DE1470995B2 - OZONE-RESISTANT VULCANIZABLE FABRIC BLEND - Google Patents

Description

1 2

It is known that anti-aging agents that can make technically useful articles of all kinds

direct attack of oxygen on the rubber- this mixture of substances can be produced, e.g. B. coating

Prevent ties and the rubber in front of the fabric, such as those used in the manufacture of upper leather

Oxidation initiated by metal catalysts can be used for shoes.

protect, no protection against the corrosive 5 The ethylene-propylene copolymer should protect

effect of ozone. Attempts have therefore been made preferably unsaturated and volcanic by means of sulfur

undertaken to use the natural rubber against the embeddable. It is carried out in a manner that is usual in itself

To protect the effect of ozone by a copolymerization of ethylene and propylene with

Ethylene-propylene-diene terpolymer added, such as at least one copolymerizable therewith

this in the magazine "Rubber World", February 1964, io dien, usually a non-conjugated diene,

P. 62 to 68, or in the Belgian patent such as dicyclopentadiene, 1,4-hexadiene, 1,5-cyclooctadiene

605 232 is described. and the like won. These include the mixed poly

From the British patent specification 946 224 one knows merisate, as it is in the British patent specification 880 904,

also that natural rubber, butadiene-sty- in U.S. Patents 2,933,480 and 3,000,866

rol rubber: or their mixtures with ethylene 15 as well as in Belgian patents 623 698 and

Propylene-butadiene terpolymers or. _r Ethylene ^ 623 741 are described. The diene component

Propylene copolymers anti-aging agents add unsaturation to the terpolymer formed

should put. From this one recognizes; that one against them and makes it vulcanizable with the help of the

Exposure to ozone-proof rubber, not _χ saturated rubbers conventional vulcanizing systems,

at the same time against the action of oxygen 20 including systems based on sulfur and

is protected, as is the case with the use of the accelerator for the sulfur vulcanization.

Antioxidants is achieved and vice versa. The saturated ethylene-

The previously known admixture of ethylene-propylene copolymers, which cause peroxide curing

To require propylene copolymers or terpolymers. Preferred dienes are the compounds

However, rubber is not enough to make natural rubber 25 dicyclopentadiene, 1,4-hexadiene and 1,5-cyclooctadiene.

and / or butadiene-styrene rubber in particular, which is also involved in the claimed mixture of substances.

if it is used for use in footwear, poly (trimethyldihydioquinoline) is a popular

should be, sufficient against the attack of ozone known material, for example by polymer

to protect. they are made from l ^ -Dihydro ^^^ - trimethylquinoline

The object of the invention now consisted in the manner in which it is presented in US Pat. No. 2,718,517

Creation of a natural rubber and / or butadiene is described.

Styrene rubber with improved protection against the mixtures of substances according to the invention

Exposure to ozone. also contain any additives as they are for the

The invention relates to an ozone-resistant, described rubbers which can be used, especially a vulcanizable mixture of 100 parts by weight of vulcanizing agents, especially sulfur or natural sulfur rubber, vulcanizing agents that split off butadiene-styrene rubber, accelerators, as well as or mixtures thereof, 5 to 50 parts by weight of a filler , Pigments, plasticizers, processing ethylene-propylene copolymers or an ethylening auxiliary, etc.
len-propylene-diene terpolymer, and 0.5 to Beisoiel
5 parts by weight of an antioxidant, the 4 °
is characterized in that it is used as an oxidation The following mixture was prepared

Protective agent poly ^^ A-trimethyl-l ^ -dihydroquinoline "_,. ,

...... ^J .... ■■ '·· ■' ■ ^J ■■ ■ · ... ■■ Stock weight

contains. , -,. . ■ _tejle ■■■ · _tejle

The invention is based on the surprising Ent natural rubber (smoked sheets No. 1) 80,68

ivsckung that a mixture of substances consisting of the three 45 ethylene-propylene-diene terpolymsrisate 10.20

called constituent ^ consists of a remarkable butadiene-styrene rubber. 9.12

Has resistance to the action of ozone. Polytrimethyldihydroquinoline 4.00

The extent of this resistance goes far beyond the semi-reinforcing furnace black 9,12

Ozone resistance, i.e. from the well-known whipped chalk (natural calcium

Expect effects of the individual components themselves 50 carbonate V 37 57

could. There is a 'surprising synergistic zinc oxide' 3'47

Interaction between these components when wax 050

in the present novel combination they are N-Phenyi-N'-cyclöhexyl-p-phenyien- '' '

be agreed. diamine 0 41

Although polytrimethyldihydroquinoline as aging phthalic anhydride '.'. '.'. '.'. '.'. '.'. '.'. '.'. '. o ', 16

Protective agent for rubber from the USA.-Patent- 2-Benzthiazyl disulfide 0 69

Writings 2 718 517 and 3 047 521 was known, could tri- (nonylphenyl) -phosphk "'.'.'.'.'.'.'.'.'. Θ! Θ9

one does not conclude from this that it is also called ozone-chlorinated paraffin ... 0.21

Protective agent works, and certainly not that it acts as sulfur 1 69

Ozone protection agent known Ethylene-Propylene-Co- 60 ' '

polymers or ethylene-propylene-diene-terpoly- The ethylene-propylene-diene-terpoly-

merisate is able to influence synergistically. merisat consisted of 41% ethylene, 55% propylene and

The components of the claimed mixture of substances 4% 1,4-hexadiene.

can be incorporated in any suitable known manner The rubbers, poly (trimethyldihydroquinoline) mixed together, e.g. B. on a rubber 65 and the carbon black will be in this order for 5 minutes Knead, and the mixture can then be mixed on for a long time in a Banbury mixer with low agitation Way brought into any desired shape speed mixed together. The remaining be e.g. B. by calendering, compression molding and the like. Ingredients are then mixed in, except

the sulfur. The batch is then unloaded from the mixer and allowed to cool. The cooled batch is then poured back into the mixer, sulfur is added and everything is mixed with one another at a slow stirring speed in order to obtain the finished batch. The material is then calendered onto a fabric at a temperature of 99 to 113 ° C in order to produce upper leather for shoes. The material is vulcanized at 132.degree. C. for 2 ¹ I _{2 hours under conventional conditions.}

Of course, many modifications can be made in the preceding example, as is well known to those skilled in the art be made.

In order to demonstrate the synergistic effect occurring, the following four different Materials made:

1. As in the example, but with only 2 parts of poly (trimethyldihydroquinoline), but without ethylene-propylene-diene terpolymer.

2. As in the example, but without ethylene-propylene-diene terpolymer, contains 4 parts poly (trimethyldihydroquinoline).

3. Same as in the example, but without poly (trimethyldihydroquinoline) contains 10 parts of ethylene-propylene-diene terpolymer.

4. Mixture according to Example [4 parts of poly (trimethyldihydroquinoline), 10 parts of ethylene-propylene-diene terpolymer].

These four mixtures underwent a particularly severe ozone resistance test in the vulcanized state subjected, by putting them in an ozonometer to the action of 50 parts per ozone Exposing 1 million parts to air at 38 ° C. Here were get the following results:

material State degree of
Cracking 1 Breaks after an exposure 1- duration of 2 hours and 40 minutes 2 Breaks after an exposure ■ 1- duration of 2 hours and 40 minutes 3 Breaks after an exposure 1- duration of 2 hours and 40 minutes 4th No cracks after 100 hours - 100 *) - 80 - 20th

Time in hours until the sample breaks in the ozonometer when exposed to 50 parts of ozone per 100 million parts of air at 38 ⁰ C (material for footwear)

ο · . ■
Antioxidants Series A
NR-SBR Series A
NR-SBR ¹ +
10 parts EPRD ₁₀ 1. Without oxidation 7th 13th protective agent 2. poly (trimethyldi- 9 in good hydroquinoline) nature after 272 hours 3. Antioxidant 16 16 medium a) 4. Antioxidant 16 11th medium b) _ao 5. Antioxidant 11th 16 medium c) 6. Antioxidant (Jl 16 medium d) 7. Antioxidant 7th 56 2 ₅ medium e)

45 days to break the specimen outdoors (material for footwear)

Antioxidants Series A
NR-SBR Series B
NR-SBR +
10 parts EPRD 1. Without oxidation 5 5 protective agent 2. poly (trimethyldi- 11th good condition hydroquinoline) fineness after 104 days 3. Antioxidant (Jl (Jl medium a) 4. Antioxidant 5 7th medium b) 5. Antioxidant 5 19th medium c) 6. Antioxidant 13th 56 medium d) 7. Antioxidant 5 11th medium e)

*) The first number indicates the number of cracks; the second number indicates the surface in ° / o over which the crack extends extends.

It can be seen that the combination of ethylene-propylene-diene terpolymer and poly (trimethyldihydroquinoline) (mixture 4 according to the invention) in the mixture of natural rubber and butadiene-styrene rubber has a stabilizing effect, which is the result of the addition of ethylene-propylene-diene terpolymer alone or from poly (trimethyldihydroquinoline) alone to the mixture of natural rubber and butadiene-styrene rubber are not achieved. The invention also produces excellent results cracking tests carried out in outside air.

Test report

The basic mixture given in the example was made with various anti-aging agents accordingly offset from the information in the following tables.

Remarks:

NR = natural rubber SBR
EPRD

Antioxidant a)
Antioxidant b)
Antioxidant c)
Antioxidant d)

■■ Butadiene-styrene rubber.

Ethylene propylene diene terpoly

merisat.
■■ Reaction product of diisobutene

and diphenylamine.

Reaction product amine and acetone.

of diphenyl

Reaction product of phenyl- / 3-naphthylamine and acetone. Complex of 65% diarylamine-ketone reaction product and 35 ° / o Ν, Ν'-diphenyl-p-phenylenediamine. Antioxidant e) = alkylated bisphenol.

From this test report it can be clearly seen that only that proposed according to the invention Poly (trimethyldihydroquinoline) has a synergistic effect together with ethylene-propylene-diene terpolymers able to exercise.

Claims (1)

'Claim: Ozone-resistant, vulcanizable mixture of 100 parts by weight of natural rubber, butadiene-styrene rubber or mixtures thereof, 5 to 50 _{parts by weight of an ethylene-propylene copolymer or an ethylene-propylene-diene:} Terpi) lyrnerisates and 0.5 to 5 parts by weight of an antioxidant , characterized in that the mixture of substances contains poly-2,2,4-trimethyl-1,2-dihydroquinoline as an antioxidant ..