DE1470924A1 - Process for the basic mixing of carbon black and rubber-like polymers - Google Patents

Description

DR F. ZUMSTElN - DR. E. ASSMANN - DR. R. KOENlQSBEReER ^PATENT LAWYERS U70924 TELEPHONE: 22 34 76 8 MUNICH TELEGRAMS, ZUMPAT _BRÄU HAU3STRASSE 4 / » CHECK ACCOUNT: MÖNCHEN 91139

BANK ACCOUNT:
BANK H. HOUSES

S / k
2/2/1
65 722

Phillips Petroleum Company

ss33SX3ss: ass = sss = as3sa = 2s

Bartleaville, Oklahoma, USA

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Process for the basic mixing of carbon black and chewy-like polymers

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The present invention is based on a method of basic mixing of carbon black and solution polymers.

Hydrocarbons solvents are usually made in our manufacture of chewy-like polymers using used by organometallic dictators. At the end of the polymerization If the reaction is stopped quickly, it becomes an antioxidant

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sug added and the polymer τοη separated from the solvent Subsequent to the removal of the solvent, the rubber can be dried and mixed can be run on an orphan mill or in an indoor mixer such as a Banbury mixer. One One of the most troublesome operations involved in making rubber is handling carbon black, but it is largely used in the Blending rubber applied to its valuable reinforcing gel get au

A first suggestion to mix Büß with these polymers, was based on a process in which carbon black was poured directly into the

Rubber solution was dispersed. Another developed

Driving soot was based on the use of a dispersion filter in one Hydrocarbon and mixing this dispersion with the rubber solution. Generally, the dispersion was using of the same hydrocarbon as it is in the polymerization reaction was used. This procedure, although admitting, is based on the use of the proportionate expensive hydrocarbons, which are separated and summed up Oebrauoh surüok must be won.

The main aim of the present invention is directed to an improved one Process for the production of τοη Orundmisohungen from Kautsohuk, BuI and desired ηίall of a plasticizer or Strtoköls

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The present invention is accompanied by a paper that is shown in schematic form a suitable for the execution of the invention Device shows.

The present invention relates to a base grinding method of carbon black and kautachuk-like polymer, with carbon black dispersed in water, the resulting carbon black dispersion with a solution of a rubber-like polymer in a liquid which is a solvent for the mentioned rubber, but not for the mentioned carbon black and the chewing stick solvent τοη is stripped off with pleasure! βoh, whereby a polymeric carbon black base mixture is obtained.

The production of soot dispersions in water is well known and methods known in the art could be used. Also, the processes for recovering the rubber from the solution and the better process used can be combined from one the methods known in the Teohnlk exist.Probably a steam stripping method is used to a large extent, in which the rubber in the form of crumbs is obtained by placing the solution in an oiler several, fed with steam Introduces zones.

The present invention was made on the basis of the discovery

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wiokelt that "mixed in the aqueous mixture Rußdiepereion and the rubber solution and that, after this mixing £ n _t of RuS KU the Kautwohuklösung migrates and is thoroughly diepergiert in the rubber, is carried out whereupon the coagulation of the mixture.

For this

furnace soot or soot can be used according to the Channel-Pro ^

will.

The amount of carbon black in the aqueous dispersion can be in one vary fairly broad range, in general τοη 2 to 15 percent by weight, preferably 9 to 10 percent by weight The amount of carbon black used should be less than the amount that will produce a stiff slurry · The amount of carbon black used Dispersion naturally depends on the amount of rubber in the material desired soot. Usually the range of 10 to 10 parts carbon black per 100 parts rubber is used. One

Amount within the Grenjsen from 20 - 80 parts of carbon black on the

the
The same base is considered to be a 4 «e-preferred range.

The best results are obtained when the amount of rubber in solution is in the range of 3 - 25 #, preferably 10 - 20 percent by weight. Suitable solvents for the polymerization are known. This sjstehen ■ · example from the alkanes such as pentane, hexane and iso-octane, 0yoloalkanen _/ how Oyolohexan and Methylofolohexan and aromatic compounds such as benzene and Tolool.

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A plasticizer is often used in the process of the invention or Streoköl when dividing the Kautsohuk soot - (* nindmisohung added «Bas oil can be added to the chewing nut solution, which is then mixed with the carbon black water dispersion.

Suitable UIe ₁ in the Teohnik variously called extenders, plasticizers and plasticizers, are well known * and hundreds of them have been described in the literature. Typieoh are 2. Bo petroleum distillates, vegetable oils _; such as glue oil and soybean oil, esters, such as butyl-Oelloaolve-Pelargonat, di-n-ÜeadL ^ adipat and Triootylphoephat, chlorinated hydrocarbons, ethers, ketones, terpenes, gum turpentine, resin, pine tar, coal tar products such as liquids of distillates, including alkyl naphthalene Aromatics and semi-solid substances from coal tar, including polymers of coumarone-indene and related types of liquid polymers of conjugated dienes, such as liquid polybutadiene and liquid polyisoprene and font polymers.

An apparatus for carrying out the invention is shown in the drawing with the main device components shown consist of a jet mixer 10, «inta Kauteohuklösung-Ruödiepereionemieoher 11, Abstrelfem 12 and 13 • 1 »first and second stage, a separator 14 and a Trookner 1 |.

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_ 6 -

The jet mixer 10 can be of any suitable type

exist in which a dispersion of the carbon black is made

Water / can be. In this Hieoher the RuS meets / & ampf

Sound of high speed and is as a result of impact

the incoming streams are thorough and uniform in water

Water/
dispersed. The / fcampf is through line 17 and the water

duroh line 18 leads. IuS will be through line 19 suge-) leads. Line 21 is for the addition of a dispersant sum jet mixer 10 and line 22 for the addition τon Ul sur Rubber solution seen in goal. As these two last additions are optional, valves 23 and 24 have been sloped in these lines, respectively. The generated in the jet mixer 10 Dispersion is transferred to mixer 11 through line 26 and is introduced into the rubber solution with duroh line 27 mixed"

The misoing in mixer 11 can be done with a pump with high

Vision

e, but certain pumps with lower

Soher voltages are also satisfactory. The Gifford Wood Homomixer is an example of the high-nutrient type which was used. Typical examples of the pump The Oabb Shear-flow pumps (at which occurs in the flow Soherung) and the Hettoo flomix-

Water pump. If Terwendbate Misoher changes i. B. from / 6 ampf-

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- 7 jet mixers, pump mixers * and storage tank mixers.

As a result of this mess, the Rufl migrates over ■ hydrocarbon solution and the remaining stage consists in obtaining the örundaiechung. This can be done by transferring the Oemieohes duroh line 28 can be carried out in scraper 12 The boiler product from scraper 12 is rubber crumbs dispersed in water with a small amount of solvent duroh line 29 transferred to scraper 13. You * above extracted steam hydrocarbon vapors from the scraper 13 are fed through line 31 into the lower part of the scraper 12. Steam is fed through line 32 to the scraper 13

Bug leads. The traction sucked off by scraper 12 above, the

V / a s s he /

practically as a solvent and / or vapor, is duroh conduction 33 removed, condensed in heat exchanger 34 and passed into the separation device 14, in the solvent and the Water can be separated by recirculation in the Terfahren. Rubber crumbs and water are removed from the bottom of the scraper 13 j Duroh line 36 'removed, free water removed and the moist crumbs dried in Trookner 16 and added as a product 37 away

Steam stripping is generally carried out in the presence of a dispersant carried out because this is the product in a better crumb shape. Is can use many dispersants be used. Am a suitable dispersant

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consists of that sold under the trademark Tamol 731 Product »which consists of a copolymer of maleic acid and Diisobutylene is made. The product is commonly called aqueous Solution of the Hatriumsalees sold. Generally this connection makes an example of the larger group of suitable substances, which are composed of copolymers of maleic acid or its Anhydride with 1-olefins and the salts of these copolymers exist.

Suitable for use as dispersants are alkali »■ all of alkyl sulfates and alkylbeneol fulfonates. Sodium lauryl sulfate is a preferred sulfate because it is commercially available. However, salts with 8-18 carbon atoms in the chain can also be used. Typical examples are sodium n-oo $ yl sulfate, potassium oapryl sulfate, lithium n-deoyl sulfate, rubidium aryristyl sulfate, potassium ethyl sulfate and sodium tetearyl sulfate. Mixtures can be used. A useful starting point for making sulfates is the blend of fatty alcohols made by reducing the mixed fatty acids in coconut oil. The ·· Miaohung consists of about 15 5 * mixed Og- and O ₁₀ -alcohols, 40 Ji O ₁₂ alcohol, 30 * C _u alcohol, and 15 ^ mixed O ₁ ^ - and 0 ^ alcohols. Various «modifications of this Gemiso are also used ·

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In the class of sulfonates, the Kat / iumsali de · Hatlumdodeoylbensoleulfonats widely used. If the sulfonet contains an alkyl group of 8-18 carbon atoms, It is suitable for use in the present invention. Typical, business example · sum sodium dodeoylbene oil sulfonate are lithium ethylbenBOleulfonate, sodium nonylbene sulfonate, Potassium deoylben-bolsulfonate, RuKbldiumundeoylben-bolsulfonate, Oaaiumtrideoylbeneoleulfonat, Lithiumethyldodeoylbeneoleulfonat, Hatriua hexadeoylbeneol sulfonate, potassium ootadeoylbeneol sulfonate. Mixtures can be used. In some cases the hamdelsUbllohe product contains sulfonates with an öemieoh of alkyl groups »Such a substance exists from the Kerylbeneolsulfonat, welohes duroh alkylation of Benaol with a keroein fraction which has an average of about 14 carbon atoms contains per molecule.

Alkali lignin sulfonates represent another class of suitable ones The lithium, latrium, Potassium, rubidium and carbonium lignin sulfonates are used You lattium and potassium lignosulfonates are prevented. latrium lignosulfonate is available in courses haadelsmäeig »and • In Terfahren but its manufacture is in Industrial and engineering chemistry jg, Ir. 4, Selten 570-576 (1956) • ohrleben. Ia this article are also the partially sulfonated Use lignin sulfenate, ale for carrion as well Invention techniques can be used. Since alkali

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Ligginsulfonat is in a sufficient amount in the aqueous Solution used to achieve good crumb formation * u. Finally, zinc oxide was used.

These dispersants can be used at any stage of the recovery process be admitted Ea is preferred, however, IU add them to the water in which the carbon black is dispersed. In many cases this results in an improvement in the fine dispersion as well as the production of a good crumb the Kauteohuk.

The following examples illustrate the invention without restricting it in any way.

example 1

A number of approaches were carried out using rubber solutions of ice 1,4-polybutadiene in toluene of various concentrations. The polymer was fcefclldet by 95 ^ ice 1,4-addition in the presence of a triisobutylaltminium, titanium tetra chloride, iodine initiator system. Uric acid was used in the course of the polymerization, and 2.2 ^{liters of} methylenebi4-methyl-6-tert-butylphenol was given as an antioxidant. This solution was mixed with a Rufdlapersion (Philblaek 1) and the Kautsohuk -wifeV

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U70924

As shown above, the sodium salt of a diiosbutylene maleic acid copolymer was used as a dispersant rerwendet · Seed 4 showed poor results when this Substance has been omitted. From this and from other work it was concluded that this dispersing agent is preferred in an amount of 0.04-0.8 parts by weight per 100 parts by weight Rubber (phr) is used · Run 8 was made with the rubber cement at 88 ° C (190 ° F) and the carbon black slurry carried out at 60 ° C (140 ° I) · The other runs were carried out with the rubber cement at room temperature. The higher temperature mixing appeared to be more effective, as evidenced by the fact that in the return water there was less soot during this approach than during the previous approaches. You concentration of soot in the return water became duroh Yergleioh with samples with acquaintances Soot concentrations in water determined.

Example 2

The fluid mixes produced according to the system according to the invention were mixed and hardened with subsequent drying of the crumb in an extruder or in a forced circulation oven. Sin Tergleiohsversuoh was carried out in which the ingredients to be mixed were added to a Banbury. Except for the differences shown in the oil content, contained the mixed materials

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all the same thing. Approaches 1 and 2 were dried in an extruder while the seed 3 and 4 were dried in a forced circulation oven.

with a/
Aneat * 5 is a comparison / Ansäte, welolier in a "Banbury Miecter was mixed AND ALL · Hardening took 45 minutes at 232 ⁰ C (450 ⁰ F) (20,000 lbs) at 9070 kg on the press. Tensile strength and elongation are given in the following table!

Tatxll

approach Penance analysis
(phr) no extra processing.
Tensile strength - ** tt-
kg / cm ² elongation + ^ ■ "■ £
440 Durohftänxe through
mill (Ti * ht Mill Elongation ^ 169.0 690 Tensile strength. 510 1 56 156.4 350 176.7 710 2 45 114.0 590 175.3 460 3 56 135.4 400 163.4 720 4th 45 85.8 152.9 620 5 50 152.2

This affirmation shows that the process according to the invention is close to that • A good dispersion is obtained, since the availability of a thermally hardened sample a good knowledge of ale quality represents the bufidispersion. When the soot dispersion beater the tensile strength increases. The values given represent an average value of the different seeds, but the actual

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Equal values are completely consistent. The tensile strength was tested on the base mixture as it was made and then on a milled sample. If the basic mixture is generally treated in a Banbury or a sttxmühle after its preparation, the tensile strength of the milled sample is the best indicator of the quality of the dispersion. The arrangement in the table of Example 2 is in descending order near the tensile strength of the milled sample arranged “The following BUsole nuts are obvious; The seeds 1-4 (the invention) are significantly better than the e comparison sjH ^ s yerBuoh. Mixtures dried with an extruder (seeds 1 and 2) have higher tensile strengths than oven-dried material (seeds 3 and 4) because of the extrusion process PERFORMANCE WORK

With this «system it is possible to KautsohukkMuaen ron yer-Bohiedenen win chewy cheesecloth cards Polymers are produced by creating a monomeric system, which is a former * monomeric β or a mixture, which contains at least a larger proportion of conjugated dienes with 4-8 carbon atoms, polymerizes Typical usable conjugated dienes are 1,3-butadiene, Isoprene, 2,3-21 * · thyi-butadiene, 2-methoxybutadiene, 1,3-hexadiene and 1,3-oetadiene. The ·· conjugated diene · can either alone

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or in terms of each other and / or with one or more other compounds which contain an active * CHg-C ^, welohe so that «^ polymerizable sand can be polymerized. fypisohe suitable Monomers that contain this group are c B. styrene, Acrylonitrile, rfethyl aorylate, methyl methaerylate, yinylochloride, Ethyl vinyl ethers, ethylene, propylene, 1-butene, 1-propene and 1-ootene. An important group of polymers are those with essentially a single structure type, such as ois-polybutadiene, frans-polybftadiene, ois-polyisoprene and trane-polyisoprene. Bs but can polymers which contain substantial amounts of 2 or contain several types of configuration, such as polybutadiene, welohes by approximately equal amounts of ois and trans-1,4 addition should be treated in accordance with the present invention.

A large number of Initiitorspsteme is * Ur the production of the Suitable for polymers.

Its type of initiator system consists of a catalyst with 2 or more components, in which one component consists of a brganometallic compound, one sole, in the case of dtntn «one or more organic groups by a halogen, a metal hydride, or a metal of the I ·, II · © of the III · group are first and the other component from a ter-

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BADOTOGiNAt i

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binding the IY. - TI · group, e · B · a SaIs or alcoholate consists. This type of InitiatorejpstemB is in depth with a group of examples in columns 5-8 of US Pat. No. 288,696.

Another suitable initiator system is based on use a compound of the formula R (Li), in the R is a carbon residue from the group of aliphatic, oyoloaliphatic and aromatic residues and combinations these residues and χ mean an index from 1-4 inclusive *. The aliphatic and oyoloaliphatic can see best Be saturated or contain olefinic light saturation.

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6AO ORJQJNAi.

Claims (1)

H70924 - 17 claims 1 · j process eur production of BuB and chewy-like Polymer, the aforementioned penalty in a solution of the above-mentioned polymers are dispersed and then the solvent is separated from the dispersion, because that buss dispersed in water, the resulting buss dispersion with a solution of a Kautsohukpolymeri sat in a liquid which is a solvent for the aforementioned chewing gum, but not for the aforementioned penance v / ird / puts / and stripped the chewing solution from the mixture becomes what a Polymerisat-Buß-örundmieohung is obtained. 2 · Procedure according to Claim 1, because it is known that as polymer oie-1,4-polybutadiene, tear-1,4-poly ⁽ butadiene, oie-1,4-polyoprene and / or trans-1,4-polyisoprene be used. 3 · Method according to claim 1 or 2 »daduroh gekennielohnet, that the mentioned water contains a dispersing agent 4 · Procedure according to claim 1, 2 or 3, because it is known to be rewarded, that 2 - 15 pelts of penitentiary are dispersed in 100 piles of water 009833/1797 BATH H70924 • There is a dispersion ait your 3-25 usual sprouts Iusung the mentioned polymer mixed and so Tiel this Bufidisperslon is used, see 10-190 in part Hufl per 100 filings of polymer result in 5 · Torfahren according to claim 4 »daduroh gekennaelohnet _v da * 3 10 felle BuS dispersed in 100 ropes of water, the fiftieth dispersion mixed with a 10-20 well-sprouting solution of the anticipated polymer and" if this carbon black dispersion is rewamd that see 20-60 Tells BuB per 100 files yield ¹ polymer. 6 procedure according to claims 1-5 daduroh recognized, because the Ctrundmisohung is obtained in the form of crumbs 009833/1797 BATH ORIGINAL