FI59109B - FOERFARANDE FOER HOMOPOLYMERISERING AV BUTADIEN ELLER ISOPREN ELLER KOPOLYMERISERING MED VARANDRA ELLER MED STYREN SAMT VID FOERFARANDET ANVAEND KATALYTISK KOMPOSITION - Google Patents

Description

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France-France (FR) 7 ^ / 19 ^ 75 (71) Michelin & Cie (Compagnie Generale des Etablissements Michelin), Clermont-Ferrand, France-France (FR) (72) Yves de Zarauz, Gergcvie, Le Cendre, France- Frankrike (FR) (7h) Oy Kolster Ab (5M Process for the homopolymerization or copolymerization of butadiene or isoprene with each other or with styrene and the catalytic composition used in the process komposition

The invention relates to a process for the homopolymerization of butadiene or isoprene with one another or with styrene to homopolymers or copolymers having a high number of trans-1, U-bonds and a low number of 1,2- or 3,1-bonds, and to the catalytic composition used in the process.

Several catalytic systems are already known which make it possible to prepare highly stereospecific diene polymers in solution in a hydrocarbon medium: high content of cis-1, α-bonds (example: polybutadiene, polyisoprene), or high trans-1, α- or also 1,2- or 3, Concentration of ^ bonds. The polymers thus prepared, which have a high content of trans-1, U bonds (more than 95%), have a very strong tendency to crystallize at normal temperatures.

They behave in the form of plastic materials rather than elastomers and are therefore not useful as the main compound in the manufacture of elastic articles, in particular alloys used in the manufacture of outer rings.

It is also well known that polymers of paired dienes or 2,510,109 copolymers, either together or with vinyl aromatic compounds, prepared in a hydrocarbon medium by a lithium-catalytic system do not have high steric purity. In reality, polymers and copolymers obtained by means of lithium-catalytic systems always have a content of 1,2- or 3,4-chains of the diene moiety of more than 6% and a content of trans-1,4-chains of less than 60% at viscosity values of 2 or 3. The concentrations are therefore as follows: - For polybutadienes and copolymers of butadiene, * ♦ 5-55% trans-1,4 7-12% 1,2 40-1 * 5% cis-1,4 - For polyisoprenes and copolymers of isoprene 10-25% trans -1.4 6-10% 3.4 70-85% cis-1.4

At higher viscosities, at least 6, it can be seen, especially in the case of isoprene and its copolymers, that the cis-1,4 content increases up to 95%, causing a detriment to the trans-1,4 and 1,2 or 3,4 contents.

Lithium-catalytic systems can increase the proportions of 1,2 or 3,4 chains in the ranges below compared to 1,4 chains by resorting to certain means, e.g., modifying the polarity of the reaction medium.

In contrast, there are no methods to vary the trans-1.4 content of the chains over a wide range while keeping the concentration of the chains 1,2 or 3,4 at a very low level.

The present invention seeks to improve this by providing a means of obtaining butadiene or isoprene homopolymers or copolymers having a high content of 1,4-trans chains in the diene moieties of a compound, either in the entire chain of the polymer or copolymer or in only a portion of the chain length, and has a very low concentration of 1,2 or 3,4 in the chains.

Thus, it is an object of the invention, on the other hand, to provide a process for homopolymerizing or copolymerizing butadiene or isoprene either with each other or with styrene compounds, resulting in products with a high 1,4-trans content and at the same time a low 1,2- or 3-chain chain. 4 concentration.

Another object of the invention is to provide a catalytic composition.

The catalytic composition of the invention contains: a) an organolithium initiator

(b) a cocatalyst containing a barium or strontium compound and an organometallic compound in Group II B of the Periodic Table of the Elements

3 59109 or III A of metals which are zinc or cadmium (II B) or aluminum or boron (III A).

By organolithium initiator is meant, firstly, any organometallic compound containing one or more carbon-lithium bonds, secondly all ionic radical combinations of lithium and certain polynuclear aromatic hydrocarbons, thirdly lithium metal itself, and finally oligomeric products obtained by pairing with substituted styrenes.

Examples of the organolithium initiator include the following compounds:

Aliphatic organolithiums such as ethyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, isopropyllithium, n-amyllithium, isoamyllithium *, alkenic organolithiums such as alkyllithium, propenyllithium, isobutenyllithium, polybutyllithium, "live" , polystyryllithium; dilithium polymethylenes such as 1,1'-di-lithiobutane, 1,5 "dilithiopentane, 1-20-dilithioicosane; aromatic organolithium such as benzyllithium, phenyllithium, 1,1-diphenylmethyllithium; such as 1,1-diphenylethylene, trans-stilbene, tetraphenylethylene, radical ions such as lithium naphthalene, lithium anthracene, lithium chrysene, lithium diphenyl, as well as derivatives substituted by one or more alkyl.

As regards the components of the cocatalyst, the term "barium or strontium compound" means: hydrides H 2 Ba and H 2 Sr, mono- or polyfunctional salts of organic acids, the formulas (R 1 -COCO 2 Ba or -Sr, R - (COO 2 Ba or - Sr, wherein R 1 and R 2 are organic radicals, the first of which is monovalent and the second divalent and which are not sensitive to inactivation of the organic lithium initiator, and the corresponding thioacids, as well as mono- or polyfunctional alcoholates and corresponding thiolates; polyfunctional phenolates and corresponding thiophenolates, salts of barium or strontium with alcohol and phenolic acids and the like, thio-strontium γ-diketonates such as the reaction products of barium or strontium with barium or strontium with barium-triethyl acetone, dibenzylmethane, phenyltrifluoroacetyl, phenyltrifluoroacetyl derivatives such as 1,1-diphenylethylene, 1,2-acenaphthylene, tetraphenyl ylbutane, o (methylstyrene derivatives or further such as barium or strontium diphenyl, barium or strontium bis-cyclopentadienyl, barium or strontium trialkylsilyls, barium or strontium triphenylsilyl; mixed organic derivatives such as phenylbarium iodide, methyltrontium iodide, barium or strontium salts of secondary amines; ketone metal compounds such as barium or 59109 1+ strontium benzophenone, or strontium cinnamone and similar alkyl products, as well as sulfur-containing homologues; naphthalene, anthracene, chrysene, diphenyl compounds of barium or strontium.

Examples of Group II B or III A organometallic compounds are:

Dialkyl zinc or cadmium such as diethyl zinc, diethyl cadmium; halogenated or non-halogenated organoaluminum such as triethylaluminum, triisotylated aluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum sesquichloride; dialkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride, etc.

The Kbcatalytic system can be formed by the following two preferred alternatives:

According to a first alternative, the various components of the cocatalyst system are dissolved separately in a hydrocarbon solvent, preferably the same one used later in the polymerization or copolymerization reaction, so that the additions to the reaction system can be carried out separately. Alternatively, the cocatalyst is "preformed" by mixing the barium or strontium compound and the Group II B or III A organometallic compound in a hydrocarbon solvent. These formed cocatalysts are special in that they are more soluble in hydrocarbon solvents and in that they retain their high activity for a long time. Indeed, this mixture of the two parts of a cocatalyst has the complete or partial solubility of a barium or strontium compound, especially compounds normally insoluble in a carbon medium, such as hydrides, acetylacetonates and most alcoholates. As a result, the use of a preformed co-catalytic system is particularly advantageous. According to a first alternative, the components of the cocatalytic system dissolved in the hydrocarbon solvent are separately introduced into a reaction at the beginning of the reaction at the same time as the organic lithium initiator to form the catalytic compound "in situ", or during the polymerization together in small portions or once, or one after the other. This method is particularly suitable for those barium or strontium compounds which are soluble in the solvents considered.

It is self-evident that only from the moment when the cocatalyst system added to the reaction conditions has reacted with the organolithium compound can the desired effect be exploited, namely an increase in the 1,1-trans-content of the chains and a decrease in the 1,2- or 3-trans-concentrations. decrease. It follows that when the entire cocatalytic system is present immediately from the beginning of the reaction, a high content of 1, t-trans in the chains and a very low content of 1,2 or 3, 4, along the entire length of the polymer or copolymer are obtained.

5 59109

On the other hand, when the components of the cocatalytic system are truncated during the reaction, either together in small amounts or one after the other, products with multiple moieties and different steric structures can be prepared, whereby the cocatalytic systemic addition causes the formation of moieties with a trans-1, U content. high and 1.2 or 3.1 * is low.

Alternatively, when a cocatalytic system in "preformed" form is used, it may be added to the organic lithium initiator either at the beginning of the reaction to obtain a product with a constant end-to-end content of 1,1 * trans or one or more times during the reaction. , in which case it is not desired to obtain changes in the steric structure except from the addition of this or when it is desired to change the structure progressively.

The cocatalytic system of the invention has activity over a wide range of ratios of catalyst concentration to system components.

Depending on the conditions under which the reaction takes place (nature of the solvent, monomers or monomer present, temperature, etc.), the molar ratios between all parts of the cocatalytic system and between these and either the organic lithium initiator or the "living" lithium polymer or copolymers may be different. to obtain the specified concentrations of trans-1, H and 1,2. Thus, these different molar ratios must be arranged according to the reaction conditions in which they operate and the desired steric structures. Thus, for example, in the case of polybutadiene or butadiene-based copolymers, the concentrations are adjusted to 1 * 5 ~ 95% for trans-1, α-bonds and 12-3% for 1,2-bonds, and in the case of polyisoprene or isoprene-based copolymers to 25 ~ 1 * To 5% (trans 1.1 *) and 10-5% (3.1 *) · As a result, the optimum concentration of one catalyst part depends on the concentration of the other parts of the catalyst. However, certain limits can be set for different molar ratios to achieve optimal trans-1,1 + concentrations and minimum 1,2 or 3,1 * concentrations in the chains.

These limits are as follows:

mol (R) Me IIIA or (R) Me IIB

0.2 £ ----- 10 mol of Ba or Sr compound and 0.25 / mol of Ba or Sr compound ^ ^ mol of Li and preferably: „c mol of (R) - Me IIIA or (R) - Me IIB ^ 0.5 ^ _3 _2_ ^ 6 * “mol of Ba or Sr compound 6 59109 and n * mole of Ba or Sr compound ^ Λ ^ O j ^« T · "" J- * !? mol Li wherein the radicals R, which may be the same or different, denote a hydrogen atom or an alkyl group which may be substituted by one or more halogen atoms, and Me IIB is zinc or cadmium and M IIIA is aluminum or boron.

Using the catalytic composition according to the invention, products are obtained which have a high content of chains 1, 7 and a low content of chains 1, 2 or 3, but which nevertheless retain their elastomeric nature, a process for polymerizing and copolymerizing monomers to obtain these products. .

According to the first polymerization alternative, a product with a high content of 1, L-trans chains and a low content of 1,2- or 3, 4-chains along the entire length of the polymer or copolymer is obtained when the catalytic compound is added at the beginning of the reaction.

According to another alternative, the polymerization results in polymers and copolymers having moieties and different or progressive steric structures when the moieties of the catalytic compound are added to the reaction conditions one or more times together or separately.

Products with a high trans-1 '^ chain content, prepared using a lithium-based catalyst system, have a special ability to be elastomeric and also suitable in blend form for the manufacture of rubbers, in contrast to other polymers with a high trans-1,1 content, which have hitherto been prepared by various catalytic systems and which are plastic and frangible at ordinary temperature because they are crystalline.

Mixtures made from the products obtained by the process of the invention in a vulcanized state have, due to their high trans-1, li content, such properties as improved green strength, very high breaking strength and length, better dimensional stability.

These blends with improved properties are thus suitable for providing better rubbers which can be used especially in the manufacture of outer tires.

The following examples are provided to illustrate the invention.

Example 1

Butadiene-styrene copolymerization with n-butyllithium-cinnamone-barium-triethylaluminum

Preparation of the ecocatalyst

As the cinnamone-barium complex is soluble in toluene, it has been possible to study the specific effect of each part of the cocatalyst, the ratio Ba / Al has not been determined under the reaction conditions due to solubility.

7 59109. . 3 · ·

The cinnamon-barium complex is prepared in a 250 cm Steime flask under a purified nitrogen atmosphere by dissolving 0.1 mole of cinnamon (diphenyl-1,6-pentane).

O

diene-1,1-ion-3) 50 cm. tetrahydrofuran with a suspension of 1.5 g of finely ground barium metal. After stirring for about 20 hours at room temperature, a red solution is obtained which is filtered. Evaporate this solution in vacuo. After two washes, the resulting brown precipitate is dissolved in heptane with toluene, still under a purified nitrogen atmosphere, to give a 0.025 molar barium solution.

Copolymerization 3. .

Two sets of experimental copolymerization are carried out by adding 250 cm Steinie flasks as a catalytic system: varying amounts from 0 to 200.10 moles of triethylaluminum.

—Ö ... ...

- 50.10 moles of active n-butyllithium as defined above.

No barium compound has been used in the first series. 50.10 moles of cinnamonibarium have been added to each flask in the second series.

O

The copolymerization is carried out in a flask with cyclohexane (123 g per 250 cm in a Steinie flask) and 9.225 g of butadiene and 3.075 g of styrene.

The reaction flasks are placed in a heat bath at 70 ° C where they are mixed for varying times to obtain samples corresponding to increasing percentages of change.

Tables IA and IB give the results obtained with a 50% change rate. First set (/ b & J = Q)

Table I A

Moles AI-trig Time 50% change-% \% 1.2 wt% styrene-log.

ethyl x 10 to achieve a trans-1, copolymer viscosity (Steinie bottle site i) number ^ 0 30 min. 53 8 2 2.6 100 <* 30 min. 5b 8 2 1.2 i 200 <30 min. 5b 8 i 2 0.9 --— [- 1

Second series (fB & J = 50.10 ° moles / bottle):

Table I B

Moles of Al-Tri- Time 50% Change% J% 1.2; weight% styrene-log.

ethyl x 10 “6 to achieve trans-l, k j copolymer viscosity (in Steinie bottles per thesis) ________ number *> 1 0! 300 min. 5b \ 9 16 2.0 25 210 min. 62.5 | 6 12.5 1.6 50 150 min. 75 b 11.5 1.3 75 105 min. 80 I 3.5 9 1.1 100 90 min. 78 5.5 7.5 1.0 200 50 min. 76 j 6! 5.5 0.9 I ': 1 8 59109

Looking at these results, the effect of each added compound on the ether structure ($ trans-1,4 and io 1,2 concentration) of the resulting copolymers and further on the reaction kinetics, the resulting specificity and the styrene coupling mode is observed.

With respect to the effect on the etheric structure and in particular on the trans-1,4 and 1,2 concentrations, it can be seen that a reliable effect is obtained only when all three parts of the catalytic system are present in one reaction; if one is absent, an etheric structure is obtained which is quite close to that obtained by the use of n-butyllithium alone.

Example 2

Polymerization of butadiene with n-butyllithium and a "preformed" co-catalyst by means of its system: barium acetylacetonate-aluminum-aluminum

Manufacture of cocatalyst

Barium acetylacetonate is prepared directly by the reaction of acetylacetone and barite in anhydride methanol.

The manufactured product is insoluble in hydrocarbons. A soluble llsa-talytic system is obtained with stirring, under a purified nitrogen atmosphere, for 15 min. time at room temperature, barium acetylacetonate and trialkylaluminum in the presence of a hydrocarbon solvent.

Three systems are manufactured:

System A: 5.52 millimoles of barium ethyl acetonate is suspended in 170 g of normal heptane, 23.4 millimoles of commercial triethylaluminum at a concentration of 0.92 M are added. After mixing, a clear solution is obtained with a barium content of 2.9.10 -M and an aluminum content of 11.3.10 -M.

System B »To 5.85 mmol of barium acetylacetonate suspended in 170 g of toluene is added 26.3 mmol of commercial triethylaluminum, 0.92-M. After mixing, a clear solution is obtained with a -2 -2 • barium content of 3.2.10 -M and an aluminum content of 11.6.10 -M.

System C: To 5.58 millimoles of barium acetylacetonate suspended in 170 g of heptane is added 25.1 millimoles of commercial triisobutylaluminum, 0.79-M. After stirring, a clear solution is obtained, -2 -2 with a barium content of 2.4 to 10 -M and an aluminum content of 11.8.10 -M.

Polymerylate These three additional catalyst compounds are used in combination with normal butyllithium to polymerize butadiene in heptane solution (first series of experiments) or toluene solution (second series of experiments).

9 59109 These sets of tests are placed in 250 cm3 Steinie bottles closed with a rubber stopper through which the various substances necessary for the polymerization are added. To these flasks are added, in a purified nitrogen atmosphere (about 1 bar), 123 8 solvent (heptane or toluene), then 12.3 g of butadiene, then one of the above-mentioned additional catalytic systems and finally n-butyllithium. The flasks are placed in a heat bath at 60 ° C where they are stirred for three hours.

After three hours, the polymerization is stopped by adding to each vessel a solution of 0,25 cm3 of methanol in toluene at a concentration of 60 g / l. A phenolic antioxidant (Agerite Geltrol, manufactured by Societe Vanderbilt) (2 cm3 of a 246 g / l solution) is also added.

The polymers are then recovered by coagulation with a methanol-acetone mixture and dried under reduced pressure in an oven (80 ° C to 0.2 bar for 15 hours).

From the samples thus obtained, the degree of conversion of butadiene to polybutadiene obtained is determined, the intrinsic viscosities determined at 25 ° C in a toluene solution of 1 g / l and the ethereal forms.

The results obtained are summarized in Tables IIA and IIB:

First series (hentane solvent)

Table II A

active log · 1 trans_

Kbcatalytic initiator Conversion viscosity 1.2 system - n-BuLi ^ -1 sio /% ratio 1 __ (x 10 moles) ___ number V______ (Reference polymer) 50 100 2.4 51 8 (42.10 "6 moles Ba 66 54 1.6 77 4 j 104.10 "6 moles of AI 85 61 1.5 03 3 S45.10" 6 moles of Ba 41 59 1.8 73 4 163.1C "6 moles of AI 77 71 1.6 82 4! ^ 34.10" 6 moles Ba 45 56 1, 7 73 4 ^] 167.10 "6 moles AI 81 70 1.5 33 3

In addition to the amounts shown, calculated as active, additional doses of n-BuLi are added to remove impurities left over from the reaction conditions.

10 5 91 0 9

Second series (toluene solvent)

Table II B

Kbcatalytic active conversion / τ. _ t initiator sio / Ji viscosity * * -% 1.2 system n-BuLi * thesis Ί »^ ____ (x 10 ~ ° moles) ___ figure η ___ (Vertol lupolymer) 50 100 2.5 51 12 ί 42.10” ^ moles Ba 28 24 0.8 74 5 164.10 ”^ moles Ai ζζ ηξ, 1.3 72 5 S 45.10” ^ moles Ba 50 58 1.0 72 5 163.10 ”6 moles AI 77 33 1.1 70 5 (34.10” 6 moles Ba 50 40 1.0 76 5 ^) 167.10 ”6 moles of Al 36 70 1f2 78 5 * Additional amounts of n-BuLi are added to the slurry of the indicated amounts, calculated as active, in order to eliminate the impurities of the reaction conditions.

Example 5

Catalyst for the "preformed" formation of butadiene with n-butyllithium by means of its system: barium dimethylbenzylmethane-triethylaluminum

Manufacture of cocatalyst

Dibenzylmethane barium chelate is prepared from dibenzylmethane and barite in anhydride methanol.

The product prepared is insoluble in hydrocarbons, the hocatalytic system is prepared with stirring, under a purified nitrogen atmosphere, as a suspension of 125 g of heptane, 5 · 2 millimoles of dibenzylmethane barium and 26 millimoles of commercial triethylaluminum, 0.84-M. This mixture is heated to 60 ° C for 1/2 hour with stirring to dissolve the chelate. A yellow solution is obtained which remains clear after lowering to room temperature. It has a concentration of 5.10 -M for barium and 15.10 -M for aluminum.

Polymerol This cocatalytic compound is used in combination with normal butyllithium to polymerize butadiene in heptane solution.

The polymerization conditions are the same as above (250 cm 5 Steinie flask, 125 g heptane and 12.3 g butadiene, 3 hours, 60 ° C).

11 5 910 9

Received results

Table III

- --H read.-1 -; -—-----% trans

Kbcatalytic, viscosity, 1 RT% system 1.2 act. n-BuLi sio /> chapter - ~ -— --— ----_______________ {20.10 moles 3a Λ_. ,, “6 ,, _, _. __ _ _) _ 6 12.10 moles 55? .0 77 2.9

^ 100.10 moles of AI

20.10 “^ aool 65 1.9 81 2.6 2G.10- (inol 70 1.9 32 3.0 (40.10 ^ moles Ba„ _-6 η y n_ _ _ / _ g 40.10 moles 63 i »^ 36 2.0

^ 200.10 moles of AI

(60.10 ** ^ moles Ba A ,,.-6 _, Λ „) _ s 20.10 moles 47 78 2.6

^ 300.10 ™ moles of AI

36.10_vinol 51 1.1 87 2.3 59.10 ~ ^ol; 61 1.1 90 2.4 75.10_iol; 65 i, 1 90 2.7 122.1 (Trawl. 74 0.9 31 4.2

Example 4

Copolymer foundation of butadiene, 1a styrene with n-butyllithium .1a using the "prefabricated" kbcatalytic system of Example 5 The same cocatalytic compound dibenzylmethane barium triethylaluminum is used.

The copolymerization is carried out in a 250 cm 3 Steinie flask as above under the same experimental conditions.

To each reaction flask is added: - 123 g of heptane - 12.3 S of monomers: 9.225 g of butadiene and 3.075 g of styrene (i.e. 25 per dose) - 65.10 ** ^ moles of active n-BuLi - 60.10 "^ moles of cocatalyst based on the complex as barium (i.e. with 300.10 moles of Al).

The results obtained at 80 ° C as a function of reaction time are as follows:

Table IV

12 591 09 I '- r - 1 weights of styrene Etheric structure of the polybutadiene moiety

Conversion in copolymer - ______— $% trans 1.4 1 * 2 25 min 28 9 86 4 60 min 56 10 86 4 120 min 71 13 85 4 180 min 84 15 36 4 18 hours 94 21 86 4

The final copolymer obtained in 1 hour had an intrinsic viscosity of 1.1.

Example 5

Preparation of n-butyllithium-barium-nonylphenolate-triethylaluminum or diethylzinc cocatalyst for a butadiene-styrene copolymerol system

Barium nonylphenolate is prepared by contacting nonylphenol (0.02 mol) and barite (0.01 mol of BaiOH) in the presence of 100 cm3 of toluene. The mixture is stirred hot (60-80 ° C) until the barite is completely gone. About half of the solvent is evaporated off under vacuum so that all the water formed is removed and the concentrated solution is then made up to 100 cm3 with fresh toluene. A solution of anhydride-barium nonylphenate in toluene at a concentration of about n / ίο is thus obtained.

Konolymerisointl

Copolymerize butadiene and styrene in 250 cm3 Steinie flasks with added: - Heptane 123 g - Butadiene 9 * 225 g - Styrene 5 * 075 g - n-butyllithium 50,10 8 moles (calculated as active product) - barium nonylphenolate 50,10 ' ^ moles

To complete the catalytic system, the following are added: - either 100.10- ^ moles of triethylaluminum - or 100.10 ^ moles of diethylzinc 13 591 09

Neither of these compounds is added in the comparative experiment. The copolymerization is carried out at 70 ° C for varying times, as defined in Table V, which shows the results obtained.

Table V

.

weight-%

Time, min. Conversion of / styrene ^ brons ^ ^ »2 copolymer

45 I

60 45 13 52 11 [Ai] * [Zn] = 0 90 120 58 16 53 10 180 45 60 46 9 71 5 [AI] = 100 p- 90 moles „„ 120 1Q0 72 12 72 4 45 37 δ 75 5 60 [Zn] = 100 p- $ o 59 8 75 4 moles 120 180 j 72_ 13 77 4

Example 6

Butadiene-styrene copolymer, 1a copolymers. having two specific moieties with different ether structures This copolymer is obtained by adding, during the polymer foundation, one of the three components of the catalytic system, triethylaluminum under conditions, with normal butyllithium and barium compound added together immediately at the beginning of the reaction.

To 250 cm 3 Steinie flasks, still under a purified nitrogen atmosphere, are added 123 S heptane, 9 * 225 S butadiene, 3.075 g styrene, 50.10 moles of active n-butyllithium, 50.10 moles of barium nonylphenol, prepared as in the previous example. . Allow to copolymerize for one and a half hours at 70 ° CtBsa.

and 59109

The conversion achieved is $ 54. The copolymer contains 16 l of styrene and has the following ether structure: $ 53 trans-1,4 and 10 1,2 (in its polybutadiene moiety).

-6

100.10 moles of triethylaluminum per flask are then added, then the copolymerization is allowed to continue at 70 ° C for one and a half hours. The final copolymer contains $ 14 styrene. In addition, an average of 61% of butadiene chains have joined the 1,4-trans forms and 8 $ to the 1,2-forms. The total conversion rate is $ 76>.

This means that the resulting copolymer contains two parts - the first, which represents 71 .mu.l of the total copolymer, contains, on the one hand, 16 .mu.l of styrene and $ 53 .mu.l of trans-1,4-formations, structure.

the second, representing 29 l of the total copolymer, contains on the one hand 9 l of styrene and on the other hand 79 l of trans-1,4- and 4 l of 1,2-formations from the polybutadiene moiety.

Example 7

Butadiene Polymer Foundation n-Butyllithium .1a "preformed" cocatalyst for its system; barium alcoholate-chlorinated or non-chlorinated organic aluminum

Manufacture of cocatalyst

Various barium alcoholates and various organoaluminum compounds are used to form various cocatalytic systems under the following general conditions:

Add about 2 g of barium alcoholate 250 cm? In stein bottles in a purified nitrogen atmosphere. 100 cm3 of heptane are added, then the amount of alkyl or chloroalkylaluminum given in the following table.

The flasks are then placed in a heat bath at 60 ° C where they are stirred for six hours. Any barium alcoholate which has become insoluble is filtered under a purified nitrogen atmosphere and the barium in solution is determined.

Table VII A Brochure For each alcoholate and organoaluminum used, the amounts of product added (per 100 cm3 of heptane), the amount of barium (mol / t) obtained after dissolution and filtration, as well as the yield of dissolved barium compared to the amount of barium alcohol added and cocatalyst thus prepared. code.

Table Over A

15 591 09

Barium Organic Moles Grams- Ba-Alko- Saan- Code Alcohol- Aluminum Barium- Alcohol Cholate to Drawn Carbate- Aluminum Final Tia Concentration _____ __________ moles / l ______

Triethyl 8.6 .10 "3 25.8.10" 3 7.4 .10 "2 86 A

aluminum 9.05.10 "3 18.1.10-3 4.5 .10" 2 49.3 B

Barium- 5

methano-9.5.10 J 9.5.10 5 1.5.10 15.9 C

tile ---- r- --r ------

tri-isobu- 7.3 .10 ”21.8.10" J 1.9.10 "* 26 B

tyixalu- 3 0 .10 "3 16,0.10" 3 1,6 .10 "2 20 E

muni 9 - λ. 2

3.9.10 "J 8.9.10" J 0.75.10 "8.4 F

triethyl 8.8.10 "3 26.3.10" 3 2.9.10 "2 32.8 G

aluminum 9.15.10 "3 18.3.10" 3 1.5. 10 "2 16.4 H

Λ A A

ethano 9.5 .1C "· 5 9.5.10" 0 0.5 .10 "* 5.2 I

methacrylate --------- r ji --- ----

ethyl alcohol 8.0.10 "J 24.0.10 * J 2.3.10" 28.7 J

chloride 8.6 »10 17.2.10 1.15.10 13.4 K

9.2 .10 "3 9.2.10" 3 0.3 .10 "2 3.3 L

triethyl-9.1.10 "3 27.2.10-3 6.2.10-2 68.2 M

aluminum 9.3 _10 * 3 18.6.10 "3 5.5 .10" 2 59.2 N

Barium-ethyl al- -8.3 .10 "3 25.0.10" 3 1.85.10 "2 22.2 0

tert mine — sesqui— - _ m- ^ 17 f- in ”^ o in ~ ^ 79 S P

butanol chloride 6.3 .10 17.6.10 2.6 .10 29, o P

prepared triisobutyl- 7.9.10-3 23.7.10-3 4.35.10 "2 61.5 C

liuminium g, 5.10 * 3 17.0.10 * 3 3.95.10 * 2 46.5 R

ethylaluminum ί 8.05.10 "3 24.2.10 * ~ 3.67.10 * 2 45.6 S

nidichloride 8f6, 10 "3 17.2.10 * 3 0.35.10- 2 4 T

Polymer Foundations These cocatalytic systems polymerize Buta diene under the following conditions:

Add 250 cm3 to the Steinie flask: - heptane 123 g - butadiene 12.3 g - additional catalytic system 50.10 moles of barium - active n-butyllithium: amount specified in the following table.

16,591 09

The polymerization reaction is carried out with stirring for 14 hours at 70 ° C.

The results obtained with Sri additional catalytic systems are shown in Table VII Bt

Table Over B

........... 1 I ---- p-f ------- moles log.

acti- viscose-. . „. Λ

Cocatalytic vista. K? NX ^ r_ thesis- ^ 1 * 4-trans% 1,2 system Bu-Li6 310 ^ number X 10 y \ __ A (methanolate - Et 2 Al) 127 93 1 * 41 36 3 B () 99 99, 5 1.43 85 3 D (methanolate - iso-Bu 2 L) 56.5 97.5 0.72 38 3 G (ethanolate - Et 2 Al) 56.5 73 1.66 79 3 M (tert-butanolate EtjAl) 103.5 94.5 1.65 83 3 N () 56.5 97.5 2.15 85 4 0 (tert-butanolate) 80 94 0.61 87 2

Et, Cl, Al2 / P (1 *) 33 90 0.91 85 3 Q (tert-butanolate iso-) 141 100 1.28 S1 3 R - _Bu3A1 ^ go 58 1f90 70 5

Example 8

Polymerization of Butadiene The n-butyllithium, 1a "preformed" cocatalyst of its system is: strontium alcoholate-chlorinated or el-chlorinated organoaluminum compound. through.

Manufacture of cocatalytic system_

Same conditions as in the previous example (except stirring for 7 hours at 70 ° C instead of 6 hours and 60 ° C).

The amounts reported also correspond to 100 cm3 of heptane.

Stronti- Organic Moles Grams- Sr-Alcohol- I get- Code * umalko- Aluminum- Strontium Atomic Preparation Lolto Cholate Compound Alcoholate- Aluminum Chubby 56 tia Concentration

triethyl-6.10-3 3 25.9.10 "3 2.7.10" 2 31.4 U

aluminum _______ _ _ _ *

Strontium diethyl al- J8,15.10 ”3 24,5.10” 3 0,95.10 2 11,6 V

methanolate mine chloride

Sr-Ethaethylaluminum 7.8.10 "3 23.4.10" 3 1.05.10 "2 13.5 W

nolate nisicchloridel - Χϊ 59109

Polymerization

Same conditions as in the previous example, except: - polymerization for 6 hours at 70 ° C and 50.10 "** moles of etronium alkoxolate per bottle.

Table VIII 3 Moles Conversion

Catalytic act.BuLi sio /% viscosity bonds- ^ * | f4_trans% 1.2 system x 10 “6 tllu ^ u '23.5 94 0.76 80 5 tr (methanolate 42.3 99 O, Cl 82 4

Et3A1) 61.1 100 0.83 31 4 94 100 0.32 Cl 5

Example 9

Polymerization of Butadiene by a "preformed" cocatalytic system, which is a barium hydride-chlorinated or non-chlorinated organoaluminum compound Preparation of a cocatalytic system

Preparation conditions according to Example 7 (6 hours, 60 ° C), 2 g of barium alcoholate are replaced by 5 l of barium hydride.

Prepare two sets of cocatalytic systems, one in heptane (100 cm 3 / Steinie pulp), the other in toluene (20 cm 3 flask).

Tables IX A and IX B show for each series, the products added per Steinie bottle, the final amount of barium in solution after filtration, as well as the yield of barium as before and the product code.

Table IX A

Preparation in heptane (100 cm / Steinie flask) ___ H2Ba final Organic grammatical pi- Yield, Code aluminum atom moles HgBa content, io compound aluminum mole / l

20.7.10 "3 20.7 * 10" 3 1.5.10 "2 9 I

Et "Al 53.6.10" 3 26.3.10 "3 2.4.10" 2 12 II

58.2.10 "3 19.4.10" 3 1.7.10 "2 12 III

24.9.10 "3 24.9.10" 3 0.21 .10 ~ 1.2 IV

Et3Al2Cl3 53.2.10 "3 26.6.10" 3 4.2 .10-2 24 V

78.3.10 "3 26.1.10- 3 6.4 .10 ~ 2 43 VI

23.6.10 "3 23.6.10" 3 0.06.10-2 0.3 VII

It would be 46.4.10 "3 23.2.10- 3 0.1 .1C-2 0.6 VIII

90.3.10 "3 30.1 .10- 3 0.1, 1 <Γ 2 0.5 IX

20.2.10 "3 20.2.10" 3 0.15.10- 2 0.9 X

EtgClAl 30.4.10 "3 15.2.10" 3 0.18, -10-2 1.4 XI

43.2.10 "3 14.4.10" 3 0.6 .10- 2 5.8 XII

Table IX τ »59109 18

Preparation in toluene (2o cm3 / Steinie flask) j j -

Organic gram-moles »w n, H2Ba 1θ“! 0 aluminum compound {'atom tt2Ba bulging Yield Code diete aluminum content, --——-----— _ _

21.0. 10 21, o..i0- 3 7.3.10 “2 11.5 XIII

Et3Al 43.4.10 21.7 <10- 3 7.2.10 “2 15.8 XIV

__58 * 2 <1 ° 19 * 4 ^ 10 ~ 3 5.2.10 “2 15.1 XV

17.3 * 10 3 17 »3.10 ~ 3 18.6.10“ 2 39 XVI

Et3A12Cl3 41.3.10 ^ 20.9.10- 3 21.3.1θ "2 61 XVII

__ »10 1 ° f7.10“ 3 22.7.10 “2 89 XVIII

19.9.1 ° 3 19.9.io ~ 3 10 .10 "2 17 XIX

EtClgAl 25.3.10 17.9.io ~ 3 19.4.10 “2 49.5 XX

__51 »ΰ · 10 17.2.io“ 3 21.7.10 "2 70.5 XXI

21.0. 10 3 21, o, 10- 3 1,3.10 “2 2 XXII

EtgClAl 35.8.10 * 17.5.10 “3 1.2.10“ 2 2.8 XXIII

55.2.10 1ö, 4.10 “3 1.4.10“ 2 4.1 XXIV

Polymerlseiptl

Same conditions as in Example 7 * - polymerization at 70 ° C for 24 hours in heptane - amount of BaH 2/250 cm 3 reaction flask »50, 10 moles.

The results obtained as a function of the amounts of n-butyllithium used are shown in Table IX C: 19 591 09

Table IX C

log.

Organic al- Kokata- Mole Conver- viscosine compound lytic ab. sxo /% thet number% 1,4-trans% 1.2 BuLi of the system.

identifier x I0_t> I 418 84 0.72 90 3

Et3Al II 836 100 0.48 86 3 III 1 265 100 0.34 86 3 E u V 1 522 100 0.57 85 3 6 2 * VI 1 458 100 0.57 84 4 XIII 340 100 0.71 86 2, 4

Et ^ al XIV 654 1 00 0.50 89 2.8 XV 1 064 1 00 0.39 84 4 XVI. 556 100 1.07 67 3

EtyUgCLj XVII 610 97 0.91 78 3.7 XVIII 740 83 0.74 86 2.7

EtCl Al XIX 540 92 1 · 15 70 5 2 XX 497 100 1.14 71 5

Example 10

Polymerization of Butadiene with n-Butyllithium-Barium Naphthenate Diethyl Zinc System Catalyst Preparation

Barium naphthenate, prepared from commercial naphthenic acid by neutralization with soda in water and doping with barium chloride, is a salt soluble in toluene »A barium naphthenate solution of 0.113 mol / liter of barium in toluene is used.

Polymerization

The butadiene is polymerized under the same conditions as before in a 250 cm 2 Steinle flask, 12.3 S butadiene 123 S per heptane, in addition to 50.10 moles of barium naphthenate and 50.10 moles of active n-butyllithium per flask, for 6 hours. at 70 ° Ciesa.

The results, as a function of the amount of zinc diethyl added, are shown in Table X.

Table X

? σ 59109

Moles of diethylzinc K J & oeiteel. X 1,4-tran. X 1,2 X 10 ~ 6 __ ^ __ t slider η ___ 100 54 1.72 77 5 200 57 1.45 79 5

Example 11

Polymerization of Iso-prene by the n-butylmethyl barium nonylphenolate triethylaluminum or diethylzinc system A solution of barium nonylphenate in toluene has been prepared as in Example 5 ·

O

Isoprene (12.3 g) is polymerized in 250 [mu] m Steinie flasks in heptane (123 g) for 6 hours at 70 [deg.] C., per reaction flask: 50.10 moles of active n-BuLi or 50.10 moles of barium nonylphenate - 0, 100 or 200.10 moles of triethylaluminum or diethylzinc. Table XI compares the effect of the combination of these different additives.

Table XI

Moolia Moolia Ba Konver— log. |

Et ^ Altai Et Zn ^ sio /% viscosities -% 1.4- ^ rans% 3.4 3 62 x 1C ~ 6 by volume x 10 η 0 0 100 1.54 18 8 0 50 84.5 1.19 14 10 - 1 - - - - * - --- - 1111 - 100 Et2AI 0 100 1.15 22 6 100 Et ^ Λ1 50 93.5 1.06 35 8 200 Et ^ Al 0 100 0.83 21 6 200 Et3Al 50 97.5 0.74 40 8 100 EtgZn 0 100 1.35 21 7 100 EtgZn 50 96.5 1.05 25 7 200 Εΐ ^ Ζη 0 100 1.21 23 6 200 Et ^ Zn 50 92.5 0, 87 25 7 2i 59109

Example 12

Copolymerization of isoprene-styrene using the same system as in Example 11.

Operate under the same polymerization conditions in 230 cm 2 Steinie flasks, heptane (123 S) with the addition of 9 * 24 g of isoprene and 3.08 g of styrene (25 # relative to isoprene). Copolymerize for 2 hours at 70 ° C in the presence of 50.10 mol of active n-BuLi.

Table XII

Moolia log.

Et ^ Al or Et Zn Moles Ba Conver- viscose- $ styrene-% 1,4-trans% 3,4 J - 62 x 10 ”6 I sio /% tea ^ volume | ni I il x 10 O 50 57 0.96 10 13 12 100 EttyM - 33 0.63 17 24 7 200 Et3Al - 70 0.71 15 33 9 100 EtgZn - 73 0.37 17 26 7 200 EtgZn - 73 0, 80 17 25 8

Example 13

Copolymerization of butadiene-vinyltoluene with n-butrelithium barium nonylphenolate-triethylaluminum 3

Copolymerize in 250 cm flasks: - 9 * 24 g butadiene - 3 * 08 g vinyltoluene (commercial mixture with 2/3 methamethylstyrene and 1/3 paramethylstyrene) - 123 g heptane - 50,10- ^ moles of active n-BuLi - 50 , 10 moles of barium nonylphenate to 200.10 moles of triethylaluminum for 3 hours at 70 ° C.

The results obtained are as follows: - degree of conversion obtained: $ 64> - 0.97 - 9 vinyltoluene present in the copolymer -82 io trans-1,4-chains and $ 3 1,2-chains in the polybutadiene phase.

Example 14

Conolymerization of butadiene-tert-butylstyrene using the same system as in Example 15 3 25Ο cm Per Steinie flask add: - 9 * 24 g of butadiene - 3 * 08 g of tert-butylstyrene (95 para - 5 # ortho) 22 591 09 - 123 g of heptane - 50.10 moles of n-BuLi, active - 50.10- ^ moles of barium nonylphenolate - 200.10- ^ moles of triethylaluminum are copolymerized for 5.5 hours at 70 ° C.

The results obtained are as follows - * 7 - 1.12 -7 i »tert-butylstyrene present in the copolymer -85 $> trans-1,4 chains and $ 3> 1,2 chains Example 15

Mechanical properties of a mixture for rubber based on butadiene-styrene copolymer. with a high trans-1.4 content and a low 12 content 1. Preparation of the copolymer The same catalytic system as in Example 3 or 4 * - n-butyllithium - preformed cocatalyst system is used. barium dibenzylmethane-triethylaluminum.

The polymerization is carried out in a 10 liter reactor, under a purified nitrogen atmosphere, containing ons - solvent: heptane: 5040 g / "butadiene: 378 g - monomers \ (styrene: 126 g ^ - z - catalyst: n-butyllithium, active: 1.64.10 ' moles (barium: 1,64,10- ^ moles

- additional catalytic system S

(Aluminum: 8.2.10 μmol for two hours at 80 ° C.

The conversion is 75% and the logarithmic viscosity number 3.4 is obtained.

Triple-chain grafting is then carried out with the addition of 1.64.10 mol of diphenyl carbonate to the active conditions, according to FR patent 2,055,786. Allow to react for 20 min at 80UC. Methanol is then added to stop the reaction as well as the antioxidant (0 # 5 by weight relative to the gum) and the elastomer (about 380 g) is recovered by removing the solvent with steam and drying in vacuo.

The final viscosity after grafting has changed to 1.9. The Mooney viscosity (1 + 3 at 100 ° C) is thus 45 ·

The resulting copolymer has the following ether structure: 5,910 9 to 75 trans-1,4 l for the butadiene moiety

- $ 5> 1.2 J

The combined styrene content is 8 ft.

2. Rubber compound The elastomer described below is used in the preparation of a mixture having the following composition: - elastomer 100 - stearic acid 2 - ZnO 3 - Antioxidant (4010 ΝΑ) 1 - Black HAF Philblack 0 50 - Process oil Sundes 8125 5 (aromatic) - santocure 1 - sulfur 1, 6

Prepare the same blend with a commercial butadiene-styrene copolymer (SBR 1500) for comparison. These unvulcanized alloy samples are subjected to force-elongation measurements (green-stretch measurement).

The results obtained are as follows:

Table XV A

Comparison of SBR 1500 Experience SBR

Elongation at break (f <·) 380 1490

Breaking strength (g / mm2) 20 92

Maximum force (g / mm2) 36.5 105

The mixture made with the elastomer according to the invention has better mechanical strength than the reference mixture.

Both mixtures are then cured for 60 min. time at 144 ° 0. The mechanical properties obtained are shown in Table XV B.

Table XV B

Comparison SBR 1500 SBR, according to the invention 1 io elongation factor (kg / cm2) 20 22.5 $ 300 elongation factor (kg / cm2) 95 110

Hysteresis loss 60 ° C: sea ($) 32.8 24.7

Shore durability 68 70

Elongation at break ($) 665 500

Breaking force (kg / cm2) 250 225 t -------- _ _ - - - - - - - - 2U 5 910 9

It can be seen that the elastomer according to the invention, i.e. SBR with a high trans-1,4 content and a low 1,2-content, has rubber properties and even good rubber, considering the level of hysteresis losses obtained.

Claims (8)

A process for homopolymerization of butadiene or isoprene or copolymerization of each other or with styrene to homo- or copolymers exhibiting a high content of trans-1, + bonds and a small amount of 1,2 or 3-U bonds , characterized in that the monomers are reacted with a catalytic composition consisting of a lithium organic initiator and a cocatalyst compound comprising a barium or strontium compound and a metal organic compound of a group IIB metal in Mendeleev's periodic system, which metal is zinc or cadmium, or a metal-organic compound of a metal of group IIIA, which metal is aluminum or boron, and that the catalytic composition is added to the reaction space such that the content of trans-1,1 * bonds is continuously adjusted to a value of a U5-95%> wherein the content of 1,2-bonds is 3-12 in the case of polybutadiene and copolymers based on butadiene, b) 10-1 * 5%, the content of 3,1 * -b inhalations are 5-10%, as it applies to polyisoprene and copolymers based on isoprene. 2. A process according to claim 1, characterized in that the cocatalyst is formed in advance and added to the reaction space at the same time as the lithium organic initiator at the beginning of the reaction. 3. A process according to claim 1, characterized in that the cocatalyst is formed in advance and added to the reaction space. at once or in portions during the course of the reaction, which was initially initiated with the lithium compound. H. Process according to claim 1, characterized in that the components of the cocatalytic system are added to the reaction space a) each at the beginning of the reaction at once or in portions simultaneously with the lithium organic initiator, b) one after another in arbitrary (c) together in one or more portions during the course of the reaction, which was initially initiated with the lithium organic initiator. Process according to any of claims 1-Π, characterized in that butadiene is homopolymerized or copolymerized with styrene in the presence of a catalytic composition consisting of n-butyllithium, barium phenolate. and trialkyl aluminum.