FI62107C - SAETT ATT HOMOPOLYMERISERA BUTADIEN ELLER KOPOLYMERISERA DET MED OSUBSTITUERAD ELLER MED EN ALKYLRADIKAL SUBSTITUERAD STYREN - Google Patents

Description

EA * ·! r, HEARING PUBLICATION z 'Ο d Π * 7 JOa ™ (11) UTLÄGGNINCSSKIUFT <> 2Vj7 4§55nB> c Patent r.y’inn ·: tty 10 11 1912

Patent e la t (sijftJuVa.3 0 08 F 36/06 '4/54 FINLAND —FINLAND (21) PMwttlhikumui - Pttwttmeknlni 7 ^ 0 ^ 1 β (22) H »kuml» pllvi - Anuöknlnftdtg 27.02.76 (23) Alkupllvt —GlMchaud ·! 27-02.76 (41) Gotten stuck - Latches offuntllg 28. θ8.76 PMCtl · and register germination> (+4) | t month | mm.MM date__

Patent and registration authorities AiwOkun utiagd och utUkrifttn pubikurmd 30-07-82 (32) (33) (31) h7 «i« t) r utuolkuu * - Bugtrd prlorltut 27.02.75

France-France (FR) 75/06239 (71) Michelin & Cie (Compagnie Generale des Etablissements Michelin), Clermont-Ferrand, France-France (FR) (72) Yves de Zarauz, Gergovie, France-France (FR) (7) ^) 0y Kolster Ah (5 ^) Method for homopolymerizing but copolymerizing butadiene with unsubstituted or alkyl-substituted styrene - Set of homopolymerized butadiene or copolymerized with substituents or with alkyl radicals substituted with styrene

The invention relates to a process for homopolymerizing but copolymerizing butadiene with unsubstituted or alkyl-radical-substituted styrene.

GB Patent 1,246,914 discloses a process for the preparation of solution-conjugated diene polymers and copolymers in which the dienes are conjugated either to each other or to a vinyl aromatic compound using alkaline earth metal organometallic compounds of the formula Mj 1 R 3 R 2 R 2 R 4 and R 1, R 2, R 3 and R 2 represent a hydrocarbon radical. The intrinsic viscosity of the obtained compounds is very low, 0.24-0.62.

Also known is Chemical Abstracts, 78 (1973) 85 514 and RAPRA No. 23 738 L (1974) for the preparation of polymers or copolymers of dienes and / or vinyl aromatic compounds conjugated in solution and in a hydrocarbon medium, using organometallic compounds of alkaline earth metal and aluminum However, the viscosity of the compounds obtained by this method as well as those mentioned above is very low 62107 and therefore they are not sufficiently elastomeric to be used as the main ingredient in alloys used in the manufacture of automobile tires, and such a method is not suitable for industrial use. the copolyme reaction is very slow.

It is also well known that organoaluminum compounds have very poor catalytic activity, almost non-existent, and are not considered to be initiators of the polymerization or copolymerization of conjugated dienes.

A new process has now been invented which makes it possible to obtain, on a factory basis, in a relatively short time and with high efficiency, inexpensive homopolymers or copolymers of butadiene with substituted or unsubstituted styrene, which polymers have a rubber-like elasticity and can be used for car tires.

It is an object of the invention to polymerize the monomer or monomers dissolved in an inert solvent at a temperature of 50-120 ° C in the presence of a catalytic system consisting of the reaction product of the following compounds: a) Group III A metal organic compound of the Mendelejeff Table of Periodic Table of Elements

Me i MR.j R2R3R4,

Me2 ^ ^ 2 R2 R3 R4- ^ 2 'MR1R2R3 or Me1OMR1R2 in which formulas Me1 represents an alkali metal, Me2 represents an alkaline earth metal, M is aluminum or boron, R1, R2 and R1 represent an alkyl or aralkyl radical and R4 is an alkyl- or an aralkyl radical or XB, wherein X represents an oxygen, sulfur or nitrogen atom and B is an alkyl or aralkyl radical or M (RgRg), in which R1 and Rg denote an alkyl or aralkyl radical, and b) one or more electron-donating compounds containing one or more heteroatoms and which is a polar aprotic compound, a polar protic compound or a compound which is the reaction product of a polar protic compound and an alkali metal or alkaline earth metal, wherein the electron-donating compound is an ether, a tertiary amine, a phosphorus-containing compound, a ketone , nitrile, amide, thiol, phenol, water or a compound which is the reaction product of an alcohol, phenol or primary 62107 or secondary amine with an alkali metal or alkaline earth metal or a compound of formula R (OCH 2 CH 2) n ° Me 2 or R 2 NCH 2 CH 2 OMe. In which formulas Me 2 represents an alkali metal, R is an alkyl radical and n is an integer.

It has now surprisingly been found that the reaction product of compounds which alone do not initiate the homopolymerization or copolymerization of butadiene with styrene or whose reaction-initiating capacity is infinitely weak forms a catalytic system which initiates polymerization and copolymerization, and this can be used, for.

Organic compounds of Group III A metals in which the alkali metal is lithium, sodium or potassium and those in which the alkaline earth metal is magnesium, calcium, strontium, barium are particularly well suited as components of the catalytic system. Examples which may be mentioned are the following compounds: Al (CH3) 3, Al (C2H5) 3, Al (i-C4H9) 3, Li / Al (C2H5) 47, Na / Al (C2H5) 47, K / Al (C2H5) 47, Li / Al (C2H5) 30 C ^ H ^, Li ^ A1 (C2H5) 3 'Al (C2H5) 2> 7,

Mg / Al (C2H5) 472, C2H5Mg Al (C2H5) 4, Ca / Al (CjHg) ^,

Sr / Al (C2H5) 472, Ba / Al (C2H5) 472, Ba / Al (C2) 302,

Ba / Xl - (iso C4Hg) 472, Li O Al (C2H5) 2, Na O Al (C2H5) 2, B (CH3) 3, B (C2H5) 3, Li B (C2H5) 4, Li B (C2H5) 3 C ^ Hg.

Suitable polar aprotic compounds are, in particular, ethers and in particular cyclic ethers such as tetrahydrofuran and dioxane, as well as the corresponding thioethers, tertiary amines such as N, N, N ', N'-tetramethylethylenediamine, aromatic amines and especially pyridine derivatives, and the like pyridine derivatives and the like containing compounds such as phosphines and their oxides, phosphites, phosphoramides and especially hexamethylphosphorotriaamide, ketones and especially acetone, nitriles and especially acetonitrile, aldehydes, esters, amides, nitro-aliphatic or aromatic compounds, sulfoxides and sulfoxides, sulfoxides sulfites.

Of the polar protic compounds, water, alcohols and in particular methanol, primary or secondary amines, thiols are particularly suitable.

Of the compounds which are the reaction products of polar protic compounds and alkali or alkaline earth metals, alkali metal or alkaline earth metal alcoholates and phenonates, 4 62107 alkali or alkaline earth mercapto and thiophenolates, as well as ether alcoholates and amine alcoholates are particularly suitable.

The organic compound and the polar compound or compounds of the Group III A metal may be added to the reaction solution either separately in any order or prepared. According to another variant, the catalytic system is "prefabricated" by mixing the various components together and then raising the temperature of the mixture to between 20-85 ° C.

5-60 min. for the duration of.

Both components of the catalytic system can be used in varying proportions, but it is preferred to use them in such proportions that the molar ratio of the polar compound or compounds to the organic compound of the Group III A metal is between 0.01 and 100. At a given concentration of a Group III A metal organic compound, a change in the value of the molar ratio causes both a change in the viscosity and microstructure of the product formed and a change in the polymerization and copolymerization rate. Of the organic compounds of Group III A metals, organoaluminum compounds are most preferably used both because of their preferred method of preparation and because they are readily available commercially.

In the case of a catalytic system consisting of an organoaluminum compound of the formula Me2 / ^ 11 ^ 1 ^ 283 ^ 472 as defined above and one or more polar compounds from the group of aprotic compounds, the molar ratio of the polar aprotic compound or compounds to the organoaluminum compound, when the concentration of the latter compound is the same, the reaction rate and the viscosity of the polymer formed increase without changing the microstructure of the polymer. This is all the more surprising because the addition of polar compounds to the initiating organolithium compounds provides a system that does not change the viscosity of the polymer but alters the microstructure.

In the case where the catalytic systems consist of an organoaluminum compound of the formula Μβ2 (MR1R2R3R4) 2 as defined above and a polar compound of the formula of the formula R (OCl2Cl2) nOMe2 or (R2) NCH2C4MOe -j, in which formulas Me 1 represents an alkali metal, R is an alkyl radical and n is an integer, polymers and copolymers can be obtained which are very rich in 1,4-trans chains (up to 92%) and very few 1,2- or 3, 4-chains, namely less than 4%, and the elastomeric nature is retained. The copolymers of butadiene and styrene thus obtained have a tensile strength analogous to natural rubber, crude (not vulcanized) and containing additives according to conventional compositions used in the manufacture of automobile tires.

The polymerization and copolymerization reaction is carried out in either an inert solvent which may be, for example, an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, isooctane, cyclohexane or an aromatic hydrocarbon such as benzene, toluene, xylene or pulp.

The reaction is usually carried out at a temperature of 50 to 120 ° C, and preferably 80 to 100 ° C, at a pressure corresponding to the vapor pressure of the reactants. The method according to the invention can be implemented in a continuous or continuous manner.

Thanks to the method, macromolecular compounds are obtained, the yield of which is not only higher per unit weight of the catalytic system, but at the same time the molecular weight of the polymers and copolymers prepared in the desired amount can also be controlled.

The process further provides polymers and copolymers in which crosslinking with all reactants that can react with reactive "living" polymers can occur during the reaction.

Suitable examples of vinyl aromatic compounds include styrene, ortho-, meta- and paramethylstyrene.

The products obtained by the production process using the catalytic system according to the invention have not only a high molecular weight distribution and a high intrinsic viscosity, i.e. a viscosity high enough to be used as the main component of tire blends, but also a highly variable microstructure. The amount of 1,4-chains can be 20-90% and the number of 1,2-chains 1-60%. In addition to this, these products are very well suited for mechanical machining.

The invention will become more fully apparent from the following examples, which illustrate ways in which the invention may be practiced. In all examples, the intrinsic viscosities are determined at 25 ° C in a solution of 1 g / l toluene, the catalyst concentrations are expressed in micromoles per 100 g of monomer and the polymerization and copolymerization reactions are stopped when the conversion product is increased to 80% by addition of methanol. 1%). The percentages of 1,4-trans-6,621 07 and 1-2 linkages are expressed relative to the polybutadiene moiety, while the percentage of styrene is expressed relative to the total amount of polymer obtained.

Example 1

For the reaction / under the pressure of rectified nitrogen, 2 l of heptane are poured into the solvent, then 205 g of butadiene and 69 g of styrene are poured and the temperature is raised to 80 ° C. A catalytic system consisting of Ba, / Al 2 and tetrahydrofuran (THF) in varying amounts is then added sequentially. When the degree of conversion is reached, the reaction is inhibited and the copolymer is recovered.

The results are in the following table.

Table I

Catalytic System Reaction Copolymers __ time ____

Experiment Ba / Al THF h characteristic ether configuration: viscosity tert tr. 1.4 1.2 styrene%%% T 1820 0 40 0.8 85 3 15 1 1100 1100 8.5 1.6 81 3 15 2 1100 2200 6 2.1 80 3 16 | 3 I 1100 4400 4 2.45 80 4 16 j |

It is noted that the reaction time is 5-10 times shorter, and as the THF / Ba / Al $ 2 ratio increases, the reaction rate and the viscosity of the copolymer increase, while the microstructure of the copolymer remains unchanged.

Example 2

4 experiments are performed following the procedure of Example 1 and using different catalytic systems. The results are shown in Table II below: 7 62107

Table II

Catalytic System Reaction Copolymers ___-__ time ____________

Experiment Mell ^ Al (CjHe) 472 THF h characteristic configuration viscosity te tr. 1.4 l, 2 styrene ......................%%% 1 Ca 2 Al (C 2 H 5) 472 640 1920 3 1.3 73 7 10 2 SrZAl (C2H5) 472 1100 3500 2.33 1.4 73 7 12 3 Ba ^ Al (C2H5) 472 1100 3300 4.5 2.25 80 4 16 4 Ba ^ S1 (isoC ^ Hg) 4/2 860 2580 2 1 74 5 15 _ ^^^^^^ _!

Example 3

3 experiments are performed. A 250 ml Steinie flask under rectified nitrogen pressure is charged with 100 ml of heptane as solvent and 13.6 g of butadiene. A catalytic system consisting of Baj / Al (CjHg) 472 and methanol is then added. Place the flask in a thermostat vessel at 80 ° C and mix.

After completion of the reaction, the polybutadiene is recovered according to the usual method. The results are indicated in Table III below

Table III

Catalytic system Reaction time Polybutadiene

Experiment Ba / Al (C2Hc) 472 methanol specific characteristic Viscosity tertiary tr. 1.4 1.2%% 1,100 74 7 1.64 86 3 2 1100 222 6 1.59 84 3 3 1100 444 5 1.50 81 3 8 62107

Example 4

The experiment is performed by repeating the procedure of Example 3 and following similar conditions except that a catalytic system consisting of Ba / Al 2 O 4 Da in water is used. The results are shown in the following Table IV:

Table IV

Catalytic System Reaction Polybutadiene ____time _______

Experiment The specific viscosity of Ba 2 Al (C 2 H 2) 2 2 H 2 O 2 was determined to be tr.1.4 1.2%% 1! 1100 440 17 1.55 87 2!

Example 5

3 experiments are performed in which the reaction takes place in a reactor under the pressure of rectified nitrogen. The solvent is 2 l of heptane, then 191 g of butadiene and 82 g of styrene. The temperature is raised to 80 ° C and a catalytic system consisting of Ba / Al (C 1 H 3) 472 3a lithium isopropylate is added. After completion of the reaction, the copolymer is recovered according to a conventional method. The results are indicated in the following Table B:

Table V

; Catalytic System Reaction Copolymers Time "I h .....

Experiment No. Ba ^ / Al (C2H5) ^ 2 lithium iso-specific Steric configuration propylate viscosity tr. 1.4 1.2 styrene%%% I ...

I ——————————______ | 1 340 2400 4 3 83 4 21 j 2 380 2600 4 2.6 83 3 20! 3,550 1380 4 1.7 81 4 23: _ _ ____ _ ___ _ 9 62107

Example 6

Perform 2 experiments. A reactor under rectified nitrogen pressure is charged with 2 liters of solvent (heptane), followed by 205 g of butadiene and 69 g of styrene. The temperature is raised to 80 ° C and then the components of the catalytic system Ν, Ν, Ν ', Ν'-tetramethylethylenediamine (TMED) and Ba / Al (CjH 2) 2 are added sequentially. The results are indicated in the following Table VI:

Table VI

Catalytic System Reaction Copolymers __time ....... ........................ .. ___________ _, specific- Steric config-

Experiment Ba / Al (CjHc) ^ 72 TMED viscosity no. 1.4 1.2 styrene% *% 1! 2440 1220 5.75 0.8 84 4 15 I 2! 2440 2440 5 1,5 81 4 16 i_i_l_I ___ I _ ^ _

Example 7

A reactor under purified nitrogen pressure is charged with 2 liters of heptane, 205 g of butadiene and 69 g of styrene, then the temperature is raised to 80 ° C and the following are added successively: methyl-4-pyridine, i.e. Y 2 -picoline and Ba / Al (C 2 H 5) 2. The results are indicated in Table VII below:

Table VII

Catalytic System Reaction Copolymers I l I I 'time ------------- - *' ““ .. ...

characteristic- Static configu- jö / il, / -, tr \ -7 s / tf "...... h viscosity | Ba ^ Al (C2H5) 472 Y-pxkolxini tea tr. 1.4 1.2 sty-jene%%% 1 ti 00 1100 1, 40 1, 30 60 7 18 10 621 07

Example 8

2 experiments are performed, repeating the procedure of Example 3 and using the following catalytic system:

Ba / Al (C2Hg) £ 2, acetonitrile. The results are summarized in the following Table VIII:

Table VIII

Catalytic System Reaction Polybutadiene Time

Experiment No. Ba ^ Al (C2Hc) Acetones-specific ether configurational viscosity j tra. 1.4 1.2%% i i! 1 1100 74 3.75 1.6 77 3 2 I 1100 222 3.25 1.7 75 4

Example 9

3 experiments are performed, repeating the procedure used in Example 3 and the same conditions, except that acetone and Ba / Al (C 2 H 2) 2 O 2 are used as the catalytic system. The results are shown in Table IX below:

Table IX

Catalytic System Reaction Polybutadiene r time „I h

Experiment No. Ba ^ Äl (C2Hg) ^ 72 acetone characteristic Steric configuration viscosity | teetti tr. 1.4 1.2 s%% 1 I 1100 74 7 1.6 82 3! 2! 1100 222 6.5 1.8 78 3! 3 | 1100 444 5.5 2.0 75 4! _I_ I _ ^ _ 11 62107

Example 10

The procedure of Example 3 is repeated and the same conditions are followed except that thiodoisobutyl and Ba / Al (C2H5) 472 are used as the catalytic system. The results are marked in the following table X:

Table X

Catalytic System Reaction Polybutadiene Time _ ___ _ ______

Ba ^ Al (C2Hg) thio-diiso- h characteristic Steric config-butyl viscosity tr. 1.4 1.2% 1100 222 22 1.50 85 2 i__i____

Example XI

3 experiments are performed, repeating the procedure of Example 3 and following similar conditions, except that hexamethylphosphoric triamide (HMPT) and Ba / Al (C 2 H 5) 2/2 are used as the catalytic system. The results are indicated in Table XI below:

Table XI

Catalytic System Reaction Polybutadiene ___________time _______________________________

Experiment Ba / Al (C2H (-) 2 HMPT characteristic Steric configuration viscosity tert. 1.4 1.2%% 1100 222 3 1.55 82 2 | 2 1100 444 2.25 1.68 80 3 | 3 1100 888 2 2.48 78 3 I — i ----

Example 12

2 experiments are performed, repeating the procedure of Example 3 and following similar conditions, except that a 12 621 07 catalytic system consisting of Ba, / Al (C2H, -) 30r72 »where OR is a nonylphenolate residue and lithium isopropylate is used. The results are summarized in the following Table XII:

Table XII

Catalytic System Reaction Polybutadiene _ Time _ ______

Experiment Ba / ^ 1 (C2Hg) 20R? 2 lithium iso- ^ characteristic Steric conf- n ~ ** propylate viscosity tr. 1.4 1.2%% j 1 1450 2900 18 1.15 76 4 2 1450 5800 17 1.33 78 4 _______

When the compound Ba / Al (O 2) / OR 2 is used under the same conditions alone, no polymer is obtained, not even after 48 h of reaction. Example 13

2 experiments are performed, repeating the procedure of Example 3 and following the same conditions, but using Li Al (C 2 H 5) 2 and lithium isopropylate as the catalytic system. The results are shown in Table XIII below:

Table XIII

i

Catalytic System Reaction Polybutadiene __ time ______________________

\ ΖΓ ~ · I I h I

In: Li Al ^ Al (C2H5). lithium iso- specific Steric propylate viscosity configuration tr. 1.4 1.2%% 1 1450 725 3.5 1.22 60 8 2 1450 1450 3.5 1.24 60 8

Using either LiAl (¢ 2 ^) ^ or lithium isopropylate alone under the same conditions, no polymer is obtained at all, not even after 48 h of reaction.

13 621 0 7

Example 14

Experiment 1 is performed, repeating the procedure of Example 3 and using the following as components of the catalytic system: LiAl (C2H5) 4, lithium isopropylate and barium nonylphenate. The results are shown in Table XIV below:

Table XIV

Catalytic system Reaction Polybutadiene __time L1A1 (C2h,) 4 bartononyl-1 lithium iso- h J, tl0 phenate propylate 1.4 1.2%% 1450 725 2900 1.5 2.3 79 4

Compared to the previous example above, it is found that the addition of barium nonylphenate causes a change in the microstructure.

Example 15

Experiment 1 is performed according to the procedure of Example 3 using the following catalytic system: LiAl (C2H, j) 4 sodium tertiary amylate. The results are shown in Table XV below:

Table XV

Catalytic System Reaction Polybutadiene Time

LiAl (C 2 H 4) 4 sodium t-amylate characteristic steric configuration visc. 1.4 1.2%% 1450 290 14 3.30 34 36

Example 16

2 experiments are performed, repeating the procedure of Example 3, except that a catalytic system comprising the following: NaAl (C 2 H 2) 4 and potassium tertiary amylate (ROK) is used. The results are shown in the following Table XVI: 62107 I Catalytic System Reaction Polybutadiene ί ____ time _____ 14

Table XVI

Experiment with NaAl (C2Hc-) 4 ROK ^ characteristic Steric configuration | n viscosity tr. 1.4 1.2% by weight I 1 1450 725 5 3.12 37 38 2 1450 1450 5 2.55 40 36 L - _ l ----- - _L L - I -

Under the same conditions, the use of NaAl (C2H5) 4 alone does not lead to the formation of the polymer in the slightest amount, even 48 h after the reaction.

Example 17

2 experiments are performed, repeating the procedure of Example 3, except that a catalytic system consisting of KA1 (C2H, -) 4 and potassium tertiary amylate (ROK) is used. The results are indicated in the following Table XVII:

Table XVII

Catalytic System Reaction Polybutadiene time j ^

Experiment KAl (C2H [-) 4 ROK characteristic configuration No. viscosit. 1.4 1.2% of% 1 1450 360 4.5 1.37 50 26! t I j] l

When KAI (CH 2 Cl 2) alone is used under the same conditions, no polymer is obtained even after 48 h of reaction.

Example 18

Perform 1 experiment, repeating the procedure of Example 3 and using

CH

the following catalytic system: Li Al (C2Hg) 3 and barium XCH3 nonylphenolate.

The results are shown in the following Table XVIII:

Catalytic System Reaction-1 Polybutadiene Time 15 6210 7

Table XVIII

_.

--ch3

LiAl (C2H4) 30-CH2-barium-nonyl- (specific tr. 1,4 1,2 ^ CH.-, phenate viscos%%) \ - ..........— - 11 - - - - '- -' '- "—f" 1450 725 10 1,6 80 4 j

CE

If only LiAl (C-H, -) is used under the same conditions, O-CH does not obtain any polymer even after 48 h of reaction. 3

Example 19

Experiment 1 is performed following the procedure of Example 3 and using the following catalytic system: Li O Al (O 2) 3 and barium nonyl phenolate. The polymerization reaction is stopped when the degree of conversion is 60%. The results are indicated in the following Table XIX:

Table XIX

Catalytic system Polybutadiene

LiOAl (C2H3) 2 barium nonyl Reaction time phenolate characteristic steric configuration viscosity tr. 1.4 1.2%% 2960 740 5 1.9 63 6

If LiOAl3 # alone is used under the same conditions, no polymer is obtained even after 48 h of reaction.

Example 20

2 experiments are performed, repeating the procedure of Example 3 and using the following catalytic system:

Li / Al (C2H3) 3OAl (C2H5) ^ 7 and lithium isopropylate. The results are indicated in the following Table XX: 16

Catalytic System Reaction Polybutadiene time 621 07

Table XX

Experiment No. Li / Al (C2H5) 3OAL (C2Hc) _7 lithium-specific steric cons isopropyl-viscosity configuration platelet t tr> 1f4 Λ 2%% _______ ___________ _____________ ______ 1 1100 370 5.5 1.78 58 9 2 1100 1100 5.5 1.95 59 9

When Li1 Al (C2H5) 3OAI (C2Hj.) 2J7 is used exclusively under the same conditions, no polymer is obtained, even after 48 h of reaction.

Example 21

2 experiments are performed, repeating the procedure of Example 3 and using the following catalytic system: Al (C 2 H 4) 3, lithium isopropylate and barium nonylphenolate. The results are shown in Table XXI below:

Table XXI

S Catalytic system Reaction Polybutadiene time

Experiment No. A1 (C2H2O) 3 lithium barium no-specific steric confisopropylpheno-viscosity pylate plate tr. 1.4 1.2%% 1,2900 3600 360 5 1.7 88 3 2 2900 3600 720 5 1.35 85 3 17 621 07

When Compound AI is used alone under the same conditions, no polymer is obtained even after 48 h of reaction.

Example 22

Experiment 1 is performed, repeating the procedure of Example 3, except that the following catalytic system is used: LiB (O 2) gCl 2 Hg and barium nonylphenolate. The results are indicated in the following Table XXII:

Table XXII

Catalytic System Reaction Polybutadiene Time _ ___

Experiment h No. LiB (C 2 H 2) barium specific steric configuration 1 nonyl viscosit. 1.4 1.2! phenate commissioned%%! j___! 1 5900 1100 4 1.6 83 3 1 - 1 -----. 1. _ ---... 1 .. l

When LiB (C2H2), C4Hg alone is used under the same conditions, no polymer is obtained even after 48 h of reaction.

Example 23

A mixture of heptane, butadiene and styrene is added continuously to the reactor and the weight ratio of monomers / solvent is 1/5 and the weight ratio of butadiene / styrene is 3. Similarly, the compound Ba / Al (C 2 H is 1/10 and the flow rate is such that the reactor contains 960 moles of Ba / Al (C2H5) 2 per 100 g of monomers, and the average residence time of the substances in the reactor is 1.5 h. The copolymerization is carried out at 90 ° C and the conversion rate increases To 60%. The copolymer is recovered as it exits the reactor. It contains 16% styrene and has an intrinsic viscosity of 1.64, 1,4-chains 81% and 1,2-chains 3%. Example 24

2 L of heptane, 191 g of butadiene and 82 g of styrene are poured into a reactor under reactive nitrogen pressure and the temperature is raised to 80 ° C. A catalytic system consisting of 460 .mu.mol of Ba / Al (Cl2H2), 100 g per monomer and 1380 .mu.mol of lithium isopropylate per 100 g of monomers is then added successively. When the conversion rate is 80%, (2 h), 50 cm of copolymer are recovered in the usual manner, and the reaction is stopped by adding methanol. An amount of diphenyl carbonate (CDP) is then added to the reactor such that the ratio 18 621 07

CDR

- is 0,5.

Ba / A1 (C2H5) 472

The obtained copolymer is recovered according to a conventional method. The microstructure of the copolymer obtained before network formation and the microstructure of the crosslinked copolymer are as follows: 81% trans. 1,4-chains and 4% 1,2-chains, and contains 24% styrene.

The viscosity of the non-crosslinked copolymer is 1.7 and the viscosity of the crosslinked copolymer is 2.6.

Example 25 1) Preparation of copolymer: 2 l of heptane, 191 g of butadiene and 82 g of styrene are charged to a reactor under rectified nitrogen pressure, after which the temperature is raised to 80 ° C. A catalytic system consisting of Ba / Al (C 2 H 2) 7 72 3a lithium isopropylate is then added sequentially. When the conversion rate has reached 80%, the reaction is stopped and the copolymer is recovered in the usual manner. The resulting elastomer is then diluted with 37.5 parts of aromatic oil "(Exarol MX 140)" sold by Compagnie Francaise de Raffinage) per 100 parts of dry elastomer. The results are indicated in the following Table XXV A:

Table XXV A

Catalytic system Reactionic steric configuration I_ time _ _________ 'Ba ^ Äl (C2H [-) lithium iso- h characteristic tr. 1,4 1,2 sty-i propylate viscose%% rhenium j tion% before after with oil I thinning | where from ! 1000 7100 5.5 2.67 1.96 84 4 22 i i ------ 2) rubber compound: The elastomer described above is used to prepare a mixture corresponding to the following formula: - elastomer diluted with 37.5 parts of aromatic oil - stearic acid 19 62107

- ZnO

- antioxidant / "Samtoflex 13": N- (dimethyl-1,3-butyl) -N'-phenyl-p-phenylenediamine7 - carbon black HAF ("Philblack 0") - aromatic oil ("Sundex 8125, PM 380" , density 0.995) sold by Sun Oil - 'Santocure' (n-cyclohexyl-mercaptobenzothiazole sulfenamide) - sulfur.

For comparison, the same mixture is prepared using a commercially available butadiene-styrene copolymer (SBR 1712). Both mixtures are then vulcanized for 60 minutes at 144 ° C.

The mechanical properties obtained are indicated in the following Table XXV B:

Table XXV B:

Properties Reference substance Test SBR

2 100% elongation modulus kg / cm 16 14.9 2,300% elongation modulus kg / cm 67.5 58

Hysteresis loss at 60 ° C (kg / cm 2) 29 24.6

Friction index at 20 ° C (SRT) 100 84

Cassage Scott index: elongation at break 5% 570 540 2 breaking force kg / cm 231 222

Shore A Hardness 62 60 SBR 1712 is a butadiene-styrene copolymer containing 23.5% styrene, 15-16%, 1,2-chains, 60% 1,4-trans chains, 37.5 parts of aromatic oil.

It is found that the properties of the elastomer according to the invention are almost the same as those of the classical elastomer. It can be used as the main ingredient in a mixture from which rings can be made. Example 26 This example relates to the preparation of butadiene-styrene copolymers: 6 experiments are performed.

The copolymerization is carried out in a reactor under an inert atmosphere (reacted nitrogen) at 80 ° C, with heptane as solvent. The weight ratio of monomers / solvent is 1/5. The reaction is stopped when the degree of conversion rises to 80%. The conditions and results of the experiments are indicated in Table XXVI.

20 6 2 1 07

Table XXVI

Catalytic System Experiments

Ba (Al (C2H5) 4) 2- 1 2 3 4 5 6 C2H5 (OCH2CH2) 2OLi

Molar ratio Li / Ba 1 1 1.5 1.5 2 2

Initial styrene content (w / w) 24 32 24 32 24 32

The amount of Ba (Al (C2H5) 4) 2 is 760,600,910,750,400 1,300

Reaction time (minutes) 140 '200' 190 '270' 270 '330'

copolymers

Intrinsic viscosity 2.17 2.08 1.86 2.09 2.1 1.90 Number of 1,4-trans bonds (%) 85 85 87 87 90 90 Number of 1,2-bonds (%) 3333 33

Styrene content in the copolymer (wt.%)

Test pieces of the copolymer of Experiment 5 and natural rubber (NR) to which substances of the formula of Example 25 have been added but which have not been vulcanized are subjected to green strength measurements at 25 ° C. Tensile force measurements use test rod-like ("halteres") test rods with a thickness of 2.5 mm, using an electronic dynamometer "Instron" 24 hours after casting, drawing speed 10 cm / min. The results obtained are shown in Figure 1, the ordinate of which shows the force applied in g / mm and the abscissa shows the elongation (in%). It is noted that the tensile strength of the copolymer prepared according to the improved method is analogous to the tensile strength of natural rubber.

Example 27

A mixture of toluene, butadiene and styrene is continuously poured into the reactor in such proportions that the weight ratio of monomers / solvent is 1/5 and the ratio of butadiene / styrene is 3. Similarly, the compounds Ba / Al (C2Hg) 4 and C2Hg are added continuously. (OCH2CH2) 2OLi in amounts such that their molar ratio is 1/2. The flow rate of the substances is such that the reactor contains 1000 micromoles of Ba / AKC 2 H 2 O per 100 g of monomers, and the residence time of the substances in the reactor is on average 1 h.

The copolymerization is carried out at 90 ° C and the conversion rate is allowed to rise to 65%. The copolymer formed is recovered on leaving the reactor. It contains 15% by weight of styrene and has a specific viscosity of 1.6 62107. 1,2-chains are 3% and 1,4-trans chains are 83%.

Example 28 The catalytic system Ba / Al (C2Hg) 472 '^ C2H5 ^ 2 NCH2 CH2OLi is used. To a 250 ml Steinie flask under rectified nitrogen pressure is placed 100 ml of heptane as solvent and 13.6 g of butadiene. The catalytic system is then added, and the flask is then placed in a thermostat vessel at 80 ° C and stirred thereby.

After completion of the reaction, when the conversion rate has reached 80%, the polybutadiene formed is recovered in the usual manner. The results are shown in Table XXVIII.

Table XXVIII

I '| Catalytic system Reaction- Polybutadiene j___ time ........................................ ............ .. ..

ίTest Ba ^ Äl (C2H5) 472 (C2H ^ NCH2CH2OLi min characteristic | viscosity 1.4 1.4%%% | 1 100 200 60 1.75 85 4

Example 29

The experiment is carried out repeating the procedure of Example 28 and under the same conditions, except that a catalytic system consisting of Ba 2 Al (C 2 H 2) 2 2, C 2 H 5 (OCH 2 CH 2) 2 ONa is used. The results are shown in Table XXIX below.

Table XXIX

Catalytic System Reaction Polybutadiene Time

Experiment with the characteristic viscosity of Ba 2 Al (C 2 H 2) 2 Cl 2 (OCH 2 CH 2) 2 ONa. 1.4 1.2% of% 1 100 100 3 5 88 3 22 6 2 1 0 7

Example 30

An experiment is performed in which the procedure of Example 29 is repeated and similar conditions are followed, except that a catalytic system consisting of Ba / Al (C2H5) ^ 2 C2H, - (OCH2CH2) 3OL1 is used. Results in Table XXX below:

Table XXX

Catalytic system Reaction time Polybutadiene

Koe "] I min ..........

No. Ba / Al (C2H2 )22C2Hg (OCH2CH2) ^ OLi characteristic viscosity tr. 1.4 1.2% "—————" ——-! 1 100 100 60 2.8 80 4! ! : i ___] _ L_I_l_

Claims (9)

23 621 07 A process for homopolymerizing but copolymerizing butadiene with unsubstituted or alkyl-radical-substituted styrene, characterized in that the monomer or monomers are polymerized in an inert solvent at a temperature of 50 to 120 ° C in the presence of a catalytic system consisting of the reaction product an organic compound of the metal of Group III A of the system having the formula Me ^ MR ^ R2R3R4, Me2 ^ MR-j 1 * 2 ^ 3 ^ 4-7 2 'MR-jRjRs or MelOMR1R2 in which formulas Me ^ means an alkali metal, Me2 means an earth metal an alkali metal, M is aluminum or boron, R 1, R 2 and represent an alkyl or aralkyl radical and is an alkyl or Aralkyl radical or XB, where X represents an oxygen, sulfur or nitrogen atom and B is an alkyl or aralkyl radical or M (R 1, R 8), wherein R 8 and R 8 represent an alkyl or aralkyl radical, and b) one or more electron donating compounds containing one or more a heteroatom and which is a polar aprotic compound, a polar protic compound or a compound which is a reaction product of a polar protic compound and an alkali metal or alkaline earth metal, wherein the electron donating compound is an ether, a tertiary amine, a phosphorus-containing compound, a ketone, a nitrile , an amide, thiol, phenol, water or a compound which is the reaction product of an alcohol, phenol or primary or secondary amine with an alkali metal or alkaline earth metal, or a compound of the formula R (OCH 2 CH 2) n OMe 2 or R 2 NCH 2 CH 2 OMe 2 wherein Me 2 represents an alkali metal , R is an alkyl radical and n is an integer. Process according to Claim 1, characterized in that the electron-donating compound is tetrahydrofuran, lithium isopropylate, water, methanol, acetone, acetonitrile, hexamethylphosphoric triamide, N, N, N ', N1-tetramethylethylenediamine, barium nonylphenolate or ethyl diglycolate n, n-diethylamino-2-litiumetanolaatti. 24 6 2 1 07 Process according to Claim 1 or 2, characterized in that the molar ratio between the electron-donating compound and the organic compound of the Group III A metal is 0.01 to 100. Process according to Claim 1, characterized in that the aluminum or boron compound is Ba / Al (C 2 O 4) 2 / Li Al ( Ba ^ Al (i-C ^ Hg) 2 »Sr / Al (C2H5) 472 'CaZAl (C2H5) 472' Li / Al (CLjHg) 47, Na / Al (C2H5), k / a1 (C2H5) £, Li O A1 (C2H5) 2, NaO A1 (C2H5) 2, B (C2H5) 3 or Li B (C2H5) 3C4H9. Process according to one of Claims 1 to 4, characterized in that the catalytic system consists of the reaction product of the reaction compound Ba / Al (C 2 H 2) 272 in tetrahydrofuran or lithium isopropylate or Ν, or with N, N-diethylamino-2-lithium ethanolate. Process according to one of Claims 1 to 4, characterized in that the catalytic system consists of the reaction product of Li / Al (C 1 H 2) 7 with barium nonylphenolate and lithium isopropylate. Process according to one of Claims 1 to 4, characterized in that the catalytic system consists of the reaction product of compound A1 (C 2 H 5) 3 with barium nonylphenolate and lithium isopropylate. Process according to one of Claims 1 to 4, characterized in that the catalytic system consists of the reaction product of the compound Li O Al (C 2 H 2) 2 with barium nonylphenolate. Process according to one of Claims 1 to 4, characterized in that the catalytic system consists of the reaction product of Li B (C 2 H 9) 3 C 4 H 9 with barium nonylphenolate. 25 621 07