Process for producing liquid polybutadiene
United States Patent 1 Yasui et al.  
 [ PROCESS FOR PRODUCING LIQUID POLYBUTADIENE [75] Inventors: Seimei Yasui, Ibataki; Takanobu Noguchi; Michio Yai&#39;nmoto, both of TakatsukhYoshihara Yagi, Toyonaka&#39;, all 6f Osaka, Japan [73] Assignee: Sumitomo ChemicaP-Company,  
 Limited, Osaka-shi, Osaku-fu, Japan [22] Filed: July 3, 1973 [2]] Appl. No.: 376,168  
 [30] Foreign Application Priority Data Primary Examiner-Paul M. Coughlin, Jr. Attorney, Agent, or F irm--Craig &amp; Antonelli i4 1 Apr. 8, 1975 571 ABS-Timer &#34;Process for producing liquid polybutadiene having predominantly cis-l,4-struetii re, which comprises polymerizing 1,3-butadiene&#34; in the presence of a novel catalyst system comprising 1. an organic aluminum compound of the formula: AIR R R wherein R, is hydrogen, fluorine, alkyl cycloalkyl, aryl or aralkyl; R and R are each alkyl, cycloalkyl, aryl or aralkyl:  
 2. at least one of nickel compounds selected from the group consisting of a. a nickel salt of a carboxylic acid,  
 b. an organic nickel complex compound,  
 c. nickel tetracarbonyl, and  
 d. rr-bond type organic nickel compound; and  
 3. at least one of hal&#39;jngen-containing organic compounds selected from the group consisting of a. a halogenated aliphatic or alicyclic hydrocarbon, b. a benzotrihalogenide, c. an alkynyl halogenidmafnd d. a ketone compound containing chlorine or bromine in the molecule.  
 26 Claims Na Drawings 1 PROCESS FORPRODUCING LlQUlD POLYBUTADIENE The present invention relates to a process for producing liquid polybutadiene. More particularly. relates .to a process for producingliquid polybutadiene having predominantly cis-l,4&#39;-structure b y polymerization of butadiene in the presence of a novelcatalyst system comprising 1&#39;) an organic aluminum compound. (2) a nickel compound and (3) a &#39;halogen-containing organic compound. i &#34;I For production of liquid polybutadiene, there have. hitherto, been known various catalysts, such as butyl lithium. metal sodium and boron trifluoride. However. when such catalysts are used. the. obtained liquid polybutadiene has predominantly vinyland trans-1,4- structure and 60 percent or less cis-l.4-structure.  
  Furthermore, there are. described various other processes for the production of liquid polybutadiene&#39;in some literatures. for instance. a process by using a catalyst system comprising a halogenated alkyl aluminum. an organic nickel compound and a vinylcycloolefin in Japanese Patent Publication No. 1351 1/1969; a process for producing liquid polybutadiene having 70 percent or more cis-l .4-structure by using a catalyst system comprising a halogenated alkylaluminum. an or ganic nickel compound and an electron donative compound containing nitrogen, oxygen or the like in U.S. Pat. No. 3.428.699; a process by using a threecomponents catalyst system comprising an organic metal compound. a nickel compound and a halogencontaining inorganic compound in Japanese Pat. Opening No. 5645/1971; and a process by using a catalyst system comprising an organic aluminum compound of the formula: R,,,AlCl,, wherein m n 3. R is alkyl and Cl is chlorine. a nickel compound and a halogencontaining aromatic compound or a halogencontaining unsaturated hydrocarbon in US. Pat. No. 3.458.493.  
  It has been studied to find out a novel process for producing liquid polybutadiene having predominantly cis-l .4-structure, and then there has now been found a novel catalyst system valuable for te purpose.  
  The present invention provides a novel process for producing liquid polybutadiene having predominantly cis-l.4-structure. which comprises polymerizing 1,3- butadiene in the presence of a novel catalyst system comprising the following three components:  
  1. an organic aluminum compound having the formula: AlR R R wherein R is hydrogen, fluorine. alkyl, cycloalkyl. aryl or aralkyl; R and R are each alkyl. cycloalkyl, aryl or aralkyl:  
  2. at least one of nickel compounds selected group consisting of a. a nickel salt of a carboxylic acid.  
 b. an organic nickel complex compound.  
 c. nickel tetracarbonyl. and I d. rr-bond type organic nickel compound; and  
  3. at least one of halogen-containing organic compounds selected from the groupconsisting of a. a halogenated aliphatic or&#39;alicyclic hydrocarbon,  
 b. a benzotrihalogenide.  
 c. an alkynyl halogenide. and  
 d. a ketone compound containing chlorine or bromine in the molecule.  
  According to the present invention. a low molecular weight polymer can be obtained regardless of the order from the of addition of the catalyst components. The polymerization speed is rapid and the polymerization is completed around 3 hours. When a dialkylaluminum fluoride is used as the organic aluminum compound. the polymerization speed is more rapid and the polymer having 4,000 or more molecular weight can be readily obtained. For producing a polymer having 4.000 or more molecular weight. it has been known to add water to the reaction system. However. according to such a method. gelation is promoted during the polymerization reaction, which is significantly disadvantageous for the industrial production. On the contrary, according to the present invention, such gelation is not observed when dialkylaluminum fluoride is used, even in case of production of high molecular polymer. Therefore. the present polymerization reaction can be advantageously carried out even in high&#39;concentration ofthe reaction system.  
  Furthermore, according to the present invention. a polymerhaving low molecular weight. e.g. 2.000 or less molecular weight can be advantageously produced. For producing a polymer having 2,000 or less molecular weight, it has been known to do the polymerization reaction under a condition of low polymerization activity. However, even by such method. a polymer having at lowest 1.500 of molecular weight is only obtained. There has never been known any process for producing a polybutadiene having less than 1.000 of molecular weight as the present invention.  
  The organic aluminum compound used as the component (l) in the present invention has the formula: AlR1R2R wherein R is hydrogen, fluorine, an alkyl, a cycloalkyl, an aryl or an aralkyl group; R and R are each an alkyl, a cycloalkyl, an aryl or an aralkyl group. The term alkyl means a straight or branched alkyl having 1 to 8 carbon atoms. such as methyl. ethyl. propyl. isopropyl. butyl. isobutyl. te&#39;rt-butyl. pentyl. isopentyl. hexyl. heptyl. or octyl; the term cycloalkyl means a cycloalkyl having 3 to 7 carbon&#39;atoms. such as cyclopropyl. cyclobutyl. cyclopentyl. cyclohexyl. or cycloheptyl; the term aryll means an aryl. such as phenyl. o-tolyl. m-tolyl, p-tolyl. oxylyl. m-xylyl, or p-xylyl; and the term aralkyl&#34; means an aralkyl. such as benzyl or phenethyl. As the suitable examples of the organic aluminum compound. there may be diethylaluminum hydride, dim-propylaluminum hydride. di-nbutylaluminum hydride. diisobutylaluminum hydride. diphenylaluminum hydride. phenylethylaluminum hydride, dibenzylaluminum hydride, phenyl-npropylaluminum hydride. p-tolyl-isopropylaluminum hydride, trimethylaluminum. triethylaluminum. tri-npropylaluminum, triisopropylaluminum. tri-nbutylaluminum. triisobutylaluminum. tripentylaluminum. tricyclohexylaluminum. triphenylaluminum. diethylaluminum fluoride. di-npropylaluminum fluoride. di-n-butylaluminum fluoride. diisobutylaluminum fluoride, dihexylaluminum fluoride. dioctylaluminum fluoride, diphenylaluminum fluoride. and the like.  
  As the suitable examples of the nickel salt of a carboxylic acid or the organic nickel complex compound used as the component (2). there may be a nickel salt of an organic carboxylic acid. such as nickel acetate. nickel naphthenate. nickel octate, or nickel benzoate; an organic nickel complex compound. such as complex of nickel chloride and pyridine. tris(dipyridine).nickel chloride. bis(ethylenediamine).nickel sulfate; and a chelate compound, such as bis(ace ty1 acetonate). nickel, bis(ethy1acctoacetate).nickel, and bis(dimethyl glyoximate).nicke1. As the rr-bond type organic nickel compounds, there may be, for instance, bis( 11&#39;- a11y1)nicke1, bis(1r-metha11y1)nickel, bis(1rcroty1)nicke1, bis(1r-cyc1ooctenyl)nicke1, and bis (1r-cyc1openteny1)nicke1. i  
  Among the halogen-containing organic compounds of the component(3), as the halogenated aliphatic or alicyclic hydrocarbon (a), there may be, for instance, carbon tetrachloride, chloroform, bromoform, iodoform, dichloroethane, bromochloromethane, dibromoethane, diiodomethane, ethyl bromide, ethyl chloride, isobutyl chloride, isobutyl bromide, n-butyl bromide, tert-butyl bromide, tert-butyl chloride, 2- iodopropane, 2&#39;-bromodecane, 1,1 1 -trich1oroethane, 1,1 ,2-trichloroethane, pentachloroethane, hexachloroethane, 5-chloronorbornene, 5-ch1oromethy1norbornene, S-bromonorbornene, and S-bromomethylnorbornene. As the benzotrihalogenide (b), there may be, for instance, benzotrichloride, 2,4-dichlorobenzotrichloride, and benzotribromide. As the alkynyl halogenide (c), there may be, for instance, propargyl chloride, and propargyl bromide. And as the ketone compound containing chlorine or bromine in the molecule (d), there may be, for instance, 1,3-dich1oroacetone, 1,1.3,3-tetrachloroacetone&#39;, bromoaeetone, 1,3-dibromoacetone, and hcxachloroacetone.  
  1n the present process, the organic aluminum compound may be used in an amount of 0.0001 to 0.1 mol, preferably 0.0001 to 0.01 mol on the basis of one mol of butadiene monomer. The nickel compound may be used in an amount of 0.01 to 0.6 mol, preferably 0.05  
 &#39; to 0.25 mol on the basis of one mol of the organic alumium compound, and the halogencontaining organic compound may be used in an amount of 0.05 to 100 mol, preferably 0.2 to mol on the basis of one mol of the organic aluminum compound.  
  in the-present process, there may be used an inert solvent as a diluent of the catalyst and as a solvent for the polymerization reaction. As the inert solvent. there may be an aliphatic, alicyclic or aromatic hydrocarbon having 4 to 12 carbon atoms, for instance, butane. butene-l, butene-2, pentane, heptane, cyclohexane, benzene, toluene, xylene, and a mixture thereof. The. inert solvent may be used in an amount of 0.3 to 10 times, preferably 0.5 to 3 times of the amount of butadiene monomer.  
 The polymerization reaction of the present invention &#34;is carried out in an atmosphere of an inert gas such as perature, and there is no specific limitation, but it is usually selected from the range of 1 to 10 atmospheres.  
  The butadiene monomer is added to the polymerization vessel in gaseous or liquid form and made contact with the catalyst. After the polymerization reaction, the reaction mixture is treated by a conventional method. The polymerization reaction and post-treatment can be carried out either batch system or continuous system.  
  at 37C in benzene solution by a vapor pressure osmometer. The molecular weight of the polybutadiene can becontrolled by. the polymerization temperature, the concentration of the monomer, and the ratio of water and the catalyst.  
  When the present liquid polybutadiene having predominantly cis-1,4-structure is used in a paint composition, it shows excellent properties, such as excellent corrosion resistance, hardening velocity, epoxylation velocity and operability in comparison with natural oil and 1,2-viny1 type polybutadiene.  
  The present invention is illustrated by the following examples but not limited thereto.  
 EXAMPLE 1 Into a 200 ml glass made pressure bottle was added a solution of nickel naphthenate (0.02 mmol/ml) in toluene (2 ml) in nitrogen stream, and thereto was further added anhydrous toluene ml). The mixture was cooled at 10C and then liquefied butadiene (24.9 g) was added thereto. Furthermore, to the mixture were added a solution of triethylaluminum (1 mmol/ml) in toluene (0.4 ml), a fixed amount of a toluene solution of one (1 mmol/ml) of the halogencontaining organic compounds as mentioned in Table l, in order. Then, the bottle ,was stoppered and shaken on constant temperature water bath at 40C for a prescribed period to subject the mixture to polymerization reaction. After the polymerization reaction, a solution of butylcatechol (2 g/l) in methanol (20 ml) was added to the reaction mixture for stopping the reaction. The mixture was distilled under a reduced pressure to remove unreacted butadiene, toluene. methanol and additives until there was observed no absorption of any aromatic compound by infrared spectrum.  
  The test results of the liquid polybutadiene thus obtained are shown in Table-1.  
 Table 1 Halogen-containing Polymerization Polymerization product Test compound period Yield 1 [1;] Micro structure (71) No. Kind Amount Cis- Vinyl Trans- (mmol) (hr.) (2) (7d (dl/g) 1,4 1.4  
 1* 5 0 0 2 Carbon tetra- 0.4 5 10.5 42.1 0.13  
  chloride 3 Carbon tetra- 4.0 5 11.2 45.0 0.13 75.6 1.9 22.5  
  chloride 4 5-Chloro- 6,0 5 25.1 0.12  
 norbornene EXAMPLE 2 In the same manner as described in Example 1. the  
 polymerization was carried out. except that benzotrihalogenide was&#39;used as&#39;the halogen-containing organic compound.-.The benzotrihalogenide was used in a toluene solution (concentration: 1 mmol/ml). Thee test results are shown in Table 2.  
 Table 2 added a solution of nickel naphthenate (0.01 mmol/ml) in benzene(4 ml) in nitrogen stream, and thereto were further added&#39;anhydro us benzene (80 ml). liquefied butadiene g). a solution of triethylaluminum (1 mmol/ml) in benzene (0.4 ml) and a solution of hexachloroacetone (0.1 mmol/ml) in benzene (2.4 ml). in order. The vessel was sealedand then shaken on con- Halogen-containing- Poly- Polymerization product Test compound meri- Yield [1;] Micro-structure (&#39;7!) Medium zation 7 molecular No. Kind Amount period Cis- Vinyl Transweight (mmol) (hr.) (g) (7r) (dl/g) 1.4 1.4  
 1* 5 0 0 2 Benzotri- 0.4 3 24.3 97.6 0.35  
  chloride 3 Benzotri- 4.0 3 21.6 86.8 0.081 75.1 3.3 21.6 1400 chloride I [Note I: &#34;Halogenatcd hydrocairhon was not used.  
 E X A M PL E 3 One liter stainless steel autoclave provided with an anchor type stirrer. in which air was replaced by nitrogen. was cooled at -15C. and thereto were added in nitrogen stream a solution of nickel capronate (0.02 mmol/ml) in toluene (8ml). anhydrous toluene (65 ml). liquefied butadiene (125 g). liquefied butene-l (120 g). a solution of triethylaluminum (1 mol/l) in toluene (2 ml) and a solution of benzotrichloride (1 mol/l) in toluene (10 ml). in order. After sealing the autoclave. the mixture was stirred at C for 3 hours to subject it to polymerization reaction. After the polymerization reaction. methanol ml) containing a stabilizer was added to the reaction mixture for stopping the reaction. and then the mixturewas distilled under a reduced pressure to remove methanol. toluene and the like.  
  Thus. the desired liquid polybutadiene (125 g) was obtained. The product had the micro, structure of cis- 1.4 (76.1 percent). vinyl (1.9 percent) and trans-1.4 (22 percent). and. had intrinsic viscosity [1 0.080 dl/g.  
 EXAMPLE 4 Into a 200 ml glass made pressure polymerization vessel was added a solution of nickel naphthenate (0.02  
  mmol/ml) in toluene (1.5 ml)in nitrogen stream. and  
 on constant temperature water bath at 40C for 5 hours to&#39;subject the mixture to polymerization reaction. The reaction mixture was treated in the same manner as described in Example 1 to give&#39;liquid polybutadiene (25.0 g). The product had intrinsic viscosity [1 0.021 dl/g and medium molecular weight: 394. When the viscosity stant temperature water bath at 40C for 5 hours to subject the mixture to polymerization reaction. After the polymerization reaction. the reaction mixture was treated in the same manner as described in Example 1 to give liquid polybutadiene (18.6 g).  
  The product had intrinsic viscosity [1 0.111 dl/g and the micro structure of cis-l.4 (76.3 percent). vinyl (1.6 percent) and trans-1.4 (22.1 percent).  
 EXAMPLE 6 lnto a 200 ml pressure polymerization vessel were added in nitrogen stream a solution of diethylaluminum fluoride (0.8 mmol) in toluene 1.6 ml). anhydrous toluene (70 ml). a solution of hexachloro acetone (0.3 mmol) in toluene 1.5 ml). anhydrous butadiene (22 g) and a solution of nickel stearate (0.04 mmol) in toluene (1 ml). in order. After stoppering the vessel. the mixture was heated at 50C for 3 hours to subject it to polymerization reaction. After the polymerization reaction. the reaction mixture was treated in the same manner as described in Example 1 to give low molecular weight polybutadiene (20.3 g). Theproduct had a viscosity of 4830 cps (molecular weight: 5200) a t 30C and the micro structure of cis-l .4 (78.5 percent). vinyl (1.3 percent) and trans-1.4 (20.2 percent). No gelation was observed in the polymer by measurement of the gel ratio.  
 EXAMPLE 7 tied butadiene at -78C: 22 g) and a solution of nickel of the product was measured at 30C by a falling-ball viscometer. it was 107 cps.  
 EXAMPLE -5 lnto a 200 ml pressure polymerization vessel was naphthenate (0.04 mmol) in toluene (1 ml). in order. The vessel was stoppered and&#39;then&#39; heated at 50C&#39;for 3 hours to subject the mixture to polymerization reaction. After the polymerization reaction. the mixture was treated in the same manner as&#39;described in Example 1 to give low molecular weight polybutadiene (20.7 g: 94.1 7c). The product had viscosity of 7833 cps at 30C&#39;and the micro structure of cis-1.4 (83.3 percent). vinyl 1.8 percent) and trans-1.4 (8.4 percent). The gel ratio of the product was 0.&#34;  
 What is claimed is:  
  l. A process for producing liquid polybutadiene having a predominantly cisl ,4-structure, which comprises polymerizing 1,3-butadiene in the presence of a catalyst system comprising 1. an organic aluminum compound of the formula:  
 AIR ,R R wherein R, is hydrogen, fluorine, alkyl,  
 cycloalkyl, aryl or aralkyl and in which R and R are each alkyl, cycloalkyl, aryl or aralkyl;  
 2. at least one of nickel compound selected from the group consisting of a. a nickel salt of a carboxylic acid.  
 b. an organic nickel complex compound selected from the group consisting of a complex of nickel chloride and pyridine, tris(dipyridine).nickel chloride. bis(ethylenediamine). nickel sulfate, bis(acetyl acetonat).nickel, bis(ethyl acetoacetate).nickel and bis(dimethyl glyoximate).nickel,  
 c. Nickel tetracarbonyl, and  
 d. ir-bond type organic nickel compound selected from the group consisting of bis(rr-allyl) nickel, bis (1r-methallyl)nickel, bis (n-crotyhnickel, bis(1r-cyclooctenyllnickel and bis( 11&#39;- cyclopentenyHnickel; and  
 3. at least one halogen-containing organic compound selected from the group consisting of a. a halogen norbornene selected from the group consisting of S-chloronorbornene, -chloromethylnorbornene. S-bromonorbornene and 5-bromomethylnorbornene.  
 b. a benzotrihalogenide.  
 c. an alkynyl halogenide. and  
 d. a ketone compound containing chlorine or bromine in the molecule,  
 the organic aluminum compound being used in an amount of 0.0001 to 0.l mole on the basis of one mole of butadiene monomer, the nickel compound being used in an amount of 0.0l to 0.6 mole on the basis of one mole of the organic aluminum compound and the halogencontaining organic compound being used in an amount of 0.05 to I00 mole on the basis&#39;of one mole of the organic aluminum compound. the organic aluminum compound and the halogen-containing compound being added to the reaction system after the addition of Lil-butadiene.  
  2. The process according to claim 1, wherein the polymerization reaction is carried out in an inert solvent selected from aliphatic, alicyclic and aromatic hydrocarbons having 4 to 12 carbon atoms in an amount of 0.3 to times of the amount of butadiene monomer.  
  3. The process according to claim 2, wherein said inert solvent is selected from the group consisting of butane. butene-l, butene-Z, pentane, heptane. cyclohexane, benzene. toluene, xylene. and mixtures thereof.  
  4. The process according to claim 3, wherein the inert solvent is used in an amount of about 0.5 to 3 times the amount of butadiene monomer.  
  5. The process according to claim 1, wherein the polymerization is carried out in an atmosphere of an inert gas at a temperature of 0 to l00C.  
  6. The process according to claim 5, wherein polymerization is carried out at a temperature of about to 60C under a pressure of about 1 to 10 atmospheres.  
  7. The process according to claim 1, wherein the organic aluminum compound is a member selected from the group consisting of diethylaluminum hydride, di-npropylaluminum hydride, di-n-butylaluminum hydride.  
  8 diisobutylaluminum hydride, diphenylaluminum hydride, phenylethylaluminum hydride, di-  
 benzylaluminum hydride, phenyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, trim-butylaluminum, triisobutylaluminum, tripentylaluminum, ylaluminum, triphenylaluminum, diethylaluminum fluoride, dim-propylaluminum fluoride, di-nbutylaluminum fluoride, di-isobutylaluminum fluoride, dihexylaluminum fluoride, dioctylaluminum fluoride and diphenylaluminum fluoride.  
  8. The process according to claim 1, wherein the haolgen-containing organic compound is a member selected from the group consisting of 5-chloronorbor- &#39;nene, S-chloromethylnorbornene, S-bromonorbor- &#39;nene, S-bromoethylnorbornene, benzotrichloride, 2,4-dichlorobenzotrichloride, benzotribromide, propargyl chloride, propargyl bromide, 1,3- dichloroacetone, 1,1,3,3-tetrachloroacetone, bromoacetone. 1,3-dibromoacetone and hexachloroacetone.  
 9. The process according to claim 1, wherein said halogenated norbornene is selected from the group consisting of 5-chloronorbornene. 5-chloromethylnorbornene, 5-bromonorbornene and S-bromomethylnorbornene.  
  10. The process according to claim 1, wherein said organic aluminum compoundis trialkyl aluminum.  
  11. The process according to claim 10, wherein said trialkyl aluminum is triethyl aluminum.  
  12. The process according to claim 1, wherein R, is fluorine. 7  
  13. The process according to claim 12, wherein polymerization is continued until the liquid polybutadiene has an average molecular weight of at least about 4.000.  
  14. The process according to claim 1, wherein said nickel salt of a carboxylic acid is selected from the group consisting of nickel acetate. nickel naphthenate. nickel octate, and nickel benzoate.  
  15. The process according to claim 1, wherein said benzotrihalogenide is selected from the group consisting of benzotrichloride. 2,4-dichlorobenzotrichloride and benzotribromide.  
  16. The process according to claim 1, wherein said alkynyl halogenide is selected from the group consisting of propargyl chloride and propargyl bromide.  
  17. The process according to claim 1, wherein said ketone compound containing chlorine or bromine is selected from the group consisting of 1.3- dichloroacetone. l.l.3.3-tetrachloroacetone. bromoacetone. l,3-dibromoacetone and hexachloroacetone.  
  18. The process according to claim 1, wherein the organic aluminum compound is used in an amount of 0.000l to 0.01 mole on the basis of l mole of butadiene monomer.  
  19. The process according to claim 1, wherein the nickel compound is used in an amount of 0.05 to 0.25 mole on the basis of one mole of the organic aluminum compound.  
  20. The process according to claim 1, wherein the halogencontaining organic compound is used in an amount of 0.2 to 20 mole on the basis of one mole of the organic aluminum compound.  
 tricyclohex 21. The process according to claim I. wherein the organic aluminum compound is used irl an amount of about 0.000l to 0.0l mole on the basis of one mole of hutadiene monomer. the nickel compound is used in an amount of 0.05 to 0.25 mole on the basis of one mole of the organic aluminum compound, and the halogencontaining organic compound is used in an amount of about 0.2 to 20 mole on the basis of one mole of orgahic aluminum compound. v I  
  22. The process according to claim 1. wherein said catalyst system consists essentially of said organic aluminum compound. said at least one nickel compound and said at least one halogencontaining organic compound.  
  23. The process according to claim 22., wherein said catalyst system consists of said organic aluminum compound. said at least one nickel compound and said at 16 least one halogen-containing organic compound.  
 24. The process accordiiig to claim I, wherein polymcrizing is accomplished ata temperature of about 20 minum fluoride.