DE2017478A1 - Vulcanizable copolymers, their manufacture and use - Google Patents

Description

DR.-ING. BY KREISLER DR.-ING. SCHÖNWALD DR.-ING. TH. MEYER DR. FUES DIPL-CHEM. ALEK VON KREISLER DIPL-CHEM. CAROLA KELLER DR-ING. KLOPSCH

COLOGNE 1, DEICHMANNHAUS

Cologne, April 10, 1970 ^l Ke / Ax / Hz

MONTECATINI EDISON SpA, Foro Buonaparte 31, Milan (Italy). .

Vulcanizable copolymers, their production and.use

The invention relates to ethylene-propylene-ethylidene norbornene. Butadiene copolymers and a process for their preparation with the help of catalysts of the Ziegler-Natta type.

The Italian patent specification 816,508 describes the preparation of the Anmelderiri A'thylen-propylene-ethylidenenorbornene copolymer with the aid of soluble catalysts or catalysts, which are finely dispersed in the liquid polymerization j The thus obtained co-polymeric λ are due to a low content at. unsaturated points (1.5 to 2 wt .-%) easily vulcanizable by conventional methods, since they show particularly high vulcanization rates. <"

It has now surprisingly been found that ethylene-propylene elastomers with the same curing behavior and with high curing speeds: manufactured v / can ground if = the ithylidene norbornene during the course of the production of these elastomers by a Mixture of ethylidene norbornene and 1,3-butadiene in a molar ratio between 5: 1 and 1: 5 is replaced.

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This replacement gives a great economic advantage ^ < in the process of producing the ethylene-propylene * Ethylidene norbornene copolymers, since it is possible to use at least half the necessary amount of the ethylidene norbornene by another service, namely 1,3-3utaäien, that known to be cheaper and, if it is not implemented, is more easily recoverable from the reaction mixture, can be replaced.

Another advantage is that by replacing a Part of the ethylidene norbornene obtained from 1,3-butadiene copolymers with a much lower molecular weight so that it is unnecessary under suitable conditions is to use molecular weight regulators. If necessary, however, the known molecular weight regulators, e.g. hydrogen or zinc alkyls can be used.

The ethylene-propylene-ethylidene norbornene-butadiene copolymers according to the invention are prepared by processes described in the above-mentioned Anraelderin patent are described. In detail, the copolymerization is carried out using catalysts, which are preferably soluble in the polymerization medium or, are finely dispersed, contain a halogen and are through; Implementation of the following connections are formed:

- a) Hydrides or organometallic compounds of beryllium ^ aluminum or lithium-aluminum, eg beryllium dialkyls | Aluminum trialkyls, lithium aluminum tetralkyls, beryl- '-: - liumalklylchloride, aluminum alkyl chlorides (mono-, di-, or sesquichloride), aluminumi) henylbromide, lithium / aluminum monofluorotrialkyls and: beryllium phenyl iodide.

i j - - - ■ -. '■ i

b) Vanadium compounds which are soluble in hydrocarbons;

are, ζ

.B. Vanadium halides or oxyhalides,

Vanadium or vanadyl alcoholates, vanadium and vanadyl acetylacetonates ^ Vanadium «· and vanadyl halide alcoholates and haloacetylacetonates and complexes consisting of

U INSPECTED

Vanadium halides and oxyhalides with Lewis bases '· Be obtained.

The copolymerization is carried out at temperatures between -80 ° and + 125 ° C, but preferably between -30 ° and + 3O ⁰ C • 5, since the above-mentioned catalysts have a higher activity and stability in this range *

The polymerization is in the liquid phase in the presence or absence of solvents for the copolymers formed. Suitable solvents are for example aliphatic *, aromatic and cycloaliphatic » table hydrocarbons. Furthermore, chlorinated hydrocarbons can be used, which are used with the Catalysts are not reactive, e.g. chlorobenzene, tetrachlorethylene and methylene chloride.

When working without a solvent, the liquid polymerization medium consists predominantly of a liquid one Ethylen-Propylen-Geraisch, in which the terpolynere formed is insoluble. In this case, the polymerization thus proceeds "in suspension".

In order to obtain copolymers with a very homogeneous composition, it is necessary to keep the ratio between the concentrations of the four monomers in the liquid polymerization medium constant during the entire course of the polymerization. By changing these ratios, the * composition of the copolymers can be varied within a wide range. For the production of amorphous polymers which contain less than 85 mol% ethylene, an ethylene / propylene-oil ratio between 1: 200 and 114- in the liquid phase is preferred. If with ratios above 1: working 4 ×, polymers are generally obtained _v showing stallinität typical for polyethylene crisis. The preferred propylene content is between 50 and 15 mol%. The total proportion of the two dienes is preferably between 0.1 and 20 mol%

009842/1832

That. preferred Molverhäl / tnis between butadiene and ethylidenenorbornene formed in the tetrapolymer is between 5 x 1 and 1: 5 "- but is a good vulcanizability with copolymers reached in which this proportionality nis xj is si between 1:10 and 10. FIG.

The copolymers according to the invention are linear Structure, ie they do not contain long branches, recognizable by the fact that they are practically the same Properties, especially the same viscosity behavior like known linear ethylene-propylene copolymers.

The molecular weights of the copolymers according to the invention are - generally higher than 20,000, i.e. their intrinsic Viscosity is, above 0.5 dl / g, "determined in tetrahydronaphthalene at 135 ° C (or in toluene at 30 ° C).

When the content of double bonds is higher than 0.4 mol%, the copolymer prepared by conventional Vulkanisationverfahren, for example can easily _s vulcanized with sulfur, accelerators and carbon black. Some cure rates are given in the following examples. These examples further illustrate that the vulcanized 'copolymers have excellent physical, chemical and dynamic properties with the properties of the best iithylen Z-propylene-ethylidenenorbornene copolymer transactions comparable.

Because of these properties, the copolymers according to the invention are used in all fields in which Natural rubber and other synthetic rubbers can be used since they can easily replace the latter.

example 1

The reaction apparatus consists of a glass cylinder, which has a diameter of 8 cm and a capacity of 3000 ml and with a stirrer, thermometer and Inlet and outlet pipes for the gases is provided.

009842/1832
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The inlet pipe for the gases is to the bottom of the Reactor out and ends in a fritted disc. /

^{150 ml of toluene and 2 ml of 5- ^ ibli} yliö- ^e n .- '2-norbornene were introduced into the reactor, which was kept at 5 ° C. by immersion in a temperature bath "... * a mixture of propylene, ethylene and butadiene is introduced into the reactor; these three monomers, are circulated in the following amounts : _,;

Propylene A5Ö 1 / hour,

Ethylene 300 l / h

Butadiene 2 1 / hour

After a saturation time of 30 minutes, 6 ml of ../ AIp (GpHc-) 2Gl ₃ , and 0.15 mmol of vanadium triacetylacetonate, are added as a solution in 10 ml of toluene to the reactor. During the experiment, the gaseous propylene-ethylene-butadiene mixture is continuously fed in and discharged. After 60 minutes, calculated from the addition of the catalyst, the polymerization was interrupted by adding 10 ml of methanol. That. Product was cleaned in a separating funnel by washing several times with dilute hydrochloric acid and then with water and finally coagulated with an acetone and methanol mixture. After drying under reduced pressure, 26 g of a solid product were obtained which was X-ray amorphous, looked like a non-vulcanized elastomer and was completely soluble in boiling n-heptane.

The infrared analysis showed that the product ^; . + Ö ~ wt% propylene, 1.3 wt -% of butadiene and 3.5 wt ->% Ithylidennorbor-..; ^: '.nen contained. The Mooney viscosity (ML-4 at 100 ⁰ G) was 111. »"'... //

100 parts by weight of the copolymer with 80 parts by weight; ISAF carbon black, 55 parts by weight of "Flexon 766" oil, 1 part by weight of stearic acid, 5 parts by weight of zinc oxide, 0.75 - ^ w »- Part.eA. Mercaptobensothiazol, 1.5 parts by GeVi ₀ tetramethylthiuram nnä 1.75 percent. ~ Parts Sch? / Efel mixed "

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The mixture was vulcanized in a press at 150 ° C. for different lengths of time. The properties of the volcanicates are mentioned in the following table »

Vulcanization time.,. 'Min. 15 30 60 90 .120 180 240

Tensile strength, kg / cm ² 221 20? 196 200 198 201 195

Elongation at break, % 520 420 590 380 380 390 380 Modulus of elasticity

at 200% elongation _s

kg / cra ^ 52 70 73 75 79 73 72

at 3QO ^ elongation ",

kg / cm ² 98 129 140 '149 147 140 138

Deformation rest, % 24 16 10 10 8 8 10

The above data show that the maximum degree of crosslinking is derivable _$ of the 'from the values of the modulus of elasticity, after a Vulkanisationszeit'von 90 minutes reached α is After 30 minutes, the modulus value. "About 90% of the maximum value"

The GoodrichΔΤ index was 19 ⁰ C ₉ determined on a 60 minute vulcanized sample »-

in this and in the following examples-was the ■ 'ΔΤ index with a Goodrich flexometer according to ASTM 623 is determined (25 minutes at 100 ⁰ C, mm stroke length of _4.445? 1800 cycles / minute, load the sample 10 _s 01 kg / cm ² , diameter of the sample 1 _S 78 _{cm 1} height of the sample 2.54 cm) _o

. Example_iel_2 -

The experiment described in Example 1 was wiederholt-, but using 1 ml JLthylidennorborneiu case 25 ₉ 7 S was obtained an amorphous copolymer, "■ the 41 wt« «# propylene, 1.8 wt ₀ -% ■ Ithylidennorbornen and I ₅ , 7 wt ₀ - contained and% butadiene Mooney Viskositä-ϊ of 106 would "·"

The copolymer was used in; the same mixture and under the same conditions as in Example 1 he wrote. $ vulcanized ο The properties of the VuXIc ani sate z ± n & in

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in the following table.

Vulcanization time, min. 15 30 60 90 120 180 240

Tensile strength, kg / cm ² 238 221 224 214 210 215 207

Elongation at break, % 630 510 490 460 '460 480 460 Modulus of elasticity, - -

kg / cm

at 200% elongation 42. 51 55 "56 54 53 56

at 300% elongation 80 102 113 112 108 106 109

Change in shape sr e st _t % 28 20 16 16 16 14 16 Goodrich ΔΤ-Index, ⁰ C 24

Example 5

Ethylene, propylene and butadiene were among the
Game 1 mentioned conditions copolymerized, but the butadiene is supplied in an amount of 4 l / hour
became. This gave 20 g of a product which

Contained 39 wt .-% propylene and 4 wt .-% butadiene and one Mooney viscosity of 93.

The copolymer was in the same blend and under
the same conditions as described in example 1,
vulcanized. The properties of the vulcanizates are in
in the following table.

Vulcanization time, Win. Tensile strength, kg / cm "Elongation at break, %

25 modulus of elasticity,

ρ
kg / cm

at 200% elongation at 300 '£ elongation deformation rest,% 30 Goodrich ΔΤ index,

The above values show that the yields of copolymer and the properties of the vulcanizates are inferior to those described in Examples 1 and 2 Try.

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15th 30th 60 90 120 180 240 206 209 212 189 187 181 190 680 620 630 590 580 580 580 30th 33 33 35 37 36 35 58 67 71 68 71 66 70 42 30th 32 30th 30th 26th 28 38

Example 4

An ethylene-propylene-ethylidenenorbornene copolymer containing 35 wt _# -% of propylene and 3 ₅ 5 96 parts by weight and containing ethylidenenorbornene had a Mooney viscosity of 129, was dissolved in the same mixture and under the same conditions as in Example 1 described, vulcanized. The properties of the vulcanizates are given in the following table «

Vulcanization time, min «, 10 tensile strength, kg / cm» elongation at break, %

Modulus of elasticity,

ο
kg / cm

at 200% elongation 15 at 300% elongation residual deformation, Goodrich A1

Min. 15th 30th 60 90 120 180 240 2 227 192 186 183 190 186 184 560 440 370 340 350 340 340 45 57 81 86 79 80 87 87 109 146 162 158 159 166 28 20th 10 10 8th 8th 8th ⁰ C 21st

The values in the table above show that the rate of vulcanization is lower than in the copolymers described in Examples 1 and 2.

About 7O? 5 of the maximum modulus were only obtained after a vulcanization period reached within 30 minutes.

009842/1832 * W «Win *.

Claims (1)

Claims 1) j High molecular weight, unsaturated vulcanizable with sulfur Copolymers of ethylene, propylene, 1,3-butadiene and ethylidene norbornene. 2) Copolymers according to claim 1 with one in Te trahydrοnaphthalin at Γ
0.5 dl / g. lin at 135 ° C determined intrinsic viscosity of more than 3) copolymers according to claim 1 and 2, containing 15 to 50 Mole propylene units and 0.1 to 20 mole total diene units. 4) Copolymers according to claim 3 * containing at least 0.4 l1ol% unsaturation. · 5) copolymers according to claim 1 to 4, containing butadiene and ethylidene norbornene units in a molar ratio between 1:10 and 10: 1, preferably between 1: 5 and 5: 1. 6) copolymers according to claim 1 to 5 / characterized in, that they contain less than 85 mol $ ethylene units and are amorphous when examined by X-rays. 7) Use of copolymers according to claim 1 to 6 in optionally filler-containing mixtures, the sulfur or sulfur-releasing compounds as crosslinking vulcanization accelerators for the production of vulcanized elastomers. 009842/1832 ίο 8) Process for the production of products according to claim 1 to 7 *, characterized in that ethylene, propylene ,, 1,3-Butadiene and Ethylidenno.rbornen at temperatures in Between -80 ° and + 125 ° C in the presence of a catalyst system the end a) at least one organometallic compound or a hydride of beryllium, aluminum or lithium aluminum and : _a b) at least one soluble in hydrocarbons Vanadium compound ■ copolymerized and the copolymers obtained in this way, if appropriate vulcanized, 9) Method according to claim 8, characterized in that one used as component a) of the catalyst system aluminum trialkyls or aluminum alkyl halides "■ ID) Method according to claim 8 ,, characterized in that as component a) of the catalyst system, aluminum ethyl sesquichloride is used. 11) The method according to claim 8 to 10, characterized in that as component b) of the Katälysatorsystem vanadium halides ,, Vanadiumoxyhalcgenide _Ä vanadium or vanadyl alcoholates * Vanadium · = or vanadyl halo alcoholates., Vanadium or Vanadylaceiylaeetonate or vanadium or vanadyl halo acetyl acetonate used 12) Method according to claim 8 to 10 =, dadureh 'gekennxelehnet _p that iaan as component b) of the catalyst system iiowplex = - compounds of vanadium or oxyhalides: -. den used with Lewis phases. SAD OfHGINAL - Ii - lj>) Process according to Claims 8 to 12, characterized in that a catalyst system is used in which at least one component contains halogen. 14) Process according to claim 8 to .VJ, characterized in that the copolymerization is carried out at temperatures in the range between -30 ° and +30 ⁰ C. 15) Method according to claim 8 to l4, characterized in that that the copolymerization is carried out in the liquid phase and in the absence of a solvent for the copolymer formed performs. 16) Method according to claim 8 to 14, characterized in that that the copolymerization in the liquid phase and in Presence of a solvent for the copolymer formed performs. 17) Method according to claim] 6, characterized in that chlorinated hydrocarbons which are inert towards the catalyst system are used as the solvent for the copolymer, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons or their mixtures are used. 18) Method according to claim 8 to 17, characterized in that one works with a molar ratio between ethylene and propylene in the liquid polymerization phase in the range between 1: 200 and 1: k . 009842/1832