753 Calculated total wt. of (g) 349 329 370 739 Weight out 347 320 372 741 Reactor at Start (ml) 250 220 220 450Flush of lines 50 30 50 110Flush lines g 39 23 39 86PM (CH) g 30 30 25 30 Butyllithium added CH ml 32 32 26 154 Butyllithium CH (g) 25 25 20 120 volume total solution (ml) 431 406 456 912Target Wt.% PiP 4.7% 6.72% 8.33% 5.60%PiP (g) 16.500 21.504 31.000 41.500PiP (mole) 0.115 0.150 0.216 0.290wt. as PiP-Li when originally formulated 17.18 22.40 32.28 43.22wt.% PiP-Li (at 1.0 equiv Li) 4.92% 7.00% 8.68% 5.83%wt. % as Catalyst 5.05% 6.99% 8.97% 6.00%mole Alkali Metal / mole PM 1.500 1.500 1.500 1.500w-Butyllithium vol, ml 69.12 90.09 129.86 173.85BuLi mole 0.1728 0.2252 0.3247 0.4346 Mass of BuLi solution g 55.349 72.140 103.988 139.210BuLi neat mass, g 11.07 14.43 20.80 27.84*Not filtered. **Supematant Liquid. ***Not including CH in BuLi.Table 10: Intial screening Examples to determine 1 -pipendino-sec -‘-butanol (PsB) based LOXSH catalyst solubility and stability.Example 33 34 35 36 37 38 3925- 2P374- ressure range Catalyst formed 28-37 27-33 23-27 28-37 23-27 Temperature 42° 42° 42° 43° 42° 42° 42°211. 274. 365.6 313.7 429.5 351.7 416.2 Hydride content (ppm)6 2LiH content (ppm) 1669 2163 2883 2474 3387 2773 3282 Wt. of solvent to reactor (g) 260 260 233 250 230 242 235 Volume (ml) of CH * 334 334 299 321 295 311 302 approximate total wt. of final335 371 381 380 421 392 426 solution (g)Weight out 332 374 377 390 421 401 432 Reactor at Start (ml) 230 230 220 200 200 210 220 Flush of lines (ml) 40 40 40 50 50 40 40 Flush lines g 31 31 31 39 39 31 31 1 -Piperidino-2 -butanol (CH) ml 32 32 39 51 39 45 32 1 -Piperidino-2 -butanol (CH) g 25 25 30 40 30 35 25 Butyllithium added CH ml 32 32 0 19 6 13 6 Butyllithium CH (g) 25 25 0 15 5 10 5413 457 470 469 520 484 526 volume total solution (ml)6.48 8.56 11.41 9.65 13.14 11.06 12.97 Target Wt.% PsB% % % % % % % 21.5 32.0 43.00 37.64 55.34 43.36 55.24 PsB (g)04 00 0 0 0 0 0 013 0.20PsB (mole)0 273 0 239 0 352 0 276 0 3512223 33 2wt. as [PsB] Li 44.62 39.06 57.43 45.00 57.336.67 8.96 11.72 10.28 13.63 11.48 13.46 wt.% [PsB]Li% % % % % % % 6.83 9.18 12.01 10.53 13.97 11.76 13.79 wt. % as Catalyst% % % % % % % mole Alkali Metal / mole PsB1-500 1 507 1 510 1 507 1 50882.5 122. 164.0 144.2 212.5 166.2 211.8 w-Butyllithium vol, ml6 10 7 9 3 5 6 0.20 0.30 0.410 0.360 0.531 0.415 0.529 BuLi mole64 52 2 7 3 6 7 66.1 97.7 131.3 115.5 170.1 133.1 169.6 Mass of BuLi solution g10 70 79 40 80 27 50 13 2 1952 526.28 23.11 34.04 26.63 33.93 BuLi neat mass, g*Not including CH in BuLiTable 11: Examples to determine process parameter effects on 1 -piperidmo-se -butanol (PsB) based LOXSH catalyst quality.Example 40 41 42 43 45 46 4714 to 14 to 15 to -I to 16 to. Pressure range Catalyst formed 27-3.3 15 to 48 15 4 2 6 Temperature 43° 43° 43° 43° 43° 43° 43° Hydride content (ppm) 294.1 306.8 229.3 392.0 327.9 319.8 299.6 LiH content (ppm) 2319 2419 1808 3092 2586 2522 2363306 9 2806* Hydride ppm (hydride test) _ 302.8 226,6 400,4 331,2 319,2 22 Wt. of solvent to reactor (g) 784 273 273 273 505 521 273 Volume (ml) of CH **** 1007 351 351 351 648 668 351 approximate total wt. of final1173 403 395 413 768 786 440 solution (g)Weight out 1224 395 395 406 747 771 514 Reactor at Start (ml) 700 200 200 200 350 350 200 Flush of lines (ml) 50 80 80 80 80 100 80 Flush lines g 39 62 62 62 62 78 62 l-Piperidino-2 -butanol (CH)50 30 30 30 50 50 30 mll-Piperidino-2-butanol (CH) g 193 32 32 32 154 154 32 Butyllithium added CH ml 150 25 25 25 120 120 25 Butyllithium CH (g) 1449 497 488 509 948 970 5439.25 9.53 9.54 9.28 10.23 9.98 Target Wt.% PsB% % % % % % ' / o113.1 37.64 37.67 37.67 76.42 76.93PsB (g) 4846970 8 2 0 8 7PsB (mole) 0.720 0.239 0.240 0.2400 4860.489 0.3081174wt. as [PsB] Li 4 39.07 39.10 39.09 79.32 79.84 50.309.60 9.89 9.90 9.63 10.62 10.36 wt.% [PsB]Li% % % % % % / X / ,)9.83 10.13 10.14 9.86 10.88 10.61 10.02 wt. % as Catalyst% % % % % % % mole Alkali Metal / mole PM 1.496 1.502 1.375 1.659 1.500 1.500 1.496430.7 143.8 131.7 158.9 291.6 293.5 n-Butyllithium vol, ml1 O 11 6 6 8 2 6184 431.076 0.359 0.329 0.397 0.729 0.733 BuLi molen 1A1 18 6 4 5 0 90 4611344.8 115.1 105.5 127.3 233.5 235.0 147.67 Mass of BuLi solution g90 93 09 07 12 68 9BuLi neat mass, g 68.98 23.04 21.10 25.46 46.70 47.01 29.54 * Example 44 is described in the text. **Measured at three months, 314.22 at 6 months.***281.6 ppm after four months. ****Not including CH in BuLiTable 12: Larger scale process for preparat ion of l-piperidino-sec-butanol (PsB) based LOXSH catalyst solutions and blends.Example 48 49 50 51 52* LiH content (ppm) 2507 2491 2561 2352 2924 Hydride content (ppm) 317.87 315.87 324.71 298.23 370.78 Hydride ppm (hydride test) 314.30 316.70 322.60 298.23 361.8 Wt. of solvent to reactor (g) 683 683 683 683 683 Volume (ml) 0% of BuLi 877 877 877 877 877 Volume with 66.7% BuLi (ml) 1137 1137 1140 1132 1159 Volume with 100% BuLi (ml) 1267 1267 1272 1260 1300 approximate total wt. of final solution1035 1035 1040 1032 1057 (g)Weight out 1036 1046 1028 1029 1085 Reactor at Start (ml) 570 570 570 570 570 Flush of lines (ml) 50 50 50 50 50 Flush lines (g) 39 39 39 39 39 l-Piperidino-2 -butanol (CH) ml 64 64 64 64 64 1 -Piperidino-2 -butanol (CH) g 50 50 50 50 50 Butyllithium added CH ml 193 193 193 193 193 Butyllithium CH (g) 150 150 150 150 150 Target Wt.% PsB 9.86% 9.75% 10.06% 10.00% 9.54%102.14 102.02 103.41 102.90 103.50 PsB (g)3 6 9 6 8 PsB (mole) 0.650 0.649 0.658 0.654 0.658 wt. as [PsB] Li 106.00 105.88 107.33 106.79 107.42 wt.% [PsB]Li 10.23% 10.12% 10.44% 10.38% 9.90% wt. % as Catalyst 10.48% 10.36% 10.69% 10.63% 10.15% mole Alkali Metal / mole PM 1.503 1.505 1.504 1.465 1.606 n-Butyllithium vol, ml 390.50 390.69 395.53 383.58 422.87 BuLi mole 0.9763 0.9767 0.9888 0.9590 1.0572312.69 312.84 316.72 307.15 338.61 Mass of BuLi solution g4 8 0 3 6BuLi neat mass, g 62.54 62.57 63.34 61.43 67.72 * Two 2.0-liter blends. Examples 53 and 54. were formed by blending 500 ml each of Examples 49-52. The blends having on average 314.8 ppm hydride vs. 318.0 calculated hydride content (2508 ppm as LiH)Table 13: Applications test of aged PsB based LOXSH catalyst solutions for making Low Vinyl HN PBD. Applica. _ total total 1,2- Viscos tionsAgeTePreVinyl Vinyl Vinyl / TestIodm lty(LV- mEpx.lae / (wee m £p.; (pSs'i. w(1Ht.%N (wBtC.%N 1RVNCPM NNuem “ field I C- MnDPI HMPBks) g)MR) MR) Rber250c D)31 9 35 9 ’ 10 1 Ap-27 33 9 98 38 % % 4.96 461 250 98.0 04JAp-28 34 9 98 3634)24.89 456 262 99. J?70 70 i 14 / kO272 33 3 " 10 1 Ap-29 35 9** 99 360 08.22 457 254 99.70 70 / 8Ap-30 36 9 98 382J84.64 468 258 99.E / 0 / 0 2^<7 / Ap- 377 43 1 ’ 10 1 38 9** 97 32 6.23 467 330 93. “?g31*6pr 36 9 97 313;6 426.15 463 334 94.32* / o / o 447 / EoAp-33 36 17 ° 403733 84.47 429 281 98!“ b 1 % % 84Ap-34 34 17 1° 412!;3 33;34.27 440 254 99. 12 J-770 / 0 ^ 15 8 / o33 17103828i4 3 E25.22 454 254 99. ^2kAp-354 / o / oo2 / 838Ap-36 35 18 50382 4 3 85.22 450 295 98.Ap-37 35 2110393?;4 34'74.51 451 301 97.1 70 70 5 J 1 01Ap-38 38 2110383?;8 34 14.85 448 293 97.1 70 70 Q 30 851. Ap-39 372F \° 403“ *:34.25 454 270 98!“* 1 % % 26 85 22* 10 31 4 37 8 ' 10 1. Ap-40 39 * 39 ' 4.41 454 272 97.i / O / O 85 10 292 33 7 ’ 10 1.Ap-41 36 30 „ 40n; 4.24 449 252 1003 % % 21 801. Ap-42 373^* \° 392?;64.35 447 263 100 ™** 1 % % 28 79*Trace THF added. ** Aged one week at 42°C to redissolve crystals of [PsB]Li. *** 17 weeks at room temperature then 13 weeks at 42°CTable 14: Applications test of fresh and aged PsB based LOXSH catalyst solutions for making Low Vinyl HMPBDApplica. _ total total 1,2- ViscostionsTereVinyl Vinvl Vinyl / °111Rlty, „ _ Test (LV- mEpX? / mp.? le (wee (ps’. wt.% wt.% VCP ®B™kI- M si1rn (13cn 1rnmNum field CnDEI HMPBks)MR) MR) RberD) Ap-43 40 1 101 39 29.7% 32.0% 4.62 440 282 98.o\361 81Ap-44 40 13 101 41 29.6% 33.2% 4.33 447 257 100Ap-45 40 25 102 42 30.6% 32.0% 3.91 438 254 99. ™5 Ap-46 45 1 101 40 30.6% 33.5% 4.42 448 245 9o9.02 ok3 o Ap-47 46 1 101 41 29.9% 32.6% 4.28 449 252 99.k82 / yAp-48 41 3 101 40 29.8% 33.6% 4.26 450 253 99.Ap-49 45 3 101 39 28.4% 31.9% 4.08 450 245 101Ap-50 43 3 101 40 29.3% 32.3% 4.40 451 252 100k5 ™ Ap-51 43 3 101 40 28.4% 32.3% 4.08 444 245 101k.225 81Ap-52 42 3 106 50 30.0% 34.1% 4.20 441 260 100 ™0 03 okoAP-53 44 4 101 39 28.7% 35.4% 5.22 447 251 100k.0 Ap-54 44 13 101 39 32.0% 30.0% 3.84 427 266 99.322 8 / Ap-55 53 1 101 41 30.6% 36.6% 4.24 439 250 99. *223 oOAp-56 54 1 101 42 30.3% 34.0% 3.98 430 243 99.0Ap-57 40 52 104 43 31.3 30.2 4.33 452 255 99.Table 15: Applications test of PsB based LOXSH catalyst formed in situ to form Low Vinyl HMPBD.Comp. „ total total, _ ViscositPres 1Applicatio 2- Tern s. Vinyl / V °dhnTg, PD ns Testo„.. wt.% wt.% Numb Brookfle ® Mn T(LV- P-C<iy ('HNM (13CNM, crerId cP, ®C 1HMPBD)s> R) R) >™MR25-C 102 1 7 Comp-1 97 32 40.4% 39.3% 6.17 451 304 92.r'36 1Comp-2 97 34 31.4% 35.0% 4.80 460 276 98.194V 21 3109 1 7 Comp-3 105 41 28.2% 30.0% 4.17 459 288 99. / n66 9Comp-4 97 31 37.0% 41.7% 5.92 466 322 94.1(J5V 2J 7Comp-5 101 40 31.8% 35.9% 4.68 435 282 97.190 1_8o9 3Comp-6 101 39 36.1% 40.5% 6.22 424 424 9g1.1|° '.8 58Comp-7 101 39 29.7% 32.0% 4.62 440 282 98.19631 110^ 1 R Comp- 8 101 43 30.4% 32.0% 4.27 447 266 99. ',72 4Comp-9 101 40 31.6% 33.4% 4.17 437 245 NA191

Claims

THAT WHICH IS CLAIMED:

1. A shelf-stable LOXSH catalyst solution composition comprising from about 120 ppm to about 1200 ppm hydride ion concentration (from about 950 to about 9600 ppm as lithium hydride) as a homogenous hydrocarbon solvent solution formed from at least one cr-p polar modifier (PM) lithium alkoxylate, an alkyl lithium reagent, molecular hydrogen, and a hydrocarbon solvent wherein the stoichiometric formula of the catalyst is represented by [PM]xLiyHz wherein PM is a c-p polar modifier, z = y - x, x and y are independently whole or fractional numbers greater than zero, and y>x.

2. The composition of Claim 1 wherein the shelf-stable LOXSH catalyst solution retains its catalytic activity, selectivity and lithium hydride titer for a period of at least two months.

3. The composition of Claim 1 wherein the a— p polar modifier (PM) lithium alkoxylate is formed from at least one p-aminoalcohol and one or more of an alkyllithium, lithium hydride, or lithium metal in a hydrocarbon solvent.

4. The composition of Claim 1 wherein the hydrocarbon soluble LOXSH catalyst concentration is in the range of about 175 ppm to about 1075 ppm hydride ion concentration (1380 ppm to about 8500 ppm lithium hydride).

5. The composition of Claim 1 wherein the hydrocarbon soluble LOXSH catalyst concentration is in the range of about 200 ppm to about 1050 ppm hydride ion concentration (1800 ppm to about 8300 ppm lithium hydride.)6. The composition of Claim 1 wherein the ratio of y:x is in the range of about 1.3:1 to about 3.5:1.

7. The composition of Claim 1 wherein the ratio ofy:x is in the range of about 1.4:1 to about 3.0:1.

8. The composition of Claim 1 wherein the hydrocarbon solvent comprises one or more of a C4 to C8 hydrocarbon, butanes, pentanes, hexanes, heptanes, cyclopentane, cyclohexane, methylcyclohexane, and / or ethylbenzene.

9. The composition of Claim 1 wherein the G— p polar modifier (PM) lithium alkoxylate comprises the lithium alkoxylate of one or more of N, N-dimethylethanolamine, 1- (dimethylamino)-2-propanol, 1 -(dimethylamino)-2-butanol, trans-2-(dimethylamino)cyclohexanol; 2-piperidinoethanol; l-piperidino-2-propanol; l-piperidino-2-butanol, trans-2-piperidinocyclohexan-l-ol, 1-pyrrolidinoethanol, pyrrolidinylpropan-2-ol, l-(l-pyrolidinyl)-2-butanol, 2-pyrolidinocyclohexanol, 4-methyl-l -piperazineethanol, l-(4-methyl-l-piperazinyl)-2-propanol; 1 -(4-methyl- 1 -piperazinyl)-2-butanol; trans-2-(4-methyl- 1 -piperazinyl)-cyclohexanol, 2-morpholinoethanol, 1 -(4-morpholinyl)-2-propanol, l-(4-morpholinyl)-2-butanol, lrans-2-morpholin-4-y Icyclohexanol, 1 -methy 1-2-piperidinemethanol. l-methyl-2-pyrrolidinemethanol, dimethylaminoethanol, N-methyl-diethanolamine, 3-dimethylamino-l -propanol, l,3-bis(dimethylamino)-2-propanol, 2-{[2-dimethylamino)ethyl]methylamino} ethanol, 2-[2-(dimethylamino)ethoxy]ethanol, 2-(2-(piperidyl)ethoxy)ethanol, 2- [2-(4-morpholinyl)ethoxy] ethanol, 2-[2-(l-pyrrolidinyl)ethoxy] ethanol, 2-[2-(4-methyl-l-piperazinyl)ethoxy]ethanol; and optionally from about 50 mole% to greater than 0 mole% of an ether-alcohol G— p polar modifier selected from one or more of 2-methoxy ethanol, 1 -methoxy propan-2-ol, 1 -methoxybutan-2-ol, 2-methoxycyclohexan-l-ol, tetrahydrofurfur l alcohol, tetrahydropyran-2-methanol, diethylene glycol monomethyl ether.

10. The composition of Claim 1 wherein the G— p polar modifier (PM) lithium alkoxylate comprises the lithium alkoxylate of one or more of V,7V-dimethylethanolamine, 1-(dimethylamino)-2-propanol, 1 -(dimethylamino)-2-butanol, 2-piperidinoethanol; 1-pipendmo-2-propanol; 1 -piperidino-2-butanok and optionally from about 50 mole% to greater than 0 mole% of an lithium alkoxylate formed from an ether-alcohol G— p polar modifier selected from one or more of 2-methoxy ethanol, 1 -methoxy propan-2-ol, l-methoxybutan-2-ol. 2-methoxycyclohexan-l-ol, tetrahydrofurfuryl alcohol.

11. A process for forming a composition of Claim 1 wherein a hydrocarbon solvent solution comprising at least one G— polar modifier (PM) lithium alkoxylate, is combined with an alkyl lithium reagent, and molecular hydrogen in a hydrogenolysis reactor, wherein the relative molar amount of molecular hydrogen consumed in forming the LOXSH catalyst is given by “z” of the stoichiometric formula [PM]xLiyHz and wherein the catalyst solution is kept isolated and is transferred from the hydrogenolysis reactor to a storage vessel under hydrogen or an inert atmosphere or fed under a hydrogen atmosphere to another reactor continuously or in portions for use as a hydrogen mediated anionic polymerization catalyst.

12. The process of Claim 11 wherein the alkyllithium reagent, is reacted with the polar modifier to form the a— p polar modifier (PM) lithium alkoxylate and a volatile hydrocarbon gas and wherein the feed of the alkyllithium is interrupted once the [PM]Li is fully formed and wherein for the hydrogenolysis reactor: a) is established the desired hydrogenolysis reaction temperature, b) all or a portion of the co-product lite hydrocarbon gas is vented from the hydrogenolysis reactor to about 0 psig; c) to it is optionally charged with a known quantity of molecular hydrogen to the reactor; d) to it is fed the balance of the alkyllithium at a controlled rate; and e) to it is cofed hydrogen gas while maintaining efficient gas dispersion into the condensed phase reaction mixture wherein the total amount of hydrogen fed in steps c) and e) is the molar quantity z wherein z = y - x, where y is total mole of alkyllithium used and x is the total mole of the polar modifier used to prepare the formulation [PM]xLiyHz.

13. The process of Claim 11 wherein a preformed a-p polar modifier lithium alkoxylate, [PM]Li, is charged to the hydrogenolysis reactor under a hydrogen atmosphere and then for the hydrogenolysis reactor: a) is establish the desired hydrogenolysis reaction temperature, b) the headspace hydrogen gas is vented from the hydrogenolysis reactor to about 0 psig; c) to it is optionally charged with a known quantity of molecular hydrogen to the reactor; d) to it is fed the molar amount of the alkydlithium, z, at a controlled rate; and e) to it is cofed hydrogen gas while maintaining efficient gas dispersion into the condensed phase reaction mixture wherein the total amount of hydrogen fed of steps c) and e) is also at least the molar quantity z wherein z = y - x, where y is total lithium atoms used and x is the total mole of the polar modifier used to prepare the LOXSH formulation [PM]xLiyHz.

14. The process of Claim 11 wherein the o— p polar modifier (PM) lithium alkoxylates are formed from the PM and an alky lithium reagent.

15. The process of Claim 11 wherein the G— p polar modifier (PM) lithium alkoxylates are formed from the PM and one or more of lithium metal or lithium hydride.

16. The process of Claim 11 methods wherein to the hydrocarbon solvent solution of the c- polar modifier (PM) lithium alkoxylates [PM]Li is co-fed hydrogen gas and an alkyllithium reagent wherein the hydrogen feed is controlled externally by a regulated hydrogen pressure in the range of -4 to about 100 psig.

17. A process of Claim 11 wherein hydrogenolysis reactor's pressure is maintained in the range of about -4 psig to about 35 psig.

18. The process of Claim 9 wherein to the a— p polar modifier (PM) lithium alkoxylates is co-fed hydrogen gas and a alkyllithium reagent wherein the hydrogenolysis reactor’s pressure is either: 1) held constant or near constant; or 2) is allowed to vary; wherein the relative hydrogen feed rate to the reactor is controlled external to the reactor and the total molar amount of hydrogen charged to the reactor is limited to at least the amount “z”.

19. A process of Claim 11 wherein the pressure of the hydrogenolysis reactor is controlled externally by maintaining a regulated pressure in the range of 1 to 35 psig of a demand regulator that feeds hydrogen to the reactor such that the hydrogen pressure is kept constant or near constant and wherein the hydrogenolysis reactor progress is monitored thermally.

20. A process of Claim 11 wherein the hydrogenolysis reactor pressure is maintained over the range of -4 to 35 psig and is controlled externally by regulating the hydrogen feed rate as a function of time and wherein the total molar quantity of hydrogen charged is at least equal to the theoretical molar amount of hydrogen “z” of the equation z = y - x related to the stoichiometry [PM]xLiyHz wherein x mole of the polar modifier lithium alkoxylate are combined with z mole of an alkyllithium such that y = x + z.

21. A process of Claim 11 wherein the reactor pressure is maintained in the range of -4 to 35 psig and controlled internally by regulating a variable hydrogen feed rate such that the pressure in the reactor either: 1) does not substantially change; or 2) is varied based on a planned program rate, wherein the total molar quantity' of hydrogen charged is at least equal to the theoretical molar amount of hydrogen “z” of the equation z = y-x related to the stoichiometry [PM]xLiyHz wherein x mole of the polar modifier lithium alkoxylate are combined with z mole of an alkyllithium such that y = x + z.

22. A process of Claim 11 wherein the PM lithium alkoxylate is pre-formed in a separate reactor and then charged to the hydrogenolysis reactor to which is then co-fed an alkyllithium reagent and molecular hydrogen.

23. A process of Claim 11 wherein the PM lithium alkoxylate is formed in the hydrogenolysis reactor and then to which is co-fed an alkyllithium reagent and molecular hydrogen.

24. A process of Claim 11 wherein both a steady state pressure and a steady state activity of the alkyllithium reagent are achieved wherein the relative feed rates of hydrogen and of the alkyllithium reagent are balanced such that both components are consumed at the same rate.

25. A process of Claim 11 wherein the hydrogenolysis reactor is maintained at a temperature in the range of about 10°C to about 60°C during the cofeed of hydrogen and the alkydlithium reagent and undesired decomposition side reactions are suppressed by efficient mass transfer of hydrogen via agitation impellers designed for gas dispersion during the catalyst forming steps, such side reactions involving attack of the complexed alkyllithium superbase upon the concentrate of the polar modifier.

26. A process of forming a hydrogen mediated anionically polymerized hydrocarbon monomer polymer product distributions which entails: 1) pre-forming a shelf-stable concentrated LOXSH catalysts solution in a separate operation; 2) forming a reaction mixture under a hydrogen atmosphere with the preformed LOXSH catalysts and optionally additional hydrocarbon solvent; 3) co-feeding at least one anionically polymerizable hydrocarbon monomer with hydrogen gas in a specified relative feed ratio; 4) allowing the reaction to go to completion; and 5) quenching the reaction mixture.

27. A continuous process of forming a hydrogen mediated anionically polymerized hydrocarbon monomer polymer product distribution which entails: 1) pre-forming a shelfstable concentrated LOXSH catalysts solution in a separate operation; 2) forming a reaction mixture under a hydrogen atmosphere by feeding with time the preformed LOXSH catalysts and optionally additional hydrocarbon solvent; 3) co-feeding with the preformed LOXSH catalysts at least one anionically polymerizable hydrocarbon monomer with hydrogen gas in a specified relative feed ratio; 4) allowing the reaction to go to completion; and 5) quenching the reaction mixture.

28. A process of Claim 26 or Claim 27 wherein the hydrocarbon monomer is one or more of a conjugated diene and / or a vinyl aromatic hydrocarbon monomer.

29. A process for hydride reduction of carbonyl compounds which entails forming a reaction mixture of one or more carbonyl compound with a concentrated LOXSH reducing agent solution composition optionally in an ethereal solvent.

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