DE1544722C3 - - Google Patents

Description

Makers, fatty acids, metal oxides, dyes, vulcanizing agents and vulcanization accelerators.

The present curable molding compositions represent highly aging-resistant rubber mixtures Basis of ethylene-a-butylene polyenes, which are either other mixtures with low unsaturated polymer components with the same formulation structure, such as butyl rubber or ethylene-propylene-polyene-rubber mixtures at the same level are superior to the vulcanizate properties in terms of their processability or in terms of the possibility of use higher amounts of fillers result in approximately the same vulcanizate and processing properties.

The invention is explained in more detail using the following example:

example

I. The apparatus used to produce the copolymers consists of a 3-1 polymerization vessel, the one with a stirrer, three graduated dropping funnels and gas inlet and outlet devices provided and connected to a decomposition vessel by overflow.

100 liters of α-butylene are precondensed in 500 ml of hexane in the reaction vessel. The mixture is cooled to about 0 to -5 ° C., 25 l / hour of ethylene is passed in and 120 ml of a 1-n-diethylaluminum chloride solution (120 mol), 100 ml of a 0.1 ln. Vanadium acetylacetonate solution (10 mol) and 26.4 g (200 mol) of dicyclopentadiene in hexane. The polymerization starts within the first half an hour; one then the solution is cooled to - from 30 ° C and polymerized without exhaust the remaining 3 ¹ Z ₂ hours. If the amount of liquid in the reaction vessel has increased too much, an overflow is drained into the decomposition vessel, where the catalyst is destroyed with methanol and then washed with water. The same thing happens after 4 hours with the entire reaction mixture. The polymer is finally precipitated with acetone and dried in vacuo at 5O ⁰ C for 24 hours.

150 to 200 g of a colorless, rubber-like polymer with the reduced specific viscosity (RSV) 0.9 to 1.1 (measured in 0.1% strength xylene solution at HO ⁰ C) are obtained.

From the ultra-red analysis, the butyl content is determined to be 33 to 34 percent by weight and the double bond content to be 8 C = / 1000 C atoms. The "pro- duct is gel-free and has a Mooney plasticity of ML-4 = 10.

II. The polymer thus obtained is in a laboratory internal mixer of 2 liters Net at 40 rpm and 50 ⁰ C cooling water temperature according to Table 1 again given formulation with the other constituents of the rubber mixtures-(mixture A) and with the products manufactured in the same manner mixtures B , C and D, but instead of the ethylene-a-butylene-dicyclopentadiene terpolymer

Ethylene-propylene-dicyclopentadiene terpolymers contain similar Mooney viscosity or with similar mechanical vulcanizate properties, compared. From the properties shown in Table 2 it can be seen that with the same processing properties, as represented by the Mooneyplasticities of the raw polymer and the finished mixtures, the vulcanizate properties the mixture with the ethylene - «- butylene-dicyclopentadiene terpolymers are considerably better than those obtained with mixtures B and C of the ethylene-propylene-dicyclopentadiene terpolymer can be obtained. On the other hand, using ethylene-propylene terpolymers becomes a Mixture D obtained with a profile of vulcanizate properties similar to Mixture A is just that when using polymers with a significantly higher initial Mooney value and thus worse To achieve processing properties (mixture Mooney value twice as high). An addition of higher However, amounts of filler and plasticizer to improve the processability of Mixture D would inevitably a deterioration in the mechanical and also electrical vulcanizate properties entail.

Table I.

A I Recipe
BICI 100
50 D. Ethylene-a-butylene-dicyclopentadiene terpolymer,
ML-4 = 10, C = / 1000 C atoms = 8
Ethylene-propylene-dicyclopentadiene terpolymer,
C = / 1000 C atoms = 8.4 100
50 100
50 - Ethylene-propylene-dicyclopentadiene terpolymer,
C = / 1000 carbon atoms - 4.7 1 1 5 Ethylene-propylene-dicyclopentadiene terpolymer,
ML-4 = 33, C = / 1000 C atoms - 4.9
HAF carbon black 5 5 10
1.5 100
50 Stearic acid 10
1.5 10
1.5 1.5
0.75 1 zinc oxide 1.5
0.75 1.5
0.75 5 Naphtha, oil 10 sulfur 1.5 Tetramethylthiuram disulfide 1.5
0.75 Mercaptobenzothiozole

Table 2

Recipe Polym
Defd ML-4 Mishu
Defo- ngs-
ML-4 F. D. M ₃₀₀ bl. D. H. St. E. 22 E « A. 100/9 10 475/4 23 186 390 135 14th 73 11th 40 45 B. - 17th 1700/18 55 137 325 130 9 71 10 40 45 C. 130/10 14th 950/7 31 125 ' ^; ·; 3'25 112. 10 70 12th 40 46 D. 680/31 33 1125/16 47 190 -445. 117 16 66 11th 42 44

Vulcanization of 4 mm thick Prüfköerper 30 'at 160 ⁰ C. audit was conducted in accordance with the relevant provisions of the German DIN.

Claims (1)

1 2 Light are particularly stable. Such polymers are Claim · · ^z " ^ - butyl rubber or unsaturated ethylene Propylene rubber. Precisely these elastomers are >' but on the one hand because of their excellent Curable molding compounds with improved processing properties, on the other hand because of their excellent properties and good mechanical properties, existing electrical properties for certain uses from areas, e.g. B. in the isolation area, of particular Interest. A) Ethylene-a-olefin-polyene copolymers, ^Es ^ ⁰ * now found / that you can curable form io masses with improved processability and good B) customary vulcanizing agents and additional mechanical properties, consisting of ■
fabrics, A) Ethylene-α-olefin-polyene copolymers thereby g e k e η η ζ e i c h η e t that as b) customary vulcanizing agents and additives Component A copolymers of ethylene, 15 «-Butylene and polyenes and optionally 0.1 to obtained by using mixed-20 as component A Mol percent of another -olefin with 3 to polymers of ethylene, -butylene and polyenes 5 carbon atoms are used and that these and optionally 0.1 to 20 mol percent of one Copolymers a Mooney value ML-4 of other "olefins with 3 to 5 carbon atoms are used 5 to 35. 20 and that these copolymers have a Mooney value ML-4s range from 5 to 35. Copolymers of ethylene, -butylene and polyenes which! _v \ by polymerizing the corresponding monomers, - 25 z. B. with an organometallic mixed catalyst according to Ziegler. These copolymers are made by polymerizing the comonomers made in excess a-butylene as a diluent. ' It is known that the processability of rubber- 30 The ethylene as well as the catalyst components Mixtures in the application sense by and the non-conjugated diolefin are ^ here various measures - to · improve. Examples added continuously. The gassed ethylene such Measures are z. B. the decrease in the amount determined depending on the type and amount Molecular weight or the Mooneyplasticity of the catalyst the ethylene content of the terpolymer, the increase in the plasticizer content 35 mers. or the lowering of the filler content or something like that Borrowed measures of a mixed technical nature. Butylene are replenished during the reaction, When setting a more favorable processing that the butylene content of the solution in the reactivity by one of the measures described, z. B. vessel remains approximately constant. The molecular weight by lowering the molecular weight or the 4 ° of the terpolymers that are produced by this process. Mooneyplasticity will now generally be produced, depends on their properties of butylene anisate, such as strength and rebound content; high butylene content corresponds to elasticity or permanent elongation worsened. especially low molecular weight. On the other hand, this also applies when the plasticizer content is increased, the molecular weight of the terpolymers is reduced by the amount of chuk and when the filler content of the chew is decreased, the aluminum-vanadium ratio is increased in the manner of a chuk mixture. it is true that with enlargement of the aluminum van So can be with elastomers, which in a din-ratios the molecular weight of the Terpoly-Mooney range from Z. B. ML-4 = 10 to 20 lie meren decreases. . and the - these low plasticity numbers (Mooney- The low molecular weight can also be due to Values) because of '-' the mixtures produced from it 50 give hydrogen control or catalyst additives for excellent processability, only VuI-known processes are set,
Canisate properties of relatively low. As polyenes, z. B. Connections such as 1.5- set practical value. For this reason too, hexadiene, 1,4-hexadiene, dicyclopentadiene, 1,5-cyclo come types within the mentioned octadiene, 1,4,9-decatriene, 1,2,4-trivinylcyclohexane, Mooney range in the usual elastomers in 55 Dimethyloctadiene, 5-methylene-norbornene and Adden commercial ranges are practically non-existent. However, other unsaturated compounds can be processed by cyclogutes for special anpentadiene, such as butenylnorbornene.
Turns of phrase, e.g. B. the encapsulation of metal according to a particular embodiment wires in the wire and cable industry, for the molding compositions according to the invention such can be used position of cellular rubber or articles according to 60 use copolymers, which in addition to the a-Butydem Injection molding process, of particular importance. len in addition another α-olefin with from 3 to A lowering of 5 carbon atoms in amounts of 0.1 to 20 mol percent has a particularly strong effect Plasticity or the molecular weight for behavior. Improvement of the processability on the vulcanization As «olefins, propylene and isobutylene come into play properties of mixtures with additional use 65 consideration. They are made in amounts of 0.1 to 20 mol of such polymers that a relative percentage is used in addition to butylene,
have rings of unsaturation and the components according to the invention the aging effects of heat, oxygen and moderately curable molding compounds, fillers, soft