DE1258098B - Process for the polymerization of 1,3-butadiene - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

Number:
File number:
Registration date:
Display day:

C08d

German class: 39 c - 25/05

1258 098
P33247IVd / 39c
December 20, 1963
4th January 1968

Much work has been done in recent years to develop processes for producing olefin polymers done. Polymers of monoolefins, such as ethylene and propylene, according to these Processes have found widespread adoption by many industries. The recent one Invention of so-called stereospecific catalysts in the field of diene polymerization, the enables the formation of polymers with the desired configuration is of considerable interest awakened. The polymers formed when using these catalysts are often exceptional physical properties that make them equal or even superior to natural rubber. The present Invention relates to a new and improved method for making polybutadiene with a high percentage of cis-1,4 addition.

The invention relates to a process for the polymerization of 1,3-butadiene in the presence of a catalyst, which has been made by mixing the following ingredients:

a) an organometallic compound of the formula R _M M or R ₂ AlH, in which R is alkyl, cycloalkyl or aryl radicals or combinations of these radicals, M is magnesium or aluminum and η is an integer which is equal to the valence of the metal M,

b) a titanium halide of the formula TiX ₂ /, wherein X is chlorine or bromine and y is an integer of

2 to 4 inclusive, and

c) an inorganic iodine compound, which is characterized in that a catalyst is used used, which contains hydrogen iodide as an inorganic iodine compound.

When using this catalyst system, a polymer is obtained which has 85 to 98% and more has cis-1,4 addition. It has already been proposed to add 1,3-butadiene with a catalyst polymerize by mixing an organometallic compound with a titanium chloride or bromide was obtained. The polymer product of this latter process is not a polybutadiene with high cis content; the product generally contains less than 70%, for example 45 to 60% cis-1,4 addition. It was therefore completely unexpected that the addition of hydrogen iodide to a mixture an organometallic compound and a titanium chloride or bromide results in a catalyst system, that is the polymerization of butadiene on a polybutadiene with a high cis-1,4-content. • From the German Auslegeschrift 1134 202 is a Process for the polymerization of 1,3-butadiene

Applicant:

Phillips Petroleum Company,

Bartlesville, OkIa. (V. St. A.)

Representative:

Dr. F. Zumstein, Dr. E. Assmann

and Dr. R. Koenigsberger, patent attorneys,

8000 Munich 2, Bräuhausstr. 4th

Named as inventor:
Floyd Edmond Naylor,
Ralph Coleman Farrar,
Robert Paul Zelinski,
Bartlesville, OkIa. (V. St. A.)

Claimed priority:

V. St. v. America December 20, 1962

(246 001),

dated December 26, 1962

(247 317)

Process for the preparation of butadiene polymers is known, which is characterized in that butadiene is polymerized in the presence of a catalyst system which has been obtained by mixing a component of the formula MeCIj ₁ (OR) ₄ -B with at least one second component, which is a compound of the formula A1R'R "J or a mixture of an organoaluminum compound of the formula A1R'R" R '"and a reactive iodine-containing compound (where Me is a metal from Group IVb of the Periodic Table, R and R' are hydrocarbon radicals having 1 to 12 carbon atoms, R "Hydrogen, a carbon radical with 1 to 12 carbon atoms or an oxyhydrocarbon radical with 1 to 12 carbon atoms, R '" denotes hydrogen or a hydrocarbon radical with 1 to 12 carbon atoms and η = 1, 2 or 3).

The process according to the invention differs from the polymerization process described in German Auslegeschrift 1134 202 in that the catalysts used in each case differ in terms of the titanium component, namely a titanium halide of the formula TiX ₂ / is used according to the invention, while in the known process for producing the catalyst a Titanium chloride alkoxide of the formula TiCl »(OR) ₄ -» is used.

709 717/626

3 4

Furthermore, at no point is the German ausuminium, tri- (2,4,5,7-tetraethyl-l-naphthyl) -aluminium

Legeschrift 1134 202 a reference to find that nium, tri- (4,5-dipentyl-2-naphthyl) aluminum, tri-

when using hydrogen iodide compared to cyclohexylaluminum, tricyclopentylaluminum, metal

the other iodine compounds mentioned, for example tnyldicyclohexylaluminum, tri- (4-pentadecylcyclo-

wise iodine monochloride, any advantages to 5 pentyl) aluminum, tri- (4-ethylcyclohexyl) aluminum,

be achieved. In no single example is iodine tri-p ^ -diäthylcyclohexy ^ -alumioiunijTri-CS-isobutyl-

hydrogen as the third catalyst component, cyclohexyl ammonium, tri- (2,4,6-tri-n-propylcyclo-

turns. This is not surprising in that iodine hexyl) aluminum, tri- (2-n-propylcyclopentyl) aluminum

hydrogen compared to the others in the mentioned minium, tri- (2-ethylcyclohexyl) aluminum, tri-

German Auslegeschrift listed iodine compound io (2-cyclohexylethyl) aluminum, tri- (3-cyclopentylbu-

gen a very aggressive and corrosive acting tyl) aluminum, tri- (14-cyclohexyltetradecyl) -alumini-

Substance is. um, dimethylaluminum hydride, diethylaluminum

Surprisingly, however, when using hydride, diisobutylaluminum hydride, didecylaluminum

generation of hydrogen iodide for catalyst production nium hydride, dieicosylaluminum hydride, dicyclo-

according to the invention significantly better sales 15 pentylaluminium hydride, dicyclooctylaluminium hy-

achieved. . . drid, di- (3-ethylphenyl) aluminum hydride, diphenyl

The amount of the catalyst aluminum hydride, propylphenyl aluminum hydride, di-

systems used organometallic compound (3-cyclohexylpropyl) aluminum hydride, di- (4-cyck>

depends on the particular metallorga- heptyldecyl ^ -aluminium hydride used, di (3-phenylbutyl) -alu-

niche connection. The molar ratio of metal- 20 minium hydride, dibenzylaluminium hydride, di- (2,4-di-

organic compound to hydrogen iodide is larger phenyloctyl) aluminum hydride, di- (2-methylcyclopen-

than 1: 1. If an organoaluminum compound is tyl) aluminum hydride, di- (5-nonylcyclononyl) aluminum

is used, the molar ratio of the mole nium hydride, di- (2-phenylcyclopentyl) aluminum hy-

organometallic compound minus the moles of iodide, di- (2,4-diphenylcyclooctyl) aluminum hydride,

Hydrogen to the moles of titanium halide in the general 25 di- (2-methylphenyl) aluminum hydride, di- (2,4-dibu-

mean in the range of 2: 1 to 20: 1. When a matylphenyl) aluminum hydride, di- (2,4-dioctylphenyl) -

The organic magnesium compound used is aluminum hydride, di- (4-cyclobutylphenyl) -alurainium-

the molar ratio of the moles of organometallic hydride, di- (2,4-dicyclopentylphenyl) aluminum hy-

bond minus moles of hydrogen iodide to moles of drid, di- (2,4-dicyclooctylphenyl) aluminum hydride.

Titanium halide usually in the range of 0.75: 1 30 Examples of specific catalyst systems used in

up to 3: 1. The molar ratio of titanium halide to iodine for carrying out the present invention

Compound is preferably in the range of 0.1: 1 can be used, include those through

up to 2: 1. The concentration of the whole formed when mixing the following ingredients;

The catalyst used in the present process is diethyl magnesium, titanium tetrachloride and iodine water

can vary over a fairly wide range. 35 fabric; Diphenylmagnesium, titanium tetrachloride and iodine

The catalyst level is generally hydrogen; Diphenyl magnesium, titanium tetrabromide

Range from 1 to 20 g Müümol organometallic hydrogen and iodine; Dicyclohexylmagnesium, titanium «

bond per 100 g of 1,3-butadiene to be polymerized. tetrachloride and hydrogen iodide; Di-1-naphthylmagne-

The actual catalyst level used will be sium, titanium tetrabromide and hydrogen iodide; Di-4-tolyl-

generally by the molecular weight of the magnesium, titanium trichloride and hydrogen iodide; Tri-

desired product. ethyl aluminum, titanium tetrachloride and hydrogen iodide;

The use of iodine monochloride in catalysis- tri-n-butylaluminum, titanium tetrabromide and iodine

Sator system is often preferred. hydrogen; Triisobutyl aluminum, titanium tetrachloride

Examples of organometallic compounds * and hydrogen iodide; Tri-n-hexylaluminum, titanium tetradie for use in the present catalyst 45 bromide and hydrogen iodide; Triphenyl aluminum, System suitable include dimethylmagnesiumi titanium tetrachloride and hydrogen iodide; Tri-2-tolyl diethyl magnesium, Di-n-propyhnesium, di-tert. aluminum, titanium trichloride and hydrogen iodide; Tributyl magnesium, Di-n-hexyhnagnesium, didecylmacyclohexylaluminum, titanium tetrachloride and iodine magnesium, Di- (tridecyl) -magnesium, Dieicosyhnagne- hydrogen; Dimethyl aluminum hydride, titanium tetrasium, Dicyclohexyl magnesium, di-4-methylcyclohexyl chloride and hydrogen iodide; Dipropyl aluminum hydride, magnesium, dibenzylmagnesium, di- (4-phenyl- titanium tribromide and hydrogen iodide; diisobutylalu-4-butyi) magnesium, Diphenyl magnesium, di-1-naphminium hydride, titanium tetrachloride and hydrogen iodide; ethylmagnesium, di-4-itolylmagnesium, di- (2,4-diethyl-diphenylaluminum hydride, titanium tetrabromide and iodophenyl) magnesium, Di- (3,5-di-n-heptylphenyl) hydrogen; Dibenzyl aluminum hydride, titanium tetragnesium ,. Methylethylmagnesium, methylphenyhna- 55 chloride and hydrogen iodide; Dimethyl magnesium, magnesium, butylbenzyl magnesium, triethylaluminum, titanium dichloride and hydrogen iodide; Tri-n-propylalu-. Tri-n-propylaluminum ,. Tri-n-butylaluminum, triiso-minium, titanium dibromide and hydrogen iodide and butyl aluminum, tri-n-heptyl aluminum, tridodecyl di-n-butyl aluminum hydride, titanium dichloride and iodine aluminum, Trieicosyl aluminum, triphenyl aluminum, hydrogen.

Tribenzyl aluminum, tri- (2-phenylethyl) aluminum, 60 The polymerization process according to the invention

Tri- (6-phenymexyl) aluminum, tri- [6- (l-naphthyl) - is usually used in the presence of a diluent

hexyl / aluminum, tri- [9- (2-naphthyl) nonyl] aluminum. Diluents used for

nium, tri-2-tolylaluminum, tri- (2,4-dimethylphenyl) - suitable for use in the present process

aluminum, tri- (S-ethylphenyl) -aluminum, tri- are, are hydrocarbons that are used for the poly-

(2,4-dimethyl-6-ethylphenyl) aluminum, tri- (4-n-polymerization reaction are not harmful. Suitable

tylphenyl) aluminum, tri- (2-n-hexylphenyl) -alumini- diluents include aromatics, such as

um, tri- (2,4,6-isobutylphenyl) aluminum, tri- (4-do- wise benzene, toluene, the xylenes, ethylbenzenes and

decylphenyl) aluminum, tri- (2-methyl-1-naphthyl) - mixtures thereof. It is also within the scope of the invention, '

5 6

to use straight-chain and branched paraffins, which are harmful. These materials include up to and including 12 carbon atoms per carbon dioxide, oxygen and water. It is therefore Molecule included. Examples of suitable paraffins usually desirably include the butadiene of these include propane, η-butane, n-pentane, isopentane, materials as well as of all other materials η-hexane, isohexane, 2,2,4-trimethylpentane (isooctane), 5 is freed, which inactivate the catalyst n-decane, n-dodecane. Mixtures of these paraffinic can. Any known method can be used Hydrocarbons can also be used to dilute such contaminants funds to be used in carrying out the procedure. In addition, if there is a diluent in the will. Cycloparaffins, such as the cyclohexane process used, should use this material and methylcyclohexane, can also be used as a comparison, preferably practically free of impurities, thinners can be used. It will be habitual like water, oxygen and the like. It is in this borrowed preferred, the polymerization in the presence of a context also desirable air and moist aromatic Carry out hydrocarbons, since the activity of the reaction vessel in which the PolyPolymerisate are produced with a higher cis content, merization is to be carried out, remove, when working with this diluent. 15 Although it is preferred to undergo the polymerization

The polymerization process according to the invention the anhydrous or substantially anhydrous conditions, at temperatures proportionate to perform a but of course geweiten area can vary, for example from -75 to know small amounts of this catalyst are carried out inactivated-125 ⁰ C. Usually, it is preferred to allow four materials in the reaction mixture to be at a temperature in the range of ²⁰ . Of course, however, the amount of -35 to 70 ° C may work. The polymerization of such materials that can be allowed to react may be carried out under autogenous pressure or under any pressure insufficient to completely deactivate the catalyst sufficient to cause the catalyst. . to keep the reaction mixture practically in the liquid phase. The pressure therefore depends on the diluent used, especially when a batch process is used, and on the total reaction mixture used to inactivate the temperature at which the polymerization is carried out and the rubber is recovered. However, higher-like product can be treated if desired. Any suitable pressures can be used, these pressures being applied to methods of carrying out this treatment in any suitable manner such as sub-reaction mixture. When the reaction vessel is pressurized with a process, the polymer is obtained by evaporation of the polymerization reaction inert gas, the diluent obtained from the polymer. Of course, it is within the scope of the invention. In another suitable mode of operation, a range of material that inactivates the catalyst is carried out in the solid phase. 35, for example, an alcohol, added to the mixture.

The inventive method can discontinuously to inactivate the catalyst and the Ausierlich be carried out by bringing 1,3-butadiene into precipitation of the polymer. The polyein Reaction vessel is introduced, the catalyst is then merisate from the alcohol and from the diluent Contains thinner. While each agent can be used in any suitable manner, for example appropriate filling procedures may be used, but 40 separately by decanting or filtering. Often will it is often preferred to include the monomer in one reaction; it is preferred to initially only use an amount of the den To bring a vessel containing the diluent, to add catalyst inactivating material, the and thereafter introducing the catalyst components. sufficient to inactivate the catalyst without the It goes without saying that it is also within the scope of the invention to bring about precipitation of the polymer. It has dung, the catalyst by mixing the catalyst 45 also proved to be advantageous, antioxidant, constituents in a separate vessel to the catalysis such as phenyl - ^ - naphthylamine, to the to pre-form the production of sator. The reaction polymer solution obtained before the recovery of the polytion mixture can then be added to the reaction vessel. After adding the den be brought, which monomer and Ver catalyst inactivating material and the anti-fertilizer contains, or these latter materia- so oxidizing agent can be the one present in solution lien can be added after the catalyst. Polymer by adding an excess of one The process can also be carried out continuously material, such as ethyl alcohol or isopropyl alcohol, ' by separating the above-mentioned concentrations. If the process is continuous is carried out on reactants for a suitable residence time, all of the effluent from the be kept in the reaction vessel. The residence time 55 reaction vessel becomes a zone for inactivation In a continuous process, the natural catalyst will fluctuate where the effluent is pumped borrowed within fairly wide limits, depending on from the reaction vessel with a suitable, den such variables as temperature, pressure, catalyst inactivating material, such as example ratio of catalyst components and catalyst an alcohol, is brought into contact, satellite concentration. In the case of a continuous process of 60 If alcohol is used as a material for inactivating the If the residence time falls within the range of the catalyst used, it is also used for driving from one second to 2 hours if conditions precipitate the polymer. If materials for can be used in the specified areas. When the catalyst is inactivated, Application of a batch, i.e. a discount, which does not fulfill this double role, can be a The reaction time can be up to 65 suitable material, such as an alcohol, 24 hours or more. be added to precipitate the polymer.

Many materials are known to be suitable for the Of course it is within the scope of the invention

Catalyst composition of the present invention other suitable procedures for obtaining the

Apply polymer solution. After separation • from the water or alcohols from the diluent the polymer is dried by filtration or in another suitable manner.

The polymers produced according to the invention are rubber-like polymers. The polymers can be mixed by a wide variety of methods that were previously used for mixing natural and Synthetic rubbers were applied. Vulcanization accelerators, vulcanizing agents, reinforcing agents and fillers such as those used in natural or synthetic rubbers can be used in the same way are used when mixing the rubbers which can be produced according to the invention. The polymers can also be used with other polymer materials, such as natural rubber, cis-l ^ -polyisoprene, polyethylene, be mixed. As already mentioned, the polymers prepared in accordance with the invention have a very high high cis content, and this property makes them very suitable for applications where a low Hysteresis, high resilience and high abrasion resistance required skid. In general The products are useful in applications where natural rubbers and synthetic rubbers are used will. They are particularly suitable for use in the manufacture of automobile and truck tires and other rubber-like products such as gaskets.

'The following examples serve to provide a more detailed explanation of the invention without limiting it.

Samples of certain of the approaches described in the examples prepared polymer products were through Infrared analysis examined. This work was done by the percentage of the cis-1,4-addition, trans-1,4-addition and 1,2-addition of butadiene to determine formed polymer. For these determinations the one described below was used Working method applied.

; Polymer samples were taken in carbon disulfide Formation of a solution with 25 g of polymer dissolved per liter of solution. The infrared spectrum of each of these Solutions (% transmittance) were then determined in a conventional infrared spectrometer.

The percentage of total non-saturation present as trans-1,4 addition was determined from the following Equation and determined with the following units:

_ E_ te '

Here, ε means the extinction coefficient (1 · mol- ¹ · cm- ¹ ), E the extinction (log IJI), t the path length (cm) and c the concentration of moles of double bonds per liter). The absorbance was determined at the 10.35 ^ band, and the extinction coefficient used was 146 (1 mol "" ¹ · cm ^-1 ). The percentage of total 1,2 (or vinyl) unsaturation present was determined according to the above equation using the ΙΙ, Ο-µ, band and an extinction coefficient of 209 (1 x mol ^-1 x cm ^-1 ).

ίο The percentage of total unsaturation present as cis-1,4 was calculated by subtracting the trans 1,4 unsaturation and 1,2 (vinyl) unsaturation determined by the above procedures from the theoretical unsaturation below the Assumption of a double bond for each C ₄ unit in the polymer is determined.

^: Example

A number of approaches have been made using 1,3-butadiene with one by mixing Triisobutyl aluminum, titanium tetrachloride and hydrogen iodide Catalyst was polymerized. The recipe used in the approaches was like follows:

Recipe
- parts by weight

1,3-butadiene 100

Toluene 1000

Triisobutylaluminum (TBA) 0.634 (3.2 mmol) Hydrogen iodide (HJ) ....... alternating Titanium tetrachloride (TTC) ... 0.076 (0.4 mmol)

Time 2 hours

Temperature 5 ° C

In each of the batches, toluene was first poured into the reaction vessel. After purging the reaction vessel with nitrogen, butadiene was added. Then Trnsobutylaluminium and hydrogen iodide were added, after which the mixture to 5 ⁰ C was cooled, and titanium tetrachloride was charged. After 2 hours of polymerization, the reaction was terminated by adding 1 part by weight of 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol) dissolved in a mixture of equal volumes of isopropyl alcohol and toluene. The polymer was then coagulated in isopropyl alcohol, separated off and dried.

The results of the tests are given in Table II below:

.Approach HJ Molar ratio TTC: HJ Around
change Own gel Micro structure (%) ice cream trans vinyl No. mhm TBArTTC 0.69: 1 viscosity ¹ ) % 1 0.58 8: 1 0.58: 1 41 1.82 0 - - - 2 0.69 8: 1 0.46: 1 58 2.02 0 95.2 1.9 2.9 3 0.87 8: 1 0.34: 1 78 3.02 0 - - - • 4 1.16 8: 1 0.23: 1 84 2.90 0 94.4 2.7 2.9 5 1.73 8: 1 87 3.77 0

^J ) 0.1 g of polymer were placed in a wire cage made of wire mesh with a mesh size of 0.175 mm, and the cage was placed in 100 ml of toluene in a 120 ecm wide neck bottle. After standing at room temperature for 24 hours (about 25 ° Q, the cage was removed and the solution was filtered through a sulfur absorption tube of porosity C to remove any solids present ⁰ C was located. the viscometer was previously calibrated with toluene. the relative viscosity is the ratio of the viscosity of the polymer solution to that of toluene. the intrinsic viscosity is obtained by dividing the natural logarithm of the relative viscosity due to the weight of the soluble portion of the original sample.

The values given in the tables above show that according to the process according to the invention a high cis polybutadiene is obtained.

Experiments have also been carried out in which 1,3-butadiene polymerizes with catalyst systems made by mixing the following ingredients:

1. Didodecyl aluminum hydride, titanium tetrabromide
and hydrogen iodide;

2. diisobutyl magnesium, titanium trichloride and hydrogen iodide;

3. Di-n-octylmagnesium, titanium dichloride and hydrogen iodide;

4. Diethyl magnesium, titanium dibromide and hydrogen iodide.

The recipes and procedures used in these approaches were essentially the same as described above. The Polymerisatprodukte obtained were polybutadienes with * ° high percentage of cis-l, 4-addition.

Claims (3)

Patent claims: 1. A process for the polymerization of 1,3-butadiene in the presence of a catalyst obtained by mixing of the following components has been manufactured: a) an organometallic compound of the formula R _M M or R ₂ AlH, in which R is alkyl, cycloalkyl or aryl radicals or combinations of these radicals, M is magnesium or aluminum and η is an integer which is equal to the valency of the metal M, b) a titanium halide of the formula TiX ₂ /, in which X is chlorine or bromine and y is an integer from 2 to 4 inclusive and c) an inorganic iodine compound, characterized by that one a catalyst is used which contains hydrogen iodide as an inorganic iodine compound. 2. The method according to claim 1, characterized in that the molar ratio of the titanium halide to hydrogen iodide in the range from 0.1: 1 to 2: 1. 3. The method according to claim 1 or 2, characterized in that when using an organoaluminum Compound as an organometallic compound is the molar ratio of the moles of organometallic compounds minus the moles of hydrogen iodide to moles of titanium halide in the range of 2 ": 1 to 20: 1. Considered publications:
German publication No. 1134 202. Legacy Patents Considered:
German Patent No. 1160 186. 709 717/626 12.67 ® Bundesdruckerei Berlin