DE1570287C - Process for the production of copolymers from butadiene and styrenes - Google Patents

Description

1 2

The invention relates to a method for producing hold of at least 70 ° / ₀ , are practically whole

of high cis-1,4-fractions containing mixed poly or almost gel-free and are produced in a stable form

Keep merisates of butadiene and styrene or α-alkylstyrene without being affected by the ratio of

through copolymerization in the presence of a ter- catalyst component, the type of catalyst

Nary catalyst combination under pressure. 5 preparation and the interpolymerization

Numerous methods of manufacturing conditions are known to be influenced. This represents one of the of copolymers of butadiene-styrene or important characteristics of the new catalyst-butadiene-Λ-alkylstyrene, with the following catalyst combinations being.

systems have been applied: alkyllithium compound, can io polymer _(c) The molecular weight of the produced mixed lithium and sodium metals, trialkylaluminum by modifying the Bedingun-titanium tetrachloride, aluminum metal mercury ^) - _gene of the catalyst recovery and the mixed chloride cobalt (II ) chloride and molybdenum-aluminum polymerisation can be set. Rubber hydride-calcium hydride as well as Friedel-Crafts and _kind j _ge copolymers with high molecular weight radical catalysts. weight can be determined by a two-stage mixing

In application of these catalyst systems totaled 15 polymerization easily manufactured as below

however - with the exception of the catalyst system.

Aluminiummetali-QuecksilberUlJ chloride-KobaltOI) - Dj _e amount of Homopolystyiol is in the mixed chloride - the cis-1,4 content in the resulting polymeric mixing small; by suitable selection of the polymer to below about 60 ° / ₀ (under "cis-1,4-fraction" polymerization conditions, the corresponding value, based on the butadiene-ao polystyrene-free products, is to be understood). The aluminum catalyst system - _{(d) Dfc according to the invention made} mixed poly. m.nium-Quecks.lber D-chlond-KobaltaO-chlond _meren ^^ ^ _n . It is true that heat-hardening properties have been used to produce a butadiene mixed _{poly- ^ 16n and greater hardness than} cis ^ polybeams with a relatively high content of es- _{djcn with lei (} £ _{em modo} , _value

Catalyst components in organic solution To justify the fact that from the suitability of are insoluble in the medium, each component can only be handled with difficulty as a catalyst combination for butadiene homo, so that the preparation of the catalyst is by no means dependent on its suitability lysator combination is cumbersome and difficult. for butadiene-styrene copolymerization

The object on which the invention is based is to be concluded, it is emphasized that the for

is in the process of developing a process for the homopolymerization of cis-1,4-butadiene known

Positioning of high cis-1,4-fractions containing mixed and proven polymerization catalysts from

polymers of butadiene with styrene or «-alkyl- Shell, Montecatini, Phillips and Z i e g-

styrenes, such as α-methyl, α-ethyl or a-propyl I e r for the copolymerization in question

styrene, cannot be used through interpolymerization by means of temporary 33, as experiments

Catalyst combinations. clearly showed. The process according to the invention relates to an ab- 1. If a typical cis-1,4 catalyst is used

Modification of the process for polymerizing von Shell according to the British patent

Butadiene using a ternary catalyst combination 890139 for. Butadiene-styrene mixed polymerization, see above

nation that by reaction of 40 is the degree of copolymerization of styrene with

(A) metallic nickel or cobalt with large buttes less than 15% as from the following specific surface table can be seen. Consequently, there is a mixed

(B) Boron trifluoride or its complex with a polymerisation of butadiene with styrene only extremely organic oxygen ^{compound and * hw} ' ^c P8 ^ν ° " ⁸ S ¹ " * "* ΪΓ? Ί« e ^ nsic.? " ^P Γ

(C) an organometallic compound of lithium, "^" ¹ Jf. Mixtures of polybutene and polystyrene. Zinc, cadmium or aluminum of the formulas For the preparation of butiene-styrene copolymers R _n M or R ₁ AIOR, where R is a monovalent J " ¹ * ^hoh 5 ^m cie-l, 4-Gehajt s.nd thus the prescribed e-carbon residue and / 1 the valency of the» ί * ^η « ^η catalyst combinations unsuitable, although Mobile ti :. _t in the patent the copolymerization as

IVieiaJIS IVl I3i. . - .... «. . ... . . . ·

30 is indicated feasible; this information is therefore

has been obtained, in a diluent at after as a pure "desk" increase in temperatures between - 30 and - | - ISO ⁰ C under actual invention. Pressure in the liquid phase and inert atmosphere according to 2. When using a typical cis-1,4-butadiene patent 1 (30 172 and is characterized in that the catalyst from Montecatini according to the belman through the use of styrene or «-alkyl- 33 are Patent specification 575 307 for mixed polymer isastyrenes produces mixed polymers. Tion of butadiene with styrene occurs a mixed polymeri-The catalyst combination used according to the invention does not occur at all, but exclusively differ significantly from the previous butadiene homopolymerization, as from the 'following catalyst combinations and ways The following table also shows the following advantageous features: 60 3. If one uses for butadiene-styrene mixed poly-

merization one made of triisobutylaluminum and titanium

(a) Two of the three components are soluble in excellent cis-1,4-buta-solutions consisting of organic tetraiodide. The inventive to diene catalyst from Phillips according to Example 3 using catalyst combinations have ^ r Japanese laid-open application No. 6,917/66, high activity for the mixed polymerization and 65 takes place in this way - just as in the experiments for 2 - lead to reproducible results. no interpolymerization because the styrene (experiment 3)

(b) The mixed poly produced according to the invention - just like toluene (experiment 1/2) - at all In the butadiene content, mers have a cis-1,4-Cic acid that prevents the polymer from entering.

As tests for 1 to 3 showed, styrene is used largely either as a solvent in these or diluent, or it is simply homopolymerized.

4. If Ziegler dimeric butadiene catalyst combinations, e.g. TiCl ₄ + Al (C _t H ₅ ) ₃ , are used for the copolymerization of butadiene with styrene, violent gelling occurs, as in the PB reports from the Rock Island Arsenal Laboratory, Illinois / USA., No. 143 885 of July 28, 1959 ("Synthesis of rubber copolymers by some new method" by W. Jurgeleit and RR Freeman) and No. 147 230 of January 5, 1960 ("Synthesis of stereoregulated homopolymeres and copolymers of butadiene and styrene ”by Ronald RR Freeman). Further experiments showed that both the cis content of the butadiene structure and the degree of interpolymerization of styrene with butadiene are low.

From the above it follows that the best-known homopolymerization catalysts for cis-1,4-butadiene either do not polymerize their interpolymerization with styrene at all catalyze or only to such a weak extent that their use is out of the question. The cases where one is for the butadiene homopoly merisalion excellently suitable catalyst combination for a butadiene-styrene copolymerization actually usable are very rare; this is known to be the case with alkali metal catalysts. Accordingly, it is demonstrated again by the method according to the invention that only very specific ternary Catalyst combinations that are suitable for the homopolymerization of cis-l, 4-butadiene with Surprising success also for the copolymerization of butadiene with styrene with the production of Mixed polymers with a high cis-1,4-butadiene content are suitable.

In order to carry out the comparative tests discussed above, the results of which are shown in the table below, were prepared according to British patent specification 890 139 in gasoline by mixing (C) in sequence with (B) and (A) and allowing to stand for 1 minute A mixture of 0.25 mol each of butadiene and ao styrene was added to the catalyst mixtures and ^{polymerized in one stage at 20 °} C., specifically according to an example which was found to be most suitable for the homopolymerization of butadiene. The preparation and use of the catalyst mixtures according to Belgian patent 575 507 a5 took place according to the information in the patent.

Polymer aesthetic conditions and results c

Trials based on the example of British Patent 890 139

3 I 7 I 7

Belgian patent 575 507 1

Composition of the catalyst mixtures, millimoles Co-naphthenate (A)

(C ₁ H ₁ J ₄ AlCl (B)

C ₁ HjAIO, (υ) .....

CoClj-Pytidiia Al: Co ratio Volume ratio of solvent to butadiene Polymerization time, hours Polymerization yield, g Degree of implementation, ° /, Total styrene content of the copolymer, "/ ·

Degree of interpolymerization of styrene with butadiene, · / ·

The measuring method used is described in example 1 of the patent (Oflfentegungsschrift 1 570 286); the degree of interpolymerization is expressed by the shape! (S / - SH / ST) x 100, where ST is the total amount of styrene polymerized and SH is the amount of Hofliopolystyrene.

MikrostnikEur of the butadiene part in the mixed polymer, · /,

cis-1.4

trans-1,4

vinyl. ,

Component A

Metallic nickel or cobalt with a large surface area, based on weight, is made from reduced Metals selected and applied to supports or used in the form of a colloid, fine Powder or porous solid. In addition to reduced nickel and cobalt, Raney nickel and Rancy cobalt are applicable. These metals have a relatively large surface area, based on weight, 0.072 0.960

13.3: 1

4: 1 6th

31.6 80.0 60.5

90.4 6.8 2.8

0.0072

0.288

0.672

0.0072

0.384

0.576

133:

4: 6th

14.9 37.7 48.8

10.3

94 /) 4.0 2fl

133:

4:

5.6 14.2 34.2

14.7

96.8 1.8 1.4

2.24

0.088 25: 1

7.2: 1 40 9.3 23.5 -0

96.2 1.8 2.0

and can be produced by various known processes, for example by reducing the oxides. Hydroxides or salts, which are optionally arranged on a carrier, by means of hydrogen, carbon monoxide or other reducing gases in a suitable temperature range, the sintering of the reduced nickel being prevented. - Usually in a range from 150 to 60O ¹¹ C. The sal / c used are carboxylates such as t'ormiate. Oxalates and citrates. Thermal decomposition of nickel

5 6

formial.-oxalate or tetracarbonyl in vacuo or in and Raney nickel boron trifluoride etherate triethyl or

an inert medium can use catalytically active triisobutylaluminum.

colloidal nickel can also be obtained. The preferred molar ratio of the metal components

The reduced metals can also be reduced by component (A) compared to the C component is 0.01

Production of easily reducible anhydrous salts of these 5 to about 10.0.

Metals, dissolved or dispersed in an inert molar ratio to the C component Medium, as a fine powder with a strong reduction in the B component is usually around 0.1 to

average, e.g. B. organometallic compounds of 5.0, preferably at about 0.3 to 2.0.

Alkali metals. Magnesium, cadmium. Zinc or The catalyst system can be obtained by mixing the Aluminum, optionally with heating, obtained io three components in an anhydrous, liquid

will. So there is no noticeable change in hydrocarbon diluents - usually

20'C a. if Nickclcarbonat-Diatomecnerde-Pul- at a temperature of about - 50 ⁰ C to + 80 ⁰ C,

\ cr in an Iknzollösung of triethylaluminum dis- preferably at about -5 to -f 40 ⁰ C - produced

is pergiert, but a conversion takes place, and if necessary for the purpose of modifying the cataly-

wcnn the mixture 1 hour hei 40 ^c C is heated 15 schematically function of the catalyst system of

the originally greenish-yellow powder being subjected to aging or heat treatment

colored, reduced nickel diatomaceous earth.

being transformed. Metal salts of the higher organ-

niscluη acids, such as nickel naphthenate and cobalt ions stored at room temperature, remain

octanate. dissolved in benzene, remain unchanged with a benzene activity over a longer period of time,

solution of triethylaluminum at room temperature.

in the formation of slightly colored metal colloid combinations, do not come into contact with water and oxygen.

duzicrt. tion, however, is the effect of these substances on the

The carrier used is a po copolymerization activity and the cis-1,4-Bilrüser solid, which has a suitable surface. The formation activity of the catalyst system is not so strong like diatomaceous earth. Silica-alumina. Silica as with the Ziegler and Li catalysts. Titanium dioxide. Zirconia, active clay. Kaolin or the catalyst used for interpolymerization in another solid containing these substances. amount is not of particular importance; habitual

Rancy-Nickcl cder Raney cobalt is obtained from borrowed it is at least 0.5 mmol per 1 mol of the

powdery or granular alloys composed of 30 total quantities of the monomers.

Nickel iird.odcr consist of cobalt, as well as aluminum. According to one embodiment, the mixed poly Sili7iii! Ti, zinc. Contain magnesium or mercury; merization carried out in one stage, in that both mono-

dicsc F remdmctallc is removed by alkali or mers and the diluent at the same time in the

Acid treatment or by means of vacuum evaporation - catalyst system can be introduced. After a

if possible in the absence of air. The obtained cata- 35 other embodiment is worked in two stages,

Iysator should be in anhydrous inert solvents by first polymerizing butadiene

to be hired. The nickel or cobalt content of the and then the mixed polymerization with styrene

Starting alloy is not critical, amount leads to the first stage at one temperature

However, usually at about 20 to about 60 ° / _0th from about -30 to 150 ^c C, preferably at about 0 to

The A component is preferably reduced to 40-80 ^° C., whereas the second stage is at one temperature Nickci diatomaceous earth or Rancy nickel. from about 0 to 150 ^c C, preferably about 30 to 120 ° C.

The following is used as the B component: Boron trifluoride In both cases the pressure must be sufficient to or its complex with an organic acid to keep the mixture in a liquid state. Compound such as ether, e.g. B. ethyl, isopropyl and means of two-stage copolymerization, butyl ether and anisole, or alcohol, e.g. B. Ethanol 45 NEN preferred copolymers are obtained, butanol wound. Carboxylic acids, e.g. B. acetic acid, organi- at the butadiene with a satisfactory Gesche acid ester, z. B. Essigsäureäthylestei or Phe speed to a polymer with a frontier mole; preferred are: Borlrifluoridäthylätherat. viscosity of at least 1.0 is converted, Boron trifluoride butyl alcoholate or boron trifluoride phenolate. whereas styrenes differ in comparison to butadiene

Organometallic interpolymerization is used as the C component. however can through

bonds of lithium. Zinc. Cadmium or AIu increase the copolymerization temperature

minium of the formulas R «M or R ₁ AIOR. in which M copolymerization speeds are increased,

the metal. K is the monovalent hydrocarbon radical. The two-stage, in particular with a catalytic converter

like Alcvl. Aryl. Aralkyl or cycloalkyl, and η the combination that is metallic nickel and a trialkyl radical of M. Examples of the C component aluminum contains, are obtained copolymers

th are: triethyl-. Tripropyl, triisopropyl. Tri- usually rubbery solids with boundary

butyl-. Triisohutvl-. Tri-hexyl and triphenylaluminum viscosities from about 1.0 to 5.0. the single-stage

nium. Diethyl and dihutyl zinc. Diethyl cadmium. products, on the other hand, usually sticky solid

Butyllilhiuin and diethylethoxyaluminum: triethyl substances. The copolymers have cis-1.4 components and triisobulyl aluminum are preferred. 60 of 70 ° / ,, or more: when using metallic

These three catalyst components have more than nickel as A-componentc amounts to the content

surprisingly the same required functions usually at 90 to 98 degrees.

nen for the eis-M-Uutiulicn-Mischpolymcrisation. The cis-1,4-portion of the Butadicn-F.inhciten and the

as for the cis-M-Huladicn homopolymerization gc- (ialt of styrene or v-alkylslyrole in the obtained MuH patent I 130 172. 65 copolymers are infrared spectroscopic. the

Ik-vnr / ugtcDrcikiimponcnlcnkatalysüloren exist (ircn / .viscosity is determined in toluene at 30'C,

'from:' Kcilu / ieitem Nickel - Diiilomcenerdc - Horlri- Dei (ΊοΙμοΙκιΙΙ of the copolymers is replaced by IiI-

llii (iiul; ilher; il-1 iiällivl- (Hler I riisnluitylaluminium liieren tier llcn / ollösimgcn by a table with a

clear mesh size of 0.075 mm and is usually zero.

A diluent is used to facilitate control of the interpolymerization process. usually in an amount within 40 percent by volume of the monomer mixture. As a diluent for the Catalyst are liquid aromatic, aliphatic and alicyclic hydrocarbons, such as benzene, Toluene, xylene, pentane, hexane, heptane, isooctane and gasoline, hydrogenated aromatic hydrocarbons such as Tetra- and decahydronaphthalene, diisopropyl ether and mixtures thereof. Aliphatic hydrocarbons or their mixtures with aromatic hydrocarbons are used to obtain copolymers with a high molecular weight, on the other hand aromatic hydrocarbons or their mixtures with aliphatic hydrocarbons, such as toluene-isooctane, preferred for copolymerization. The diluents should - just like the starting monomers —7 be practically free of catalyst poisons such as oxygen and water.

After the copolymerization, a small amount of phenyl - /? - naphthylamine can optionally be added to the mixture containing solvent to completely dissolve the copolymer or to Reduce the viscosity of the mixture and then add the mixture in a large amount of one Nonsolvents, such as methanol, isopropanol or methanol-acetone, for the purpose of precipitating the copolymer be poured.

The polymers are usually completely dissolved in the solvent, whereas the solid catalyst particles gradually fail and the separation of the mixed polymer solution easily by siphoning or Filtering can be performed; if the viscosity of the solution is too high, there is more solvent to add. The mixed polymer solution, completely freed from solids, is in vacuo at room temperature concentrated and then, as indicated above, submerged in a large amount of a lower alcohol Decomposition and removal of the soluble catalyst components and simultaneous precipitation of the copolymer poured.

Reinforcers, vulcanizers, fillers and other customary materials can be incorporated into the copolymers obtained Rubber additives are incorporated.

example 1

91.5 ml of anhydrous benzene are charged with 0.4 g of reduced nickel diatomaceous earth, 2.0 mmol of boron trifluoride etherate and 2.0 mmol of triethylaluminum in the order given. After addition of 0.4 mole of butadiene is allowed to the vessel in the thermostat at 40 ⁰ C revolve, is after 2 hours, 0.4 moles of styrene were added and is circulated further 7 hours at 6O ⁰ C. Yield 13.9 g, intrinsic viscosity 3.98, gel-free. Infrared analysis showed 1.6% styrene (based on total polymer) and 95.6% cis-1,4, 2.4% trans-1,4 and 2.1% vinyl components (based on butadiene content).

Example 2

The copolymerization is carried out according to Example 1 with a catalyst composed of 1.0 g of Raney nickel, 2.5 mmoles of boron trifluoride etherate and 2.0 mmoles of triethylaluminum. Yield 7.1 g, intrinsic viscosity 4.65, gel-free. Infrared analysis showed 94.5% cis-1,4, 3.1% trans-1,4 and 2.4% vinyl proportions (based on Butadiene content) and 1.9% styrene (based on total polymer).

According to the invention, mixed polymers are obtained which have better heat aging properties and larger ones Have hardness than cis-1,4-polybutadiene with the same modulus value. Hence the copolymers able to improve the rigidity of tires against deformation when cornering by improving the To reinforce the hardness of the tire compound without its resistance to the growth of the tendency to wear, which affects the tear resistance of the tires is reduced.

Example 3

The catalyst is made from 0.4 g of reduced nickel diatomaceous earth, 2.0 mmol of boron trifluoride ether and 2.0 mmol of triethylaluminum produced, the polymerization carried out in 22 hours at 40 "C with a mixture of 0.4 mol of butadiene and 0.4 mol of styrene. Yield 8.1 g, intrinsic viscosity 0.55, gel-free. Infrared analysis yielded 9.3% styrene (based on total polymer) and 93.1% cis-1,4-, 4.5% trans-1,4- and 2.4% vinyl content (based on the butadiene content of the polymer).

Example 4

The catalyst is obtained from 1.0 g of Raney nickel, 2.5 mmol of boron trifluoride etherate and 2.0 mmol Triethylaluminum; the polymerization takes place according to Example 3 with a mixture of 0.4 mol of butadiene and 0.1 mole of styrene. Yield 2.5 g, intrinsic viscosity 1.30, gel-free. Infrared analysis found 1.2% styrene (based on total polymer) and 93.9% cis-1,4, 3.6% trans-1,4 and 2.5% vinyl components (based on Butadiene content).

Claims (1)

Claim: Modification of the process for the polymerization of butadiene in the presence of a ternary catalyst combination, implemented by (A) metallic nickel or cobalt with a large specific surface, (B) boron trifluoride or its complex with an organic oxygen compound and (C) an organometallic compound of lithium, zinc, cadmium or aluminum of the formulas R _n M or R ₂ Al OR, where R is a monovalent hydrocarbon radical and η is the valence of the metal M, has been obtained, in a diluent at temperatures between -30 and -f-150 ° C under pressure in the liquid phase and in an inert atmosphere according to patent 1130 172, characterized in that that by using styrene or α-alkylstyrene copolymers manufactures. 109 641/145