DE2017872C3 - Process for the polymerization of isoprene or butadiene - Google Patents

Description

wherein the radicals R is Li or F, Br or Cl and one of the radicals R is lithium, and one lesser amount of an allyl tin compound of the general formula

R 'H

R '

H
H

SnR ;. '

wherein χ is an integer from 1 to 4, the sum of y and χ is 4, R 'is hydrogen or an alkyl or cycloalkyl carbon radical having 1 to 6 carbon atoms and R "is an alkyl, cycloalkyl or an aryl hydrocarbon radical having 1 to 25 carbon atoms means, characterized in that the allyl tin compound is only added after at least 25% and at most 80% of the monomer have been converted into polymer.

2. The method according to claim 1, characterized in that that the polymerization is carried out in a series of reactors, the Percentage of reactant polymerized in the first reactor in the range of 25 to 80% and the tetraallyl tin compound exclusively is added in one or more reactors after the first reactor.

lithium-substituted lithium phenates, which are used as initiators serve to produce polydienes with a high content of cis structure. By using These initiators and modifiers can reduce the inherent viscosity of the polymer without A large change in the cis content can be varied. In addition, the U SA patent specification 32 78 508 shows that the addition of an organotin compound, such as Tetraallyl tin, an organo-lithium initiator, a lowering of the inherent viscosity of the Polydiene, for example of 'polyisoprene, causes without reducing the cis content.

The USA patent specification 32 15 679 shows that 3-halogen substituted Aryl-lithium compounds, for example 3-bromophenyllithium, as initiators the polymerization of 1,3-butadiene and isoprene result in polymers with desirable properties Some advantages of these initiators are their structure and inherent viscosity the polymer produced with it is less sensitive to changes in the initiator concentration than is the case when using other organo-lithium initiators. Furthermore, the cis content of isoprene polymers higher than dcr-

some which are obtained using other lithium initiators. Finally there are also the induction periods are shortened.

The aim of the invention is a method for Polymori- ' sation of isoprene and butadiene in the presence of a

Halogen-lithium catalyst, the polyisoprene or polybutadiene with compared to the known Polymerizates produced by the process provides improved physical properties, since high percentages of eis-1 / »- addition product contains and where the cis-polyisoprene or cis-polybutadiene is a discontinued one Has a ratio of high and low molecular weight fractions.

In particular, the polymers obtained by such a process should have better processing properties, such as better mixability, better extrusion properties and improved Have tensile strength in the unmixed state and at elevated temperatures.

The invention relates to a process for the polymerization of isoprene or butadiene in the presence a haloaryllithium catalyst of the general formula

35

40

45

55

6o

Organotin compounds act as modifiers as organo-lithium initiators in polymeriion of dienes, in particular 1,3-butadiene and iprene, for the formation of rubber-like polymers cannl. For example, British patent specification 32 875 describes the use of organotin compounds, like tetraallyl tin, as modifiers for

in which the radicals R are Li or F, Br or Cl and one of the radicals R is lithium, and a lesser one Amount of an allyl tin compound of the general

20th

17 872

_ncn formula

R 'H

\ i η

C = C C -

/ H
R '

SnR ;. '

wherein χ is an integer from 1 to 4, the sum of y and χ is 4, R 'is hydrogen or an alkyl or cycloalkyl hydrocarbon radical having 1 to 6 carbon atoms and R "is an alkyl, cycloalkyl or an aryl hydrocarbon radical having 1 to 25 carbon atoms means that is characterized in that the allyl tin compound is only added after at least 25% and at most 80% of the monomer have been converted into polymer.

The allyl tin modifier is used in an amount added so that about 0.005 to 5.0, preferably 0.025 to 1.25 mmol per 100 g of the in the Polymerisätionssystem used monomers are present. The allyl tin modifier is according to the invention added when 25 to 80% conversion of isoprene or butadiene to polymer has been achieved. The allybine compound is added before at least 25% of the monomer has been converted or after 80% of the monomer has been converted, so this does not lead to the maximum improvement in the processability of the polymer. Becomes the allyl tin compound added right at the beginning, the inherent viscosity of the polymer is reduced, but the required improvement in processability is not achieved. Becomes the allyl tin compound added after about 80% of the monomer has been converted, this also does not lead to the cheapest modifications. Only when the allyl tin compound according to the method of the invention is added, a polymer is obtained with an improved behavior when rolling out strips and when extruding. The polymers prepared according to the invention retain the good ones physical properties, such as tensile strength, hot tensile strength and elastic tensile strength, in general with the polymer production by halogenaryllithium initiation linked by isoprene or butadiene.

The advantages of the process of the invention can be realized in a batchwise, i.e. H. Single batch polymerization process, be achieved. Another method of obtaining the better manageable High cis cis-polyisoprene or cis-polybutadiene is made in accordance with the method of the invention in using two continuous reactors in series. That way one can made-to-measure cis-polyisoprene or cis-polybutadiene with a set ratio of High and low molecular weight fractions can be obtained. The isoprene or butadiene that Solvent and the haloaryllithium initiator can be fed to the first reactor. By optionally adjusting the ratio of catalyst to monomers! can mean molecular weight the proportion of polymer produced therein can be controlled. The temperature can be in first reactor so cinrcgulierl that the degree of monomer conversion and consequently the than The first amount of polymer produced is controlled by the amount of polymer produced. The one allowed in the first reactor Conversion is within the range of 25 to 80 percent conversion of the monomer. The reaction mixture is removed from the first reactor and mixed with the allyl tin compound, the modifier; then the polymerization is continued to to create a polymer with improved properties during processing. For this purpose this Mixture containing the modifier into one

> o given second reactor, in which the average molecular weight of the amount of polymer produced therein by the amount of remaining haloaryllium initiator and controlling the amount of allyl tin compound added as a modifier.

> 5 The monomer conversion in the second reactor is controlled by the temperature in the second reactor and determines the length of the polymerization time.

In either of the two methods, i. i.e., in the single batch or in the reactors connected in series Sufficient allyl tin compound must be introduced in the 2nd polymerization stage to ensure that the polymer produced in this stage, compared with that in the 1st polymerization stage produced polymer, has a sufficiently low average molecular weight and thus the Production of a polymer with a high cis-tone and the considerably improved processing characteristics is achieved. The optimal amount of modifier to be fed in each case depends on the modifier used, the degree of polymerization, which was prior to the addition of the modifier was reached, and according to the initiator used. The addition of the modifier can be in The scope of the method of the invention can be accomplished in considerably different ways.

Exemplary allyl tin compounds are tctraallykinn, triallylphenyltin, Diallyldiphenyltin, allyltriphenyltin, (3-hexyl-2-nonenyl) -tricyclododecyltin, (S ^ -Dicyclohexyl ^ -propcnyl) -tri- (2-naphthyl) -tin,

Di (3,3-dicyclohexyl-2-propenyl) didodecyltin; Tri- (? .- butenyl) -cyclopentyltin, tri- (3,3-dicyclopentyl-2-propenyl) -phenyltin, di- (3-methyl-2-butenyl) -dimethyltin, 2-bulenyltriphenyltin,
Tetra- (3,3-dicyclohexyl-2-propenyl) tin and tetra- (2-butynyl) tin.

Exemplary haloaryllithium compounds are 3-bromophynyllithium,

3-Broni-1-naphthyllithium,

3-chlorophenyllithium,

3-chloro-l-naphthyllithium,
3-fluorophynyllithium,

3-fluoro-l-naphthyllithium,

1 -Chlor-S-naphthyllithium,

l-fluoro-3-naphthyllithium,

1 -ΒΐΌηι-3-naplnhyllithium,
4-bromophenyllithium,

4-bromonophyllithium,

4-chlorophenyllithium,

4-Chlornaphlhyllithium,

4-fluorophenyllithium,
4-fluoronaphthyllithium,

4-bromonaphthy! Lithium

and mixtures of the above connectors.

The haloaryllithium compounds used in the process of the invention can be according to any one of desired method is produced; suitable methods for their preparation are given in U.S. Patent 32 15 679 disclosed.

The process of the invention can be carried out in conventional apparatus and under conventional conditions will. The amount of haloaryllithiuric initiator used can, depending on the selected initiator or the combination of initiators, the polymerization conditions and the desired molecular weight of the product to be produced Polymerisates vary. The amount is generally in milliequivalents of lithium per 100 g Expressed monomer. In general wi.ü der Initiator in an amount that is about 0.05 to 50 milliequivalents Lithium per 100 g of monomer, preferably about 0.1 to 10 milliequivalents of lithium per 100 g of monomer is used.

The temperatures used during the polymerization and admixing of the allyl tin compound are generally in the range of about

- 100 to 150 C, preferably in the range of about

- 30 to 120 C. The specific temperature used depends on the initiator and the desired degree of polymerization. The during the Polymerization applied pressure is such that the reaction mixtures essentially in the liquid phase are kept.

The polymerization is preferably carried out in the presence of an inert hydrocarbon diluent accomplished. As such, are aromatic hydrocarbons. Parafine or Cycloparaffinc, the

4 to 10 carbon atoms contain, such as Benzene. Toluene, cyclohexane, methylcyclohexane, xylene. n-bulane, η-hexane. n-pentane, n-heptane. Isooctane and mixtures thereof, are suitable.

The polymerization process can also be carried out in the presence of known additives, such as 1,3-dibromobenzene generally in an amount such that about 0.01 to

5 moles of the additive are present per mole of halocnaryllithium initiator. This Additives are known to be processing aids for the haloaryllithium initiators are.

To the Vcrarbcilbarkcil the Polyisoprcns produced or to improve polybutadienes, the polymerization of the monomers can be carried out with the addition of Tetraallyl tin. Generally from about 0.05 to 5, preferably from about 0.025 to about 1.25 nmoles Tetraallyl tin used per 100 g of monomeric isoprene or butadiene. The tetraallyl tin becomes one Point in time after the polymerization has taken place to 25% and before it has reached 80%, admitted.

The products resulting from the polymerization of isoprene or butadiene are generally obtained as solutions that can be treated with various reagents to make functional Generate groups by adding the terminal Lilhiiimalomc of the polymerization itself obtained polymeric molecules replaced. For example, the polymer can be in solution with carbon dioxide and then with a sauna. ' kontakticrl be to the To replace lithium alome with · - COOI! Groups. To other funklionelleii groups that introduced belong to the SH and the —OH groups. The still active Polymerisallösungen can also with an alcohol or a treated with another reagent in order to inactivate the initiator and / or to precipitate the polymer, which is then obtained without functional groups.

The rubber-like polymers of isoprene produced according to the process of the invention or butadiene can be compounded by known methods such as those used in the past of rubbers used can be compounded. Vulcanizing agents, vulcanization accelerators, Activators for accelerators, reinforcing agents, antioxidants, plasticizers, plasticizers. Fillers and other blending additives normally used in rubbers can also be used in the polymers of the present invention. According to the invention rubber-like polymers produced are used in areas of application where Both natural and synthetic rubbers can be used. For example, at the Manufacture of car tires and seals are used. In addition, after the Rubber-like polymers prepared by any suitable method of the present invention Method can be mixed with other synthetic rubbers and / or natural rubber.

example 1

A haloaryllithium initiator was prepared by reacting 40 mmol of n-butyllithium and 40 mmol of 1,3-dibromobenzene in 200 ml of toluene. These compounds were introduced into a reactor which had been purged in an oven and dried with nitrogen gas, and then for 2 hours at 50 ⁰ C kontakliert. The initiator yield, which was used to determine the amount of initiator used in the subsequent polymerization reactions, was determined as the total alkalinity by acid titration of hydrolyzed fractions using phenolphthalein as an indicator. Therefore, the normality of the toluene dispersion was determined. The above general method was followed to prepare the haloaryllithium initiators used in the following examples.

The 3-bromophenyl lithium initiator was then used to polymerize isoprene. The approaches were carried out by charging 40 g of isoprene into the reactor for each approach, after this reactor had been washed with cyclohexane, flushed with 3 liters of nitrogen per minute for 5 minutes and filled with cyclohexane thinner. After the monomers had been filled with the aid of a closed filling device at 3.4 atm absolute Slick fuel pressure, the Halogenaryllithiuminitiator was added via syringe and rolled up, the reactor of every batch at 70 ⁰ C. After a variable time, the tetraallyl tin modifier was filled in with the aid of a syringe and the reactor containing the reaction mixture was rolled further at 70 ° C. until the end of the polymerization. After each reaction had ended, the polymer was coagulated with isopropanol and stabilized with 1% 2.2'-methylene-bis (4-methyl-6-tert-butylphenol). All polymers turned out to be

as Gcl-frci. The following polymerization recipe was used applied:

Isoprene. Parts by weight 100

Cyclohexane, parts by weight 1000

3-brompheny! Lithium

(Milliäqiiivalenle Li

per 100 g of monomer) variable

Table I.

Tetraallyl tin

(Millimoles per 100 grams of monomer) 0.3
Total time of polymerization

(Hours) 1.5

The results of the isoprene polymerisation are shown in Table 1.

3-bromine % Conversion l-.nd- Cis 3.4- In- Lapse Turn Final rotation acceptance phcnyl- at the time University- 1.4- Structural hiircnle when rolling ⁴ ) moment moment ⁵ ) of the rotation iilhium the addition of Wall- Slruk- tur ² ! Viscose at the moments Tclraallyl / inn ') lung door) liil ³ ) Beginning ⁵ ) at a (MiIIi- drop ⁵ ) equivalent cntc Li pro 100 g Mono meres) (%) (%) (%) (m-gm) (m-gm) 1.3 38 96 80 5.6 3.77 excellent 1550 1070 480 1.3 50 90 93 6.4 3.95 excellent 1610 1200 410 1.3 68 89 - - 4.64 excellent 1610 1330 280 1.3 73 89 89 6.3 4.44 excellent 1590 1240 350 1.5 88 88 90 6.0 4.41 loose, 1460 1420 40 no stripe 1.5 no 88 89 6.5 4.49 loose, 1430 1520 -90 Tetraallyl tin no stripe added

') Conversion as determined from a series of approaches without a modifier, but under otherwise identical conditions.

² ) The microstructure was determined as described in section "A". in column !! the US-PS 32 15 679 is described.

- ¹ I The inherent viscosity was determined as in section "B". in column II of US Pat. No. 3,215,679.

*) The evaluations of the rolling behavior were made with 50 g batches of material provided with carbon black on a preheated to 70.degree

Rolling mill made with 9.5 cm rolls and 0.76 mm roll absland. The carbon black material was made according to the following

Recipe made:

»Phr«

Brabender delivery (g)

Polymer 100 34 Highly abrasive furnace soot 50 17th Highly aromatic ul 5 1.7 Stearic acid 3 1.0

⁵ ) For this purpose, the oil and the stearic acid were mixed with the carbon black and this mixture was slowly (2 to 3 minutes) added to the polymer in the Brabender at 25 rpm. Immediately thereafter, kneading was started at 100 and carried out for 6 minutes to determine torque values. The kneading took place in the air at I40C. (This value and the more subjective evaluations of the rolling behavior provide a good value for processability if the viscosity is satisfactory.

This example shows that, according to the process of the invention, polymers with excellent processing properties and a broad molecular weight distribution can be obtained with desirable properties such as high conversion and high cis content. remain. &>

Example 2

The polymerization was carried out according to the recipe of Example 1 using 1.2 ml equivalent 3-bromophenyllithium per 100 g of monomer. The tetraallyl tin modifier was added after about 55% monomer conversion. and the reaction was suddenly stopped after a further 65 minutes with isopropanol and stabilized with 1% 2,2'-methylenebis (4-methyl-6-tert.-butylphenol).

The final conversion was 93.5%, the percentage of 3,4 addition was 5.2%, the cis content was 93% and the inherent viscosity was 3.93. The heterogeneity index was 6.4 and it was no gel formed.

The Polymerisa obtained from this approach was mixed, tested and with a Polymerisa compared, which for comparison was prepared in the same way but without the addition of a modifier had been. The following mix recipe was used:

M isch u ngsrecpl u r

Polymer 100

Highly abrasive furnace soot 50

Zinc oxide 3

Stearic acid 3

Mixture composed for 65% of a complex diarylamine-ketone Reaklionsprodukl m and 35% from

Ν, Ν'-Diphcnyl-p-phenylenediamine ... 1 N-isopropyl-N'-phenyl-

p-phenylenediamine 2

Highly aromatic oil 5

N-nitrosodiphenylaniine 1

Sulfur 2,

N-oxy-diethylene-2-benzlhiazyl-

sulfenamide 0.65

The processing properties and physical properties of the mixed polymer are reproduced in Table II.

20 17 872 III (P 10 Microstriikuir .1.4 Content .!-Bromine- 5 pension table phenyl l "i, | Um (% l 5 Vis Aiisill / inlmiin Telra change 3 kosity iMilliniol allyl / at time 7th S. per 100 µ / inn point of mono- (MiIIi- Encore nicrcs) mol from Per Tel Ki- ice cream HX) μ iillvl / inii 93 11.81 0.3 Μηηο- 91 4.57 IO 0.3 IllCICS) 80 3.28 A *) 0.49 0 84 5.78 B *) 6.13 0.2 30th '5 IC C '**! 0.3 100 - '1 j D **) 0.3

Table Il

Machining data (7.5x- »B« -Banbury) poly comparison

mcrisat with tetraallvitin modilicutor

Mixing time (min.) 5

Stripe evaluation (0 -IO) ¹ ) 10

Mix ML-4 at 100 ° C 50

Extruded at 121 '"C

Gar vcy form M

(m./min.) 1.37

(g / min) 110

Evaluation (3-12l ') 9

5.25 6 66

1.83 19 7

¹ I The evaluation is a modified Garvey-l-orm-Bcwcrtunu on the basis of three factors; see Table IV.

The above example clearly shows that those made by the process of the present invention Polymers greatly improved carbon fiber properties own.

*) Cyclolicx undiluent agent
** 1 "Penlan Thinner.

The above polymers were then mixed according to the following recipe, the processing data and physical properties of the blended rubber are given in Table IV.

Mixture recipe ") parts by weight

Polymer 100

Highly abrasion-resistant furnace black 50

Zinc oxide 3

Stearic acid 3

Mixture consisting of 65% of a complex diarylamine-Kcton reaction product and 35% off

Ν, Ν'-DiphenyI-p-phenylenediamine .... i

N-isopropyl-N'-phenyl-

p-phenylenediamine. '!

Highly aromatic oil 5

N-nilroso-diphenylamine 1

Sulfur 2.25

N-Oxy-diethylen-2-benzthiazyl-

sulfcnamide 0.65

") As in example 2.

Table IV

Processing data ¹ )

^{Ans:; lz}

Λ Β

Example 3

Isoprene was batch polymerized using 3-bromophenyllithium initiator. Man gave the isoprene followed by the initiator after adding the diluent and a nitrogen purge in the single reactor. If used, the tetra-ethyltin modifier was added to the in Conversions given in Table III. In the following runs, 100 parts by weight of isoprene were used and 1400 parts by weight of diluent used. The data representing these approaches are given in Table III.

Mixing time (min.)
Stripes rating ')
Extrusion rating,
Garvey ² )

10 10 3 6

7 8

10 10

10 2

11 5

JT

«T JTu ^{den on a 15 x} 30 cm mill at hp; Z, Tu ^ ^U , " ^{d Rated from} ° ^{to 4} , depending on how and at what thickness they stick together. On the first repetition

^{An evaluation} similar to the A u CIne was carried out, with bdm Γ ⁵ , "? u ^{that the} temperature is S2 'C. Then in the last, lukewarm rolling, an evaluation of

chle'chti ^V h ° i? m ⁰ , ^mme .l ^The overall rating is then 0 tscnietrit) to 10 (best).

) Determined according to US-PS 3215679. Column 12, section (J), «evaluates in relation to edge. Surface and corner. No. 12 «S ™. ^e '" _L " truded product, which is considered perf <* t vnHtT ^{aneesi en} - while lower numbers indicate less perfect products.

Physical Properties
(Hardened for 30 minutes at 200 C)

Alisa U 94 B. C " 5 1) ι ς A. 106 93 84 300-Vi) -module 257 (kg cm ² ) 255 254 249 ^I0 Black tensile strength 158 (kg / cm ² ) ") 139 133 115 Hot tensile strength (kg / cm ² ) ") Tensile Machine 1.-6. "I ASTM 15-412-62T Scoll

The above example impressively demonstrates that Improvements obtained when making polyisoprene in accordance with the present invention will. Approach C represents the only approach that was carried out according to the present invention, the better processability of this polymer is clear from the higher values of the strip rating and extrusion rating, with the other properties being acceptable. the Addition of the allyl tin compound as part of the initial initiator system did not produce an improved processable Polyisoprene compared with the polymer produced according to the invention. The preservation the good physical properties of the polymers produced according to the invention also demonstrated.

Example 4

Two 38-1 reactors connected in series. designated as reactors A and B, were used for two approaches to the polymerization of isoprene. the Reactors were operated continuously, stirred and filled with liquid. In both approaches the isoprene was filled in as a liquid with n-pentane as the solvent. Before adding to the Reactor A has the feed pre-cooled to help control the temperature in the reactor. Both the 3-bromophynyllithium and dibromobenzene and the feed were thus transferred to reactor A. added that the quantities of the desired materials were continuously available. the Reactor effluent from reactor A was added using an on-line mixer Tetraallyl tin (approach E) and tetravinyltin (approach F) mixed as a comparison before the Polymerization effluent from reactor A was fed to reactor B where polymerization continued would. The amounts of additives used in these approaches, the reaction conditions and the results are given in Table V:

Table V

Polymerization results and conditions

Reactor A Major items Approach F Approach U Reactor A 700 n-pentane 700 100 Isoprene 100 0.05
(0.3 millimoles
per 100 g of monomer) 3-bromophenyllithium 0.05
(0.3 millimoles
per 100 g of monomer) 0.0117 Dibromobenzene 0.0117 68 Temperature, ⁰ C 72 47.3 (%) Conversion in reactor A 55.5 6.70 Inherent viscosity of the polymer
from reactor A 7.22 Reactor B 87 Temperature, "C 83 Tetraallyl tin 0.085
(0.3 millimoles
per 100 g of monomer) 0.0685
(0.3 millimoles
per 100 g of monomer) Tetravinyl tin 75.2 Total conversion (%) 86.5 63/37 Ratio (%) conversion reactor A / B 64/36 4.3 Inherent viscosity of that in reactor B. 1.6

generated polymer (calculated)

Inherent viscosity of the ready-mixed
Polymer obtained from reactor B

5.19 5.80

The polymers obtained from batches H and F. were mixed according to the recipe given in Example 3. The compounded rubber was then in terms of its working properties rated; the data are given in Table VI.

Table Vl
Processing data ')

Extrusion evaluation ')
Garvcy-Fonn at 121 ¹ C

(m / min.)

(g min.)

Approach 1: Ansät / 1 "

10 8

1.22 1.37

102 108

was kept between 72 and 77 ° C and the temperature in the second reactor between 84 and 86 "C. After about 55% conversion, as in Example 4 Tetraallyl tin modifier to the polymerization effluent from the first reactor. The finished one The polymer mixture consisted of about 91% cis-addition product. The polymer was mixed into the following rubber mixtures and with a technical ice-polyisoprene with a high content ίο tested on cis structure as a comparison.

Mixture recipe (parts by weight)

Ansal /

WXY Z * l

Ans; il / I

10

57
53

Ans; U / I

4th
79
56

Processing data

Strip rating
Raw Mooncy ML-4 at 100 C ² )
Compounds ML-4
at 100 ¹¹ C ³ )

¹ I See Table IV. Example λ

^: l Determined according to ASTM D-1646-fi.V

') Determined according to ASTM D-IMfi-63.

The above example actually shows that a made to measure ice-polyisoprene with a certain ratio of high and low molecular weight fractions using can be produced by two continuously working reactors connected in series if one Isoprene, Solvents, and 3-Bromophylene-Lithium Initiators feeds into the first reactor and manipulates the catalyst to monomer ratio therein, to control the molecular weight of the polymer fraction produced, the temperature in the The first reaction regulates the monomer conversion and thus the amount of the first polymer fraction to control and then in the effluent of the first reactor tetraallyl tin, the modifier of the present invention, and then introducing the mixture into the second reactor, wherein the Polymerization is continued and wherein the molecular weight of the polymer fraction is also controlled so that an improved processable polyisoprene is produced.

Example 5

Polyisoprene was prepared as in Example 4, using two 38-1 reactors connected in series working with one hour residence time per reactor was used. The amounts of all ingredients used were identical to those of Run A of this example, except that the content of 3-bromophenyllithium 0.27 mmol per 100 g of monomer fraud. The temperature in the first reactor

Polymer 100 100 100 100

Highly abrasion resistant 50 50

Furnace soot

Second high abrasion 50 50

solid furnace soot

Zinc oxide 3 3 3 3

Stearic acid 3 3 3 3

Mixture, consisting of 1111

65% from one
complex diarylamine

Ketone reaction

product and 35%

from N, N'-diphenyl-

p-phenylenediamine

N-isopronyl-N'-phenyl- 2 2 2 2

p-phenylenediamine

Highly aromatic oil 5 5 5 5

N-nitroso 1111

diphenylamine

Sulfur 2.25 2.5 2.25 2.25

N-oxy-diethylene 0.65 0.75 0.65 0.65

2-benzthiazyl-

sulfcnamin

·) Comparison: technical ice-pole) isoprene with a high content of cis structure.

Table VII contains the processing dates and physical properties of the various Polymer mixtures. Each of these rubbers was then tested for relative wear characteristics to determine when they have been incorporated into a tire. Tread tires were produced by mixing the masses in a 1-A-Banbury mixer and the tread through a 11.4 cm MRM extruder *) extruded. The retreaded tires were tested on a Ford estate car,

which was driven approximately 10 miles between Bartlesville, Oklahoma and Borger, Texas.

Speed 80 to 112 km / h

Load about 544 kg per tire

₆ - rim 15 cm

Rotation 8

*) MRM = National Rubber Manufacturers Extruder.

Table VII approach 4'55 " 1 A-Banbury) 5Ό5 " Y 4Ό5 " 7th 4'40 " 5 tensile strenght Approach X Y Z W. (kg / cm ² ) ¹ ) W. Machining data (76 χ 146 146 149 154 Elongation 263 263 10 X 10 8th 6th Maximum 270 297 52 53 64 69
(Mooney- IO tensile strenght
at 93 ° C 580 585 Vi'skosi- (kg / cm ² ) ¹ ) 665 127 175 550 12.2 11.3 10.9 did)
10.8 IT, ⁰ C
Reset
assets 152 195 15th Shore A Mixing time Half ¹ ) 21.4
73.3 23.7
72.3 (Min.) 10 24 hours at 23.2
72.4 56 58 23.0
73.1 End temperature
temperature (° C) 300% module 54 59 Stripes (kg / cm ² ) ¹ ) aged evaluation
(0-10) ■
Mixed
ML-4 at 1.12 1.09 1.22 1.42 tensile strenght 100 "C 154 166 100 ° C 25th (kg / cm ² ) ¹ ) 134 174 »Scorch« *) 11th 12- H ⁺ 1O ⁺ Elongation 182 206 at 138 ° C (%) ') 195 245 I 5 (min.) T, C ¹ ) 340 370 Extruded 3 ° Reset 400 410 at 21 ° C 22.2 23.5 Garvey shape 22.7 74.7 76.6 24.0 (m / min.) 75.0 74.1 (g / min.) evaluation (3-12)

*) Scorch I 5 refers to the increase of 5 Mooney units against a minimum Mooney value in the specified Period. The higher values in minutes that result in an increase of 5 Mooney units over the minimum Mooney value are required indicate a more processable rubber.

ability, ') As in example 3.

² ) As determined in U.S. Patent 3,215,679, Column II, Paragraph D.

Physical Properties
(Hardened for 30 minutes at 145 ° C)

approach 1.49 X 1.76 Y 1.74 Z 1.77 W. ι- χ 10 84 106 16 139 (Mol / cc) ² ) 1 300% module (kg / cm ² ) ¹ )

') As in example 3.

² ) As determined in U.S. Patent 3,215,679, column 11, paragraph D.

The results of the tire tests show that the polymers of the present invention with respect to Chipping and wear of the tread were rated satisfactorily. The polymers of the present Invention were rated better in terms of crack resistance than the comparative sample.

The above example shows that the polymers produced according to the invention have higher streak ratings and extrusion ratings were given as the comparative blends. The polymers of the present Invention not only showed excellent processing properties, but were also related to the physical properties are satisfactory compared with the comparative polymer.

Claims (1)

Patent claims: I. Process for the polymerization of isoprene or butadiene in the presence of a haloaryl lithium catalyst the general formula IO 20th