CA2247669A1 - Synthesis of 1,4-trans-polybutadiene using a lanthanide organic acid salt catalyst - Google Patents
Synthesis of 1,4-trans-polybutadiene using a lanthanide organic acid salt catalyst Download PDFInfo
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- CA2247669A1 CA2247669A1 CA002247669A CA2247669A CA2247669A1 CA 2247669 A1 CA2247669 A1 CA 2247669A1 CA 002247669 A CA002247669 A CA 002247669A CA 2247669 A CA2247669 A CA 2247669A CA 2247669 A1 CA2247669 A1 CA 2247669A1
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- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
Abstract
The invention provides a catalyst composition, comprising: (a) an organolithium compound;
and, (b) an organic acid salt of lanthanide series element; wherein: (1) only components (a) and (b) are required to promote the synthesis of 1,4-trans-polybutadiene; (2) the ratio of component (a) to component (b) is selected to maximize formation of the trans structure of said 1,4-trans-polybutadiene; and, (3) components (a) and (b) are selected for enabling further diblock synthesis.
The invention further contemplates a process for using the catalyst to synthesize 1,4-trans-polybutadiene and other polymers and copolymers having trans configuration in the conjugated diene monomer contributed units.
and, (b) an organic acid salt of lanthanide series element; wherein: (1) only components (a) and (b) are required to promote the synthesis of 1,4-trans-polybutadiene; (2) the ratio of component (a) to component (b) is selected to maximize formation of the trans structure of said 1,4-trans-polybutadiene; and, (3) components (a) and (b) are selected for enabling further diblock synthesis.
The invention further contemplates a process for using the catalyst to synthesize 1,4-trans-polybutadiene and other polymers and copolymers having trans configuration in the conjugated diene monomer contributed units.
Description
~ CA 02247669 1998-09-17 ~, .
FIELD OF THE INVENTION
The instant invention broadly relates to catalysts used in the promotion of organic chemical 2 reactions with a catalyst. More specifically, the invention relates to the use of a catAlyst composition 3 co...~ g a metallo-organic salt of a l~nthAni~le el~m~nt for promoting a polym~ri7~tion synthesis 4 which produces synthetic polymers from conjugated diene monomçrs. Still more specifically, the S invention relates to the ~ ition of a catalytically effective combination of two compo~ . (1) an 6 organic acid salt of a l~l.tl.A.. series compound, and (2) an organolithium compound, for 7 promoting the chemical synthesis of 1,4-trans-polybutadiene, while having further utility in the 8 synthesis of diblock polymers.
This invention relates to the poly.. ~ ;on of conjugated diene monomers using a catalyst 11 system co~l1S~ a co~ l of a rare earth elem~nt i.e. an çl~m~nt having an atomic number of 12 57 to 71 inclusive.
13 Use of l~nth~ni~e series catalysts in the synthesis of 1,4-trans-polybutadiene is known in the 14 prior art. For i~ ce United States patent 4,619,982 to Jenkins, discloses the use of various catalyst 15 systems c~ -g rare earth compounds for the poly..~ ;on of conjugated diene monomers, in 16 recentyears. ~Y~mples of such ~ clos.lres are (1) Mazzei A., Makromol. Chem. Suppl.4 61 (1981);
17 (2) Witte J., Angew. Makromol. Chem. 94 119 (1981), (3) Shen Tse-Chuan et al, J. Pol. Sci. Polym.
18 Chem. Ed. 18 3345 (1980); (4) Marwede G. and Sylvester G., Trans. 22nd Annual Procee-lin~ of 19 the Tntt-rn~tional Institute of Synthetic Rubber Producers, Madrid Paper III-3 (1981). Such catalyst 20 systems have two or three components, for exarnple a lanthanoid alkyl, alkoxide or salt (e.g.
' CA 02247669 1998-09-17 neodymium tricarboxylate) with an organoaluminium compound and optionally a Lewis Acid.
2 When a ll-allyl complex of a rare earth such as Ln(allyl) dioxane, where Ln also a l~nth~nide 3 element, is used which gives a polymer of predominAntly trans 1,4 content, and which needs no 4 cocatalyst. Such ~-allyl catalysts are described in the paper by Ma77ei lcr~ ,d to above and appear to proceed by an ionic meçhAni~m 6 One embodiment of the Jenkins invention ~ Oses a two co~ onelll catalyst for the homo 7 polym~ri 7Ation of a conj u~,aled diene or the copoly~ ;on of a colli ug~led diene with one or more 8 other conjugated dienes comprising (a) a salt of a rare earth element or a CO1111~1CA of a rare earth 9 element and (b) an organo mAg~ ;ulll compound. The Jenkins invention also includes the use of a catalyst, as just ~l~fin~ in the homo poly. - ;~i1l;on of a conjugated diene. Surprisingly, Jenkins 11 found that the product of such a polym~ri7~tion employing an organo m~p,~.F.~;ulll compoulld as 12 cocatalyst is a conjugated diene polymer having a very high content of trans isomer. The rare earth 13 ~lem~nt in component (a) of the catalyst of are those having an atomic number of 57 (IA-I~
14 to 71 (lulcli~n). However, the poly~ ;on activity of certain of these elements, e.g. samarium or eulop;ulll, is known to be low. Thus, a compound of cerium, praseodymium, neodyll~ilull, 16 gadolinium, terbium or dysprosium is plcr~ ,d by Jenlcins. A compound of two or more rare earth 17 elements may be used. A compound of neodymium or "didymium" (which is a mixture of rare earth 18 elements cont~ining approximately 72% neodymium, 20%1~ l.. l and 8% praseodymium) is 19 preferred. Preferably component (a) is soluble in hydrocarbon polymerizationmedium, examples 20 being the carboxylates, alkoxides and diketones. Examples of compounds for use as component (a) 21 are "didymium" versatate (derived from versatic acid, a synthetic acid composed of a mixture of 22 highly branched isomers of C,0 monocarboxylic acids, sold by Shell Chemicals), praseodymium ~ CA 02247669 1998-09-17 (2,2,6,6-tetramethyl-3,5-heptane dione). "Didymium" and especially neodymium "vc.~lale" are 2 pl~;re.l~ d on the grounds of ready solubility, ease of ple~ lion and stability. Component (b) of the 3 catalyst is an organo m~gnesium compound. Dihydrocarbyl m~..esiu", compounds of formula R2 4 Mg where each R, which may be the same or dirr.,~l.l, is for example, an alkyl (including 5 cycloalkyl), aryl, aralkyl, allyl or cyclodiene group. Dialkyl m~Sium compounds, where each 6 alkyl group has from 1 to 10 carbon atoms, are pler~ ,d. Magnesium dibutyl was particularly 7 pl~f~led by Jenkins on the g~ ds of ease of availability. The organo m~n~sjum compound may 8 also be a hydrocarbon soluble Grignard reagent of formula RMgX where R is a hydro-carbyl group 9 such as ~Y~mplified above and X is chlorine, I)r~ e or iodine. The molar ratio of collll)oll~ .lL (a) to component (b) was plc;r.,lably 0.01:1 to 0.5:1 more preferably 0.06:1 to 0.3:1. Absolute 11 concentration of component (b) may be for example, 1 to 5 millimolesper hundred grams of 12 polym~ri~ble monomer. Similarly in the publication Polymer, 1985, 2~, pl47, D.K. Jenkins 13 disclosed t;A~ nt~ ~L~e;ll high trans polybutadiene was obtained by using a catalyst system 14 co...~ ;..garareearthcompoundplusam~siumdialkyl. Thepolymeral)pealcdtocontainsome 15 "live" chain ends.
16 In another United States patent, 4,931,376, to Tkem~t~l et al, another process for the 17 homopolyl . IL~ l ;on of a high-trans polybutadiene is described. Tkem~t~ provides a process for 18 producing crystalline trans-butadiene polymers. The process compri~es using a complex~cl catalyst 19 compri~ing (a) an organic acid salt of l~nth~num or cerium and (b) an organic m~gn~.~ium compound 20 as the ess~nti~l components. T.~nth~m-m and cerium which are the main components in the 21 complexed catalyst of the Ik~m~t~l invention are metals occurring abundantly among l~nth~nide 22 transition metals (rare earth metals) and commercially readily available at relatively low cost.
TkPm~t~u unexpectedly found that a conjugated diene can be polymerized by using the complexed 2 catalyst of the present invention to provide a conjugated diene polymer having high trans content at 3 a very high activity, and yet the polymer obtained has a high molecular weight and a narrow 4 molecular weight distribution, co~ g sllbst~nti~lly no gel, the polymer thus obtained exhibiting excellent workability and physical properties. The organic acid salt of 1~ .. " or cerium which 6 is the colll~nel-l (a) in the co~plexed catalyst of the present invention can readily be obtained by, 7 for eA~ le, making an alkali metal salt of an organic acid as shown below to react with a chloride 8 of l~nll,~ .., or cerium in water or an organic solvent such as alcohols, ketones, etc. The organic 9 acidsaltofl~nth~nnmorceriummaycontaininorganicsaltsofl~ l1h~llllllorceriumororganicacids 10 as the impurities in small amounts.
FIELD OF THE INVENTION
The instant invention broadly relates to catalysts used in the promotion of organic chemical 2 reactions with a catalyst. More specifically, the invention relates to the use of a catAlyst composition 3 co...~ g a metallo-organic salt of a l~nthAni~le el~m~nt for promoting a polym~ri7~tion synthesis 4 which produces synthetic polymers from conjugated diene monomçrs. Still more specifically, the S invention relates to the ~ ition of a catalytically effective combination of two compo~ . (1) an 6 organic acid salt of a l~l.tl.A.. series compound, and (2) an organolithium compound, for 7 promoting the chemical synthesis of 1,4-trans-polybutadiene, while having further utility in the 8 synthesis of diblock polymers.
This invention relates to the poly.. ~ ;on of conjugated diene monomers using a catalyst 11 system co~l1S~ a co~ l of a rare earth elem~nt i.e. an çl~m~nt having an atomic number of 12 57 to 71 inclusive.
13 Use of l~nth~ni~e series catalysts in the synthesis of 1,4-trans-polybutadiene is known in the 14 prior art. For i~ ce United States patent 4,619,982 to Jenkins, discloses the use of various catalyst 15 systems c~ -g rare earth compounds for the poly..~ ;on of conjugated diene monomers, in 16 recentyears. ~Y~mples of such ~ clos.lres are (1) Mazzei A., Makromol. Chem. Suppl.4 61 (1981);
17 (2) Witte J., Angew. Makromol. Chem. 94 119 (1981), (3) Shen Tse-Chuan et al, J. Pol. Sci. Polym.
18 Chem. Ed. 18 3345 (1980); (4) Marwede G. and Sylvester G., Trans. 22nd Annual Procee-lin~ of 19 the Tntt-rn~tional Institute of Synthetic Rubber Producers, Madrid Paper III-3 (1981). Such catalyst 20 systems have two or three components, for exarnple a lanthanoid alkyl, alkoxide or salt (e.g.
' CA 02247669 1998-09-17 neodymium tricarboxylate) with an organoaluminium compound and optionally a Lewis Acid.
2 When a ll-allyl complex of a rare earth such as Ln(allyl) dioxane, where Ln also a l~nth~nide 3 element, is used which gives a polymer of predominAntly trans 1,4 content, and which needs no 4 cocatalyst. Such ~-allyl catalysts are described in the paper by Ma77ei lcr~ ,d to above and appear to proceed by an ionic meçhAni~m 6 One embodiment of the Jenkins invention ~ Oses a two co~ onelll catalyst for the homo 7 polym~ri 7Ation of a conj u~,aled diene or the copoly~ ;on of a colli ug~led diene with one or more 8 other conjugated dienes comprising (a) a salt of a rare earth element or a CO1111~1CA of a rare earth 9 element and (b) an organo mAg~ ;ulll compound. The Jenkins invention also includes the use of a catalyst, as just ~l~fin~ in the homo poly. - ;~i1l;on of a conjugated diene. Surprisingly, Jenkins 11 found that the product of such a polym~ri7~tion employing an organo m~p,~.F.~;ulll compoulld as 12 cocatalyst is a conjugated diene polymer having a very high content of trans isomer. The rare earth 13 ~lem~nt in component (a) of the catalyst of are those having an atomic number of 57 (IA-I~
14 to 71 (lulcli~n). However, the poly~ ;on activity of certain of these elements, e.g. samarium or eulop;ulll, is known to be low. Thus, a compound of cerium, praseodymium, neodyll~ilull, 16 gadolinium, terbium or dysprosium is plcr~ ,d by Jenlcins. A compound of two or more rare earth 17 elements may be used. A compound of neodymium or "didymium" (which is a mixture of rare earth 18 elements cont~ining approximately 72% neodymium, 20%1~ l.. l and 8% praseodymium) is 19 preferred. Preferably component (a) is soluble in hydrocarbon polymerizationmedium, examples 20 being the carboxylates, alkoxides and diketones. Examples of compounds for use as component (a) 21 are "didymium" versatate (derived from versatic acid, a synthetic acid composed of a mixture of 22 highly branched isomers of C,0 monocarboxylic acids, sold by Shell Chemicals), praseodymium ~ CA 02247669 1998-09-17 (2,2,6,6-tetramethyl-3,5-heptane dione). "Didymium" and especially neodymium "vc.~lale" are 2 pl~;re.l~ d on the grounds of ready solubility, ease of ple~ lion and stability. Component (b) of the 3 catalyst is an organo m~gnesium compound. Dihydrocarbyl m~..esiu", compounds of formula R2 4 Mg where each R, which may be the same or dirr.,~l.l, is for example, an alkyl (including 5 cycloalkyl), aryl, aralkyl, allyl or cyclodiene group. Dialkyl m~Sium compounds, where each 6 alkyl group has from 1 to 10 carbon atoms, are pler~ ,d. Magnesium dibutyl was particularly 7 pl~f~led by Jenkins on the g~ ds of ease of availability. The organo m~n~sjum compound may 8 also be a hydrocarbon soluble Grignard reagent of formula RMgX where R is a hydro-carbyl group 9 such as ~Y~mplified above and X is chlorine, I)r~ e or iodine. The molar ratio of collll)oll~ .lL (a) to component (b) was plc;r.,lably 0.01:1 to 0.5:1 more preferably 0.06:1 to 0.3:1. Absolute 11 concentration of component (b) may be for example, 1 to 5 millimolesper hundred grams of 12 polym~ri~ble monomer. Similarly in the publication Polymer, 1985, 2~, pl47, D.K. Jenkins 13 disclosed t;A~ nt~ ~L~e;ll high trans polybutadiene was obtained by using a catalyst system 14 co...~ ;..garareearthcompoundplusam~siumdialkyl. Thepolymeral)pealcdtocontainsome 15 "live" chain ends.
16 In another United States patent, 4,931,376, to Tkem~t~l et al, another process for the 17 homopolyl . IL~ l ;on of a high-trans polybutadiene is described. Tkem~t~ provides a process for 18 producing crystalline trans-butadiene polymers. The process compri~es using a complex~cl catalyst 19 compri~ing (a) an organic acid salt of l~nth~num or cerium and (b) an organic m~gn~.~ium compound 20 as the ess~nti~l components. T.~nth~m-m and cerium which are the main components in the 21 complexed catalyst of the Ik~m~t~l invention are metals occurring abundantly among l~nth~nide 22 transition metals (rare earth metals) and commercially readily available at relatively low cost.
TkPm~t~u unexpectedly found that a conjugated diene can be polymerized by using the complexed 2 catalyst of the present invention to provide a conjugated diene polymer having high trans content at 3 a very high activity, and yet the polymer obtained has a high molecular weight and a narrow 4 molecular weight distribution, co~ g sllbst~nti~lly no gel, the polymer thus obtained exhibiting excellent workability and physical properties. The organic acid salt of 1~ .. " or cerium which 6 is the colll~nel-l (a) in the co~plexed catalyst of the present invention can readily be obtained by, 7 for eA~ le, making an alkali metal salt of an organic acid as shown below to react with a chloride 8 of l~nll,~ .., or cerium in water or an organic solvent such as alcohols, ketones, etc. The organic 9 acidsaltofl~nth~nnmorceriummaycontaininorganicsaltsofl~ l1h~llllllorceriumororganicacids 10 as the impurities in small amounts.
11 Various l~nth~nide series catalysts are known by the prior art. For instance, see: J. Am.
12 Chem. Soc., vol. 104, pp. 6571-6473 (1982), Patricia L. Watson and D. Christopher Roe, 13 "Beta-Alkyl Transfer in a r ~nth~ni~le Model for Chain Te ...i~ ion;" J. Am. Chem. Soc., vol. 107, 14 pp. 8091-8103 (1985), Gerald Jeske, Harald Lauke, Heiko M~lçnn~nn, Paul N. Swepston, Herbert 15 Schl-m~nn and Tobin J. Marks, "Highly Reactive Organol~nth~nides. Systematic Routes to and 16 Olefin Chemistry of Early and Late Bis(pçnt~mPthylcyclopentadienyl) 4f Hydrocarbyl and Hydride 17 Complexes;" Also exemplary in displaying the utility of l~nth~nide series compounds in catalyst i8 systems for the production synthetic rubbers is United States Patent No. 4,152,295 teaching the 19 reaction of a conjugated diolefin with at least one compound selected from the group consisting of 20 a carboxylic acid and a carboxylic acid anhydride in the presence of oxygen and a catalyst 21 comprising a rare earth metal compound, an alkali metal compound and a halide compound.
' CA 02247669 1998-09-17 United States Patent No. 4,461,883 teaches a process for producing a conjugated diene 2 polymer, char~cteri7~cl by pol~ g at least one conjugated diene with a catalyst con~i~ting of:
3 (A) a reaction product of a Lewis base and a carboxylate of a rare earth element of the lanthanum 4 series l~p~3c~lled by Ln(R~CO2)3 wherein Ln is a rare earth Plem~nt of the l~nth~nllm series having S an atomic number of 57 to 71 and Rl is a h~ 1~OC~1JO1I s~ ;t.~ having 1 to 20 carbon atoms; (B) 6 an organic al..... i.. ..compound l~lese~lled by AIR2R3R4 wll~ in R2, R3 and R4, which may be 7 identical or di~.e.~, r~le3~"ll hydrogen atoms or hy~oc~l,on sllbstitll~nt~ having 1 to 8 carbon 8 atoms, eY~lllding the case where all of R2, R3 and R4 are hydrogen atoms at the same time, and, (C) 9 an (alkyl)~l.~ .. i.. ~ halide le~ s~lled by AlXn R53 n wherein X is Cl, Br, F or I; R5 is a hydrocarbon 10sllbstihllont having 1 to 8 carbon atoms; and n has a value of 1, 1.5, 2 or 3, or con~icting ofthese (A), 11 (B) and (C) co...l~lu..l~; and (D) a conjug~t~,d diene. A polymer obtained by the process has a high 12 cis-1,4-configuration content and is excellent in physical plope~lies of v ~ ";,~l~
13United States Patent No. 5,612,427 teaches a su~oll~d solid catalyst which can be used for 14 the polymerization and copolym~ri7~tion of conjugated dienes. The basis of the catalyst is the 15 reaction product of: A) a solid MgCl2 su~l,o~l; B) an ether, ~l~f~ bly THF, as swelling agent for 16 the ~,u~po,l, C) a metal salt selecte~ from among metals having an atomic number of belw~;en 57 and 17 71 or 92 in the periodic table of elements and, if the metal salt is not a halide; D) a halogenation 18 agentselectedfromthegroupcon~i~tingofahalogenatedcompoundofal..,~.;.,ll,.. andahalogenated 19 compound not colll;1i..i.~g alllminllm, the reaction solid being free from the swelling agent; plus, E) 20 an organic derivative of alnminllm which is obligatory when the halogenation agent is not a 21 halogenated compound of alnminum and optional when the halogenation agent is a derivative of 22 aluminum.
' CA 02247669 1998-09-17 United States Patent No. 4,696,984 teaches isoprene polymers and copolymers which are 2 prepared by a polymeri_ation process carried out in the absence of solvents and in the pl~sellce of 3 a catalytic system comprising (a) at least one element or compound of an element pe~ lg to 4 Group IIIB of the Periodic Table, (b) at least one alumin~ll alkyl de.;v~live, (C) at least one organic 5 halogen derivative or at least one halide of an element able to exist in at leasttwo valency 6 states with the halide colles~ollding to a higher state than the .,.i.~ ...., or at least one halogen or 7 at least one hydrogen halide acid, (d) at least one compound co.~ -g one or more h~ l groups 8 of which the hydrogen can be ~b~ the ratio of compoll~,.ll (b) to component (a) being equal 9 to or less than 20.
United States Patent No. 5,610,114 teaches a ~u~olled solid catalyst which can be used for 11 the polymeri_ation and copolym~ i7~tion of conjugated dienes. The basis of the catalyst is the 12 reaction product of: A) a solid MgCl2 ~u~ll, B) an ether, preferably THF, ~ swelling agent for the 13 support; C) a metal salt selected from among metals having an atomic number of belw~ell 57 and 14 71 or 92 in the periodic table of elements and, if the metal salt is not a halide; D) a halogenation agentselectedfromthegroupc~n~ -gofahalogenatedcompoundofal.lminllmandahalogenated 16 compound not cl~nt~ining alllminllm, the reaction solid being free from the swelling agent; plus, E) 17 an organic derivative of alllminllm which is obligatory when the halogenation agent is not a 18 halogenated compound of aluminum and optional when the halogenation agent is a derivative of 19 aluminum.
United States Patent No. 5,567,784 teaches the production of diene rubbers polymerized by 21 means of Nd catalysts. The rubbers have a reduced cold flow and a low intrinsic odor. The process 22 is effected by the polymeri_ation of diolefines adiabatically at temperatures of -20~ to 150~ C, in the ' CA 02247669 1998-09-17 presence of inert organic solvents and in the presence of metallo-organic mixed catalysts b~ed on 2 neodymium carboxylate. The reaction mixture obtained in this manner is depres~ ed, and 3 thereafter treated with .1i~l.lrhllr dichloride, sulphur dichloride and/or thionyl chloride sufficient to 4 impart the desired properties.
S United States Patent No.4,990,573 teaches the pr~cessability of a polybl-t~ n~ ~,vith a high 6 content of 1,4-cis-structure which is improved by means of the addition of PCI3 before the 7 polym~ri7~tion reaction is qllen~ d and when Mooney viscosity of polybutadiene h~ reached a 8 prefixed value, preferably lower than, or equal to 30; the polym~ri7~tion of butadiene is carried out 9 in a solution in an aliphatic or cyclo~liph~tic solvent, in the presence of a catalytic system b~ed on rare earths, preferably a neodylni~ ,-b~ed catalytic system.
11 United States Patent No. 4,429,089 teaches a method for the polymeri_ation or 12 copoly.. ;~ionofb~t~ n~orisoprenecon~ c~lintheplese.lceofacatalyticsystemcomposed 13 of: (A) an~ . trialkyl havingthe formula, AlR3; v~ .emRis an alkyl radical co~ g from 14 1 to 20 carbon atoms, (B) an al- ..;..~ .. halide or alkyl al.l...i~,l...~ halide having the formula AlX"
15 R3.;wherein R is an alkyl radical col.tS.il-ing from 1 to 20carbonatoms,Xischlorineor 16 bromine and a is an integer from 1 to 3, and (C) Neodymium alcoholate having the formula, 17 Nd(OR)3; wherein R is an alkyl radical co.. l 1i"i"g from 1 to 20 carbon atoms. ln one embodiment, 18 the present invention compri~es a two component catalyst for the homo polymeri_ation of a 19 conjugated diene while providing the option of a block polymeri_ation of a conjugated diene with 20 one or more other conjugated dienes. The two component catalyst or the invention comprises (a) 21 a salt of a rare earth element or a complex of a rare earth element and (b) an organo magnesium 22 compound. The invention also includes the use of a catalyst, as just defined, in the homo ' CA 02247669 1998-09-17 polymerization of a conjugated diene or the block polymerization of a conjugated diene with one or 2 more other conjugated dienes. Surprisingly the product of such a polymerization employing an 3 organo magnesium compound as cocatalyst is a conjugated diene polymer having a very high content 4 of trans isomer. The present invention contrasts with the two or three component S rare-earth-c~ prior art systems, referred to above, which use an organo al~ .lll- con~o~u~d 6 as cocatalyst and which, as already mentioned, yield a product having a high content of cis isomer.
7 However, none ofthe prior art catalyst s~ellls combines all ofthe advantages of: le.luiliilg 8 only two coml)onent catalyst system which le~luiles relatively less costly conl~o~ to vary the 9 microstructure of the polyrner product, while non~thel~ss providing the option of diblock synthesis.
Thus, a long felt need has hitherto existed for such a catalyst system.
12 It is the object of the instant invention to provide a new and improved catalyst system and 13 method of synth~ ing 1,4 trans-polybutadiene, which provides at least some ofthe advantages of 14 the prior art s~h~nn~s, while ~imlllt~n~ously çlil~ g at least some of the disadvantages of them.
It is another object of the instant invention to provide a new and improved catalyst system 16 which can be m~n~lf~ctllred at correspondingly lower cost with regard to both labor and materials, 17 and which accordingly can be sold at a correspondingly lower cost, thus promoting commerce 18 It is a further object of the instant invention to provide a new and improved catalyst system 19 which is particularly designed for accommodating the synthesis of 1,4 trans-polybutadiene having a substantially improved trans conversion.
21 Other objects, features, and advantages of the instant invention, in its details of formulation 22 and manufacture, will be seen from the above, from the following description of the preferred , ' CA 02247669 1998-09-17 embodiment when considered in light of the appended claims.
3 Figure 1 displays the comparison between the polymer product of the Examples 26 and 4 Example 27 (tin coupled).
S DETAILED DESCRIPTION OF THE INVENTION
6 The invention relates to the addition of a catalytically effective combination of two 7 components: (1) an organic acid salt of a l~nth~ni-le series compound, and (2) an alkyllithium 8 compound, and their use in a process for promoting the chemical synthesis of 1,4-trans-9 polybutadiene and has further utility in the synthesis of diblock polymers. Although the catalyst 10 system of the instant invention co~.lcll)lates more than two catalyst components, only two are 1 1 required.
12 The catalyst system ofthe present invention includes as one of the coml)ol1e.ll~ a rare earth 13 compound, normally used in the polym~ri7~tion of conjugated dienes, and preferably soluble or 14 dispersible in aliphatic hydrocarbons, cyclo~liph~tic hy~oc~lJons and aromatic hydroc~l,ons, preferably h~x~n~
16 The rare earth compound in the catalyst system contain a rare earth element (Ln) in the 17 l~nth~nide series having an atomic number of 57 to 71, and l~nth~nllm, cerium, praseo-lyiu---, 18 neodymium and gadolinium are plef~ d, and l~nth~nllm is particularly preferable for the 19 p~alalion of 1,4-trans-polybutadiene. Alternatively, the Ln may be a mixture oftwo or more rare earth elements. When such a mixture is used, at least 30% by weight of lanthanum or neodymium ' CA 02247669 1998-09-17 is preferred.
2 The lanthanum rare earth catalysts of the present invention are any complexes of a metal 3 belonging to the series of the l~nth~nides having an atomic number of 57 to 71, in which a ligand 4 isdirectly bound to the metal and is a monovalent and monodentate organic radical including butnotlimitedto:(-R'CO2), (-OR'), (-NR'R2), (-SR'), (-PR'R2)), [-OP(O)(OR)2] and 6 [-OS(O) 2 R], wherein R, R~ and R2 are indepen~ntly selected from alkyl, cycloalkyl and aryl 7 hydrocarbon s~-bstitllent~ having 1 to 20 carbon atoms. Suitable l~nth~nllm rare earth compounds 8 to be treated are lel)resented by the following structures: Ln(R~CO2)3, Ln(OR~)3, Ln(NR IR 2)3, 9 Ln(SR') 3, Ln(PRIR2)3,Ln[OP(O)(ORI)(OR2)]3, and Ln[OS(O) 2R] 3, wherein Ln is a rare earth element in the l~nth~mlm series having an atomic number of 57 to 71 and R, R~ and R2 are alkyl, 11 cycloalkyl and aryl hydrocarbon substi~ ntc> or combinations thereof, having 1 to 20 carbon atoms.
12 More specifically, R, R' and R2 may also be independently selected from the group including:
13 cycloalkylalkyl, alkylcycloalkyl, aryl, alkylaryl substihlt~nt~ and combinations thereof. Even more 14 specifically R, R~ and R2 may be in-lepenrl~ntly selecte l from the group including: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, n-decyl, 2-ethyl hexyl, 16 cyclopentyl-methyl, cyclohexyl-ethyl, cyclopentyl-ethyl, methylcyclopentylethyl, cyclopentyl, 17 dimethylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, 18 isopropylcyclohexyl and combinations thereof.
19 Other ligands contemplated by the instant invention are organic compounds represented by the forrnulae (I) to (VIII) as shown below:
' CA 02247669 1998-09-17 R3 - LH (I) 2 R4- C - LH (II) 3 il s 8 R5 - S - OH (III) 14 R6- 0 - S - OH (IV) 20R7 -O- (-CH2CH2O-)j- P -OH (V) 22 R8 o (-CH2cH2O-)k 25R9-O- (-CH2CH2O-),- P -OH (VI) 27 R'~ -O- (-cH2cH2o-)m R" - P- OH (VII) 32 Rl2 ' CA 02247669 1998-09-17 4 R13 - P- OH (VIII) 6 Rl4 9 wherein each of R3, R4 and R7 - R~~ lepl~,3elll~i an ~lirh~tic h~ oc~l,oll group or an aromatic 10 hydrocarbon group, R5 an aromatic hydrocarbon group, R6 an aliphatic hydrocarbon group, each of 11 R11 - R14 an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group or a 12 phenoxy group, L an oxygen atom or a sulfur atom, and j, k, 1 and m are integers of 1 to 6.
13The above formula (I) l~ sents alcohols, thioalcohols, phenols or thiophenols. Examples 14 of these may include methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, tert-butyl 15 alcohol, tert-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, aryl alcohol, 2-butenyl alcohol, 163-hexenyl alcohol, 2,5~1e~rli~nyl alcohol, benzyl alcohol, phenol, catechol, l-n~rhth- l, 2-n~rhthol, 172,6-di-tert-butylphenol, 2,6-di-tert-butyl~-methylphenol, 2,4,6-tri-tert-butylphenol, 4-phenylphenol, 18 eth~nethiol, l-butanethiol, 2-pç .'~ 1.iol, 2-iso-butanethiol, thiophenol, 2-.. ~p1.lh~1enthiol, 19 cyclohexane-thiol, 3-methylcyclohexanethiol, 2-n~rhth~l~n~thiol, benzene-methanethiol, 20 2-naphthalenemethanethiol and the like.
21The formula (II) l~leselll~ carboxylic acids or sulfur analogues thereo~ Examples of these 22 may include isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, 23 stearic acid, oleic acid, linoleic acid, cyclo-pentanecarboxylic acid, napthenic acid, ethylhexanoic 24 acid, pivalic acid, Versatic Acid (synthetic acid constituted of a mixture of isomers of C,0 . .
mono-carboxylic acids sold by Shell Chemical Co.), phenylacetic acid, benzoic acid, 2-nArhthoic 2 acid, h~ n-othionic acid, 2,2-dimethylbul~l~lhionic acid, tetr~dec~nethionic acid, thiobenzoic acid 3 and the like.
4 The formula (III) represents alkyl aryl sulfonic acids, as exemplified by S dodecylbe~ rs~llfonic acid, tetradecylben7~n~s-l1fonic acid, hP~ ecylb~ es~llfonic acid, 6 octadecylb~ s~lfi~nic acid, dibUlyll-Al.kll.Al~ ,s~llrol-ic acid, n-hexyl~l.lal)kll.Al~n~s -lffinic acid, 7 dibutylphenylsulfonic acid and the like.
8 The formula (IV) ~ se.ll~ mono-alcohol esters of sulfuric acid, such as sulfuric acid 9 mono-ester of lauryl alcohol, sulfuric acid mono-ester of oleyl alcohol, sulfuric acid mono-ester of stearyl alcohol and the like.
11 The fonnl-l~ (V) l.,l,les~ rhosph~te diesters of ethylene oxide adduct of alcohol or phenol.
12 Examples of these may include phnsph~te diester of ethylene oxide adduct of dodecyl alcohol, 13 phosphate diester of ethylene oxide adduct of octyl alcohol, phosphate diester of ethylene 14 oxide~d~ ct of stearyl alcohol, phosph~te diester of ethylene oxide adduct of oleyl alcohol, phosphate diester of ethylene oxide adduct of nol~lphellol, phosphate diester of ethylene oxide 16 adduct of dodecyl-phenol and the like.
17 The formula (VI) ,e~le~~ phosphite diesters of ethylene oxide adduct of alcohol or phenol.
18 Examples of these may include phosphite diester of ethylene oxide adduct of dodecyl alcohol, 19 phosphite diester of ethylene oxide adduct of stearyl alcohol, phosphite diester of ethylene oxide adduct of oleyl alcohol, phosphite diester of ethylene oxide adduct of nonylphenol, phosphite diester 21 of ethylene oxide adduct of dodecylphenol and the like.
22 The formula (VII) lep~ese~ pentavalent organic phosphoric acid compounds, including, for example, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl 2 phosphate, bis(1-methylheptyl) phosph~te, bis(2-ethyl-hexyl) phosph~te~ dilauryl phosphate, dioleyl 3 phosphate, diphenyl phosphate, bis(p-nonylphenyl) phosph~te, butyl(2-ethylhexyl) phosphate, 4 (l-methylheptyl) (2-ethylhexyl) phosphate, (2-ethylhexyl)(p-nonylphenyl) phosph~te, 5 monobutyl(2-ethylhexyl) phosphonate, mono-2-ethylhexyl(2-ethylhexyl) phosphonate, 6 mono-2-ethylhexyl phenyl phosphonate, mono-p-nol~lphellyl(2-ethylhexyl) ph()sphonate~
7 dibutylphosphinic acid, bis(2-ethylhexyl) phosphinic acid, bis(1-methylheptyl)rhosphinic acid, 8 dilaurylphosphinic acid, dioleylphosphinic acid, diphenylrhosphinic acid, 9 bis(p-nonylphenyl)phosninic acid, butyl(2-ethyhexyl)phosphinic acid, (2-ethylhexyl) 10 (1-methyl-heptyl)phosphinic acid, (2-ethylhexyl) (p-nonylphenyl)phosphinic acid and the like.
11 The formula (VIII) lc~lcse~ trivalent phosphorous acid compounds, as exemplified by 12 bis(2-ethylhexyl) phosphite, bis(1-methylheptyl) phosphite bis(2-ethylhexyl)phosphinous acid and 13 the like.
14 Still more spe~ific~lly, the ~ hAIIIIIII rare earth catalysts ofthe present invention include but 15 are not necçcs~.;ly limited to: l~nth~n~lm tris(nonylphenoxide), l~nth~mlm tris(dodecyl-p-toluene 16 sulfonate), l~nth~nllm tris[bis(2-ethylhexyl)phosphate], l~nth~mlm tris[dipropylamine], l~nth~n~lm 17 tris[propylthio], lanthanum tris[propoxyl], l~nth~nllm propionate, l~nth~nnm diethyl~cet~te, 18 lanthanum 2-ethyl hexanoate, l~nth~mlm stearate, l~nth~nllm bçn70~te, cerium ben70~te, l9 praseodymium propionate, praseodymium cyclohexane carboxylate, praseodymium 2-ethyl 20 hexanoate, neodymium diethyl acetate, neodymium 2-ethyl hexanoate, neodymium cyclohexane 21 carboxylate, neodymium stearate, neodymium oleate and neodymium ben_oate. Of the foregoing, ' CA 02247669 1998-09-17 lanthanum tris(nonylphenoxide) is the most yief~ .led.
2 The organolithium catalysts contemplated by the instant invention include but are not 3 necçs~rily limited to lithium compounds having the general formula R(Li)X, wherein R r~lesell~
4 a hydrocarbyl radical of I to 20, preferably 2 to 8, carbon atoms per R group and x is an integer from 1 to 4. Specific example of other suitable lithium catalysts include: p-tolyllithium, 4-phenylbutyl-6 lithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyl-lithi.lm, lithium dialkyl amines, lithium dialkyl 7 pho~yhil~os~ lithium aLkyl aryl pl~o~hil~, lithium diaryl phosyh;~s~ 1,3,3-trilithio-1-octyne, 1,1,3-8 trilithio-1,2-butadieneandthelike.Theyl~fell~d catalyst for use in the present invention are 9 n-butyllithium, t-butyllithium and sec-butyllithium.
The synthesis is carried out in hydroc~ul~n reaction diluent, for example, hexane, 11 cyclohexane or toluene. It is very desirable that the catalyst conlyo~ are soluble in the particular 12 reaction diluent used. An ~liph~tic solvent, e.g. hexane, or cyr,lo~lirh~tic solvent, e.g. cycloh~Y~ne, 13 or toluene are yl.,fc~led. Hexane is most prer~.led.
14 The l~nth~nide colllyoul~d and the organolithium catalysts are added to the reaction mass in a hydrocarbon diluent at a relative molar ratio within the range of from about 1: 0.1 to about 16 1:100.0; more preferably from about 1: 1.0 to about 1:50.0; still more preferably about 1: 2.0 to 1 7 about 1: 1 0.0; and most preferably about 1:3 Ø
18 A reaction temperature of about 0~ to about 120~C., is typical; while about 20~ C. to about 19 100~C. is ylefe~l~d. In order to colllyel~le for the vapor P1G~UIe of the monomer(s) under typical reaction conditions, reaction pressures of from about slightly above atmospheric to up to about 10 21 atmospheres are preferred. Generally the molecular weight of the polymer is inversely proportional to catalyst concentration. Molecular weight generally also increases in direct proportion to 2 polymerization time. This suggests that at least a portion of the catalyst system remains active 3 throughout the reaction time.
4 Examples of conjugated diene monomers which may be block polylll.,.;~cd by the process S of the invention are butadiene and isoprene although the process is not le~l~;cted to the use of one 6 or other of these two conjugated dienes. Mixtures of conjugated dienes may be used if desired. The 7 p.erell~,d order of addition of catalyst colllpol1ents is to add the monomer to the solvent first followed 8 by colllponellt (a) and then conlpol1ell~ (b) and, if used, finally cGlllponenl (c) in that order.
9 It is particularly beneficial, and thus plcr~ d, to carry out the polymeri7~tion using components (a) and (b) together in the presence of a polar diluent, typically a Lewis base such as 11 tetrahydrofuran. Exemplary of other polar compounds are (a) ethers such as din.c~lyl ether, diethyl 12 ether, 1,2 ~limeth~xy ethane, diphenyl ether, diben7yl ether and anisole; (b~ amines such as 13 trimethylamine, triethylamine pyridine or tetra methyl ethylene ~i~mine; (c) thioethers such as 14 thiophene and (d) polyethers such as glyme or diglyme. These polar compounds are well known in the art. Their use in the present invention enables higher conversions of mon~ m~r to polymer to be 16 obtained with no appreciable effect on trans content unless very high concentrations of these polar 17 compounds are used. Typical of such high concellL~a~ions is a molar ration of polar compound to 18 compound (b) of greater than about 2.5:1. Surprisingly addition of a polar compound produces no 19 increase in vinyl content ofthe polymer, in contrast to the increase in vinyl content such compounds produce in anionic polymerizations.
21 As can be seen from the above the process ofthe invention offers the possibility of pl~illg 22 a wide variety of conjugated diene polymers (1) a polymer of high trans 1,4 content, by using , components (a) and (b); (2) a block polymer having a high trans block and a second block, by 2 initi~ting the polym~ri7~tion using colllpone.ll~ (a) and (b) alone and adding a cis 1,4 component at 3 the desired degree of conversion. Some homopolymer of high trans content and high cis content 4 respectively may also be formed in this re~ctiQn; and, (4) a polymer of lllediull~ trans 1,4 content e.g.
5 50-80% by m~ifir~tion of the reaction using components (a) and (b) with lithium alkyl; optionally 6 carrying out the polye ;".I;on in the presence of a vinyl aromatic monomer, such as styrene, to 7 obtain e.g. a ~lyl~ ne-butadiene copolymer of medium trans 1,4 content.8 These polymers are rubbery (except the polymers of high trans content) and may be 9 compounded and vulcani_ed by methods well known in the art. They are of potential application in tires, general rubber goods and in the pl~a,aLion of plastics m~t~ri~l~ such as high impact 1 1 polystyrene.
12 The instant invention is plGr~ bly directed to the synthesis of 1,4 trans-butadiene polymer.
13 However, the versatile two-colllpollent catalyst system, nonetll~less provides the option of block 14 polymeri7~tiQn to further modify the primary product to include other desirable pro~l~ies such ~
improved softening telllpel~ , moldability, rigidity, strength, r~silien~, impact r~ict~ncç and the 16 like. However, the full significance of the present invention is demon~ d through a polymer 17 resin product which contains at least 30 weight % of the initial trans-polybutadiene product.
18 Other particularly pl~r~lable polymeric resin colllpollents that may be mixed with the initial 19 trans-butadiene product include, but are not necess~rily limited to: trans-isoprene polymers, trans-polyoctenamers and caprolactone polymers. In order to modify the hardness or plasticity of 21 crystalline trans-butadiene polymers compositions of the present invention, inorganic fillers or plastici_ers may be added, as desired. Similarly, conventional stabili_ers, pi~m~ntc, and the like may 2 be added in any manner and for any purpose prescribed by the prior art.
3 Inorganic fillers are typically added in amounts of about 5 to about 100 parts by weight per 4 100 parts by weight of the polymeric resin component. Such fillers include, but are not limited to:
S titanium oxide, silica, calcium c~bonate, clay, talc, mica, ~ ~lol.;Le and the like. The ~ tion of 6 fillers beyond these specified amounts have been observed to adversely lower the impact 7 of the polymeric resin product.
8 pl~ti~i7~rs are typically added in amounts ranging from about 1 to 20 parts by weight per 9 100 parts by weight of the polymeric resin product. Examples of plastici~rs may include, but are not n~cçe~rily limited to: dibutyl phth~l~te, di-(2-ethylhexyl) phth~l~tç, di-(2-ethylhexyl) ~lir~te~
11 diethylene glycol ben7l~ate, butyl ste~r~te~ butylepoxy stearate, tri-(2-ethylhexyl) phosrh~t~, and the 12 like.
13 The polymeric resin product of the present invention can easily be mixed by means of an 14 extruder, a knP~rler, rolls, or the like. These app~r~t--~es are typically ope.dled at te~ c~al~e ranges from about 60~ to about 200~C.; and, preferably from about 80~ to 1 80~C. It is also possible to mix 16 the components in a solution dissolved in a suitable solvent.
17 Polymeric resin product of the instant invention that CO~ ih~S crystalline trans-butadiene 18 polymers may generally be used without vulc~ni7~tion. However, depending uses such as golf ball 19 cover materials, and the like, it is typically preferable to impart further strength and impact rçci~t~nce to the polymeric resin product through vulcani_ation. Although, any conventional method of 21 vulcanization can be used for this purpose, it is preferable to vulcanize a trans-butadiene product of 22 the instant invention at temperatures no higher than the melting point of the product. Exemplary of ' CA 02247669 1998-09-17 these methods, are low temperature vulcanization and electron beam vulcanization.
2 Preferred vulc~ni7ing agents used in low telllpeldLIlre vulcani_ation include, but are not 3 necessarily limited to: elem~nt~l sulfur, selenium, tellurium, inorganic sulfur compounds such as 4 sulfur dichloride, sulfur chloride, etc.; organic sulfur compounds such as morpholine t~ llfide, alkylphenol disulfide, and the like. Typical vulc~ni7~tion acccleldtol~ include, but are not 6 necess~rily limited to: guanidine type vulc~ni7~tion acccleldlol~, aldehyde-amrnonia type 7 vulcani_ation acc~ler~tors, slllph~n~mide type vlll- ~ni7~tion accel-,ldlul~, thiuram type vulc~ni7~tio~n 8 accelerators, ~ type vulc~ni7~tion accelelalo,~, aldehyde-amine type vulc~ni7~tion 9 accelerators, thiazole type vulc~ni7~tion accclcldlo-s, thiourea type vulcanization acccleldlors, dithioc~l,~ulldle type vulcanization accclcldl(~l~ and mixed types ofthese. The particularly pl.,rell~d 11 vulc-~ni7ing agent is elemental sulfur. It is preferably used in an amount of about 0.1 to about 3.0 12 parts by weight per 100 parts by weight ofthe polymer. Pler~ll~l vulcani7ation acccl~ l~lol~ include, 13 but are not ~ ~ ;ly limited to: ~sIhi.l~ type vlllc~ni7~ti~n accckldl~ and dithioc~b~llate type 14 vulcani_ation accelerators. Examples of x~nth~te type vulcani_ation accelerators include, but are not n~cess~rily limited to: sodiurn isolllo~lxs~ te~ zinc isopropylx~nth~te zinc ethylx~nth~te, zinc 16 IJulylx~lllh~te~ dibut~lx~ disulfide, and the like. Examples of l,lefell~d dithioc~l,alllale type 17 vulcanization accelerators include, but are necess~rily limited to: sodium dimethyldithicarbamate, 18 sodium diethyldithiocarbamate, sodiurn di-n-butyldithiocarbamate, zinc ethylphenyldithioc~L.~ndle, 19 zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc dibenzylthiocarbamate, zinc N-penta-methylenedithiocarbamate, zinc 21 dimethylpentamethylenedithio-carbamate, zinc ethylphenyldithiocarbamate, selenium 22 dimethyldithiocarbamate, selenium diethyldithiocarbamate, tellurium diethyldithiocarbarnate, .
cadmium diethyldithioc~b~l~ate, dilllGLhylammonium dimethyldithioc~bal,.ale, dibutylammonium 2 dibutyldithioc~b~llate, diethylamine diethyldithiocarbamate, N,N'-dimethylcyclohexane salt of 3 dibutyldithioc~balnic acid, pipecolic methylpelll~llethylenedithioca,l,a"lalG, and the like.
4 Depending on the particular vulc~ni7~tion accelerator employed, p~fell~,d amounts of accelerator typically range from about 0.1 to about 3.0 parts by weight per 100 parts by weight of the polymer.
6 It is generally preferable to co~ ct the ~ll~ni7~tion at t~ s below about 90~C. Particularly 7 preferable are vulr~ni7~tion telllp~ tule in the range of about 30~ to 60~C. VU1CA~ 1 ;on times, 8 which may differ depending on the vulc~ni7ing agent, the v~llc~ni7~tion acccle.~lor and the 9 vulr~ni7~tion telll~.alul~,; may generally be from about some ten i~ cs to about several days.
The crystalline trans-polybutadienes produced by the present invention are excellent in l 1 moldability and workability at relatively lower tempel~L~es and also exhibit excellent physical 12 pl~.Lies such as rigidity, strength, re~ n~e, impact re~ict~ncç and the like. These polymers are 13 used in the fonmll~tion of rubber compounds to increase green ~L~ lh and i~ processability.
14 The trans-polyb~lt~ n~s are also used in the pl~l)alalion pl~tic m~teri~l~ such ~ high impact 1 5 polystyrene.
16 The instant invention will be described in more detail with reference to the following non-l 7 limitative examples. The following examples are present for purposes of illustration only and are 18 not to be construed in a limitin~ sense. All pelce~llages are by weight unless otherwise specified.
19 Example 1 An oven dried, 750 ml glass bottle was sealed with a butyl liner and crown cap. The bottle 21 w~ cooled then charged with 223 grams of a dry butadiene/hexane blend (22.3 wt%). T ~nth~num tris[bis(2-ethylhexyl) phosphate] (0.27 mmol) was added to the monomer solution. This was 2 followed by the addition of n-BuLi (1.08 mmol). The bottle was placed in a 65 ~ C water bath for 3 2 hours. The solvent was then allowed to evaporate yielding a white powder. The isolated yield was 4 87%. The analysis of this material is reported in Table 1.
Tablel 6 ~k Li~ ~ML~ ~r~ Pwr~ r~ M~ M~ L~w L~ 7'~1) 7 1 ~ o ss 4 65 2.0 87 52 1.37 4g 93 8 2 b 1.00 3.8 S0 2.15 67 36 1.21 88 6 49 90 9 3 t 120 3.1 S0 1.10 87 37 1.11 g2 4 47 9S
1 1 0.60 3 S0 230 gl 70 1.27 92 4 48 91 12 ~ bis(2~1h;1- ;')~' ,1' 13 b: ~ Jl ~~
14 c r ,~
16 Fxamples 2 to 4 17 In Exarnples 2 to 4, reactions similar to that described for Example 1 were carried out in 18 which di~le.lt l~nth~nl-m salts were used. These examples are summarized in Table 1 along with 19 the colles~llding results. These results show that a variety of l~nth~nllm salts are suitable for the prel)~alion of an active catalyst system.
21 Examples 5 to 13 22 In Examples S to 13, reactions similar to that described for Example 1 were carried out while 23 the ratio of catalyst to monomer was varied. The results of these examples are summarized in Table 24 2. These results show that the molecular weight can be controlled by the ratio of catalyst to monomer.
CA 02247669 l998-09-l7 3 Table2 5 ExampkmM L~l l,f/lA YJdd Un Mw/Unrm(l) rm (2) 6 phgBd (X) (kg/nwl) (~ (~7 7 Lig~nd: bis(2_ yl Yl)U
8 s 035 4.0078 73 1.44 47 91 9 6 0.45 4.0087 65 1.41 48 gl 0 7 055 4.0087 52 13~ 49 g3 8 0.65 4.00g3 41 1.46 48 91 13 Lig~nd~
14 g 030 35 87 1071.81 42 61 0.45 3.5 90 77 1.47 39 54 16 1l 0.60 35 94 59 1.44 37 49 17 12 0.75 3.5 98 47 1.26 16 37 1 8 13 0.90 35 96 37 131 39 22 F~r~mples 14 to 19 23 In E ~ llplcS14 to 19, diethylzinc was added to the butadiene solution prior to the addition 24 of n-BuLi. The polym~li7~tion~ were run in a similar manner to that described for Example 1. The amounts ofthe catalyst coll~ e~ used and the results from these poly.~ lions are listed 26 in Table 3. It is appa~lll from these results that diethylzinc can be used to lower the molecular 27 weight and narrow the polydispersity of the polymer.
Table3 3 EXAMPLE mM' La phg Li/LaZn/La Y'eld Mn Mw/M'n l,~-tran~ 1,2-vinyl Tm(l) T~2) Bd (~/) (kg/mol) (~ /) ( ~C)( ~C) Lig~nd:bis(2~l~J~ I)pho~p~te 6 140.25 4 0.5 46 58 1.61 94 4 49 93 7 150.25 4 1 42 47 1.47 95 4 47 92 8 160.25 4 3 52 40 1.33 47 93 9 170.35 4 0.5 61 52 1.48 95 4 50 93 0 180.35 4 1 63 47 1.40 96 4 48 93 190.35 4 3 61 34 1.30 95 4 47 92 13 Fxamples 20 to 23 14 In Examples 20 to 23 polymeri_ations were carried out in which the ratio of catalyst 15 components was varied. These polymeri7~tions were carried out in a manner similar to that 16 described for Example 1. The conditions used for these polymeri_ations are sllmm~n7~d in Table 17 4. The results from these examples indicate that the microstructure of the polymers can be controlled 18 by varying the ratio of the catalyst components.
19 Table 4 2I Exomple mU La l~ Pzn Pzn rclt Un Uw~Un 1,~- t,2- rm(l) rm(2) rg phglJd rcmp rmc~%) (kg/molJ ~rans n'nyl ('C~ (~ (~
22 ( ~/~hrs) (.~) (,~) 23 Ligand:bis(2-ethylhexyl)~hD '~te 24 20 0.60 3 60 1:30 95 64 1.30 92 5 48 85 21 0.60 3.5 60 1:30 95 64 1.29 91 5 47 84 26 22 0.60 4 60 1:30 92 50 1.18 79 7 15 39 -83 27 23 0.60 4.5 60 1:30 95 42 1.11 64 10 -25 -91 2 Examples 24 to 27 3 In Examples 24 to 27, two sets of polymeri_ations were carried out in a similiar manner to 4 that described in Example 1. Within each set, one polym~ri7~tion was tc i-.n~e~ with iso~lopallol 5 and the other with tin tetrachloride. The amounts of catalyst and tin tetrachloride used are shown 6 in Table 5. The effect of SnC14 ~f ....il~AIion on the molecular weight distribution of the polymer is 7 shown in Figure 1. It is clear from these SEC cl~lolllalograms that the addition of tin tetrachloride 8 causes a coupling reaction to occur. The percent coupled polymer was e~ ed from the SEC
9 chromatograms. These results establish the "living" nature of the polymeri_affon, that is, this 10 behavior is con~i~t~nt with a polymer molecule that retains a reactive chain end after the 11 Table 5 13 E~k ~UL. u~ &~ ~ Pu~ ~., ~ ~MI, ~4"' ' ' '~ r~l) r~J
p~ u r~p r~
14 (~
Ligand: bis(2-ethylhexyl)~ h-' 16 24 0.75 4 0 65 1.5 84 51 1.45 0 47 89 ~j~ 25 0.75 4 0.7 65 1.0 84 131 2.59 48 49 87 19 Ligand: r~cr~ ~YI~le 26 1.20 3.1 0 50 1:10 87 41 1.11 0 92 4 47 95 21 27 1.20 3.1 1 50 1:10 85 113 1.91 55 90 5 48 95 monomer has been con~llmed by the polym~ri7~tion reaction. This data is similar to the results that 2 are obtained with a butyllithium polymeri_ation, typically known ~ a "living" system. Therefore 3 the results of Figure 1 suggest that much of the synthetic strategies that have been used in the BuLi 4 system, such as the synthesis of block polymers, could also be considered with the Ln/BuLi system.
S Those of ol-iin~y skill in the art will appreciate that the conception upon which this 6 disclosure is based may readily be utili_ed as a basis for the ~ igning of other structures, methods 7 and systems for c~l~ing out the several purposes ofthe instant invention. It is hllpoll~ll~ therefore, 8 that the claims be regarded as including such equivalent constructions insofar as they do not depart 9 from the spirit and scope of the instant invention.
Although the invention has been described with reference to certain ~leÇ~ d embodiments, 11 it will be appreciated that many variations and modifications may be made within the scope of the 12 broad principles of the invention. Hence, it is int~n~e~l that the plefell~d embo-1im~nt.~ and all of 13 such variations and m-ulifi~tion~ be included within the scope and spirit ofthe invention, as defined 14 by the following claims.
' CA 02247669 1998-09-17 United States Patent No. 4,461,883 teaches a process for producing a conjugated diene 2 polymer, char~cteri7~cl by pol~ g at least one conjugated diene with a catalyst con~i~ting of:
3 (A) a reaction product of a Lewis base and a carboxylate of a rare earth element of the lanthanum 4 series l~p~3c~lled by Ln(R~CO2)3 wherein Ln is a rare earth Plem~nt of the l~nth~nllm series having S an atomic number of 57 to 71 and Rl is a h~ 1~OC~1JO1I s~ ;t.~ having 1 to 20 carbon atoms; (B) 6 an organic al..... i.. ..compound l~lese~lled by AIR2R3R4 wll~ in R2, R3 and R4, which may be 7 identical or di~.e.~, r~le3~"ll hydrogen atoms or hy~oc~l,on sllbstitll~nt~ having 1 to 8 carbon 8 atoms, eY~lllding the case where all of R2, R3 and R4 are hydrogen atoms at the same time, and, (C) 9 an (alkyl)~l.~ .. i.. ~ halide le~ s~lled by AlXn R53 n wherein X is Cl, Br, F or I; R5 is a hydrocarbon 10sllbstihllont having 1 to 8 carbon atoms; and n has a value of 1, 1.5, 2 or 3, or con~icting ofthese (A), 11 (B) and (C) co...l~lu..l~; and (D) a conjug~t~,d diene. A polymer obtained by the process has a high 12 cis-1,4-configuration content and is excellent in physical plope~lies of v ~ ";,~l~
13United States Patent No. 5,612,427 teaches a su~oll~d solid catalyst which can be used for 14 the polymerization and copolym~ri7~tion of conjugated dienes. The basis of the catalyst is the 15 reaction product of: A) a solid MgCl2 su~l,o~l; B) an ether, ~l~f~ bly THF, as swelling agent for 16 the ~,u~po,l, C) a metal salt selecte~ from among metals having an atomic number of belw~;en 57 and 17 71 or 92 in the periodic table of elements and, if the metal salt is not a halide; D) a halogenation 18 agentselectedfromthegroupcon~i~tingofahalogenatedcompoundofal..,~.;.,ll,.. andahalogenated 19 compound not colll;1i..i.~g alllminllm, the reaction solid being free from the swelling agent; plus, E) 20 an organic derivative of alnminllm which is obligatory when the halogenation agent is not a 21 halogenated compound of alnminum and optional when the halogenation agent is a derivative of 22 aluminum.
' CA 02247669 1998-09-17 United States Patent No. 4,696,984 teaches isoprene polymers and copolymers which are 2 prepared by a polymeri_ation process carried out in the absence of solvents and in the pl~sellce of 3 a catalytic system comprising (a) at least one element or compound of an element pe~ lg to 4 Group IIIB of the Periodic Table, (b) at least one alumin~ll alkyl de.;v~live, (C) at least one organic 5 halogen derivative or at least one halide of an element able to exist in at leasttwo valency 6 states with the halide colles~ollding to a higher state than the .,.i.~ ...., or at least one halogen or 7 at least one hydrogen halide acid, (d) at least one compound co.~ -g one or more h~ l groups 8 of which the hydrogen can be ~b~ the ratio of compoll~,.ll (b) to component (a) being equal 9 to or less than 20.
United States Patent No. 5,610,114 teaches a ~u~olled solid catalyst which can be used for 11 the polymeri_ation and copolym~ i7~tion of conjugated dienes. The basis of the catalyst is the 12 reaction product of: A) a solid MgCl2 ~u~ll, B) an ether, preferably THF, ~ swelling agent for the 13 support; C) a metal salt selected from among metals having an atomic number of belw~ell 57 and 14 71 or 92 in the periodic table of elements and, if the metal salt is not a halide; D) a halogenation agentselectedfromthegroupc~n~ -gofahalogenatedcompoundofal.lminllmandahalogenated 16 compound not cl~nt~ining alllminllm, the reaction solid being free from the swelling agent; plus, E) 17 an organic derivative of alllminllm which is obligatory when the halogenation agent is not a 18 halogenated compound of aluminum and optional when the halogenation agent is a derivative of 19 aluminum.
United States Patent No. 5,567,784 teaches the production of diene rubbers polymerized by 21 means of Nd catalysts. The rubbers have a reduced cold flow and a low intrinsic odor. The process 22 is effected by the polymeri_ation of diolefines adiabatically at temperatures of -20~ to 150~ C, in the ' CA 02247669 1998-09-17 presence of inert organic solvents and in the presence of metallo-organic mixed catalysts b~ed on 2 neodymium carboxylate. The reaction mixture obtained in this manner is depres~ ed, and 3 thereafter treated with .1i~l.lrhllr dichloride, sulphur dichloride and/or thionyl chloride sufficient to 4 impart the desired properties.
S United States Patent No.4,990,573 teaches the pr~cessability of a polybl-t~ n~ ~,vith a high 6 content of 1,4-cis-structure which is improved by means of the addition of PCI3 before the 7 polym~ri7~tion reaction is qllen~ d and when Mooney viscosity of polybutadiene h~ reached a 8 prefixed value, preferably lower than, or equal to 30; the polym~ri7~tion of butadiene is carried out 9 in a solution in an aliphatic or cyclo~liph~tic solvent, in the presence of a catalytic system b~ed on rare earths, preferably a neodylni~ ,-b~ed catalytic system.
11 United States Patent No. 4,429,089 teaches a method for the polymeri_ation or 12 copoly.. ;~ionofb~t~ n~orisoprenecon~ c~lintheplese.lceofacatalyticsystemcomposed 13 of: (A) an~ . trialkyl havingthe formula, AlR3; v~ .emRis an alkyl radical co~ g from 14 1 to 20 carbon atoms, (B) an al- ..;..~ .. halide or alkyl al.l...i~,l...~ halide having the formula AlX"
15 R3.;wherein R is an alkyl radical col.tS.il-ing from 1 to 20carbonatoms,Xischlorineor 16 bromine and a is an integer from 1 to 3, and (C) Neodymium alcoholate having the formula, 17 Nd(OR)3; wherein R is an alkyl radical co.. l 1i"i"g from 1 to 20 carbon atoms. ln one embodiment, 18 the present invention compri~es a two component catalyst for the homo polymeri_ation of a 19 conjugated diene while providing the option of a block polymeri_ation of a conjugated diene with 20 one or more other conjugated dienes. The two component catalyst or the invention comprises (a) 21 a salt of a rare earth element or a complex of a rare earth element and (b) an organo magnesium 22 compound. The invention also includes the use of a catalyst, as just defined, in the homo ' CA 02247669 1998-09-17 polymerization of a conjugated diene or the block polymerization of a conjugated diene with one or 2 more other conjugated dienes. Surprisingly the product of such a polymerization employing an 3 organo magnesium compound as cocatalyst is a conjugated diene polymer having a very high content 4 of trans isomer. The present invention contrasts with the two or three component S rare-earth-c~ prior art systems, referred to above, which use an organo al~ .lll- con~o~u~d 6 as cocatalyst and which, as already mentioned, yield a product having a high content of cis isomer.
7 However, none ofthe prior art catalyst s~ellls combines all ofthe advantages of: le.luiliilg 8 only two coml)onent catalyst system which le~luiles relatively less costly conl~o~ to vary the 9 microstructure of the polyrner product, while non~thel~ss providing the option of diblock synthesis.
Thus, a long felt need has hitherto existed for such a catalyst system.
12 It is the object of the instant invention to provide a new and improved catalyst system and 13 method of synth~ ing 1,4 trans-polybutadiene, which provides at least some ofthe advantages of 14 the prior art s~h~nn~s, while ~imlllt~n~ously çlil~ g at least some of the disadvantages of them.
It is another object of the instant invention to provide a new and improved catalyst system 16 which can be m~n~lf~ctllred at correspondingly lower cost with regard to both labor and materials, 17 and which accordingly can be sold at a correspondingly lower cost, thus promoting commerce 18 It is a further object of the instant invention to provide a new and improved catalyst system 19 which is particularly designed for accommodating the synthesis of 1,4 trans-polybutadiene having a substantially improved trans conversion.
21 Other objects, features, and advantages of the instant invention, in its details of formulation 22 and manufacture, will be seen from the above, from the following description of the preferred , ' CA 02247669 1998-09-17 embodiment when considered in light of the appended claims.
3 Figure 1 displays the comparison between the polymer product of the Examples 26 and 4 Example 27 (tin coupled).
S DETAILED DESCRIPTION OF THE INVENTION
6 The invention relates to the addition of a catalytically effective combination of two 7 components: (1) an organic acid salt of a l~nth~ni-le series compound, and (2) an alkyllithium 8 compound, and their use in a process for promoting the chemical synthesis of 1,4-trans-9 polybutadiene and has further utility in the synthesis of diblock polymers. Although the catalyst 10 system of the instant invention co~.lcll)lates more than two catalyst components, only two are 1 1 required.
12 The catalyst system ofthe present invention includes as one of the coml)ol1e.ll~ a rare earth 13 compound, normally used in the polym~ri7~tion of conjugated dienes, and preferably soluble or 14 dispersible in aliphatic hydrocarbons, cyclo~liph~tic hy~oc~lJons and aromatic hydroc~l,ons, preferably h~x~n~
16 The rare earth compound in the catalyst system contain a rare earth element (Ln) in the 17 l~nth~nide series having an atomic number of 57 to 71, and l~nth~nllm, cerium, praseo-lyiu---, 18 neodymium and gadolinium are plef~ d, and l~nth~nllm is particularly preferable for the 19 p~alalion of 1,4-trans-polybutadiene. Alternatively, the Ln may be a mixture oftwo or more rare earth elements. When such a mixture is used, at least 30% by weight of lanthanum or neodymium ' CA 02247669 1998-09-17 is preferred.
2 The lanthanum rare earth catalysts of the present invention are any complexes of a metal 3 belonging to the series of the l~nth~nides having an atomic number of 57 to 71, in which a ligand 4 isdirectly bound to the metal and is a monovalent and monodentate organic radical including butnotlimitedto:(-R'CO2), (-OR'), (-NR'R2), (-SR'), (-PR'R2)), [-OP(O)(OR)2] and 6 [-OS(O) 2 R], wherein R, R~ and R2 are indepen~ntly selected from alkyl, cycloalkyl and aryl 7 hydrocarbon s~-bstitllent~ having 1 to 20 carbon atoms. Suitable l~nth~nllm rare earth compounds 8 to be treated are lel)resented by the following structures: Ln(R~CO2)3, Ln(OR~)3, Ln(NR IR 2)3, 9 Ln(SR') 3, Ln(PRIR2)3,Ln[OP(O)(ORI)(OR2)]3, and Ln[OS(O) 2R] 3, wherein Ln is a rare earth element in the l~nth~mlm series having an atomic number of 57 to 71 and R, R~ and R2 are alkyl, 11 cycloalkyl and aryl hydrocarbon substi~ ntc> or combinations thereof, having 1 to 20 carbon atoms.
12 More specifically, R, R' and R2 may also be independently selected from the group including:
13 cycloalkylalkyl, alkylcycloalkyl, aryl, alkylaryl substihlt~nt~ and combinations thereof. Even more 14 specifically R, R~ and R2 may be in-lepenrl~ntly selecte l from the group including: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, n-decyl, 2-ethyl hexyl, 16 cyclopentyl-methyl, cyclohexyl-ethyl, cyclopentyl-ethyl, methylcyclopentylethyl, cyclopentyl, 17 dimethylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, 18 isopropylcyclohexyl and combinations thereof.
19 Other ligands contemplated by the instant invention are organic compounds represented by the forrnulae (I) to (VIII) as shown below:
' CA 02247669 1998-09-17 R3 - LH (I) 2 R4- C - LH (II) 3 il s 8 R5 - S - OH (III) 14 R6- 0 - S - OH (IV) 20R7 -O- (-CH2CH2O-)j- P -OH (V) 22 R8 o (-CH2cH2O-)k 25R9-O- (-CH2CH2O-),- P -OH (VI) 27 R'~ -O- (-cH2cH2o-)m R" - P- OH (VII) 32 Rl2 ' CA 02247669 1998-09-17 4 R13 - P- OH (VIII) 6 Rl4 9 wherein each of R3, R4 and R7 - R~~ lepl~,3elll~i an ~lirh~tic h~ oc~l,oll group or an aromatic 10 hydrocarbon group, R5 an aromatic hydrocarbon group, R6 an aliphatic hydrocarbon group, each of 11 R11 - R14 an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group or a 12 phenoxy group, L an oxygen atom or a sulfur atom, and j, k, 1 and m are integers of 1 to 6.
13The above formula (I) l~ sents alcohols, thioalcohols, phenols or thiophenols. Examples 14 of these may include methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, tert-butyl 15 alcohol, tert-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, aryl alcohol, 2-butenyl alcohol, 163-hexenyl alcohol, 2,5~1e~rli~nyl alcohol, benzyl alcohol, phenol, catechol, l-n~rhth- l, 2-n~rhthol, 172,6-di-tert-butylphenol, 2,6-di-tert-butyl~-methylphenol, 2,4,6-tri-tert-butylphenol, 4-phenylphenol, 18 eth~nethiol, l-butanethiol, 2-pç .'~ 1.iol, 2-iso-butanethiol, thiophenol, 2-.. ~p1.lh~1enthiol, 19 cyclohexane-thiol, 3-methylcyclohexanethiol, 2-n~rhth~l~n~thiol, benzene-methanethiol, 20 2-naphthalenemethanethiol and the like.
21The formula (II) l~leselll~ carboxylic acids or sulfur analogues thereo~ Examples of these 22 may include isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, 23 stearic acid, oleic acid, linoleic acid, cyclo-pentanecarboxylic acid, napthenic acid, ethylhexanoic 24 acid, pivalic acid, Versatic Acid (synthetic acid constituted of a mixture of isomers of C,0 . .
mono-carboxylic acids sold by Shell Chemical Co.), phenylacetic acid, benzoic acid, 2-nArhthoic 2 acid, h~ n-othionic acid, 2,2-dimethylbul~l~lhionic acid, tetr~dec~nethionic acid, thiobenzoic acid 3 and the like.
4 The formula (III) represents alkyl aryl sulfonic acids, as exemplified by S dodecylbe~ rs~llfonic acid, tetradecylben7~n~s-l1fonic acid, hP~ ecylb~ es~llfonic acid, 6 octadecylb~ s~lfi~nic acid, dibUlyll-Al.kll.Al~ ,s~llrol-ic acid, n-hexyl~l.lal)kll.Al~n~s -lffinic acid, 7 dibutylphenylsulfonic acid and the like.
8 The formula (IV) ~ se.ll~ mono-alcohol esters of sulfuric acid, such as sulfuric acid 9 mono-ester of lauryl alcohol, sulfuric acid mono-ester of oleyl alcohol, sulfuric acid mono-ester of stearyl alcohol and the like.
11 The fonnl-l~ (V) l.,l,les~ rhosph~te diesters of ethylene oxide adduct of alcohol or phenol.
12 Examples of these may include phnsph~te diester of ethylene oxide adduct of dodecyl alcohol, 13 phosphate diester of ethylene oxide adduct of octyl alcohol, phosphate diester of ethylene 14 oxide~d~ ct of stearyl alcohol, phosph~te diester of ethylene oxide adduct of oleyl alcohol, phosphate diester of ethylene oxide adduct of nol~lphellol, phosphate diester of ethylene oxide 16 adduct of dodecyl-phenol and the like.
17 The formula (VI) ,e~le~~ phosphite diesters of ethylene oxide adduct of alcohol or phenol.
18 Examples of these may include phosphite diester of ethylene oxide adduct of dodecyl alcohol, 19 phosphite diester of ethylene oxide adduct of stearyl alcohol, phosphite diester of ethylene oxide adduct of oleyl alcohol, phosphite diester of ethylene oxide adduct of nonylphenol, phosphite diester 21 of ethylene oxide adduct of dodecylphenol and the like.
22 The formula (VII) lep~ese~ pentavalent organic phosphoric acid compounds, including, for example, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl 2 phosphate, bis(1-methylheptyl) phosph~te, bis(2-ethyl-hexyl) phosph~te~ dilauryl phosphate, dioleyl 3 phosphate, diphenyl phosphate, bis(p-nonylphenyl) phosph~te, butyl(2-ethylhexyl) phosphate, 4 (l-methylheptyl) (2-ethylhexyl) phosphate, (2-ethylhexyl)(p-nonylphenyl) phosph~te, 5 monobutyl(2-ethylhexyl) phosphonate, mono-2-ethylhexyl(2-ethylhexyl) phosphonate, 6 mono-2-ethylhexyl phenyl phosphonate, mono-p-nol~lphellyl(2-ethylhexyl) ph()sphonate~
7 dibutylphosphinic acid, bis(2-ethylhexyl) phosphinic acid, bis(1-methylheptyl)rhosphinic acid, 8 dilaurylphosphinic acid, dioleylphosphinic acid, diphenylrhosphinic acid, 9 bis(p-nonylphenyl)phosninic acid, butyl(2-ethyhexyl)phosphinic acid, (2-ethylhexyl) 10 (1-methyl-heptyl)phosphinic acid, (2-ethylhexyl) (p-nonylphenyl)phosphinic acid and the like.
11 The formula (VIII) lc~lcse~ trivalent phosphorous acid compounds, as exemplified by 12 bis(2-ethylhexyl) phosphite, bis(1-methylheptyl) phosphite bis(2-ethylhexyl)phosphinous acid and 13 the like.
14 Still more spe~ific~lly, the ~ hAIIIIIII rare earth catalysts ofthe present invention include but 15 are not necçcs~.;ly limited to: l~nth~n~lm tris(nonylphenoxide), l~nth~mlm tris(dodecyl-p-toluene 16 sulfonate), l~nth~nllm tris[bis(2-ethylhexyl)phosphate], l~nth~mlm tris[dipropylamine], l~nth~n~lm 17 tris[propylthio], lanthanum tris[propoxyl], l~nth~nllm propionate, l~nth~nnm diethyl~cet~te, 18 lanthanum 2-ethyl hexanoate, l~nth~mlm stearate, l~nth~nllm bçn70~te, cerium ben70~te, l9 praseodymium propionate, praseodymium cyclohexane carboxylate, praseodymium 2-ethyl 20 hexanoate, neodymium diethyl acetate, neodymium 2-ethyl hexanoate, neodymium cyclohexane 21 carboxylate, neodymium stearate, neodymium oleate and neodymium ben_oate. Of the foregoing, ' CA 02247669 1998-09-17 lanthanum tris(nonylphenoxide) is the most yief~ .led.
2 The organolithium catalysts contemplated by the instant invention include but are not 3 necçs~rily limited to lithium compounds having the general formula R(Li)X, wherein R r~lesell~
4 a hydrocarbyl radical of I to 20, preferably 2 to 8, carbon atoms per R group and x is an integer from 1 to 4. Specific example of other suitable lithium catalysts include: p-tolyllithium, 4-phenylbutyl-6 lithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyl-lithi.lm, lithium dialkyl amines, lithium dialkyl 7 pho~yhil~os~ lithium aLkyl aryl pl~o~hil~, lithium diaryl phosyh;~s~ 1,3,3-trilithio-1-octyne, 1,1,3-8 trilithio-1,2-butadieneandthelike.Theyl~fell~d catalyst for use in the present invention are 9 n-butyllithium, t-butyllithium and sec-butyllithium.
The synthesis is carried out in hydroc~ul~n reaction diluent, for example, hexane, 11 cyclohexane or toluene. It is very desirable that the catalyst conlyo~ are soluble in the particular 12 reaction diluent used. An ~liph~tic solvent, e.g. hexane, or cyr,lo~lirh~tic solvent, e.g. cycloh~Y~ne, 13 or toluene are yl.,fc~led. Hexane is most prer~.led.
14 The l~nth~nide colllyoul~d and the organolithium catalysts are added to the reaction mass in a hydrocarbon diluent at a relative molar ratio within the range of from about 1: 0.1 to about 16 1:100.0; more preferably from about 1: 1.0 to about 1:50.0; still more preferably about 1: 2.0 to 1 7 about 1: 1 0.0; and most preferably about 1:3 Ø
18 A reaction temperature of about 0~ to about 120~C., is typical; while about 20~ C. to about 19 100~C. is ylefe~l~d. In order to colllyel~le for the vapor P1G~UIe of the monomer(s) under typical reaction conditions, reaction pressures of from about slightly above atmospheric to up to about 10 21 atmospheres are preferred. Generally the molecular weight of the polymer is inversely proportional to catalyst concentration. Molecular weight generally also increases in direct proportion to 2 polymerization time. This suggests that at least a portion of the catalyst system remains active 3 throughout the reaction time.
4 Examples of conjugated diene monomers which may be block polylll.,.;~cd by the process S of the invention are butadiene and isoprene although the process is not le~l~;cted to the use of one 6 or other of these two conjugated dienes. Mixtures of conjugated dienes may be used if desired. The 7 p.erell~,d order of addition of catalyst colllpol1ents is to add the monomer to the solvent first followed 8 by colllponellt (a) and then conlpol1ell~ (b) and, if used, finally cGlllponenl (c) in that order.
9 It is particularly beneficial, and thus plcr~ d, to carry out the polymeri7~tion using components (a) and (b) together in the presence of a polar diluent, typically a Lewis base such as 11 tetrahydrofuran. Exemplary of other polar compounds are (a) ethers such as din.c~lyl ether, diethyl 12 ether, 1,2 ~limeth~xy ethane, diphenyl ether, diben7yl ether and anisole; (b~ amines such as 13 trimethylamine, triethylamine pyridine or tetra methyl ethylene ~i~mine; (c) thioethers such as 14 thiophene and (d) polyethers such as glyme or diglyme. These polar compounds are well known in the art. Their use in the present invention enables higher conversions of mon~ m~r to polymer to be 16 obtained with no appreciable effect on trans content unless very high concentrations of these polar 17 compounds are used. Typical of such high concellL~a~ions is a molar ration of polar compound to 18 compound (b) of greater than about 2.5:1. Surprisingly addition of a polar compound produces no 19 increase in vinyl content ofthe polymer, in contrast to the increase in vinyl content such compounds produce in anionic polymerizations.
21 As can be seen from the above the process ofthe invention offers the possibility of pl~illg 22 a wide variety of conjugated diene polymers (1) a polymer of high trans 1,4 content, by using , components (a) and (b); (2) a block polymer having a high trans block and a second block, by 2 initi~ting the polym~ri7~tion using colllpone.ll~ (a) and (b) alone and adding a cis 1,4 component at 3 the desired degree of conversion. Some homopolymer of high trans content and high cis content 4 respectively may also be formed in this re~ctiQn; and, (4) a polymer of lllediull~ trans 1,4 content e.g.
5 50-80% by m~ifir~tion of the reaction using components (a) and (b) with lithium alkyl; optionally 6 carrying out the polye ;".I;on in the presence of a vinyl aromatic monomer, such as styrene, to 7 obtain e.g. a ~lyl~ ne-butadiene copolymer of medium trans 1,4 content.8 These polymers are rubbery (except the polymers of high trans content) and may be 9 compounded and vulcani_ed by methods well known in the art. They are of potential application in tires, general rubber goods and in the pl~a,aLion of plastics m~t~ri~l~ such as high impact 1 1 polystyrene.
12 The instant invention is plGr~ bly directed to the synthesis of 1,4 trans-butadiene polymer.
13 However, the versatile two-colllpollent catalyst system, nonetll~less provides the option of block 14 polymeri7~tiQn to further modify the primary product to include other desirable pro~l~ies such ~
improved softening telllpel~ , moldability, rigidity, strength, r~silien~, impact r~ict~ncç and the 16 like. However, the full significance of the present invention is demon~ d through a polymer 17 resin product which contains at least 30 weight % of the initial trans-polybutadiene product.
18 Other particularly pl~r~lable polymeric resin colllpollents that may be mixed with the initial 19 trans-butadiene product include, but are not necess~rily limited to: trans-isoprene polymers, trans-polyoctenamers and caprolactone polymers. In order to modify the hardness or plasticity of 21 crystalline trans-butadiene polymers compositions of the present invention, inorganic fillers or plastici_ers may be added, as desired. Similarly, conventional stabili_ers, pi~m~ntc, and the like may 2 be added in any manner and for any purpose prescribed by the prior art.
3 Inorganic fillers are typically added in amounts of about 5 to about 100 parts by weight per 4 100 parts by weight of the polymeric resin component. Such fillers include, but are not limited to:
S titanium oxide, silica, calcium c~bonate, clay, talc, mica, ~ ~lol.;Le and the like. The ~ tion of 6 fillers beyond these specified amounts have been observed to adversely lower the impact 7 of the polymeric resin product.
8 pl~ti~i7~rs are typically added in amounts ranging from about 1 to 20 parts by weight per 9 100 parts by weight of the polymeric resin product. Examples of plastici~rs may include, but are not n~cçe~rily limited to: dibutyl phth~l~te, di-(2-ethylhexyl) phth~l~tç, di-(2-ethylhexyl) ~lir~te~
11 diethylene glycol ben7l~ate, butyl ste~r~te~ butylepoxy stearate, tri-(2-ethylhexyl) phosrh~t~, and the 12 like.
13 The polymeric resin product of the present invention can easily be mixed by means of an 14 extruder, a knP~rler, rolls, or the like. These app~r~t--~es are typically ope.dled at te~ c~al~e ranges from about 60~ to about 200~C.; and, preferably from about 80~ to 1 80~C. It is also possible to mix 16 the components in a solution dissolved in a suitable solvent.
17 Polymeric resin product of the instant invention that CO~ ih~S crystalline trans-butadiene 18 polymers may generally be used without vulc~ni7~tion. However, depending uses such as golf ball 19 cover materials, and the like, it is typically preferable to impart further strength and impact rçci~t~nce to the polymeric resin product through vulcani_ation. Although, any conventional method of 21 vulcanization can be used for this purpose, it is preferable to vulcanize a trans-butadiene product of 22 the instant invention at temperatures no higher than the melting point of the product. Exemplary of ' CA 02247669 1998-09-17 these methods, are low temperature vulcanization and electron beam vulcanization.
2 Preferred vulc~ni7ing agents used in low telllpeldLIlre vulcani_ation include, but are not 3 necessarily limited to: elem~nt~l sulfur, selenium, tellurium, inorganic sulfur compounds such as 4 sulfur dichloride, sulfur chloride, etc.; organic sulfur compounds such as morpholine t~ llfide, alkylphenol disulfide, and the like. Typical vulc~ni7~tion acccleldtol~ include, but are not 6 necess~rily limited to: guanidine type vulc~ni7~tion acccleldlol~, aldehyde-amrnonia type 7 vulcani_ation acc~ler~tors, slllph~n~mide type vlll- ~ni7~tion accel-,ldlul~, thiuram type vulc~ni7~tio~n 8 accelerators, ~ type vulc~ni7~tion accelelalo,~, aldehyde-amine type vulc~ni7~tion 9 accelerators, thiazole type vulc~ni7~tion accclcldlo-s, thiourea type vulcanization acccleldlors, dithioc~l,~ulldle type vulcanization accclcldl(~l~ and mixed types ofthese. The particularly pl.,rell~d 11 vulc-~ni7ing agent is elemental sulfur. It is preferably used in an amount of about 0.1 to about 3.0 12 parts by weight per 100 parts by weight ofthe polymer. Pler~ll~l vulcani7ation acccl~ l~lol~ include, 13 but are not ~ ~ ;ly limited to: ~sIhi.l~ type vlllc~ni7~ti~n accckldl~ and dithioc~b~llate type 14 vulcani_ation accelerators. Examples of x~nth~te type vulcani_ation accelerators include, but are not n~cess~rily limited to: sodiurn isolllo~lxs~ te~ zinc isopropylx~nth~te zinc ethylx~nth~te, zinc 16 IJulylx~lllh~te~ dibut~lx~ disulfide, and the like. Examples of l,lefell~d dithioc~l,alllale type 17 vulcanization accelerators include, but are necess~rily limited to: sodium dimethyldithicarbamate, 18 sodium diethyldithiocarbamate, sodiurn di-n-butyldithiocarbamate, zinc ethylphenyldithioc~L.~ndle, 19 zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc dibenzylthiocarbamate, zinc N-penta-methylenedithiocarbamate, zinc 21 dimethylpentamethylenedithio-carbamate, zinc ethylphenyldithiocarbamate, selenium 22 dimethyldithiocarbamate, selenium diethyldithiocarbamate, tellurium diethyldithiocarbarnate, .
cadmium diethyldithioc~b~l~ate, dilllGLhylammonium dimethyldithioc~bal,.ale, dibutylammonium 2 dibutyldithioc~b~llate, diethylamine diethyldithiocarbamate, N,N'-dimethylcyclohexane salt of 3 dibutyldithioc~balnic acid, pipecolic methylpelll~llethylenedithioca,l,a"lalG, and the like.
4 Depending on the particular vulc~ni7~tion accelerator employed, p~fell~,d amounts of accelerator typically range from about 0.1 to about 3.0 parts by weight per 100 parts by weight of the polymer.
6 It is generally preferable to co~ ct the ~ll~ni7~tion at t~ s below about 90~C. Particularly 7 preferable are vulr~ni7~tion telllp~ tule in the range of about 30~ to 60~C. VU1CA~ 1 ;on times, 8 which may differ depending on the vulc~ni7ing agent, the v~llc~ni7~tion acccle.~lor and the 9 vulr~ni7~tion telll~.alul~,; may generally be from about some ten i~ cs to about several days.
The crystalline trans-polybutadienes produced by the present invention are excellent in l 1 moldability and workability at relatively lower tempel~L~es and also exhibit excellent physical 12 pl~.Lies such as rigidity, strength, re~ n~e, impact re~ict~ncç and the like. These polymers are 13 used in the fonmll~tion of rubber compounds to increase green ~L~ lh and i~ processability.
14 The trans-polyb~lt~ n~s are also used in the pl~l)alalion pl~tic m~teri~l~ such ~ high impact 1 5 polystyrene.
16 The instant invention will be described in more detail with reference to the following non-l 7 limitative examples. The following examples are present for purposes of illustration only and are 18 not to be construed in a limitin~ sense. All pelce~llages are by weight unless otherwise specified.
19 Example 1 An oven dried, 750 ml glass bottle was sealed with a butyl liner and crown cap. The bottle 21 w~ cooled then charged with 223 grams of a dry butadiene/hexane blend (22.3 wt%). T ~nth~num tris[bis(2-ethylhexyl) phosphate] (0.27 mmol) was added to the monomer solution. This was 2 followed by the addition of n-BuLi (1.08 mmol). The bottle was placed in a 65 ~ C water bath for 3 2 hours. The solvent was then allowed to evaporate yielding a white powder. The isolated yield was 4 87%. The analysis of this material is reported in Table 1.
Tablel 6 ~k Li~ ~ML~ ~r~ Pwr~ r~ M~ M~ L~w L~ 7'~1) 7 1 ~ o ss 4 65 2.0 87 52 1.37 4g 93 8 2 b 1.00 3.8 S0 2.15 67 36 1.21 88 6 49 90 9 3 t 120 3.1 S0 1.10 87 37 1.11 g2 4 47 9S
1 1 0.60 3 S0 230 gl 70 1.27 92 4 48 91 12 ~ bis(2~1h;1- ;')~' ,1' 13 b: ~ Jl ~~
14 c r ,~
16 Fxamples 2 to 4 17 In Exarnples 2 to 4, reactions similar to that described for Example 1 were carried out in 18 which di~le.lt l~nth~nl-m salts were used. These examples are summarized in Table 1 along with 19 the colles~llding results. These results show that a variety of l~nth~nllm salts are suitable for the prel)~alion of an active catalyst system.
21 Examples 5 to 13 22 In Examples S to 13, reactions similar to that described for Example 1 were carried out while 23 the ratio of catalyst to monomer was varied. The results of these examples are summarized in Table 24 2. These results show that the molecular weight can be controlled by the ratio of catalyst to monomer.
CA 02247669 l998-09-l7 3 Table2 5 ExampkmM L~l l,f/lA YJdd Un Mw/Unrm(l) rm (2) 6 phgBd (X) (kg/nwl) (~ (~7 7 Lig~nd: bis(2_ yl Yl)U
8 s 035 4.0078 73 1.44 47 91 9 6 0.45 4.0087 65 1.41 48 gl 0 7 055 4.0087 52 13~ 49 g3 8 0.65 4.00g3 41 1.46 48 91 13 Lig~nd~
14 g 030 35 87 1071.81 42 61 0.45 3.5 90 77 1.47 39 54 16 1l 0.60 35 94 59 1.44 37 49 17 12 0.75 3.5 98 47 1.26 16 37 1 8 13 0.90 35 96 37 131 39 22 F~r~mples 14 to 19 23 In E ~ llplcS14 to 19, diethylzinc was added to the butadiene solution prior to the addition 24 of n-BuLi. The polym~li7~tion~ were run in a similar manner to that described for Example 1. The amounts ofthe catalyst coll~ e~ used and the results from these poly.~ lions are listed 26 in Table 3. It is appa~lll from these results that diethylzinc can be used to lower the molecular 27 weight and narrow the polydispersity of the polymer.
Table3 3 EXAMPLE mM' La phg Li/LaZn/La Y'eld Mn Mw/M'n l,~-tran~ 1,2-vinyl Tm(l) T~2) Bd (~/) (kg/mol) (~ /) ( ~C)( ~C) Lig~nd:bis(2~l~J~ I)pho~p~te 6 140.25 4 0.5 46 58 1.61 94 4 49 93 7 150.25 4 1 42 47 1.47 95 4 47 92 8 160.25 4 3 52 40 1.33 47 93 9 170.35 4 0.5 61 52 1.48 95 4 50 93 0 180.35 4 1 63 47 1.40 96 4 48 93 190.35 4 3 61 34 1.30 95 4 47 92 13 Fxamples 20 to 23 14 In Examples 20 to 23 polymeri_ations were carried out in which the ratio of catalyst 15 components was varied. These polymeri7~tions were carried out in a manner similar to that 16 described for Example 1. The conditions used for these polymeri_ations are sllmm~n7~d in Table 17 4. The results from these examples indicate that the microstructure of the polymers can be controlled 18 by varying the ratio of the catalyst components.
19 Table 4 2I Exomple mU La l~ Pzn Pzn rclt Un Uw~Un 1,~- t,2- rm(l) rm(2) rg phglJd rcmp rmc~%) (kg/molJ ~rans n'nyl ('C~ (~ (~
22 ( ~/~hrs) (.~) (,~) 23 Ligand:bis(2-ethylhexyl)~hD '~te 24 20 0.60 3 60 1:30 95 64 1.30 92 5 48 85 21 0.60 3.5 60 1:30 95 64 1.29 91 5 47 84 26 22 0.60 4 60 1:30 92 50 1.18 79 7 15 39 -83 27 23 0.60 4.5 60 1:30 95 42 1.11 64 10 -25 -91 2 Examples 24 to 27 3 In Examples 24 to 27, two sets of polymeri_ations were carried out in a similiar manner to 4 that described in Example 1. Within each set, one polym~ri7~tion was tc i-.n~e~ with iso~lopallol 5 and the other with tin tetrachloride. The amounts of catalyst and tin tetrachloride used are shown 6 in Table 5. The effect of SnC14 ~f ....il~AIion on the molecular weight distribution of the polymer is 7 shown in Figure 1. It is clear from these SEC cl~lolllalograms that the addition of tin tetrachloride 8 causes a coupling reaction to occur. The percent coupled polymer was e~ ed from the SEC
9 chromatograms. These results establish the "living" nature of the polymeri_affon, that is, this 10 behavior is con~i~t~nt with a polymer molecule that retains a reactive chain end after the 11 Table 5 13 E~k ~UL. u~ &~ ~ Pu~ ~., ~ ~MI, ~4"' ' ' '~ r~l) r~J
p~ u r~p r~
14 (~
Ligand: bis(2-ethylhexyl)~ h-' 16 24 0.75 4 0 65 1.5 84 51 1.45 0 47 89 ~j~ 25 0.75 4 0.7 65 1.0 84 131 2.59 48 49 87 19 Ligand: r~cr~ ~YI~le 26 1.20 3.1 0 50 1:10 87 41 1.11 0 92 4 47 95 21 27 1.20 3.1 1 50 1:10 85 113 1.91 55 90 5 48 95 monomer has been con~llmed by the polym~ri7~tion reaction. This data is similar to the results that 2 are obtained with a butyllithium polymeri_ation, typically known ~ a "living" system. Therefore 3 the results of Figure 1 suggest that much of the synthetic strategies that have been used in the BuLi 4 system, such as the synthesis of block polymers, could also be considered with the Ln/BuLi system.
S Those of ol-iin~y skill in the art will appreciate that the conception upon which this 6 disclosure is based may readily be utili_ed as a basis for the ~ igning of other structures, methods 7 and systems for c~l~ing out the several purposes ofthe instant invention. It is hllpoll~ll~ therefore, 8 that the claims be regarded as including such equivalent constructions insofar as they do not depart 9 from the spirit and scope of the instant invention.
Although the invention has been described with reference to certain ~leÇ~ d embodiments, 11 it will be appreciated that many variations and modifications may be made within the scope of the 12 broad principles of the invention. Hence, it is int~n~e~l that the plefell~d embo-1im~nt.~ and all of 13 such variations and m-ulifi~tion~ be included within the scope and spirit ofthe invention, as defined 14 by the following claims.
Claims (45)
1. A catalyst composition, consisting essentially of:
(a) an organolithium compound; and, (b) an organic acid salt of lanthanide series element;
wherein: (1) only components (a) and (b) are required to promote the synthesis of 1,4-trans-polybutadiene; (2) the ratio of component (a) to component (b) is selected to maximize formation of the trans structure of said 1,4-trans-polybutadiene, and, (3) components (a) and (b), and the ratio thereof are selected for enabling further diblock synthesis.
(a) an organolithium compound; and, (b) an organic acid salt of lanthanide series element;
wherein: (1) only components (a) and (b) are required to promote the synthesis of 1,4-trans-polybutadiene; (2) the ratio of component (a) to component (b) is selected to maximize formation of the trans structure of said 1,4-trans-polybutadiene, and, (3) components (a) and (b), and the ratio thereof are selected for enabling further diblock synthesis.
2. The catalyst composition of claim 1, wherein said composition consists essentially of catalytically effective amounts of (a) n-butyllithium and (b) lanthanum tris(nonylphenoxide).
3. The catalyst composition of claim 2, wherein component (b) is a compound having a general formula selected from the group consisting of: Ln(R1CO2)3, Ln(OR1)3, Ln(NR1R2)3, Ln(SR1)3, Ln(PR1R2)3, Ln[OP(O)(OR1)(OR2)]3 and Ln(OS(O)2R)3; wherein Ln is a rare earth element in the lanthanum series having an atomic number of 57 to 71 and R, R1 and R2 are independently selected from the group of substitutents consisting of: alkyl, cycloalkyl and aryl hydrocarbon substituents having 1 to 20 carbon atoms.
4. The catalyst composition of claim 3, wherein R, R1 and R2 are independently selected from the group of substitutents consisting of: cycloalkylalkyl, alkylcycloalkyl, aryl, alkylaryl and combinations thereof.
5. The catalyst composition of claim 4, wherein R, R1 and R2 may also be independently selected from the group of substitutents consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, n-decyl, 2-ethyl hexyl, cyclopentyl-methyl, cyclohexyl-ethyl, cyclopentyl-ethyl, methylcyclopentylethyl, cyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl and combinations thereof.
6. The catalyst composition of claim 2, wherein the catalyst component (b) is derived from an organic compound of the following formulae (I) to (VIII):
R3 - LH (I) wherein each of R3, R4 and R7 -R10 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R5 an aromatic hydrocarbon group, R6 an aliphatic hydrocarbon group, each of R11-R14 an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group or a phenoxy group, L an oxygen atom or a sulfur atom, and j, k, l and m are inlegers of 1 to 6; and, combinations thereof.
R3 - LH (I) wherein each of R3, R4 and R7 -R10 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R5 an aromatic hydrocarbon group, R6 an aliphatic hydrocarbon group, each of R11-R14 an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group or a phenoxy group, L an oxygen atom or a sulfur atom, and j, k, l and m are inlegers of 1 to 6; and, combinations thereof.
7. The catalyst composition of claim 3, wherein Ln is selected from the group consisting of: lanthanum, cerium, praseodymium, neodymium, gadolinium and combinations thereof.
8. The catalyst composition of claim 7, wherein Ln is a mixture comprising at least 30% by weight of lanthanum or neodymium.
9. The catalyst composition of claim 3, wherein component (b) is lanthanum tris(nonylphenoxide).
10. The catalyst composition of claim 2, wherein compound (a) comprises a lithium compound having the general formula R(Li)x, wherein R represents a hydrocarbyl radical of 1 to 20 carbon atoms per R group and x is an integer from 1 to 4.
11. The catalyst composition of claim 10, wherein component (a) is selected from the group consisting of: p-tolyllithium, 4-phenylbutyl-lithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyllithium, lithium dialkyl amines, lithium dialkyl phosphines, lithium alkyl aryl phosphine, lithium diaryl phosphines, 1,3,3-trilithio-1-octyne, 1,1,3-trilithio-1,2-butadiene and combinations thereof.
12. The catalyst composition of claim 11, wherein component (a) is selected from the group consisting of: n-butyllithium, sec-butyllithium and t-butyllithium and combinations thereof.
13. The catalyst composition of claim 1, wherein said ratio of component (b) to component (a) is from about 1:0.1 to about 1:100Ø
14. A process for the synthesis of 1,4-trans-polybutadiene product having a substantially high yield of trans structure, comprising: polymerizing butadiene monomers in the presence of a catalyst system comprising (a) an alkyllithium catalyst; and, (b) an organic acid salt of lanthanide series element; wherein the ratio of component (a) to component (b) is selected sufficient to maximize formation of said trans structure of said 1,4-trans-polybutadiene.
15. The process of claim 14, further comprising the steps of:
adding a diethylzinc chain transfer agent prior to the addition of the alkyllithium catalyst.
adding a diethylzinc chain transfer agent prior to the addition of the alkyllithium catalyst.
16. The process of claim 14, wherein said catalyst system consists essentially of catalytic amounts of components (a) and (b).
17. The process of claim 14, wherein component (b) is a compound having a general formula selected from the group consisting of: Ln(R1CO2)3, Ln(OR1)3, Ln(NR1R2)3, Ln(SR1)3, Ln(PR1R2)3, Ln[OP(O)(OR1)(OR2)]3 and Ln(OS(O)2R)3; wherein Ln is a rare earth element in the lanthanum series having an atomic number of 57 to 71 and R, R1 and R2 are independently selected from the group of substitutents consisting of: alkyl, cycloalkyl and aryl hydrocarbon substituents having 1 to 20 carbon atoms.
18. The process of claim 17, wherein R1 and R2 may also be independently selected from the group of substitutents consisting of: cycloalkylalkyl, alkylcycloalkyl, aryl, alkylaryl and combinations thereof.
19. The process of claim 18, wherein R1 and R2 may also be independently selected from the group of substitutents consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, n-decyl, 2-ethyl hexyl, cyclopentyl-methyl, cyclohexyl-ethyl, cyclopentyl-ethyl, methylcyclopentylethyl, cyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl and combinations thereof.
20. The process of claim 14 wherein component (b) is derived from a compound having a general formula selected from the group consisting of formulae (I) to (VIII) as shown below:
R3- LH (I) wherein each of R3, R4 and R7 -R10 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R5 an aromatic hydrocarbon group, R6 an aliphatic hydrocarbon group, each of R11-R14 an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group or a phenoxy group, L an oxygen atom or a sulfur atom, and j, k, l and m are integers of 1 to 6.
R3- LH (I) wherein each of R3, R4 and R7 -R10 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R5 an aromatic hydrocarbon group, R6 an aliphatic hydrocarbon group, each of R11-R14 an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group or a phenoxy group, L an oxygen atom or a sulfur atom, and j, k, l and m are integers of 1 to 6.
21. The process of claim 14, wherein Ln is selected from the group consisting of:
lanthanum, cerium, praseodymium, neodymium, gadolinium and combinations thereof.
lanthanum, cerium, praseodymium, neodymium, gadolinium and combinations thereof.
22. The process of claim 21, wherein Ln is a mixture comprising at least 30% by weight of lanthanum or neodymium.
23. The process of claim 14, wherein component (b) is lanthanum tris(nonylphenoxide).
24. The process of claim 14, wherein compound (a) comprises a lithium compound having the general formula R(Li)x, wherein R represents a hydrocarbyl radical of 1 to 20 carbon atoms per R group and x is an integer from 1 to 4.
25. The process of claim 14, wherein component (a) is selected from the group consisting of: p-tolyllithium, 4-phenylbutyl-lithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyl-lithium, lithium dialkyl amines, lithium dialkyl phosphines, lithium alkyl aryl phosphine, lithium diaryl phosphines, 1,3,3-trilithio-1-octyne, 1,1,3-trilithio-1,2-butadiene and combinations thereof.
26. The process of claim 25, wherein component (a) is selected from the group consisting of:
n-butyllithium, sec-butyllithium, t-butyllithium and combinations thereof.
n-butyllithium, sec-butyllithium, t-butyllithium and combinations thereof.
27. The process of claim 14, wherein said ratio of component (b) to component (a) is from about from about 1:0.1 to about 1:100Ø
28. The process of claim 14, wherein said ratio of component (a) to cor.lpollent (b) is varied to obtain a trans content in the resultant polymer ranging between 50 and 96%.
29. The process of claim 14, wherein concentration ofthe catalyst system is varied to control the molecular weight of the resultant polymer.
30. The process of claim 14, further comprising the steps of adding a terminating agent the resultant polymer.
31. A process for the synthesis of polymers and copolymers containing conjugated diene contributed monomer units and having a substantially high yield of trans structure in the conjugated diene contributed monomer units comprising: polymerizing conjugated diene monomers in the presence of a catalyst system comprising: (a) an alkyllithium catalyst; and, (b) an organic acid salt of lanthanide series element Ln; wherein the ratio of component (a) to component (b) is selected sufficient to maximize formation of said trans structure in the conjugated diene contributed monomer units.
32. The process of claim 31, further comprising the steps of:
adding a diethylzinc chain transfer agent prior to the addition of the alkyllithium catalyst.
adding a diethylzinc chain transfer agent prior to the addition of the alkyllithium catalyst.
33. The process of claim 31, wherein said catalyst system consists essentially of catalytic amounts of components (a) and (b).
34. The process of claim 31, wherein component (b) is a compound having a general formula selected from the group consisting of: Ln(R1CO2)3, Ln(OR1)3, Ln(NR1R2)3, Ln(SR1)3, Ln(PR1R2)3, Ln[OP(O)(OR1)(OR2)]3 and Ln (OS(O)2R)3; wherein Ln is a rare earth element in the lanthanum series having an atomic number of 57 to 71 and R, R1 and R2 are independently selected from the group of substiutients consisting of: alkyl, cycloalkyl and aryl hydrocarbon substituents having 1 to 20 carbon atoms.
35. The process of claim 34, wherein R, R1 and R2 are independently selected from the group of substitutents consisting of: cycloalkylalkyl, alkylcycloalkyl, aryl, alkylaryl and combinations thereof.
36. The process of claim 34, wherein R, R' and R2 are independently selected from the group of substitutents comprising of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, n-decyl, 2-ethyl hexyl, cyclopentyl-methyl, cyclohexyl-ethyl, cyclopentyl-ethyl, methylcyclopentylethyl, cyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl and combinations thereof.
37. The process of claim 31 wherein component (b) is a compound having a general formula selected from the group consisting of formulae (I) to (VIII) as shown below:
R3- LH (I)
R3- LH (I)
38
39 wherein each of R3, R4 and R7 -R10 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R5 an aromatic hydrocarbon group, R6 an aliphatic hydrocarbon group, each of R11-R14 an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group or a phenoxy group, L an oxygen atom or a sulfur atom, and j, k, l and m are integers of 1 to 6.
38. The process of claim 31, wherein Ln is selected from the group consisting of:
lanthanum, cerium, praseodymium, neodymium, gadolinium and combinations thereof.
39. The process of claim 31, wherein Ln is a mixture comprising at least 30% by weight of lanthanum or neodymium.
38. The process of claim 31, wherein Ln is selected from the group consisting of:
lanthanum, cerium, praseodymium, neodymium, gadolinium and combinations thereof.
39. The process of claim 31, wherein Ln is a mixture comprising at least 30% by weight of lanthanum or neodymium.
40. The process of claim 31, wherein component (b) is lanthanum tris(nonylphenoxide).
41. The process of claim 31, wherein compound (a) comprises a lithium compound having the general formula R(Li)x, wherein R represents a hydrocarbyl radical of 1 to 20 carbon atoms per R group and x is an integer from 1 to 4.
42. The process of claim 31, wherein component (a) is selected from the group consisting of: p-tolyllithium, 4-phenylbutyl-lithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyl-lithium, lithium dialkyl amines, lithium dialkyl phosphines, lithium alkyl aryl phosphine, lithium diaryl phosphines, 1,3,3-trilithio-1-octyne, 1,1,3-trilithio-1,2-butadiene and combinations thereof.
43. The process of claim 31, wherein component (a) is selected from the group consisting of:
n-butyllithium, sec-butyllithium, t-butyllithium and combinations thereof.
n-butyllithium, sec-butyllithium, t-butyllithium and combinations thereof.
44. The process of claim 31, wherein said ratio of component (b) to component (a) is from about from about 1:0.1 to about 1:100Ø
45. The process of claim 31, wherein said ratio of component (b) to component (a) is varied to obtain a trans content in the resultant polymer ranging between 50 and 96%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/934,608 | 1997-09-22 | ||
| US08/934,608 US6018007A (en) | 1997-09-22 | 1997-09-22 | Synthesis of 1,4-trans-polybutadiene using a lanthanide organic acid salt catalyst |
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| EP (1) | EP0903357B1 (en) |
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| US6436866B1 (en) * | 1999-05-26 | 2002-08-20 | Asahi Kasei Kabushiki Kaisha | Lewis acid catalyst composition |
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| NL6411059A (en) * | 1964-09-23 | 1966-03-24 | ||
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| IT1085663B (en) * | 1977-08-01 | 1985-05-28 | Snam Progetti | (co)polymerisation of conjugated aliphatic di:olefin(s) - to predominantly 1,4-cis polymers, with catalysts contg. lanthanide complexes, Lewis acids and aluminium cpds. |
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- 1998-09-07 ES ES98116879T patent/ES2215258T3/en not_active Expired - Lifetime
- 1998-09-07 DE DE69821301T patent/DE69821301T2/en not_active Expired - Lifetime
- 1998-09-07 EP EP98116879A patent/EP0903357B1/en not_active Expired - Lifetime
- 1998-09-17 JP JP10280484A patent/JPH11158207A/en active Pending
- 1998-09-17 CA CA002247669A patent/CA2247669A1/en not_active Abandoned
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1999
- 1999-12-21 US US09/467,683 patent/US6184168B1/en not_active Expired - Lifetime
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| JPH11158207A (en) | 1999-06-15 |
| ES2215258T3 (en) | 2004-10-01 |
| US6184168B1 (en) | 2001-02-06 |
| US6018007A (en) | 2000-01-25 |
| DE69821301D1 (en) | 2004-03-04 |
| EP0903357A1 (en) | 1999-03-24 |
| EP0903357B1 (en) | 2004-01-28 |
| DE69821301T2 (en) | 2004-11-25 |
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