DE1719265A1 - Method of curing a curable hydrocarbon high polymer - Google Patents

Description

Pie invention "shall look to" .on improvements ushärtungshilf s when curing ausiiäftbaren "Kohlenwassersfcoff-high polymers and developing brauchbai'e ι * ■.

The al Ige tie ine term "aushärtoare hydrocarbon -Hochpolymere" is intended to have the usual in the art importance, thus' high molecular weight polymers include, whose recurring: vinheiten a substituted optionally substituted with alkyl, alkenyl, cyano, halogen, Alkoxyoaroonyl or similar residues Hydrochain osithalcen. These include, for example, natural capchuk, butyl-,! .. auosuhuk (al'o collective term for elastomeric polymers that are produced by ;; - »polymerisation of a larger proportion of an isoolefin, such as isobutylene, and a smaller proportion of a conjugated diene, \) ie isoprene, Butadiene, piperylene, diraetny! Butadiene and the like) , copolymers of butadiene with copolymerizable | Monomers such as ntyrene and acrylonitrile, polyisoprene, polybutadiene, neoprene. (Polychloroprene), polyethylene, ethylene-propylene-co- and ~ ter ~ polynere and the like.

Many of these curable "hydrocarbon Hochpolynie * ^1" re already are in unmodifliierter mold for the production of films, fibers coatings, and the like, but have in many application cases where it is on higher Keissfestigkeit, high ßlastizitäts-, hardness and. Ähnliehe Properties be subjected to a usable temperature, a treatment, which the skilled person is skilled in the art

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BATH ORIGINAL

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Dlsae treatment _a die Lu Hanaen der .., rl'lnüuags je,: ^ lu-zl y ^ a ^ una -kennzeicnnung "curing" is called oe known "· Stand Ce j 'fecunik, which no · closer ^ flauterun ^ requires ¹ ^ d - =. 0. äc -... ι «tk by Alliger and. Sjothun" Vulcanisation of iilaatcifc ^ o ", itäinhold F ^ olioning G'ovp. Hew York, 196 '+ entno.ii.' .ien can be.

In this:] work is also described in detail, v / ie the different Hoohpolymer-s depending on their nature aieaer · "aauä .. ^ iu _o , .. ■; -,« .- ■ -... og. For example is carried out at iiaturkaucouinik, üüüj Ikaat ^ conjugated diene -.- Hoiiio- and Gopolyvneren, £ chylen co-f ^ / lea-VO or- -ce c polyuieren and similar liehrfach unsaturated polymers, the _f \ .ashä: -Tung general IIFL in such a way that the polymer is heated in the presence of sulfur or sulfur donors, such as di-chloropholiny-disulphide, tetra-diethyldiuraiidisulphide or the like, or other curing agents, such as dicurayl peroxide (not in the case of butyl rubber), di; nethylolphenols, benzoquinone dioxilB or the like, being heated in general also a vulcanization accelerator, for example ary! substituted guanidines, aldehyde-aainkondensationsprcdukte, dithiocarbamates, thiuram sulfides or thiazoles added in the case of 3oh, -; ole hardening.

In the case of hydrocarbon polymers derived from mono-olefins, such as polyethylene, polypropylene and ethylene-propylene copolymers, one leads the curing in general by treatment with a Iereiradical formers, such as dicumyl peroxide, 2,5-bis ^ ert. butylperoxy) -2,5-dimethylhexanj 2, g-bis (tert-butylperoxy) -2,5-dimethylhexyne, with Iiochenergetic radiation and the like.

These different high polymers are usually used. wise, depending on the intended end use, auxiliary substances such as fillers, pigments, anti-aging agents, ozone protection agents, spreading agents, activators, "plasticizers, pricing agents and the like" sis _c , '-

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BATH ORIGINAL

The ¹ Ct bilge substances will be discussed in more detail at a later point, '

The. Invention is based on the knowledge that the

physical properties of cured hydrocarbon high polymers in a desirable-way-can thereby be noticeably improved, that -i'nan their hardening in the presence of ■ certain, fully "cut off" Pölyiöoayanate performs.

The invention therefore consists in the broadest sense in

an.η improved method for curing curable hydrocarbon high-quality polymers, the specialty of which is that the curing is carried out in the presence of a polyisocyanate with a functionality A between about 2.5 and about 4, the individual isocyanate groups of which are replaced by U "Coating" with a "heat-free" capping agent, capped, ie inactive against active hydrogen-containing compounds at skin temperature and up to 100 °.

It is known that by using free, ie not capped, isocyanates when curing, on the one hand, butyl rubber (according to American patent specification 2,690-80) and, on the other hand, mineral-filled ethylene-propylene terpolymers with a non-conjugated diene as a third component ( Enjoyed Wolfe, etc., Rubber Chem. Teohn. 2J_ (1964), 927), noticeable improvements with regard to certain physical properties, such as elasticity and abrasion resistance: in the former and lower scorching and increased hardening speed and module increase in other cases can achieve. On the other hand lot use free isocyanates "for the above purposes with Stieva ¹ Ct ¹ Cn disadvantages loaded, which primarily difficult manageability, 'poisoning for the A ^ beitspersonal, difficult Vei: * .. iis i-bility it the other Ansitzkoi?. iponenten and jLiapfindlichkeit against ι- you activity and other active V.'as se rs to ff containing

1 0 9 8: A / 1 2 3 B _B Ap ORIGINAL

"Connections along with a correspondingly extended endurance performance belong o This latter property makes itself particularly noticeable when curing hydrocarbon polymers. The by-products formed in the isocyanate-water reaction are generally - Unsuitable and possibly even as polymer system components harmful.

In contrast to this occur in the case of the invention Use of fully capped polyisocyanates when curing curable hydrocarbon high polymers have no such disadvantages rather, as will be explained in more detail below, one obtains Polyaierprodukte, which in their properties with equivalent I'-i-ngen the corresponding free, d. H. unscapped polyisocyanates produced polymers are superior.

The fully capped ones used according to the invention

polyisocyanates obtained by reacting a polyisocyanate with an average functionality between about 2.5 and about ifdt ^j J, 0 ill Ie abkappt isocyanate groups, each with a releasable heat Abkappungsmittel. This starting polyisocyanates are known per se and consist of triisocyanates (ie isocyanates having functionality of 3.0), such as 4,4 '^' - Triisocyanatdiphenyläther, 1,3,5-triisocyanate benzene, 2, 4,6-triisocyanate toluene, 2,4 , 4'-triisocyanate-5-: iiethyldiphenylmethane, 3utane-1,2,2-triisocyanate and the like] Tetraisocyanates (ie isocyanates with functionality 4.0), such as 4,4'-dimethyl-2,2 ', 5, 5'-t * etraisocyanatdiphenylmethane, 2,2 ^f , 4,4'-tetraisocyanatdiphenylmethane and the like, as well as polyisocyanates, such as those obtained by phosgenation of polyphenyl polyamines containing methylene bridges, which their-

be the result of the interaction of formaldehyde, rialzic acid and primary arylamines, such as aniline, o-chloroaniline, o-toluidine and the like. Such polyisocyanates are known and, for example, in the a .., C rika-.ischen patents 2,683,730, 2 J50 2β3 and 3 012 0C8; the

10983A / 1285 - 5 - ■ "

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V ₅ - '' 1713265

Canadian Patentoührif t 700 026 and the German. Auslegeschrift X Ij) I * 3 ??. Of these, preference is given in particular to those. the au about 53 to about 85 Qen, - (phenyl isocyanate), methylenebis% and consist of other iai aua Polyjiethyleri-Polyphenylisocyanaten with about 2.0 functionality and corresponding one of the amount forming-by phosgenating.

ii polyphenyl-polyamine mixtures are obtained,

en

which to ' o-ovva-35' to-about 5% by weight; £ from methyldianiliiien and in the remainder • ■ \ u,: ·. consist of polyamines and higher polyamines. Particularly preferred are polyisocyanate mixtures with the narrower methylenebis (phenylisocyanate) -G content of about 5 to about 60 wt .- ^. I.

The average functionality of such polyethylene

I-ülypir-uylisDcyanate varies depending on "the methylenedianiline content of the AUmgangs-Poiya.uiae, namely between the lowest about 2.2 at about 85 wt .-; j ,. U-oi ..- 'etv.'a 2/7 at 5G Cfew, -,. · up to about -3.0 at about 55 wt. - <$ ~

The here -iur-isocyanate-group-blocking or "A-bkappüng öinut-.fcen, by VJarrne releasable capping agents represent a zj ^ varuTce group v;> n compounds"'- which in the sense of the Zerev / itinoff- Tests (J .AACheni.Soc. 4 £ i ^^ l) * 5l8l) have at least one active hydrogen atom and see reacting with an isocyanate to form an adduct that is not exposed to groups containing active hydrogen up to about 100 ° heating to higher temperature, however, with release of the free isocyanate group decomposes into its constituents ₀ the decomposition temperature depends on the particular use isocyanate bezwV Abkappungsmittel from, the latter being so generally tuned to the relevant Irjocyanat that the disintegration of between about 100 ° and about 200 ° entry.

BAD ORIGINAL

Examples of compounds with an active hydrogen atom which can be used as capping agents include: Lactams, such as i. "Caprolaotariix, d- valerolactam, Y" -butyrolactam (2-pyrrolidone), p - »propiolactaai and the like; imides, such as succinimides, phthalimide, maphthalimide, glutarimides, and the like; secondary arylamines, such as diphenylamine, N-phenyl-P-naphthylamine , N-phenyl-O (-naphthylamine, di-o-tolylamine, di-m-tolylamine, di-p-tolylamine, N-phenyltoluidine, IJ-phenylxylidine, 2,2'-dinitrodiphenylamine, 2,2'-dichlorototdiph ^ nylamine, p-nitrosodiphenylamine, 5,10-dihydroacidine, N-phenyl-N'-isopropyl-p-phenylenediamine, N, N '-diphenyl-p-phenylenediamine, 1,2-dihydroquinoline, 1 _i 2-dihydro-2,2 , 4-trimethylquinoline and their polymeric forms, such as those sold, for example, under the protected trade name "AGERITE" resin D by RT Vanderbilt Company, Inc., 6-ethoxy-1,2-dlhydror2,2,4-trimethylquinoline, Carbazql and dergleiehenj phenols, such as phenol itself, o-, m- and p-cresol, p-tert ^ butylphenol, 2,2'-methylenebis- (4-tert-butyl-6-methylphenol), 3 * 3'-di -tert-butyl-bisphenol P, hydroquinone monobenzyl ether, 2,6-D i-tert-butyl-4-methylphenol and similar anti-oxidation phenols; Mercaptans, such as 2-mercaptobenzothiazole, dodecyln.eroaptan, 2-mercaptothiazole, phenyl mercaptan, o-aminobenzenethiol, meroaptobenzimidazole and the like, as well as N-monosubstituted aliphatic acid amides, such as N-methylacetamide, N-methylacetamide, N-a-kidylacetamide, N-methylacetamide , N-methyloctanamide and the like. The leading to the present invention used product capping happens * by simply contacting polyisocyanate MUD Abkappungsmittel in or without the presence of a neutral organic solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene OTCL like, the Abkappungsmittel preferably in something O ₁₅ Su by 1 to 5 wt .- ^ above the theoretical amount is used.

101034/1211

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719265

In many cases, polyisocyanate and Äbkappimgs / üitiel set easily and quickly without external heat supply; but one can also! for the purpose of warm up to approx. 100 ° C at a reasonably quicker conversion. The course of the reaction can be followed analytically / e.g. infrared spectroscopically, e.g. the disappearance of the isocyanate group Infrared bands indicating the end of the reaction.

That which is obtained in this way and possibly used

Solvent-free reaction product can generally be used for the curing process explained below without further work-up. Solid products can, if desired, be broken up, scraped or otherwise treated in the for addition to the other

Hardening; s- ,,,. . ., "" -, ■ ,, -. Bring the starting parts in a suitable condition.

When carrying out the invention, one works on oneself

according to the known processes for the preparation of curable hydrocarbon high polymers, and the novelty consists only in the addition of the above defined capped polyisocyanates for curable polymer " mixture.' Based on the latter, one generally brings about 0.5 hi about 10 and preferably about 2.0 to about 6% by weight of capped polyisocyanate a, ' .

So if you look, for example, natural or synthetic »M rubber according to the invention attaches, is carried out with known apparatus, for example Banburynisehern, two-roll mills or the like, by known procedures, wherein introducing the nan abgekappte polyisocyanates in any convenient stage. Rubber base material, capped polyisocyanates, fillers, anti-aging agents, curing agents, vulcanization accelerators and similar auxiliaries are preferably mixed carefully in a mixing apparatus, e.g. a Banburynis, at a temperature between about 70 ° and about 180 ° for plasticizing.

.109834 / 1281 - ⁸ -

The order in which the mixture components are introduced it doesn't matter very much, however, generally speaking, one gives the curing agents, accelerators, and the like last> ju.

Sometimes it is advantageous to subject a premix of polymer, capped polyisocyanate and filler to one Heat pre-treatment, i.e. masticated it briefly at around 175 ° to around 200 °, in order to create an interaction p-.wisch.en rubber and filler to promote, it cools down before using vulcanizing agents and accelerator, and finally vulcanizes it under known time and temperature conditions, in general_ at about 100 ° to 200 °.

The same procedure is used in the case of rubber n. non-conjugated high polymers such as polyethylene, polypropylene and Kthylen-Propyl-encopolymeren, in which one free radical generator used as a curing agent. To achieve sufficient softening, Sometimes a slightly higher mixing temperature of around 100 ° is required ': is about 18ö ° apply.

If desired, a deblocking catalyst can be added to the mixture to be cured according to the invention, that is to say a substance which facilitates the recovery of the free polyisocyanate from its capped form. Such catalysts are known, for example, from British patent specification 994 348 and consist, for example, of tin (II) octoate, dibutyltin dilaurate, dibutyltin dibutoxide and the like. Of course, one chooses a substance that is compatible with the other components of the mixture, and generally takes about 0.01 to about 2% by weight of it , on which the capped polyisocyanate is covered.

According to a preferred embodiment of the invention a compound is used as a capping agent for the oil; ioocyanate "Lit an αϊ active hydrogen atom, ie a compound like oie

10983A / 128S - * -

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-5-. '1719255

.iOi'-uiälof'w ^ ise n <> jh. ^ u an :, other purpose of deji Ansats is added «, r-jf-iop.ielowe-iüc ^ -ifafc Man-an ..; -Uisats a-αε ilauurkautsehuk. and the like. However, in the sense of the invention, this MeroapT-.ov bond can also be used as a '/ wkappu-ngs iiitcel and then creates a double-purpose abbreviation for polyisocyanate. 'You can therefore use the rubber base mass before curing the normally ".captoben.ithlazol used" as a vulcanization accelerator in full or in part in a combined form as a capping component of such a dual-purpose capping component. rolyiso-jy.anats enforce, where it then during the heating step of the * / · Lishärturigsprozesses is regenerated in situ "In a corresponding manner raan various disabilities phenols such as p-Tert.butylphenol-, ~ j, y di-tert. butylbisphenol A or the like, which is known to be added to the batches of curable hydrocarbon high polymers as anti-aging materials. wont, at the same time as. Use Polylso & yanatfbkappungsaiittel and add in the form of a double-double Abicapp polyisocyanate de, n approach. Again, anti-aging agents and polyisocyanate are regenerated in situ during the curing process.

According to a further embodiment of the invention can be a mixture of two or more differently capped Polyisocyanates, i.e. use one that is either made up of the same but with two or more different ones. Abcap ». ' means of capped isocyanates or of two or more different borrowed Isocyanates, which are capped with one and the same capping agent or with several different capping agents. Such mixtures can be created by simply adding together the individual «,, components-'manufacture. Pallo man, with a mixture of the same ^ but

10-88.34 / 12 * 9 bath ..originai /

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uatsi'scliiedliGKi blocked polyisocyanates wants to work, can, nan it by adding the appropriate capping agent to de.η ~. produce relevant polyisocyanate.

Mixtures of capped polyisocyanates are then

particularly convenient if a dual-purpose cut-off polyisocyanate is used for the curing process needed, its Singabe as the only capped polyisocyanate in Geraisch but in it an inadmissibly high content of Dual-purpose cut-off polyisocyanate. Consequently, rnan regulate its salary by keeping it in the right proportion with at least one polyisocyanate capped differently.

In addition to its general usability for everyone

As discussed above, the invention is particularly suitable for those with fillers of either the "non-black" type, such as calcium carbonate, barytes, pumice powder, natural clays, talc and similar minerals of the customary type, or of the "black" type, such as the soot customary 'hvt ₀ The selection of the respective filler depends on the required properties of the cured polymer. In this case, polyolefins such as polyethylene, polypropylene, and elastomeric polymers such as ethylene-propylene copolymers, ethylene-propylene-diene monomer terpolymers, isoprene-isobutylene copolymers and the like are particularly suitable as polymer base materials.

For example, it was found that you could get through

inventive curing of filler-containing polyolefins in the presence Fully capped polyisocyanate end products are obtained which in many ways have better properties, namely higher elongation as well as lower ones Pressure flow and lower pressure deflection according to the modified Williams test as eiitspröotiende polymers, which in the presence of a free, as © uncapped pDlyisooysnats or completely without any polylso-

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9265

-Dureh application of the invention to fuel

elastomeric hydrocarbon polymers above-mentioned type is eraislt i: i general, as higher modulus or higher voltage at fo Dehnung'zeigen 3OG, a faster and as to exhibit lower elongation values, 'more far-reaching and sometimes even higher curing Seng strength.

For this embodiment of the invention, all previously mentioned, fully capped polyisocyanates with between about 2.5 and .about 4.0 lying functionality and preferably those which are derived from polymethylene polyphenyl isoyanates, which are about .35 to about 85 wt., <-;& from methylenebis (phenyl isocyanate) and. in the . the remaining "" 3 polyethylene polyphenyl isocyanates with functionality greater than 2.0 exist. Are particularly preferred with a Lactarn ₃ insfaß sondere * £ -caprolactam, fully abgekappte polyisocyanates of this kind, to about 45 to about 60 wt * -% made from methylene bis (phenylisocyanate).

The curing according to the invention containing fillers

Curable hydrocarbon polymers are carried out in a manner known per se with the modification that about 0.5 to about 10.0 and preferably about 2 to about 6 parts by weight of capped polyisocyanate are allowed to be present for every 100 parts by weight of polymer. M.

When curing filler-containing, curable

An anti-aging agent is usually used to improve the aging resistance of the »hardened end product. If such an anti-aging agent has a Grtjppe with active hydrogen atom contains, one uses it experience » according to with advantage at the same time as a capping agent for the polyisocyanate added according to the invention and can be added to the curing batch in this way the required proportion of anti-aging agents as a whole

109834/1285. " ¹² ■"

or partially enter. Such double-acting anti-aging agents are for example hindered phenols, such as p-tert.butylphenol, -2,6-ditert.butyl - ^ - methylphenol, 2,2'-methylenebis (4-tert-butyl-6-methy! Phenol), 3,3'-Di-tert-butyl-bisphenol A, a commercially available mixture of mono-, dl- and tristyrenated phenols, also certain 1,2-dihydroquinolires, such as 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, 1,2-dihydro-2,2,4-trimethylquinoline and their polymerized forms as well as secondary ones

N, ti ¹ -diphenyl-p-phenylenediaTiJn aluins, such as N, N'-di-sec. octyl-p-phenylenediasnin / p-isopropoxydiphenyla.üirx, N ~ phenyl-0 ^ -naphthylamine, N-phenyl-zi-naphthyla-nin, mixtures of oo-tylated diphenylamines, Ν, Ν ¹ -di-ytf-naphthyl-p -ph & nylendiaiüin and the like.

If only using an A1 te ration s -Lu '■; .-:, -

using too much of it in the curing as a polyisocyanate capping agent Should be advised, use a suitable mixture of on the one hand .nit with the anti-aging agent and on the other hand otherwise capped Polyisocyanates.

Of the polyisocyanates that are used with a

If polyolefins containing filler are capped from conventional anti-aging agents, those which consist of one! Mixture of polymethylene polyphenyl isocyanates, which is composed of about 45 to about βθ wt. 2-dihydro-2,2,4-trit.iethylquinoline of the type mentioned are capped.

The use of such by an anti-aging agent capped polyisocyanates have the advantage that they are a capping agent avoids that after the release during hardening there is no real

its purpose as a finished product component. But even if the anti- aging agent is not used to cut off the polyisocyanate, but to use the hardening approach as a sorider component;! Ι ^λ ,

10983 U 128S bad original " ¹ ^"

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If you clean it ^ ortsilaaftirvieise uiit the cut-off Polyisoay & nat ■ -, ·; One : · Pre-geüsisch, because in general both are physically v ^ r.vr'itgiioh and ira Ge.iiseh long-term storable and one thereby reduces the number of anuat ^ oeatandteile so / ie- a comfortably. ' creates manageable material. \

These mixtures, which are novel in themselves, of capped oil and anti-aging agents, form a further element of the invention. % Of methylenebis (- A particularly useful form of such a mixture is 'Δη a) about 50 to about 95,' j from einenrvoll-capped € -caprolactam duroh Polyaminphosgenlerung resulting polyisocyanate to about 4-5 to about 60 wt XK. phenyl isocyanates) and Im Heat. consists of polyethylene-polyphenyl isocyanates with functionality greater than 2.0, and au b) approximately. 50 to about 5 fo from an aging agent in the form of a polymeric 1,2-dihydro-2,2,4-trimethylclinoline3.

The cured ones produced according to the invention

Hydrocarbon high polymers are used for the same purposes as the In ■ Polymers prepared in the usual way without such blocked polyisocyanates are suitable. So you can make of natural rubber, polyisoprene, Buca - dion ^ homo- and -copolymer rubber, neoprene, ethylene-propylene-co- and. -terpolymer rubber and butyl rubber according to the invention by « guided curing, molded and continuous cast bodies, vehicle tires and Produce the like, while mineral-filled, hardened polyolefins for electrical insulation and above all as electrical o » cable cladding are suitable.

The production precautions and examples described below are intended to describe the invention with respect to its implementation and use which is currently considered optimal, but are not to be interpreted in a restrictive manner , '-

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1006.34 / 1-20.6 -

He rs te 11 unggy ο rs gh r if t_l_

/ Is the starting poly isocyanate used by the applicant under the protected trade name "PAPI" is a commercially sold mixture of polymethylene-polyphenyl isocyanate the equivalent weight of 133 and the average functionality 2.7 (according to the molecular weight determination by means of O-el penetration chromatography), about 50 wt .- # from methylenebis (phenyl isocyanate) and otherwise from polymethylene polyphenyl isocyanates higher functionality exists.

Total .βΟΟ g (5.39 equivalents) of ε-caprolactam

were melted by heating to about 80 ° and in the molten state with stirring ^{mixed in portions with a total of ββθ g (2} J-, 96 equivalents) of the above polyisocyanates, the temperature rising ^{to a maximum of I37 0} °) caprolactam-capped polymethylene polyphenyl isoeyanate in the form of a brown, brittle resin with a widening range of 75 to 80 °.

Manufacturing specification 2

A total of 268 g (3.15 equivalents) of 2-pyrrolidone were melted by heating to 70 ° and mixed in portions with 400 g (3.0 equivalents) of the polyisocyanate used in Example 1 while stirring. The mixture temperature was increased during the initial exothermic reaction by means of cooling to about 100 ° to 115 ° and later. Course of the addition maintained by supplying heat to about ¹ IO I ⁰ to 150 ^0th The end product, after cooling to room temperature (about 25 °), was a polymethylene polyphenyl isocyanate capped with 2-pyrrolidone in the form of a brown, brittle solid with a softening range of 100 to

110 °: ... '. ■■

Using the same procedure, one obtained under substitute am g-PffivÄfiaiÄ; durph sine. each equivalent set <f -Vale ro Iac tarn,

- 35.BAD ORIGINAL

\ /? -? r:; pioläutau, Suecinlaid., Phthalimid _Ä Kapiithalinriäj Törfc _e but ^ j. <»alcohol, B'imethylphenylcarbinol, Triphenyloarbinol, Däphenylaoiin, -" ■ N-FhenyT- / 3-naphthylamine Di-p-tolylamine , H-phenyltoluidine, N-phenylxylidiri, p-hitrosodiphenylamine, N, N ^f -diphenyl-p-phenylenediamine,!, A-DÜrydiOchinolin,!, ^ - Dihydro-Sja ^ -triniethylquinoline, polymeric l _r 2-I) ihydro- 2.2 _J 4-triinethylcliiiiolin _i -o-cresol, p-cresol, p-tert-butylphenol, ^, ö-di-tert-butyl ^ -hiethylphenol, 2,2-.Methylenbis (4-tert-butyl-6 -rtethylphenol), 3,3'-di-tert-butyl-bisphenol A, hydroquinone monobenayläthei ", 2-mercaptobenathia <: ol or N-methylacetainide the corresponding, fully capped polyethylene polyphenyl isocyanates,

In previous years, after the working pipe

according to Example 1 with the replacement of the polyisocyanate used there by 4,4 ', 4 "-methylidine tris (phenyl isocyanate), 2,4', 4" -methylidine tri (phenyl isocyanate), 2,4,4'-triisocyanatodiphenyl ether, 1,5,5 -Triisocyanato-5-methyl-diphenylniethan, butane-1,2,2-triisocyanate, 4,4'-dimethyl-2 * 2 '., 5 * 5''-tetraisocyanatodiphenylmethane or a polymethylene-polyphenylisocyanate mixture obtained by phosgenation of a polyamine mixture , was originated from about 70 wt .- ^ methylenedianilines and in the 'remaining from tri-, tetra- and higher polyamines as the starting material the corresponding, fully £ caprolactam-capped polyisocyanates.

In a similar manner, one obtains according to Example 1 from appropriate proportions of a capping agent and a polyisocyanate of each desired type, the corresponding polyisocyanates, their I # ocyanate groups are fully capped.

Using peroxide-cured polyethylene (example 1 and 2) the effects of one * were unmodified and on the other hand ^ -caprolactam-capped polyisocyanate the same Kind of compared to each other. The hardening of the individual approaches concluded the determination of the usual physical properties

1098 3 U 128 8 '* ,' ■

16

increasing curing time. "In general, the modulus or load decrease showed faster and more extensive hardening of the test batches compared to the control samples at 10;» iger elongation, and increased elongation indicated faster and more extensive hardening of the polyethylene According to the modified Williams test, in which ASTM test D 926 is modified in such a way that it is placed in an oven at 125 ° for 30 minutes using a 10 kg weight and samples in the form of four 19 mm in diameter through inserted viscose foils without sticking • one on top of the other. Each sample is measured three times. ' .H ₁ means the initial strength, Hp the maximum strength, which can be equal to H ₁ or usually have increased somewhat within 1 to 2 minutes after introducing the Profee into the preheated plastometer, and H, the sample strength after a time of JO minutes in the oven percentage compression is calculated from the equation

^ ual compression = 2 £ ~ -Ü3- _{χ 1Q0}

Honor decrease indicates increased networking.

example 1

A mineral filler-containing approach made of low-density polyethylene, \ iie ep from Union Garbide Plastics Corp. sold under the Type DYNH-I in the trade, was prepared in the way that one closest to _r 100 parts by weight of this polyethylene at 116 ° plasticized to 1J2 ⁰ in a Banbury mixer, adding 100 parts by weight Hartton as a filler intermixed again and, finally, 2 parts by weight 2,5-bis (tert-butylperoxy) -2,5-dimethylhexane (calculated on 100 ^, active) mixed in. This basic mass was divided into three portions, of which the first (Al) remained free of additives as a control, while - each on

109834/1286 " ^1? "

BAD CMRtGINAL

" ⁷ '1718285

IDQ parts resin related - the wide sample (A2) .uiif 3 * 0 parts unniodified - \ iiert3iii and. the third sample (A3) with 5 * 6 parts of 6 -oaprolactara-abkapp-. cera (corresponding to 3 »0 parts ΐ released ai) polyisooyanate was added. The above-described merchandise from the analyst served as the polyisocyanate. Partial samples of each portion were cured for different periods of time at I.71 ⁰ under pressure and then depending on the usual physical properties, namely load (B) at 10 ^c / o elongation (in kg / cm),

2 Tensile strength (Z) at maximum elongation (in kg / cm '), elongation at break (3D) according to ASTM test D 412 (in #), durometer hardness (H) according to ASTM test I) 2240 and percentage compression (V) modified according to what has been explained above te.a Williams ASTM Test D Q26. The results obtained in this way are given in Table I.

The pronounced decrease in compression in the case of the invention Approach A3 in comparison ^ u Approach A1 and even more to Approach A2 jje ^ elst clearly that the capping of the polyisocyanate a higher Cross-linking causes. The higher elongation values also exhibit further hardening. ·

Example-2

Example 1 was repeated with the modification that the base material to 100 parts of resin 0.5 part of 1,2-dihydro-2,2,4-trimethylhydroquinoline ™ were added. This compound is a well-known anti-aging agent for peroxide-crosslinked polyethylene and is e.g. from the company R, T * Vander ~ bilt Comp. Inc. under the protected brand name "AGERIT" (Type D) im Trade sold. The results obtained with the cured samples are given in Table II. You can tell from them that in the present the anti-aging agent more effective than the capped polyisooyanate the unmodified is, as the lower charges show.

Comparing anäererseifcs the entspreohendeii Verctic & tijungswerte 'Tables I and II "öö erkemt one dm strong fördexndleK Elc ^ Xuss

on

Table 1

«Geilprobe Al

Free polyisoeyanate «- ■

Capped ". - - -. 5 ^ 6

* h vsikalis before iron is owed

'KnK pressure curing; at 171

(Min) JL- JL. BD HVBZ BD H V, BZ J) _- J £

5 125 148 20 59 72.3 146 146 10 58 66.3 139 148 30 6ö

10 122 145 20 60 '72.8 138 145 20 60 63.6 I3I 146' 50 6θ

20 104 145 20 60 72.8 I35 135 10 59 62.6 122 141 40 59

40 76 I38 20 59 75.3 135 135 10 58 61.6 110 I38 40 '58

O
CP
m
a » Partial sample A4 B Z BD H V
■■■■ MM ,1 Table II Z 0.5 H V
MNMMa ", 6 B. ζ A6 -JL CB
in *%, 0.5 122 149 50 60 33 , 9 139 3 60 22nd , 9 135 158 0.5 59 V -. 131 149 - .. 60 59 22nd ,8th I36 58 12th , 6 113 139 - 58 24, m
if « Anti-aging agents Capped "
Physical properties
after pressure hardening ^ at I7I ⁰ 128 146 50 58 20th , 5 I34 BD 57 11 , 3 110 135 5.6 57 22 Free polyisoeyanate Sour (min) 125 145 50 58 18th I32 30th 57 9 107 132 BD 57 10, ■ i ; V; - ■ 5 ■■ 20th 40 Q ■■ '■., ■ 10 B. 40 50 20th 118 5C 50 ⁴⁰ I34 50 121 115

Example 3

Following the procedure of Example 1, another series of tests was carried out B1 to B4 carried out, in which the basic mass from

Polyethylene according to Example 1 100 parts by weight Hard clay 100 "

- Dicurnyl peroxide (calculated on

■ 100 S active) 1.75 "

and'die further additives, if any, consisted of 0.5 parts of 1,2-dihydro- »2,2,4-triethylehinoline, based on 100 parts of resin, as an anti-aging agent and B- caprolactara-capped polyisocyanate according to Example 1.

From the results in Table III it can be seen that

that the inventive, capped polyisocyanate alone and in particular in the presence of the anti-aging agent the hardening state besw. Degree of crosslinking of crosslinked with dicumyl peroxide! Polyethylene improved, see BS compared to B1 and B3 compared to

- 20 -

109834/1285

Table III Te 11 pro be Bl B2 B5

Anti-aging ·;

middle -.- - . 0.5 0.5

Capped .. "'■ _. ■ ·,

Polyisocyanate - 3 3. -

Physical

Properties . .

taa chDruckaus ~

hardening at I7I,

co Duration (min) JB_ _Z_ BD HVB, Z. BD HVB Z BD HVBZ BD _1- H _- _χ_

ω 5 115 125 20 56 / 71.78 127 13 ^ '. 8θ 57 22.07 125 132 60 56 13.58 138 138 10 58'5% X)

C 10 118 .118 10 56 68.84 128 136 80 57 15.33 131 132 100 57 9.81 136 .136 10 % * 6 _f 67

£ 20 117 117 10 55 67.84 128 132 80 57 16.53 122 128 80 57 10.62 131 131 10 57 $ _Λ θ8

YY 40 115 115 10 55 70.3 ^ü 125 131 60 50 20.98 II7 127 100 56 14 ^ .18 127 127 10 56 58.37

—El · - '

CO

The following examples 4 to 12 describe the effect of ε-caprolactam-capped Polyisocyanates on the curing of typical curable hydrocarbon elastomers. Curing speed .and extent were followed by determining the usual physical Properties, where the load (B) was determined at 300% elongation after various pressure curing times. In addition, the uncured approaches - using the Mooney scorch test at 121 ° of the shear disc viscometer described in ASTM test D 1646. In the case of elastomers, lower elongation (D) and higher correspond Load (B) higher curing speed and strength while. Ä longer Mooney times compared to controls mean higher scorch resistance.

Example 4

One from Enjay Comp, under the type designation EPR 4o4 Ä'thylen-Propylencapolymerkautschuk was according to the approach

Rubber 100 parts by weight

Hartton IpO "'

Sulfur 0.32. "." ■■ '■ ".

2,5-bis (tert-butyl-

. peroxy) -2,5 ~ dimethyl-, - ''

hexane 3.5 "

(calculated on 100 % active)

worked up and in sub-samples Cl to .03 together with - based on resin weight - 0 respectively. 3 resp. 5.6 % capped polyisocyanate according to Example 1 cured.

The results in Table IV show that in the absence Insufficiently cured products from capped polyisocyanate, in However, the presence of smooth, firm curing products is more desirable Goodness receives. In addition, the polyisocyanate improves the scorch resistance of the polymer.

Example 5

The basic approach consisted of: 10983 kt 1288

- 22 -

Ethylene-propylene-diene monomer terpolymer (Type EPT 3509 from Enjay Comp.)

Hartton

* ■: * Flexon 580 process oil

(Made by Pirtna Humble Oil ft Refining Comp.)

Stearic acid

Zinc oxide

sulfur

'2-MercaptobenzothiazQl

Zinc dimethylditiiiocarbainate

Tefcraroethyithiuram disulfide

and was in · sub-samples Dl to D3 together with - based on resin weight-0 or. 3 or « % &% capped polyisocyanate like, is example 1 at I71 ⁰ cured» "

The results in Table V show that capped polyisocyanate improves cure rate and extent, such as higher module. and lower elongation prove, and also the scorch resistance elevated"

- 23 -

100 parts by weight Il I50 Il 40 Il 1 ti 5 2.5 Il 0.5 H 1.5 .J 1.5

109634 / 128S

J.V

■ ■ '' ■ ■ ■ ■■ ■
■■ '** "' ■ ■
Partial sample Cl π 28 Z 9 * Tabel BD V B. MBI Z C2 m BD * 9-5 E.
NMBWMB H -S • 7 C3 Z 39 BD Z .5.6 BD 11 H
MMMM SS Capped polyisocyanate - It V 87
132
141
I50
142 1020
870
810
770
740 20th .4 .105 3 950
800
720
670
650 m 5 ² ^ 55
59
61
63
64 19th .4 5.6 103 84ο " .0 108
.1 129
.5 132
.8 128
.6 124 950
800
720
680
650 55 Physical Properties
nack pressure curing at I7I dd Dl V 20th .4 / 106 55 20th ..9 101 820 54 Duration (min) .19 .0 105 BD 54 15th .2 .89 770 53 ■ 10 spongy H 18th .3 103 810 16 84
ι 770 * 20 ^w 50
53
55
56
57 • 800 30th 800 40 800 56 ^
60 - *
62 "O
• ^ cn Moöney - scorch test at 121 ° Curing D3 Duration (min) 38 O
co OO
Cv>
**. Partial sample J3 Wm- D2 19th
'28
34
40
43 ro Capped
Polyisocyanate 19th
29
38
43
48 .7
• 5
.0
.6
.5 3 OO
«N • Physical Properties
after pressure hardening at ifl * * Duration (min) B Z 4 15.
8 21.
12 23.
16 · 26.
■ 20 28. 119
136
132
133
132 • Moöney - lowering test at 121 ° - ^ r (min) 5
1
2
0
1

Example 6

The type of rubber used was an isoprene-isobutylene copolymer, as described below the type designation "Butyl 325" is sold by Enjay Comp. The basic approach consisted of. ■

"Butyl 325" rubber Hartton K-Stay Processing Oil

(Made on petroleum basis of the

Vanderbilt Comp.) Stearic acid paraffin Sulfur zinc oxide 2-mercaptobenzothiazole partial diethyldithiocarbamate Anti-aging agents in the form of a

hindered polyalkylpolyphenols, such as

it under the protected brand name

"AGERITE SUPERLITE" from the company

R.T.Vanderbilt Comp, 1 "is being sold

and was in subsamples E1 to EJ with - based on resin weight - O respectively. 3 resp. 5.6 % of capped polyisocyanate according to Example 1 cured at 160 °.

The results in Table VI show that in the case of this polymer too, the presence of blocked polyisocyanate increases the modulus and a decrease in elongation, i.e. an increase in curing speed and extent. Plus that improves Polyisocyanate the scorch resistance.

100 Parts by weight 100 Tt 2 dd 1 ti 1 dd 2 dd 5 dd 1 dd 1 dd

109834/1285

Table VI '- ² 5 -

Partial sample \ El E2 ,, E5

Capped polyisoeyanate - ■ 3 56

Physical properties

O
co 'after pressure hardening at 160 ° B. MB Z BD H B.
tmtmammmmm MBB Z BD H B.
• ■ WM ■■ Mt ' Z. BD • 7 . "■ H
■ Man Ό \% ■ Duration (min) 11 » ² 91 98o 40 13, 4th 98 900 45 12th , 7 97 9IO 49 κ »
β »
«Η ■ '·:. 5 ■ '■'. ■ .. ■. ■ ■ '; 13th 114 900 ^ 5 15, 5 HS 820 " 48 ¹ p , 5 114 850 53 10 14th ,8th 125 870 47 20, 4th 122 790 51 20th Λ 118 800 54 15th 15th , 5 128 850 ■. 48 22 5 116 740 53 22nd , 5 121 760 55 20th 20th Λ 134 800 50 29
t 5 113 67Ο 55 28 ,8th 106. 680 57 I. . ■ '. ■ ³⁰ '. ■ ■ · ■ ■ ^; : M. Mooney scorch test at 121 ° 8.5 6.5 Duration (min)

- 2β -

example J

The resin consisted of a butadiene-styrene copolymer, as described under the TjtpSnbezeichnung SBR 15QJ5 by the company Nägatuck Chemieal Comp, sold The basic approach consisted of

SBR I503 rubber 100 parts by weight

Hard clay * 100 "

Stearic acid 2 "

Zinc oxide. 5 "

Sulfur. 2 ₃ 5 "

g in Example 6 1

Plasticizer aui? ^ etroJ-eumbasis ^ like him under the protected brand name "Reogen" from R.T. Vanderbilt Comp, is sold 2 "

Benzthiazyl disulfide 1.5 "

Zinc dimethyl idithiocarbamate 0.5 "

and was in sub-samples Fl to F3 together with - based on resin weight respectively. 3 resp. 5 * 6 % capped polyisocyanate according to Example 1 when cured *

The results in Table VII show that capped polyisocyanate present in this type of rubber also has higher load and causes lower elongation values, i.e. curing speed and extent increased. It also improves the scorch resistance.

Example 8

Crepe rubber from Liberia was processed using the following basic approach: Rubber 100 parts by weight

Hard clay 100 "

Stearic acid 2 "

Zinc oxide 5 "

Sulfur 2.75 "

Anti-aging agents as in Example 6 1 "BenzsithiazySiulfid χ »

100834/1205

'■ ■ ■ - 27 -

Tetramethylthiuram disulfide O ₁ I parts by weight

in part samples Gl to G3 together with - based on resin weight 0 respectively. 5 resp. 5.6% capped polyisocyanate according to Example 1 was cured at 143 °.

The results in Table VIII show that, with the exception of the first 5 minutes of curing, the capped polyisooyanate Curing speed and extent of natural rubber increased and also improves its scorch resistance. With increasing polyisocyanate content the hardening activity becomes even more pronounced.

- 28 -

10983 4/128 5

'Partial sample B. Tabel Z BD Z 2 BD U VII B. JL F2 BD BD • - • * B. B. Z -ZL. ■ BD BD 33 H Capped polyisocyanate 29.5 108 85Ο 153 940 55.5 147 3 660 480 49> 9 23 135 5.6 610 45O 70 Physical Properties
after pressure curing at 152 35.9 121 760; 190 500 62.6 14.3 560 - 540 61.9 114 129 52p 5IO 71 Duration (min) 41.5 132 720 206 540 65.4 139 520 530 68.9 115 127 • 5OO 500 71 10 47.8 141 670 224 530 JL- 69 * 6 139 510 520 JL ' 68.9 119 127 480 490 72 15th 49.9 147 · 630 211 520 ^: 58 65.4 127 500 480 65 68.9 120 121 480. 480 72 20th , 61 68 30th 15th 63 23.5 33.5 69 29.5 45 Tabel 65 70 Mooney sink test at 121 ° Eq 66 G2 70 G? CD Duration (min) - 3 5.6 265 • H σ
co Partial sample , B ₁ . VIII . B. Z
.M) MMHl Z 45 00
UJ Capped polyisocyanate 61.9 13th 23 .44 65 ' 4_ Physical iron shaft »η
after QouQ hardening at 143 ° 85.8 105. 255 233 67 1281 Duration (min) 90.0 111 240 224 67 5 92.8 ft. 112 240 H 219 67 10 92.1 ^48:; 113 224 40 212 15th 54 62 . 20th 56 • 64 30th 56 64 Mooney scorch test at 121 ° 57 65 ?> except (min)

■ -; 29 -

100 Parts by weight 100 5 H 3 U δ- H Ι Ii ■ · » 1 11 '0. , 1 ^tr

Example 9,. - =

- Made of "polyisoprene rubber, as it is under the protected trade name NATSYN, type 200 from Goodyear Tire & Rubber Comp, on the market is sold, the following basic approach was established:

Isoprene rubber

Hard clay

Stearic acid, zinc oxide

Sulfur ... ■ '■ :. ·.

Plasticizer as in example 7,

Anti-aging agents as in Example 6

N-Oyclohexyl ^ -benzthiazole sulfenamide

Zinc dimethyldithiocarbamate

and in partial samples Hl to H3 together with - based on resin weight « 0 resp. 3 resp. 5.6 ^ capped polycyanate according to Example 1 143 ° pressure hardened. The results in Table IX show that the capped polyisocyanate in this isoprene rubber initially dampens the curing speed and extent, but in the end it like the related higher modulus or lower elongation values show increased. In addition, the scorch resistance is improved.

Example 10

The following basic approach was made from polybutadiene rubber, as can be obtained under the type designation "Gis ¹ J-" from Phillips Petroleum Comp:

Rubber 100 parts by weight

Hartton stearic acid zinc oxide sulfur Plasticizer as in Example 7

Anti-aging agents as in Example 6

N-Cyclohexyl-2-benzothiazole sulfenarflide

Tetramethylthiurai sulfide

and in partial samples .J1 to J3 together with - based on resin weight -

109834/1285 "'

100 5 ti 2 15th I) 5 t! 2 ti 3 It 1 Il Il O, Il

0 or * j5 or. 5.6 $ capped polyisocyanate according to Example 1 152 ° cured.

The results in Table X clearly demonstrate the favorable Influence of the capped polyisocyanate on curing speed and -ausraass mineral-filled polybutadiene rubber '.

1-0-9-834 / 12tS

Tabel

Partial professions B. ' mm St. H
■ IIIMIII-il * Capped polyisocyanate 28.8 ■ -. ■. ■■■ 48 Physical Properties 40.8 55 after pressure curing at 143 ° 46.4 56 Duration (min) 42.9 , 2; .. ' BD 57 : ·. ■ 5 ''. ' , ■ ·; ■ '■ ".'" ^: 43.6 164 650 ■ 57 219 660 '· ■ V. 15:'';':'■'; ■ ■ ^; '^; 217 650 209 640 "■ ■ 50:". ■ ■ '■■ ■' 196 620 Mooney scorch test at 121 °

Duration (min)

21.5 H2 3

-JL. ■ '. "■ -2- BP not hardened 8.4 43 540 47.8 224 630 52.7 2Ϊ9 600 57.0 205 600

5.6

HBZ . BP, .... H ₁₁

not hardened 42. not hardened 63 * 1.5 195 630

63 51.3 210 610

64 59.1 191 570

61

Subsample Abgekapptes polyisocyanate

Physical properties after pressure curing at 152 °

Duration (min) 10

45

Mooney.-S narrow test at 121 ° duration (min)

Table X

Jl Z - BD H B. J2 2 BO H ■ '■ -JL 33 Z j BD (O - 95.6 850 56 28.8 3 92.1 750 62 29.5 5, < 76.6 720 φ 85.8 820 57 34.5 72.4 670 63 35.2 65.4 620 H B. 78.7 770 58 34.5 71.0 650 64 36.6 64.0 586 64 22.5 71.7 720 58 35.2 66.8 650 64 37.3 64.0 580 67 22.5 76.6 810 57 3 ^ 5 70 * 3 660 64 36.6 64.7 600 67 23.2 67 23.2 67 7.7

44

45.;

100 Weight point It 100 It 0, 5 II ι, 5 dd k It 5

- ■■■ - 32 -

Example 11

Made of polychloroprene rubber, as it is called "Neoprene" W "is available from E.I.DuPont de Nemours Comp-, the following basic approach was established:

Rubber hard clay ■ Stearic acid, paraffin, magnesium oxide Zinc oxide

Anti-aging agents in the form of
octylated diphenylamine like it
under the protected brand name
"AGERITE STALITE" Type S from the
Company R, T. Vanderbilt Comp, sold 2 "

Petroleum based plasticizers such as.

he under under the name

"Piastogen" from Vanderbilt

Comp, sold in stores 5 "

Trimethylthiourea 0.7 "

and in sub-samples Kl to K3 in the presence of - based on resin weight or. 3 resp. 5.6 % capped polyisocyanate according to Example 1 when cured under pressure.

The results in Table XI show that the capped polyisocyanate cures at a rate that increases with the amount added the nature and extent as well as the scorch resistance of mineral fillers Improved neoprene.

Example 12

Made of butadiene-acrylonitrile rubber, as it is under the type designation

- 55 -109834/1285

"Hycar 1042" from B.F. Goodrich Chemical Comp the following basic approach was established:

Rubber 100 parts by weight

Hard clay 100 "

Stearic acid - '1 ^u

Zinc oxide. 5 "

. Sulfur 1.75 "

Dibutyl phthalate x 12.5 "

Anti-aging agents as in Example 6 1 "

Coumarone-indene resin, as it is under the '■. ■■

Type designation "Cumar P * 25" from the

Allied Chemical and Dye Corp.

is sold in stores 12.5 "

Benzthiazyl disulfide "'1 * 5", - ■

Tetramethylthiuram disulfide 0.2 "

and in sub-samples Ll to L3 together'mit ~ based on resin weight respectively. 3 bezvj. 5.6 % capped polyisocyanate cured according to Example 1 at I52 ⁰ .

The results in Table XII show that the cut off The rate of hardening of polyisocyanate increases with the amount added - Extent of nitr 11-kautachuk containing mineral fillers improved, but only slightly affected the scorch resistance.

109834/1285

Partial sample B.
MMMMWMl , 6 Z
MWMMMMMMI Kl M. 67 Tabel 5 H BD H XI B. B. Z K2 BD 50.5 BD 69 56 H B.
MMMMMM , 2 Z Κ3 24 BD 61 H Capped polyisocyanate 36, , 0 101 - , 7 53 700 42 41.5 26.0 94 3 710 730 ■ • 68 53 56, 111 5.6. 700 61 Physical properties 57, , 9 154 -3 63. 700 52 65.4 33.7 138 • 66ο 720 70 56 73, ,1 129 650 70 · after pressure hardening at 1 ^ 2 61, , 6 163 , 7 67 700 53 68.9 33.7 148 640 L2 700 72 · 56 85 ,8th 132 L3 640 72 Duration (min) _f 62, 162 .5 - 69 710 53 69.6 33.0 147 610 3 720 • 57 . 85 127 BD 5.6 630 72 10 BD
MMHMMB 670 20th 720 620 30th 750 Tabel XII 58ο 45 720 550 Mooney scorch test at 121 ° 660 Duration (min) 13 ,! V «fir MM : '■ m Partial sample B.
<ΜΜΜ , 2 Z
«■ • MM Ll Z B.
MMMMMMl , 2 Z
«■■■ ΜΜΜΒ H γ: · c *> Capped polyisocyanate 11. , 2 33, - 79 35. , 6 120 57 «S Physical Properties 23 , 9 70 114 43 , 9 117 59 "Λ nacii pressure hardening at 152 ° 23 , 5 78 108 42 , 5 110 59 ^ J Duration (min) 22nd 74, 106 41 106 60 "* 10 ■ ν% 20th NJ 30th 45 Mooney scorch test at 121 ° Duration '(min)

τ · ■■■■ ■

- 35 ■ -. ·

The next examples 13 to 15 show that the invention also applies to

rusülialtigen.jcautschukmassen brings advantages.

Example 13

The following was made from the polybutadiene rubber according to Example 10

Basic approach established:

Rubber 100 parts by weight

HAF soot '35 "

Furnace-Russ, as he did under the

Type designation "Thermax" from

the R.T. Vanderbilt Comp, im

Trade is sold 25 ".

Stearic acid 2 "

Zinc oxide 5 "

Sulfur 2 "

Plasticizers as in Example 7 ■ .5 "Anti-aging agents as in Example 11 1" N-cyclohexyl ^ -benzthiazole-sulfenamide 1.5 " Tetramethylthiurate and isulfide 0.15 "

and in sub-samples Ml and M2 together with - based on resin weight 0 besw. 3 ? ■> cured polyisocyanate according to Example 1 at I52.

The results in Table XIII show that the invention cured polybutadiene rubber filled with furnace black has higher scorch resistance.

Example 14
. 1 ■ .- - - ''
Example 13 was repeated with the modification that the HAP ^ Russ

was replaced by equal amounts of MPG soot.

The results of subsamples N1 and N2 in Table XIV show that the cured according to the invention, with channel soot filled polybutadiene chewing cheek has higher scorch resistance.

109834/1285

. ■■ · ■ ■ "'■ -36' -

Table XIII

Partial probation B. Z Ml BD Nl BD 29 H H B. M2 Z 19th Z BD * H N) Capped polyisocyanate 119 119 - 300 - 430 . 65 60 103 3 103 83.7 300 65 OI ■ Physical properties 123 123 300 390 65: 62 105 105 84.4 300 65 -> after Bruckaushärtunp; at 152 °. 117 121 310 36O 65 62 106 IO6 N2 87.2 300 65 Duration (min) 114 121 , 310 3 ^ 0 "64 62 106 112 3 91.4 320 64 10 20th 15.5 34.5 30th Tabel XIV 45 Mooney scorch test at 121 ° Duration (min) 1098 co ■ ν «. Partial sample B. Z B. BD H ro Capped polyisocyanate 51.9 106 58.4 38O 64. co Physical Properties 71.0 105 66.1 350 66 cn after pressure curing at 152 ° 71.7 98 72.4 33O 66 Duration (min) 74.5 91 73.8 320 65 10 20th 30th * 5 Mooney scorch test at 121 ° - Duration (min)

.- ■ 37 -

Example 15

Made of a butadiene-styrene copolymer rubber similar to that of Example 7, namely Type SBR 1500, the following basic approach was made:

SBR-1500 rubber 100 parts by weight

-.-. · ■ HAP-Soot .. 35 "

Furnace soot "Thermax" as in

Example IJ 25 "

Stearic acid 2 "

Zinc oxide 5 ^fI

Sulfur ■ '■■'. 2 "

Plasticizer as in Example ¹ J 2 ″ φ

Anti-aging agent as in Example 11 1 " Benzthiazyl sulfide 1.5 "

Zinc dimethyldithiocarhamate 0.2 "

and in partial protocols P1 and P2 together with '- based on resin weight 0-respectively. 3 % capped polyisocyanate according to Example 1 when cured. ·

A generally the same basic approach, but in which the HAP soot was replaced by MPC soot, was cured in the same way in partial samples PjJ and P4. '%

The results in Table XV show that regardless of of the type of soot used the curing according to the invention higher modulus and hardness values with comparable tensile strengths as well as lower compaction values.

-'38 -

109834/128

Table XV Partial sample pl

Capped polyisocyanate - HAF-Russ 35

MPC soot

Physical Z
■■■ μηηηιμι ι BD H B. Z BD H ■ B. Z BD ' 69 49 B. Z I. JSL H
mump — up properties 172 610 57 I34 168 390 65 13.4 75 9IO 53 65 " 145 550 62 after pressure 174 47O 60 I52 170 36O 66 33.7 141 750 56 114 154 400 66 curing at 176 420 61 I55 ^{] i} 177 35O 66 53.4 159 69O 59 132 161 370 61 152 0 180 400 62 159 177 330 66 77.3 I65 550 60 137 157 340 - "68 Duration (min) B 184 400 62 162 I69 320 66 89.3 159 500 141 155 330 70 10 72 121 ° 15 103 33 30th O
co 20 HS 00 30 132 40 136 —I Mooney scorch test at IO
co
cn Duration (min)

It must be mentioned again that the curing process according to the invention does not apply to the use of the method described in Examples 1 to 15 used ^ -caprolactam-capped polymethylene polyphenyl isocyanate " mixture is restricted according to manufacturing regulation 1, but just as well with any other fully capped polyisocyanate, including that described in manufacturing instruction 2 can be carried out.

- 40 -

1Ö9834 / 1285

Claims (1)

1. Procedure for / \ usha ^ tvrng a hardenable. Xohloiwaoij ".- ι fabric- Ho copolymers by> t, rhit en einer Ge-iio <üj'-ö aut; ^ .ine.ii auynä'i: oal-ulj Kohlenwasyer'sr-oi'f-Hoohpolyjier, a AushäJ'tun'-vj ^ iiiii; t'-i, cvineiu isocyanai; and / regeoenenfalls a filler α ad cloth gc-i ^ ^ .enn eiijiint, · -, aauö uVc.w alue Isooyanatko-jponente a Polyldooyaiiat nit .iner · cjurTüiHehnit.t borrowed Fünktion & .lir ät ^ fishing et ¹ ^ a 2, ^ and ^£ . 'r.vja' i, 0 VMW.'iia 'ι ,, oesytn, iuzelu iGocyanargruppen i.iit' -inem durot. V »ät-.it- fr -'- ibf. ι, 0. er ^j ta Ar. kapp un ^: ": nir.r ,; 1 abpekant.t are. -. Ancestors nacr. fnspi-uch i, dadur- '; h ^ ekennoeichnet that nan as iGo ^ yanate component ^r . in Poly.nethylfcn-Pclyr.hcnyipolyiijO'jyanatgeriiisoh - ■ as about ^ 5 to about n ^r j Gsvj.-; ' Ivietnyl6noi3 (.prj '-.- riylis->oyHagi;) and i..i remaining Foly'itithyl ^ n-Pclypnenylisocyarir .-. Th: jiu over 2.0 ο?. · Π raffend et- "unktionalitä ο νerv; end e 1 ;. y. procedure. r.aor. a ^ prucn 1, dariui-'ir. gf / i -.'- nn ^ i-.ichn & t, oa, -j3 i: an tin; · ίΐι; f —'J ar "πϊ ·, - j ta. r. 0 ■■ -r · '.-.> ■ ::. et es ^D oi.yi: i ^r ": yan ^: vtrv? end ^f :> ,. 1098 YES / Ί 285 BADORfGINAL