KR100525744B1 - Catalyst Composition Appropriate for Hydrogenation of Conjugated Diene Polymers and Their Uses - Google Patents

Abstract

The present invention provides an alkali metal hydride (b) prepared in a polymer solution from at least the titanium compound (a) of formula (1) and a living polymer added by itself or an alkali metal at the end and / or an alkali metal alkali added thereto. A catalyst composition for hydrogenation of a polymer containing ethylenic unsaturation and a method for hydrogenation of a polymer containing ethylenic unsaturation are provided.

[Formula 1]

[Formula 2]

In the above formula,

A ₁ represents an optionally substituted indenyl group of Formula 2,

Substituents R ₁ and R ₂ may be the same or different and each may contain halogen, one or more identical or different substituents, phenyl, lower alkyl, lower alkoxy, phenoxy, phenylalkoxy, benzyl and tri (lower alkyl) silyl , may be selected from ~NPh2, ~NHPh, ~BPh ₂ and ~B (OPh) ₂ a bulky substituent containing one or more heteroatoms, such as, n is 0 to 4, m is from 0 to 3,

A ₂ represents a cyclopentadienyl group having the same meaning or optionally substituted as A ₁ ,

L ₁ and L ₂ may be the same or different and each is hydrogen, halogen and preferably chlorine, lower alkyl, phenyl, aralkyl with 7 to 10 carbon atoms, lower alkoxy group, phenyloxy, 7 to 10 carbon sources And a phenylalkoxy group, carboxyl, carbonyl, B-diketone ligand, -CH ₂ P (phenyl) ₂ , -CH ₂ Si (lower alkyl) ₃ or -P (phenyl) ₂ group with a group.

Description

Catalyst Compositions Suitable for Hydrogenation of Conjugated Diene Polymers and Their Uses

The present invention relates to catalyst compositions suitable for hydrogenation of conjugated diene polymers and their use.

In particular, the present invention relates to a method for the hydrogenation of a copolymer of a polymer and a conjugated diene polymer using a hydrogenation catalyst composition comprising at least a titanium compound and an alkali metal compound.

Various catalysts are known for the hydrogenation of compounds containing unsaturated double bonds and can be classified into two groups:

(1) heterogeneous catalysts, generally consisting of metals such as Ni, Pd, Pt, Ru, etc., optionally deposited on a support such as carbon, silica, alumina, calcium, carbonate, etc .; And

(2) (a) Ziegler catalysts consisting of a combination of organic salts such as Ni, Co, Fe, Cr, and reducing agents such as organoaluminum compounds, and (b) single component organometallic compounds such as Ru, Rh, Ti, La, etc. .

Although heterogeneous catalysts are used extensively in the industry, they are less active compared to homogeneous catalysts and therefore require large amounts of catalyst and the reaction must be carried out at relatively high pressures and temperatures in order to carry out the desired hydrogenation with such heterogeneous catalysts. Homogeneous catalysts are generally more active; A small amount of catalyst is sufficient and the hydrogenation reaction can be carried out under mild pressure and temperature conditions.

Polymers of conjugated dienes such as 1,3-butadiene and isoprene and copolymers of vinylaromatic monomers such as styrene with such dienes are widely used in the industry as elastomers. Such polymers contain double bonds in the chain that allow vulcanization, but their presence results in low resistance to aging and oxidation. Some block copolymers of conjugated dienes and vinylaromatic hydrocarbons are used as thermoplastic elastomers, without vulcanization, as transparent impact resistant resins, or as modifiers or compatibilizers for polystyrene and polyolefin resins. However, these copolymers have low resistance to aging and oxidation by atmospheric oxygen and ozone due to the presence of double bonds in the chain. Thus, the use of such copolymers in applications requiring exposure to the external environment is limited. Resistance to oxidation by oxygen and ozone and, in general, resistance to aging can be significantly improved by hydrogenation such polymers to obtain total or partial saturation of double bonds. Various methods have been proposed for the hydrogenation of polymers containing olefinic double bonds. Two types of methods are generally included: the supported heterogeneous catalysts described above and the homogeneous catalysts of Ziegler type or organometallic compounds of rhodium and titanium.

In a process using supported heterogeneous catalysts, the polymer to be hydrogenated is first dissolved in a suitable solvent and contacted with hydrogen in the presence of the heterogeneous catalyst. Contact of the catalyst with the reactants is difficult because of the relatively high viscosity of the polymer solution, steric hindrance of the polymer chains, and the high adsorption of the polymer, which, once hydrogenated, remains on the surface of the catalyst and interferes with reaching the active center of the non-hydrogenated polymer. Thus, in order to achieve complete hydrogenation of the double bonds, a large amount of catalyst and heavy reaction conditions are required. Generally this causes degradation and gelation of the polymer. In addition, in the hydrogenation of conjugated dienes and vinylaromatic hydrocarbon copolymers, the aromatic nuclei are also hydrogenated and it is difficult to influence the selective hydrogenation of double bonds of polydiene units. In addition, the physical separation of the catalyst from the solution of the hydrogenated polymer is very difficult, and in some cases complete removal is impossible due to the strong adsorption of the heterogeneous catalyst bed polymer.

In the method of using the Ziegler type catalytic system (described above), the reaction takes place in a substantially homogeneous medium and the hydrogenation of the copolymer can be carried out under mild pressure and temperature conditions. Moreover, it is possible to selectively hydrogenate the double bonds of the poly (conjugated diene) blocks without the aromatic ring hydrogenation of the poly (vinylaromatic hydrocarbon) blocks by appropriate selection of the hydrogenation conditions.

However, the removal of catalyst residues from the necessary reaction products is a complex and expensive step because of these residues which adversely affect the stability of the hydrogenated polymer.

Other methods using other homogeneous catalysts, such as the rhodium compounds described in US Pat. No. 3,898,208 and Japanese Patent 01.289.805, have the disadvantages of expensiveness of rhodium catalysts.

It is known that one of the components, the hydrogenation catalyst, is a derivative of cyclopentadienyltitanium (US Pat. No. 4,501,857) which is necessarily used for the hydrogenation of olefinic double bonds of polymers of conjugated dienes in the presence of organolithium compounds.

European patent application 0460725 describes the use of similar catalyst systems for the hydrogenation of polymers which have been synthesized by organolithium compounds, in which case hydrogenation in the presence of lithium hydride formed in the final reaction required to generate the active catalyst Terminated. Examples of two publications use compound bis (cyclopentadienyl) titanium dichloride (Cp ₂ TiCl ₂ ).

Further improvement of this concept is described using at least 6: 1 molar ratio of alkali metal hydride: titanium in the polymer solution terminated in European Patent Applications Nos. 0549063 A and 0532099 A and using alkyl benzoate as further promoter during hydrogenation. It is.

An example of this foregoing publication uses only compound Cp ₂ TiCl ₂ which appears to be very little soluble in substantially industrially applied solvents.

In British Patent Application No. 2,159,819 A it was pointed out that a species of Cp ₂ TiR ₂ type (R = alkylaryl group) is a catalyst capable of selectively hydrogenating double bonds of polymers and conjugated diene copolymers without requiring the presence of organolithium compounds. .

European Patent Application No. 0434469 A2 discloses a combination of bis-cyclopentadienyl-titanium compounds with aluminum or manganese organometallic compounds and alkali metals in the presence of alkoxides of alkali metals and polar compounds in the form of ethers, ketones, sulfoxides and the like. The use of unusual complex catalyst systems composed of combinations is described. The catalyst system can hydrogenate double bonds of polymers and conjugated diene copolymers.

The claimed further improvement of the latter concept is

(a) bis (cyclopentadienyl) transition metal compounds and especially bis (cyclopentadienyl) titanium dichloride or bis (cyclopentadienyl) titanium dibenzyl,

(b) carbonyl group-containing compounds, compounds containing epoxy groups and especially esters of monobasic or dibasic acids, lactone compounds, lactam compounds and glycidyl methyl ethers, glycidyl n-butyl ethers, glycidyl allyl ethers Epoxy compounds such as glycidyl methacrylate and glycidyl acrylate; At least one polar compound selected from the group consisting of 1,2-butylene oxide, cyclohexene oxide, and

(c) organolithium compounds and especially n-butyllithium, secondary butyllithium, t-butyllithium, phenyllithium, n-hexyl lithium, p-tolyllithium, xyllithium, 1,4-dirithiobutane, alkylenedilithium And living polymers preferably at the ends thereof with lithium

(d) triethyl aluminum, tri-i-butylaluminum, diethyl aluminum chloride, ethyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, aluminum, tri-i-propoxide and aluminum tri-t-butoxide A catalyst composition comprising a reducing organometallic compound selected from the group consisting of aluminum compounds, zinc compounds and manganese compounds has been described in European Patent Application No. 0544304 A. The molar ratio between components (a) and (b) is less than 1 / 0.5 and more preferably 1/2 to 1/30; The molar ratio between components (a) and (c) is 1/1 to 1/40 and more preferably 1/3 to 1/30.

Further claimed improvements from this concept of the use of titanium compounds as hydrogenation catalyst components are described in European Patent Applications No. 0545844 A and 0601953 A, in which the cyclopentadienyl ligands are fully methylated or added to the dimethylsilylene group. Linked together by another ligand R represents an alkoxide group containing from 1 to 20 carbon atoms, or halogen atoms or CH ₂ PPh ₂ , PPh ₂ or CH ₂ SiMe ₃ or PhOR ligands.

However, the method did not provide significant advantages over the prior art described above.

In order to obtain a more economical hydrogenation process, the current industry needs a homogeneous catalyst that is more effective and stable than commonly known and active at sufficiently low concentrations, thus avoiding the expensive step of removing catalyst residues from the hydrogenated polymer. Is feeling.

One object of the present invention is thus formed by an improved hydrogenation process as defined above. It will be appreciated that other objects of the present invention are formed by the catalyst composition used for the process.

As a result of extensive research and experiments, the desired catalysts and methods were surprisingly found.

The present invention therefore provides alkali metal hydrides (b) prepared in a polymer solution from at least the titanium compound of formula (a) and a living polymer added by itself or an alkali metal terminated and / or an alkali metal alkali added thereto It relates to a catalyst composition for hydrogenation of a polymer containing ethylenic unsaturation comprising a).

[Formula 1]

[Formula 2]

Wherein A ₁ represents an optionally substituted indenyl group of formula (2),

Substituents R ₁ and R ₂ may be the same or different and each may contain halogen, one or more identical or different substituents, phenyl, lower alkyl, lower alkoxy, phenoxy, phenylalkoxy, benzyl and tri (lower alkyl) silyl It may be selected from bulky substituents containing one or more hetero atoms such as, -NPh ₂ , -NHPh, -BPh ₂ and -B (OPh) ₂ , n is 0 to 4, preferably 0 to 2 and more preferred Preferably 0 to 1 and m is 0 to 3, preferably 0 to 2, more preferably 0 to 1, and A ₂ has the same meaning as A ₁ or alternatively optionally substituted cyclopentadienyl group And L ₁ and L ₂ may be the same or different and each is hydrogen, halogen and preferably chlorine, lower alkyl, phenyl, aralkyl with 7 to 10 carbon atoms, lower alkoxy group, phenyloxy, 7 to 10 Carbon atoms Gin may be selected from the phenyl alkoxy group, carboxyl, carbonyl, B- diketone coordination body, ~CH ₂ P (phenyl) _2, -CH ₂ Si (lower alkyl) ₃ or ~P (phenyl) ₂ group.

The molar ratio of alkali metal titanium is preferably at least 2: 1.

Alkali metal hydrides preferably use lithium hydrides. The optional addition amount for forming the additional alkali metal hydride with the polymerization initiator used for the starting polymer of the at least one conjugated diene is preferably an organolithium compound. It is preferably methyllithium, ethyllithium, n-propyl lithium, n-butyllithium, secondary-butyl lithium, tertiary butyl lithium, n-hexyl lithium, phenyl lithium, p-tolyl lithium, xyl lithium, 1,4 Dirithiobutane, alkylene dilithium or butyl lithium with divinyl benzene.

Especially preferred are n-butyl lithium, secondary butyl lithium, tert-butyl lithium and phenyllithium. Most preferred are tertiary butyl lithium, secondary-butyllithium or n-butyllithium. The molar ratio of lithium hydride: titanium in the catalyst composition is preferably at least 6 and more preferably in the range of 6-25.

The titanium compound (a) is generally used for hydrogenation in amounts of 5 to 100 mg / kg of conjugated diene polymer, preferably in amounts of 20 to 60 mg / kg of conjugated diene polymer.

Preferred ligands L ₁ and L ₂ in component (a) are chlorine, bromine, carbonyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, secondary-butyl, trimethylsilyloxy, Benzyl, phenyl, hexyl, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, tert-butoxy, secondary-butoxy, pentoxy, neopentoxy, phenoxy, phenylmethoxy, Phenylethoxy and CH ₂ P (phenyl) ₂ groups.

More preferred L ₁ and L ₂ in the titanium catalyst component are both chlorine, benzyl, phenyl, methoxy, ethoxy, isopropoxy, tert-butoxy, n-butoxy, phenoxy or CH ₂ P (phenyl) ₂ Group, and most preferably both are chlorine.

If present, the cyclopentadienyl ring (A ₂ ) may be optionally substituted with one or more identical or different groups, and may include halogen, or optionally one or more identical or different substituents, phenyl, lower alkyl, lower alkoxy , Phenoxy, phenylalkoxy, benzyl and tri (lower alkyl) silyl, -NPh ₂ , -NHPh ₂ , -BPh ₂ and -B (OPh) ₂ can be selected from bulky substituents containing one or more heteroatoms. .

One or more, preferably one or two, of phenyl represented by R may be optionally substituted with one or more substituents selected from lower alkyl, halogen, preferably fluoro or chloro, and lower alkoxy.

Examples thereof are p-tert butylphenyl, pentafluorophenyl, dichlorophenyl, 3,5 di (t-butyl) -4-methoxy phenyl, and trifluorophenyl.

As used herein, the terms "lower alkyl" and "lower alkoxy" refer to groups containing from 1 to 4 carbon atoms.

Most preferred titanium compounds are bis (1-indenyl) titanium dichloride, bis (1-indenyl) titanium diphenoxide, bis (1-indenyl) titanium dimethoxide, bis (1-methylindenyl) titanium di Chloride, bis (5,6-dimethoxy-indenyl) titanium dichloride, bis (dimethoxyindenyl) titanium dichloride, bis (trimethylsilylindenyl) titanium dichloride, (dimethoxyindenyl) (cyclopenta- Dienyl) titanium dichloride, (dimethoxyindenyl) (indenyl) titanium dichloride, (dimethoxyindenyl) (indenyl) titanium dimethoxide, (methoxyindenyl) (indenyl) titanium dichloride, ( Methoxyindenyl) (indenyl) titanium dimethoxide, (1-indenyl) (cyclopentadienyl) titanium dichloride, (1-indenyl) (cyclopentadienyl) titanium dimethoxide, and (1- Indenyl) (cyclopentadienyl) titanium diphenoxide .

Another feature of the present invention is that the polymer solution is formed by a process for hydrogenation of a polymer containing ethylenic unsaturation (double CC bonds) by making strong contact with hydrogen in the presence of at least the catalyst composition components (a) and (b). Will be recognized.

According to a preferred embodiment of the hydrogenation process of the invention, one or more promoters (c) may be present in addition to the catalyst components (a) and (b) described above.

The accelerator (c) may be selected from polar ketone compounds, hydroxy group-containing ketone compounds, aldehyde compounds, ester compounds, lactone compounds, lactam compounds, epoxy compounds and reducing organometallic compounds.

Particularly preferred of the aforementioned accelerators are ketone compounds, hydroxy group-containing ketone compounds, aldehyde compounds, ester compounds and epoxy compounds.

Specific examples of preferred ketone compounds include acetone, diethyl ketone, di-n-propyl ketone, di-i-propyl ketone, di-tert-butyl ketone, di-t-butyl ketone, methyl ethyl ketone, i-propyl methyl Ketones, i-butyl methyl ketone, 2-pentanone, 3-hexanone, 3-decanone, diacetyl, acetophenone, 4′-methoxy acetophenone, 4′-methyl acetophenone, propiophenone, benzophenone , 4-methoxy benzophenone, 4,4'-dimethoxy benzophenone, benzyl phenyl ketone, benzyl acetone, benzoyl acetone, cyclopentanone, cyclohexanone, 4-methyl cyclohexanone, 1,2-cyclohexanedione , Cyclopeptanone, and acetyl acetone.

Hydroxy group-containing ketone compounds are defined as compounds having both intramolecular hydroxy groups and ketone carbonyl groups. Specific examples of preferred compounds include hydroxyacetone, acetoin, 4-hydroxy-2-butanone, 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-butanone, diacetone alcohol , 4- (p-hydroxyphenyl) -2-butanone, 2-hydroxyacetophenone, 2'-hydroxyacetophenone, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 4'- Hydroxy-3'-methoxyacetophenone, 2-hydroxyphenyl ethyl ketone, 4'-hydroxypropiophenone, 2 ', 4'-dihydroxyacetophenone, 2', 5'-dihydroxyaceto Phenone, 2 ', 6'-dihydroxyacetophenone, 3', 5'-dihydroxyacetophenone, 2 ', 3', 4'-trihydroxyacetophenone, 2-hydroxybenzophenone, 4- Hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2,2'-dihydroxybenzophenone, 2,4-dihydroxybenzo Phenone, 4,4'-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4'-trihydroxybenzophenone And benzoin.

As the aldehyde compound, an aliphatic or aromatic aldehyde compound can be used. Aliphatic groups in the aliphatic aldehyde compound may be saturated or unsaturated and may be straight or branched chain. Examples of preferred aldehyde compounds given are formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, i-butylaldehyde, n-valeraldehyde, i-valeraldehyde, pivalaldehyde, n-capronaldehyde, 2-ethylhexylaldehyde , n-heptaldehyde, n-caprylaldehyde, fel araldehyde, n-caprinaldehyde, n-undecylaldehyde, rylaldehyde, tridecylaldehyde, myristylaldehyde, pentadecylaldehyde, palmitylaldehyde, margarylaldehyde , Stearylaldehyde, glyoxal, succinaldehyde, benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, α -naphthaaldehyde, β -naphthaaldehyde, and phenylacenaphthaldehyde.

Examples of ester compounds include monobasic acids such as formic acid, acetic acid, propionic acid, butanoic acid, caproic acid, pelargonic acid, lauryl acid, palmitic acid, stearyl acid, isostearyl acid, cyclohexylpropionic acid, cyclohexyl Dibasic acids such as caproic acid, benzoic acid, phenylbutyl acid and the like are oxalic acid, maleic acid, malonic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, itaconic acid, and phthalic acid. , Isophthalic acid, terephthalic acid, azeraic acid, or polybasic acid is, for example, 1,2,3-propanetricarboxylic acid, 1,3,5-n-pentanetricarboxyl yarn, and the like, and the alcohol is, for example, methyl alcohol, Ethyl alcohol, isopropyl alcohol, n-butyl alcohol, secondary-butyl alcohol, tert-butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, phenol, cresol, 1,3-butanediol, 1,4-butanediol, blood It is ester formed with niacol, pentaerythritol, etc.

Specific examples of lactone compounds include β -propiolactone, γ -butyrolactone, ε -caprolactone, Δα, β - crotonlactone, Δβ, γ -crotonlactone, coumarin, phthalide, α -pyron, sidonone, fluorine Ran et al.

Specific examples of a given lactam compound include β -propiolactam, 2-pyrrolidone, 2-piperidone, ε -caprolactam, n-heptanlactam, 8-octanelactam, 9-nonanlactam, 10-decanelactam, 2- Quinolone, 1-isoquinolone, auxindol, iso-indigo, isatin, hydantoin and quinolidinone.

Specific examples of preferred epoxy compounds include 1,3-butadiene monooxide, 1,3-butadiene dioxide, 1,2-butylene oxide, 2,3-butylene oxide, cyclohexene oxide, 1,2-epoxy cyclododecane , 1,2-epoxy decane, 1,2-epoxy eicosane, 1,2-epoxy heptane, 1,2-epoxy hexadecane, 1,2-epoxy octadecane, 1,2-epoxy octane, ethylene glycol digly Cydyl ether, 1,2-epoxy heptane, 1,2-epoxy tetradecane, hexamethylene oxide, isobutylene oxide, 1,7-octadiene diepoxide, 2-phenylpropylene oxide, propylene oxide, trans-steel Ben oxide, styrene oxide epoxidized 1,2-polybutadiene, epoxidized linseed oil, glycidyl methyl ether, glycidyl n-butyl ether, glycidyl allyl ether, glycidyl methacrylate, and Glycidyl acrylates are included.

Suitable molar ratios of component (a): component (c) consisting of a polar ketone compound, a hydroxy ketone compound, an aldehyde compound, an ester compound, a lactone compound, a lactam compound or an epoxy compound are 10 to 1/2, more preferably 5 to 1, most preferably in the range of 2 to 1.

The reducing organometallic compound may be selected from the group consisting of aluminum compounds, zinc compounds, and magnesium compounds. Specific examples of aluminum compounds are: trimethyl aluminum, triethyl aluminum, tri-i-butyl aluminum, triphenyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, diethyl aluminum Hydride, di-i-butyl aluminum hydride, tri (2-ethylhexyl) aluminum, aluminum tri-i-propoxide, aluminum tri-t-butoxide, and diethyl aluminum ethoxide. Examples of zinc compounds are: diethyl zinc, bis (cyclopentadienyl) zinc, and diphenyl zinc; Examples of magnesium compounds are: dimethyl magnesium, diethyl magnesium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium chloride, and t-butyl magnesium chloride.

In addition to these compounds, compounds containing two or more reducing metals such as lithium aluminum hydride may be used as component (c).

Among the above-mentioned compounds, triethyl aluminum, tri-i-butyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, aluminum tri-t-propoxide, and aluminum tri-i-butoxide are characteristics of usability and ease of handling. From. The molar ratio of components (a) and (c) is preferably greater than 1/20, more preferably 1/1 to 1/18 and most preferably 1/2 to 1/15.

It is surprisingly found that polymers by highly hydrogenation can be obtained according to the process of the present invention, and that the catalyst system exhibits exceptionally high activity in a combination of high selectivity and higher of the starting polymer compared to the homogeneous Ti catalytic hydrogenation process of the prior art. This results in the use of smaller concentrations of catalyst per part by hydrogenation rate or weight of polymer. In addition, the catalyst can be administered more accurately and exhibits excellent reproducibility.

A distinct advantage of the process of the present invention is any difference in hydrogenation between different types of double CC bonds, ie 1,2 vinyl pendant groups, a backbone not containing a substituted C atom, and a carbon double bond in a backbone containing a substituted C-atom. It is formed from the fact that there is no.

The concentration in the final hydrogenated product is lower because the catalyst system in the present process can be applied at certain low concentrations. The hydrogenation process can be carried out at partial hydrogen pressure in the range of 1 to 50 bar, preferably 1 to 35 bar.

All polymers containing olefinic carbon-carbon unsaturated bonds in the polymer backbone or subchain are included in the olefinically unsaturated polymers hydrogenated by the catalyst composition of the present invention. Typical examples are conjugated diene polymers and graft polymers of optional, block, or conjugated dienes and olefins.

Copolymers formed from conjugated diene homopolymers and conjugated dienes or at least one olefin copolymerizable with at least one conjugated diene and conjugated diene are included in the conjugated diene polymer.

Typical examples of conjugated dienes used for the production of a given such conjugated diene polymer are conjugated dienes having 4 to 12 carbon atoms. Specific examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-pentadiene, 1, 3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and chloroprene.

Particular preference is given to 1,3-butadiene and isoprene from the characteristics of elastomer production with excellent properties and industrial advantages. Elastomers such as polybutadiene, polyisoprene, butadiene / isoprene copolymers are particularly preferred as polymeric materials used in the present invention. There is no specific limitation on the microstructure of the polymer. All such polymers are suitable materials for the application of hydrogenation using the catalyst composition of the present invention.

The aforementioned copolymers produced from at least one conjugated diene and at least one olefin copolymerizable with the conjugated diene are also suitable polymeric materials for hydrogenation applied using the catalyst composition of the present invention.

The conjugated diene monomers described above can be used for the preparation of this type of copolymer. Any olefin copolymerizable with such conjugated dienes is useful for the preparation of copolymers with particularly preferred vinyl-substituted aromatic hydrocarbons.

Copolymers of conjugated dienes with vinyl-substituted aromatic hydrocarbons are particularly useful for the production of industrially useful and valuable elastomers or thermoplastic elastomers. Specific examples of a given vinyl-substituted aromatic hydrocarbon used in the preparation of this type of copolymer are styrene, α -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl -p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, and vinylpyridine. Such styrene and α -methylstyrene are particularly preferred. Industrially useful hydrogenated copolymers provided by particular copolymers are butadiene / styrene copolymers, isoprene / styrene copolymers, and butadiene / α -methylstyrene copolymers.

Such copolymers include any copolymers, optionally through polymers distributed in monomers, progressively block copolymers, full block copolymers, and graft copolymers and preferably straight or multiarmed, Radial butadiene-styrene block copolymers, isoprene-styrene block copolymers are reduced.

For the production of industrially useful thermoplastic elastomers, preferred amounts of vinyl-substituted aromatic hydrocarbons range from 15 to 45% by weight.

The content of vinyl bonds in conjugated diene units of at least 10% total conjugated diene units is preferred for obtaining hydrogenated polymers having excellent properties.

Polymers of the straight, branched, or star form, by coupling with spinning or coupling agents, are also included in the polymers that can be used in the hydrogenation process using the catalyst composition of the present invention.

Also included in the hydrogenated polymers according to the invention are those having ends modified with polar groups after living anionic polymerization or other means. Hydroxy groups, carboxyl groups, ester groups, isocyanate groups, urethane groups, amide groups, urea groups, and thiourethane groups can be used as polar groups.

In addition to the polymers described above, any polymer prepared by any polymerization method, for example, anionic polymerization, enion polymerization, coordination polymerization, radical polymerization, solution polymerization, suspension polymerization, and the like, is used in the present invention. Used.

In addition, cyclic olefin polymers prepared by ring-opening polymerization using metathesis catalysts such as molybdenum and tungsten are included in polymers having olefinically unsaturated bonds.

In the hydrogenation reaction using the catalyst composition of the present invention, the olefinically unsaturated polymer can be hydrogenated under conditions where it can be dissolved in a hydrocarbon solvent, or the olefinically unsaturated polymer can be produced by polymerization in a hydrocarbon solvent and continuously hydrogenated. Can be.

Hydrocarbon solvents used in the hydrogenation reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and the like; Aliphatic ring hydrocarbons, for example cyclopentane, methyl cyclopentane, cyclohexane and the like or aromatic solvents such as toluene. Such hydrocarbon solvents may contain up to 20% by weight of ethers such as diethyl ether, tetrahydrofuran, dibutyl ether, diethoxypropane, and dioxane.

There is no restriction on the concentration of polymer in carrying out the hydrogenation process of the present invention. In general, however, the polymer concentration is in the range of 1 to 30% by weight, preferably 3 to 20% by weight. After addition of an inert gas, such as nitrogen or argon, or a hydrogenation catalyst composition under hydrogen atmosphere by hydrogen supply, it is influenced by stirring or not while maintaining the temperature of the polymer solution at a certain temperature.

Suitable temperatures for the hydrogenation reaction are in the range of 0 to 150 ° C. The temperature below 0 ° C is uneconomical because not only the catalyst activity is lowered at a temperature below 0 ° C, but also the hydrogenation rate is delayed. On the other hand, if the temperature is 150 ° C. or higher, not only the polymer decomposes or gels, but also the aromatic ring is hydrogenated simultaneously, resulting in poor hydrogenation selectivity. Preferably, the temperature is in the range of 20 to 140 ° C, more preferably 50 to 130 ° C. In the hydrogenation reaction using the catalyst composition of the present invention, the reaction can be carried out at a relatively high temperature, resulting in a large rate and high yield of the reaction.

The hydrogenation reaction is carried out in the range of 1 minute to 5 hours. The greater the amount of catalyst composition used and the higher the pressure, the shorter the reaction time.

It will be appreciated that other features of the present invention are formed by the titanium catalyst component (a) according to formula (1). This catalyst component (a) is a new compound except for unsubstituted (1-indenyl) (cytopentadienyl) titanium dichloride and bis (1-indenyl) titanium dichloride. Such compounds are known principles such as J. Organometallic Chemistry, Issue 4, pages 156-158 (1965), Organometallics 1984 (3), 223, and J Am Chem. Soc. It may be prepared by the method in 1990, 112, 2030. In particular the titanium compound of formula (1), two indenyl groups substituted by lower alkyl or lower alkoxy or halogen substituted by the aforementioned specific groups or one substituted indenyl and one optionally substituted cyclopentadienyl group desirable.

The invention will be illustrated by the following examples.

Example 1

Preparation of bis (1-methylindenyl) titanium dichloride

1.36 g of 1-methylindenyl lithium (10.1 mmol) is added to a solution of 0.91 g of TiCl ₄ (4.8 mmol) in 50 ml of dichloromethane at −20 ° C. The mixture is covered to room temperature, stirred for 1 hour, centrifuged, then the clear solution is decanted and evaporated in vacuo. The residue is washed with pentane / di-ethylether and pentane to give 80% pure product (0.2 mmol), isolated, which is the desired product in 2%.

Example 2

Preparation of bis (1- (pentafluorophenyl) indenyl) titanium dichloride

1.34 g of 1- (pentafluorophenyl) indenyl lithium (4.7 mmol) is added to a solution of 0.42 g of TiCl ₄ (4.7 mmol) in 40 ml of dichloromethane at −20 ° C. The mixture is covered to room temperature, stirred for 1 hour, centrifuged, then the clear solution is decanted and evaporated in vacuo. The residue is washed with hexane to give the desired product. One isomer is separated into 265 mg (0.4 mmol), 17%.

Example 3

Preparation of bis (5,6-dimethoxyindenyl) titanium dichloride

1.04 g of 5,6-dimethylindenyl lithium (4.1 mmol) is added to a solution of 0.38 g of titanium (IV) chloride (2.0 mmol) in 40 ml of dichloromethane at -20 ° C. The mixture is covered to room temperature and centrifuged by stirring for 1 hour. The clear solution is decanted and evaporated in vacuo. The residue is washed with diethyl ether (2 x 30 mL) and the residue is extracted with 40 mL of dichloromethane. The solvent is evaporated to yield 590 mg of the desired product (63%).

Example 4

Preparation of bis (1-indenyl) dimethylsilyl titanium dichloride

η -butyllithium (6.1 g, 1.6 M in hexane) is added to a stirred solution of dimethylsilyl-bis-indene (2 g) in dry hexane (40 mL) at -70 ° C. The reaction mixture is covered to room temperature and stirred for 20 hours. The white precipitate is separated and washed with pentane and then dried under reduced pressure. The powder obtained is slowly added to a solution of TiCl ₄ (1.5 g) in dichloromethane (60 mL) at −70 ° C. The reaction mixture is covered to room temperature and stirred for one hour. The solid formed is removed by centrifugation. The remaining solution is evaporated until the evaporation material is removed. The rough product is washed three times with pentane and dried under reduced pressure. 60 mg (2%) rac + meso bis (1-indenyl) dimethylsilyl titanium dichloride is obtained as a very dark brown crystallization derived from hexane and dichloromethane.

Example 5

Preparation of Bis (1-Indenyl) ethylene Titanium Dichloride

0.96 g TiCl ₄ (5.07 mmol) is dissolved in 40 mL of CH ₂ Cl ₂ , cooled to −40 ° C. and 1.36 g of bis- (1-indenyl) ethylene bis-lithium (5.07 mmol) is added as a solid. After stirring for 2 hours at room temperature, the reaction mixture is centrifuged to remove LiCl. The CH ₂ Cl ₂ layer is evaporated and dried to give (1-indenyl) ethylene titanium dichloride as brown crystals and washed twice with hexane.

Example 6

Preparation of Hydrogen Terminated SBS Block Copolymer

A 30 L batch of polystyrene-polybutadiene-polystyrene (SBS) block copolymers of 70,000 molecular weight are prepared by continuous anionic polymerization using secondary-butyllithium as initiator in a stainless steel reactor. Polymerization is carried out in cyclohexane and 140 ppm of diethoxypropane are added in 18% by weight solids. The 1,2-content of the SBS polymer is 40.4 weight percent.

At the end of the polymerization reactor, the reactor is sparged with hydrogen for 2 hours and terminated with a living SBS-Li polymer to produce SBS and LiH. The LiH content of the batch is measured at 2.2 mmol / L.

Example 7

Hydrogenation of Bis (indenyl) Titanium Dichloride and SBS Block Copolymers

The stainless steel reactor is filled with 190 g of SBS cement prepared as described in Example 6. The temperature of the reactor is fixed at 70 ° C. and the cement is saturated by pressurizing the reactor with 10 bar of hydrogen. In the meantime, a suspension of 14 mg (0.04 mmol) of bisdendenyl titanium dichloride in 10 ml of cyclohexane is prepared. The catalyst suspension is added to the reactor and the hydrogen pressure is raised to 50 bar. A strong exothermic reaction takes place immediately (T = 82 ° C). Hydrogenation is allowed for 3 hours, during which time the sample is withdrawn from the reactor and analyzed by 1 H NMR to determine the conversion of olefinic double bonds.

Conversion is measured at 72% after 15 minutes, 75% after 60 minutes and 77% after 180 minutes.

Example 8

Hydrogenation of Bis (indenyl) Titanium Dichloride and SBS Block Copolymers

The stainless steel reactor is filled with 800 g of SBS cement prepared as described in Example 6. The temperature of the reactor is fixed at 50 ° C. and the reactor is pressurized with 10 bar of hydrogen to saturate the cement. In the meantime, a suspension of 29 mg (0.084 mmol) of bisdendenyl titanium dichloride in 10 ml of cyclohexane is prepared. The catalyst suspension is added to the reactor and the hydrogen pressure is raised to 50 bar. A strong exothermic reaction occurs immediately. Hydrogenation is allowed for 3 hours, during which time the sample is withdrawn from the reactor and analyzed by 1 H NMR to determine the conversion of olefinic double bonds. The same method is performed twice more with 58 mg (0.168 mmol) and 87 mg (0.252 mmol) bisdendenyltitanium dichloride. The results are summarized in Table 1.

TABLE 1

Hydrogenation Results of Different Amounts of Bisdendenyl Titanium Dichloride

Comparative Example

Hydrogenation of Bis (cyclopentadienyl) titanium Dichloride and SBS Block Copolymers

The stainless steel reactor is filled with 800 g of SBS cement prepared as described in Example 6. The temperature of the reactor is fixed at 50 ° C. and the reactor is pressurized with 10 bar of hydrogen to saturate the cement. In the meantime, a suspension of 21 mg (0.084 mmol) of biscyclopentadienyltitanium dichloride in 10 ml of cyclohexane is prepared. The catalyst suspension is added to the reactor and the hydrogen pressure is raised to 50 bar. Hydrogenation is allowed for 3 hours, during which time the sample is withdrawn from the reactor and analyzed by 1 H NMR to determine the conversion of olefinic double bonds. The conversion is determined to be 22% by weight after 15 minutes, 51% by 60 minutes and 60% by 180 minutes, which is much lower than the same amount of bisdendenyltitanium dichloride.

Example 9-11

Hydrogenation of Substituted Bis (indenyl) Titanium Dichloride Compounds with SBS Block Copolymers

Three further hydrogenation experiments were carried out using 0.04 mmol of the catalyst prepared in Examples 1-3 in the same manner as described in Example 7. The results are shown in Table 2.

TABLE 2

Hydrogenation Results with Different Indenyl Titanium Catalysts

Example 12-14

Hydrogenation of bis (indenyl) titanium dichloride and SBS block copolymers in the presence of dimethyloxalate

The stainless steel reactor is filled with 190 g of SBS cement prepared as described in Example 6. To the reactor is added 4.7 mg (0.04 mmol) dimethyloxalate in 10 ml of cyclohexane. The temperature of the reactor is fixed at 70 ° C. and the cement is saturated by pressurizing the reactor with 10 bar of hydrogen. In the meantime, a suspension of 14 mg (0.04 mmol) of bisindenyltitanium-dichloride in 10 ml of cyclohexane is prepared. The catalyst suspension is added to the reactor and the hydrogen pressure is raised to 50 bar. Hydrogenation is allowed for 3 hours, during which time the sample is withdrawn from the reactor and analyzed by 1 H NMR to determine the conversion of olefinic double bonds. The results are shown in Table 3.

TABLE 3

Hydrogenation Results with Bisdendenyl Titanium Dichloride Modified with Dimethyl Oxalate

Example 15-16

Hydrogenation of Bridged Bis (indenyl) Titanium Dichloride Compounds and SBS Block Copolymers

According to the same method as described in Example 7, two hydrogenation experiments are carried out using 0.04 mmol of the catalyst of Examples 4 and 5. The results are shown in Table 4.

TABLE 4

Hydrogenation Results with Bridged Bisdendenyl Titanium Compounds

From this example relating to Examples 7-12 it will be appreciated that the introduction of bridging substituents between indenyl groups does not certainly improve the hydrogenation process.

Example 17

(Indenyl) (cyclopentadienyl) hydrogenation of titanium dichloride and SBS block copolymer

The stainless steel reactor is filled with 800 g of SBS cement prepared as described in Example 6. The temperature of the reactor is fixed at 50 ° C. and the reactor is pressurized with 10 bar of hydrogen to saturate the cement. To the reactor is added 0.109 mmol of (indenyl) (cyclopentadienyl) titanium chloride in 10 ml of cyclohexane. The catalyst suspension is added to the reactor and the hydrogen pressure is raised to 50 bar. An exothermic reaction occurs immediately. Hydrogenation is allowed for 3 hours, during which time the sample is withdrawn from the reactor and analyzed by 1 H NMR to determine the conversion of olefinic double bonds. In the same way it is carried out twice more with 0.109 mmol of (5-methoxyindenyl) (cyclopentadienyl)-and (5,6-dimethoxyindenyl) (cyclopentadienyl) titanium dichloride. The results are summarized in Table 5.

TABLE 5

Hydrogenation with optionally substituted (indenyl) (cyclopentadienyl) titanium dichloride

Claims (2)

(a) a titanium compound of formula 1, and (b) alkali metal hydrides prepared in situ in the polymer solution either from themselves, or from a living polymer with an alkali metal at the end and / or from an additionally added alkali metal alkyl. As a catalyst composition for hydrogenation of a polymer containing ethylenic unsaturation comprising: [Formula 1]

[Formula 2]

In the above formula, A ₁ represents an optionally substituted indenyl group of Formula 2, Substituents R ₁ and R ₂ are the same or different and each contains halogen, phenyl, lower alkyl, alkoxy, phenoxy, phenylalkoxy, benzyl and one or more hetero atoms, which may optionally include one or more identical or different substituents Selected from bulky substituents, n is an integer from 0 to 4 and m is 0 to 3, A ₂ represents a cyclopentadienyl group having the same meaning or optionally substituted as A ₁ , L ₁ and L ₂ are the same or different and each is hydrogen, halogen, lower alkyl, phenyl, aralkyl having 7 to 10 carbon atoms, lower alkoxy group, phenyloxy, phenylalkoxy group having 7 to 10 carbon atoms , Carboxyl, carbonyl, B-diketone coordination, -CH ₂ P (phenyl) ₂ , -CH ₂ Si (lower alkyl) ₃ or -P (phenyl) ₂ group. A process for hydrogenating an polymer containing ethylenic unsaturation comprising strongly contacting a polymer solution with hydrogen in the presence of at least one catalyst composition according to claim 1.