DE1720112A1 - Stabilizer mixtures for oil-extended rubber-like polymers - Google Patents

Description

uduii ^ uutrifl't ayner ^ iutioche stabili aa ^ x \ ir ülj_, oö (. straighten ötereo-re ^ ulUre ^ omopolymers of conjugated diolefins i _u i υ 4 and 5 carbon autoineri and their copolymers iüit olcfinen, intiüLia special for the cupoiyiuer from butadien utyrol, and pre.

i ^ iui'te interlinked i-olyniece cind noiehe, u with which the Viakoüit'lt and that., olekulc.r ^ ev / icht a sudden "Natie ^ learn or on other" eiüe considerably been increased wind duz-Ci, iieaction of the beginning cr'iieu ^ ten linear

with a pati ^ ending Kea _o ^- enz to dan ... ο lekular ^ ewicht uniieiti ^ die Verzw & i ^ uufcj den lOlymern to t, ra "n»; iio ^ iel for υ LIiU wulcne Kealction iüt the iieaktion d ,, o Ji I. ic.1 win te Lr-.Uiilori i ^ jiit ■ .; Lnun v ^ achuend'jn l'olybuLuui cn, dai; dux'ch ι ijiji, ^; VX ^. .J, υ i ου V ( jij jjutudi ^ ix LXJ <.; Liieui xxicut - ^//: i:; (x 'i,; s with l'Jio elxioa x..italy, atora auf_ L.

109823/1884 _BAD ομ

and

(ζ. B. üutyllituium odor lie trauiethylendilithium) was produced, whereby the linked I-olymers a Jilieiuiiiatoiii in the center with four KOulenwasserGtof women ten dee iolyuiers, who assume with the formation of an "uter", iüire others ^ rt einx ' Such a linkage reaction, called "opringen", is used by Li.F. ün ^ el among others in RUB '.) -, Ί \ AGE, bez. 19b4, ~>. 4I0-415 and illustrated the procedure described. .j. ^c ; iLatiii.jedea unsaturated kautechukarti ^ e i'oljiaer tipruu _o hu.ft be change, - indo: ii i ^ an es ..iii a CiU ^ &quot; share beateucnden catalyst, which consists of a! '' ri (Ji · .. L ¹ Lc-Kata.l ^ Lüatox * pluü einu; Co ₁ - :. italytator beotent, like L'i tanletrachlorLd and l'hionylc al or Id or quiChlorid and, .asüer, treated.

ijine other ^ rt -.ve afc tion zur üraöiiun ^ · des: ..- ^ or Linkj,: fanfareL.klion is by the ii2;, ktion ti-ics Ji un_ec_.t lists kau cchukarti ^ en u ο "Iy mere iiit a rten Oi- ^ jiii ^ unen connection ( zo ^ thyl ^ -aich] orid)

Ln 'Je _b enwart a strong base (^... 3 butyllitiiiuia) zv <gon j ^ ^ rübUtjUn a Gemiücneß höiier. ^ Olekularar kr.ut & cliukr.rti ^ he i'olymerer XAIT verzwüigtem 3AU beibpielaweiüe veranuchauliciit, uid typiocn ueiüpielawGise vex * It is visible through a mixture of polymers which have a molecular weight distribution which is equal to that of the original molecular eV. iclit Jos unrea £; ierten kauttcnukai'tiijeii ioJvaiers biy:; u iuul ^ Kul ^ r ^ ev-'iiuiten of dining, Ti'iiin. con, Te mourn and nohere.i t'olyiaemn dv.i uraprün ^ - Liciien kaui-uchukai'L i _o en iOlViueru υ inuchl ici.it «All these Λ) l ^ tncrc ·« mi L u riiüii Lc-ui n ; o L ocular jt.'W i t, with the κ üich die VjvV i nduii; j, uti'ai.it, iiuhinfii Jti't.ckuii -öl ue. 1 el · auf and bi.:;it:'en

109823/188 * eADOR, _eiNA1 .

;:. ucii improved Vei'wa'i zburkeit and jixtrudierei., eriac ^ a ("/ erai oeituri ₀ £ i" -avi _c ; sn3Cxiarteii) i; a comparison with dai ·; ursprungiicneri linear kautschukarti _{above sea} ^- en polymer.

üich b ^ hwieri ^ abilities in stabilizing many -ij _o 63 lreuKt ^ rk ^^ scnukur ti _; er new polymers. The syner -._ ibti ^ cnen ot; .i; -: lisatrkombinatioiieii ^ c ^ UB the ^ rfindmi / -; λ ieTorn aub ^ eüeichnete Ütübilioi ^ rung unvulkai-ioicx-ter, oil und-wreinander linked (linear rubber

erer), d. a. an unvulcanized is. '' inecrcs kautacnuüurti _o es rpolymer, the verkiuoft and; nit υΐ ^ eatruckt wcrdüi "i iüt. JjI ^ Ji-fijiäu] 'i _o 1'iij.iet furthest anv.o.niunv- at the otauilisiurun ^ ϋυΐurun ^ er Gopolyiüerer from butadiene and otyrol, iut also nütsJicii with other interconnected CiiukarLi _o -en roiy.neren, and inobe ^ onderu the iciybutudien,. olj> ^! i;, opreiien and iSutiadien-Isüpren-Gopolyineren, polymers, diupren .- LCiI door the shortcuts ei _o nen, kor;: "- en convenient oei ^ pieltV ^ ei L. &; iucn den« iutnoden aer urii ^ enen i_ teiijchriften ol7 υ'33ι ol 7 "95 uiiu ^ 1} 13S geinaciit will.

each ^ l, d- ^ s ^ ewönnlicii at the Str-cckun ^ of

_O o 01 "JiUCUt v; ix * d, used v * erden, especially higher , ra '! Fractional, like uit- i. _U i.uaüel üekaiir.ter; napnthea; .r.Jiac.ti-BCiiun« .i ..er- .. i -.,. 1 ■ :, a ^ esc.: os. en. At the ^ trucKuh _o from / »auttcnukeii with ol-wjj v.'ci'dei: iuliciier-vei ^ e about 37.5 x> - i 1 e ul jiii t loo -icilün j.oljmer used ob- ^, ltJcä aie ... ι.; Ι ₆ θ ^ l vun Ij · J ^ 75 x'c ilen inoLr c- cr less. er

J-

109823/1884

can vary. The UEL is preferably the polymer after the polymerization and coupling reactions are completed, added, but it _s k nn optionally added before each reaction will be. The synergistic stabilizer combination can be added before the oil is added, it can be added with the oil, or it can be added soon after.

The stabilizer is a synergistic mixture of one or more fatty acids having 12 to 22 carbon atoms each Liiolekül and from a disubstituted p-phenylenediamine and can use a phenolic stabilizer such as dibutyl-p-cresol lock in. (p-phenylenediamine is referred to here as PPD). Usually acids with 18 carbon atoms are used, for example oleic acid, stearic acid, linoleic acid and linolenic acid, although the other fatty acids with ice 22 Carbon atoms can be used including palmitic acid, myristic acid, ricinoleic acid, erucic acid, Elaostearic acid, arachidic acid, clupanodonic acid and licanic acid.

The PPD derivatives include dialkyl, diaryl, and alkylaryl PPD. The diaryl derivatives, such as Diphenyl PPD, have been used in the rubber industry Bescaränkte application found because it is proportionate are insoluble. However, when executing the Er-. Finding only a small amount is needed, and you can work with more soluble ones PPD derivatives or without such can be used. The PPD derivatives, which are used in the synergistic mixture are

4 -109823/1884

BATH ORIGINAL

of the following formula:

R- ü ti

in which R and R ^{1 are} identical or different .be koi.iien and Je -jiitn Juijsti Luenfciiii. uul df- .; r class Phenyl, ToIy 1 and ketti ^ us i.lkyl, branched ci ^ es alkyl, cycloalkyl and hydroxyalkyl. iX'Lippen with 3 to 8 Loulenstoffatomen marked ₀ Before ^ u ^ tG 7crüiiiduii_en cind ^, ^ '- Di (sei · ;, -hexyl, iioptyl and octyl) iJ'L »and χ · .- (:.: οκ. -ae ^ yl, üeptyl and octyl), Ii ¹ -phenyl iPD. αϊ, io \., _ oi \ V (J _x J j. · '..';.; cn tu Ui v <j V

ii, x. ^! -l) i (, ^ ek.-butyl) -p-piienylfcndlcuiiin i., i -'- Di-3 (5-iüc tiiyluü

i (, i \ i'-Lii-2 - (^ - iiietiiylhexyl) -p-phenylenediaiiiin u, u '-Dicyeluhexyl-p-phenylenediaxuin i, -2 (4-i «i ^f -triyl-4-hydroxypentyl) - i «'-puenyl-p-phenylenediarain i * -2 (4- ^ e thylpen tyl) -iJ' -phenyl-pp ^ enylenediarain

-u '-phenyl-p-phen./lendiar.iin -L ¹ - piienyl-p-phenylenediamine Γ, -2-Oc tyl-i <' -piieriyl-p-phenylenediamine

-p-puenylendiaifiiri

yJ cnuLainin i.-Gy c iune. yl-ig '-plionyl-p-phfiiyl' .- ridiuinin

BATH ORIGINAL

The phenyl substituent of the above compounds can be replaced by tolyl.

The synergistic mixture is introduced into the polymer in the usual manner and the components can be added separately or they can be seen and then added to the polyol. The acid improves the solubility of the PPD derivative in the organic solvent in which the polymer is dissolved when it is made. Any substantial amount of acid used with any substantial rPD derivative will provide the desired polymer stabilization effect. The amount of oil is at least 0.1 part per 100 parts of polymer (referred to here as "phr") and is preferably at least 0.3 phr; usually no more than 1 part acid per 100 parts polymer is used as this would be unnecessary expense. The narrow ItD derivative varies from 0.005 to 5 phr, usually from ϋ, ύΙ> 7 uic J, U pnr. The total amount of the synergistic combination is preferably at least 0.3 ph. and no more than about 2 phr.

The synonymous effect is shown by the reduction in the decrease in the viscosity of the polymer with heat aging. na can also be a puenolischer stabilizer such as dibutyl 2,6-ji-cresol (DBPC) are used, but obviously it works with any of the other two types of stabilizer alone syn ^ rgiutiach. 3yner _o ismuü is made by

- 6 109823/1884

BATH ORIGINAL

the use of the petic acid both with the rPD derivative ala also your phenol! asaen stabilizer.

The effectiveness of the various n'jiscauii_.en he. ^ Iot arise from dei. romping tables. Dj e labels refer to the stabilization df: S roiyuers. The synergisti; - .. e-: erj hc-ibIna deeper are added to protect the j / oiymer during the La..y; rur.g and processing. The vulcanizates are -i'o : ^, 1.1, where KciU u & ci ^ ukvulkanisate used v,; order] t; ind, riüv / Iie;., V.ie in the case of the division of iteiter., Sculäu;: iiei! and ar-v -roi ^: I, ^ .-. n :: i, o; Falti _o ness of products.

The irolyiner, the. ir. the
irufun ^ en uses wunif. was ¹ Vr ₁ - _</:::, -Cl ^ with WACN & End: i iJUtadi ^ -n-styrene -Gopolyn;. i ·, the fiurc; i C) ^tv: 'c: ieriro x'olviüei'isatioi: under YersiVtndun ^ vonButyll.i: hia ::; il °; I-.c + elysalor received wurüy _t iier ^ eetel-1. Yes was 37.5 mil piir. Jtrfickun ^ 'i ~ oil stretched. The Vickouities are i.'Ooney-ΥΐίΓί'.οαΙ + -ater: (iiiL / A / loo C). The ΑομΓ Γί.ΐ. in the last column see ticli on aie obtained ^ eblicoone viscosity (Iietuined Viscosity); M.

the forgiving values and the percentages of the original greenish viscosities which, after aging, have remained withheld for any long period of time. On the first line ^ i the it. ΐ. for the product nacii three days of aging and in every fol _ö the row it is the viscosity that has remained after four days aging.

109L823 / 1884

1_09L

007 0 B. Table I. Daily change
in aging 36.0 1
Day 2.
Days in the viscosity R.T. 007 , 0 Oleic acid O
phr days 37o5 30.0 22.0 3
Days 4th
Days 47 007 0 DPBG
phr 37.0 29.0 23.5 17.0 WT ⁺ 46.5 stabilizer
phr 007 0.3 0.1 36.0 33.5 28.0 21.5 17.5 62 Α.- 0.3 0.5 27.0 32.0 28.0 25.5 23.0 57 O, 0.3 0.3 1.0 28.0 24.5 25.5 26.0 2o.5 100 0. .2 0.3 0.3 25.5 26.0 28.0 25.0 28.5 loo O. .3 0.5 25.0 23.5 25.0 28.0 28.5 100 0. .5 0.5 25.0 27.0 26.5 27.5 100 0.5 26.5 26.5

⁺ OT means that the polymer became too soft for the test as it aged.

- 8th

109823/1884

In the previous table and also in the following tables, the stabilizer Λ vi _t iv'-Di (l-ethyl-3-methylpentyl) PPD, known as Luanandel as Eastozone 31 and U.0.i _o 88, is and the Lbabilicü.tor 3 is u-2 (4-methylpentyl) - Xi * -phenyl i ^J i ^; D, also known as Suntoflex 13. The quantities of the various otabilization constituents are given in parts per 100 parts of rubber. The stabilized polymers were placed in a forced air oven

<-> G aged, and their viscosities were determined as usual.

Lie viscosities are given as iviooney viscosity (Ivil / 4/100 G) an _o etragen and are for the original polymer prior to aging, and during the four-day aging, Man cient that the Stabilisiürungseffekt is synergiütisch. As little as 0.1 part of acid has little effect, and 0.3 part or more is normally used to 100 parts of the polymer. The table shows the excellent stabilizing effect when treating as little fatty acid as 0.3 phr with the PPD derivative. The reading viscosities are percentages of the original viscosities after 4tägigem aging odor währond a shorter time of 1, 2 or 3 days if dusProdukt 4-t .. _o strength Allorn was too soft to check it remained ™, bie last four samples in i'abellfc; I were generally well stabilized and did not show any verifiable loss over the course of the 4-day stay.

- 3
109823/1884

Tables II, III and IV show the results obtained with Testing of the synergistic effect of acids and PPD derivatives in an oil-stretched, unvulcanized, among each other linked (linear copolymer of butadiene and styrene), the produced by a different linking reaction. When you compare the results with those Comparing Table I, you can see that the values are additive,

- Io -

109823/1884

Table II

dtaoilizer

pure,

ogure, phr Daily change in the
Tern viscosity on Al

ÜP.X 0 1 2 3 4 RT £ v ^{iir olein} Linole Ta ^ e day Ta ^ e days days

0. ^ 07

Ü.üO7 ο.007 0.007 0.5

0.5 or 5 1.0

0.3

O. 3 0. 5 0. 4th 43.0 O. 3 0. 5 0. 9 43.0 0. 3 • 4o.5 35.0

0.5

0.3 O .3 O. 3 0.2 0 .3 O. 5 0. 5 0. 5 Bliiidprobe

41.5 31.0 22.5 16.5 KT ⁺ 40

30.0 24.5 22.0 51

33.0 26.5 24.5 57

3o.5 25.0 20.5 51

35.0 32.0 31.0 32.5 32.0 91 * 5

41.0 38.5 37.0 34.5 32.5 73

41.5 35.5 32.0 27.5 2? .5 61.5

38.5 34.0 30.0 26.5 25.0 65

44.0 42.5 41.0 38.5 38.5 87

42.0 44.0 41.5 38.5 37.5 89.5 24.5 15.0 HT ⁺ HT ⁺ HT ⁺

26.5 22.0 15.0 UT ⁺ KT ⁺ 56

25.0 18.5 14.0 LT ⁺ HT ⁺ 56 28.5 17.0 ST ⁺ hT ^ T ⁺

⁺ i \ ii eeaeucct, daio the lolyrner bei.a aging too soft for

the irafunj became «,

109823/1

13th

it

The synergistic effect is evident when one takes into account the results in the last two Lines before the blind test after 2 days were too soft for the test, while with the one indicated in the 4th line Combination, the viscosity can be measured after aging for 4 days was.

Table III

0 12 3 4 RT stabilizer, phr. Days TaK Ta ^ e days days

Stabilizer B. 0.5

Oleic acid 0.5 32.0 29.5 27.5 27.5 27.0 84

Stabilizer B 0.5

Stearic acid 0.5 32.0 30.5 29.5 29.0 28.5 89

Stabilizer B 0.5

ümery 3325 0.5 31.5 3o.O 28.5 29.0 27.5 87

Stabilizer B 0.5 34.0 31.0 26.5 22.0 2o.O 6o

Stabilizer B 0.5

Kniery 3325 1.0 31.0 28.5 28.0 28.0 27.5 9o

Stabilizer B C.5

Acintol üPG 0.5 3o.5 28.5 27.0 26.5 26.0 85

10 9.8 2 S ₂ MJ 8 4

, plir Tabel A. IV 2
Ta , 0 3
Days , 5 4th
Taj 1 720112 B. 0
Days otabilizer 0.5 28 , 5 24 , 0 23, ft. To otabilizer B. υ, 5 32.5 Oleic acid 0.5 3ü , 5 28 »0 26, "O 71 btuDilizer B. 0.5 34.0 , 0 , 5 otearic acid 0.5 30th 27 25, , 5 78.5 otabilizer B. υ, 5 33.5 25th , 0 19 » »0 17, üifiiery 3325 B. 0.5 36.0 0 74 otabilizer o, 5 29 »0 26, , 0 25, !> 48 otaDilizer B. o, 5 34.5 -.ciiitoi ^ a o, 5 27: , 5 25, 5 24, 5 74 otabilizer B. o, 5 33.5 , .cintol ΪΆ-1 0.5 27 _: , 5 25, 5 23, 0 72 ot; -. ilizer B. υ, 5 34.5 .co, or : 'e υ, 5 31, , 5 29 5 28, 5 63 dtuuilizer B. 0.5 34.5 5 i? '- Go i''eti, üuui ν, 5 35, 0 23, 0 29 0 81 utaoil L ^ a tor 1.0 33.5 Ib, 15, finery 3325 1.0 33.0 IB, 12, 12, 87 .tcarinsauro 1.0 34.5 5o ^ uory 3325 C? 34

109823/1884

ORIGINAL

Tables 1 and II show that oil stretched with one another linked polymers after aging too soft for uormey determinations if not stabilized according to the invention will. Such unstabilized or insufficiently stabilized polymers actually lose after aging their chewy-like properties and have little or not a commercial one. Liquid rubbery Polymers are simply not for sale to rubber manufacturers, who are interested in chewing gauze-like polymers for common ones Processing in a rubber mill or a Danbury mixer for the purpose of mixing with compounding ingredients to buy vulcanizable chewable compounds useful in the manufacture of pneumatic tires and other chewable articles.

In Table IV, certain of the stabilizer mixtures listed in Table III are repeated. This has its ürund therein, DAT, the polymers of both Table ill and Tables I obtained undll simply by the organic jjösun _o Smit iel, in welcnem the "iolymer nergeatelit was evaporated. The results in Table IV refer to itself di <- stabilization of polymers Durca Dampfab expulsion d ^ s organ !, cixen i.ösun _o smittels obtained .füllen both were the polymers obtained under interlinked (linear kautscnukarti _o e iolymere) and they were in an oven. Jjuftuiiiwulzun _o aged at 75 ° G. The viscose bags are used as 4iiooney viscosities (xuL / 4/100 ° C): eiclinet and :: ind for the i'olyuieren before aging and during aging

10 "982 ¹ I / 1884 BAD ORIGINAL

during the indicated times indicated and Proezent-Vvcrte the ursprünflicken viscosity t 4 by: remained _o eraalten strength Alterun, a ^ nd listed in the last column (RT), in each paragraph, the PPD derivative was the stabilizer B (referred to as stabilizer B in the tables). A mixed acid of about 44% oleic acid, 23% stearic acid, 30% palmitic acid and 3% ivristic acid was used in various approaches and is designated as Emery 3325. The j) -6o inspects fatty acid to a similar mixture of fatty acid, the Wirde manufactured by Proctor Gamble cc A ueiuiL-cn of fatty acids which is substantially 43 · 5 ^ Λ linoleic acid and 51.2 '/' entnält oleic acid, is as Acintol EPG denotes, ücintol FA-I is i; u essentially 41.6 / o linoleic acid, 49.6% oleic acid and 3, ö; o saturated fatty acid. Acofor is wesentlicuen 48.5 / o etisaure oleic acid, 46 / ό linoleic acid and 3% saturated /. The above information relates to acid preparations which contain some unsaponifiable constituents.

The stabilized, oil-extended polymers according to the invention are practical, useful in any abundance, where conventional oil Λ stretched ^ BR ₁ oil ^ estreckter Laturkautscnuk and oil-extended linear kauLscnukartitje polyI & ere have proven to be useful einscnlieulicü use in LuftreifenlSufflächen, page wounds and Karkas. en materials without restriction. The stabilized lolymeren n <.ch of the invention can also be mixed with other polymers bekannueü to deliver jiitzliche ko.rjneri-ial misc.iurj _c s that are verarüeitet into useful shaped articles and ue _f, ^ ensi Naen. The stabilized

'Ο ¹ *

- 15 -

109823/1884

BAD ORlQJNAL

x ^J olymeren uach the invention are advantageously mixed with known rubbers (such as natural rubber, SBR, BR, IR, HR. CB, IBR) with or without additional stretching oils, to form vulcanizates of great technical meaning. The new stabilized polymers are advantageously mixed with known reinforcing carbon blacks to produce useful commercial materials which can also contain one or more additional chewable polymers and can also extract from 5 to 100 phr of additional extender oil or plasticizer. Sulfur and other known Vulkanisierun ^ smittel for natural rubber and the technical Synthe _s ekautscnuke suitable for the production of vulcanizable materials, the new stabilized polymer containing soft. Known antioxidants and antiozonants for vulcanized natural and synthetic rubbers on the market can also be used in vulcanized products containing the new stabilized polymers; however, the PPD-b't,. According to the invention, an effective antioxidant and antiozoniurum with oil in vulcanization materials which are made from such a new polymer can be used Technical synthetic rubbers are applied to the formulations which contain the new stabilized poly ( ₁ ,) '' ren according to the original, and are useful in this regard. Liie new polymers are ^ "Gonders useful in LuftreifenlauffläcaenT, sidewall and Karkassenmiachungen and the Betrc.chtun_eii in this paragraph apply in particular for the Vej'wendun _o of new polymers in tires.

10 ^ 2 37 188 4 BATH ORIGINAL

Claims (1)

guess 1. Urivulcanized, elongated, interlinked (linear kaulscnukurti ^ es polymer), containing a stabilizing nee of an ayncr ^ iotic mixture of (&) a ctabi-Ji ^a J- ^fc ' ^ren d- ^en ^ itnjie one or more i `` et tciluren with up to 22 carbon atoms in a molecule and (b) an essential one in _a compound of the formula in wt-lcxicr ii and a * each one ihenyl-, tolyl-, straight-chain Al> iyl-, branched chain alkyl, Cyciot-lk ^ l- or n>: yI ₀ XV ^ _x each iui t 3 to 8 Koulünbtof ! atoms denotes » 2 »i.iiJuAUn ^ after i.nopruch 1, thereby ^ ekennzeiennet that they 2, G-Dibut.yl-p-creaol contains. J, iuLudiuiiij ii, .ch iMüyrucii 1 or 2, characterized in that the linked polymer is derived from butadiene-styrene. 4. iiiiucuuri ^ iiuou Knüpx'uch 1-3, characterized in that the oleic acid is sometimes oleic acid » ^s j, i "iiochun £ xiLtcn jinijracht ι - 3" by gikounzul cianet that the uuure iiau] .j üüixhl Loh ^ teaririöäuro iut, - IY - SAD 6. ki ac aurig according to claim 1-3 »characterized that the acid is mainly linoleic acid 7. Mixture according to claim 1 to 6, characterized in that that an i'etxsäuregeiaisch is used, the acids with Contains 12 to 22 carbon atoms. 8. Miocüun ^ nuch "nspruch 1-7" characterized in that the (b) component from the class ft, ij ^f -ui-sek _e -hexyl-, disec.-neptyl- and di-secT-octyl-p- puenylenediamine ibt. ^ ^C J. i.iiiichun _ö according to claims 1-7 »characterized ^, that the (u) component from the class i ^ -Pi.enyl-, l \ i '(sec.-he _x yl-, sec.-heptyl- and secv-octyl) is p-pnenylendiaioiue. lü. Mixture according to claims 1-8, characterized in that that the (b) component N, W-3 (5-methylheptyl) -p-phenylenediamine is. 11. wübchun * j nac.j Anapruch 1 - 1 o, characterized in that aaß uie (u) component u-2 (4-methylpentyl) -u ^l -piienyl-p- ψ phenylünuiaiiiiri iüt. 12. stabilized unvulkaniüierte, ölgestr CRAZY, kauti.chukartige irolymere, in v; uicnen the dtabilisator a £ jynerkiotiüches üemlüch from a Fettaüure and a p-uisubstituierten iHUIi ₁ Vlendiaiiiin is to provide methods for .herstellung such IOL ^ au inerer and the use of a Icher L; .Di L Liierter · lOlymerer üe L der iiersbellun _o before. vulkunit; lt-rten Kc. u uiJ 109823/1884 - 18 -