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WO1996018660A1 - Hydrogenation de polymeres insatures en presence de catalyseurs metalliques du groupe iv contenant un dienyle anionique non aromatique bivalent - Google Patents

Hydrogenation de polymeres insatures en presence de catalyseurs metalliques du groupe iv contenant un dienyle anionique non aromatique bivalent Download PDF

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Publication number
WO1996018660A1
WO1996018660A1 PCT/US1995/016005 US9516005W WO9618660A1 WO 1996018660 A1 WO1996018660 A1 WO 1996018660A1 US 9516005 W US9516005 W US 9516005W WO 9618660 A1 WO9618660 A1 WO 9618660A1
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polymer
group
copolymer
hydrogenation
pentadienyl
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English (en)
Inventor
David R. Wilson
Stephen F. Hahn
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Dow Chemical Co
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation

Definitions

  • This invention relates to a process for hydrogenating olefinically unsaturated polymers.
  • the most notable of these are polymers of conjugated dienes such as poly(butadiene), which contain olefinic unsaturation sites either in the polymer chain itself or pendant thereto. For various reasons, it is sometimes desired to eliminate this unsaturation.
  • the olefinic unsaturation is subject to attack by oxidants, heat and/or radiation. This causes the polymer to perform poorly in applications where it is exposed to such conditions.
  • Heterogeneous catalysts are often lower in activity than homogeneous catalysts and also often require higher temperature and pressure conditions in order to achieve acceptable reaction rates. The higher temperatures increase cost and can cause the polymer to decompose or the reaction system to gel. Furthermore, a larger amount of heterogeneous catalyst is usually needed on a weight basis, particularly when a high molecular weight polymer is hydrogenated. Also, heterogeneous catalysts are often not selective and can sometimes catalyze hydrogenation of other portions of the polymer, particularly aromatic rings, which may be undesirable for some applications.
  • 5,017,660 describes the hydrogenation of butadiene and styrene-butadiene polymers using di- p-tolylbis-(cyclopentadienyl)titanium (IV) as the catalyst.
  • U.S. Patent No. 5,206,307 describes the use of various bis(cyclopentadienyl)titanium (IV) compounds to hydrogenate unsaturated polymers.
  • the catalyst provides reasonably facile hydrogenation under mild or moderate conditions, leaves colorless residues and which does not present environmental or disposal problems. It is further desirable that the catalyst provides for selective hydrogenation. This is particularly the case where the polymer being hydrogenated contains, in addition to the olefinic unsaturation, other sites which are also subject to hydrogenation or reduction.
  • a prominent example of such a polymer is a copolymer of a diene such as butadiene and a vinyl aromatic such as styrene. Often it is desired to remove "the residual unsaturation which is inherent in diene polymers without hydrogenating the rings of the vinyl aromatic monomers. In such instances, the catalyst desirably is highly selective for the olefinic unsaturation, yet provides for facile reaction.
  • This invention is a process for hydrogenating a copolymer of a conjugated diene and a vinyl aromatic monomer, which copolymer contains olefinic unsaturation, comprising reacting said copolymer with a hydrogenating agent in the presence of a catalytic amount of a divalent Group IV metal compound which is represented by the structure:
  • AD (C 5 R" 5 ) 2 - a M L c
  • M is titanium, zirconium or hafnium
  • AD is a group having a non-aromatic anionic dienyl moiety incorporated into a chain of at least 5 carbon atoms
  • a is 1 or 2
  • c is a number from about 0 to about 4
  • L represents a ligand which is coordinated with the metal atom
  • R" is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl, hydrocarbyloxy, siloxy or halogen.
  • a copolymer containing olefinic unsaturation is hydrogenated in the presence of a divalent titanium, zirconium or hafnium compound, which can be represented by the structure:
  • AD (C 5 R" 5 ) 2 - a M L c
  • M is titanium, zicronium or hafnium
  • AD is a group having a non-aromatic anionic dienyl moiety incorporated into a chain of at least 5 carbon atoms
  • a is 1 or 2
  • c is a number from about 0 to about 4
  • L represents a ligand which is coordinated with the metal atom
  • R" is independently hydrogen, hydrocarbyl, inertly substituted hydrocarbyl, silyl, hydrocarbyloxy, siloxy or halogen.
  • inertly substituted means that the subject group contains no substituent which undesirably affects the ability of the compound to catalyze the hydrogenation of an olefinically unsaturated polymer.
  • the group AD contains a non-aromatic anionic dienyl moiety incorporated into a chain of at least 5 carbon atoms.
  • the chain containing the conjugated diene group can be acyclic or cyclic.
  • the AD anion excludes aromatic anions such as cyclopentadienyl and substituted cyclopentadienyl.
  • the AD anion may contain substituent groups such as hydrocarbyl, inertly substituted hydrocarbyl, hydrocarbyloxy, siloxy, silyl, or halogen.
  • Preferred substituent groups include C alkyl, phenyl ortri(C C-j alkyl)silyl, with methyl, t-butyl ortrimethylsilyl being more preferred.
  • the substituent groups may also be in the form of a ring fused to the chain of carbon atoms containing the dienyl group.
  • the AD anion includes acyclic dienyl anions having about 5 to about 12 carbon atoms in the chain containing the anionic dienyl moiety, preferably about 5 to 8 carbon atoms, more preferably 5 to 6 carbon atoms. It also includes cycloaliphatic dienyl anions having greater than 5 carbon atoms in the ring, such as substituted or unsubstituted cyclohexadienyl anions, cycloheptadienyl anions, cyclooctadienyl anions, and the like.
  • Preferred AD anions include pentadienyl, 2-methylpentadienyl, 2,4- dimethylpentadienyl, 3-methylpentadienyl, 2, 3-dimethyl pentadienyl, 1-(trimethyl- silyl)pentadienyl, 1 ,5-bis(trimethylsilyl)pentadienyl, cycloheptadienyl, cyclooctadienyl, cyclohexadienyl, tetrahydronaphthalenyl, octahydroanthracenyl and 6,6- dimethylcyclohexadienyl anions.
  • the C5R"s group is a cyclopentadienyl anion wherein the R" groups are hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, siloxy, silyl, or halogen, preferably C alkyl, phenyl, silyl or hydrogen, with methyl and hydrogen being more preferred.
  • the R" groups on the cyclopentadienyl group may be the same or different from each other. When the R" group is a substituted hydrocarbyl, the substituted group is "inert" as described below by reference to the group L.
  • cyclopentadienyl groups include cyclopentadienyl, methylcyclopentadienyl, trimethylsilylcyclopentadienyl, t-butyl- cyclopentadienyl, tetramethylcyclopentadienyl, and pentamethylcyclopentadienyl groups.
  • M is preferably titanium or zirconium and more preferably titanium.
  • the L group is any inert group which forms a coordinate bond with the metal atom.
  • suitable ligands include Lewis bases which have an unshared electron pair which can complex with the M atom (first type), and neutral conjugated dienes which are coordinated with the M atom via ⁇ -complexation through the diene double bonds (second type).
  • the preferred ligands of the first type are neutral Lewis bases such as phosphines, phosphites, carbonyl, amines and ethers.
  • More preferred ligands of the first type are phosphines, phosphites, carbonyl and aromatic amines. Especially preferred ligands of the first type are carbonyl, trimethylphosphine, tri ethyl phosphine, dimethylphenylphosphine, trimethylphosphite and pyridine. Preferably, c is from 0 to about 2, more preferably 0 to 1, most preferably 0.
  • the ligand of the second type is a conjugated, neutral diene which is coordinated via ⁇ -complexation through the diene double bonds, and not through i-bonds which form a metallacycle (i-bound diene).
  • diene be substituted in either or both of the 1 and 4 positions.
  • ⁇ -complex it is meant that both the donation and back acceptance of electron density by the ligand are accomplished using ligand ⁇ -orbitals ( ⁇ -bound diene).
  • a suitable method of determining the existence of a ⁇ - or l-complex in conjugated diene-containing metal complexes is by measuring metal-carbon atomic spacings for the four carbons which constitute the conjugated diene group, using common X-ray crystal analysis techniques. Measurements of atomic spacings between the metal and C1, C2, C3, and C4 (M-C1 , M-C2, M-C3, M-C4, respectively) (where C1 and C4 are the terminal carbons of the 4 carbon conjugated diene group and C2 and C3 are the internal carbons of the 4 carbon conjugated diene group) are made. If the difference between these bond distances, id, using the following formula:
  • the diene is considered to form a ⁇ -complex with M.
  • Another method of distinguishing a ⁇ -complex from a i-bound diene is by using nuclear magnetic resonance spectroscopy techniques as described in Erker, e al., supra, C. Kruger, et al. Orqanometallics, 4, 215-223, (1985), and Yasuda et al., Orqanometallics, 1 , 388
  • Preferred ligands of the second type include, for example, ⁇ -1-4-diphenyl-1,3- butadiene; i 4 -2,4-hexadiene; ⁇ 4 -3-methyl-1 ,3-pentadiene; ⁇ 4 -1 ,3-pentadiene; i 4 -1,4- bis(trimethylsilyl)-1 ,3-butadiene; and ⁇ 4 -1 ,4-dibenzyl-1-3-butadiene.
  • Any of the ligands can be in the cis or trans form.
  • titanium complexes when prepared, a mixture of the ⁇ -complexed and ⁇ -complexed diene compounds is often obtained. It is within the scope of this invention to employ a titanium complex as described in combination with the corresponding ⁇ -complex as an impurity. Alternatively, the ⁇ -compiex may be separated out using techniques such as disclosed in Yasuda and Erker.
  • Especially preferred catalysts include bis(pentadienyl)titanium, bis(6,6- dimethylcyclohexadienyl)titanium, bis(6,6-dimethylcyclohexadienyl)zirconium triethylphosphine, bis(2,4-dimethylpentadienyl)titanium, bis(2,4-dimethylpentadienyl)- zirconium triethylphosphite, (2,4-(dimethylpentadienyl)(cyclopentadienyl)titanium triethylphosphine, (2,4-dimethylpentadienyl)(cyclopentadienyl)zirconium trimethyl- phosphine, (pentadienyl)(pentamethylcyclopentadienyl)titanium, (2-methylpentadienyl)- (cyclopentadieny
  • the catalyst used in this invention can be prepared by contacting the corresponding dienide anion with a di-, tri- or tetravalent Group IV metal halide complex in the presence of an inert solvent such as tetrahydrofuran, optionally in the presence of L.
  • the dienide anion is advantageously used in the form of a salt, particularly an alkali metal salt.
  • the ligand L is present as a reagent in the reaction mixture.
  • Such syntheses are described in J. Am. Chem. Soc. 1985, 104, 3737, 1982 and J. Am. Chem. Soc. 1985, 107, 5016, both incorporated herein by reference. This reaction generally proceeds well at room temperature or below.
  • the catalyst used in this invention can be prepared by contacting the corresponding dienide anion with a monocyclopentadienyl Group IV metal halide complex in an inert solvent such as tetrahydrofuran, optionally in the presence of L.
  • the Group IV metal halide complex may be coordinated with a Lewis base.
  • the ligand L is present as a reagent in the reaction mixture.
  • the catalyst often contains as a byproduct a quantity of the coupled diene, especially when starting from a trivalent or tetravalent metal starting material.
  • this coupled diene does not interfere substantially with the activity of the catalyst, and it is not necessary to remove it.
  • the catalyst can be recovered from the reaction mixture by extraction with a solvent such as pentane or toluene and then stripping off the solvent. If desired, the catalyst may be treated with an alkyl metal complex prior to the commencement of the hydrogenation reaction. Suitable such alkyl metal complexes include those represented by the structures R"'-Na, R"'-Li, R" 2 Mg, '"3AI, R'"MgW, where W is a halogen and the like, wherein R"' is an alkyl group having from one to ten, preferably from 1-4 carbon atoms.
  • the catalyst is advantageously treated with the alkyl metal complex at room o temperature for a short period. This may be done in the presence of the polymer to be hydrogenated, or prior to contacting with the polymer to be hydrogenated.
  • the hydrogenating agent is introduced into the system prior to, during or after this step.
  • the copolymer to be hydrogenated in this process is characterized by having olefinic unsaturation either within the polymer chain, pendant to it, or both.
  • copolymers of one or more conjugated dienes such as butadiene, isoprene, 2,3- dimethylbutadiene, 1 ,3-pentadiene, 2-methylpentadiene and 1 ,3-hexadiene, and a vinyl aromatic monomer.
  • conjugated dienes such as butadiene, isoprene, 2,3- dimethylbutadiene, 1 ,3-pentadiene, 2-methylpentadiene and 1 ,3-hexadiene, and a vinyl aromatic monomer.
  • copolymers of butadiene and isoprene, and especially polymers of butadiene are preferred on the basis of cost, availability, and beneficial properties.
  • copolymerized vinyl aromatic monomer is generally not important, provided that any functional group which may be present is not undesirably affected by and does not interfere with the hydrogenation reaction.
  • any functional group which may be present is not undesirably affected by and does not interfere with the hydrogenation reaction.
  • the copolymer of the conjugated diene may be of any type, such as a random, block, tapered block, or graft copolymer.
  • Block copolymers are preferred, particularly AB-type diblock or ABA-type triblock copolymers, wherein A represents a poly(vinyl aromatic) block and B represents a poly(diene) block.
  • A represents a poly(vinyl aromatic) block
  • B represents a poly(diene) block.
  • the poly(diene) 0 portion constitutes about 10 to about 99, more preferably about 25 to about 85% of the total weight of the polymer.
  • Most preferred are block copolymers of butadiene and styrene of the AB or ABA type.
  • the process of this invention is also applicable to the so-called living copolymers of conjugated dienes which contain terminal metal atoms. These copolymers may be reacted 5 with hydrogen to remove the terminal metal atoms. This step may be done in conjunction with the hydrogenation of this invention. This may be achieved by contacting hydrogen, the catalyst and the metal-terminated polymer in any order, thereby hydrogenating the copolymer and removing the terminal metal atom.
  • the molecular weight of the copolymer is not critical, and is mainly determined according to the properties required in the particular applications in which the hydrogenated polymer will be used. However, since it is preferred to conduct the hydrogenation in the liquid phase, the copolymer is preferably molten or dissolved in some solvent in which the hydrogenation can be conducted. Thus, a number average molecular weight of from less than 1000 to 5,000,000 or more is suitable. If the copolymer is crosslinked, it is preferably swellable in a solvent in which the hydrogenation can be conducted.
  • the hydrogenation is conducted by contacting the copolymer with a hydrogenating agent in the presence of the catalyst described before.
  • the hydrogenating o agent can be any material which provides hydrogen to the reartion, but hydrogen gas is highly preferred because it is inexpensive and easy to use.
  • the reaction is advantageously conducted by contacting the copolymer and catalyst with the hydrogen gas at an elevated pressure. Suitable hydrogen partial pressures are in the range from about 20 to about 5000 psig, preferably from about 100 to about 2000 psig, more 5 preferably from about 100 to about 400 psig.
  • the hydrogenation reaction may be conducted at any temperature at which an adequate reaction rate is achieved. Generally, however, an elevated temperature is used, since the reartion normally proceeds slowly at room temperature. On the other hand, the use of the catalyst described herein allows for an acceptable reartion rate at mild to moderate 0 temperatures. Thus, a temperature in the range from about 25° to about 100°C is suitable, and a preferred temperature range is from about 40° to about 75°C.
  • the amount of catalyst is chosen to provide an acceptable reaction rate. Typically, about 1 part by weight catalyst is used per 10 to 50,000, preferably 50 to 5000 parts per weight of the copolymer. Higher amounts of catalyst tend to increase the reartion rate.
  • the 5 hydrogenating agent is normally used in large stoichiometric excess, particularly if hydrogen is used.
  • the hydrogenation it is preferred to conduct the hydrogenation homogeneously with the copolymer in a liquid state. Accordingly, unless the polymer is a liquid at room temperature or at a slightly elevated temperature (up to about 75°C), it is preferred to conduct the hydrogenation in an 0 inert solvent in which the catalyst is dissolved and the copolymer is dissolved or swollen. Any solvent which dissolves the copolymer and which does not engage in any undesirable side reactions with the reagents present in the hydrogenation reaction can be used.
  • Suitable such solvents include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, and the like; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, 5 cycloheptane, and the like; and aromatic solvents such as toluene, xylene, ethylbenzene and benzene.
  • the solvent is ordinarily used in an amount sufficient to dissolve the copolymer, and to bring the viscosity of the resulting solution down to a workable range.
  • the hydrogenating agent, copolymer and catalyst are contacted under conditions such that thorough contact of the hydrogenating agent with the copolymer is achieved.
  • this is readily achieved by adding hydrogen gas to a mixture of the copolymer and the catalyst with sufficient agitation to disperse hydrogen gas bubbles through the polymer.
  • Contact times depend somewhat on the degree of hydrogenation desired; however, from about 15 minutes to about 24 hours, preferably about 1 to about 8 hours is ordinarily sufficient.
  • the hydrogenated copolymer can be recovered from the solvent if any is used.
  • the hydrogenated copolymer may be caused to o precipitate out of the solvent by the addition of a polar solvent such as acetone or an alcohol.
  • the solvent may be distilled off, or hot water may be added and a water-solvent azeotrope distilled off.
  • the hydrogenated copolymer may be cleaned up to remove residual catalyst or other impurities, but since the catalyst typically is used in small amounts, such is not usually necessary. 5
  • the following examples are provided to illustrate the invention, but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated. Example 1
  • a 1000 mL Parr pressure reactor is cleaned, evacuated, and repressurized with 0 nitrogen.
  • To the reactor are added 500 mL cyclohexane, which is then deoxygenated thoroughly.
  • 77 g 1,3-butadiene are added, the temperature is raised to 55°C, and 2.7 mL of a 0.567 M solution of sec-butyl lithium in cyclohexane are added.
  • the polymerization reaction proceeds for two hours at 55°C.
  • the reactor is pressurized with hydrogen gas to 300 psig and stirred for 30 minutes.
  • the hydrogen is then vented and 27.7 L of a 0.05 M solution of bis(2,4- dimethylpentadienyl) titanium solution in pentane are added by syringe while the contents of the reartion vessel are at a temperature of 55°C.
  • the vessel is then repressurized with hydrogen to 300 psig. Following an initial exotherm, the reaction vessel is maintained at a temperature of 55°C for 24 hours. The vessel is periodically repressurized with hydrogen as hydrogen is consumed.
  • the reartion vessel is then depressurized and drained.
  • the vessel is washed with toluene to remove residual polymer, and this is added to the drained contents of the reartion vessel.
  • the reaction mixture is very dark, but it turns yellow on exposure to air. Upon drying, the polymer solidifies.
  • Example 2 A 1000 mL Parr pressure reactor is cleaned, evacuated, and repressurized with nitrogen. To the reactor are added 500 mL cyclohexane and 1.2 mL distilled THF, which are then deoxygenated thoroughly. Then, 7.5 g styrene are added, the temperature is raised to 50°C, and 1.5 mL of a 0.57 M solution of sec-butyl lithium in cyclohexane are added. After an initial exotherm, the polymerization reartion proceeds for 40 minutes at 50°C.
  • the reaction vessel is then depressurized and drained.
  • the vessel is washed with toluene to remove residual polymer, and this is added to the drained contents of the reaction vessel.
  • the polymer solution is treated with methanol to precipitate the polymer.
  • the precipitated polymer is dried. Proton NMR analysis of the dried polymer indicates that the polymer contains 30.2 wt.-% styrene. Of the original butadiene block, 84% of the unsaturated sites have been hydrogenated. The polystyrene blocks have not been measurably hydrogenated.

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Abstract

Des composés organiques sont hydrogénés en présence de certains complexes métalliques mono ou bis(pentadiényl) bivalents du groupe IV. Ces complexes titaniques constituent des catalyseurs d'hydrogénation efficaces pour des polymères à insaturation éthylénique. Ils permettent en outre une hydrogénation sélective de sites d'insaturation éthylénique en présence de groupes aromatiques.
PCT/US1995/016005 1994-12-12 1995-12-11 Hydrogenation de polymeres insatures en presence de catalyseurs metalliques du groupe iv contenant un dienyle anionique non aromatique bivalent Ceased WO1996018660A1 (fr)

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AU43773/96A AU4377396A (en) 1994-12-12 1995-12-11 Hydrogenation of unsaturated polymers using divalent non-aromatic anionic dienyl-containing group iv metal catalysts

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US08/353,871 1994-12-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017165521A1 (fr) * 2016-03-24 2017-09-28 Kraton Polymers U.S. Llc Copolymères séquencés semi-cristallins et compositions les contenant

Citations (3)

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Publication number Priority date Publication date Assignee Title
JPS6133132A (ja) * 1984-07-25 1986-02-17 Asahi Chem Ind Co Ltd オレフインの水添方法
EP0434469A2 (fr) * 1989-12-22 1991-06-26 Japan Synthetic Rubber Co., Ltd. Composition de catalyseur d'hydrogénation et procédé pour hydrogéner un polymère à insaturations oléfiniques en utilisant celles-ci
US5075394A (en) * 1990-06-07 1991-12-24 Phillips Petroleum Company Olefin polymerization using supported pentadienyl derivative-transition metal complexes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6133132A (ja) * 1984-07-25 1986-02-17 Asahi Chem Ind Co Ltd オレフインの水添方法
EP0434469A2 (fr) * 1989-12-22 1991-06-26 Japan Synthetic Rubber Co., Ltd. Composition de catalyseur d'hydrogénation et procédé pour hydrogéner un polymère à insaturations oléfiniques en utilisant celles-ci
US5075394A (en) * 1990-06-07 1991-12-24 Phillips Petroleum Company Olefin polymerization using supported pentadienyl derivative-transition metal complexes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8613, Derwent World Patents Index; AN 86-085712 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017165521A1 (fr) * 2016-03-24 2017-09-28 Kraton Polymers U.S. Llc Copolymères séquencés semi-cristallins et compositions les contenant

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