DE1694589B2 - USE OF ORGANIC HYDROPEROXYDES AND CARBONIC ACIDS, COBALT OR MANGANE SALT FOR COLD VULCANIZATION OF MIXED ETHYLENE POLYMERISATES - Google Patents

Description

The German Patent 15 69 181 relates be use-ing from 0.01 to 20Gew.- _cent of an organic Hydroperoxyds of the general formula R - OOH is in d'ir R is a tertiary aliphatic, cycloaliphatic or aromatic radical, for Kaltvulkanisieren of molding compositions , the from A) a high molecular weight, unsaturated, amorphous and essentially linear terpolymer of a) 20 to 80Mol- ° _o ethylene, b) 0.1 to 18 mol% of a cyclic or acyclic polyene with non-conjugated double bonds and c) a Λ-olefin, and B) carbon black as a reinforcing filler and optionally C) antioxidants, pigments and other additives.

In practice it has been shown that in certain cases long lines are necessary to convert these terpolymers to vulcanize, so that their practical use is often called into question. Ice is believed that the vulcanization rate of said terpolymers at a temperature in the vicinity of Room temperature on the reactivity of the residual double bonds introduced, d. H. from the type of polymer used in the terpolymerization and containing non-conjugated double bonds depends.

The invention was based on the object of eliminating this deficiency, it was found that the Addition of a cobalt or manganese salt of an aliphatic or cycloaliphatic long-chain Carboxylic acid chosen so that the salt is oil-soluble is, helps to significantly increase the vulcanization rate at low temperature.

The invention is the use of 0 01 to 20 weight ^'1 ,, an organic Hydroperoxyds of the general formula R - (OOH, where R is a ti-rtiärer is aliphatic, cycloaliphatic or aromatic radical, for Kaltvulkanisieren of molding compositions, consisting of A) a high molecular weight, unsaturated, amorphous and im. essential linear terpolymer of a) 20 to 80 mol percent ethylene, b) 0.1 to 18 mol percent of a cyclic or acyclic polyene with non-conjugated double bonds and c) a \ -01efin, and B) carbon black as a reinforcing filler and optionally C) antioxidants, pigments and other additives, characterized by the additional use of 0.1 to 2 parts by weight, based on 100 parts by weight of A, of a kebalt or manganese salt of an aliphatic or cycloaliphatic carboxylic acid with 8 to 18 carbon atoms as a vulcanization accelerator. From US-PS 30 17 376 it is known to crosslink polyethylene or ethylene-containing copolymers in the presence of manganese or cobalt compounds, but the crosslinking takes place in the presence of free oxygen, since peroxides allegedly bring disadvantages during crosslinking ;

in addition, terpolymers are not mentioned. The US-PS 31 40 279 deals only with the crosslinking of polyethylene, the product optionally being given increased rigidity and strength. Since these are undesirable properties in an elastomer, the teaching of this patent to crosslink polyethylene in the presence of manganese or cobalt salts of organic acids and a hydroperoxide did not allow any conclusions to be drawn about the vulcanization of the above-mentioned terpolymers.

It should also be taken into account here that the crosslinking speed is fundamentally different from the degree of networking; because while the crosslinking rate of a peroxide at a temperature depends only on the rate of decomposition of the peroxide, this is There is no dependency on the degree of crosslinking. The degree of crosslinking, on the other hand, depends on the im Peroxide used during the same period and is closely related to the number of cross-linking bridges that are formed and to some Characteristics of the crosslinking product, for example with the gel content in the case of polyethylene In contrast to elongation at break, the modulus of elasticity and the deformation rest in the case of an elastomer. In practice this means that when using a networking promoter together with a Hydroperoxide an increase in the crosslinking rate is achieved, so that at lower temperatures within the same crosslinking times or at the same temperatures within shorter crosslinking times can be worked, but in each case the actual mechanical properties of the end product remain unchanged.

It has also been experimentally found that vulcanization using a; Hydroperoxides and manganese or cobalt compounds in the case of weakly unsaturated terpolymers only lead to insufficiently vulcanized products that do not? have adequate elastomeric properties when working at temperatures which are usually used in peroxidic vulcanization, d. h above 120 C. For example, cine Mi deglutition on the basis of 100 parts of a Tcrpolymerisats of ethylene, 49 weight ",, propylene and cyclo octadiene having a Mooney Viskosiiät (ML [I f-4] be 100 ^c C ) of 84.50 parts of an HAF carbon black, 5.7 parts of cumyl hydroperoxide (70 ",; cumene) and 0.5 part of cobalt-2-ethyl lexanoate vulcanized at 50 ° C. for 60 minutes, so the vulcanization product obtained thereby has a Tensile strength of 8 kg / cm ² , a fracture diameter; of 110 ', Ό ^{un (} J has a modulus of elasticity at 200 ",

! 6 94 589

Elongation of 10 kg / cm ² , but the sample breaks when the deformation rest is determined at 100 ° C. It also follows from this that it was not foreseeable that a cross-linking system used in the cross-linking of polyethylene at temperatures above 60 ° C. would be weak in the case of a weak Unsaturated terpolymer at temperatures below 60 ~ C would deliver vulcanizates, which would be characterized by greatly improved and especially important properties for an elastomer.

The system used in the vulcanizable compositions according to the invention can increase the rate of vulcanization of the terpolymers and, in some cases, reduce the vulcanization time from 12 to 30 days to 48 to 72 hours, in some cases even to 2 to 48 hours. Depending on the type and amount of the peroxide used and / or the accelerator, the masses are expediently at temperatures below ambient temperature, at ambient temperature or at temperatures above 30.degree. C., preferably above 35 ^; C vulcanized.

Terpolymers are selected as component A in the vulcanizable compositions according to the invention Ethylene used with propylene or butene-1 and a polyene with non-conjugated double bonds, where the polydiene is preferably dicyclopentadiene, cyclooctadiene-1,5, cyclooctadiene-1,4, cyclododecadiene-1,6, Cyclododecadiene-1,7, cyclododecatriene-1,5,9, 1,4-cycloheptadiene, 1,4-cyclohexadiene, norbornadiene, Methylene-norborncn, 2-methylpentadiene-1,4, hexadiene-1,5, heptadiene-1,6 or 5-methyhetrahydroindene is. Preferred few terpolymers with a molecular weight between 60,000 and 500,000.

Suitable organic hydroperoxides are cumyl hydroperoxide, p-mentane hydroperoxide, tert-amyl hydroperoxide, Brom-lert.-butylhydropcroxyd, m, p - diisopropylbenzene monohydroperoxide or m.p-Diisopropylbenzene dihydroperoxide used.

Examples of component D contained in the valcanizable compositions according to the invention are Cobalt or manganese salts of n-octanoic acid, 2 ■ ethylhexanoic acid, Lauric acid, palmitic acid, stearic acid, linoleic acid and k'aphthenic acid.

example 1

ίο Three mixes are made in a standard mixer manufactured at room temperature from the following components:

Ethylene / propylene 1 2 100 - 3 - 0.5 15th {49Weight- ° ") / Cvclo- Parts by weight octadiene (0.277 mol / kg) - 100 100 Terpolymer (ML (I-M) 20th at 100 C = 84 HAF carbon black 50 \ -Cumyl hydroperoxide 5.7 (70% cumene) 50 50 Kobult-2-ethylhexanoate 5.7 1.0 5.7 25th (Accelerator) Cobalt naphthenate 0.5 (Accelerator) .._ 30th

These mixtures are used to produce samples from 0.4 to 0.6 mm thick, which during the specified Time to be kept at room temperature (25 "'C). The mechanical properties of the samples are determined periodically as a function of time. The results are given in the table below.

Table 1

Mix no.
1 Break elastic
deh module Shape-
change 2 Fractional E ₂₀₀
deh Shape-
change 3 fracture
deh E200 certainly 75 certainly 107 Shape-
change Accelerator, type, amount
Co-2-ethylhexanoate voltage at 200% foresight
rest tion foresight
rest tion 350 275 111 foresight
rcst 0.5 parts by weight b. 100% Co-2-ethylhexanoate Co-naphthenate 245 216 Time, days train
firm ¹ % kg / cm ⁵ 0 / 1 part by weight ^! % kg cm ² /O 0.5 part by weight c ! O/
/O kg / cm ² 215 - ■ /O speed 330 63 14th train
firm 335 88 12th train
firm 415 45 170 20th 300 87 14th speed 250 108 12th speed kg / cm ^! certainly certainly 14th 2 131 245 109 14th kg / cnv 210 127 12th kg / cnv 3 140 230 114 12th 172 220 134 12.5 128 11th 4th not certainly 147 certainly not 10.5 5 145 200 143 10 not 205 Π 2 12.5 172 10.5 6th 130 200 128 ge
broke 137 180 ge
brocl not ge
broke 8th not 141 169 11th 143 not 152 16 128 115 130 99 95
iien

Example 2

Mixtures of the following composition are made in a conventional mixer:

Ethylene / propylene
(45% by weight) / 5-methyl-tetrahydroindene
(0.246 mol / kg) terpolymer (Ml (I +4)

at 100 ^c C = 84) 100 parts by weight

ΗΑΓ carbon black 50 parts by weight

Λ-cumyl hydroperoxide

(70 ",; cumene)

accelerator
(different types) .

5.7 parts by weight different

These mixtures are used to produce samples 0.4 to 0.6 mm thick. The samples are during kept at room temperature for the specified time. The mechanical properties as a function of Time are compared to the properties of blends that do not have a vulcanization accelerator included in Table 2.

Table 2

lead,
Days Mix no.
4th '"200 Shape-
inducing
rest 5 • -'- 200 Shape-
changing
rcst Accelerator. Type, amount kg / cm " 0 / Cobalt naphthenate
0.5 weight lcile kg / cm ² Tensile break
strength elongation Tensile break
strength elongation 99 11.5 kg / cm ² % kg'cm ¹ % 0.75 unvulkaninicrl 211 330 1 unvulcanized 38 18th not determined 202 6th 1.75 unvulcanized not determined Ϊ 144 500 100 10 216 210 i, 75 not determined not determined 4th 196 310 117 8.5 not determined - Broken % not determined not determined 6th 209 300 172 190

Table 2 (continued)

£ cit,
"Days Mix no.
6th Shape-
changing
rcst 7th ^ 200 shape
change
rest Accelerator, type, amount
Cobalt laurate
0.5 weight part ° / Manganese stearate
0.75 parts by weight kg / cm ² O/
/ 0 Tensile fracture Fj ""
strength elongation 10 Tensile break
strength elongation 24 36 kg / em ^! % kg / cm ² 8.5 kg / cm ² % 37 25th 0.75 206 250 147 80 510 1 178 190 119 460 87 13th 1.75 not determined 8th not determined 102 11th 2 not determined 200 360 2.75 167 180 Broken 194 310 134 8.5 4th not determined not determined 5 79 120 172 240 6th not determined not determined

Example 3

Mixtures of the following composition are with the same mixer and under the same conditions as in the previous examples called, manufactured:

Ethylene / propylene
(45% by weight) /
1,4-hexadicne (0.425 mol /

kg) terpolymer 100 parts by weight

HAF carbon black 50 parts by weight

Λ-Curnyl hydroperoxide

(70% cumene)

accelerator
(different types) ..

5.7 parts by weight
different

These mixtures are used to produce samples 0.4 to 0.6 mm thick. The samples are during Maintained at room temperature (25 ° C) for the specified time. The mechanical properties as a function the times are given for the vulcanizates obtained in Table 3 and with the corresponding Compared properties of a mixture that does not contain an accelerator.

Tabel 3 Mix no.
8th shape
change
rest 9 % t-200 shape
change
rest Time,
Days Accelerator, type, amount /O 580 kg / cm ^! % Tensile breakage E ₂₀₀
strength elongation certainly 12th 34 kg / cm ^s % kg / cm ² Co-2-ethylxanoate
0.5 parts by weight 560 unvulcanized Tensile break
strength elongation 510 18th 20th 3 unvulcanized kg / cm certainly 24 23 4th unvulcanized 23 430 5 unvulcanized 42 not 360 28 20th 6th unvulcanized 71 53 16 8th 18 440 14 84 11th not determined not 16 109 125

Table 3 (continued)

Time,
Days Mix no.
10 E ₅₀₀ shape
change
rest 11th E ₅₀₀ shape
change
rest Accelerator, type, amount
Co-2-ethylhexanoate
1 part by weight kg / cm ¹ ■> /
/O Manganese octoal
0.5 parts by weight kg / cm ^s X Tensile break
strength elongation 11th 34 Tensile break
strength elongation kg / cm ⁵ % kg / cm «% 16 26th 3 39 540 23 20th not determined 20th 19th 4th not determined 33 21 48 560 5 83 470 76 550 26th 19th 6th 82 370 55 20.5 not determined 34 18th 8th not determined 63 14.5 96 480 11th 110 320 118 410 Ifi 106 MO not determined

Example 4

A mixture having the same composition is prepared in a conventional mixer at room temperature like the mixture mentioned in Example 2 and has 0.5 part by weight of cobalt laurate as an accelerator

contains. With this mixture, samples with a thickness of 0.4-0.6 mm are prepared for determination the mechanical properties of the vulcanizates are used. That depends on the vulcanization time mechanical properties determined and temperature are given in Table 4.

Table 4

mixture No. 13th 12th 25 ° C temperature 60 ⁰ C 4th Time, hours 2 123 Tensile strength, kg / cm ² 198 310 Elongation at break,% 320 52 Modulus of elasticity at 200%, 89 kg / cm ² 112 Modulus of elasticity at 300%, 180 kg / cm ² 16 Deformation rest at 10 100% elongation,%

Claims (1)

Claim: Use of 0.01 to 20% by weight of an organic hydroperoxide of the general formula R - OOH, in which R is a tertiary aliphatic, cycloaliphatic or aromatic radical, for Cold vulcanization of molding compounds, consisting of A) a high molecular weight, unsaturated, amorphous and essentially linear terpolymer from a) 20 to 80 mol percent ethylene, b) 0.1 to 18 mole percent of a cyclic or acyclic polyene with non-conjugated double bonds and c) a Λ-olefin, and B) carbon black as Reinforcing filler and, if applicable, C) antioxidants, pigments and other additives, characterized by the additional use of 0.1 to 2 parts by weight, based on to 100 parts by weight of A, of a cobalt or manganese salt of an aliphatic or cycloaliphatic Carboxylic acid with 8 to 18 carbon atoms as a vulcanization accelerator.