DE2345755A1 - METHOD OF MANUFACTURING DIESEL ELASTOMERS USING ALKYLLITHIUM AS A CATALYST - Google Patents

Description

PATENT ADVOCATE BÜfiO TlEDTKE - BüHLING - * KlNNE

TEL. (0811) 539653-58 TELEX: 524845 tlpat CABLE ADDRESS: Germaniapatent Munich

_{O /} rnrr 8000 M Ü Π CH β Π 2

34b / bb Bavariaring4

P.O. Box 202403 H. September 1973 B 5582 / case F-4486

Uniroyal, Inc.
New York (USA)

Process for the preparation of diene elastomers using alkyl lithium as a catalyst

The invention relates to a process for the preparation of conjugated diene copolymers by a solvent process. In the process according to the invention, a soluble cocatalyst is used, which consists of an organic Lithium compound and a complex of potassium phenolate will. The invention also relates to pseudorandom copolymers obtained by this solution process.

. The following patents are in this area. In U.S. Patent 2,975,160 a method of manufacture is disclosed of random styrene butadiene rubber. The rubber, obtained by this process is characterized by having an increased vinyl content (as much as 27%) what by the presence of a polar organic compound in the polymerization reaction mixture. In the process, organic lithium

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catalysts and a liquid solvent mixture containing a hydrocarbon and a polar organic compound contains, used. Tetrahydrofuran is the polar organic solvent of choice for industrial processes. If the copolymer is to contain styrene in amounts on the order of 35% or more, even higher vinyl contents can be used when using this procedure.

U.S. Patent 3,094,512 relates to a process for making random styrene-butadiene rubber with a low vinyl content. An organic lithium compound is used as the catalyst. The new feature of this procedure is that the monomers are introduced into the polymerization zone at a rate which is slower than the normal rate of polymerization of the system, and it is a requirement that the monomers be controlled with such Speed to be introduced. Polar connections are essentially excluded from the system, in order to obtain copolymers with a low vinyl content.

U.S. Patent 3,294,768 relates to a method for the production of styrene-butadiene rubber. In this case, a catalyst mixture is used which is an organic Lithium compound and an organic sodium, potassium salt or the like salt. The latter salts are completely insoluble in the hydrocarbon solvents and are therefore added to the reaction mixture as solid

substances added. This is in continuous operation or very difficult and complicated when operating on a larger scale. The patent proprietor tried this To eliminate the disadvantage, and proposed that the salt is allowed to pre-react with the organic lithium compound.

In U.S. Patent 3,324,191 a method for the polymerization of styrene and butadiene in the presence of an organic lithium compound, an organic one Sodium, potassium or similar compounds and a polar material such as water and alcohols are described. The usage of water and alcohols, if they are added as such, does not increase the solubility of the sodium, Potassium or similar compounds with itself. The presence of an aromatic hydrocarbon with benzylic Hydrogen atoms like toluene are required to regulate molecular weight. Aging in the warmth is intended to facilitate the solubilization of the catalyst. However, this entails that the catalyst is destroyed.

British patent specification 994 726 describes a polymerization process for styrene and butadiene. Butadiene is added proportionally, but this is a process stage that is extremely difficult to regulate because it is necessary that the conditions in the reactor are exactly known at all times. If the reaction is not exactly

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trolled, the products contain long blocks, especially at the end of the chain. '

US Patent 3,520,858 teaches a solution method for the production of styrene-butadiene rubber described in the hydrogen with an organic lithium catalyst is used. The use of hydrogen keeps the gel formation minimal and enables a strong one Reduction in the amount of catalyst used. The use of hydrogen also results in a regulation of the Molecular weight.

The process according to the invention for the preparation of conjugated diene copolymers is based on the use of a co-catalyst which is an organic lithium compound and contains a potassium salt which is used in the form of a complex with water or an alcohol. The usage such a complex gives a completely soluble catalyst, and thereby control of the polymerization process is possible and copolymers with optimal Establish properties. The molecular weight range of the products according to the invention is usually in the range of 5000 to about 1,000,000.

The copolymers according to the invention are mainly used as rubber for tire treads. To this end

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the copolymers are preferably completely random or pseudorandom-like and have a vinyl content of 0 to 10%, a low Tg (glass transition temperature) and a Vinyl-substituted aromatic hydrocarbon content from 15 to 45%. These properties are easily obtained in the process of the invention. It was further found that the pseudorandom copolymers according to the invention had very good chewing skills for tire profiles or tire treads result. Vulcanizates of the copolymers which contain long styrene blocks have poor hysteresis properties; this results in the undesirable effect that heat builds up or heats up in tires made from such copolymers. accumulates.

The conjugated dienes which are suitable for the process according to the invention preferably contain 4 to 12 carbon atoms in the molecule and include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene and 4,5-diethyl-1,3-octadiene. The vinyl substituted aromatic hydrocarbons that can be used are hydrocarbons, in which the vinyl group is bonded to a core carbon atom. Examples of preferred vinyl substituted aromatic hydrocarbons are styrene, 1-vinyl naphthalene and 3-methylstyrene. Examples from others Compounds of this type that can be used are

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for example 3,5-diethylstyrene, 4-n-propylstyrene, 2,4,6-trimethylstyrene, 4-dodecylstyrene, 3-methyl-5-n-hexylstyrene, 4-phenylstyrene, 2-ethyl-4-benzylstyrene, 4-p -Tolylstyrene, 3,5-diphenylstyrene, 2,3,4,5-tetraethylstyrene, 3- (4-n-hexylphenyl) -styrene, 3-ethyl-i-vinylnaphthalene, 6-isopropyl-1-vinylnaphthalene, 3,6 -Di-p-tolyl-i-vinylnaphthalene, 6-cyclohexyl-i-vinylnaphthalene, 8-phenyl-i-vinylnaphthalene, 7-dodecyl-2-vinylnaphthalene, α-methylstyrene and others. It is desirable that the vinyl-substituted aromatic hydrocarbon in one Amount of about 5 to about 50 parts by weight based on 100 parts by weight of the total monomers is used.

The organic lithium component of the catalyst is similar to the organic lithium compounds used in the known methods can be used. The formula of the lithium compound is RLi, where R is aliphatic, cycloaliphatic or / and denotes an aromatic hydrocarbon group. The group R in the formula preferably contains 1 to 20 carbon atoms, although compounds of higher molecular weight can be used. Examples of suitable organic lithium compounds are methyl lithium, isopropyllithium, n-butyllithium, sec.-butyllithium, tert.-octyllithium, n-decyllithium, phenyllithium, naphthyllithium, 4-butylphenyllithium, p-tolyllithium, 4-phenylbutyllithium, Cyclohexyllithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyllithium i.a.

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The other component of the catalyst is a

Complex of the formula

Rt - Ar - OK · HOR "

where R ¹ denotes an alkyl group which contains at least 8 carbon atoms per group and which contains a maximum of 26 carbon atoms in one or more such groups, R "denotes a hydrogen atom, an aliphatic, cycloaliphatic or aromatic hydrocarbon group, Ar an arylene group which contains an aromatic ring , and y is an integer from 1 to inclusive 3. Such soluble catalysts containing potassium are prepared by reacting certain alkylphenols which are soluble in hydrocarbons with potassium hydroxide or alcoholate, whereby a potassium phenolate is formed in the form of a complex obtained with the reaction by-product.

Rt _ // W-OH + KOR "5 * R '- // \\ - 0 ~ K ⁺ · HOR"

The best way to prepare such soluble complexes is that, for example, potassium t-butoxide with Converting phenol into, for example, heptane, the mixture if desired stirred under an inert gas atmosphere, for example nitrogen, for several hours at room temperature. at In the preparation of the potassium-containing catalyst component, preferred phenols are octylphenol, nonylphenol and polyisobutylphenol. The polyxobutyl group in the latter compound contains an average of 26 carbon atoms.

ι - 0 9 8 U / 0 8 8 7

Suitable potassium-containing reactants are potassium hydroxide and potassium t-butoxide. Other suitable reactants containing potassium as potassium derivatives of the following alcohols: ethanol, 3-propenol, propynol, 1-butene-3-ol _f Methylisopropylcarbinol, n-heptanol, Triptanol, tri-t-butyl carbinol, 1-dodecanol, cyclopentanol, cyclohexanol , oc-terpinol., phenyl carbinol, benzyl carbinol, styryl carbinol, phenol and symmetrical xylenol.

The amount of the organic lithium compound that is used is about 0.1 to about 20 mmol / 100 g Mixture of monomeric hydrocarbons. The amount of potassium-containing complex that is used is referred to as the Li / K molar ratio of the co-catalyst expressed. This ratio should be from about 4/1 to about 25/1 if one an aliphatic hydrocarbon solvent is used in the polymerization reaction mixture, and it should be of be about 20/1 to about 90/1 when using an aromatic hydrocarbon solvent. Becomes a If complete random copolymer is desired, the Li / K molar ratio of the co-catalyst should be from about 4/1 to about 5/1 can be adjusted if an aliphatic hydrocarbon solvent is used, and it should be set from about 20/1 to about 30/1 if a aromatic hydrocarbon solvent is used. If it is desired to make a pseudo-marginal cm copolymer, which blocks up to 3 to 4 units of the vinyl sub-

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• i

containing substituted aromatic hydrocarbons or dispersed in the copolymer chain, should that Li / K-Mo! Ratio of the co-catalyst of over 5/1 to about 25/1 if an aliphatic hydrocarbon solvent is used, and from over 30/1 to 9O / 1 if an aromatic hydrocarbon solvent is used. If a mixture of aliphatic and aromatic hydrocarbon solvents is used, so a complete random copolymer is obtained if the Li / K molar ratio of the co-catalyst to a value im Range of 4+ (0.24 χ vol% of the aromatic hydrocarbon solvent) to less than 6 + (0.24 χ vol-% des aromatic hydrocarbon solvent). It will be similar when a mixture of aliphatic and aromatic Hydrocarbon solvents is used and it is desired to obtain a pseudorandom copolymer which Li / K molar ratio of the co-catalyst to a value in the range of 6+ (0.24 χ vol% of the aromatic hydrocarbon solvent) up to 25 + (0.65 x vol-% of the aromatic Hydrocarbon solvent). Becomes an aromatic If hydrocarbon solvents are used alone and if it is desired to produce a random copolymer, then it is a preferred Li / K molar ratio of the co-catalyst of 25/1 to 30/1. Similarly, if a pseudorandom copolymer is to be formed, the preferred Li / K molar ratio of the co-catalyst of 75/1 to 85/1, if one as

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The solvent used is an aromatic hydrocarbon, and from 15/1 to 22/1 if the solvent used is an aliphatic one Used hydrocarbon. In all cases, a preferable range for the amount of organic is Lithium compound used from 0.25 to 1.5 mmol / 100 g of total hydrocarbon monomers.

As the solvent in which the polymerization reaction is carried out, saturated aliphatic ones are used Hydrocarbons and / or aromatic hydrocarbons, which do not contain any benzylic hydrogen atoms. Aromatic hydrocarbons containing benzylic hydrogen atoms regulate the molecular weight, so that one can use such hydrocarbons when this effect is desired. As aliphatic Hydrocarbons One can use any hydrocarbons as long as they are at the polymerization temperature are liquid. Suitable saturated aliphatic hydrocarbon solvents are, for example, 2,5-dimethylhexane, n-decane, di-t-amyl, n-hexadecane, cyclohexane and methylcyclohexane. Suitable aromatic hydrocarbon solvents are for example benzene, tert-butylbenzene, naphthalene and diphenyl.

The amount of solvent used is not critical and is generally determined by the viscosity of the

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Reaction mixture, so that it can be conveniently handled, determined. The preferred amount is that at which the Solids content in the solution towards the end of the polymerization is of the order of 5 to 15% by weight.

The polymerization temperature is not critical in the process according to the invention. In general, it is preferred to carry out the polymerization reaction at a temperature between 0 and 100 ^° C. or at higher temperatures.

The pseudorandom copolymers according to the invention are new products. They have been stated to differ from the full random copolymers in that they contain blocks containing 3 to 4 units of vinyl substituted aromatic hydrocarbons in which the vinyl group is attached to a core carbon atom and which are interspersed within the copolymer chain . They are also by a vinyl content of about 7 to about 15 wt.% And characterized and low Tg of about -70 ° to -80 ⁰ C, wherein the Tg of at least 10 ° C lower than the Tg of a random copolymer containing the has the same vinyl-substituted aromatic hydrocarbon content. Tire tread compounds with a Tg in the specified range have an excellent ratio of tread wear and grip. An advantage of the pseudorandom

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Copolymers is that they can be made to contain more of the cheap vinyl substituted aromatic Contain hydrocarbons without the desired property · ^ shafts of the copolymer are adversely affected.

This is in contrast to the situation observed with the fully random copolymers which an increase in the amount of vinyl-substituted aromatic hydrocarbon in the copolymer is marked Has an effect on the properties of the copolymer. Desirable amounts of vinyl substituted aromatic Hydrocarbons in the pseudorandome copolymers range from about 24 to about 50 weight percent based on the copolymer. The pseudorandom copolymer can be viewed as a copolymer that "tapers", that is, the first The polymerized part of each chain contains less styrene than the last polymerized part of each chain. When the vinyl substituted aromatic hydrocarbon is present in the copolymers in larger blocks than specified is, the properties of the vulcanizate become like the hysteresis adversely affected.

The following examples illustrate the invention without restricting it.

- 13 -

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• Example

This example describes the preparation of the catalyst and a typical process for the preparation of Random or pseudo-random copolymers of styrene and butadiene described.

(a) Soluble catalyst

22.0 g (0.1 mol) of nonylphenol are dissolved in dry, anaerobic heptane, so that 100 ml are obtained. To this 11.2 g of potassium t-butoxide are added to the solution and then it is shaken under a nitrogen atmosphere for several hours the, whereby the KOtBu dissolves and you get a clear solution. This solution that

contains is 1.0 molar, so that 1 ml contains 1.0 mM. The solution is used with BuLi to create random and pseudorandom copolymers made from styrene and butadiene.

(b) Typical polymerization for the production of random copolymers

In a 500 ml bottle with a rubber disc, a Teflon seal and a metal cap with holes, add 300 ml of solvent (dry, anaerobic) (e.g. benzene). Then 30 g of butadiene and 10 g of pure styrene are added. To do this, one passes through

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the holes in the stopper 0.02 mmol of the one prepared above soluble catalyst. Then 0.25 ml of 1.6N BuLi (in Hexane) added. The mixture can react to completion. This generally takes 2 to 3 hours at room temperature or a shorter time is required if higher temperatures are used. The reaction mixture is produced with 5 ml of an alcohol (e.g. isopropanol), which may contain acetic acid (sufficient to To neutralize the basicity of the catalyst), and an antioxidant such as Santowhite - [4,4 * -Thiobis- (6-t-butyl-mcresol) J crystals stopped briefly. The polymer bottle is opened and the contents are washed with methanol, ethanol, isopropanol or similar compounds (1 1 contains 1 to 2 g of antioxidant). The polymer crumbs are through Separated by filtration and dried in a vacuum oven. The yield is 100%. This polymer that after the above The typical conditions described above yields a random SBR polymer containing from 20 to 22% vinyl (normalized, i.e. xom-converted so that the cis and trans-vinyl contents total 100%). The Li / K ratio that was used is 20/1. Using an 80/1 ratio, a low Tg pseudorandom copolymer product is obtained. Using a 20/1 ratio with heptane or another aliphatic solvent, one obtains a pseudorandom product and more potassium salt complex (around 4/1 Li / K to yield) would be required to be a random copolymer to manufacture.

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Example 2

This example uses a soluble catalyst (prepared according to that described in Example 1 Method) as a means to randomly polymerize styrene and butadiene and the effect of Li / K ratio explained in an aromatic medium.

In this series of experiments, all polymerizations were carried out as follows:
Pour into a dry, anaerobic bottle:

(a) 300 ml of pure benzene,

(b) Different amounts of the soluble salt, produced by reacting polyisobutylphenol with KOH (as an O, 2N solution in benzene),

(c) 10 grams of styrene; the bottle is then closed, with holes in the stopper through which:

(d) 30 g of butadiene,

(e) 0.5 ml 1.6N BuLi (in hexane

Rohm and Haas "Polyisobuty! Phenol 450".

After the BuLi was added, the polymerization begins immediately. The rate of polymerization depends on the amount of potassium salt added. At the beginning it is shaken and then it is no longer stirred. The polymerization is started at room temperature and the exothermic heat development causes the reaction temperature to un-

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about 45 ° C rises. To the extent of randomization ^ education of a random polymer), samples were taken from each bottle at different conversions and the percentage of styrene in the formed copolymer was determined by the refractive index. The results of this Samples in which the Li / K ratio was varied by adding when the amount of potassium salt added was changed, they are shown below.

description of 1 2 3 4th 5 6th 7th sample 0.4 0.16 0.08 0.04 0.03 0.02 0.01 mmol KOArR'-HOR " 0.8 0.8 0.8 0.8 0.8 0.8 0.8 mmol BuLi 2/1 5/1 10/1 20/1 27/1 40/0 80/1 Li / K 68 68 24.6 15.7 14th 16 10 % Conversion 40.5 36.8 41 28 24 19.5 8th % Styrene 72 100 59.5 43 26th 38 22nd % Conversion 39.1 26th 34.6 28 25th 21 9 % Styrene 75 - 97 85 89 77 37 % Conversion 39.1 - 28.4 25.5 25th 21 11 % Styrene 100 - 100 100 100 100 100 % Conversion 25th 25th 25th 25th 25th 25th % Styrene

From these results it can be seen that a maximum randomization (equal amounts of styrene at all stages polymerization) occurs when the soluble salt has a Li / K ratio of 27/1 (i.e. a very low one Amount of potassium salt).

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2 - ι 3 4th • 5 CSI 6th 345755 1 26th 26th 27 27 26th 7th % Styrene - ⁺ 28 30th 36 35 37 25th % cis (++) 39 41 45 47 46 39 % trans (++) - 34 28 23 21 18th 49 % Vinyl (++) - -70 -60 -63 -64 -67 13th Tg (+++) R. R. R. R. R. -80 NMR SB

+ means that no results were obtained

++ determined by infrared spectroscopy

+++ determined by differential thermal analysis

R random styrene

SB short blocks (3 to 4 units) of styrene.

It can be seen that the vinyl content decreases as the amount of potassium used is decreased.

Example 3

This example is intended to illustrate that the soluble potassium salts are more effective randomizers in aromatic Medium (see Example 2) compared to the insoluble KOtBu salt disclosed in US Pat. No. 3,294,768 is described. This example was carried out the same as Example 2 except that it replaced the potassium salt and that this salt is insoluble.

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0.4 0.2 0.13 0.08 0.8 0.8 0.8 0.8 2/1 4/1 6/1 10/1 32 17.5 16 17th 43 31 19th 13th 61 50 31 33 36 29 20th 14th 100 61 50 63 24 29 22nd 17th - - 100 100 100 24 24 24

Designation of the samples 8 9 10 11

KOtBu, mmol BuLi, mmol Li / K ratio

% Conversion % styrene

% Conversion % styrene

% Conversion % styrene

% Conversion % styrene

The values clearly show that a maximum randomization occurs at an approximate 4/1 to 6/1 Li / K ratio occurs and that the soluble potassium salts used in Example 2 are more potent randomizers in benzene are considered to be the insoluble KOtBu catalyst.

Example 4

In contrast to the series of experiments listed in Example 2, this example explains the randomization of styrene-butadiene polymerizations, whereby the soluble Salt used in an alkane medium. The polymerizations in these runs were under exactly the same Conditions as described in Example 2 carried out with except that heptane was used as the solvent.

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25th 11.7 6, "4 6.8 50 23 9 3.2 35 27 20th 18th 47 27 15.3 6.8 96 100 100 100 25th 25th 25th 25th

Designation of the samples 12 13 14 15

Li / K ratio 2/1 4/1 8/1 16/1

% Conversion%. Styrene

% Conversion % styrene

% Conversion % styrene

From these values it is clear that the maximum randomization at a Li / K ratio of approximately 4/1 occurs when using alkane solvents and the soluble salt.

Example 5

This example shows the effect of mixed solvents (alkane / aromatic compounds) on the Ability of the soluble potassium salt to give products with maximum randomness and on the properties of the resulting product Polymers explained. In this series of experiments, the polymerizations were carried out under exactly the same conditions carried out as described in Example 2, with used a Li / K ratio of 20/1 in each trial except that the solvent was varied.

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Name of the sample 16 17 18 19

solvent

Heptane (ml added) 300 295 250 150 Benzene ("") 0-5 50 150

% Conversion 17.4 15.9 13 10.6 '16.5

% Styrene 7.9 8.3 9.2 10.8 27

% Conversion 22.4 23.1 29.4 31.2 47.5

% Styrene 9.2 10 11.8 14.3 27

% Conversion 100 100 32.8 64.3 67.5

% Styrene 25 25 13.2 15.3 25.4

% Conversion - ⁺ 72 83

% Styrene - 16.3 25

% Conversion - - 100

% Styrene - - - 25

Properties of the polymer

% Styrene 24

% ice 41

% trans 52

% Vinyl 11

Tg -85

means that no values were obtained

From this example it can be seen that the extent of statistical distribution and the physical properties of the corresponding polymers which are obtained when the soluble potassium salt is used as a randomizing agent depend on the type of solvent and that these properties are determined either by a suitable choice of the solvent or the solvent mixtures can be varied.

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23 26th 27 27 39 39 40 26th 49 50 51 33 12th 12th 14th 21 -87 -84 -78 -63

example

In this example, random and pseudorandom polymers are made by adding different amounts of Styrene is polymerized with butadiene, using pseudorandom (in heptane as solvent) and random (in benzene as Solvent) copolymers are obtained if the soluble potassium salt and a Li / K ratio of 20/1 are used. All Polymerizations were carried out exactly as described in Example 2, except that the heptane solvent was used as indicated. It can be seen from the following results that both types of polymers are different for different Styrene can be obtained using the glass transition temperatures listed below and Block styrene content is obtained.

Solvent effect with BuLi / KOArR "HOR" catalyst

Solvent - benzene (Li / K = 20/1) % Styrene % Vinyl (nor - 6 Blockstvrol 0 Designation 0 malized) Tg +22 NHR 0 d. sample 12.5 -07, + 50 ⁺ 0 0 21 25th '-75, +53 ⁺ 0 0 22nd 37.5 0 0 23 '' 50 0 0 24 62.5 -86 0 0 25th 75 -74 0 26th 87.5 -63 0 27 90 -46 medium 46% 28 20-22 -28 medium 41% 29 so far >

+ The two Tg values are signs of block formation,

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Solvent - heptane (Li / Κ = 20/1)

Block styrene

Designation % Styrene % Vinyl (nor Day d. sample 0 malized) -97 30th 12.5 T -88 31 25th 8-10 -80 32 37.5 I. -75 33 50 -73 34

NMR w.

0 0

0 0

short 0

short 0

short 0

This series of experiments shows that a low Tg is maintained for the pseudorandom polymers, in spite of the The fact that no long styrene sequences can be seen, either by NMR (short = 3 to 4 units) or by ozonolysis methods. Therefore, when using the Technique used in making pseudorandom polymers, low Tg polymers that have a high Contain percentage of styrene. Such polymers have good styrene blocks because of their short block length Vulcanizing properties, in particular low heat build-up (or heat accumulation) (hysteresis), low Tg and good abrasion resistance. Vulcanizates that have these properties can be used with advantage in the production of such items as used by car tires.

When determining the amount of block styrene through Ozonolysis is the first reaction of the sample in a hydrocarbon solvent (benzene) with ozone and then in alcohol flocculated. Block styrene containing 5 or more styrene units per

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Block contains, is precipitated in the alcohol and can be isolated. In the case of 5O / 5O mixtures of butadiene and styrene homopolymers, 95% of the polystyrene can be recovered and determined using this method.

Example 7

This example illustrates that pseudo-random polymers (characterized by low vinyl content and low Tg) can be made in either alkane solvents or aromatic solvents by controlling the Li / K ratio. As the polymerization method, the same as described in Example 2 were used.
Designation of the sample 35 36

solvent benzene Heptane Li / K ratio 80/1 20/1 Polymer properties % Styrene 25th 23 % ice 39 39 % trans 49 48 % Vinyl 13th 14th Day -80 -80 NMR short blocks short blocks

Example 8

This example illustrates the production of pseudorandom polymers in a pilot plant .

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The polymerization was carried out in a 189 l (50 gallon) stirred steel autoclave carried out. The reactor was charged as follows:

Hexane 100 kg

Butadiene 15 | 4 kg

Styrene 4.6 kg

BuLi 112 mmoles

KOArR ¹ * HOR " ⁺ 2 g

Li / K 15/1

Reaction temperature 43 to 49 ° C (110-120 ⁰ F) + soluble complex of the potassium salt of nonylphenol.

The polymerization was carried out overnight, after 6 hours a conversion of 94% was obtained. The total styrene content of the polymer was 24%. For the first 25% conversion, the polymer contained 16% styrene; the second 25% conversion 18% styrene, next 25% conversion 26%, and last quarter 36% styrene. D ^ e properties of these products are:

% cig 31

% trans 39

% Vinyl 8

Tg -81 (DTA)

-85 (TP) ¹

Molecular weight distribution narrow

Mn ^3,163,000

Ml ^ 110

NMR short styrene blocks

= Torsion pendulum 2 = determined by gel permeation

chromatography = number average molecular weight 4 = Mooney viscosity at 100 ° C (212 ° F), determined with
an osmometer

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If in the present application of "random copolyraeren" is spoken, it is understood to mean copolymers which contain the monomers in a randomly distributed manner. This expression corresponds to the Anglo-Saxon expression "random copolymer". Used in the present application When speaking of "randomization", this is understood to mean that the copolymers are produced with a maximum of random scatter or, in other words, that a random process is used is used, which guarantees an unadulterated selection of monomers.

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Claims (12)

Claims 1. Process for the preparation of conjugated diene copolymers by treating a monomeric mixture of a conjugated diene carbon and approximately 5 to about 50 parts by weight based on 100 parts by weight of the total monomers, a vinyl substituted aromatic Hydrocarbon in which the vinyl group is attached to a core carbon atom is bonded, with a catalyst, characterized in that the catalyst contains essentially (a) a complex of the formula R ¹ - Ar - OK · HOR "wherein R 'is an alkyl group with a minimum of 8 carbon atoms contains per group and a maximum of 26 carbon atoms in one or more such groups, means, R "is a hydrogen atom or an aliphatic, cycloaliphatic or aromatic hydrocarbon group, Ar is an arylene group containing an aromatic ring, and y is an integer from 1 to 3 and inclusive, and from about 0.1 to about 20 mmol / 100 g of the monomers Mixture, 4098U / 0887 (b) an organic lithium compound of the formula R Li
wherein R is an aliphatic, cycloaliphatic or aromatic hydrocarbon group, the treatment being carried out in the presence of a solvent which is liquid at the polymerization temperature, and using saturated aliphatic hydrocarbons or aromatic hydrocarbons as solvents, which contain no benzylic hydrogen atoms, and wherein the Li / K molar ratio of the co-catalyst of about 4/1 is to about 25/1 when an aliphatic hydrocarbon solvent is used and from about 20/1 to 90/1 when an aromatic hydrocarbon solvent is used. 2. The method according to claim 1, characterized in that that the random copolymer is prepared by changing the Li / K molar ratio of the co-catalyst from about 4/1 to about 5/1> if an aliphatic hydrocarbon solvent is used, and sets from about 20/1 to about 30/1 when an aromatic hydrocarbon solvent is used. 3. The method according to claim 1, characterized in that that the random copolymer is made by using the A0981A / 08 8 7 Li / K molar ratio of the co-catalyst to a value of 4 to less than 6 + (0.24 χ vol% of the aromatic coal water solvent) when using a mixture of aliphatic and aromatic hydrocarbon solvents used. 4. The method according to claim 1, characterized in that a pseudorandom copolymer, which blocks with up to 3 up to 4 units on the vinyl substituted aromatic hydrocarbon Contains interspersed in the copolymer chain, is prepared by changing the Li / K molar ratio of the co-catalyst sets from about 5/1 to about 25/1 when using an aliphatic colloidal hydrogen solvent and from about 30/1 to 90 / i if an aromatic Hydrocarbon solvent is used. 5. The method according to claim 1, characterized in that a pseudorandom copolymer, the blocks with up to 3 to 4 units of vinyl-substituted aromatic hydrocarbon interspersed within the copolymer chain by increasing the Li / K molar ratio of the co-catalyst to a value of 6+ (0.24 χ vol-? 6 of the aromatic Hydrocarbon solvent) to 25+ (0.65 x vol-96 of the aromatic hydrocarbon solvent) when a mixture of aliphatic and aromatic hydrocarbon solvents are used. 409814/0887 6. The method according to claim 1, characterized in that a random copolymer is prepared using butadiene as diene hydrocarbon and 5 to 50 parts by weight, based on 100 parts by weight of the total monomers, of an-styrene, (a) a complex that is formed by converting equimolar Amounts of polyisobutylphenol and potassium hydroxide formed, and 0.25 to 1.5 mmol / 100 g of total monomers from (b) Butyllithium and benzene as the solvent used, the Li / K mol ratio being from 25/1 to 30/1. 7. The method according to claim 6, characterized in that the potassium-containing catalyst is a complex used, which is prepared by reacting equimolar amounts of nonylphenol and Kaliura t-butylate. 8. The method according to claim 7, characterized in that that the solvent used is heptane and that the Li / K molar ratio is from 4/1 to 5/1. 9. The method according to claim 1, characterized in that the pseudorandome copolymer is prepared by adding butadiene as the diene hydrocarbon and 5 to 50 parts by weight, based on 100 parts by weight of the total monomers, styrene, (a) a complex which is by Implementation of equimolar amounts of polyisobutylphenol and potassium hydroxide was obtained, and 4098 14/0887 0.25 to 1.5 mmol / 100 g of the total monomers of (b) Butyllithium and benzene as solvent used and that the Li / K molar ratio is from 75/1 to 85/1. 10. The method according to claim 9, characterized in that the solvent used is heptane and that the Li / K molar ratio is from 15/1 to 22/1. 11. The method according to claim 10, characterized in that the solvent used is hexane. 12. Pseudorandom copolymer of a conjugated diene hydrocarbon and from about 24 to about 50% by weight, based on the copolymer, of a vinyl-substituted aromatic hydrocarbon in which the vinyl group is bonded to a core carbon atom, characterized in that it has blocks with 3 to 4 units from the vinyl-substituted aromatic hydrocarbon interspersed within the copolymer contains, has a vinyl content of about 7 to about 15 Gew.?o and having a Tg which is at least 10 ⁰ C lower than the Tg of the random copolymer containing the same content vinyl-substituted aromatic hydrocarbon possessed. 13- copolymer according to claim 12, containing butadiene as Diene hydrocarbon and 24 to 50% by weight, based on the copolymer, of styrene. 4098U / 0887