DE1495862A1 - Process for the copolymerization of cyclic oxides - Google Patents

Description

Patent attorneys .. Dipi.-ing. Walter Meissner Dipi-ing. Herbert Tischer

BERLIN-GRUNEWALD MUNCHENa ₁ TALTI

Telephoning 2βΟβΒ7 Munich 2, December 15th, 1961

Valley 71

The General Tire & Ilubbor Oomjjany Akron, Ohio (V. 3t · A.)

Process for the copolymerization of cyclic oxides

The invention relates to a process for the copolymerization of cyclic oxides using alkyl * alkenyl, cycloalkyl or cycloalkenyl, Berrylliu "" -, cadmium and / or xinc catalysts and a co-catalyst; eie relates to cyclic oxydmieohpoiymerieate which are obtained by this process, mixtures or reaction products of alkyl, alkenyl, cycloalkyl or cycloalkenyl, beryllium and / or cadmium catalysts and co-catalysts, and also a process for the production of these mixtures and reaction products as well as pneumatic tires old Kieohpolymerieaten manufactured according to the loan of the invention.

The object of the invention is a process for copolymerizing cyclic oxides using

909823/1096

Alkyl, alkenyl, cycloalkyl or cycloalkenyl beryllium »cadmium and / or zinc catalysts and of co-catalysts or their reaction products on the preparation of copolymers of cyclic oxides by polymerizing the oxides in the presence of alkyl, alkenyl -, Cycloalkyl- or Cyoloalkenylberyllium-, -cadmium- and / or -zinc catalysts and of co-catalysts or their pe & ction products, masses which aur I & sohpolymeri & atlon of cyclic oxides and which are made from mixtures or reaction products of alkyl-, alkenyl- , Cycloalkyl- or Cyoloalkenylberyllium- and / or -oadmiumcatalysts and co-catalysts exist for activation of the catalyst, furthermore in a process for the production of mixtures or ieaktionsprodukte from Alkyl-, Alkenyl-, Cycloalkyl- or Cyoloalkenylberyllium- and / or oadmium catalysts uzid co-catalysts and in pneumatic tires made of copolymers of cyclic oxides »especially pneumatic tires with a tread en part of copolymers produced according to the invention

According to the invention, it has been found that a few or more organic cyclic oxides are readily mixed with relatively small amounts or reaction products from a catalyst and a Co-Katftlyeator on activation of the catalyst mischpolymerislert «Can ground · The copolymers obtained are amorphous and / or crystalline substances. Many dor. Mixed polymers have average molecular weights of about 0.0000 to 3,000,000 or more. Such copolymers

909823/1096 BADORiGiNAL

U95862

«, 3 - ■

With unsaturated groups, "· aliphatic carbon-carbon double bonds, can be vulcanized with conventional crosslinking agents, a.3 · sulfur or organic sulfur-supplying compounds." Vulkanisierungsaitteln door Füaehpolyraeriaate äusserot with little or no carbon-carbon aliphatlsohen Sappelblndungen or gown irradiation by electrons with high speed and similar Tulkanisiert wraenm The liquid or fettähnliohen / · ■ _; ' (paeteniihnllehen) Mischpolyraerisato old low molecular weight can be used as Welchsaoher for synthetic and natural rubber, polystyrene, polyvinyl chloride and used similar · The rubbery copolymers can sur Her * ^x position of flat Tilesien, V-Hiemen, Help, drill, HOC]: 0rigen objects (oarselbaok), BchlMuohen, foils eur packaging, coated fabrics, Helßwasserflaschon * paints, printer whales, gloves, shoe heels and soles, wire insulation, golf ball cores and yarns, sponges, Sch & usoaatratsen and similar »can be used for the hard * tüi * n Mlsohpolymer Manufacture of Urehscheibewalsen (pallet rollers), impact-resistant Hatten, Helaen, golf ballt! Coverings, floor tiles, Zuoohneidplatten and Uhiilichen can be used.

J ₀ Some ionomers, such as those with diepoxyd or polyoyoll

ca see oxide groups, can also in the presence of the catalyst

(^ mixture or of the product are networked in such a way that it is easy tiaai t veroiacht und sur Manufacture of casting · tticken or sur

co Manufacture of casting compounds for electrical instruments ·, gluing

fabrics, lighting fabrics and the like can be used

Γ ■■■■■■■■■■ '· ^-,: Η95862

WIA ana Aar enclosed leichnun * ·, a "aeakreohten Bohnitt-» lld eima "Eeifene, iat ereiehtlioh * ittUt 1 a eohlauohloeen heIp represent the ouch 4am Lauffläohenteil 2 and the Saltaavisaaft 9-3 aaataht ₉ dia in alma * BtUok ouch Amr Haaaa 1 "Btra""upa * iir" rfahran htrf eettllt aain ieunaan · HatUrlioh köantn _# "aim waiaaa 5" itamnmdr "ifan hareuatalXtn ein, the running surface and side wall separately fepreeet" a. The rereohiedeaaa or üi> er * oeenen Sohiohtetoffe ein »ei 4 aa ^ eceben. Ka kBanen one or more honorable sons, yes naeh dam

Tire Torgeeenen eeia. The Oewebeeohiohtcn

Eevtehan aua Hayon or Hylon fabric or other "Textileewefee, dia" it kauteohukarti "en Staff am kaJLandriert" overmogait lind. Ma Indan der öewebeeohiohten and generally a utt utti & hte 5 "5 eewiokelt, which can also be made of steel wire, and the inner surface of the Ueifena contains a layer 6 aua a ButjrlkauteohutaMiee · (a üiaolipaXyaobutaria atue a Diolefin "with 4 bia 9 tohlenatoffatoaen beeteht) or another suitable staff" .Β "ana a" ttleahpeljnMriea "next to the present" Srfinätrag "with the fetrüneohten Dioke, with the Ileraudiffuse % with air or Oaa also the inside of the KainiIfana · Mr Butylkeuteohuk can be rorvulkaniaiert. If Ealfan is to be used with a »smarter ear, dia

be wegcelaeaen. Bar tire can

ttftULohan Varfahran be built up on a brewery Baifanbau-Ujsa and in the usual fora «wieohen • twm! 9S ⁰ O to 154 ⁰ O (280 to 310 ⁰ P) about 1? bi »60 minutes

909823/1096 BADORtGlNAL

vulcanized under Druok. The individual layers of LaufflHohenniaeae and ao waitar can be made sticky like heptane, old heptene and similar glue, or old adhesives aua a * Mieohpolymerieat after the invention asked about 15 $ patties In elnea luaungaaitttl "like heptane, sticky" and awar when aia is placed on the building table · Damping legs (ouahion atooke) and Biaaätaw can be used during da · Heifen constructionaa awiechen dem 3 tut »tissue (breaker), trap and, if necessary, the disparate Sohiohten» as far as aia necessary a »ua dia Fahr * and Ver» ohlelaselganaoh * f Also improve, as well as the familiar contour and the familiar cross-section 1 »data of the finished tire. Warden Sohaueratreifen just fall la general during dea Zueaaaenbauene close dan Zueetidröhten eye type, including dia duroh touch old daa hand (rim) verureaohte Heibung on elnea Miniaua au hold * Säatliohe at Aw Heretellung dee Half ana used kautaohukartigen substances, one or more Mieohpolyaerieate naoh ^ mt In addition, treads, cross winds, schiohtatoffe can be the same or also different copolymers depending on the invention, in which the monomers or the low and low ratio are varied, and even the properties required for the same component. Various vulcanization processes can be used at dleeen Waaeen in order to obtain the desired vulcanization in the finished Heifan au. Help the old a chewing-owl-like Mieohpolvaerieat after the invention "a" B. elnea old atwm 90 parts propylene oxide and 10 parts allyl glyoid ether, structured and suitable

909823/1096

conpounded, BtIgMi a lower ifarm thawing, a « greasers Zuhigkelt and tensile strength, better properties at low temperatures (flexibility), reduced tearing in “bending and increased resistance to damage by Oson Ih help that from a Kauteohukortlsen butadiene-1,3-styrene ^ lfisohpolynerieatmasaa divided one

If the carcass or one or more composite masses, sides-- “I find and resemble another chewy substance than those made according to the invention are »» · Β · aue one « Chewable copolymer of 1,3-butadiene and styrene, natttrlehen Kautsohuk, oie-Polyisoprsn, cis-Polybutadiene-1,3 and the like, as well as oils from their mixtures, uniquely Adhesives can be used to join the rubber near the invention or binders that make these rubber substances with taring ! Narrow of the chewy-like copolymers near the founding Contained, if necessary, to be used to make ale Approved gluing swisohen the other chewing chukka-like maize and the rubber-like copolymers according to the invention must be sealed. if so desired, for example, one etrangTsrpresste Laufflftohen- and a rare wall mass a chewy-stick-like hollow polymer after the invention, s.B · from a chewing material-like copolymer of propylenoacyd and allylglyoidylÄ «» er, on a carcass from a chew ~ Tjshslrsrtigen butadiene-1,5-styrene-ÜberpolymeriBatiiaaBβ * u bind, becomes a binder with a larger kenge BM-eTY-odor polymer and a smaller amount of FO-AOB-

909823/1096 'bad oriqinaT

U95862

Mixed polymer is spread onto the outer surface of the carcass and dried.Then the blend layer is made from approximately equal proportions of BIffi ~ & TY «4 resin and P (KAOS * mixed polymer on the first layer and a third layer is dried and then dried and then added Meng · BLW STY Misohpolysierisat and greater Meng · PO-AOE-Mlsohpolyaerisat and dried · di · ^"y ·· letmte Sohioht iet dasu determined _t in contact old tread and the side kornnen su when di · arrangement is sueamaengebaut · The carcass with the three binder layers then let the cross winds and the tread complete · laugh the finished seed and the vulcanization, the running part and the skin wall stick strongly to the carcass. Foil · running part, side walls, ply stooka and other parts from Misohungea the mixed polymer according to the invention and natural rubber, rubber-like * n butodiene-1 _and 3-styrene ~ Mlsohpolymerisat «n and similar are made, one or more similar binder" layers can be used "if necessary.

The was the practice of the invention DurohfUhrung sur preparation of the copolymer from the oyolieohen · · Terwendet oxides catalyst besltst di · · following general formelt Me (I) _2, wherein E £ a metal * * .g. 3erylliu » _t cadmium or ZUu .« Represents. Osmisohes of these catalysts can also be used, λ has 1 to 20 carbon atoms and can be unsubstituted hydrogen hydrogen. Di groups a can be.

909823/1098

-S-

equal or Tereohitden »and know alkyl, alkenyl, Cycloalkyl and Cycloalkenylreete and their Oemleohe mean. Koasinatlanen this Tieete Bind in the above definition these lUidikmlgruppen elngeeohloneen. Examples are Alkyl-alkenyl-, alkyl-cyoloalkyl-, alkyl-syoloalkenyl-, alkenyl-oyoloalkyl-, Alkenyl-Cycloalkenyl-, Cycloalkyl- ^ yoloalkenyl-, Alkyl-Alkenyl-Oyoloalkyl-, Alkyl-OyoloeOkyl-Cyoloalkenyl-, AlkeÄyl-Oyeloelkyl-Oycloalkenyl-, Alkyl-Alkenyl'-Cycloalkyl-Oyoloalkenjl-Ileete and ahnllohs

Examples of useful catalytic Berylllunyerblndungsn are the following: Diaethylberylliu ", Dläthylberylliua, LipropylberyllluM, Bl-n-butylberylllttm" Methyl-1-octenylberylliiw ₉ Hethyloyelohezylberyl-eyelyl-ayl-1-yl-eylberyl-oyl-oyl-methyl-1-yl-eylberyl-oyl-methyl-1-ethyl-enyl-oumyl-ethyl eyolohegylberyllin ", Dieiooeejaylberylliu", methyl

1-Batenyl-i ^ heptenylberyHiu ", Cyelebutyl-Oyolopentxl-oyolohexenylberyllluB" Di-Di- (2,5-di "* ethyl-cyelohexyl) -beryllitt ·, -berylli" m _t

UBt M - / X \ -butenyl) -2-cyolopentenyt ^r -beryl- XlLwm ₀ 31 ^ '? l ^ yoloheKylen-eyolobutenyl-3) -berylliu «and ·. whose

: mohssrs OeAeHstrerbinduncen sur usage: 'f'T .-; stf? e »sindt Blsethyleaiaiua ₉ Dilthyleevdeiusi» W-

4 ^r ^> «yV-5-» Btyloyele _{(eexyl) -eadmiua t} Di- (2-hexenyl) • 909823/1096

BATH ORIGINAL

U95862

Ittoy * l «h« qrl «* ialuB» »Μ> -« y lohre — jrX)

»· Dl ~ (> - b« tylayolop «it — arl) —irti, Qyolopwit-yX

ei oat himiiolf

d «B general <—In— formally corresponded and Ib im ftorftüuraa of the Brflndun« mogtmtuuät v + rdmn kOnmm, «ladt I> la« thyl * lmk ₉ WL-Ithjlmlak, Din ^ propylelnk, m - ^) mtjlelBk _v c ₉ Di - (oyel # p «atyl) -« lak _t Bl- (

slak «2) l-

Hncenylslnk «1-But« nyl-prop «iyl« lnk _t ! & - (3 ₉ 3-dl-tliyl-1

h «t« njl) - »lnJc,

oyoloh «xyl) -slBk, Dl
slak ₉ Dl- (oy «lop« i

909823/1096

• ίο- H95862

BU QrtßXuomtmlXk * tmXj9 *% t> TiL kOuMA β.B, slightly moa 4m • tohoato * 3M * tlono #! OlOABAfM hoxgootollt

(C ₂ H ₅ J ₂ Xa ♦ MJ ₂ , «» am iM

lolofet

Stak can auta el »· head» r «Zliik-L« el «rune τ ·, «• t min · on« 1 · xlaküAlksrl · ΙμπμΜΙμ. 01 ««

sB Ithyl — jn — ImJo ^ IA • romps urine, «o« «i R ₂ OA-TMrMBiHiIiSm« rhalWn «« ri «n« where 1 SB «la · AlkjUrttif · WteaUt. D & ·

MMi Ia jl · Ιο1μιγ Vsl · ·

tar aar AktlYUrame i ·· Katal / Mtor · taaBtlft · Oo-Catalj »mtor

, ViO

«• It Ithaaol« Prtyeaol »Isopropeael · Bntaaol» Fmtaaolt ölykol, intMüel »BwtoUTthrit vai riy1ty1« mlth> rglyfcol ·,

M OjMrIA ₉ 1,2,4-aosMtrlol, Bit OiAM MlMAlAfVMiMt Ai · M OtM «00.

BATH ORIGINAL

909823/1096

The above-mentioned aerklleh löeliohe or old "Taeeer nleohftar · allpoatlaoh · alcohol, polyel or daa Polyttherpolyol alt nledrlfaa Helekulargewloht aaeh to be used without Waaaer al Oo-Xatalyaator

Another kind of suitable Co-Xataljamtoraa toataftt la da «ren üxyd de · AlualnloaoxTd · (» Aluaixxlaaoxrd) or eina · ι ran Oxyd daa Altminiuaa and alnaa or aahraran oxides of parts of the groups ZX bla ITa daa Parladlaohanea Syetaa ·rd <der ^ eaente, Since · 586-391, "Handeoek ef Obealatry aaHftyelaa", Chaalaal Snbaar BiMIaMm Oa ·· 01 · * · - L ₉ Ohio, Ü.8.A., 36th. Hi ·· 1954), ». ■. aaa

oxide, AlQBlnluBOxyd-Tborluaoxyd, Al-1 ntiiaaacy * -aijrkojMi «j4 ■ 01V«

oxyd — Si T ^ fMtXy A and ^^^ Ί Ιο Κ ^ η Alualttiuaoxydaii · SdUMM oxyde und Alimrt «1 ^ tmorydreTeigungan» ollen free ader andttleali free tob einceaahloaeenea 3aeeer aein, be ^ ror elaie · alto eetor and den earth. Jedoeh they Aellen ■ :: '■ - £ GSS OH Qruppen en their OberflMohe geemden "ufwelaen, cited daa" ale ale eauer au consider elnd.

Oeeieohe also of these rereohied Oo-letalyaators kJSauma. 4 should be used.

Sa · Terhaltnie τοη Xatalyaator _v veewa ^ aamee vom alna · aehreren, «ur Gecaataange dee or dar (T ratalyaatar—

909823/1096

• tm 1 · 0.05 ¥ 1 · 1 ι 1 Ml. Catalyst and Oa-Cataljraator var dar iMtaktianau; alt dam MnoMram altainamttr Yar · ■ iaafat varaaa, adar · 1 · Mmm »in the fcaliaalcar Beihonf olg · daa

eftfll AVMMaMNHa SflMflflMMPflfla «qM | BCMMHMaatPttfi wflMLflMuA

in the «iMiiJiittf Lftwafalttal» (AOU rarwoadtt) Mlatium «» Lfpne anfagoWa «ariam · Ba Mavallam ewlaohtn catalyst wi Oa-Kataljvatar aiaa laaktlam wfrlg% ₉ kaaa also« ^ «Raaktl ^^ 'f ··a« ^ «Raaktl ^^' f ··a« ^ i Salt maw.) old tan Koaaaaran because "Monoaaraa fJaaiigwiittalfaaltaa adar dta Xdanfaalttal and ömllohaa vandaaat vardaa, oth AlaAT" aaaa kakaMit 1st, "aa while represents falfaarlaatlaa gaaealaht · warda FTMA * &, daa · event · dia IiMlHm mm catalyst w * Ca-Kataljraatar adar an Raaktl pcadaltt adar daa Sviaakaasvadmkt or dar Kaaplax daraaa _f dia tarar TaaaUataa «« atataham, Biaat «la aler» aaohrlofcaii

alrd "aia · · gairUif adar aaah feaia · Kolyaaria" il% t vird · Katalraatar mA Oa * Satalyaator koaaan cuaaaaan in ti, -i case aaa alaaa "represents w" ht999m is to r "rwaadamdaa M vam adav la miam laartaa trgaalaaaaa LBaaacaalttal (Haptan, ■ aBMit totaa, 3mam ₉ Baaaal »talaal« 00I ₄ uad Hmllehaa) aatat a4av iwt * «aeLaaat« atd «i« I daaa aXlai * odar alt daa

IvMB) 0Mt | VWHL MHI MMMMMSV ^ I a4 <idP dMl MtMNMQNB QaMl Uli

•• tat i adar wagrtiMrt faaparatarMi al · μ 200 ^β σ, aia «a · 0 * 0, Umm mw BnaMiTwwi # 111114 dar aildtiBf daa

(a MmAmIk ₉ W & msXm "d ahnllaha") It MWk Aaatalla f "Ttiwafit ttels'" a dia laaktlaa im dar Ihm ia ^ nijMwti 1 "iav iaartan odar

«.S« fUeAstaff ₉ AtMMi or HaIi-

909823/1098

Di · aitt ·! · D «v Catalysts according to the present invention su polymeric monomers are organic, eyolleobe oxides. Diethylene orolieehen, door using co-ind <n (feqrde beetehen au · belie · • igen "white" of Hehr ojrolieohen Oxjd 'n With a · "od · *

and «In ·» BmmwwtQttmtom in des fiiag and »iad • ättlft or uagMttttigtt tnthaltm« In · od «r mtinr * » Xiphati- • oh · Kohl «n« toff-Kohlen2wtoff-Zlopp «lbindu & eftn _v and iBtUfw ö · - Biaoh« n. BMh dta? «Rf« hr «» naoh der Srfindunc h * rg * »t * llt ·

«Tttnalt»! MBit ew * i or e »hrer · di« e «r

M «rtn. Se kuaceA aneli Bpo3qrde ₀ Diepoxyde, Polyepo * yde _# Oxetane »Similar« Bfe ** tti * t · oyelleefa · Oxyde «her · elijfeatieeh, ejrole» aliphatieeh or Apoeetieoh rincsttbetitulerten Derirmte, sB- o * Doloqltall-tubet erirate and their «eter-» halogen-, ither · and nitro-substituted derivatives and ähi borrowed, rerwendet «earth · iüaige epic example · for usable · eyoXieoh · oxides» in Xthjrlenoxydt Kitroepoiyätthan, Propylenoxyd, 2,3-epoxybutane, 1 »2- epoxybutane, Xpoxybutane "1 _V 2" £ pe9grdedee "ii ₉ Butadiene dioxide, Ieolmtylenoxyd, Butadienaonozyd, methyloxetan, 3-Tynyl->3" Bethyloxetan "Styroloxyd, ttther, Xthylglyeidyläther, Allylhexdecu tynyl" Eloyo-grottoUtinyl "Eloyoleoylflyeidyläther, / -XetendyrdiosUtiny» lyoidylftther ron pentanediol, 2 lenox / d, flienrlgljeidjltther »p-ChlerplienyTgljoidjlttthear» djlmethaerylat «G * eten (O ₅ H ^ O), 3» 3 -]> iAtfearlezeta « _v 2-MthrleB · 1,3-epoxyprop ·» -M · thyleno-ketane), 3 * tinyl-3 «« ethgrloaEetaA, V-allyloxetane, J-ethyl-Vbut ylejtetaa, 3,5-dimethyloxetam, 3 "3-Di · (ohlore * tayl) - <" etan _t ^ -Methjl-V-ehloamethjlexetam

909823/1096

U95862

Um BMktloaiprodnkt ana tea Bl «lyol * yXlth * r« «ft UsilMnoX A« 1-βρο ^ «] φ1 · 9.4 ^ ρ · Χ7 ·? · 3ΑΐΜΧ · Μ,

, 1 »a-n ·» »·· !! Ivwnj <, 1, a "B" pt * i "nt wioiy

inA «« It · «· himUch · fabric ·. «· Χο1μ Mji 4 wA aar lp «qr- o4wr« at bi · m XetttmtofffctMM t »tl» l% «i,« ni BuOlol ». iveh Owl "oh" al β! 4 · τ oyeliach— Ooqrte kflnnmi ^ »wmait r oi »Htwttttlq» ly — rl — f kUnowi el «l <üifmXl nth «« ν Mining h «rg *« t «llt v« rd «m ·

0 _t 5 M * 15 Molpwwrt T «m» lawi · «·» «HRNMItti # ->

elt «UphitlMlm l ^ a« Mt «ff-K«] a «M« «ff

85 Um 99> 5 "a"#"i" oU * Oaqr * · "month" l% "ii. ImUs 41

wtvtea «tea · aas %% m wAit

«Raut« te · «tarn 0 * 5 M · 15 * ·! - *

al 99§5 awi 95 J β β4 %% 1β% Go ^ Smmmmw

909823/1096 badoriginal

a quantity of clay 5 to 30 mol-9 & results in "In Miaohpolymerieet, which aur formation of γόη binders withn mixing with natural chewing alcohol, butadiene-etyrene-Mieohpolyaerieeten, polybutadiene" Polyisoprene, Butadiene-Aorylnltril-Hleohpolymerieaten and Ihn- For common vulcanization, there is also how polyalkylene ether cauteohukaaeeen after the invention can serve in admixture with it or only forming double layers with layers of these materials or with the same lower, lower surfaces of the same.

When using τοη about O ₉ 5 to 15 moles of "* £ unsaturated oytlisehen oxides give eioh rulkanislerbare and kautsohnlu ^ rtlge Kleohpolyswrisatsmssen" the ewe alone or in admixture with other Kautsohukstoffen, natürllohw rubber, Batelalle "· styrene · polybutadiene polyisoprene, iritril - and Mtmllohem unsaturated Mlsohpolyneiisatare can be used to tire treads · Tire covers, tubes, shoe soles or Rlemenmasssllen · 3a is aUa aUea is preferred, in order to the optimal stability of the cash register "the duroh insole enveloped" Oxygen is bound to age at high temperatures With unshortable Vulkanislerungselgensehaf «· obtained, see below, use about 0.5 bla 3.0 mol-jt unsaturated oyolleebe oxides, whereby the! test ordered from one or more, saturated oyoll-sohen oxides.

A characteristic of the procedure based on the detection under Ti the combination ron catalyst «md Oo-Ce.talysater bes ^ aat aarin that uniform« leehpelymejrisate with

909823/1096

«! • fet« tWnw wl · Uaehpolyawrleftte «It aliphatic coals *

41 · me Vernataung aar Ter-

fBgang StIUMm ₉ can be obtained * Offenaiohtlioh let 4a · * erwan ~ data Katalyeator-eo-katalyaator-Sratea In dleeer Hlneioht einlgartig aelektl * «dna · ee rolllcwmen auareleht» vm d «n Bpoxydstt öffÄ · su daea% · see muereloht for a Folyeerleatlen or rare Terder FolTserlemtlon about the allphatleohe "Kohleaetoff"

. Overlea »shares the experience

Amt BrfiadVBg el »·« Way siur «pus YarHanm« the properties of this preservationaaan «leohpolymeriamte» Belaplelewelae alnd dia HlaeApeljneerleate nlt a & η · * · τ · η proportion of Ded «oennonoxyd» in Acetone Practical Oxide and a * smaller proportion of propylewelae Effenelehtlioh due to the nlahtfolaren Katur dee TiQdeoennmMMrjrile, while Xlaehpalynerlaate old a larger share Frejarlenexyd and an "ideal share Badeeennonmqrd In Aeeten lOeXloh elnd.

la let an elnaleartle ·· md ttbernwohendee nerknal der KrflndMaft «aaa da mttele dar Toretehend eeeohrleienen Kataljreateran« Mi Oo-CataXyaatoren nesieatalltan Vlaohpolynerlaate an anenaejinH highe Kolekularfewloht »the Happiness will be in the nearness YlatealWtaaafclen eaaltaan, the cew «hnlleh nlndeetena I ₉ O * etra« an «al im« lalan FllXen lie closer. XHaaa «leohwa Waltaen $ 9 naeh dam AaaKtaen ein · awitjfca Ink · tlam« nd a Metalline fmkUam · Salaat dlanerpne Tnuctlen,

\ '■■■■■ ^;

UM »PÄtlwn, ü · Ia MSMm Mm * mitlaHt IAeIUh let, aaigt

909823/1096

BADORlGtNAL ^!

.. _17i - 'U95862

usually a basal molar 7iekoaityesahl above 2 · Dia eoetonunlBaliche fraction, ι · Β · main aäohllch aua the kriatallinen Phaae respiring »bealtat also a high molecule ** · weighs» waa sioh aua the high basal molar Ylakealoitatea fr am higher results There is generally a general finding of palyneriaatlon of oxide products, which also contain fatty or fibrous substances. In a few cases it has been reported that a chewable polymeric acid was obtained, dooh argab ο a more detailed examination, that the aaerphiohe in large AuanaJ aua a crietalline Phaee beetand and the Krietalline Sfeaae have a relatively high molecular weight such as the molecular weight of aaerphiohe or la acetone In the order of magnitude of 10,000 to 40,000, the high proportion of crystalline Phaee naohta the known materials "la kautaohukartiga Polyaeriaata was not very suitable. In addition, substances were not old or vulcanized sulfur. BiAige day Mlao ^ "polymers, aD those which contain a larger proportion of propylene oxide", as will ala hold when the invention is carried out, contain a crietalline traction and the crietalline fraction can, depending on the choice of the catalysts, the Polyaeriaatlonabadlngan and aw Manga dar Oo Uonotran be present in varying amounts · The crietalline Phaaa can be from 0 / to au about 45 t daa geaasten Poljmorengewiohta · Theee Kriatalllnlt & t can through the ^ öntgenatstrahlapektran (eeharfe Spitsan) dieeer Hieohpolyneriureate even «la wall ·) Can be recognized and can be evidenced by the facts that daaa «la is a minor one

909823/1096

. _1β . Η95862

Increase in inclination by 711, as would be expected with amorphous polymers This crystal instability is higher than the good polymerisation, as it is caused by the more commonly used catalyst cocatalysts . Although the · ·· Hisohpolyaerisate old crystalline-IMa saturated or unsaturated fractiona for the intended purposes "special in Cbersugsn, foils and the like, are brewable""load them, if they are kmutechuk-like" load "in the processing with grinding and Preeeen but manufacture of chewed-o-chukary products, such as Hleaen, Helfen and the like · », about · eohwierig see Terarb« iteA · Also dlejenigea Hi »« hpol7meri «ate _t dl a main part of propylene oxide • divide up and up to about 10 mol -? i contain unsaturated co-ltonomers, white an unrequited, reducible crystal structure "da ·· al · owierlg are to be worked out, however, as- • h · meohpolymerleate τοη de" oeeiohtpunkt au · «daan ·· e old can be seen , "Honestly" wishes, "However," la w "lterep Kerkaal the Brfladuag in that · an appearance ·" of this crystal intersection through mixed polymerisation of one of the "more of the ojolleohen oxide · with crystallizing type τοη" tMi 0.5 to 20 mol - ^ precaution white γοη 1 hl · 10 mol * ^ _t dar esssatasng · dee or the saturated or unsaturated iposides or oxetanes old 4 ml · 12 carbon atoms, sB · τοη 1,2 * latenoxide, 2,5 boteaozyd, 1,2 * P « ntenoxyd, Ieepentenoxyd, 1,2 "Hez" noxyd, 2,5 * BsjHMOxyi _f 1,2-Heptenoxyd, 1,2-1 eoheptensxydf-OzStSA ₉ Ootenooqrd, Ionenozyd, Butadieamonoxyd, AllylglysldylMth «r, Sss" aoayAt Bsendeoenoxyd, and tihnreral «den or irsraladsrt« svdsa can · Misohpolymeri-

-I ₉ - U95862

Eats which contain the monomers in sufficient quantity are amorphous or practically amorphous and have xolocular widths of 150,000 or more. Furthermore, such claw polymers are relatively easy to process insofar as they are easy to work with allow to unite »no protruding file form (ar · not laoy} and generally clear, rubbery masses possessing» a tendency to flow and little or no kiletallinitfit, which can be seen by X-rays (in the unstretched state at room temperature) » · door easy handling is not over $ 2> nichtvulkanieierte · · · kautachukartig polymer in crystalline Haas · before "which is insoluble in cold acetone. Both the saturated and unsaturated comonomers contribute to the reduction of crystallinity in the Polymeriaaten" as ilauptoenge lenozyd or other l'onomers contain _t dl · a crystalline ·· polymer results in · but the rest are required. X1- »gs nsohaften, such as Yulkanieation, stability, tensile strength and the like, beetiaaen how much of each »is used ·

Thus, it results that the method according to the invention tintil way to make copolymers το & high Uolekulargewleftt from cyclic oxides with varying phyeikolisohen and weak ;. Properties are also preserved. Crystallinity ₍ LO and vulcanizability can be varied for pre-heating fswolD WBA wendungsabsiohtan

The total amount of the catalyst used (catalyst mA Go catalyst) varies "how GewtUmlion" old the

909823/1096

Temperature. Itaisplttlawelse beträft at JLaumtemperutur (about 23 ⁰ C) of geounte catalyst which is used in CINOR! Laeoensiiaohpolymeriaation, about 1 Koi catalyst sueammen with sufficient activator or co-catalyst per 100 moles of total available · ionomers. At higher temperatures, up to 0 ° 0, 10O ⁰ G, 150 ° C or even higher, less catalyst is required, while at lower temperatures, 2O ⁰ C to ^{0 0} C or lower, more catalyst is required. When adding a solvent, more catalyst or a higher temperature should normally be used in order to obtain higher rates of interpolymerization see below. In general, it is preferable to work at moderate temperatures of about 20 ⁰ C to 1OD ⁰ O cu, because high temperatures can cause undesirable Kebenreoktlonen, while "necessary at very low temperatures long Zeiträum to see sufrledensteilende yields, although in general the molecular weights are higher than at higher temperatures · In general, the total amount of catalyst product used (catalyst plus co-catalyst) varies • between about 0.05 to 10% per 100 moles in total · monomer ·, although the total amount of catalyst used is preferably about 0 , 2 to 7.5 Holes per 100 holes polymerized Monomer in total is

SI · Monomers are converted in the measure or in solvents. It goes without saying that when changing the route in the viaso · some monomer · as a solvent for that Copolymer act when it is formed. examples for

909823/1096 bad original

- 21 -. ¹ ^

Usable Lueungsmittel aiad Toluol »Benaol» xloxan »Heptane, Octane, xylene »cyolohexane, diethyl ether» carbon tetrachloride, Dloxan, Trlohlor & thylen and similar. Sa is preferred »inert or relatively inert and non-polar · hydrocarbon solvents also use · When solvents are used »aoll a sufficient amount should be used for daa or the monomers and daa or dispersing the copolymer au and / or au solve.

The polymerization can be carried out in pressure vessels or under pressure and all under a non-oxidizing atmosphere The non-oxidizing atmosphere can also be carried out by steaming the monomers and / or the chemical agent, although ea is anticipated »the polymariaation in the present einaa Niohtrsaktlonafähigen or inert gas, see B. from Sticketoff, Helium »Argon» Neon and similar »or their Oemieohen durohsufuhr · Dia Dtruoke can also be atmospheric pressure and bia su 150 Ataoephars vary, although they are generally awlaohen be about 1 and 25 atmospheres · Yoraugawelaa becomes dia Failure or the reaction agafaa "daa the mixture contains" agitated during the polyeerieation. The polymorphic sides vary depending on the temperature »dam Katalyeatorgemiaoh» of the kind daa latalyeatora and Oo-Katalyaatora and dar Monomers »as the experts aelbatvaratändlioh iat. SIa Polymerlaation can be done in the dark or with suitable inhibitors for free radicals, like a.S. Nitrobensol »Dialtr © toluol» Bl * nitrodiphenyl, litrodiphenylamine or chloronitrobenaol, thermoset in order to avoid a non-resistant reaction of the carbon

909823/1096

.22. H95862

Avoid lensttff carbon double bonds (cross-linking).

The monomers can the reaction vessel & ss susommen with the solvent, trap used _v be sugegeben, or these substances kunnen sugegeben separately · catalyst and co-Katalyeator can be separated sugegeben and in the Heaktionsgefäas "either with each other or sueammen mixed with the solvent or umgeeetst together · The catalyst can be added to the reaction vessel with the monomers and the Go catalyst with the solvent or vice versa · Dl · monomers can be added to the reaction vessel · together or separately · Furthermore, a monomer can be practically polymerized and then another honey be suggested and melt polymerized »

Catalyst residues from the catalyst and catalyst can remain in the misohmerged polymer harvests obtained after the invention. However, they can also be removed for limited use by reducing the amount of inorganic impurities ) and similar »must be removed. On the other hand, alkaline Katerialien gewUnsohtenfall · can sugesetst · JhJOm will see the Misehpolymerisat leioht in solvents dissolve "the solution can be treated in the solvent containing these substances" form below to waseerlösliohe Sals · of catalysts or tatalysaterrUokständen, and then the copolymer in water can be precipitated and gewaeohen are means against the

909823/1096 bad original

• Z) -

Bau "like antioxidants or free-iladücal-Ptin ^ er, can do the Monomers or the copolymer τογ or during the polymerization are given «to such an 'ohut« during the Isolation of the polymer obtained below · These same substances or more of these soleplates can after the end of the polymerization and can be added to further processing

The copolymers obtained after the practical implementation of the invention can be mixed with fillers, such as thickeners, pigments, fillers, extenders, softeners, trelts, antioxidants, etc. Examples of such substances are gaeruee, titanium dioxide, ^Siu 2 ^ ¹ * ^{1 s} ^ ° 2 * "containing substances, fibrous fllieonon oxide, carbonate, clay, barytes, mica, wood cellulose, glass fibers, asbestos, nylon flakes, phthalooyane oxide, stearic acid, stearic acid dyes , Zinc Oxide, The "like mineral oils" Bls-CbeneothlaByD-dlBulfid, BIs- (morpholyl) -dieulfid, Bis- (morpholyl) -tetraBulfid, Phenyl-8-naphthylamln, Tetramethyl- (or ethyl) -thluramdphthallat, Zinc stearylat, Antimony oxide "Hohwefel," natural rubber "Polyethylene" Polypropylene "Ohloreulfoniortes Polyethylene" Butyl rubber "Polyester" Polychloroprene, butadiene-ntyrene-Xautsohuk "Polyaoryl acid ester chewing materials" ois-Polybutadlen "oie-Polybutadlen" Oie-Poly-polyisoprene "Butidyn-Polyisoprene polyether - and polyether urethanes, chlorinated rubber "balata", trmns-polyisoprene, hard polymeric polymers with a high styrene-butadiene content, reoroin or phenol-formaldehyde resins, alkyd resin e «Melamlnharse und tthnliohe · The oaerues can come from KanalrusD or furnace-

909823/1096

-2 *. H95862

ruse exist and will in a lesser degree of weight Compare see below chewable mixed polymer, usually between about M> up to 70 parts by weight of oaruss per 100 parts by weight of the mixed polymer, used · Blowing agents can be mixed with the polymers according to the invention » to get ropes fabrics

The following examples serve to further explain the invention to those skilled in the art.

A clean thick-walled glass tube reaction gefties - of about 25 ob x 2.54 ob (10 "χ 1") was purged with nitrogen gas. The drilling was then carried out with nitrogen under pressure of 5 atmospheres filled »and there was a Klechung τοη dry propylene oxide and Allylglyoidylüther la das! leaktlonsgefäß introduced · λιι-. sohlieaeend a Qectiech made of propylene oxide with UTaeser "added" and then diet was sugssetst · The drilling became Ttreohlosstn and the contents of the tube are stirred at room temperature, the contents solidified "The contents were Js do oh in acetone mnieslioh. In another search, Iltrobensol was sugssetst «Ad the reaction carried out in the dark. The product obtained was then taken out of the drill and mixed with acetone. 1 "then became a small" tightly concentrated aqueous HCl solution Suggested to sweeten the catalyst to a water vellcaee Form SaIs of the catalyst (Ritekstiade) su. The Misehumg It would then be put in "aaser" to remove the "adhesive polymer"

909823/1096 ^

.25- U95862

Aueauffall, which is filtered off by the tea solution, accustomed and was dried in a vacuum oven at 50 ° C · Continue · Experiment · were dt Vinylcyclohexennonoxyd in the light without nitrobene sol and carried out without causing gelation. Experiments were also carried out with butadiene nonoxide in the dark Dl The copolymers obtained could, if not easily, be bought. The amounts of monomers and catalysts used, the Heaktionebondiuagen and the received · »Brgebnie ·· are listed in the following table A.

909823/1096

Monomer "anno ü table A Art λΟ1 · ϊ ■ *
noper Raw materials Mol } · mol
Zinc ethyl
(0o-cataly-
aator) 90 etzuxxR the AGS ( ) 10 üinkUthyl 0.8 96 CoBonoraer ASIi 4th Mole x 4 x 100
Mole B'ono-
mer (Kata
lyser) 0.8 At-
MtS
ISr ₁ 96 Conditions 4th 5 0.8 1 97 AGE 3 3.6 0.8 2 90 THE END 10 3.6 1.0 3 90 Y3i £.! 0 (· O ίο 1.2 0.8 4th 90 YOfIMO 10 0.10 0.8 5 99 YCiIMO 1 5.9 1.0 6th 97 YO ^ iItO 3 1.0 1.0 7th 50 ! 3HO {& ) 50 1.0 1.0 8th 99 IiDMO 1 1.0 1.0 9 91.4 BMlO 0.6 2.5 1.0 10 97 BDi'O 3 2.3 1.0 11 0.041 12th 1.0 13th

909823/1096

T - - ■ - -,
ΙιΠΒΙΙΙΙΙΤΒμι 3edi ngunffen 86 yield - 21 I.
i
i At-
Mju. time
8 do—
the 'üempe- 40 Oraom / Orme »
Katalraatoy 40 1 Heptane 72 25th 20th 7.4 43 i
i 2 Bensol 16 25th 90 5.3 15th \ 3 Heptane 16 25th 6.6 2.6 18th 4th Bensol 96 25th 50 (b) 36 1075 no· 96 80 40 35 45 6th Heptane 72 25th 73 7th Heptane 72 25th 91 8th Heptane 96 25th 74 9 Heptane 96 25th U7 10 Heptane 96 25th 75 11 Heptane 144 25th 95 12th none 48 80 ⁴ 13th no· 120 25th

909823/1 §96

product

Anaats

Intrinsic viscosity

4.5 8.1 4.3 2.25 2.40 3.23 4.17 3.11 1.92 3.3 «2.95 2.57

Asohe gel (β)

0.15 0.17 0.07

1.04

0.09

unlöalioh (2) 7 ⁵ 3O ⁵ no ⁵ no ⁵ no no no no no ⁵ no ⁵ no ⁵ no ⁵

Information by User 41 · HieohpolyMerieation

Infrared infrared vulcanization

Infrared vulcanization vulcanization

Infrared Infrared Vulcanization Vulcanization

(a) propylene oxide

(1) Volumsnrhiatnle von Löaungeeittel eu Monomsrsm in all cases - I ₉ O ₉ in which a solution alttsl is used «··

(2) Vwmuu » in 25.4 ca (10") wide pipe, dl «de» lioht from * feeetst were, run through. Gelierun «rerautlloh through Ver ~ MtWBUt swiaohen allyl double mouths, which

An attack by free radicals i «MJ * r ti H l _T

(3) Versuohe 1 "Darkness in the presence of 0.1 oew.-9t of the lionoeere • A Hltrswsasol durohiefahrt ·

rmtur

PO stirred for 24 hours, * * dl * f «was increased.

909823/1096

BATH ORIGINAL

-. 29 -

H95862

(♦) Allyl glyoidyl ether

(-M-) Yinyloyolohexenuonoxyd (double bond το «unconjugated Alkaline type and free-cooling bath normally not eu

expected). 1,2-3poxy-4-vinyloyclohexane.

Butadisone monoxide
(// Αέ) 0.3 g misoh polymorleate / 100 οοα Densol (b) approximated
(ο) Oil networking

The anettse listed in Table A explain the use of Tereohiedener unsaturated Couononerer in lowerohiedliohen ratios and furthermore the use of Tereohiedener Verj aaltales * τοη catalysts and Go catalysts "both with Poly"<merlsation in solvents as well as in the Maeee.Kreiohtlioh j steps the polymerization at moderate temperatures fork "ad \ gives good yields of letstlloh obtained copolymer, high Molekulargewioht" Ss 1st ersiehtlloh that la dependence τοη the AHL of the monomers and other conditions, copolymers with Tarilerender BlgeaTlskosltit and according to different molecular weight can be obtained. The Bigenriekositat measured in Bensol for this polymer is about the same as the fundamental molar variability, which in turn is lied to the Daroheehcutemolekulargewioht from osmotic pressure measurements. It was found that its base molar Ylakosltätssahl swiaohen swsi and 2.5 an osmetlsoh measured Ifolekulargewloht which is about 165,000. Blown basic molar viscosity grades of 4 and 4.5 correspond to a molecular weight of about 500,000, while a value τοη (I) (basic molar viscosity grade) 8 corresponds to a molecular weight of about 500,000. 809823/1096

U95862

GAME 2

Bmi procedures in these iieiepiel was iihnlioh döwjenigen de 'previous 3eiopielo 1 iuit the Abweiohung, oxidase ternure polymers horsse · shares were · The polymerization was carried out in the dark "and it was iii trabensol used · HX Uleoapolyneriaute obtained could leloht ve grind The know the The substances used and the reaction conditions and the results obtained are listed in table J below:

111,

Propylene

80
70
70
70
68
80
70

ηΐ \ ^ ηϊΨt

1,2-butene difunctional

10 20 20 20 29 10 20

TOlIUO

Λ02 AQB AGE ΒΰΚΟ

MT

Moles / 100

10 2 10 2 10 0.25 10 ItO 3.0 1.0 10 1.0 10 1.0

909823/1096

BATH ORIGINAL

Table B Vortue tzunxt

άβΧ * raw materials

An * sets

21 22 25 24 25 26 27

1 1 1 1 1 1 1

Heptane

Heptane

no

no

no

no

no

Tent lamp. Yield ^

Voltage ratio

never lioness

1
1

25th

25th

25th

25th

25th

25th

25th

38 61 14 44 62 52, «100

Table B.

Auee duck

An * Qrmam / Qi • ate catalyst

21 10 22nd 17th 25th 53 24 24 25th 33 26th 28 27 51

Kigen

viek

tttt

2.32 1.12 3.62 3.77 3, β2 1.26 0.04
0.06

product

Information about the MlBohpolTwerieation

vulcanization

Vulcanization Vulcanization Vulcanization Vulcanization

HisohpolTBsrieat 100 ocm each of Bensol

909823/1096

We see from the aneeteen listed in Table B, copolymers can be produced according to the invention using three monomers, one of which is dl-functional, i.e. unsaturated, let · These couonomers are * ur Polymerization in solvents and in bulk suitable and give good yields under moderate rolymorieationsbedingungen. The copolymers obtained can have an entire molecular weight range possessed that was 150,000 or more. It is interesting «u mention» that Ansats 25 with 29 MoI- / 1,2-butene oxide Kischpolymcrisat yielded a polymer having an Elgen risk of clay 3.77. This amount of butene oxide resulted in a corresponding reduction in the proportion of propylene oxide niohtkrlstallinee polymer, which röllig in cold acetone löelioh is. TTiβ indicated, however, lies even if it is non-crystalline and therefore amorphous, its molecular weight in the clay range about 300,000.

BeiBDiel 3

Some of the Mlsoh- and Terpolymerlsate of the above Examples 1 and 2 were compounded (with filler)
and Tttlkanlsiert.
The Tulkanlsationeansats was as follows:

809823/1096 bad original

U95862

frfoff Qewiohtatall "

Pol / »erieat 100

ZJjEÜCQSQFd 5 Tetraethylthluraadisulfld 1

, 2

Qfmtanum 40

phthyl -Iw 1

Dl "ait fUUetoff TvrMUtMi Kmia were 45 minutes Wl 142 ⁰ C (207 ⁰ V)« OkmaUiwrt · 2U · b «l of your Uiit« jreuohi «f

- «ind listed in the following table C ι

Table C. AasetS-Kr
Tabel
j. or B. SMSVHMSssesV
79.5 dedal Spe «!
ην ιιηβ 7th 33.4 1136 οι Brueh Physical UlitenschaXten 8th 19.3 475 103 .4 1481 Aft »
• mti
ICi. Being on the
above
Tables ₉ (D 52.7 275 33 .7 475 siMNssja
31 Tabel
~ A or
B. 9 106 750 52 ,8th 750 32 A. 4th 84.4 1524 66 »0 950 33 A. 12th 47.5 1200 148 2097 34 A. 13th 60.5 675 157 2225 35 A. 25th 123.0 860 185 2625 36 A. 24 63.3 1750 162 2300 37 A. 26th 121.5 900 123 1750 38 A. 27 1725 100 • 1575 39 B. 130 1850 40 B. 41 B. B.

909823/1098

BAb ORIGINAL

?, 9TT9lBB-
strain
'* - 35 - Shore hardness A
Luroueter U95862 400 Table 0 Forteetsuzuc 79 300 PhvoikaliBohe Si / renechaften 80 At-
eats
} ίτ. 510 permanent
deformation 58 Increasing cr
Verecliloiee
(creecent tear) 31 370 3β 81 - 32 380 63 69 - 33 465 43 69 - 34 750 56 67 - 35 700 16 62 - 36 300 41 72 260 37 450 44 55 350 33 320 28 71 300 39 - 115 40 19th 110 41 16 260

(1) Koiapounded without lift »see B. Oiunmiraaose

As can be seen from the table above, the polynerients according to Examples 1 and 2 can be rulkanieiert on the rorl-living JTiohteättlgung old sulfur In Yergleloh on other eynthetleohen chewed owl carllgen materials

903823 / 109S B _Ao

The · procedure in dl · * · «example was similar to« 1 »the one d ·· previous example «1 salt of the respiration, since ·· da · Propylene oxide or other monomers, such as phenylglycidyl ether, Styrene oxide, dodeoenoxide and ethylene oxide, aleohpolymerieiert * The polymerization was carried out in the light without Vltrobensol carried out. Dl · reaction conditions and dl · obtained results «Ind in the following table I):

Table D.

Ansats

Propylene

63 93 74 97 91 97 90 90

P03 (1)

FOS

80 (2)

SO

DDO (3)

DDO

JBO (4)

SO

Ooaaonoaere

MoI- * Go

17 7

26 3 9 3

10

10

Moles / 100 moles mole ² / mole monomer fWWftft

6.8 6.4 7.5 6.1 6.5 6.2 2.0 2.0

0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8

909823/1096

BATH ORIGINAL

-.37 U95862

D 7 <Mrtae

IMaBIWMIfIi Yoluaenver-

An * nältnle IB tent eata eunemlttel hours ffr. au monomers at 25 ⁰ O product

Heptane 1

73

51 Heptane 1 73 52 Heptane 1 72 53 Heptane 1 72 54 Heptane 1 120 55 Heptane 1 72 56 3enaol 10 96 57 ftenaol | 96

Oew./
Weight
Kata-
lTaatoj Bi & en- del Details Ub *
daa Nleeh-
polymeric
i aaF 5.9 Tie-
koei-
r did 20th Kautaohuk-
like bl
geneohaf sound 70 3 4.3 0 * » 36 7.3 2.88 0 - 87 4.6 1.04 0 mm 56 5.6 0.79 0 - ** 5.9 1.26 0 - 70 2.5 0.86 - htnere Wa-
eerlOalioh »
kelt 10 -

24 6.0

(1) Phenylglyoldyl ether

(2) styroloxjrd

(3) dodeoic oxide

(4) ethylene oxide

(5) 0.3 g polyoleate / 100 oom benaol

When the procedure was repeated as described in Belaplel 1 bia 4 (Toretehend), whereby either the catalysis (Slnkdlttthyl) or the 0o ~ catal / eater (H ₂ O) were discarded, in the same days (168 levels) at 25 ⁰ C no Mleohpolynerleat or no noticeable amounts of polyaerleate received

909823/1096

'AL

-30- Example 5

The process in the same way was similar to that of the previous examples.250 g of 1,2-butene oxide was mixed with 13 oom allyl glyoidyl ether (oil-coated 97: 3) in a polymer atlonac flask under non-oxidizing conditions bit 1.3 g of phenylfl ~ naphthylalene and O ₉ 23 ooa Hitrobensol in the presence of a talytleohen M & sse »the outer 3.7 coa zinc diet and 0.51 ooa (UoXTerhUltni» 1 ₉ 0. · O ₉ B) beetand ₉ polymerized. For five days at 25 ⁰ O, the conversion of the monomers to the Mieehpolymtrieat was about 100%. 100 parts of the Mieohpolymerieates were then in a »Benbury Mieoher with 40 parts of Oaeruee, 5 parts of ßearine acid, 1 part of TetreJMthyltMuraedieulfid, 5 parts of SlAkMtJd ₉ 1 part of sulfur and 1 part of Bie-benaothiamyldieulXid VWrBIeOAt ₉ wobble! Slatliobe parts on the Oewioht are sucked. S «r Behulfel and the Tetraaetbyltniureuedieullid were cleaned in a cold twowmlBechautohukmohl rerBie. The old filler was then rereetste in a fora 45 minutes whale 153 ⁰ O (306 °?) Yulkenislert and then mioht. The · at the time of the taking of the · chewing “ohukertigem Tulkaniaat · preserved Krgebala” · were «1 · followed

909823/1096

U95862

- 59 «-

Ungoldertι under- At 149 ⁰ C (30O ⁰ F)

euoht during construction »· during 24 hours« e-

teriperntur ages; examined

(25 ° ü) frfi i ^

300 Ji Kodul ks / oa ² , pal 45 _t 7 650 ü2.2 1175

Orenssugfestigkelt

lCfi / om ² , pel 1E4 2625 100.2 1425

SOO 550

Tensile deformation / <53 22 Shore hardness A 59 66 Increasing wear kg / o »73» β

lbe / ln. 410

Example β

The method used in this example was similar to the above-mentioned examples, with the difference that propylene oxide and allyl gljroidyl ether (Holwerhaltnie 97-3) were used as monomers. They were prepared using the zinc diethyl-HgO catalyst system. 100 parts of Mleohpolynerisat were then amf dea Banbury-Klsoher old 50 parts of hoohabriebfeetea Ofenrues, 1 part of stearic acid, 5 parts of zinc oxide, 1 part of phenyl-O-naphthylic acid, 1 part of tetraethylthiuraadisulfide and 1 part of Sohwefel rer-Bleeht · »aoh volcanic acid in 45 minutes ^The rubber volcanic acid was examined at 0 O (30 β ° Ρ), whereby the following results were obtained.

909823/1096

- 680 1150 1495862 50 2600 1-robe β * 1 _α
• 96 * 0 (205 ⁰ F) Sample at 75 49.9 710 80.9 99 ·
555 118 1680 83 650 • 83.7
465

500 / 'module, kg / o « ² , p« l

Qrea »« ugfeetigkeitg

kg / on f pci 1

Tensile elongation />
Eugverforamg ','
Ohore I Shepherd A

Increased Vereohleiö kg / o "

lbs / in

Sin · Prob · de · vulcanized Ilauteohuketoff ·· after the Krfindun £ vurd · against Omon in a dynamic bid test bti Rau «·» temperature 24 hours and 60 ppi00 »Gson auegeeetet without any ado of Riiibildune. Μβββ · let special · be «recognize« irert ₍ lnebeeondtr ·· when it is taken into account that ·· since «applied Ilärtun €» «y * teB eur antiotonicity,« • loh ·· Ublioherweiee la «Ι» · »brewed chewing · - • yet · »in order to reduce the · inclination of the KauteohOk ·« ur llie formation in the event of a resolution against oson su reraimin, is built in · KIn natural Kauteohuk or a chew-like butadiene-Ijj-atyrol-raeohpolymerieatiiaeee, dl · with an optimal hardening process, but hardening without an anti-ionic agent, results in formation in less than a few hours, and an anti-ionide kit in 24 hours.

£ lne rrob «de · old filler reet and hardened rubber · (without Osoiild), whereby the Kauteohulc au · a «iTopylen- «Cyd- tmi Allylglyoidylther-Ilieohpoljfeerieat in Molrrehaltni · f »m 90t10 VeatanA, was also the iynamieohen ü» onkraokte «t

909823/1096

BATH ORIGINAL

Subjected · The proba showed no occurrence or ati * eiohen clay cracking noon 96 hours was room temperature and 60 ppi00 "Oson · Je was unexpected" because the frobe with the greater proportion of IJiohtalttigung υ was qvöb * qt9 Wlderetandefähigksit against the attack duroh Oaon

Example 7

Dos method in this sample was similar to the above example old except the dees Molvorhilltnie of propylene oxide su Allylglyoldyl'ither 9ü, 5 t was 1.5, and that the Tetramethylthiuraradiöulfid was raised to "vrei parts and Sohwefel ebenfeJki increased to SWEi parts · Up was obtained in the vulcanization kauteohukartigen masses were examined "and that \ get iurden UXM following results:

300 /. iiodul kg / approx ² , pel

ZerrelOehnunf Ehore Hürte A Increasing tersole kg / o « ²

lbe / in.

Sample bsi

66.1

940

Sample at _A 96 ° 0 (205 ° y)

64.3 915

200 (2650) 121 (> 1715)

605 37 _f 5 64 114.3 635

7-650

89.1 495

909823/1096

■ .42-. ■ H95862

BeisPleX 3

The procedure in this episode was similar to the previous BelepieX with the difference that the monomers used were made from mixtures of IropyXenoxide, AXlyXglyoidyluther and 1,2-butene oxide in a ratio of 91 * 3: 6 and other large amounts of 91 : 1 »5: 7» 5 passed. The terpolymer resulting from A was mixed in a chicken, as in the previous example, with PIlXl β to ff with the difference "that the oil ratio was sohwefsl Ku? HiuraadisuXnd 1s1" while in the reference to the terpolymer B, the terpolymer B was used raw sulfur su ThlursmdisuXfid 2: 2 Onwiohtstoile was

Sample at
liaumtSA-
oermtur Sample at Sample at
raucous breath
psrature Prob « 300 t KoduX ₉ kg / em ² , 62.9
895 60.8
865 60.8
865 000 * Orenssu ^ estiftkeitg 174
2475 126
1790 174
2475 124
1790 lerreifldehnung f * 745 635 809 765 Xurrerformm « > · 31 17th 47 28 Shore hardness A 61 - 64 • Increasing wear 88.2
490 75.6
420 97 _f 2
540 89.1
495 BATH ORIGINAL

909823/1096

Iteiapjel

The procedure in this Deiepiel was similar to the introductory one Äelapiel with the deviation, daee ale '.ononere propylene oxide and / llylnlycidyl & ther (97 s 3 * oil -'- ratio) elnceeetst were »and all Katalyantor a mixture of Zinkdi. thyl and ibo-xiropanol was used «and the monomers were 7 at 0 ° C were polymerized · 2> ae obtained copolymer ie at a Ziirenviakoeität of about 4 * 00 and was in an aneatt Vulcanized similar to that of the above Beleplele and undermioht. Se roped at home οine suction capability of 105 kß / c & (1500 pel), a 300; .C module of 31 * 6 k ^ / oBj (450 pei) and a ZerrelQaehnuni; from 670; '.

Example ip

The method of polymoreation in the Beleplel before Uhn * borrowed from the above examples 1 and 2, the deviation from the fact that oxetanes were used. You polymer! Eat 1 onebedl, ngun & en and the received Grgobnieee elnd in the Tubelle: listedι

90 S 8 2 3/10 96

U95862

dragonfly ii

Monomer

catalyst

An • att

Ox tan

OjMtan

Ox «tan
/ vllylgljroldylather

Propylene oxide

0x «taa
Fropylmoxide

Oxetane
Propylane oxide

Oxatane

MoI
10

0.56
10

1 * 15
10

2.00
10

0.49
10

10
2.33

£ mole tern

ffiÜL 97/3

94/6 90/10

95/5

90/10

00/20 ΔΕΙ.

H ₂ O

Get

0.051

0.498

0.053

0.514

0.055

0.537

0.064

0.472

0.066

0.500

0.071

0.561

909823/1098

BATH ORIGINAL

iats
Six SM * 70 192 71 192 72 192 73 210 74 210 75 210

U95862

mm 45 "»

Table £ ffortaetsmut Beaarkunjten

AoetonlOslloh, clear guioialar tiger substance; aoaton-insoluble, viscous Lölohtgs-colored

Auetonlüslioh, clear guniuiartigsr fabric » AoetonunlOslioh, something like «iriskos ·

AoetonunlöeXlüh,
ZUh and brUoMg
2UIi and brüuiiifi
Tough and brittle

All polymerizations were made. Iu 10 ooa ll «ptan at Xlauat» mp «ratur duroliä« XUhrt. E "lh" 2iTolg · accessories au H "aktlonse" foot 1 Löeu & gtraittelt monomers, H ₂ O and intestine

Vie Torhergehend stated dl besitsen the new naoh the VerXahren and dam Katalyuatorsyete "to represent invention Hieohpolymurieate produced · very wtinsohanswerte Sigeneohaft τοη about natural ICautaoaulc in menrerer Ilinaioht when did ·· · copolymer with JTUllstoff ·" and dam beiepieleweis · dan in Examples 3 and 5 to 9 an "e" * sanam Tulkaniaatlanasjstam were made with soulfur reretat. So these lUsahpoljaerieate are made of a saturated oil monomers and an unsaturated 01 "fino3qrdmonomere _t as mentioned above" from a linaaren Katt "old stw · isotaktl rave about it / tandan unsaturated Oruppem wise — angs s «tst * W« lterhim saalitaam sie snsnshmamd hohas m »lekttlsjrga« iaht ₉

909823/1096 bath

U95862

BRA. 200,000 and above, τ / io see both duroh iJx? «Älgenviekoeitliton as well as duroh di «basic molar viscosity numbers Anaeigt who ran above 2 "AIa ^ rgebnl · at least this Iw i the factors resulted in thin streaks of old and. vulcanized '! aoson, especially when on iiiaohpolyiaörisatan, which contains a large proportion of propylsurayd, on go builds eiad when exposed to X-ray radiation a youth grid, v; elohee «las rh'inonen der Ilriatallieation Seigt when stretching.

?, a thin vulcanized strip au · se of NaOH AnaatB 3Ü (Table l) prepared "with Ull3toff vereetsten Mae, aue in the copolymer of 91 '' ol- 1 propylene oxide, 6 mol - '- _f 1 2-3utenoxyd and 5 i! ol-; ' Allylglyeidyltither "is ueasuctngteetzt under Verwendunc heptane al · Löeun" · - was hergeetellt Biittel and at a fesper & structure of 7O ⁰ C, auegeaetzt an X-ray, and it was Beugungegitter both "because · preserved it the strip in Ttuhe al · AUOH at a Elongation of 500 pounds analyzed. In the middle, the diffraction grating formed a diffuse halo that does not indicate a crystalline phase · t7enn ά · τ Γ meet to 500 '/ ■> has been stretched, «• there · there · arcs, grouped or spaced apart, in Correct arrangement removed from · center »point d« · file ·. Dl · · «indicates that when the · stripes · el * h are stretched, an inner crystalline Pn ··· forms ·» in which the · claws were oriented. Bm was Ebeneo gefeade », then ·· near to» lying «r Bttepnmae d ·· Btreif ·» · da ·

BAÖ ORIGINAL 909823/1096

I H OOO Ό

again a diffuse liof orgab, v.eloher the overturning of the oriented »crystalline! 'haue anselgt ··

It was also found that "you ·· UieahpolyMrtsatetreifen from uniformly manufactured] robes, such as Ansät jb and the τογ-etehen" in vrelohen however the liisohpolyaorisat without the use of a third monomer, such as 1,2-butene oxide, was produced "in: Ktntg" nstrahlbeugungsgitt "R found at rest * elohee that the presence of τοη crystallinity". In “Otrekken the same irobe on 500” the “X-ray diffraction grating again eoharfe bends” the un and 1 “Distance of the center point arranged“ aran ”was anxious” that the crystallinity had increased and that the crystals were oriented, aioh also came up with the undepension of the stripes aa X-ray diffraction smoother, because the orientation was lost and crystallinity was reduced to its original height *

Guaalaaesen from xiOpylonoxyd / AOE-üieohpolyeerieetttaeBen in «· ISolTorhaltnie τοη 97/3, which had been produced with the» Katolyeatoreyeteo Zinkdittthyl / Waeser »resulted in a Hisohpolymerisat old of a basic polar okositutoliahle hunomen dor Krietalli * · ti ierunc at "iJtreoken for example, a iUechpolyBsrisat.» according Aneat · 4 (table a), old except that (eptan ale POlyBerlsatlonslusungsaltttl Tsrwendet was _t gelltet in acetone and cooled to -2O ⁰ O ·: ine unholy group

909823/1096

- 45 -

▼ on 15 Qow · -? '· And »It a, jrundmolarön ViscoitüteBahl la Xsopropanol at 6O ⁰ C τοη 3 # C, dl · is about glaioh an IJigenviskoeität in benzene of 7.0, was filtered off · The soluble part (05 / ') with a basic Viakoeltätssahl in Isopro * panol at 6O ⁰ O of 2.44 (approximately equal to a JSigenTlekoeitUt in Benssol τοη 4.8) with a suitable vulcanization system *, κ.D. Tvuids, sulfur, zinc oxide, etc., Tulcan / Blart. A thin strip of it gave, on X-ray irradiation, a diffuse suction, indicating the absence of any crietalline Ihaee. When the same strip was stretched to 1100 ', it gave an X-ray diffraction tagged old defined' constant radius' which was located in the center of the diffraction plate, indicating the presence of oriented crystalline I ¹ HaS *. The same sample showed a tensile strength above 10 $ kg / o « ² (1500 pel). The formation of the more oriented crystalline phase during elongation is a phenomenon that occurs in natural chewing, and is considered to be the factor responsible for the firmness of natural chewing, but it is absent in most other synthetic chewing substances It is also assumed that the * • es symptoms are conditional on the height ’freedom of movement in natural chewing liquid. As can be seen from Examples 6 and 7, the rubber is suitable for natural rubber with regard to its high tensile strength at roughness temperature.

909823/1096 ^BAD

U95862

- 40 -

It is evident that the present invention is a high molecular weight polymer, both for the crystalline unlyoliclie.u preparations as well as for the amorphous fx 'actions that occur with. ohwefel rulkanlnierbur and kauteohukahii-Ii3h oind, results not only in many! 'oetigkolteeigenochaften, ZugfoatigiCoit »! iQisafeBtiijkoit etc. beuitzeii, diy comparable to those of natural rubber, sondorn \ / pushin aiip-iifiliant ir "Jiinblick auf ein i-; chüd: l £ ung" 3uroh ozone and oxygen are even forbidden.

Patent claims

909823/1096

Claims (1)

yatontansprlloha A method for the production of τοη polymers from oyol-like oxides, in that, under a non-oxidizing atmosphere, in a polymer-soluble mixture, there are always different organic oyollaehen, each of which ends up a ring with two and three carbon atoms an oxygen atom contains «n _v sit of a catalyst,» .B. Oil-based (I) from A and B or (II) sit a reaction product from A and B _{9 is} polymerized, the ratio of the suame of these blonomers to the catalyst about 100 ι 0.05 Me 100 ι 10 ₉ O mol and that The ratio of A to B 1 0.05 to 1 ι 1 Hol, where A is at least "in" a compound of the formula Mo (R) ₂ , in which it is a metal such as Beryllius, Cadsius and zinc, while α is a organic radicals, such as alkyl, alkenyl, cycloalkyl »and Oyeloslkenylrsste as well as their Oeslsohe, sit I ice represents 20 carbon atoms, and B represents at least one active vase substance containing Oo catalyst for the activation of A» 2 «Method according to claim 1, characterized in that the Ratio of the sum of these monomers to the catalyst is about 100 ι 0.2 Ms 100 t 7.5 KoI. 909823/1096 BATH ORIGINAL U95862 9 * Method according to claim 2, characterized by the fact that the Oo-Katalyaator consists of (a) Waaaer or (b) Geaieohen of Waaaer and aindeetena an aklloh WaaeerlOellchen allphatlaohan connection, β · Β · anea alcohol, an «aenrpolyoligen alcohol or aineal polyolkylene ether , old a molecular weight bia au 60O ₉ (ο) aua aindeatana an aklioh waaaerlOeliohen allphatlaohan compound, such as alcohols, polyhydric alcohols and polyalkylene ether polyols, old a molecular weight blue au about 600 and (d) aindeatana ana oxide and alu oxyd aD aD aural aluminum oxide aindeatana ainea further oxide of a metals belonging to groups II bia IV dee perlodeneyeteae of the elements, beeteth. 4 · Procedure naoh Anepruoh 9 "daduroh g" k "nnaeiohnet, daa · aindeetens one · dle «r monomers in dea polyairable to Oeaiaoh an allphatieohe carbon-carbon double bloom dung aufwalat and in dea polyaerleable Oealooh in one Amount of about 0.5 ble 30 KoI- * is present 5 · Procedure naoh Auepruoh 4, daduroh gekennaelohnet, daaa daa Maao — ro old of the Kohlanatoff-carbon double bond la dea polvaerlelarbaren Oeaieeh in a »narrow of about 5 bla 30 KoI- /. is present. 6 «Proceed * naoh Aaapruoh 4, thereby keanaelohnet, daaa« as oaao old dor carbon "^ ohlonatoff double ended in daa poljaarlolarbaren I-i> ah in an amount of about 0.5 If MoI- * is available. 909823/1096 U95862 7. Method according to claim 6, characterized in that da · monomer · with dtr Kohlanetoff-Xohlenetoff double bond Uses all glyoidyl ether and the other monomer au Propylene oxide consists. Θ. Method according to claim 3 "characterized in that at least" in the profit in the polymeric mixture consists of a saturated 8poxy monom "ren with 4 to 12 carbon atoms and in the poly" obtainable oil "anyway in an amount of τοη O ₁ S lead KoI- ^ is present. 9 · Terfahrea Anepruoh to 8, characterized g "mark * _t eiahnet as ·· as" geaüttigt · Bpoxydeonoaere ± i de "poly" erieierbar "n Geeieoh in an amount swi" around about 1 bie 10 MOI ^ rorliegt. 10 · Process · »naoh Anepruoh 3 _t daduroh eekennmeichnet, that (A) at least · one of the oyclieohen urydnonoeeren in the polymerizable Oeaieoh from a Rpoxyd Kit a Koh-Ienetoff-Rohl * n * toff-double-bond bed" ht "and in the poly - ■ • Oealvch that can be mixed in an amount of about 0.5 to 15 mol * is present »and that ·· (B) at least · one of the ojroli- ■ ohen oxidized monomers« n in the »polymerisierber ·» Oemisoh from a · « The saturated kpoxyd bit consists of 4 to 12 carbon atoms and in the pelyeierbaren Oemisoh in a kenge svisahen about 1 to 10 KoI- * rorUd the "the poly-" arisittrbar · Oe "i" eh susätslioh (O) at least sin organiseh ·· erelisohee Osqrdmonoaare with at least one Hing contains two carbon atoms and one oxygen atom, tr * 909823/1096 badoriginal U95862 da · tin represents other * monomers »than (A) and (B) and la this polyraerislerbartm mixture in a sufficient amount is present around dtn floodplain to about 100 mol-> au bring «» · 11. The method according to claim 1O _9, characterized in that ·· (A) consists of Allylglyoidylüthsr. 12 · Procedure according to claim 10 »daduroh gtkennstlohnst * that (A) consists of 3utadienaonoxide 13. Ancestors according to claim 10 »daduroh known» that (B) composed of 1,2-phenoxide. 14 · Method according to claim 10 »because (A) consist of AHylglyoldyläthsr» (B) consist of 1 _f 2-3utene oxide and (0) consist of propylene oxide « 15 · Polymeric fabric »produced according to the method specified in claim 1 · 16 · Polyaerer fabric, produced according to the method according to claim 3 · 17 · Polymeric substance »manufactured naoh de« procedure naoh
spoke 10 909823/1096 H95862 1Ü. Polymeric substance with an average molecular weight of at least about $ 0,000, consisting of a mixed polymer of at least two isolated organic cyclic oxydmonoaers, all of which contain one or two or 9 carbon atoms and one "Saueratoffatoa" 19 · Jfolymerer fabric NaOH Anepruoh 1R, gekennseionnett characterized dme "aindeetene a" of these monomers, in the erlaat Mleohpoly- "a · aliphatieohe Kohlenetoff-Koalenatoff-Dopp · - blndung beeltst and in the Mlechpolyaerieat In a ueen" e O ₉ S until 30 MoI- * is available. 20 »polymeric fabric naoh Anepruoh 19 · thereby identified, daes da · Monoaer · with the carbon-carbon double bond into the Mieohpolymerleat in a Ues ^ e swleohen $ and 30 MoI- ^ is present 21 polymeric fabric naoh Anepruoh 19t characterized daee dae monomers alt the carbon-carbon double bond la de MieohpolTmerieat of 0.5 to 15 MoI- * is present. 22 · JPolynerar fabric iymtft pineapple reali 21, dartiiroh daee dae moaemer · with the lohlenetoff ^ iCohleiftoff double ^ einaag au «Allylglyeiaylätaar eeeteht and then · mere au «propylene oxide e« «t« ht · 909823/1096 ORIGINAL BATHROOM -55- U95862 25. Polyaerer substance according to Anopruoh 1U _t characterized in that the "minimum olnoe of the monomers In the Hieohpolymerisat consists of a saturated spoxide with 4 to 12 carbon atoms and in the r.lechpolyniorieat in an amount" between about 0 ₉ 5 to 20 ϊ ' οΐ- 'rorhanden is 24 polyamide material according to claim 23, characterized in that daee the saturated epoxydeonomer in the copolymer in a !! close like about 1 bia 10 .MoI- ',' vorhm.den let. 25 · Polyaerer C to ff according to claim 10, d η by gokenneielohnot, dASfi (A) mindoetene one of these cyclic oxide monomers in the miochpolytaorisat from a »Bpooqrd with a carbon-carbon double bond consists and in the IUeohpolymerisat on a slope, about 0.5 to 15 colons Torhanden iat and (3) that at least one of the cyoli see Cxydmononoren In the! "Isohpolymerisat from a ^ saturated Epoxy contains 4 bio 12 carbon atoms and in which Mischpolyneriout in a range of about 1 to 10 I'ol- ^ present let «and furthermore (C) at least one organosome cycliechee Oxydnonomores Bit Bindeetens a Hing on · swei Carbon atoms and one oxygen atom are not available » which consists of another clayey al (A) and (B) and in the Mioohpolynerleat in a sufficient Vang · is available to bring the heat practically to 100 mol -: * su · 26 · Polymeric substance according to Annpruoh 25 »characterized» that (A) consists of allylilyoid ether. 909823/1096 27 · Polyaerer material according to claim 25 »characterized by since (A) consists of Vinyloyclohox nmonoxyd 28 polymeric fabric according to Anepruch 25, characterized that (B) consists of 1,2-butene oxide 29 · Polyiwrer fabric still claim 25 «thereby known» daea (A) au · AXIyl ^ lyoldylather, (B) au · 1,2-butene oxide and (J) consist of propylene oxide 30 · KAtaXysatormaese, consisting of a Hasse, such as (I) mixtures of A and B and (II) the Jteaktioneprodulct from A and 3, where the ratio τοη A and B is about 1 to 0.05 and 1: 1 mol, A At least one compound of the formula Me (R) ₂ stelXtf in which Ue is a metal, such as beryllium or cadmium, and R is a nest, such as alkyl, alkenyl, cycloalkyl and cyoloalkenyl radicals and their compounds, with 1 to 20 carbon atoms and in which B at least one active hydrogen-containing Co »XataXyaator sur Aktlrierung darsteXXt · 31 · Katalyeatoraaeee naoh Anepruah 30, thereby known, that B consists of at least one Oo catalyst, such as (1) water, (2) Oemlsohen ron \ raseer and at least one noticeably water- •• rlöellehen Connection, e.D. an alcohol, a polyhydric alcohol and a PolyaXkylenfttherpolyol with HoIekulargewehten until «u about € 00, (3) at least one noticeable water-soluble compound, such as alcohols, polyvalent 909823/1096 BAD original -57 «U95862 gen alcohols and polyalkylene ether polyols with a HoIekulargawioht up to at about 600 and (4) at least one oxide " 2.3. an acidic oxide of aluminum oxide * and an acidic one Aluminum oxide with at least one · »« purulent oxide of a metal of groups II to IV dea periodenuyatema der ilernante » consists· 52. Katalyaatormaaae naoh claim> 1, characterized in that that -i represents a Gycloalkylreat 33 · ^ atalyaatormaaae naoh «\ napruoh 31« identified by this » duae λ represents an alkenyl creat 34 · Katalyatitormaas · naoii Anaprueh 31, thereby identified « dues ^ a JüLkylrest dar · romps. 35 · Katalyeatormaoae naoh, 'oiepruoh 34 »thus being able to« t _{t t} that :: e beryllium means · 36 · iCatalyaatormaaa · naoh Anapruoh 34 »characterized daee Ma Cadaiua means. 37 · Process for Katalyaatoraerβteilung, thereby gekennaeichnat, iiaaa A and 3 in the molar ratio of AiuB from about 1: 0.5 to 1 ι 1 uiügeaetat, where ^ "dndiatena sina TarbiA" denotes the JPonMl UIi (U) ₂ , where Ua a metal, such as beryllium and admium, iet, while a raat, «it 909823/1096 Alkenyl, cycloalkyl and Oycloalkeuylreste oowle their Genlsohet nit means 1 to 20 carbon atoms, and -> at least one active hydrogen-containing co- * lat4JLyeattu * to activate A represents 3β · Method according to claim 37, characterized in that gdkannaeichnot, dose the Üü-Katalyautor aue at least one 3o-catalyst, like (1) water, (2) goxal of water and at least one excessively whimsical compound, like alcohol " a prepared alcohol and a polyalkylene ether polyol old molecular weight up to about 600 »(3) or at least one noticeably water-soluble, non-alcoholic, respectable people Alcohols and polyalkyl anhydride polyols have a molecular weight up to about 600 and (4) at least one oxide, one acidic aluminum oxide and one acidic aluminum oxide with at least one other oxide of a metal Groups II to IV of the. eriodeneyetome the ^ lezaente, consists · 39 · The method according to claim 3Ü, characterized in that the procedure on the unsettlement of Λ and 3 in an inert Atmosphere is carried out 40 · The method according to claim 38, characterized in that it does not interfere with the · the solution of Λ and B was carried out in an inert organic solvent 909823/1096 ORIGINAL BATHROOM U95862 41 · The method according to claim 3U, characterized in that ·· du UaeetmungBTerfahren Λ and 3 in Zusejuaenmiachung with an organic oyolieohan uxyd with oindeetene a « Carbon acids off ring with 2 bio 5 carbon atoms and a · «SaueretoffatOB, such as oyoliochen oxides, which are no unsaturated aliphatic · carbon-carbon double bond aside, and oyolieohon oxides, which a · alijüiatisohe Carbon-i: ohlenetoff-LH) ppelbindunß aside, bch how their genes are carried out 42. Ancestors according to claim 41 »known thereby without« the · H represents an alkyl reet 43 · The method NaOH ioiapruoh 42, characterized ßtkcnnx · lohnet as ·· Ι'λ beryllium means · 44 · The method according to claim 42, characterized in that the " LIe Jadffliuzu dare divides 45 · Pneumatic rubber tire, consisting of a tread part, riding walls and at least one layer of fabric and wires that rulcanized a Buaarauentfeeeteten .erkatUok uind, with you chewing Bchukarti ^ · Ketoriol de ».leifone The polyiaeren Ctoff naoh Auopruoh 1 bosteht. ! Lautaohukluftrelfen, consisting of a tread part, Sidewalls and "indoetens of a fabric and wires, which are vulcanized at the same time 909823/1096 and ₉ wobtii the chewing shoulder-like? 47 ·} auteahukluftrelfen, consists of a running surface. · Part, wide walls and at least one fabric layer and wires, the su tiinoia zuoaarriongeeozten v / Erkatücls. Tulkanieiert are «where the chew-like material of the heating material the polymeric iJtoff according to claim 10 consists 48 Pneumatic tires consisting of a rubber-like tread part and rubber-like side walls, which are built up on a base support part, which consists of a number of layers of clay-rubber-equipped fabrics that extend between circular rests and sio join together and which are vulcanized to a susanmenge- "otzten v / erkstUck, wherein the rubbery material of the Heifons of a polymeric substance old _v a Durchachnittsmolekulargewloht of mindtstene about 50,000 is and is constructed of a rfischpolymerisat of at least two different organic cyclic Oxydnonoaeren" , each of these monoaeric children having at least one linearity with 2 to 3 carbon atoms and one oxygenation. 49 · Pneumatic tire according to claim 48, characterized in that at least one of the monomers in the copolymer has an aliphatic carbon-carbon double bond ttesitst and in the iiisohpolrnerieat in a ktnge of 0.5 Us 50 mol-f. advantage iet. 909823/1096 ORIGINAL BATHROOM .61 .. 'H95862 50 · pneumatic tire as claimed in claim 49 "that the -!.! Onoraere with the carbon-carbon double bond in the" i isohpolymerleat in a Renga 5-30 ^ ol available 1st · 51 · Pneumatic tire according to claim 49 »characterized in that the« the monomer with the carbon-carbon double bond in the micropolyester in an amount between about 0.5 up to 15 KoI - / - available iet. 52. Pneumatic tire according to claim 51t, characterized in that the oneonere with the carbon-'ohlonatoff "double bond t.uB Allylglyeidyläther and the other monomer from Propylenoxytl to beat. 53 · Pneumatic tire according to claim 48, characterized in that at least one of these monomers in the copolymer auo a saturated spoxyd with 4 to 12 carbon atoms consists and in the copolymer in an amount between about 0.5 to) D col- < is available. 54 · Pneumatic tire according to claim 53> characterized »that dna gesHtti £ te 3poxydnononere In the copolymer In an amount of about 1 to 10 moles of "<" is present. 55 · Pneumatic tires, consisting of a »chewy tread shell and chewy cheesecloth-like back walls, which have a 909823/1096 U95862 lcaeae umon, which consist of several light layers of nit ~ au ~ teohuk equipped tissues, which extend between circular wire parts and connect them to one another _; den, zuaaianengeoetzt and deformed and vulcanized to a susnrnnengesetsten '* Erkatüok iet, v / obei dan kautschukartiejo .material, dan mindeotene the baptismal font part of the löifona, from "iner" anoe huh (I) an Uborwie ^ ondeu.' tight eiach (. auo '.) a !! ononeren with a' ohlenotoff-Aohlenetoff-Ioppolbindung, dns in the 'ischpolymerisat in an ^r' close OTWA between 0.5 and 15 -OL-: 'Ibt present, (B) a mindoBtons Monomers with 4 to 12 carbon atoms, which in the * ^f if3chpolymerlaat in a '' narrow between about 1 to 10 ^? Tol- ^ · is present, and (C) (jinom of (A) and (1) different '.'onoraeren that in the'! Ichpolymerleate in an amount rich in "enfre is present in order to compensate to practically 1v ^ 0 "Oil- * to give, v / o" in all dioee '! onoraere from eiiiora orcRnii? chen cyclic oxide monomers ruit aindeetene a thing of two carbon atoms and one oxygen atom, and (II) stroke a smaller amount of weight of reinforcing gas black consists" 5β # Pneumatic tire according to Claim 55, characterized in that (A) made of allylglyoidyllither. 57 · pneumatic tire according to claim 55, characterized in that the « (A) consists of Vinyloyclohexenraonoxyd BAD ORIGINAL 909823/1096 I ΗΌΌΟΌΔ 50. Pneumatic tires according to; au> prueh b'j, thereby t; ekenii £ eichjiet _f that (λ) consists of uradiene monoxide. 59 · Pneumatic tire according to Claim 55t, characterized in that {:>) consists of 1,2- ^ utenoxide 60 · Pneumatic tire according to claim 55, characterized in that (λ) from -illylßlycidyliither, (B) from 1,2-jutene oxide and (ü) consist of propylene oxide 61. The pneumatic tire of claim 55t further including one inner lining vulcanized onto the carcass let and spread over the entire inner surface of the carcass extends between and in abutment with their wire parts, the inner lining being a practical one air-impermeable chew-like polymer "asue bed" eht. 62. Pneumatic tire according to claim 61, characterized in that the the airtight, rubber-like polymeric 3toff from a lüschpolymerieat τοη about 90 to 95t5 '/ isobutylene and that, read from elnesa. Diolefin with 4 to 8 carbon atoms consists· The patent attorneys. 909823/1096 Blank page