DE2316618A1 - METHOD OF MANUFACTURING A MODIFIED POLYMER OF A CONJUGATED SERVICE - Google Patents

Description

for the production of a modified polymer of a conjugated d en "

The invention relates to a method for producing a modified polymer from a homopolymer or Conjugated diene copolymer. It also relates to a method of making a vulcanizable, sulphurous mass and a process for vulcanizing, this hate.

The term "vulcanizable composition" means a composition in which all necessary for vulcanization or desirable ingredients are present and thus ready to be vulcanized.

309841/0955

ORKsHNAL INSPECTED

The term "sulfur-containing mass" is to be understood as a mass which, calculated on the polymer, contains at least 0.5 wt .- ^ free sulfur or sulfur-releasing vulcanization accelerator. Such compositions preferably also contain an oxide and / or a salt of a divalent metal (e.g. zinc oxide, Lead oxide, zinc stearate, lead stearate or combinations of the mentioned oxides with stearic acid). Also can optionally other additives, in particular reinforcing fillers, may be present.

The inventive method is particularly applicable to isoprene rubber, preferably one with the aid of a Lithiumhydrοcarbylverbindungen as initiator or with the help isoprene polymer made of a Ziegler catalyst. Furthermore, the method is applicable to other polymers of conjugated dienes, e.g. on polybutadiene and on styrene-butadiene copolymers, it "does not matter what catalyst system and medium in their production was used. In addition, the average molecular weights of the diene polymers can be within relatively wide limits vary. The isoprene rubbers can have a limiting viscosity number (LVIT) of 2 to 8.

It is known that hydrocarbon polymers including cis-1,4-polyisoprene, polybutadiene and styrene-butadiene rubber, but especially polypropylene and polyisobutylene, can be modified by treating them with a monosulfonyl azide of the formula ESO ₀ ] J ₇ , in which E stands for an organic Eest, heated. As a modifying agent, m-carboxybenzenesulfonyl azide (ie, 3-azidosulfonylbenzoic acid) can be used, its proportion

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between 0.01 and 20% by weight, "calculated on the to modifying polymer. The sulfonyl azide can be mixed with the polymer on a standard rubber mill be mixed in a solid state. The modification process is carried out by making the resulting Mixture heated to a temperature at which the sulfonyl azide decomposes and which are about 90 to 300 ° 0 can. Polypropylene is modified, for example, by adding 2%, calculated on the weight of the polymer, 3-Pyridinsulfonylazid mixed and the mixture for 2 hours holds at 150 ° C. The aim of the known modification process is the production of products with improved dyeability, Emulsifiability and adhesion to other substances.

It has now been found that the mechanical properties ("green strength") of homopolymers or copolymers of conjugated dienes can be improved by a mixture of the polymer with certain azides in solid State mixed in two stages.

The inventive method for producing a modified) polymer of a homopolymer or copolymer of a conjugated Dieris is characterized in that the diene polymer in question in a solid state at a temperature of 40-140 ⁰ C is mixed with 0.01 to 5 wt .-% of a aromatic monosulfonylazids, in which one or more carboxyl groups sit on the aromatic nucleus and which has a melting point below 14O ° C (stage A), whereupon (stage B) the resulting mixture in the solid state at least JO see and no more than 10 min at a temperature between 140 and 250 ⁰ C holds.

The melting point of the azide is set so that the beginning

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a possible melting range is included if, for example, as a result of an impurity or because a mixture of different sulfonyl azides was used, a larger melting range is in question
comes.

Stage A can be carried out at a temperature which is at least so high that the azide begins to melt (if a melting range is present, this is the lowest temperature in this range), a temperature at which all of the azide is preferred for this stage has melted and which is at least 1G ⁰ C. higher than the temperature at which the azide begins to melt

The azide can with the diene polymer at least 15 see and preferably mixed for 1 to 5 years, preferably in a closed mixing device provided with rotors, e.g. an internal mixer or a Extruder. The stages A and B are usually carried out in the same mixer. It may also be advisable to ve'rfflischen the azide before the beginning of stage A with a portion of the polymer to be modified, so that the resulting mixture can be processed more easily with the rest of the polymer to form a homogeneous mixture.

Mixing the azide with the diene polymer at temperatures above 140 C is not advisable due to the risk of

that the azide reacts with the polymer and / or itself

too quickly and therefore prematurely (i.e. before it is sufficient

is mixed with the polymer) decomposed, in which case the decomposition

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Settlement product (sulfonylnitrene) also too quickly can react with the polymer.

Step B v / ill be preferably | carried out at a temperature below 200 ⁰ G.

The amount of azide used is calculated on that original polymer, preferably between 0.1 and 1.0 wt. amounts of 0.1 to 0.5% by weight are preferred.

The modifying agent used is preferably 3-azidosulfonylbenzoic acid. More examples of suitable Azides are 2-hydroxy-5-azidosulfonylbenzoic acid, 2-chloro-5-azidosulfonylbenzoic acid, 1-azidosulfonyl-4-carboxymethoxybenzoic acid, 4-azidosulfonyl-1,2-benzenedicarboxylic acid, 4-neopentyl-5-azidosulfonylbenzoic acid and 4- & 'thyl-5-azidosulfonylbenzoic acid.

In the production of a vulcanizable, sulfur-containing compound, the desired ingredients with the exception of the sulfur and usually also the accelerator, after stage B has been carried out all in one separate internal mixer (or extruder) or in the same facility in which stage B was carried out with mixed with the modified polymer. The sulfur and the accelerator are then at a lower temperature mixed in, e.g. on a roller mill. If necessary, all of the constituents that are after stage B must be supplied, mixed in on a roller mill.

Often one wants to come to vulcanisable masses, the except

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the modified polymer, sulfur and others for components necessary for vulcanization (such as accelerators and oxides and / or salts of divalent metals) " Contain reinforcing fillers, e.g. carbon black or so-called "white" reinforcing fillers such as. Silica.

If such reinforcing fillers are used, the mechanical properties reach the. Vulcanisable mixtures have optimum values when all of these fillers and all of the other constituents mentioned are mixed with the polymer obtained in stage B only after this stage has been completed and preferably at mixing temperatures below 100.degree. In some cases, however, it is preferred that the reinforcing filler is already present while stage A is being carried out (and thus also during stage B). This is true both when mixing the diene polymer in the solid state and when mixing a solution of the diene polymer. In these cases, however, it is necessary that the sulfur is only mixed with the modified polymer when stage B has been completed ₍ otherwise premature vulcanization would take place. Here, too, temperatures below 100 ^° C. are preferably used during the As a rule, the accelerator is added together with the sulfur. Likewise, the oxides and / or salts of divalent metals are preferably only mixed with the modified polymer after stage B has been carried out completely, because if these components were added earlier react quickly with the azide or its decomposition product, thus preventing the modification reaction, when steps A and B are carried out in the presence of a reinforcing filler and a little more azide has been used than is needed

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if the strengthening filler after stage B had been added, the vulcanizable compositions finally obtained still have a favorable green strength.

If necessary, a small amount (e.g. 1 to 10 wt. Parts per 100 parts of polymer to be modified) of a processing oil use together with the reinforcing filler in level A «You can use level A in presence other additives, e.g. antioxidants, antiozonants, pigments and non-reinforcing agents Fillers perform, provided that these substances not too much during stage A and / or stage B. react quickly with the azide or its decomposition product. If you use extender oils that are usually found in relatively large amount are incorporated, these are generally only after completion of stage B. added.

The invention also relates to the manufacture of vulcanizable compounds that do not contain reinforcing fillers.

The examples explain the invention in more detail. example 1

A number of attempts (1 to 5) were carried out an internal mixer of the "Meili" type was used, in which, at a rotor speed of 60 rev / min. and an initial emp era door of 100 ° C 180 g of an isoprene

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rubber (IR-305) were mixed with 0.2% by weight of 3-azidosulfonylbenzoic acid in each case in the manner to be specified. The melting point (melting range) of the azide was 120 to 122 ⁰ C. The isoprene had been prepared by solution polymerization in the presence of sec-Butyllithiura as an initiator and had a cis-1,4 content of ~ 90 ° / o (as determined by Nuclear- magnetic resonance), an LVIT (at 25 G in toluene) of 7 »0 and a Hoekstra plasticity value of 71. The Hoekstra value was determined at 100 ^° C. using the method of EW Duck and JA Waterman, described in Rubber and Plastics Age 42 (1961) 1079-83 using an apparatus described in Rubber Technology Conference, London, 1938, p. 362.

Mixing stage A was started at 100 ° C, whereupon one the temperature to 120 ° C within half a minute increased and kept it at 120 ° for 1 1/2 minutes with continued stirring. After a mixing time of 1 1/2 minutes (calculated from the start of mixing) half of the total HAF carbon black to be used was added, i.e. 25 phr were used (that is 25 parts by weight per 100 parts by weight Rubber), while another 25 phr was retained became. The consecutive mishaps that last 2 minutes after the start of level A and half a minute before the start of Stage B are in the table below A listed. The speed of rotation of the rotor remained unchanged during the two stages A and B. The Overall formulation (other than the azide) for the ingredients used was the following:

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Polymer 100 phr

HAF carbon black - 50 phr

ZnO 5 phr

Stearic acid 3 phr

Flectol H (1) 1 phr

Santoflex 13 (2) 1 phr

Dutrex 729 HP (3) 4- phr

Sulfur 2.25 phr

Santocure (4) 0.9 phr

(1) to (4-) are protected trade names for:

(1) polymerized trimethyldihydroquinoline

(2) N-1,3-dimethylbutyl-N'-phenyl-paraphenylenediamine

(3) an aromatic processing oil

(4) N-Cyclohexyl-2-benzothiazole ~ sulfenamide.

As can be seen from Table A, these ingredients were partly added at the end of mixing stage A and partly after reaction stage B.

After the Misehstufe A lasted 2 1/2 minutes was started by increased temperature to 150 ⁰ C with the level B. This stage was carried out in the same Meili mixer as stage A. The period of time between the start of stage A and the reaching of the temperature of 150 ° C is shown in Table B. Stage B was ended in all experiments by tipping the reaction mixture out of the mixer 5 minutes after the start of stage A. After the other ingredients had been added to the mixture at 60 to 70 ° C on a roller mill of the Troester type, it was used on this device for a further 5 to 7 minutes at the same temperature with the

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Mixing continued, taking all this time the mixture was easy to process. Then the mechanical properties (green strength) of the resulting Vulcanizable masses determined. The results are shown in Table B.

Finally the vulcanizable masses were vulcanized, by keeping it at 14-5 ° C for the time indicated in (Table B as "OCT" (optimal curing time); the optimal Cure time was determined on a Monsanto rheometer. The properties of the resulting vulcanizates.

TABLE A:

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- Ii -

TABEL

Time in temp.

min after. O _n τ,. _ _Λ Beginning ^{in G Bel! 3} p.1

the stage
A.

Mixing scheme

Example 2 Example 3 Example 4 Example 5

J
> step > 2.5 < 100 rubber + 120 120 Rubber Rubber Rubber Rubber HAF HAF ZnO Am Jo, 5 ) Azide 120 HAF + Azide + Azide + Azide + Azide (Rest) (Rest) stearin Level J Mile- H.5 ) (Half) - - acid A j Mi ) 120-HAF HAF HAF HAF HAj? - - Flectol in the j shear > 2 h 5- 125 (rest) 150 (Half) (half) (half) (half) H Mixer _< ) ^ 3.5 * ZnO HAF Flectol - Santo- (Meili) ) stearin 150 Auskip (Rest) H flex 13 i ) ] acid pen ZnO Santo- _ _ < ) Mix < Flectol stearin flex 13 4th on H 6Ο-7Ο sulfur acid Dutrex Dutrex HAi ¹ (remainder) Santo- Santo- 729 HP 729 HP and Troester-r '' flex 13 cure Dutrex Roller < Dutrex 729 HP mill 729 HP Dutrex 729 HP auskip pen 4- to auskip auskip min pen pen sulfur Santo- sulfur sulfur cure Santo- Santo- auskip cure your pen _ Flectol • H sulfur - Santo- Santo- flex 13 • your ZnO ZnO Flectol stearin stearin H acid acid Santo- flex 13

* see table B for further details

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3 0 9841/0955

TABLE B.

Mixing scheme according to table

Time in which the temperature of 15O ⁰ C after ^{35O "3 f} 2 ^{1 ^".}
Beginning of level A has been reached

7.2 11.5 12, 2 5 , 5 8.4 17.4 17, VJi 13th ,8th 740 670 600 1000

Mechanical properties *

Composition after mixing on the Troester mill and before vulcanization:

300 % modulus in kg / cm ² 7.1

Tensile strength in kg / cm 10.1 Elongation at break in %

Properties of the VuI canisate **

OCT *** at 145 ° C in min 300 % module in kg / cm ² 500% module in kg / cm ² tensile strength in kg / cm elongation at break in % Eest elongation in%

Determined according to ASTM-D-412/68, method for vulcanized Rubbers, but the test strips are punched out of 0.15 cm thick test plates using a 1 cm wide mold became; the plates had been produced by pressing the masses at 80 ° C. for 5 minutes after

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21 18.5 19.5 18th 21 110 110 120 120 110 220 220 230; 210 220 240 240 240 220 . 250 570 540 530 500 560 21 18th 18th 12th 24

the latter left to stand overnight at room temperature had been; the mechanical properties were also measured after the panels had protruded Night at room temperature.

Determined in accordance with ASTM-D-412/68, Form 0.

*** Optimal curing time (also vulcanization time), determined by means of a Monsanto rheometer.

From Table B it can be seen that in all of these experiments (i.e. where the reaction with the azide in the presence of HAF carbon black) had very good green strength was achieved. However, the best results were obtained when neither zinc oxide was used during this reaction nor stearic acid (and therefore no zinc stearate) were present.

It should also be pointed out that if the tests are repeated (for comparison purposes only), where no azide was used in stage A and stage B was omitted, the resulting vulcanizable, The following compounds containing sulfur and accelerators

Properties had: tensile strength not more than 4.0 kg / cm,

300% modulus at most 3.7 kg / cm, maximum tensile strength

only 2.2 kg / cm and elongation at break not greater than 320% " Example 2

Further experiments (1 to 12) were carried out,

again being isoprene chuke and 3-azidosulfonylbenzoic acid and a Meili mixer were used. The level A

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was started in each case at 12O ⁰ O and the step B was held at 15O ° C in the same mixer. Here, too, the eotor speed in both stages A and B was 60 rev / min. In Experiments 1 to 10, the isoprene rubber was the same as in Example 1. For experiment 11, a lithium isoprene rubber (referred to as M36) was selected whose I / VN (at 25 ° C. in toluene) was only 2.5, while for experiment 12 a Ziegler polyisoprene (designated as Natsyn 2200) was used, its LVN 4.2 and its cis-1,4 content (determined by means of nuclear magnetic resonance) was 98%. The amounts of rubber and azide were varied and are shown in Table C. The other ingredients added and their amounts were the same as in Example 1, except that no processing oil was used and that all ingredients were only added after completion of reaction stage B (again by tipping the mixture out of the mixer). These constituents were incorporated on a Troester mill, again at 60 to 70 ⁰ G ₁ , but in this case mixing was continued for 15 minutes.

In experiments 8, 9'- and 10, 250 g of rubber were mixed in stage Δ with a mixture prepared beforehand and separately from the total azide and 50 g of the same rubber. In experiment 1, which as a comparative experiment does not correspond to the process according to the invention, the mixture of rubber and azide was ^{heated to a maximum of 1.20 °} C., which means that stage B did not take place. ^{In DETL} experiments 2-12, the temperature increase from 120 to 15O ⁰ C was 30 lake. achieved. The results are shown in Table C. ■

Table C.

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TABEL

Ver Asid search quantity / hour no.

Kaifcs.ch.uk

conditions

Type

Amount of level

step

Hoekstra plasticity value at

mechanical properties of
vulcanizable mass

0.20 IR-305 in g A. B. _ 10O ⁰ G after Limit Tensile strength ρ kg / cm fracture 0.20 Il 4,150 ⁰ O Level B. firm speed 10 strain 0.20 It ti speed ρ 31 in 0.05 It ti kg / cm > 61 % 1*
CaJ 0.075 dd 200 4,120 ⁰ O It 62 _ 5 790 ο 2 0.10 ti 200 30 "12O ⁰ O It 50 - 6th 910 co
co 3 0.20 U 200 2,120 ⁰ C It 50 - > 25 > 1100 O 4 0.05 dd 300 ti dd 38 4.4 > 62 1010 ' o 5 0.075 It 300 Il dd 40 4.5 9 1010 Vi CD 6 0.10 dd 300 ti dd 42 - 7th > 1100 ' ⁰¹ 7
cn / 0.20 M 36 300 Il ti 42 > 21 > 1100 8th. 0.20 Hatsyn
-2200 300 ti ti 34 - > 19 1060 9 300 dd 36 - 38 990 10 300 ti 40 - > 1O8O 11 300 It 20th - > 1100 12th 300 It 34 . 900

* Comparative experiment

cn ι

A dash means in the above table, that no- off "booty was achieved · ■ - ■ -, .-, - ^·;.. X -, *.

The mass obtained in Experiment 7 was 16 minutes at.:. 145 ° G "vulcanized (optimal curing time according to the Monsanto bheometer). The resulting vulcanizate had a 300 % ~

2 °

Modulus of 153 kg / cm, a tensile strength of 200 kg / cm ^, an elongation at break of 480 % and a tensile resistance (ASTM-D-624, Form G) of 53 kg / cm. ■ - "

Example 3 . - _■; ^. _i;

To 10 ^ ^l hexane solution of the isoprene rubber IR-305 v / urde with stirring at room temperature, a solution described in Example 1 of 0.2 wt * -% "(calculated on rubber) of 3-azidosulfonylbenzoic acid in acetone'zugegeben where * "The volume of acetone was 5% of the hexane used.

After the solvents through. After steam distillation had been removed, the resulting homogeneous mixture of rubber and azide was divided into three portions. "One portion was kept in the oven at 150 ° C for 5 minutes (experiment no. 1), another portion was also held at 150 ° C for 5 minutes, but in this case in a closed mold, and the third portion was in a 'Brabender mixer (speed: 56 rpm.) was heated gradually over 5 minutes from 120 to 150 ° C ¹ ^..

Of the resulting modified rubbers ^"λ" was then LVN determines (at-25 ^o C in toluene), whereupon the ^ - ⁰ · ¹ '' rubbers in a öchwabenthän-V / alzen mill at 15 min

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up to 70 ° 0 with the values in the list in example 1 indicated ingredients were mixed, * but the Dutrex 729 HP was omitted. The amounts used corresponded to those given in the list in Example 1 Weight ratios. When blended, all three modified rubbers had good processability on. The mechanical properties of the resulting mixtures were determined and are listed in Table D «

T LVU des ABELL E D Hate 10 Tensile strength Fracture-. Ver modified 18th speed ρ
in kg / cm strain search Rubber module 15th in % mechanical properties of the vulcanizable 5OO % 21 JMr. in kg / p 61 1000 cm 38 1070 module 980 5.2 300 % ρ 1 5.0 in kg / cm 2 2.9 3 spat 7th at 11 9 1 4

A number of trials were carried out, with lithium isoprene rubber IE-305 in Trials 1 to 6 'according to example 1 and in experiments 7 to 8 that in example 2 mentioned Ziegler isoprene rubber, Natsyn-2200 is used became. In all cases, 3-azidosulfonylbenzoic acid was used as the modifier used, of which 0.1% by weight in each experiment

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after two minutes at 120 G ⁰ mixed (relative to polymer) in a Meili mixer (60 Umdr./inin speed)
with 300 g rubber (level A). The starting temperature was again 120 ^° C. The resulting mixture was then in
the same mixer ^{heated to 150 0} O, with the rotor continuing to run; the duration of this heating (level B) was
varies. After the reaction stage B by dumping the
Reaction product was completed, were each
Experiment 200 'g of the reaction product in one! Eroester-roll mill for 15 minutes at 60 to 70 ⁰ C processed
according to the overall approach given in Example 1, wherein
however, no Dutrex 729 HP was used here either. During processing all showed modified rubbers
good workability. The resulting compositions were vulcanized at 145 ° C. for 14 minutes. The mechanical
Properties of the compositions in the unvulcanized state and of the vulcanizates are listed in Table E.

TABLE E:

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TABEL

Ver rubber
looking for a guy
Kr. IE-305 duration
from
Step.
B (150 ° C)
in min Hoekstra-
Plasticic
worth of money
according to Stu
fe 3 mechanical properties
the vulcanizable
Dimensions Tensile strength
speed
in kg / cm fracture
deh
tion module
kg / cm mechanical properties
of the vulcanizate Fracture-
stretch
■ young
"in yi> not determined 175 217 480 Train-
viider-
was standing *)_
in kg / cur CO
λ
JT * 1 It 1 62 Gxenz-
consolidate
speed ρ
in kg / cm > 24 > 1100 150 Train-
¹ firm
speed
in kg / cm ' 520 175 291 475 56 Ca)
O
CD 2 Il
Il 2 52 no > 23 > 11OO 140 274 510 54, JS 3
4th . Il ■ 4 CM UN
UN KN Il KN CM
CM KN
AA > 11OO
> 11OO 140
140 268 530
490 61 Cd
! ■ * ■ «,
'S3
αϊ
-fi 5 "ti 5 32 Il
H 22nd 1100 150 276
259 490 54 6th Katsyn
2200 10 20th » 8th . 400 267 7th Il 3 .32 3.5 ^ .110O . 54 S. ■ 4 21 3.8 20th : 1060 3.8

»*) ASTM-D 624, Form C.

OO

Example 5

In the following experiments, 70% of the isoprene rubber listed in Example 1 were modified in a Brab ender mixer (speed: 56 rev / min) with a sulfonyl azide, the formula and length of which can be found in Table ΐ ¹ . The Aussangstemperatur was 120 ⁰ C and was increased within 2 to 3 minutes at 150 ⁰ C; the product was tipped out of the Brabender mixer 5 minutes after the start. The modified rubbers obtained in this way were then processed in a Schwabenthan roller mill for 15 minutes at 60 to 70 ° C., using the total amount from Example 1 with the exception of the processing oil. The mechanical properties of the resulting vulcanizing '; The available masses can be found in table Έ .

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ORiGlNAL INSPECTED

IABELLE

Used azide
search

No.

2 OH COOH Uv / λΙι -τ • ^f 5 co Melting range 128- O P ¹ OOOH CD OO I (oil Ö SO ₂ ^ 5! cn
αϊ

Wt% azide

modified product mechanical properties of the vulcanizable compound

■ D _Λ Ί, rm _Λ ^^ Hoekstra-LVN Polymer) _{Vert (2) oluene}

Melting range 130-135 C

ι Melt range & I 123-129 ° 0

0.1 0.2

0.2

58 60

0.2 62 4.7 0.5 62 4.9 1.0 70 4.2

Limit strength modulus tensile strength fracture ^ 300% ki in kg / cm

300% speed ₂ elongation in kg / in kg / cm in % om ^

5 , 3 12th , 2 1040 I. 7th , 7 > 36 > 1110 ro 9 ,8th 53 , 7 1060

7.3

11.2

ITorts. TABLE i ¹

17.4 57

970 1080

990

N.) CO

Ports, too

TABEL

attempt

■ No.

azide used

Wt % azide

modified product

mechanical properties of the vulcanizable compound

■ ρΧι ^, λ Hoekstra-LVN polymer) _value . (Toluene

25 ⁰ C)

■ Limit module strength 300 %

in 'ρ in

kg / cm kg / cm

tensile strenght

in ο kg / cm

Elongation at break

in %

co

co OO

O (D Cfl cn

.7

COOK

COOH

Pp - 138 ^U O. ".

COOH

137 ⁰ G

0.2

0.2

0.2

67

5.1

4.2

7.0

9.7

6.0

3.7

28.2

16.0

2.2

820

IO5O

320

Experiment 9 serves only as a comparative experiment and was not cb according to the invention carried out. The dash means no yield. '

B is ρ ie 1

200 g of the lithium isoprene rubber (IR-305) used in Example 1 were mixed in a Meili mixer (60 rpm) with 0.2% by weight of 3-azidosulfonylbenzoic acid. Stage A was started at 120 ° C, while the stage B was in the same mixer ehgeführt so dm?, That the temperature dex- ^ autschuk-azide Misehung in 30 see at 150 ⁰ C and the mixture brought to 5 minutes after The start of the experiment was held at this temperature. 5 minutes after the start of the experiment, the reaction product was tipped out of the mixer and divided into three portions. The first portion was processed using the entire batch from Example 1 with the exception of the processing oil (experiment ITr. 1). The second portion was processed into a vulcanizable mass in the same way, but in this case the HAF carbon black was also omitted (experiment ITr. 2). The third portion was mixed in the same way as the first, except that carbon black, but no zinc oxide, was used in this batch (test ITr. 3). The mechanical properties of the resulting vulcanizable compositions are shown in Table G.

TABLE G _x

Ver Grenafestig- Iiodul, 300 % tensile strength- elongation at break in in kg / cm ² in%

search speed in kg / cm ² speed ip. in Kr.

l £ P * /QVr.il T * -iT * J <- »vn £ -

1 , - , 15.2 37.2 690 2 - 3.6 12th 1100 3 3.6 3.6 1040

PATENT CLAIMS:

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Claims (11)

P A 0} E N T A · N S P H Ü C H E 1l) Process for the preparation of a modified polymer from a homopolymer or a copolymer of a conjugated diene, characterized in that in a first stage (A) the diene polymer is mixed with the diene polymer in the solid state at a temperature between 40 and 140 C. 0.01 to 5% by weight of an aromatic. Monosulfonyl azides, in which one or more carboxyl groups are attached to the aromatic ring and which "has a melting point" below 140 C, whereupon in a second stage (B) the resulting mixture is in the solid state for at least 30 seconds and at most 10 minutes at one temperature holds between 140 and 25O ⁰ G. &quot; - .-. ^ - 2) Method according to claim 1, characterized in that g e k e η η draw t that stage A is carried out in this way is that the diene polymer with the azide at a Mixed temperature that is at least so high that the Azide begins to melt. L 2. - 3 0 3841/0955 ORIGINAL INSPECTED 3) Method according to claim 2, characterized in that step A at a Performs temperature at which all of the azide has melted and which is at least 10 ° 0 higher than the temperature at which the azide begins to melt. 4) Method according to one of claims 1 to 3 »thereby marked that stage B begins, after the stage ,, at least a minute and at most took five minutes., 5) Method according to one of the preceding claims, dadux'ch marked that one both ' Stages A and B in a rotated closed Mixing device performs. ' 6) 'A method according to any one of the preceding claims, characterized in' that one carries out the step B at a temperature below 200 ⁰ G. 7) Method according to one of the preceding claims, characterized in that the azide is cechnet in an amount of 0.1 to 1.0% by weight on the starting polymer. 8) Method according to one of the preceding claims ^ characterized in that the azide used is 3-azidosulfonylbenzoic acid. 9) Use of the obtained according to one of the preceding claims modified polymer for the production of a volcanic - 3 309841/0955 sable, sulphurous mass, thereby g e k e η marked , that he. adding vulcanizing agent to the modified polymer. 10) Use of the modified polymer according to claim 9, characterized in that. the vulcanization components, with the exception of the sulfur and usually also the accelerator, are mixed with the modified polymer prepared according to one of claims 1 to 8, the mixing being carried out after completion of stage B in a separate internal mixer or extruder or in the same device in which had passed stage B _} , whereupon the sulfur and the accelerator are incorporated at a lower temperature, for example on a roller mill. 11) Use of the modified polymer according to the example 9 or 10, characterized in that one a modified polymer used, which according to the method according to any one of claims 1 to 8 with co-use of a reinforcing filler in stage A. 3098-41 / 0955