DE1418620A1 - Process for the production of liquid polymers from alpha-olefins - Google Patents

Description

DR. F. ZUMSTEIN - DR. E. ASSMANN - DR. R. KOENIGSBERQER

PATENT LAWYERS

PHONE; 223476

TELEGRAMS: ZUMPAT CHECK ACCOUNT MANCHES 91T39

BANK ACCOUNT: BANK H. HOUSES

Egg / L

Λ! 54 685

MUNICH 2, BRÄUHAUS3TRA3SE 4 / '"

Atlautio

Ytrlalirtn eut lleretstellung iron liquid

ouch

a-ülefijicn

The Töriegenaa invention relates to tin YtrffthTfö «iar merlilerun / t τΰη higher., - ültnaea zur iür «tell« 5e Ton nornalorwelae riüsoigcn Pol ^ neriiatea, inabteoiidcr «la Y * rXehren zur Iltrattllung nornalfrirtle« IBlselgüi Pol ^ nafri »attö duroh PoljEjerieI »ruiis γόη,« Ol * fln «n * dta '

where E is an alkyIrast with 4 t & »U b # dtutet _f under temmüm & 9tmm tigern m &

BATH

80-9802 / 0223

Contained catalyz oatora, whereby the Ätoraverhaltnia van Bi tan eu aluminum reads within a late kifieciien Berroicim, and ret «Uta bt applies to the present rfisdimg the iol ^ neriBation of the tone of higher α-OXtflfitn only Ilerotollunßelihtnee ole a

Throughout these years were ücliiiitraio by liiiffinioren of flohöldf ttiUmtfraktionen β in · ο btitiranten I.Iolckulargowicbtebtrtioh «htrgfatellt, whereby

mm Ätftrnunß vaitrwüntcüit tr DXt and v / acijc · Atta der "Ditst Uohmitriilt, die eis LiJ" unß "were used

oils btkannt worth it, we will continue to go through Ytraohiedtntr Suaötee ttr ^ etßtrt »to get your« St * - gtftii oxidation to heat uad äit Teup «rntur, b« i the dft «O ^ td & ht ** hr fliiflt» ie »dta JOitßpunkt» »U emitdrigen, ftret» wupdtn 2u «Ät» t naetintadt, among other things dit Vieltoaitäteemp / iiidlioli kiit gtftnübtr dir Tttaptratur dt «UIs au T * rbtea« rn and ust die

d · * oils, inebtiOüdtr «bti hohta Teaptratures, see below where the terbteatrunss as "Viakoaltätöiriaer ^ 3r ~ i # t.

oil * «of Brd ^ lb & sie sogax bti dtr b * «t * n means« «tr ümitdrißung de» Pließpimkt ·

809802/0223

and improving the YleteoeitUteindex 'can not be sufficiently improved to meet the requirements of lubricating oil "in gewiesen- machines under extremely harsh Bedingunßßn gtt ^ entif ün _# example ropes this Oohöieröle into operation not the properties that _t a 3chsi * r51 dan in a ütrahlaaociiine to be tuißewandt in aviation are required · Dsrientepr ^ cliend it became a Siel many PoroGhuncsfiemeinochaf th oil hersuiitellen "a" ynthetische "that a large Oxydatione * stability, a high Tißkositätsinöex and a low pour point fiddles and on a ent ·

the
BechEiieren / liaachine _t ".ewäiirleistet» ^ o were

rcichc Vereuclie aur Heratellung of oils "di" all ülem egg Genochaftcn aufweiöen performed _t includ ^ ieBlich the Herotellun £ polyxaeren of 3Jdtern and / Itheam and pol ^ weren fc-GLE

The po inside u-OIefine seemed to be tr light Ii el j s Ifoöe VorausOGt surigen to Herat "llunc the cewiineohten highly qualified o ^ iithetiöchen lubricant to l 'ßitzen _f because eie" la "great thermißchc ßtalsllität have · The Polyjaerieate were hot Hirer production ungcsattißt and dalier borrowed quite oxytlationp SENS, even in the presence of an oxidation · - iiüiibitora, Hach the hydrogenation of poly ^ erieeta but btieß dno ^ eoiittigte Ol exceptionally good ^ üacydationiinhibitore & pfindlichkeit _"t ie (oariöatlon inhibitor" Uöceptil ili1gr?)

BAD ORfQiMAL,

SQ3002 / G223

the addition of oxidation inhibitors did not require "oils extraordinarily resistant to oxidation" & it was difficult, however " the ee polymeric a-oissfine with the well-known I & taiyeatox «« divide out or through thermal inlet seams, since green is wet ic long periods of exposure and high temperatures required was. Furthermore, it was extraordinarily ochwieilij that after polymers produced by this process are completely acceptable hydrogenate t a8gl ± ratherweiee deeljalb because they are all possible Types of olefinic or European structures contained.

In the case of Terrahren aur po ^'ierunß of α-olefins »which do not have the ΙΜηββΙ of the earlier Veriahreii, eahlreioha Katalyu & i: oren entifici; old _for those who were similar, diö aur ^ .ülyncriölcruiJ ^ of ethylene sur the production of ieoten High molecular weight polyesters have been used. There are also aluminum trialkyls in connection with titanium trachloride. Those obtained by using these catalysts polymeric products beeai3en an out or dontliah high Üolekulur & ewlcht in the range of 500C to 10ü 000 and Ma su 3 000 000, and ee acted verifiable ma ÄToduitte · the in normal room were feet temperature and therefore al ο Jclimiorüle completely unsuitable "

The present Jirfiadun will be in Veriajrcn fen zur Ueretelluuc noriaaler.ieiae ilUcuiger Polyaerisate aua «.-Olefins der Öllacneinen Pornel U-OHe (JIL ,, in which K an

BATH ORIGINAL

S09002 / Ü223

AIlEy! Remainder with 4 to 12 carbon atoms "means, where the c-olefin is a" catalyst contacting, which contains a titanium halide in connection with a niche compound of all the common porosity AlU ¹ X- ^ "where Al means aluminum , HV means a group ι X means waoeeretofX or halogen and η eii] β whole number from 1 to 3 and where the ratio of sitane to aluminum in the i'xitaiyaator is in the range from 21 to 20 $ 1.

Geu.iß the lär ^ indung becomes a ^ -ulfin of the general fool
kcI lif-0H * CH _2f in which H denotes an alkyl reaction with 4 to 14 carbon toifatonane, in the presence of an icatalyoator polymeric olt "which in vreuuntiiclien from a 'J in connection with an aluminum organisulien compound dtr general a porno ali" _ft X- ^ _ß , where Al is AluisLnius, ii 'denotes a hydrocarbyl group, X denotes water or liquid and η denotes a whole number from 1 to 3 and where the atomic ratio of X'itan to aluminum in the catalyst is in the range from 21 to 20i1 ^ t, whereby tin normal white liquid polymer is "rhftlttn" d & e btiBt, "in polyaeripat, since with normal room temperature doors ran 20 hl * 27 * ö (70 fei» 80 ° f) liquid i * t »

2u dtn Eur litre position ton norimlerwtist

a · · »aten geaüß der Brfiadussg valuable * JV01 * ilis« ii geaör «»

809802/0223

with 6 to 16 Kohleiisto £ fatoiaitn in ZIoiekul, i.e. - ulofinc, wit 2.13. HQXGii-1, He pt α η-1, Ooten-1, 2ίοηο: ι-1, Deccn-U Undeeen-1, Dodeoen-ri »ITriöecen-1» 2etrsdeeen-1 * XentadQCön-1 »and Hexadeoen-I, ßa the pure blends or mixtures thereof, including the addition of these olefins, can be extracted from UrdUlparariimfaahaau by expensive oil extraction.

be »applied * All dia ο ο connections through the aXlgeneine Porciel K-CIi ^ JII ₂ charuktoiiolart, where E is an alkyl radical iiit 4 to 14 ^ ohlenotoiTatouen bode Ut et. Although β © prefers that the Al ^ l residue reads a straight chain, kUnuen fltisroige i ^j oly £ ierlaate n ± t veiawtiesskettigen Alkylreeten received »orclan. Vn ^ -οIy-BHirleate Kit obtained exceptionally high ViekoöitatoindiciB and low pour points and thus polymers,

The use of -olefins is necessary, in which the dtri there is B or the alkyl group dto H-CHeuHg-olefins 6 to 10 carboni-fiatcioe and, without the exception, 8 carbon-tiM are used Kertrellunß dtr lyuthetiechen llochqualitate "" ehslerfiittel i * te "furthermore also a" rford "rlioh _t that the" AUgrlre "te fttredkettige" it "and" d "nn if you" v "rÄweißtktttli aind" dl "are held by polyaerieitrung n Po-2gr "erieÄte weseatlioh etrinstrefViekoeitataindioos and higher"

'BAD ORIGINAL

803802/0223

Have pouring points «- alo the iOlyaeriöäte that use Long-chain and oil lines will cool down, even if Alkylreote lie in the ßöwüneahten Cg-bie OjQ-area

In particular, it has become much more apparent that the average molecular weight of these straight-chain olefins depressurizes about an o ^ o ^ olefin because in the presence of large quantities of ^ -olefins with higher or lower molecular weights, the average is somewhat lower is above or below the C ^ _Q -13 cross-section, the tie-oil index and rupture point of polymers made from such compounds corresponds to the corresponding elements of polymeric soldering "which are also made from olefinic substances that are divided into oil-containing compounds are, are inferior *

1 ^ a i; ur connection with the aliminiutaorg & ttiseiien connections was preceded by Sitanlialogenid jsur lleretierung der erfindtmgel · liatalyüatoreij iöt l'itantetraehloridf obwolil saidere

di} önßewaiidt will know * like a.B »2ita» te.trabromid, xitmitriciiloritl and

The alun-niuraor ^ iaiiecbea connection di € the «broad essential component deo iiatßlyeiitorß according to the origins of it len, the all ^ ciaeine Poriael Alii * X- »In this one

GOS802 / 0223

ael means Al aluminum, E ¹ a hydrocarbon carbyl chloride, X hydrogen or haloene _f and swar preferably chlorine "bromine or fluorine" and η "ine gladly Sahl from 1 to 3, the preferred aluminum organic compounds and the aluminum" siinium trilydrocerbyls , Aiii * "( n iet 3 $ there is no X-substituenteii) and the Alurainiuodihydrocarbyllsydiitlei AHt ¹ ^ H * Die AluaiaiuHtrihydrocBarbyle ßiad vorsu ^ ew ^ es "Aliisiuiatri * · alkyls with 1 biocarbyl sydiitlei © 18 Eohlönetotfatomeja and ixswait "Wn ~ nen ₉ as e * B" Arylrößte _t Alliarylreete or Aralkylreetö · Bs let preferred 'that serve Iiydrocorbylreate 6 to B carbon "nut offs tonic each aufweioeii, and ^ ntrialkylen in Alumini is preferred that each AXkylrest.2 to 4 Kohien offends,

More preferred for the second group
Links! the AlusdniisadinydroQarby! hydriden "the Kohltawasenrntoffoubetituent of any of the Kühleßwaoeeretoffreet listed for the Aluciinluiatrliiiydrocarbylen can be found, whereby the ÄluminiUBdialJ ^ le are most preferred component" Zn the end-of-the-line compounds were applied dee catalyst kfinnen "Aluuiüiimtrinethyl, Aluniniuiatriüthyl, Aluniniiuatripropyl, Alurainiimtrlbutyi _t AIuaiiiiumtriieobutyl, Aluoiniumdläthylaethyl" Aliaainiucidiiitliyl-Aluainlutadiiithylleobutylf Aluaiiiiumtr! phenyl _# Aluminiun. "

BAD ORlQiNAL

809802/0 223

tribensyl

Aliminituadiisabutyljytiride and the like.

Inilere applicable aluminiuraorganiöciie Yerfeindtißge »aind the iiluminiimhyilrocarbyldiftydrides _for like ss» B * A oils ^ xurainluiadihydroearbylbbiogenide and the carbyldihalogönicle> a * B · Äluisiniumdiethylehlorid respectlve

The ü'itaiiliölogünid "kunnext naoh bekaantea" erden "and the aXuminituaorßenieohe" verbiadusgen could also be produced according to known methods. Iet as ös fcelcsnnt _t of Satalyestor should in the absence τοπ I ¹ ness tad mideror sohüdliclier li & terialien "like s herceatellt be gehßndhabt" nd, 2iee Immi according to known Xeehniken ^ elmudhabt · * τ & * η * by m & the Estalysator miter eiiiati temi th Cran as suB · iitiekatof ^ here shares »Landhabt or UbQrxilhrt. Doö ratio τοη 2it »niialogenid m aluiaini connection should be set in such a way that the» w »£ itan au Almainitta la de» Bertiüh reads from Zt % to 2 () it, so with the polyiterlolerunc attr tteachr! Even u-olefins » orimlerweis * flUeoige PoXyacriiatit inherited · !!

· \. 'Tnn da · liolyerhaltui »by Titan su AlualJnium £« rine.er

BAO OBSGINAL 809802/0223

- to ~

2: 1 lot * su UI or below, nwc will be Xeata

Palyneriü & tö prepared "" tUiröü £ l _f if ratio of Sltna su Aterfninn greater iat Alö Ott "dia lfong, e aii aluMsliiBwrjsKiaeiier Verbliidmiti au low iat mid daiäOütapreGhezid the liiasiandlui lent Ueq ti ^^ iötg EIIT of rgal ^» _t Iloe that Iu

Poljraeriattt eriiaXteii becomes »3e» iex liatjen die iiit but 20t 1 liergöatelltea Pol ^ rierla & te a r; u large Tielcoaiiiat, uei in ei «eö for a Sobnleröl rreriArallüii

to. lie · 7oraa0ciieiae reads atm AtonrerhUltnlo from u i.luniuiijn in. of the area from 2it "biy 7t t _t cia the nit such Ksttalyostoren iiergeeteltei Pol ^ crlstae in the best ^ uelieiiteii animaldeii unti the possibility of killing was therefore not possible at denissiddic found that the verliäXtiiie von 2itan ^ u, nlniurs in the all catalyst aritiemindteii

«Üu0« rat ki'itisoh

Si "l'Qlymerieierttng is carried out with a fenteii liatalye" torphaet ale diaperaion in an inert "flüosigon üoaktioneditttHf d" h "in an iJbhlenwatenerBtoff ^ which in Anwsue iheit de" Pol ^ i3 "ritjortioÄiatio" ritjatio " rdUunutt £ * altttX door ämm u-01 «fin serves» if urn a-01tfim al »Ewtktiojieuediua, in des d« ri ^ t »lyeator ditaL« r £ i * rt wixd _t ii ^ eMSdt becomes «ad no Tegttfnmar & iwrttt»! Text is used,

SAD ORiQiNAl. 80980 2/0223

«. 11 -

predominantly volatile po ^ raerioate la a sv / iciitabwich, and üiS0 © liabon therefore a hook viscosity, άΐα in general lies outside the »which for a liolimlerül desired * <£ r &# although äieae also height IndioGD uiid nisdriße flow points booit ^ on lot es voiEUEiöhe «, an iaertös, fiueslges

"Ie ale ilUaaißeB iia & iitionsmediuia and Verdünnuagssiittel to" ·· are künneii, umüfeöesn diegeeüttigten UNOE aromatic hydrocarbons at 205 ⁰ C (4Qü * P). Specifically used substances are di $ pentenes * hexanes, heptanes, octanes * ifonan « _for deofins, -the oyoloparaffins _for such as gyelohexane», the JittetliylcycloheKane ιιηά the aromatic like benzene »toluene and you can use xylene © * Bteifklla

difißer Eohlenwasöerotoffe narrowimndt yieraen, iot er: orderlioh _# 'that the river cabbage ^ n ^ smßerBtoÜrsal ucdiun or thinner below about 205 ° 0 (400 * 3?) ei «det | δα eg liäöh der rolynerislenxnß öuxch I) sstiWLe, tion iron AtB-JO **

must be separated. If the Y "rdUnaü" geeitt * l etv / a 205 ° 0 (400 * P) 0iedet _f can not be separated from the polyæeriaat by sea partition _f da eioö then dlt öieöeboreiche dee Pol ^ iaerisats and dee T "rdünnun £ «B £ itteiii excess.

BATH ORIGINAL

309002/0223.

The tightness of the flow or the diluent in the range of 20 and 80 Volutn *, caused the oil trolimon of the dilution and the oil to lie in an advantageous range of 35 to 65% on the volume von Verdiiiuiunßfinittel and

The Meiißo an TitanliDlodonid / Öluniniumor ^ aiiiGühe connection can in the Ua empire from 1 to 10 üewichto- ^, based on that genius de *? te-Olefia-iionoiaeren lieeen «vorÄUgeweiet jeöGch cheats di «K & talysatornerye 4 to 6 üewiclite - ^ -, btzogtti on the basis of the u-olefino given in the ^ QGktion,

The Polymeriuierujie liauxi in! Dempenitursii in the Iicreioh ron 4 to 95 * ö (40 to 200 ⁰ F) and preferred wheat from 15 to 50 * 0 <6 (ibio 120 ⁰ ^ i can be carried out · Bs has calibrated "that

gi f- ,, /

p ,, Temperatures that are slightly above normal w tempera tures »

to d, h, e wieohen 23 "" * 30 C (80 to 90 X ^) ₉ particularly valuable and are advantageous "

B's cool reactions range from about 1 to about 15 hours of engmyandt trerrden, although a little "oteisserun" the Polynerioatauüljeute at Pplysterielerungo & eiten something Over 2 iltundin were found * Satisfying Bolyaerie exploit «earth not achieved pages under an hour if

SAD ORIGINAL δ G 9 0 0 2 / Ü 2 2 3

the lOlyEseriBierung at the upper linden tree dee S is carried out. When the polymerisation is complete, the catalyst is activated "in the sa» s, B * the esactionaioohixng in water »in a v / aeorigc solution of an alcohol, such as e» B »aqueous 2» & tbylallcobo3f or in a «dilute aqueous oil acid solution. The watery Hiaae wlnä after usual decantation processes from the Kolilenwaaoerotoffphase ab ^ ctrez ^ it, and the azalea ^ eaktiononediun or Ttr-

of the iolynerioat by reading the separated Kohlvfaoöer0toffphaae removed «

The nit the catalyst and the method geialiß of the invention, the polymers produced have a UE in weoentlichen linear vruktur, wherein the lCohlenetorfatonie r ä * linear chain bit Alkylreotcn associated alvternierend "corresponding to the alkyl radical dee α-0 efine the allgeceintn formula K-GHvCH ₂ 1 in which the alkylate has 4 to 14 carbon atoms

Those made up of oils with 6 to 16 carbon atoms liquid Polymerlaate ges & B of the invention baoit.ien «in average molecular weight in the range of about 300 to about 2000 "In polyaeriosis more straight a ~ Qle ~ flue nit 6 to 12 Kolileno toff atoms per HolekUX and duroh-

BAO

G09802 / Ö223

aohnittliali VO .Iohlenatof.fa tonen |> ro Holshtll £ e & ^: iS der ^ x- £ ixidwa & receives kb3 predominantly full lolynisriL-ate with a Z) urahDü! iiiittanoIe ^ uJBrßev / lcIjt of about ^ 400 "la bit about 700, where essential "** ^ or the second Xohlenotofraton in the linear ro yaerisaticette nit oincia caradkettigen AUiylrest is _f vfofo with the ^ Radkettige Alkylrest 6 bio 10 olds and on average one: long 8 Kohleastof.r & toEie» ·

The old fiflßi iiatalyaatur and after the Terfalirenl'l'issed

of erJticides) oils are old at the top

Vißkoßitäteindex, although they may have a "low pour point or not, wan of dom each polyneriaierten t.-01efi74 or the u-öleXln-Mlsohung depends · fmirn e bio 12 KöhlenstoffBtOEie and an average of 10 iiohlenetoffatome per UalekUl containing the polymer beeitst a Yiskoeltät & lndex of "at least about 140 and a target which is not Ulser about -45 ^e G (-50 *?), corresponding to this or these olymmers without further treatment as all sci-ial drugs valuable. However, since the rolyserieate partially in their iierotellune unge & ättlgt ALND, ie in allgec ^ inen are about 50 '/ ■> the molecules ungeeättigt _9, it is preferred that the xolyiaerieat lintfernunf zvtx: is hydrogenated by lingeoätti & theit ιναά infolgedeoeen the Osydationslnhibitoraiapflndliohkeit doe oil

SAD ORIGINAL

809802/0223

t will, olmohl serve the treatment of the JlieBpwnkt-any exhtihcn · The Gi ad of the iirhcShunc of the Plieiipunkts hii & gt from the Uei ^ c of the exposed olefins old low * Holeku- » lax & Qvilcht of the £ 02 ^ * uex lea t product, Yfenn ßonlt Examples «· Weioeere from the Poltftierifcschtia: odulit would not be removed _t 'if (lac Ii odukt liytlriei % ViIrU ₉ " ktmn ügx VlteBpuntet dta. Hydrogenated "I ^j roduktö." 55 * 0 (100 * P) ■ About the PließpunUt -rofluktß in front of the Äer L ^ rdzdorung, V / ojiii the raeißttn Pimsrcn away ciM »lurnri the 2? lispunkt only among other things about 11 rock 22 * 0 (2U to 4ü * r) will be granted» ·

The% Üriörunii the I ^ l ^ iaerieGtö Iciuiii according beisaanteii and Mt ¹ Ibekannteii IiydriGrkat & lyäatoreii done "Be is · ge '- ftmdWji' MB the I'o5yncriaate '""wherein J & MOUEN in Üetj Xiereieb of' 141 ¹ UiEi £ 11 JJgZ ⁷ Cn ² {2üGü to 20ü0 μοί) at 2eapfcrfttur "s iö don, iereien vom 177 liib''232 * 0 {350 bif 4SO ^) hydrogenated ner" den 'liuxnioa * where ^ either a nandelßliisliölisr \ iio Hioliei on KiQoelßUr _#

«Kanri * Iia general will heaktionsijeiten foil 0 hours aii /; (? ITanat _T around a full hour lfydri« ruag de «

zn a «V7iihrleißten * £ 9 liöniien oo ^ ülil lower elo higher diueke, il.h,« twa? 0 Mo about -700 k / em ² {1000 10,000 pßi) and lower and higher esaction file peraturta

SAD

09002/0223

Any suitable hydrogenation catalyst can be used are used »although those available in! imide 1 are used beware

the following examples are intended to explain the invention. In the examples, the Yiekoaitätsindea according to Λ32Μ D 567 * 53 and the pour point according to AüTM D 97-57 was agreed

Salilreichs Versualie ssür X ^ lynKsriaierung von Deoen-1 under Vsrwendtssg a'Helte von Titanetetraolilorid / Aluainiuiatrii80butyl * £ ata ^ satoren, whereby the atoio ratio Titan au Alumisiua from / catalyst to catalyst was varied from 26 »7 to 35 ⁰ O '{60 to 95 ⁰ P) t the reaction times were 8 to 16 hours and 100 al Icooat & n per 100 g uacen-1 were used as a reaction medium or V®rdttoai, ma1 ttel» The Usmgs & n in l $ ami Tsrsuoa applied catalyst was 5 Gcwiohta-ίώ, btsogaa on Dsßön ^ i. The salt this test will get ^ n results € 3lad in £ & bell $ 1

8AD CRJGJNAl

^r '0 2 / ü22 3

Sabalia 1

Ver
search
Mr. Atomic
hold
Ti: Al im
Kutalyüö / tor üeaant-
ausboute
at poly. oat Vioko-
eitiLt iJ3U
at | 0 ° G aat visco
sity ψυ
(210 ^S P) Vieko-
index
deο poly
merisate ^. 'olyneri
Plieflptm 1 1:10 17.5 - - - feet at
laerteape 2 1: 1 65.3 ' - «Mt - firmly at
sertenpe 3 2: 1 70.0 225 62.5 157.0 -51 4th 3: 1 S2.F 202 5-1 »2 151.5 -54 5 5: 1 01.7 192.6 52.5 153, ü -57 6th 7: 1 75.3 tü6, e 54.9 159.5 -4ε 7th n--. ι
£. v ..: ι 56, c 350.0 not not not be;

136.4

'Weight -' / ^, based on the Uewioni of üecen-1, naohdea dae monomers of de © Iolyiasriaat was removed by distillation

The r ^ ix these experiments 2rgobniooe obtained show that "the Atoisyerhültnia of titanium su" Aluminiua iatalyaai in the _A within the krltlsohon 0η? Held ΐΐ2βη of 2x1 bia 20t 1 nut, as obtained in VerhliltniDsen under 2i1 Xeete to, while in 20 "1 the achieved ^ is noticeably below that of 7s1"

Copy

803 0 02/0223

BATH

- 16 ~

Ώα is au ersehenι that the viscosity of the -i.olyueriea.ta, measured in iiaybolt! Seconds Univeroal at 3 ° ö (1 (Xf'J) and 90 ⁰ G (2tC * i?) Decreases when the Ätonverhäl & tiiß tan su ^ lusiinlum from 2 * t to 7: 1 sets · Bsi tier.2Oj 1 Atur-vwhiiltnie von £ itan su Almalnium ^ odooh v / iid the yield on - © erieat v && the rulinaierisatvi0koeität leiclit the Henge an alim compound present in the ketalysator eerin ^ is m: d infolßeöefjeen traces from Yerunreinißmgen, viie Peroatydej polat-e organic £ öaungordttel ₉ wio ζ · Β * acetone and the glcioh & ii ₉ a noticeable '..irkuriß on the Poiyiaerissierungßrefiction should be avoided * about 20: 1 -Atoiaver -refiction therefore about will·

At the same time, it can also be seen from these requests that in ilinaiclite on the polyamide formation as well as on the flow point of the poly ueri8at5 the specified range of the ratio of to oil in the catalyst is 2: 1 and 7s1

Example 2

m, a second Verouohoreihe sur lOl ^ iseriaierung vou ieöten-1 using the lurtalycuiars of lioiu ^ ial 1, leoootauverdUunuiiiieiBi ttelu of Example 1 and the same itotai ^ -aat or concentrate ion eowie u "? jEutlonateaperaturexi and times of üeiepiel t duxchcaJTUhit. üei

BAD ORfGlNAL

809002/0223

Ί * f I ö D C U

Attempts were also made to produce the polyoleat in the critical area iron i'iiun to aluminum yerhaitnlsoen tor 2 t 1 bio 2OtIf although the pea! bodies in the critical area. rich were with 2iiaaertemperetttr wachoartiß and kieferig while with catalysts outside Lake kr i ti ο whether s areas were obtained in ^ iioiaertemperatur rigid solids Ki '' e ^v ask tendency "that α-Olefice CIIT wonißer than 6 I £ o! il" n »toff atoms 1» liolekül nioht cur liter division of flUuai ^ en liohlfn waoeeretoffen according to the ^ iindune au ^ raanat «being able to earth»

:> a vrde a tired & licihe iron

carried out using iron Hexadöcsn-I alo nonomereo, you these examples were "benfalle clilorid / Alurdniuatrilcobutyl ^ F ^ italyaQtürsri in nen of 5 weightB-ίί, better on the oewlcht des üono" tr * a _f eneewandt · As i ^ eaktionsraodlua or Ygeseräittel Löooctane was applied in a YerMtXtuis ton 100 ml to 100 g Monoa * r «e and the F.eaktloriBtojnperfttur tmd -aeii; Were the same as in example 1, in lamelle 2 there are the caretakers, ViokoBitfitsinclioea imöTüeBputtktt

08 80 2/0 2 23

141ÖÖ2U

labclie 2

Gcüßint polymer polymer Viekosl Polynerii auöbsu- viscosity viscosity tiitain- ^ li]

Ver 2iiAl In te an S £ 5ü "at SSU at the dec

you Bataly- i ^J ~ 3G olyßa ° C 99 C polymethyl C

He. ißator · risat · »-) (1.ρο ⁰ ϊ). (21Ο ° Ρ) risate

9 1-2 74.5

10 3s1 91 * 2 374

5i-1 93.2 397 7-1 »0

7t1 91.0 235 57> 9

10ι1 82.8 290 64, Ü

α » Xeot 144 21 137 21 149 21 147 21

triggered on the gear of Hexade cen-1, nacbden dna Ilonoiaere was removed by etillation.

Uleoa iiireebßiaae aoleon, that the same Kritischo Beraich voj i'itan au aluminum on ο in C ^ -Ilononereo endwendbai lot. ISi lot jodocii ebenoo croicht that en when using oiiiea lionoiaerea with a higher Uolekularcewlclit miciüglicli iat at 2iaaaerteiaperatur flüaolce polynerioates su obtained, although Katalyeatoren in the critical area aneev. - ".., - ■

& AÖ

8 0 G G 0 2 / ü 2 2 ο

A sample of wax-like define In dsm Cg-1) Ie G ^ -IJereioh, which had been produced by thermal cracking of urethil paraffin wax at low hydrocarbon partial pressures and which contained an excess excess of u-olefins, were used in the same as The reaction conditions applied in Example 1 polymerized using a titanium chloride / aluminum trilobutyl catalyst with an atomic ratio of titanium to aluminum of 7 * 1%, a polymer yield of 68.2% weight ^{* -1} ; *, based on the value ^ icht of the sweet C.efine, preserved · Jiea. Polymer has a Yin viscosity in üaybolt Seconds Universal of 246 at 3B ⁹ G (100 °?) And 58.9 at 99 ⁰ C (210 ^a P), the Viokooitutoindex dea Polynerisato v; ar 140 and the pour point 4 ^ C (40 ⁰ P). This VerQuoh aeigt that qb nciglich iet _t Hiaohungen au «} ^ iandelsUblichen olefins: u ^ polyuii rioiaren and flUeeige FolymerieatQ get nit viscosities in üohExierölbereioh and high ViskoBitUtoindloee-, ite lot seen that the Plieöpunkt higher alo ßewtlnscht, vjao However, this can be explained by the fact that the 3) number of carbon atoms in the ^ -olefins in the sample was greater than 10 bits shows that it is necessary to sweeten a-olefins with an average of 10 carbon atoms in the molecule, if aohoitrmitttl with extremely low pour points of the in Example 1 *

8 0 SC 0 2 ^; ü 2 2 3

BATH

copy

Kind received mvaen aollen

Samples of the polymers investigated in experiments 5, 5 and 6 from Beiapiel 1 boron © were distilled at a pressure of about 2 esa mercury on the lintion of the diesters from 205 to 232 ⁰ O (400 ble 450 * 2 *) »at pressures of 70 and 140 kg / cm ² (1000 to 2000 pcl3), for β hours and using τοη liickel auX Kieael ^ ur as a hydrogenation catalyst. The hydrogenated polymers obtained were distilled in a liquid distillation apparatus at a very low pressure with 5 fractions, each fraction being about 20 volumes of the esacite polymer. The Viekositiitelindicea, pour points and molecular weights (uurohochnitt) were for the 1., J>, and b. Internship takes part. The properties of the hydrogenated polymers prior to distillation are shown in Table 3a and the properties of the actions obtained by distillation are shown in Table 3b.

SAD ORlGUNAL

809802/0223

I ÖD ^ U

Mr. of Versuolis before. der Jjyfo ^ j ff fflf

from example 1 ._ ..

deo index 0 index. ciaikt

141 ~ 4S 141 -51.

141 «48

144 -45

■ show üieee data that a syßtbttiechec aoliaitröl ait tint * Viekoeitäteitwlex of aindeeteno 155 and "lnem pour point not et above about -31 ⁰ C mountains slit Jeana be * Since these oils are geelittifit she soaps high OxydRtioneiiihibltorempfindlichktit. "Dee duroiiühnittliche llololecular weight oisaer $ ö2 $ mQTiM & 1 * 9 naob the Hydrieiwng lies in the range of about 400 rock? Ö0»

IT action 0- 8r, d «a Atossver «* Viakoaitiit ? 210 ^ö J?) Tislso- Molecular Versuohß hiiltuiö 47.6 "Itätß" ßewioht from at «» by Ii ι Al * B δ 58.5 - meanwhile game 1 In KBt .v.
Beiep * 1 CI00 · ») 38f8 Bölinltt) 1 3 2i1 167.1 144.6 140 420 1 5 5 * 1 79.4 ■ 55i0 146 420 1 ' <s TtI Ö1.8 47t3 146 405 5 \ 5 2 * 1 i27ß, 0 201.0 129 655 5 ■ 5 5i1 250.0 230.0 .W 1 ^ 0 5 6th 7 * 1 162.8 151.6 141 560 5 5 8t1 2613.0 2 3 % 2 & 1920 5 5 5i1 2185fO 127 1515 5 6th 7i1 117B> 0 152 12f0 809 002/02

Hit a Sitan to AluminumWitoEtverhaitnle of 2t 1 lies The greater part of the polynerioatin molecules in the product in the higher viscosity ranges than in the product, that when using 2ite «au AluE & nium-Yerhiiltnieeen from 5 * 1 and 7tt received «ird. 3) The viscosities of the Kit Slitan au Aluiainltua «Y # reports of 5 * 1 and 7s 1 received products

he, are in a week-week range for standard products * Furthermore, the 5t 1 and 7 * 1 Atoanrerhilltnieoe polymer products xait somewhat superior yiokoeitfiteindlcee. ileoe also lead ropes that lait de »eriindunGS borrowed from such procedures valuable ski oil products are produced can

Example 6

Sine Xtobe of 2) eo "n-1 was poiyaerioiert einee under Yorweiidung! CiteAtetraohlcrid / Aluiainiuiadiisobutylh ^ arids oils catalyst Mt Tittm a ^ u ^ AluniniumWitozsv rhiilttiis of 5» 1 Strootman with a Katolyeatorkonsentration of 5 Gcwlohte ^ t loading ZOcon on dae Deoen -1 · AIa heating medium or diluent nurde laoootan in a kenge corresponding to 100 al Ieooctane per 100 & decene-1 applied · Bs was a lieaktlone- · teoperatur of 35.0 * c (95 ⁰ I ¹ ) and a ^ eaktioneeelt from 16 to 17 hours "neewandt · the yield of rolymarieat after Bntilrnung of the monomer 89, C ^ ewlohta * ^ _t based on the ^u« wiobt to ssugegebenem üeccn -1. Among other things, “Polymerioat possessed

BATH ORIGINAL. 809002/0223

a viscosity of 339 Saybolt Seconds Universal at? 8 ^a C (1CO ⁰ P) and 67f1 Saybo.lt Seconds Universal at 99 * C (210 ^ö i ') »a viscosity index of 142 and a Pließpu & fct of -51 ⁰ (-60 ⁰ selgt I), Mesee experiment "that the Sitantetrachlorid / AXnßiiniiiiaalkjlbaloßenid-Katalyeßtoren liquid rotyafflrlsate .geoäß the preparation can be applied iirfindunß aur Her,

Example?

Bine I'robe of Becen-1 was palymerisiört lait 2 weights · »^ eineö a'itfmtetrachlorid / AluainiUEitriiBobutyl-'Kjatalysatore with a i'itan ^ u Aliuninima-Atocnrerhältniö 5s 1 · ^ s was not VerdünnunfiBiaittel applied _t the Katalysntor was in 2eoen-1 suspended. Me reaction vmrde for 16 hours at about 27 * C (60 * 1?) Duran out * He was a / tuebeute of polymer of 84 ^ ewiohts «^, lied on the decene-1, obtained · l) ae polymer besaa a Viekosität of 525 Saybolt üecondo Universal at 58 ° C (100 * 3?) And 109 # 5 Saybolt Stoonde at 99 ° C (21 ° F) _# from which it can be seen that the viscosities in the absence of a hydrocarbon as YerdUimungsiaittel x'polymeriüato are much higher than the Viekositäten of goods produced in the presence of a Verdiinnuüßsialttele polymers ^ X ^ Iysierlsate had a Tiskoeitateindex of 140 and a pour point of -42 * 0 (-45 *?) § whence it appears t that a good quality au I ₁ rait dös the of example 1 comparable 1st «was produced *

BATH ORIGINAL

80-9802 / 0223

Beiep ieX,

One I ¹ XObS of 2ecen »1 was polyEierioiert rait einiri Sitan-tetraoliXorl (V'Ali ^ i» iüiaäthyidiöl3lori <i-'iüitalyBator Bit a 6 * Wtonverhilltnio von 'xitan su aluminum · The catalyst «· Konaentxation was 5 ßeniciite- ^» based on the uecen-1, and Ißooctaii as Verdüimuiigsiaitel was used in a length corresponding to 100 nX iooctane per 100 β decene-1 aae. The reaction was carried out at about 27 ^e (80 * 3?) for 20 hours * of liquid lolyaerieate of 7% by weight, based on the i) ecen ~ 1. This experiment £ _f seigt that aex TitantetrGChlorldy ^ J-Uiuiniutialkylhalogonid-Katalyeator lait İltan efinon to Aluminluo-Atomverhältnieeen in the üeraich 2s 1 flüacige 20ii to polymers of a-0 ", the» lietort the required Kolilonotot fsalal beeitsen ceaäi3 of the invention "

Un the use of the erf iaducgegeoliatn PoXymeriswat "aXa iJcbJaienai ttel at VerbrenuungBtiaecliinen to _f pointer was a big Meng" Deo "& - 1 polyiaerißitrt and dao xolyaerleat was tested in awai üiiechintB-Teatfi.

The applied deodorant was the same as clay was titanium tetrachloride / aluminum oxide butyl nit

BATH OR1G5WAL

809802/0223

an atora ratio of Sütan au Aluminum of 7t1. The iCatalyaatoraeiissQ used was 5 uewiciita-i ^ based on the weight of uecen-1, and the uecen-1 was diluted with an equal amount of liuiideloUliliclieia hexane to give a solution of 5u YoIueHü 3eoen-1 and 50 volumes of hexane uuide. Eo was ei "D Xveaktioneteraiieratttr vcöa 35 ^e C (95 ° i ^T) and a Jieafctionßseit of sä 6 Btuttfiim βΐΐββνίοηαΐ · jJie ^ oiioiaeren and ffurden Jiaeren aue eng Polyrieriaatprodukt by IJeetillation at 200 ° east at a pressure of 2isbs Queok * · eiroer removed. The Tolytierisate were untei * ä, ör * eelUsxi BedJU ^ ungen ιαια vat denoGlbcii ioittilytator iviu iii Dclopicl 0 liydriert

The Vißkoeitüt deo i'erti ^ en PoXyia ^ risatprodukte \? Urdü guT das * ο clue r.iveau ^ g L revenges like the one ti hcua de I ^ t) usual Sohiaierölß on LrdOlbaoiDf inde »the hydrogenated iolyöerioatproäukt was distilled in an Ilolardeotille _t wherein a $ 0 Voluia - ^ - 1laktion was removed and "ine 10 Voluu-iUlraktion surüakblieb, the lost-ene was" the Q ^ - Prftk.tion had a Viekoöitat of 217 öaybolt litoonde tinivereml at 3 * ß (iuo ⁰ I ¹ ) and from 51 _f 4 öoybolt Oeconds linivereal at 99 * ö (^ tO *! ¹ ) ♦ The koeitätöindex was 139 *

ORIGINAL BATHROOM

C0S802 / Ü228

Bin ΐαϋ dieoee oils was JUi a Briß & e and S stepped ton, llodell 5-S ₉ £ in-2-cylinder air-cooled X ^ Copf-YerbrennunfiaEaeoiiine tested for the effect on the reduction of the octane requirement (octane requirement) of the machine because dieoeo oil iiit a commercial SAB 5W-2O-Ö1 should be compared "Wirden 10 £ a commercial Rejni £ ungsmittels _t d * h * a ö HU ο Liehe α alkßlisohse Bcsrimasulfonatzusatsisittel" and 1.1 ^ a commercial OsydationöinhibitorSf ie Sinkdialliyldithiophosphat, zn the PolynoricatÜl außesetat, I & s Commercial 5Vf-.2O-Schiaiaröl on Brdülbaeia contained the same hens of these 2uaäts9 and & uß®rdea C ₉ 4 ^ of a commercial improvement for the YiskoQltäteindez of the type sinee polymeric Verdiokunsosilttelaolez, ie a Mieohaeterung of polyiiericoerethoreten and iiioerico-aniole. Sfts Pdlyosrisatöl sweetness of the invention er & fruerta of course no 7trb88O «rux3ßs» ittel £

The iAaachiß «« urd @ with an isobutane / butylene slightly alkylateda Bs * «nnatoff operated th« r 3 oom Ubliohee liquid lead «tr» ethyl per 5§7 l (1 gftXlon) contained «Each liaachin red drifted 60 hours with synchronous operation» although with each cycle the & rosiieiv * ntil is throttled for 5 minutes "ar bit of a bffeohickunßflceiiaii ^ indissktit of the fuel of 3 1/3 cc" per Kiniite and a line with full Droaaalventil _f that is far dro "a9lV9ntilf was worked over air / broni. ataff-

BAD ORIGINAL COPY.

G09G0 2./Ü223

141862Ü

Ratio became connotant during each l'eete to 12.5i1 held· . '

Octanone required the liaachine at the beginning of the% and in 20-13 hour intervals bit to the end of the ate beotisaat. After the last determination of the Oe tan, yerif orderung, di * nach was carried out for a period of 60 hours, the I & achine dismantled, cleaned of debris, back to hookup and the crankcase was suerst Rait kerosene and then rinsed with the next best oil, before the next teat was started · Dio received Krgebnieoe are listed in Subelle 4,

Table 4

Checked Qο oil

Octane requirement increase naoh 20 40 Ötd. iitd · hrs.

Change in viscosity of deodorant oils after 60 hours SStJ at 3ß * C _A 99Ό ? 1Ο · Ρ) (210 ^β ?)

Change the Viok tutaindex * dee ul almost 60 hours

SXE. 5 * 7-20

Polyn eat oil

3.0 6.0 8.5

+ 1

♦ 1 # 7

0 _o 2

-8 (decrease) 0

There are data that the polyotrieate oil is used trading on lirdölbasia in Besug auf ein®

BATH ORIGINAL

η η 9 ρ- η? / ο? ? π

Increase in Cctanaiifund the lüaechine and Dar Vit »- kosoetobilitlit skip 1st,

Ik a quarrel Hrtechinentest was another -oil de a PolymerinEtö his Ox ^ dationeeigenociiaftoa caprüft "oil was eeprüft after decaying, dan in" Develop ment of ßeaeeroh Technique for Study of the oxidation

Oils
Characteristics of Crankcase / in the CHI Oil Teat ling ine "!» • is written (published by Coordinating Research Council, Ine ·, llew York 20, NSW York, isai 1959 _f Appendix III, ^H OEß Dituation 1-38-559 ") "the X gerkorroaionseigenschaft th (in ng l ^ gergeTfichtmrerluet) dee Polyiacrloataic the invention have been räit same properties m Hochqualltätfsölt compared and SVR & r nit an OEC Beaugeöl in the GEO L-38 ~ 559 ~ £ eet Mt & ex Fuianer Rl ^ O 7, dao contained both an inhibitor and a Heinigungeiiittel and a HO- BTN: a £ erkorroöionßwer1; prepared (that is, that it does not have a corrosive effect on the bearings) and a ride in ül entoprechüiid. of the militüriooiien SposiXiEierunöoqualitiit 2104-A. The Srg «b-Bisst of this EirujylindtrimaGhinen-Teßto are in Table 5

SAD ORIGINAL

809802/0 22 3

oil

Polynerioate

IlQZUgBÜl

(ίίΙΙ.-2104-Α QuftXitlt)

loss

27 32

IUc oe Baten aei & ea, dnü äi «

5Ie extraordinarily overlapping OxydBtioGB »t * bilitätselß * n

809802 / 0-223

Claims (1)

ö b Z υ ratentanoprUcbe 1.) Method sur Hero telluric a nonaalerwelsezi Πϋβοΐββη ν polymers from u-01sf ± nen of the general formula E-CJH-OH ₂ »where E is an alfeyl radical with 4 to 14 ÄohlenetoXfen, characterized * that dos u-01efin with a Katalyeator contacted, which consists of a 'Xitanlialogeaid in connection with an aluminiuiaoreaniachgn compound of the & 11-geoiin «a formula AHC _n X. _n , in which Al Aluniniua, E * eltte Hydroxyoarbylgruppc, oxygen or iialogen and η a gang» Number from 1 to 3, and where the Atoaverhaltnie του I ¹ UaH jsu Alucinium in the catalyst is in the range Ton 2: 1 to 20tt · Z *) Method according to claim 1 * characterized in that »titanium chloride is used as titanium analogue · 3 ·} VerXüiuren according to claim 1 or 2, characterized in that td " aluminum organic compound" is used in aluminum trialkyl * 4 ·} travel »according to one of claims 1 to 3» characterized thereby be without »AaJ as an aluminum compound aluminum triethyl is applied. SAD ORIGINAL 80 9 8 Ot / 0223 5 ·) Process according to one of claims 1 to 3 »thereby ge« k-cijuiÄeiciiaetj that ale alvuaiiiiujaorganieGhe connection Aluminum tripropyl is used 6.) "experience according to one of claims 1 to 3> as a result ale
denotes "that / almainiuEtorganiöclie connection Alumi" niumtriioobutyl is used » 7.) Process according to claims 1 or 2, characterized in that deß as an aluKiniumorßönieche connection Aluniniuradialkyihydrid © ngevTandt is # ε.) Method according to claim 7, characterized in that ala Aluöiniiuadialli ^ lhydrid AluiainiuadiitJobutylhydrid an will· Q.) Method according to one of the preceding claims, dedurch gekennxeichzieti that the ratio το »2itft & eu aluminum in dtm catalyst in the range toh 2t t bis 7 * 1 reads. By Ernest of the preceding claims, daduroh ßekenngeichiiet 10} VerXahren that the l ¹ ENL "erature of iolymerieierung in dent area ^ ron etna 4-95 ° C (40 to 200 ⁰ F), BATH S0SHD2 / U223 IT I Yorsu white tone 15 to 50 ° ö (60 to 120 ⁰ P) 11 ·) Method one more of the preceding, Anöprliclie »da duxcii gekeflaseiotoet ρ dais L ·. a ^ exaclkettigör A sdt 6 to 1ü carbon atoms and ais l Yon B is lCohleiiütüffatonen and that the products under
neniallß - «w formation of a saturated oil are hydrogenated, whereby oyiithetloclie üchoierölo with a Viokouitateindejt τοπ sdndeistena 135 and a yiitü point not higher than -51 ° 0 (» 25 °?) are obtained. © AD ORIGINAL 80980 2/0 2 23