DE2214511C3 - Mixtures of processing aids for rubber processing - Google Patents

Description

3. Mixtures according to claim 1, characterized in that they are acidic and larger amounts of mineral oils, that the fatty acid components of the metal grow and / or contain petrolatum, which thereby salts [component e)] iodine values are characterized by approximately that they

to 95.

a) 5 to 15% diaryl or dialkylaryl phthalates,

60 diaryl or dialkylaryl monoglycol ether phthalate

late, phthalic acid esters of aryl or alkylaryl

polyglycol monoethers with 2 to 6 ethoxy groups

in the polyglycol chain, dibenzoates of ethylene glycol, propylene glycol or their dimers or 65 trimers or a mixture of these compounds,

In known processes for the production of rubber b) 5 to 30% branched or unbranched aliphatic products was until recently the first of the table alcohols with 8 to 20 carbon atoms in the

polymer raw rubber degraded (mastication). Main chain, alkylphenoxy ethers of glycols

3 '4

or polyglycols with up to 12 carbon atoms in that of hydrogenated tallow or hydrogenated vegetable

Main chain of the alkyl group and a maximum of 6 ethoxy or animal oils.

groups in the polyglycol chain.Polypropylene- The fatty acid component of the component e)

glycol with 3 propoxy groups in the molecule or metal salts used derives z. B. of plants Mixture of these compounds, oils or oil fractions of animal origin, e.g. B.

c) 5 to 15% potassium or sodium salts of red oil. It is preferable to use technical ones common, essentially saturated fatty acids oleic acid.

or fatty acid mixtures with 12 to 18 carbon atoms The mineral waxes used as component f)

in the main chain, the main chains preferably having melting points of approximately have more than 50% 18 carbon atoms, io 49 to 77 ° C; the petrolatum is preferably derived

d) 10 to 30% essentially saturated fatty acids from petroleum fractions and has melting points of with 12 to 18 carbon atoms in the main chain, with about 38 to 57 ° C.

the main chains to over 50% 18 carbon atoms The mixtures according to the invention of processing

have processing auxiliaries for rubber processing

e) 5 to 10% zinc, magnesium, calcium and / or xs usually produced by the ange-barium salts of fatty acids with 12 to 18 carbon atoms are heated together until a men in the main chain, the main chain forming a clear melt. The alkali metal salts or the mostly have a double bond, and sake is made of divalent metals of the fatty acids

f) 15 to 60% mineral oils, mineral waxes, petroleum in a known manner from oxides, or hydroxides latum or their mixture as carbonates of the metals and the desired acids

or acid anhydrides, the resulting water

contain. is evaporated.

The potassium or sodium salts of component c) are preferably prepared according to the invention

and the fatty acids of component d) have mixtures of processing aids for chewing

preferably iodine levels of about 5 to 15. The as-chukver & jbeitung by the fact that the metal

Metal salts of component e) have more double salts and the hydrocarbon in a suitable one

ties on; They have iodine values of about the reaction vessel and the mixture to about HO ⁰ C

Heated to 95. and stir thoroughly until the salt

Mixtures which are homogeneously distributed are particularly preferred. The fatty acids are then mixed together

up to 15% dipropylene glycol dibenzoate, 3 to 20% 30 to, whereby if necessary to facilitate the mixing

Nonylphenoxytetraethylene glycol, 2 to 10% tri-process, the temperature is increased by about 1O ⁰ C,

propylene glycol, 5 to 15% potassium stearate, 10 to 30% Next are the potassium or sodium salts

Stearic acid, 5 to 10% zinc oleate and 15 to 60% of the fatty acids, then the alcohol or glycol

Petrolatum included. components stirred in. Mix the obtained

Specific examples of the mass mixed as component a) with stirring until it is clear and homogeneous

used aromatic esters are is. The aromatic compounds are then added

and mix them thoroughly. The mixtures of

Dibenzyl phthalate, rubber processing aids can then be used in

Diphenyl phthalate, suitable containers to be filled in which they are located

Di- (2-phenoxyethyl) phthalate, 40 solidify.

Di (nonylphenoxyethyl) phthalate, when using the mixtures according to the invention

Di- (nonylphenoxytetraethylene glycol) phthalate, of processing aids for rubber

Benzyl-dodecylphenoxyhexaethylene glycol work is the usual degradation

phthalate, natural or synthetic rubbers are not

Di- (octylphenoxyhexaethylene glycol) phthalate, 45 required, or it is facilitated so that the

Diethylene glycol dibenzoate, number of mixing cycles in the Banbury mixer, d. H.

Dipropylene glycol dibenzoate reduced mixing time by approximately 25 to 50%.

Triethylene glycol dibenzoate. In addition, rubber dispersions have the

smaller amounts of the mixtures according to the invention

Specific examples of those used as component b) contain processing aids that are better used in-house Alcohols or glycols are created as dispersions, which after prolonged mixing

without using these mixtures of processing

2-ethylhexanol, auxiliaries were obtained. Other advantages of the

Cetyl alcohol, mixtures according to the invention of processing aids

Stearyl alcohol, 55 substances used in rubber processing are

Nonylphenoxyglycol, wise the low mixing temperatures, which improve

Nonylphenoxy diglycol, th flow properties and mechanical properties

Nonylphenoxytetraethylene glycol, shafts of the rubber compounds, z. B. improved

Dodecylhexaethylene Glycol, Miscibility, Moldability, and Processability. the

Dipropylene glycol, 60 capacity the Banbury mixer can also use

Tripropylene glycol. be fully exploited.

The mixtures according to the invention of processing

The potassium or processing auxiliaries used as component c) for rubber processing were sodium salts derive, for example, from the hydrogenated rubber usually at the beginning of the Tallow, hydrogenated vegetable or animal oils 65 incorporated in the mixing process. In known processes or oil or fat fractions, the iodine values for rubber processing are subject to approx 5 to 15. initially lent the raw rubber to mastication and The fatty acids used are usually derived making it more plastic. Then you mix

other additives such as pigments, e.g. B. carbon black, fillers, e.g. B. oxides of zinc, magnesium, lead or calcium, or vulcanizing agents, e.g. B. sulfur, too. Using of the mixtures of processing aids according to the invention these additives can be incorporated into the raw rubber after it has been mixed with the mixtures of processing aids for a short time was kneaded.

The rubber compounds usually contain approximately 0.5 to 3, preferably 1 to 2% of the mixtures of processing aids, based on the total weight of rubber. The mixtures according to the invention of processing aids for rubber processing any type of rubber can be added, e.g. B. natural, synthetic or regenerated rubber.

The following mixtures are specific examples of adjuvants according to the invention. The specified components can be of technical quality, ie contain similar compounds and by-products.

Mixture A

10.0 kg 15.0 kg 8.0 kg 6.0 kg

17.0 kg 10.0 kg 34.0 kg

Mixture B 5.0 kg

10.0 kg 10.0 kg

10.0 kg 15.0 kg 10.0 kg 10.0 kg 20.0 kg 10.0 kg

Mixture C 15.0 kg

5.0 kg 10.0 kg 5.0 kg 10.0 kg 10.0 kg 20.0 kg 5.0 kg 5.0 kg 15.0 kg

Mixture D

7.0 kg 8.0 kg 3.0 kg

10.0 kg 13.0 kg 30.0 kg 5.0 kg

24.0 kg

Dipropylene glycol dibenzoate,

Nonylphenoxytetraethylene glycol,

Tripropylene glycol,

Potassium salts of hydrogenated sebum,

Stearic acid,

Zinc oleate,

Petrolatum.

techn. Di-nonyl phenoxy glycol phthalate

and di-nonylphenoxy diglycol phthalate

(approximately 1: 1),

Cetyl alcohol,

techn. Nonylphenoxyglycol and nonyl

phenoxy diglycol (approximately 1: 1),

Dodecylphenoxy-hexaethylene glycol,

Sodium stearate,

Stearic acid,

Calcium oleate,

paraffinic mineral oil 100/100,

Paraffin wax, refined.

Benzyl-dodecylphenoxyhexaethylene

glycol phthalate,

2-ethylhexanol,

Cetyl alcohol,

Dodecylphenoxy-hexaethylene glycol,

Nonylphenoxy-tetraethylene glycol,

Potassium stearate,

Stearic acid,

Barium oleate,

Magnesium oleate,

Petrolatum.

Diphenyl phthalate,

Dipropylene glycol dibenzoate,

Cetyl alcohol,

Tripropylene glycol,

Potassium stearate,

Stearic acid,

Zinc oleate,

Petrolatum.

Mixture E.

9.0 kg diphenyl phthalate,

5.0 kg of cetyl alcohol,

5.0 kg potassium stearate,
19.0 kg stearic acid,

8.0 kg zinc stearate,
55.0 kg of petrolatum.

Mixture F

10.0 kg diphenyl phthalate,

3.5 kg of cetyl alcohol,
14.0 kg nonylphenoxytetraethylene glycol,

7.0 kg tripropylene glycol,

5.0 kg of potassium salts of hydrogenated sebum,
15.0 kg stearic acid,
10.0 kg zinc oleate,
35.5 kg of petrolatum.

Each of the above blends was used as an approximately 1 to 2% additive in various Rubber compounds, ζ. B. based on natural and synthetic rubber used. In the The following examples show the results of investigations from which the advantageous Effect of the auxiliaries according to the invention in EPDM rubber compositions emerges.

Test report

There are three differently composed tools according to those given below Recipes made. Recipe No. 1 corresponds to the state of the art according to GB-PS 10 64 189. Recipes No. 2 and 3 correspond to the teaching of the invention,

d. that is, they additionally contain component (a).

Each tool was used to make a

Rubber mixture for pressure-resistant steam hoses

used, an ethylene-propylene terpolymer was used and mixing according to the "upsidedown" technique took place. 1 mixing cycle was used in each case in the Banbury mixer.

The results obtained are shown in the table.

Auxiliary materials Prescription of the components 10 2 10 3 10 (Shares in parts by weight) 1 1 1 1 4th 4th 4th 40 40 40 oleic acid (d) 20th 20th 20th Zinc oxide (s) 2 2 2 Cetyl alcohol, techn. (b) 17th 17th 17th 55 Petrolatum, N. F. (f) Stearic acid, techn. (egg) Potassium hydroxide, 45% (c) 8th 8th 8th Mono (noylphenoxy) - - 10 8th _β tetraethylene glycol ether - - 2 (b) Tripropylene glycol (b) 47. 4th 3 Diphenyl phthalate (a) 115.6 110 104.4 Dipropylene glycol dienzoate 65 (a) Mixing time (min.) Temperature ( ⁰ C)

Recipe # 1 requires the longest mixing time and also has the highest temperature rise.

By using component (a) according to the invention, both process parameters in surprisingly reduced

example 1

(Comparison) EPDM rubber compound

IO

100 parts EPDM rubber, 5 parts of zinc oxide,

1 part stearic acid,

180 parts quickly injectable furnace soot, 90 parts of oil (ζ. Β. Aromatic mineral oil),

2 parts of mercaptobenzothiazole,

1.5 parts of tetramethylthiuram monosulfide, 1.5 parts of sulfur.

The indicated ingredients are placed in an ao Banbury mixer. After 6 minutes the temperature rises to 124 ^° C., the Mooney viscosity ML-4 at 100 ^° C. is 110, the tensile strength 117.5 kg / cm * and the elongation 260%.

The above rubber compound does not contain any as Mixtures of processing aids according to the invention; therefore, mixing in a Banbury mixer for 6 minutes is necessary in order to achieve a satisfactory distribution of the constituents.

30 Example 2

100 parts of the EPDM rubber composition according to Example 1 and 3.75 parts of mixture A are placed in a Banbury mixer. After 15 seconds, all other ingredients with the exception of the vulcanizing agent are mixed in. After 4 minutes, a temperature of 115.5 ° C provides a, the Mooney viscosity ML-4 at 100 ⁰ C is 71, the tensile strength of 125 kg / cm * and elongation 250%.

Example 3

100 parts of the EPDM rubber composition according to Example 1 and 7.5 parts of mixture A are in given a Banbury mixer. After 15 seconds, all other ingredients except the Vulcanizing agent mixed in. After 4 minutes, the temperature reached 115.5 ° C., the Mooney viscosity ML-4 at 100 ° C. was 72, the tensile strength was 111 kg / cm * and the elongation was 260%.

Example 4

100 Tefle of the EPDM rubber composition according to Example 1 and 7.5 TeOe of mixture B are placed in a Banbury mixer. After 15 seconds, all other ingredients are mixed together with the exception of the VnTcanising agent. After 5 minutes provides a Trr of 121 ° C a, the Mooney viscosity ML-4 is at 100 ⁰ C 74, tensile strength 119 kg / cm * and elongation 290%.

Example p

100 teas of the EPDM KaBchuk mass according to Example 1 and 7.5 teas of mixture C are in given a Banbury mixer. After IS seconds, all other components except the Volatile agent mixed in after 5 minutes

The viscosity of ML-4 at 100 ^° C. is 71, the tensile strength is 117 kg / cm * and the elongation is 230%.

Example 6

100 parts of the EPDM rubber composition according to Example 1 and 7.5 parts of mixture D are placed in a Banbury mixer. After 15 seconds, all other ingredients with the exception of the vulcanizing agent are mixed in. After 5 minutes, a temperature of 121 ° C provides a, the Mooney viscosity ML-4 at 100 ⁰ C is 73, the tensile strength of 117 kg / cm * and elongation 250%.

Example 7

100 parts of the EPDM rubber composition according to Example 1 and 7.5 parts of mixture E are placed in a Banbury mixer. After 15 seconds, all other ingredients are mixed with the exception of the vulcanizing agent After 5 minutes, a temperature of 115.5 represents ⁰ C a, the Mooney viscosity ML-4 is at 100 ⁰ C 72, tensile strength 110 kg / cm * and Elongation 280%.

Example 8

100 parts of the EPDM rubber composition according to Example 1 and 7.5 parts of the mixture F are placed in a Banbury mixer. After 15 seconds, all other constituents, with the exception of the vulcanizing agent, are mixed in. After 5 minutes, the temperature is 110 ^° C., the Mooney viscosity ML-4 at 100 ^° C. is 73, the tensile strength is 122 kg / cm * and the elongation is 310 %.

To determine the tensile strength and elongation at break in accordance with ASTM D 412, the rubber compositions in the above examples are ^{vulcanized at 160 °} C. for 20 minutes.

The use of the mixtures according to the invention of processing aids for rubber processing in neoprene rubber compositions is described in the following examples.

Example 9

(Comparison) Chloroprene rubber compound

100 parts of polymerized chloroprene,

5 parts of zinc oxide,

2 parts magnesium oxide, 0.5 parts of stearic acid,

17OTeUe fine thermal black,

26 parts mineral oil,

1 part di-o-tolylguanidine,

1 TeQ tetramethylthiuram monosulfide,

ITeO sulfur

This adhesive rubber compound is suitable for the manufacture of hoses manufactured that one afle ingredients with acceptance of DisMolylg ^ anidm.TetramethyuiiiuranMBonosul-Sd and sulfur in a Banbury mixer gives way 9 minutes the temperature is 160 ° C. Bd the examination of the mixture ta microscope shows that the ffftstrnnffflil * jjtJtutdriflmicHBnd

_ are dispergieit. Even if you repeat it several times

always be a temperature of 11O ⁰ C a, the Mooney of the Mischvotgaags proves a 9flrisStiges

Mix as needed to get satisfactory results to achieve.

Example 10 100 parts polymerized chloroprene, 3 parts Mixture B, 5 parts Zinc oxide, 2 parts Magnesium oxide, 0.5 parts Stearic acid, 170 parts medium-fine thermal soot, 26 parts Mineral oil, Part 1 Di-o-tolylguanidine, Part 1 Tetramethylthiuram monosulfide, !Part Sulfur.

This oil-resistant rubber compound with a content of approximately 1 % of the mixture B is also suitable for the production of hoses. It is made by adding polymerized chloroprene, Mixture B, and 10 parts of medium fine thermal carbon to a Banbury mixer. After 15 seconds, all other ingredients with the exception of the vulcanizing agent are mixed in. After 6 minutes, a temperature of 149 ° C. is reached. A microscopic examination of the rubber mass shows that the constituents are dispersed in a manner similar to that in Example 9. If the mixing process is repeated several times, essentially the same results are achieved.

Example 11

In a known and customary in the industry, a styrene-butadiene rubber is prepared which in hardness tester the value of 70 results in the mixing in the Banbury mixer requires 3 ¹ / min, the removal temperature amounts to 138 ° C. Upon addition of 1% of Mixing F to the above-mentioned rubber compound shortens the mixing time to 2 ¹ I ₂ minutes, at the same time the removal temperature is lowered ^{to 121 ° C.}

Examples 10 and 11 clearly show that when using the mixtures according to the invention of Processing aids for Kantschuk processing not only shortens the mixing time, but low withdrawal temperatures are also possible. Natural rubber can also be used Use of the auxiliaries according to the invention achieve excellent results.

Natural rubber compound 5 rubber:

100 parts natural rubber (smoked sheet),

1 part peptizer (sulfonic acid),

S parts of zinc oxide,

1 part stearic acid,

¹⁰ 1 part phenyl- / 3-naphthylamine,

20 parts quickly injectable furnace soot,

40 parts of semi-reinforcing furnace soot,

10 parts mineral oil,

2 parts sulfur,

¹⁵ 1 part dibenzthiazyl disulfide,

0.2 parts of zinc diethyl dithiocarbamate.

The individual components are mixed in the following sequence:

⁴⁰ 0 minutes: Smoked Sheets and Peptizers

4 minutes: zinc oxide, stearic acid, phenyl

/ 9-naphthylamine,

5 minutes: half of the soot components,

6 minutes: Remaining soot components and * ⁵ mineral oil,

8 minutes: sulfur and accelerator,

9 minutes: Removal of the rubber compound.

The tensile strength according to ASTM D 412 is 30 210.9 kg / cm *.

Example 12 The rubber composition according to Example 11 is with

1.7 parts of the mixture F added, the peptizer

However, medium is omitted. The parts

are mixed in the following chronological order:

0 minutes 4 minutes

Smoked Sheets, Mixture F, All other components with

take the accelerator

Accelerator, Removal of the rubber compound.

The tensile strength according to ASTM D 412 is 45 217 kg / a ¹ .

Claims (2)

Here you have processing aids for rubber patent claims: use!, Which primarily serve to better disperse the fillers, as described in the US patent 1. Mixtures of processing aids for 34 34 991 is described, or for ease of use Rubber processing that dissolves at least 5% 5 of the ready-mixed rubber from the rolling mill to be added to aliphatic alcohol groups or from the walls of the kneader, Compounds, at least 5% of an alkali metal - whereby a certain plasticization occurs and salt of at least one saturated fatty acid, the duration of the miscibility can be reduced At least one zinc, magnesium, calcium or can, as the statements in GB-OS 10 64 189 Barium salt of a higher molecular weight fatty acid and teach io. Such processing aids exist larger amounts of mineral oils, mineral wax mixtures have aliphatic alcohol groups and / or contain petrolatum, thereby at least one alkali metal salt of the compounds indicates that it contains a saturated fatty acid, at least one zinc, a) 5 to 15% diaral or dialkylaryl phthalate, magnesium, calcium or barium salt of a higher diaryl or dialkylaryl noglycol ether: “molecular fatty acid and larger amounts of phthalates, phthalic esters of aryl or mineral oils, mineral waxes and / or petrolatum. Alkylaryl polyglycol monoethers with 2 to only recently have been used for certain elastomers 6 Äihoxygnipien in the polyglycol, di- ^me _u ^r V ^B / ethylene-propylene-diene modinzierte Kaubenzoate of Athylenglykoi Propylengiykol tschuke (hereinafter EPDM) the so-called or their dimers or trimers or a ^ao impside-dowm-mixing method. This stands out ™ ^^ P "^" * ^from PSFTS * 1 ip Mixture of these compounds, ™ ^^ P "^" * ^from ' PS-FTS * 1 b) 5 to 30% branched oW unbranched most of the additives and auxiliaries already from aliphatic alcohols with 8 to 20 carbon atoms ^{An at} S ^at ° ^the *? an early stage of mixed in the main chain, alkylphenoxy ethers of ^ ⁸ Sf * " ⁸ .. ^ ¹ " rubber compound are incorporated. Glycols or polyglycols with up to 12C- '»The implementation of this process ζ B. in one Atoms in the main chain of the alkyl group and Banbury mixer, but does not always lead to at most 6 ethoxy groups in the poly- satisfactory results. So let the glycol chain, polypropylene glycol with 3 mixing times ro with the aforementioned known ones poxy groups in the molecule or a mixture of processing aids is not yet more satisfactory lower these connections ³ ° ^way. c) 5 to 15% potassium or sodium salts of _v ^Avt Jf ** the invention is therefore to create auxiliaries for conventional, essentially saturated fat? ie rubber processing based on the acidic or fatty acid mixtures with 12 to mixing rubber compounds of 18 carbon atoms in the main chain, wherein the natural or synthetic rubber in the environmental main chains of more than 50% 18 C-atoms up view 35 on the mixing time so _W1 e before time sequence, "- :. £" and sequence of the Facilitate auxiliary product additives. d) 10 to 30% essentially saturated fat ^Dl ? ^se . Auxiliaries should also allow uninterrupted acidification with 12 to 18 C atoms in the main working with the rubber ^compound and for chain, with the main chains having more than 50% of the purpose and thus safe 18 C atoms ⁴ ° ^tem allow temperatures without the mechanical e) 5 to 10% zinc, magnesium, calcium properties of the rubber compounds to worsen, and / or barium salts of fatty acids with _A ^E } f ^now .. it has been found that the 12 to 18 carbon atoms in the main chain, where Tasks can be solved if the main chains mostly have double the aforementioned processing aids in addition to the binding? and ⁴⁵ neutral alkoxylieite esters are also used and 15 to 60% mineral oils, mineral waxes, ^the specific proportions of each Petrolatum or its mixture complies with components in the mixture. The invention thus relates to mixtures of contain. Processing aids for rubber processing 2. Mixtures according to Claim 1, characterized in that they contain at least 5% of aliphatic alcohol, that the compounds containing potassium or sodium salts, at least 5% [Component c)] and the fatty acids [grain of an alkali metal salt of at least one saturated Component d)] Iodine values of about 5 to 15 - fatty acid, at least one zinc, magnesium, calcium content. cium or barium salt of a higher molecular weight fatty