DE1420148C - Process for the production of elastic plastics - Google Patents

Description

ι 2

From the German patent specification 1 004 370 it is elastic plastics stand out against VuI-

known, natural or synthetic rubber cans made from natural or synthetic oil

with unsaturated polyester resins and liquid vinyl finically unsaturated elastomers through a high

compounds in the presence of peroxides for resistance to atmospheric influences,

knead. Subsequently, the reaction mixture 5, in particular with respect to oxygen and ozone, is turned off.

the usual vulcanization auxiliaries such as sulfur, the invention now relates to a method

Vulcanization accelerators and fillers added for the production of elastic plastics by

and these mixtures are then subjected to vulcanization - co-vulcanization of elastomers and mixed poly-

threw. merizaten of ethylene with the help of organic

From British patent specification 757 523 it is i ° peroxides using elevated temperatures,

further known, natural rubber together characterized in that one copolymers

with polystyrene in the presence of organic per- from ethylene with 10 to 60 percent by weight vinyl

to crosslink oxides in order to increase the hardness of these mixtures acetate and, if necessary, additionally polymerize

to improve. bare compounds with at least two olefinic

British Patent 718,571 relates to the 15 unsaturated groups used. Plasticization of resinous polymers derived from suitable elastomers for carrying out the monovinylaromatic hydrocarbons, claimed processes are, for example, natural with synthetic rubbers with a soft rubber, synthetic elastomers based on macher, the mixture being conjugated at 140 to 230 ° C with diolefins how copolymers are kneaded. The procedure is continued for ^{3 to 15 minutes after adding a 3} ° butadiene and / or isoprene with styrene and / or peroxide. Acrylonitrile, polyisoprene, polychlorobutadiene, and the subject of the invention can be the pre-butyl rubber. Furthermore, olefinically unsaturated patents cannot be found. saturated groups, for example alkylene groups entin the British patent 572133 is the holding polyadducts from compounds vulcanization of monoolefin-diolefin mixed poly »5 with several reactive hydrogen atoms, merisates with copolymers, eg. B. from ethylene such as polyethers containing hydroxyl end groups and vinyl acetate in the presence of sulfur and / or polyesters, with polyisocyanates application ben. Similar blends can be found from the.

USA.-Patent 2,474,309 known, namely Mi- Due to the exceptionally good skewing made of rubbery butadiene-acrylonitrile 3 <> The copolymers and optionally saponified polyhomogeneous mixtures with the olefinically unsatvinylacetate can be used for the copolymers mentioned or vinyl acetate-vinyl chloride copolymers produced elastomers, the mixture sates, which are vulcanized with the help of sulfur. Ratios can be varied within wide limits In the case of sulfur vulcanization, only they can take. To have a noticeable effect of improvement It is essential to achieve oxygen and ozone resistance in the double bonds present in rubber the crosslinking part, but not saturated polymers. but advantageously in the mixtures mentioned From the Italian patent specification 583 502 it is at least 10 percent by weight of interpolymer known to incorporate olefinically unsaturated elastomers, seeds. The amount of used such as butadiene-styrene or butadiene-acrylonitrile copolymers depends on the desired polymers with ethylene-propylene copolymers 40 properties of the vulcanized mixtures and seeds to vulcanize in the presence of peroxides. can be up to about 90 percent by weight. How, however, from the following comparative for carrying out the claimed test As can be seen, the vulcanizates can achieve the same processing conditionally of the Italian patent specification after a certain application, as it is in that of the German ozone treatment do not see the favorable strength 45 patent specification 1136 485 and the German values as explained in more detail for the products according to the invention of Auslegeschrift 1 169 126, own. The claimed method is suitable for the German Auslegeschrift 1 052 676 is to develop molded articles such. B. to take, that polymers of ethylene or mixed position of cable sheaths, of white wall polymers of ethylene, which have been chlorosulphonated, so mature for motor vehicles, of ozone-resistant dichin Mixing with an unsaturated elastomer and profiles, raincoat rubber linings, after vulcanization with sulfur an improved tarpaulin of all kinds, leather substitutes, hoses and Have aging resistance to ozone. A pipe. Furthermore, the method for manufacturing The disadvantage of these mixtures is that they are of all types of composite bodies with high weather and Due to the relatively high chlorine content, they can be used for chlorine ozone resistance. For splitting off underwater tend and thus for numerous support of the composite effect of the rich fields of application according to the invention are out of the question. Mixtures used can also be used here Finally, in the German patent specification, adhesion promoters, such as polyfunctional isocyanates, are a-1 136 485 or the German Auslegeschrift 1 169 126. It can be made out of composite bodies Already proposed copolymers 6o metals, fabrics, glass and other materials obtained from ethylene and at least one tertiary carbon with layers of crosslinked elastomers, vinyl compounds containing atomic atoms, in particular the following examples illustrate the invention: their vinyl esters, with the help of radical formers

to crosslink elevated temperatures. There are also comparative tests against the Italian patent for the implementation of this procedure in addition 65 script 583 502 polymerizable organic compounds with at least two, preferably three olefinic double On a rolling mill were at room temperature bindings have been used. The following mixtures thus obtained are made:

Light crepe

Copolymer of 45 parts of vinyl acetate and 55 parts of ethylene

Copolymer of 45 parts of propylene and 55 parts of ethylene

Highly active, precipitated silica

Non-discolouring anti-aging agent

Titanium dioxide

Dioctyl phthalate

Dicumyl peroxide

Triallyl cyanurate

Invention

according to

example

Parts

50

50

30th

1 5 5 1.2

Comparative experiment

Parts

50

50 30

1.2

The mixtures were (4 atm steam pressure =) vulcanized 25 minutes at 151 ° C, whereupon the obtained test specimens at 30% ^it was exposed to an ozone concentration of 2 x 10 ~ ⁴ strain.

judged on an empirical scale (0 - without cracks, 1 -: traces of cracking, 2 - ■■ clear cracking, 3 - strong cracking, 4 = very strong cracking, 5 = breakage). The following 5 assessments resulted:

»5

Invention
according to
example Comparative
example Crack formation after
6 hours O O O O O O O 1
3
4th
5 12 hours 0
0
0 36 hours 60 hours 84 hours 107 hours - 131 hours 155 hours 240 hours. .. 300 hours

After just 36 hours, the VuI test specimens produced in accordance with Italian patent specification 583 502 showed very severe cracking after various periods of time. The specimens cleared examined for crack formation and these were already broken after 60 hours.

In the following examples the parts given are parts by weight.

example 1

The following mixtures are produced on a rolling mill at room temperature:

Light crepe

Copolymer of 45 parts of vinyl acetate and 55 parts Ethylene

Highly active, precipitated silica

Non-discolouring anti-aging agent

Titanium dioxide dioctyl phthalate dicumyl peroxide triallyl cyanurate

A parts

100

30th

1.2

Parts

50

C TeUe

50 25th 30th 30th 1 1 5 5 5 5 1.2 1.2 2 2

The mixtures were for 25 minutes at 151 ° C 65 The test pieces were after various time

(= 4 atmospheres vapor pressure) vulcanized, whereupon the clearing is examined for crack formation and this after the

held test specimens at 30 ° / ₀ iger tension assessed on an empirical scale listed above.

Ozone concentrations of 2 · 10 ~ ^{e were} exposed. The following assessments were made:

Crack formation after

6 hours .

12 hours .

36 hours.

60 hours.

84 hours.

107 hours .

131 hours .

155 hours .

240 hours .

300 hours .

Vulcanizate from mixture A B

0
Obis I

3
3 to 4

O O O O O O O O O O

O to 1 O to 1

Example 2

The following mixtures were produced on a rolling mill at room temperature:

A.
Parts B.
Parts C.
Parts Butadiene - styrene - M ischpoly meri-
sat from 70 parts of butadiene and
30 parts of styrene
Ethylene - vinyl acetate - mixed poly
merisat from 45 parts vinyl
acetate and 55 parts of ethylene
Semi-active soot
Discolouring anti-aging protection
medium 100
50
1
5
1.5
2.0 50
50
50
1
5
1.5
2.0 75
25th
50
1
5
1.5
2.0 Dioctyl phthalate
di-tert-butyl peroxide
Triallyl phosphate

The mixtures were for 40 minutes at 151 ^c C (-. 4.0 atm steam pressure vulcanized were · subjected whereupon the obtained test specimens at 40 ° / oigcr voltage of an ozone concentration of 2 * 10 * These Vuklanisate showed a similar behavior as in the Example 1 show blends of natural rubber in comparison with the mixture produced only from natural rubber.

example

The following mixtures were produced on a rolling mill:

Butadiene - acrylonitrile - mixed polymer (38 ° / o acrylonitrile) ...

Copolymer of 30% vinyl-5 acetate and 70% ethylene ....

paraffin

Discolouring anti-aging agent

Active carbon black

^ϊ0 dioctyl phthalate

Dicumyl peroxide

Triallyl cyanurate

The compatibility of the elastomers can be seen from the J ₅ physical values of the 40 minutes at 150 ^° C. volcanic samples.

A. B. C. Parts Parts Parts 100 75 50 _ 25th 50 1 1 1 1 1 1 40 40 40 5 5 5 1.5 1.5 1.5 1 1

Tensile strength (kg / cm ¹ )

Elongation (° / ₀ )

Hardness (Shore):

Room temperature

75 = C

Rebound resilience ( ⁰ I ₀ ):

Room temperature

75 ^C C

Vulcanizate from mixture

AIBIC

180 180 510 340

60 48

20 45

75 62

24 46

In all cases, the addition of the ethylene-vinyl acetate copolymers results an improvement in ozone resistance.

Claims (1)

Claim: Process for the production of elastic plastics by co-vulcanization of elastomers and copolymers of ethylene with the aid of organic peroxides using elevated temperatures, characterized thereby. that one uses copolymers of ethylene with 10 to 60 percent by weight of vinyl acetate and optionally additionally polymerizable compounds with at least two olefinically unsaturated groups.