DE1906174A1 - Masterbatch process for the production of white rubber filler containing highly dispersed cross-linked aminoplasts - Google Patents

Description

Cabot Corporation, Billerioa ,, Maßsachusettö, ÜSA _P and Oiba Basel, Switzerland

suz · Manufacture of white

filler that contains highly cLiaperglorte trexuotate aminoplasts.

'S) Xe Etötinäwag he'tei $ £ t a Terfahren for the production of

Elao'fcoaeKiaiselmngea after, the latex "Masterbatch" »Where there are blast scales with volksoiisates

2a Meehasiiseiien Sigenochafteii result, "and the process does not exist in that a latex contains an elastosasrea with a slightly aqueous dispersion

iüiii

imter 5 Micron homogea mixed ./ird ^T, and the aqueous dispersion by the Kondensat.ton Jkrainoverbiaauag, the dan Aminoixaxz forms _v ait üeai iaäehyd in w £ L0rigeia MetUum is obtained eolelisn Esalrtionebcdingungea. a highly operational phase is formed; and then what is held, Syotesij liked that two dioperso phases are carried out with, in the pralrfeioch dry state.

HooMispergierte active iiPillstoffie on the easia of soot odes Siliciumdio3cyd v / earth in large orafang aur reinforcement of üatux'licliem. or syatUetieohcm rubber used «

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This! Fillers are worked in äUgeateiaen in troo & aiiesi state in the plastic föaoso a llaßtoisörea using suitable ter Mschverrichtuiagen Ofalgen Knoter _s etc.) ei. When using this technology, dust development cannot be boiled, which is particularly unpleasant during the Farwentimg of BuS. lead ereetst by the so-called latex ⁿ Ha8terbatch Verfaiiren ~ ^t ', d »h. . It is usually a very low level of soot slump with one. Blastomer latex is non-existent and hybrids are clehydrated. In particular, BuB is dispersed in water, the resulting dispersion is _{filtered with rubber latex venaisehi ;, koaguli @ rt F} and dried. Weaving the Bstrie ^ sssauberköit gilit ee some economic advantages, which depend on the location of the blow molding company of the rubber manufacturer .

white * irenhancement. Billet offm, ₉ z * B «ealehsn auf Baois von Siiiclumdioagrä, the Staabexi'ung is by no means as unpleasant as in the case of Emß» ^B Maeterfoatehes ^B for pasta Kautsehukfüllatof te ßQvnm & misher Ms no industrial importance today.

Better properties of SautsoliuIriml ^ aBisaten are generally not ^{obtained when using ^ feeterbatcfeee 11.} (Daily eg * the monograph "Reiiiforcsaent of Elastomers" by Gerard Kraus "Intcrecicnoö Biblisharsg John Wiley and Sons, ITew Xorlt, 1965).

In addition, French patent specification 1 422 099 a process for the production of rubber milkasates, the highly dispersed cross-linked ^ minoaldehyde resins ("Amino" « plastic *) contain reinforcing fillers, described » The process for the production of highly dispersed aminoplasts are in French patents 1 043 45? and

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1 455 750. Aminoplast-forming substances such as Melamine, urea, etc., are mixed with iOraaldehyde in aqueous Solution 'in the presence of a surface-active agent or a protective colloid implemented. You’re so preserved macroiaolelailaren, networked gels or presipitates are dehydrated or filtered, dried and ground * The dry polymers consist of. Primary part with diameters below 5 microns, but less than 1000 Å, the au larger units can be conglomerated with relatively low stability They show excellent properties in natural rubber and synthetic elastomers and are in in some respects superior to the previously known white, reinforcing fillers.

With this state of the art, it was not to be expected that a significant improvement in the reinforcing properties of highly disperse aminoplasts would be achieved if an aqueous dispersion of a crosslinked, macromolecular jelly or a product of an aminoplant is mixed with a rubber latex and dried. Han can also coagulate and filter the plague substances before drying. Yulcanizates produced from the "hasterbatches" described above show better tear strength, tensile strength and improved modulus compared to those produced from the separate dry components. Lift the improved properties has an economic Vorteili as the joint processing of latex und.Aminoplastdispersion is nail far less expensive than the isolation of the individual "components ii a dry state \ x <l their subsequent compounding. The present invention thus creates a process for the production of filler-elastomer mixtures according to the latex "Hasterbatchiug ^ technique, these elastomer mixtures producing vulcanized compounds with improved mechanical properties, and this process thereby

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w »4 *

gekenjtuseiehnet is that an Iiat © 3c elaeeElastomere! " with an aqueous dispersion of a wraetEtea, tml8slichen ₉ macromolecular Ajalnoalaehydpolyiserisatec eijaer ait .2? eilchengsöße below 5 microns homogeneously mixed Vixa that wäirige dispersion by condensation fi © r ÄiBinover amino resin forms _f. with the Aeliyd in Airlgeia Messiun? Such reaction ebedins are obtained when a disperse bubble of a cross-linked »20 Ocroiao3.ekular@n hydpolym © rlßates is formed; and then the-ezhal "th © ₈ mixed system, dae SWEi disperse phase contains * la is transferred to the substantially dry state" Bie mixture or · dispersion can either directly getrod ^ net to or her solids lcönnen by £ & agulierung be precipitated, filtered, or centrifuged and then dried.

The term «Aminoalaohydha ^^ - baw. "Aminoplast" let Indian Technology generally recognized * Br includes in particular the Eon » Densation products of formaldehyde or its polymers Connections that are at least once the

contain,

X means O, S, HH, Ii-,

^ S z- ■

I,

^ RH means SH ₅ , IIHfi. ¹ , H " ₈ 0"> and

wherein X and E may also form an aromatic or heterocyclic nucleus of _t by amino, hydroxyl, or alkyl suif hydryi- ^ 'groups may be substituted · Typical Terbindungen this Eiasee Items since urea, lEhiohamstoff, guanidine, dicyandiamide, melamine, BenEoguanamin, Shioammelin, Aniline and acrylic acid amide.

Cm general, all KLastomere that can be yaws in water zur'Herstellung of ⁿ masterbatch © ß ⁿ

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vendot.verden. The trend of ooloher Elaatomerer, dl · by Estulaione or suaymial inopolymer laatlon technologies are excluded is economically advantageous, it is therefore a preferred object of the present invention. ELaatomers of this type are «the polymers of butadiene, Isoprene and 2-chlorobutaien and their copolymers with Styrene, acrylonitrile, acrylamide, esters of acrylic or methacrylic acid, isobutylene or vinyl pyridine. Let it be understood, of course, that natural rubber latex can be used in accordance with the present invention - Further groups of usable elastomers are ferpolymerieate of ethylene, Propylene and a diolefin "ie dioyclopentadiene or cyclooctadiene, chlorosulfonated polyethylene, elastomers on the BaaiB of xthylenoaryd, propylenoaryd and epichlorohydrin; fluorinated elastomers (s «B · based on hexafluoropropylene and its eporyds), as well as silicone chewing

Inventions "Haaterbatchee ™ can contain extender oils, dyes, Pigments and other highly dispersed PUllatoffe, intioaydantien, sulfur and accelerators, as far as their activity not is changed by the contact with Waeoar, contain "Further sources of the invention are formed chewing flea vulcanizates, which were made from the above-mentioned" Hosterbatchefl · · and those according to the chewing tachuktechnology well known methods are fabricated

In the following examples the ropes and Prosenteätae represent Qevichtsteile and Öewichtsprosentaätee «

example 1

a) Manufacture of a melamine-iormaldehyde diaperiont

A 60 liter Ittflirt tank reactor old from a Waeeerdaapfueeantelung is made with a stirrer, a thermometer, a distillation «-

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column with a cooling unit and a pH yeast concentration fitted. It is desalinated with 45 parts of water, 0.2 Ropes of the sodium salt of a high molecular weight carboxymethyl cellulose and 16.2 ropes of a 30-pound length «corrugated forma ·» linldsung charged, the mixture is heated to 93 ° 0 and adjusted to a pH of 6.0. 5.11 parts of melamine are quickly added added and keeps the pH by adding 10biger aqueous Sulfuric acid carefully to pH 6. Within a few minutes a thlxotropic precipitate is formed, which is caused by violent Stirring will destroy xauB. One leaves at 93 to 95 ° C the pH rise to 6.5 and maintain these conditions for 12 hours with stirring. Uten adds 0.1 rope of sodium carboxymethyl cellulose added, stirred for 3 hours and distilled off 24.6 ropes of water, cooled and adjusted to pH 9. 41 parts of a dispersion (Part A) of a crosslinked one are obtained Melamia-iormaläeiiydpoljiaeriQatea with the consistency of a soft Cream. The solids content is 17.5 # and that specific gravity 1.08 g / cm, The dispersion thus obtained Is stable and has no tendency to move when stored and drop off the transport

For purposes of comparison, part (B) of the dispersion was used Entnoasnen the distillation stage, filtered, washed, dried and milled in a porcelain ball mill for 2 hours. The white powder obtained in this way had a specific Surface area of 151 a / g and an average part » size of about 350 5L

b) Production of the "masterbatch":

Han uses eirunSBK (styrene "> butadiene-s: autschuk) -Xiatex of the type 1500, from the Firestone Tire and Rubber Company, with the designation" Fr-S-236 ⁿ . Its solids content is 66 pounds, pH s 10.2 .

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Kan carefully mixes 3 ?. Place the above latex 54,14 filing the ol> on described sieve aion of a rernetated melaain-formaldehyde-polyEierisate? 3 _c Pour into bowls and dry in a stream of air at 40 ⁰ O. Flat for 24 hours one breaks into small pieces and then the drying operation continues, until a constant weight is achieved. The "masterbatch" obtained in this way contains 66.6% by weight of elastomer and 33.4% by weight of highly diapered aminoplast.

■ For the comparison example, a toilet (B) of the same styrene butadione * Kautßchul: latex was dried _f without the killer agent dispersion being added «

c) Vulcanization: ..

Two TuUcaniebaren EautflGhukaaßaon (A) and (B) were in a sweival ^ igon rolling mill auo those in the following table I compounded the specified ingredients.

At the KautcchulanaBoo (A) the Styi'Ol-Butadien-Kaut « ochuk and melamine-fonpaldoliyoUiars-irullotofX in Fore dee "Hasterbatob." from example 1 b) above »added»

In the case of the Eautsohukmaose (B), the styrene-butadiene-iron (rope H dee example a 1 b)) and the ITolain-formaldehyde resin PUllötoff (XeIl B doe example 1a)) were entered separately in the hawing device.

The lightly colored Xeetett bags obtained by vulcanization at 145 ⁰ O had the Eigonochafton indicated in the table below.

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- 8 -Table Z

Loud ear mass 1.5 . 540 Kaut schukmass e "Masterbatch" according to example 1 b) (A) 5.0 78 (B) SBE (rope B) Parts 2.0 84 Ropes HF filler (Part B) 150 1.0 59 - Stearic acid mm 5.0 100 Zinc oxide - 5.0 50 sulfur 2.0 1.5 Honox WSL ¹ ' 0.1 5.0 tolyethylene glycol (M «6000) 15 minutes 2.0 bircolight Process Oil ' 210 1.0 ptercapto ^ benzthiazolyl disulfide Module at 50056 elongation (kg / cm ^z ) | 96.5 5.0 Dl ~ tetramethylthiur & ro-al sulfide Elongation at break ($ 5) 5.0 Vulcanization at 145 ° C Tear strength (Urs / cm) 2.0 Tensile strength (kg / om ^z ) Shore hardness © A OpI Back impact elasticity (*) 15 minutes 172 77.2 545 48 79 36

1) »Antioxidant from I.C.I. (Imperial Chemical Unduetriee

Ltd.)

2) β plasticizer from the Sun 011 Coapany (a naphthenic leohe

Petroleum fraction with a flash point of 165 ° O, which contains 19 aromatic carbon atoms, 40 f> Haphthen carbon atoms and 41 f * Paraffin carbon atoms) «

NB a Melaain-formaldehyde resin

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Claims (1)

- 9 patent claims 1 · Method of making. PtULlstoff-Elaetoeraisohungen after the "Iateip-Haeterbati & ing ^ -Technik, whereby these EIastomeralsohungen result Vulkanlsate with improved mechanical properties, characterized in that a latex of an elastomer alt an aqueous dispersion of a crosslinked, insoluble, macromolecular aldehyde polymer with an Xeilohen size less than 5 microns is homogeneous, this aqueous dispersion being obtained by condensation of the asinol compound _f which forms the aldehyde with the aldehyde in a water medium under such reaction conditions that a highly disperse phase of a cross-linked, macromolecular ΛΒΐηο-aldehyde polynerate is formed; and then that mixed Syateii obtained, which contains two disperse phases, is converted into the practically dry state. 2 · The method according to claim 1, characterized in that the Amino-aldehyde polymerizate a melamine-foraaldohydpolyerisat is. 3 · The method according to claim 1, characterized in that the Amino-aldehyde polyetherate is a urea-polyaldehyde polyetherate 1st. 4 «Yerfahren according to claim 1, characterized in that the liquid mixture of dispersed filler and the dispersed elastomer is dried directly. 5 · The method according to claim 1, characterized in that the liquid mixture of the dispersed nilstoff and dispersed blastoara suerot is co-represented by xoagulation and then it is dried 909835 / U44