Method of obtaining a catalyst for polymerization of olefins

FIELD OF THE INVENTION The present invention relates to a process for the production of olefin catalysts. The use of soluble Ziegler-Natta catalysts in polyolefinic olefins is widely known. In principle, the soluble latolytic system contains a group IV-B malt compound and a methylalkyl compound. As a localizer, especially an alllloglycollate. A subgroup of these Ornw catalysts are catalysts suspending bis / cyclopentadiene compounds / mtals from group IV-B as well as kokalizator iII ^ o ^^ I ^ I ^^ c. Although there is only speculation regarding the matter of the initial construction of active centers in the subgroup of soluble Zitgltrl-Nattc type catalysts for the polymerization of olefins, in principle it seems that the view that the active catalytic center is the ion or a product of its decomposition which alkylates the ilefin in the presence of an unstable stabilizing anion. This theory was first published by Breslow and Newburg and by Long and Brtzlow in J. Am. Chem. Sic. 1959, tim 81, pp. 81-86 and in J. Am. Chem. Sic. 196 (0, volume 82, pages 1953-1957. As noted in these articles, the results of various studies suggest that the active center of the catalyst is Titanium Alkyl Complex or its derivative, when what catalyst or catalyst precursor a titanium compound is used, e.g. dihalogtitk bis / Jykllpentadieiyll / titanium and alkylaluminium. The presence of ions in equilibrium also suggested D <achholsZii, Vysokinai, Soyed. 1965, tim 7, pages 114-115 and DyacCholsZii, Shilova and Shiliv,

J. Polym. Sci., Fart C, 1967, pages 2333 - 2339. Ti, that the active catalytic center is a cationic complex when a titanium compound is used, also with Eisch et al., J. Am. Chem. Soc. 1985, volume 107, pages 7219 - 7221.

However, the above articles claim or suggest that the active katallCJZicym center is the ion pair, and in particular the ion pair, in which the derivative of the metal id occurs as a cation or a Jegi decomposition product, and that the chemistry of the formation of active catalytic centers is coordinating in all these articles are written and using a cocatalyst which is Lewwsi acid, thanks to which active Ionic catalytic centers are formed or stabilized. Active kata6

159 The lysator is most likely formed as a result of the Lewis acid-Lewis principle reaction between two inert components / metallocer and alkyglog / leading to a balance between the neutral, seemingly non-active adduct and the Ionic pair, presumably active catalyst. As a result of this equilibrium, it is necessary for an anion to exist that must be occipient in order to stabilize the active catalytic center. The balance is of course reversible and the opposite reaction will lead to the deactivation of the catalyst. These catalytic systems are also susceptible to poisoning at otocities of basic impurities in the system. In addition, many, if not all Lewis acids proposed for use in soluble Ziegler-Naaty catalyst systems are chain transfer agents, which in effect prevents effective regulation of molecular ms and molecular distribution of the product. It should also be noted that most, if not all of the catalysts proposed so far, have strong self-ignition properties and therefore such compounds are somewhat dangerous to use.

The catalyst systems mentioned above are not usually particularly active when the metal of group IV-B used is zirconium or hafnium. Recently, however, it has been found that active Ziegler-Natta catalysts can be obtained when using bis / cyclopantadlenyl / hafnium and bis / cycopsopsadienyl / zirconium compounds together with the compounds. As is well known, such systems show a number of advantages, which include a much higher catalyst activity compared to supported bis / cyclopentadienyl / tyain <wtmi catalysts, and the possibility of producing polymers with a greater distribution of molecular ms than conventional Ziegler-Natta cataliaoorto. These systems, however, are prone to intoxication by the presence of alkaline contamination and require the use of an undesirable excess of aliMoxane to work effectively. In addition, it should be noted that catalyst systems containing hafnium are not as active as systems containing zirconium, which is the case when I use them in polymetry. Zasu ^^ roo ^ it is Giamrneti, Nicoletti and Nazzocchi, J. Polym. Sci., Polym ^ hem 1985, volume 23, pages 2117 - 2133, who stated that the rate of polymerization of ethylene in the presence of bis / cyclopentadienyl / hafnium compounds is 5-10 times lower than for similar bis / compounds ct'klopentadientlo / zirconium with a slight difference in the molecular bowl of polyethylene obtained in the presence of these two catalysts.

Bochmann and Wlson found in J. Chem. Soc., Chem. Comm. 1986, pages 1610-1611, that bis / cyclopentadienyl / dimethylthitane reacts with quaternary acid to form tetraflooboyphose bis / cycloptadityl / mettlotttaiu. This anion is not mobile enough to be substituted with ethics ^^

In a number of disadvantages of the aforementioned coordination systems of catalytic systems, there is an obvious need for an improved coordination system that l / h ^ and ^ i. Would have easier regulation of the molecular bowl and the distribution of molecular ms, 2 / in activated form would not have to be in a state of equilibrium and 3 / would not require the use of an undesirable cocatalyst.

It has been found that the above and other disadvantages of the known ionic catalyst for olefin polymerization can be bypassed or at least reduced by using ionic catalysts produced by the process according to the coating. These are catalysts that differ fundamentally from known catalytic systems, because they contain mt ^ locene and do not require the use of aluminum alloys_AND

The method of producing an olefin polymerization catalyst using a bis / cyclopentaditylcyclic vinegar, bis / cyclo-tetntadiene / titanium or bis / cyclopoptadadyl / hafnium compound is based on the fact that / a / combines in a solvent or diluent to form one first cyclone compound / metal containing at least one substituent. One substituent capable of reacting with a proton in which zirconium is

159 193 titanium or hafnium, defined by the general formula /Cp/CCp*/ax.X₂, / Cp / CCp * // X-X2, / Cp // Cp * / ML and / or /Cp//CTp*CH2/MX.y, in which formulas / means zirconium, titanium or hafnium, and Cp and Cp *⁵are the same or different cyclopentadienyl radicals, optionally substituted with one or more substituents selected from the group consisting of a Cp-C8-alkyl radical, a triCCp-C1-6alkyl / silyl radical and a cyclopentadieryl radical, L is a C-ligand_FROM- {C - dwullefinowy.

Xj and X₂ are independently selected from the group consisting of hydrogen, Cp-C ^ -akak, phenyl and benzyl, Xj and Xg are connected to each other and bonded to a zirconium, titanium or hafnium atom, forming a 4-6 membered mtalacyclic ring containing in addition to zirconium, titanium or hafnium, a silicon atom substituted with two Cp-C-alkyl groups, and at least one other compound containing a cation capable of donating a proton and containing a large volume of boron atoms, mobile and capable of stabilil <oαtiα of a metal cation hollow in the reaction between two compounds defined by the formula / "1 / -H 7 // CH ^ / BH / ^^ in which I / H is the H + radical, the tr // Cp- radical Cg-akkyl / yltN or radical N, N-diCC - C —- 8 ^ 110/8 ^ 1 ^^^, B, C and H are respectively boro, carbon and hydrogen, and b are integers - 0, c is an integer 1, the sum of a + b ♦ c is an even number from an even number from 2 to about 8, and m is an integer from 5 to about 22, and / tob by formula / _^_l / -H_7 / "/" ć ~^CCH/_e/ BH /_m'^ And ^_J' -⁷° ~-^J2^{Mn +} »In which L'hH tells the story

H +, radical tΓi / CpCJg-aiklloyyltnlowr or radical N, N-di / C - C_and- alkyl / anthyloyl, B, C, H and M denote boron, carbon, hydrogen and metal, such as iron, kobaat and nickel, and 'ib' oz ^ and ^^ are the same or various ϋοζϊ ^ integers fi 0, c means Ιίοζΐ ^ integer 2, the sum of '+ b' + c 'is an even integer from 4 to 8, m' is an integer from 6 to about 12, n means such an integer, that the difference 2c'-n is equal to d, ad is a whole number 1, wherein contacting is carried out at a temperature from about room temperature to about 160 ° C, preferably at atmospheric pressure to about 150 MPa, / b / maintains the contzktooatit from step / a / for a period of time sufficient for the proton reaction supplied by the cation of said second compound to take place with pw ^: ^^; ao ^^ k: i ^ y contained in the said metal compound and / c / isolates active catalyst as a direct product or as a degradation product of one or more direct products from step / b /.

In the case of an advanced catalyst according to the present invention, there is no inverse equilibrium ion reaction, in the presence of such a catalyst it is easier to control the molecular weight and the distribution of molecular races of the polymer produced, whereby the catalyst can be used with a lower risk of fire. Plliπ] eric products produced in the presence of such an improved W catalyst are characterized by a relatively narrow dispersion of molecular mesons and do not contain certain tartaric impurities. These and other features and advantages of the shot will become apparent after reading the description below and the examples included in it.

Thus, according to the invention, the catalyst is prepared by combining at least two components, the first component, which is soluble bis / ciclpentαditnyl / -pldstθOilty zirconium, hafnium or titanium compound containing at least one ligand, which can combine with Lewis or Bronsted acid to form a cation me ^ lu, injury of the second component, which is a compound containing a cation capable of donating a proton and pΓztrtαgooatia in an irreversible manner with said Iggand in the first compound to form a free, neutral by-product, and the corresponding VedrtLl compatible anion with a series of boron atoms, which is the corresponding t durable, bulky and mobile. The resolvable first tmsi compound be able to form a cation, formally with a coordination number of 3 and a valence of +4 after release of said ligand. The anion of the second compound must be able to stabilize the cation complex without affecting the capacity of the cation or product of its

159 193 decay to function, As a catalyst, and also must be sufficiently mobile to be able to be substituted with olefin during polymorphism.

All dimensions on the subject of the periodic table primrose! refer to the periodic table of the square root! published and published by CRC Press, Inc. in 1984 Also any mention of a group or groups of the periodic table of the element! refer to the group or groups represented in the listed periodic table root !.

In the sense of the description, the term correspondingly non-coordinating anion means an anion that either does not coordinate at all with the listed catoon, or only poorly coordinates with this catoon, remaining mobile enough to be substituted by an indifferent Lewis principle.

In particular, the term correspondingly compatible non-coordinating anion means an anion which, acting as a stabilizing anion in the cathode system does not transfer the anionic substituent or fragment thereof to said cation to form an inert tetra-coordinated mtalocene and an inert boron by-product. Correspondingly are those anions that do not degenerate to neutral when the complex initially breaks down.

According to a preferred variant of the process according to the invention, compound 2 is used as the second compound^andthat^k roe^śtench^t by ogfanjrm / JL^--H_7 in which ^L'-H is the H + radical, the tΓi // χ-Cg-eHkyl / iioni radical or the Ν, di-di / Cl-C radical_loam-aCkili / cnilini {wt »B, C and H are boron, carbon and hydrogen, respectively, ax is 0 or 1, cz 1 or 2, the sum of ax + cx is 2, and bx is an integer of 10 - 12, or a compound determined by the general formula / L> -H_7 ΛΥ / Η / ο ^ ΒΗ / η H / yj /⁵/”, ⁱⁿ in which L ^ h determines the H + radical, the triZ / ic / g / indoor radical 3.ub rMnik ^N/ Ei // C^ceC^c-8Bt^H1.0ί^{| a}n-l.ⁿl^andin^y BC and ^H are from^abouthead^dnio, boron, carbon and hydrogen, ay is an integer from 0 to 2, to be an integer from 1 to 3, cy is 1, the sum of ay + by + cy is 4, and we are integer from 9 - 18 or the compound represented by the general formula.

/ 'L'-H 7 / “ΓΓΙάΙ Iow! η, 7⁰² ?,/FROM^{n +} ^²^ where L'-H means^and H radical + triCC-cCgα radical₈H | (ilαiiioniMt or the radical N, N-di / Cy-CceLakHli / anilinium, 0, C and H, and MZ stand i / o <witiii boron, carbon, hydrogen and transition metal atom such as iron, kobaat or nickel, az means 2, bz is zero, cz is 2, mz is 9, the sum of az + bz ♦ cz is 4, nz is 3, and dz is 1.

The chemical reactions involved can be represented, as a reference to the general formulas above:

A. / Cp // Cp^,'MK₁X₂+ / L'-H 7 * / __ B'_7 ~ »/“ / Cp / CCp * / MXi 7Γ EjT + hx₂ + L 'or / "/ Op / OCp' // ^ // * '/ ^' _7 '♦ ΗΧχ + L'

o. / Cp // Cp * / MXjx2 + / _l'-h_7 * / o '7 - / - / - / ^ / ^: ^ / ^ jx / H ~ Γ' J + l 'or / _ / Cp // Cp ^ / X₁'x2H7 FBI

c. / ^ // ορ * /! * /. ' l'-h_7 * / “b '_ / -» / - / cr // cp * / M / LH / _7 * 7_- b'7 + l'

D. / Cp // Cp * CH₂// H₁- · // L'-H 7 / ~^Β2 / - ~ / _7Cp / C ^ H3Cp ^^ / X₁_7 * / b'7 + L 'or / _7Cp // <H₂Cp * / M 7 Fb 'J + ΗΧ-eL'

In the above equations, the reaction o 'means idp <corresponding Jon with the structure shown in the general formulas of the second compounds! shown above ^ and ^ above. The mtalocene reaction! from each of the four groups AD from bis / 7,8 / dHC8rαaιm / ekaboraniikHialtacim / iII / NiN-dimtyloanilininwyi As examples, the second compound was tested by spekkiroskoppi and ^ C NMR methods.

In each case, idp <products with the above oidanf'® compounds were observed.

159 193

For example, but not limited to, bis / cyclopentadienyl / zirconium compounds that can be used to prepare the improved catalyst of the present invention include bis / cyclopentadlenyl / dimethyl zirconium, bis / p-caratyl cyclopentadlenyl / dimethyl zirconium, bis / 1,3-bis / triaethyl silyl / cyclopeneadiene^dimethy zirconium, bis / methylcyclopentadienyl / zirconium dihydride, 1-bSs0 / yl-thieadadienyl-zirconium-3-dimethylsilacyclobutane, bis / thi-tetramethyl-cyclo] p-neadienyl / dimethoxy-zirconium, bis / 2,3-yl / zirconium, / pintamiylcyclopropeneadiene / o / titraTCtyltyklocyclopeneneadienyl / meylino / finylOcykonium i / pentaiiy / ocyyloiPietdiein / c> l / 3l, 3-bi3 / tΓimitylsili / o / cycloententyl diethylcyl.

Clients of hafnium and titanium which can be used to prepare an improved catalyst according to the formula include bis / cyclopentadienyl / dlmitylohBfn, bis / thiocetylsilocycloi> entadieniio / diitylohafn, 1-bisC / ykkoJi ^ n -dimitylosiaacykkobutane, bis / c / klopentadienn / ol / 2,3-dimethyl-1,3-butadiene / hafnium, / pentameylcyclene^dienn / o // tetΓ · imitylcyclopintadienyl / hafnium and 1-bisOcykOpintadienyl / titan-3dimethylsilocyclobutane.

In addition to the above zirconium compounds, which are root compounds, bls / cyclopentadienyl / diets Oocyrkle, bis / cyclopentadienyl / dipropylcyclene, bis / c / klopeetadiene / lo / iibutyOcyΓkon, bis / cyclopietadiyldiekylkircene / den ^ opent / locyΓkon, bis / cycl] p3neadiein / o0di / m-tolyl0 </ lΓkon, bis / cicl] Pieodieiyl // di- / p-tolylOcyΓkon, etc. ,, compounds /mlno0.y·yiokseΓlb/lo-Ikdstawilrli Cyclops ^ ^^ and ^^ and ^^ e lo / c ^ i ^ k ^ -one, such as /Mtylocyfcl.lcpeeadiein/ol/cyklo]p!neadiene/o/- and bis / methylyklopintadlenylΛdimethylzirconium, / ethylcyclopententdieI'nr / o // c / klopent8dle] ry /^about/ and bis / ethylcycl.opintadienyl / -diilet / loc / Γkon, /prlpyllcy/k.openeadieey/ol-/oyklkpent8diern/o/i bis / propyloylcopentadiinyl / -dii) thiocyclone, / n-butyloc / clopentadienyl // cyclopentadienyl and bis / e-butyOcyclopopadadienyl / -diπtethylcyclene, / tert-Uu / ylo / ykko] fentadienyl / / cyclopent8dieny / o / - and bis / tert-Uu / ylc / ykOoientadieeylk / -dimethylcycloxylcycloxycycloxycycloxycycloxy / - i bis / o / kllhiksyloMeylycyclopent8dienylo / -iimityloo / τkon, / benzyllcykllpneadiernrlo // oykllpentadieIn / o / - i bis / binz / llc / kllpintadienyl / -dimethyl zirconium, / dfeelylmitylcyclopentadiethyl / oO / cyclJX! neadieity / o / - and bis / methylene cycloethylene // cycloJ »ntaiieπyl / zirconium, dihydrogen / ethiocyclopentaiiinyl // cyclylpentadieity / o / - and bis / ethylcyclopropadiadiyll / cirkoeu, dihydride / propylcyclopeneadiene / ll / cyclopeneneadiene / propyl / cyclisadium dihydride / n-butylloylknepneadienn / o // c / clopentadlenyl / - and bis / n-butyl / clopentadieyl / cyclene, dihydrate / tirt-bu / ylo (/ cycloJintadien / lo / Ocykiopintadiinyl / - and bis / tett-buett ykloiιena8dienyloC / yΓkonium, dihydride / o / klohiks / loie ^ thylcyclopentadieeyll // cyclopentadienyl / - and bis / cyclohex / IIm ^ iylcyclopintadienyl / cyclene, diildecyl / benzylcyclo] pieadίenyl / cyclopentene / cyclopentene dihydride / dfeenyl-ethylcyclo] pϊneθdierer / o // oykllpinn8dienn / o / - and bis / dfeeynylitylcyclopentadiinyl / zirconium, etc., compounds / pllihydrocarbyl-Ik> and / or cyclycenta / cycladentyl / cyclopentene, i-methylcyclopentadiinyl / dimethylcyclo, / t-dimethylcyclopint8iiinyll / c / kllpentadieny / o / - and bis / trilMϊylcyclopropadadiinyl / -dimityloo / Γkon, / tetrimethylcyclc / klipneadiene / ι1 / cyclopentadiernir / o / - and bis / tet.r8methyloylpentadiileyl / dimethylcyclone, / permiylcycloeadiene / oO / cyclpentadiene / o / cyclopentylcycloethylene o / - and bis / ethyltittriIi / lio / cycloIe ^ n'thiienyl / -dimityloyrkon, / endinyl // yoylpentadienyl / - and bis / endenyl / di-diethiocyclene, dihydroxyl / cycloperentadiethyl / - and bis / diπlityiycyclopentaiiieyll / oczone, iiwoioΓik / tΓimetyiycyclopintadiiπylo // cyclopentadieny / o / - and bis / triie / ylc / ylioIi! etaiienyl / zirconium, diioylrik / tetramethyllcyclopent8dienn / o // oyklopent8dieny / o / - i bisny tklopimim_CyΓkon, ϋϋ ^ 10

159 193 rec / perraethylcyclopint8-diethyl // cyclopentadienyl / zirconium, dihydride / ethyltetremethylcyclopentedienyl / zirconium, dihydride / tndenyl // cyclopentadienyl / - and bis (inde] nyl / -circonium etc., compounds / methylcyclo-ethylcyclone t-dimethylslocyclic-ennαidieryyl // ckkn-pent8dienyl / zirconium, / trinEdylogermanylcyclopentadiethylo // cyclopettediethyl / - and bis / trimethylgerilanylcyclopentadienyl / -dimethylcyckyl, / TΓiπetylocynlmoclklopentadientyoO / cyklopentadieΛty^aboutBis O- and / tΓαattynocynianocyklnp ^ ntadienylo / -dimetylΛcyΓknn, / triπetynooOwiαnocyklnpntadierylon / Cyclops! Ntadierflo / Bi3 and / rriιnetynoo0wαtnocyklo-entadienyln / -dlmetylocyrknn, Uwodorek / triiιetylnsiUOocyklnpent8dienylo // cyklnp ntadienylo ^ / - bis and / tri [IetyloslUlocykl-ptntidierynoCcykkonu, dihydride / triπetylogerranyl^aboutcyklol: pntaeientlol / cykloI »nttdientyo / - bis 1 / tri [Mttyno ^^ rmαtylncyklo-entadienylo / -cyΓknnu, diwoddlek / tΓiretyllcynlanolyllooρntadientloO / cyklopenttdienylo and / bis / tr Minety Occynaanocyklopentadienyln / - <ykkonu, di- and <nionek / trimetyloołwianocylŁl.op> ntadietyll // clklopsntadieιtyl^about/ - and bls / rrimetyOoonwαβnocyklopettadienyln / -circlotte, etc., compounds / chloΓllico-pnistawiont - cyclo-pnttdieryyl / -cykonium, such as / triflnrnrπ! ethylncycnpentadiery^lo// cyclope 1 ^ 0016 ^ 1 ° / "and bis / tripropylphosphinocyclopropadienyl / -diiletylcyclo> n, dihydride / trifluorrtethynylcyclopropene n-tadieltyl // cyclp ^ nt8-diethyl / - and bis / tri-n-n-n-n-n-n-n-n-n-n-cyclene-cyclene) -liStaawiotle compounds bis / clklopattadietllo / clrkotu such as bis / cyclnpnntdiennlo.ltriΓmeyllnlUlo // methyl / ccyΓkon, bis / clklopεntBdiertlll / / triftlylo3llll / r / Ethyl / lrΓkon, bithyl / cyclyl / dimethyl / cyclyl bis / clklo-bis entadientlll // / rzyltlolsilll^about7 // retllo / cyrklt, bis / cyclopropadadiethyl // trtπ! Ethyl3iliOo // trimεlylosilll /// iri [thylolloyl and 3-cyclo-cyclo-cyclotot, bis / cyclopropadienyl // triethylmethyl] cyclene, cyclene, cyclone, cyclone / cyclopntadienyl / dimethyl zirconium, ethylbetis / cyclopntadiethyl / dimethyl zirconium, dimethylsilylbis / lkll-ptnt9dieldyl dihydroethyl cirkot, imeethetisis / cyclpntadienyl / zinc, dihydrinated cyclene dihydrite dihydrate dir ^ eylsilllbbS // lkkl-penaadienllo / zirconium, etc., circular compounds, such as bis / pntamethylcyclpntαdienyln / cycloaccyclnione cyclone cyclocyclene cyclocyclictracyclate ., dionephine or aramid, such as bis / cyclnpntθdierylon / 1,3-buaadiene / zirconium, bis / cyclo-ettadietllo // benzyl / zirconium, etc., hydride compounds / hydrocarbyl / bis / cyclopentadiethyl / zirconium, such as the above mentioned bis / p-methylcyclo-entediethyl / bis / p-methyl-cyclopropadiethyl / methyl-zirconium hydride, etc., and also with: bis / cyclopettedienlln / circlate, in which a substituent at the cycloptadadny ring is combined with mtal, such as hydride / p-methylcyclopnnadienyl // eeΓtrmetyOockkn-pntiditnyOrmethylene / cyrinite, ltp.

Similar bis / cyclopropadiethyl / hafnium and bis / cyclopropadenene / titanium compounds can also be used. However, those skilled in the art are aware that the bis / cyclopropadienyl / hαft.and bis / cyclo-etadadiethyl / titanium compounds corresponding to certain bis / cyclopntadienyl / zirconium compounds are not known. Therefore, these lists should be reduced by such relationships. For those skilled in the art, however, other bis / cyclo-ettedienyl / hefene compounds and other bis / cyclpntαdienyl / titanium compounds as well as other bis / clklopentadiethyl / clonium compounds that can be used in catalysts made according to the invention are obvious.

Compounds useful As the second component in the preparation of the catalyst according to the invention, they contain a Bronsted acid cation capable of donating a proton, and an anionic compatible anion containing a number of boron atoms, the anion being relatively large, capable of being the active catalytic center formed in as a result of the combination of two compounds, and mobile enough to be substituted with naphtha substrates or other neutral Lewis bases, such as ethers, nitriles and it ^ p.

Preferred second compounds. in the method according to the invention, there are 7,8-dicarbaundek-booantl2 / trtn-butylormonives, 7,8-di) abautdekabon8ntl3 /, 1,2-ditaarbaundek159 193 borane / 13 /, octadelkborane / 22 /, tridehydrido-7-carbene-butylborane / ammonium, 1-carbadodekaborate tri./nobuyylo//moni<wy, nonekaborau tri / n-buyylo // monr <wy, budelkbyynane-1-kaokburnlekaboran Uri / nbbuyy lo / mronowy, 0is / 7,8-dilkιrtkbude ^ kbOdabo / dobo0aan / UII / N_fN-ninkdyloarU.liniowy_f bis / centarmdytliytlodecldiUaind / o / ieżdzaan / iiI / N, N-diImdutoibillniwy, 01s / 7,8-dikθrbab / dieaborono / niUlθn / IiI / triinobutyl // ϋoniwtf bis / 7,8idiaabbaLUndbabbybanban bis / 7,8-dilaabb8bunelωbodabo / do'td0ban / III /

N, N-Nitylenilylivt.

Examples of other second compounds which, in addition to the above-mentioned preferred compounds, can be used as the second component in the catalysts prepared according to the present invention are the ammonium salts of 1-kbrbaddecarborane / dylammonium, 1-kaondondkabrran eUyO-oammonium ^ i ^ l ^^^ oneka ^^ an propylamduiϋwyf 1 - ^^ 0 ^ nekeOoran isopropyls / o / iowy, / n-bbtyOob / mrniσwyf 1-kbrltb ^ nonekbOnilane aniline and 1-kbΓbanonekbbrrbn / p-tolrlb // d / nr-tolrlb // d / nr e.t.c., diyydrokarO> yl-Jddioniond ammonium salts such as 1-carbodddekbbbbu dimeUyOoβmoniwyf 1-kbrbbdddekbborbu nontylamine, 1-kbΓ0bdonekbboΓan dipΓocy^ΓOoamoniwyf 1-kbΓbbnrnekabϋΓau niliopdOJtribimdnlw^sf 1-karbandnekbbrran ni / n-butyla / minib-Jtf 1-kyltblnonecarbane nlfelt | Obabouiwyf 1-kbr0b) doddkbborau ni / p-Ollilbiiϋiniwy etc., Uryhyddolb ^ bbonyo-added bisbiumbiumbiumbene Urdutylbimoniwtf 1-karltbJdondkbborbn tripropylammoniumf 1-kbΓbadonekbborau UΓid / yylb / IlOiLiowyf 1-kbΓbadonekbOorane UriCptdolyl / Allium, l-1-tablabene

Dr, but not Jens, no long-term compounds corresponding to the formula £ L - H_7 IJchI iB / Hb-7^C"What Jon UrlinoUutylb / moiLlσiy / Is an example but not

The salts are non-boronane -is / tri / n-bbUyloa / mrniwy / f uudekaboran bls / tri / n-butyl // ϋoniwy / f nodekaborau bls / UΓiin-bbtylr / ammonium /, nek8Chldronekaboran bis / tri / n-butyl / iϋoniwy / f nodekachlrrnonekbOrran bis / tri / n-bbUyloa / mdnioi7f 1-kbΓl! b> nondkb0orbnyl-nbion / n- buty lo / ami / iwy, 1-UΓimdUylsllilo-lakobn8dndebaboran UΓi / n-butyl // moniowtf dibrrmorl-kbrbadonekbbrran Ur / in-butyl / imonioiy, etc., bdranwe and carborane complexes and salts containing braanwd and carborane anions, such as nekθbodabnl4 / f 2f7-nicarbaundelkbooabil3 / f bndekbydiidir7,8-nimdyl-7,8idibrbb ^ undekbboranf urnie dabodan / l4 / UΓi / n-butylb // donivyf 6-kabanel · kboo8bil2 / tibiabiobutyridyl n-Uutylb / idonivyf 2f9-dicaobaunie ^ kbooab // 2 / Uri / nobutyl // iwonivyf nodidabytnidii8-πmeuto-7f9-dikaobunndk8boran UΓiobobutyro // monidium bendeckbhdnador8-butyrbene-7 // // n-Uutylo ϋonrwyf bJniekabhtiano-8-aliyl-9, nicarobteundelbium borate tri / n-butylGa- / lonium borate, hydroxyhydro-d-tΓ-γ-methylamoyl-7,8-dibabbaunddkbOorane U-quinobutyl / ionivtf-t-butb-7-tbound la / mroni ye, etc., borates and carborant and salts of borates and carbans, such as 4-karbanorβbodab / l4 / fl, 3idibabbanonabooab // 3 / f 6f9-nikbrbbne ^ ka — dθbil4 / f dodelfabyyiidirl-fentlo-1,3 -kakθraedilb ^ boranf nodekabyynadirl-meylr-1,3idibrob / noiMboranf

-l, -idiιretyio-l, i-carorbaoibaborane, etc.

Dr. crztkładwychf but not Jenynych nrgni rnpw Wadajujące wzowi / 1 / -8 // - / - / - 7^0-^ / B^-/^/^-/^-'_7 ^C ”@2^{m / + / p}government^s part^sm Jon ^atr^-/ I ^ -^bat^t^^aboutabout^andMDIL^aboutin^t It is an example, but not a counterion of the anion counterpart pϋnantcy humble / include salts from ania / ami mtBlakbrOd) Γan <wtmi i / ϊθ ^ -οτι / ι ™! /!, Such as bis / nonahydΓino-l, 3idibabbidorbibora / o / kob-atta / m / tΓiin-butyl // monrιwyf bis / ^ mndkθhyynadOi7,8-nicarbaundieabodβbo / miiddianaiiI / UI · l ^ / r ^ - ^ Uι ^ t ^]. a // dond: wyf bis / unddte> hyynidOi7, 8-nikbrbaιuuiidkborino / i / oiiabnIII / Uriin-buUylo / bis / nrI / 3hyynadir7,8-diImeutOr7,8-nikbr0e! ΙuInikabbornbnżrlazaanb // I / tri / n-butyli / amoniwy, bis / ninahyynadOi7,9-nimtyli-7,8idibaobaunnekθbodabi0chyrdθnbiII / Uriin-bbUyli / ιι / οι / Ιπ ^ bis / tΓ-rdimioktahydnido-7,8-nikbΓbab ^ iiidaborinc> idobi0tanbiiI / UΓiin /

159 193, bis / dodecahydridocarbadodekaborano / cobaltan / III / tri / n-butyl / arnoniwy, bis / dodecahydridododekaborano / niklan / ll / bis / Jtri / o - butyla / atonicwy /, bisbι / neekbhyerido-7-ba-'^JΓbno / chΓOi / n // II / tris /^-ti '/ ^ / r ^ -but ^' ^ J / o / o / ndwy _ /, -is / ιn ^ cekbhydΓido-7aba-bbl / ndeko-oΓono / / niknon / iv / bis / 'iΓi / b-buty / b / etennw «» y_7, etc.

Generally, it can be said that although most of the first components are combined with most of the second components to obtain an active olefin polymerization catalyst, it is important to carry out the polymerization so that the pre-formed cation / thallium product or its degradation product is relatively stable / catalyst poly / olefin projections. Istotre It is also important that the second compound be resistant to hyirolysis when the ammonium salt is used. It is also important that the acidity of the second composition / dnrkb is high enough in relation to the first to facilitate the necessary transfer of the proton. And vice versa, the basicity of the mesl complex must also be sufficient to facilitate the necessary transfer of this proton. Certain compounds, which, for example but not excluding, include bis / pe / ioratylcyclopentadirtylt / dibetylthofn, are resistant to reaction with all Bro / steda compounds, except for non-strong ones, and therefore are not suitable as the first components in the production of the described catalysis. In principle, -is / cyclopentadie / yl / metal compounds that can be hydranized in an aqueous solution can be considered as the first components in the preparation of the catalysts described.

Regarding kt kt-nn / Ci of the desired cation and stabilizing o / ron in the formation of the active catalyst produced sptso-e / according to the invention, it should be noted that the two compounds joining in the preparation of the active catalyst should have goodness to ensure anion substitution with a monomer or another indifferent Lewis principle. This can be achieved due to the spacious with / w / dtm as a result of substitutions at ctaltpentodiesel carbon atoms, as well as as a result of substitutions at / niinir alone. The use of metai perwegllwctioΓ compounds (Orfo-base / light at the ctkltpret / dketyiOTy / i ring) of large components with a large volume does not substantially prevent the formation of the desired connection and in fact the more actively mobile a / ro / y. It follows that the compounds and / or the first constituents / containing perhydrogenhydrogen-cyclo-cyclententieyl radicals can be successfully used with a broader range of second compounds than the compounds they / they / the first are / containing non-pyrogenic cyclyprevirogenic radicals. And indeed, the first compounds containing the dihydrocarbyl-cycloid / todientlowr radicals can be essentially effective if they are used in conjunction with second components containing larger or smaller ones. However, as the amount and size of substituents on the cyclosphodienyl radicals increases, more effective catalysts are obtained for second compounds containing larger onins, such as the compounds tkΓrślter formula / l'-H / /^_//^_/ CH / '/ BH /' / h /. · 7^C"7, M^{n +} 7 ~ and those compounds of formula / JL'-H 7 / pdJbHmHb -7 ° "» in which the Ra values ​​are higher. In such cases, it is even more preferable to use the second compounds of formula 7 / Z // H / a / BH / mHb in which the sum of + - '+ c is equal to 2. The use of second compounds, in which the sum of + - + c ozeocio an even number equal to 4 lul more, especially if they contain acidic BHB moieties that can further react with repeat / ^ ϋοηθπι containing / meal, leads to catalytically inactive compounds.

The catalyst is also suitable for use in poly (erase), but it can also be used for the polymerization of solid monomers containing from 2 to about 18 carbon atoms and dibilils containing from 4 to about 18 carbon atoms , both individually and in ^ π / Οπ // ^. The catalyst can also be used in the polymer of yzzoci o / -olefi /, diblfl and / uucetin nirnbsycin mononmró * in ^ ιη / Οη // ^ with other non-sycamore / οηοπι / ^ ΓηΙ. In principle, polymerization is carried out under the same conditions as known polymerizations of monomers of this type. It is clear that the catalytic system will be formed and / situ, if its components will be added directly

159 193 in the polymerization process and a suitable solvent or diluent will be used. Preferably, however, the catalyst is prepared in a separate stage before being used in the polymerization stage. Although the catalyst does not contain self-combustible fragments, the catalyst components are sensitive to moisture and oxygen and therefore must be stored and transported in an atmosphere such as nitrogen, argon or helium

As noted above, the catalyst is generally prepared in a suitable solvent or diluent. Suitable solvents or diluents include any solvents in which they are known to be useful in the polymerization of olefins. Suitable solvents include, but are not limited to, straight chain or branched chain hydrocarbons such as isobutane, butane, pintene, hexane, heptane, octane, etc., cyclic hydrocarbons and allcyclic hydrocarbons such as cyclohexane, cycloheptane, meeylcyclohexane, methylcycloheat p · and atomic and aromatic compounds with substituents alkyds such as benzene, toluene, xylene top. Other important solvents are also dissolved¹basic salts not previously used as solvents in polymerizates when using conventional Ziegler-Natta type catalanizZoolool aza-dimers, such as dichloro-mane and propyl chloride.

Although it is not the intention of the inventors to bind to Any particular theory, it is believed that If the two compounds used to make the improved catalzzaZok <i are combined in a suitable solvent or diluent, all or part of the catoon from the second compound / protons / combine with one of the substituents; with the first / metal containing component. In the case where the first one is given by the formula / Ca // ^ Cp^ί6/ ^ K₁X2, an inert compound is released which either stays in solution or escapes as a gas. In this case, it should be noted that if the catoon in the second compound is a proton, and X ^ or X₂ In the fuller meal containing compound, it means a hydride radical, hydrogen gas may be excreted. Similarly, if the catoon in the second compound is a proton, and X ^ or X^g denotes the m> posterior radical, gaseous mt ^ n can be produced. In those cases where the first relationship is defined by One of the general formulas // p / Z / p ^ MK · ^ »and / or // p / CCp / ^ / ^ ·., One for <z ^ stβwiiki at / ρίβ ^ ^ ^ / the component containing meeal is protonated, but essentially no substituent is cleaved from the me ^ OL atom. Preferably the ratio of aiexw; tiegz of the component containing meal to cathone <in the second component is equal to or greater than 1: J Conjugated cation principle of the second compound, If any such part remains, should be an inert compound that stays in solution or forms a co-complex with the resulting catater flesh, although in principle the cation is chosen so that Any binding of the neutral conjugate base to the mealtic caton is weak or absent. Thus, as the spatial volume of such a conjugate base increases, it will simply remain in solution without interfering with the catalyst activity. For example, if the catoon in the second compound is an ammonium ion, this ion will use a hydrogen atom, which will then be able to react, and then react as if the catoon is a hydrogen atom to produce hydrogen gas, methane, etc., and the conjugated base of the cation will be an amoziac molecule a hydrogen atom could react in the same way as if the hydrogen ion is a catoon and the conjugated cation base would be an amine.

Although it is still not the intention of the inventor to bind to any particular theory, it is believed that if the first component containing imeal reacts with the second component, the non-coordinated output anion present in the second component used in the production of the catalyst combines and stabilizes the cation as ^ irradiating meal, formally with a coordinate number of 3 and valence +4, or a product of His decay. The cation and anion remain in this connection to the mornnt when the catalyst contacts one or kilooma olefirs, either alone or in kzmOirwaZi with one or kUooma other monomer. Like this

159 193 noted above, the anion present in the second compound must be mobile enough to allow its rapid substitution with olefin to facilitate polymerization.

As noted above, most of the first relationships listed above will merge with most of the second relationships! listed after the formation of a catalyst, in particular an active polymerization catalyst. The actual active catalytic center is not always durable enough to be dialed and then identified. Also, although many of the initial cationose meals are relatively stable, it has become clear that the initially rising cation meal may break down to form an active polymerization center or a catalytically inactive fragment. However, most decomposition products have laticidal activity. However, in this case it is not the intention of the creators to bind with Any specific theory, it is believed that active catalytic centers that have not been separated, including active degradation products, are of the same type as the centers that have been separated and fully zideotyflicwaoe, or at least they retain the basic structure necessary to function as a catalyst, e.g. reactive mrtao-bond bonding.

Still not intending to be bound by any particular theory, it is believed, however, that the degree and type of substitution in the cyclipeotadeenyiywyi ring determines the size of the stabilizing anion necessary for the production of a particularly active polymer of jefin. In this regard, it is believed that, as the number of substituents on the cyclopentadrenyl radical in the imthalene cation change from 5 to 0, the given anion becomes more and more mobile to me. Therefore, it is suggested that as the number of substituents on the yyklopentadrenyl radical in the mtalodd cation varies from 5 to 0, larger or named reactive anions should be used to ensure their mobility and to reduce the formation of particularly active calcium centers ^ t ^^ different.

Accordingly, stable, characterizable and characterizable ροΙίϋϊΓχζθ ^ ί oil catalysts were obtained when bis / ϊ -methylcyclopopeotadieoyli / dimethylcycloalkyl was reacted with 7,8-dicabbaundekaboranenmi2 / tΓiOn-Uutilaiammicium / θΓ-borborborbor ym or 7,8-dikaΓbaundrkaboΓanemil3 /. Stable, separable and characterizable oil polymerization catalyst P ^ was also used when bis / ethyrotetimethylcyclopropadiroyl / dimethyl-cyyl zirconium was combined with 7,8-di^karbaundekaboO8nor / l3 /. In each of these cases, a stable polymerization catalyst was obtained by adding the reagents to a suitable solvent or diluent at a temperature ranging from room temperature to about 160 ° C. Based on this and other available information to the inventors, it seems clear that oxidizable and chemically polymerizable catalysts can also be obtained when the bis / IerhydΓOkartyio-and Deformed yyliplipentyl diene / metal compound is combined with one or more of the second compounds listed below. Active but non-duplicate polymerization catalysts are also obtained if bis / cyclopadtadienyl / cyclone compounds containing less than 5 hydroxyl substituents on each of the cyclopradienyl radicals₁ it is reacted with a suitable second compound containing a cation capable of cleaving a proton and an anion capable of stabilizing the mealocene cation and mobile enough to be substituted with olefin at the time of pilimeryzzail, especially with those second compounds that contain larger anions.

The substantially stable, expandable catalysts obtained by the process of the invention can be separated from the solvent and stored for later use. Unsupported catalysts can also basically be stored in solution until their final use in olefin polymerization. Any of the catalysts prepared in the process of the invention should alternatively be stored in solution for later use or used immediately after being obtained As a polymerization catalyst. Further, as noted above, catalysts can be made in situ by introducing iddielieieie ingredients into the tank into

159 193 polymerization, in which these components will contact and react with each other by the method of the invention, forming an improved catalyst.

In principle, as noted above, the improved catalyst is suitable for olefin polymerization, including dihydrate, and can also be used for polymerization and copolymerization of unsaturated monomer *. Polymerization is carried out under the same conditions as what is known Ziegler-Natta catalysis. It turned out that in the polymerization process carried out with the use of the mentioned catalyst, the molecular weight in ms depends on the catalyst concentration, polymerization temperature and pclieecitza pressure. In principle, polymers produced in the presence of catalysts made according to the invention, obtained in an atmosphere containing no hydrogen or other chain terminating agents will contain unsaturated groups at the ends.

The products produced in the presence of dim totalizató will obviously not contain some trace mttles usually found in polymers produced in the presence of kltaliaaOoó (in the Ziegler-Natta type, such as aluminum, mg, and e.t.c. Accordingly, the polyester products made in the presence of catalytic compounds produced in the process of the invention should find a broader application than polymers made in the presence of more-quieter ziegler-Natta-containing kataizaao compounds containing mealoalkite compounds such as alkylglycines.

The invention is illustrated by the following examples in which, in the case of isolation and identification, aralysis was performed with honeycombs? C NMR in solid state and trtroscopy ¹H in the solution.

Example 1. In this example, an active olefin polyolation catalyst was obtained and isolated by combining 1.0 g bis /? Methylamethylcyclopropramadinyl / dimethylcirconium and 50 cm? toluene followed by addition^0,82 ^g 7^,8-^dikabtaur) ^ dec booalu^about12 / tri^en-bot^ylt / ammonium. The mixture was stirred at room temperature for 30 minutes, after which the solvent was evaporated to half of its original volume and pentane added until mixed. After cooling overnight at -20 ° C, the yellow colored precipitate was filtered off, washed with pentane and dried. 0.75 g of active totalizer was obtained. Part of this product was analyzed by identifying it as bis / pcmtamCyltó: ykltpent8dicnylo / eeeylt / dodetolyyridOt7,8-dicarbaundekabora no / zirconium.

Example II In this example, an active olefin ptlimer catalyst was obtained with a dissolution^1.2GBis /] ^ "e^tαmtyloc^kebablo^pers^dien^slo / dimrt^ZTz o. o ¹⁰⁰ cm? pentaeo^, a rast^ęTrunks for 5 years? solution it^aboutuenoyc^gt containing ^{0.38 g} 7,⁸-dikarbaondeeθlot8cn / l3 /. A light yellow colored precipitate formed from the solution. After 30 minutes, the precipitate was filtered off, washed with pentane and dried. 0.95 g product was obtained. Part of this product was analyzed by identifying it as bis / ϊc! Ntaeethylcyclopenmadienyto / meylt / -dtdekahyddido-7,8-dilaΓlonldickabcrano / zirconium, the same active catalyst, which is the third in Example I.

Example III. In this example, an active depleting polymerization catalyst was obtained^0.425GBis / ety^tabout^cetaei½ty^tOCY^k0o] c: ntad^renes⁰from^elIcty^tzirconium in 60 cm? pentane and instillation⁵ cn? toluene solution containing^0,1²5 ^{g 7.8}-dikabbaumdekabotatn^about13 /. A light yellow precipitate formed from the solution. After 15 minutes, the precipitate was filtered off, washed with pentane and dried. 0.502 g of product was obtained. Part of the product was subjected to anHzie identifying it as bis / etyttCetreιcitytocyktop ^ ntadCenytoemetyto / dodckahydrido-7,8-dikaΓbaundekaborano / zirconium.

Example IV In this example, polymerization of ethylene was carried out using^Hi the catalyst obtained in the example ^ANDI. 50 m^g totalizator ch^pdamage to ¹⁰0 cm? toluene, after which the catalyst solution was transferred to a static nitrogen atmosphere^andutoklay^at of a capacity ¹ s^ypwasp^fromoncgt ⁱⁿ stirrer, ^whor^s at^przednio ^przcdeuc^hαmo with nitrogen.

159 193

The autoclave was filled with ethylene at 2.1 MFa and then its contents were mixed at 60 ° C. After 30 minutes, the reactor was degassed and opened. 22.95 g of flax polyethylene were obtained.

Example V. In this example, polymerization of ethylene was carried out using the catalyst obtained in example III. 50 mg of the catalyst were dissolved in 100 cm toluene, after^sm the co-catalyst solution was transferred in a nitrogen sphere to a mixed steel reactor with a capacity ^{1 d}n^5, at^psculpture^dnio ^psculpture^dmuc^hane^gabout ^andzotem. The reactor was charged with et ^^ e ^ and ^^ m under pressure ^ ^ n ^ ^ m 2.8 MFa, after which its contents were stirred at 40 ° C.

After 1 hour, the reactor was degassed and opened. 74.6 g of flax polyethylene were obtained.

Example VI. In this example, ethylene polymerization was again carried out using part of the catalyst obtained in example II. 75 mg of catalyst was dissolved in¹⁰⁰ cm? corotenzene and transferred in a nitrogen atmosphere to a mixed-capacity SKIL reactor¹ dn?^, previously flushed with nitrogen. The autoclave was filled with ethylene under a pressure of 1.05 MPa and stirring was continued at 40^ABOUTC. After 20 minutes, the reactor was degassed and opened. 3.3 g of total polyethylene were obtained.

Example WI. In this example, polymerization of ethylene was carried out in the presence of active catalyst obtained in situ by dissolving 80 mg of bis / pαntamlylicclipent^dien^ylo / ^ diπl you^andocyrkonu ^{and 3}5 mg 1,2-dicabbaim^de^kabooann / l3 / w ²° en? dichloromtanu. The barbit solution is then pushed with ethylene at atmospheric pressure for 1 minute, after which the suspension is poured into excess ethanol. The solid polyethylene was filtered off, washed with water and dried. 1.6 g of polyethylene were obtained.

Example VII. In this example, an active catalyst was obtained by reacting 46 mg bisipentamethylcyclopentadilyl / dimethiocirconium with 20 mg octabdeibborane / 22 / w^{5 en}? toluene. There was significantⁱⁿsyllables^gmanhole. Prov^s passing the ethylene through the solution within 1 minute the solution warmed up. The vial was opened and acetone was added to precipitate the polymer, which was filtered off, washed with acetone and dried. 0.32 g of polymer separated out was obtained.

DC example. In this example, it activates the active catalyst by reacting 40 mg bis / p ^ nttaethylcyclopentyldilyl / dihydriocirconium zirconia with 30 mg tridelkhydrido-7 and 8-baundltatoran^tri / n-but^andlb^andAIMR^about.wrfe^gand ^{in 5}0 en? Sluenu in a round necklace with a closure. The solution changed color from colorless ne poIMbrbccics-yellow. While ethylene was bubbled through the solution for 1 minute, the solution gradually warmed up in m2, as the polymer precipitated out of it.

Example X. In this example, an active catalyst was prepared in a test tube for NMR analysis, combining 50 mg bis / blntamtylcyclipentbdilnyli / dimethyl zirconium and ⁴⁰ mg ¹-^andkrbk^dand^dl^ikbiranu ^triⁿn^atat^sylb^andandother^andWeight in 1 cm? hl^ks ^^deutlro^bIncense and placing the solution in an N4R tube. After observing young NMR spectroscopy, the disappearance of the starting material was injected into the NMR tube with ethylene. A solid polymer precipitated from the solution.

Example 11 In this example, an active catalyst was also prepared in an NMR tube by dissolving 100 mg bis / 1,3-bts / trimyyisiilyl / iyiio]: nntadinyyio77-dimethyl^cyrkonu and ⁶⁰ mg lik8b^kadodl^kabiranu ^tΓi / n-but^andlb / ailnniswegi in 1 en? he^ks^adlutl iiblnzlnu and placing the solution in an NMR tube. The disappearance of the starting subsidence ή t in the H NMR spectrum was observed. After all of the zirconium compound had disappeared, ethylene was injected into the tube and solid polymer precipitated out of solution.

Example XII. In this example, an active catalyst was also prepared in a NMR tube by dissolving 100 mg / IPnnkkytytociCyopontanibnyln // 0, 3-bisttΓimty.'l.oslliio / cyilopnnb8dinyyl_7dίπιltyiocirconium and 70 mg of 1-iarbadodlkbiruyaniumⁱⁿg^{ow 1 en}? ^hl^ksb^deutlΓo^benzlnu, after^sm solution obtained^aboutr was placed in NMR tube.

159 193

The disappearance of the starting material was assessed by NMR and after complete disappearance of the starting zirconium compound ethylene was injected into the tube. A solid ethylene polymer precipitated from the solution.

Example XIII. In the example of tyra, the active catalyst was obtained by suspending 80 mg of bis (p-methylamethylcyclopentadienyl) / dimethyirconium and 50 mg of trin-butyl dodecarborate /^andmonio in 7 crn? toluene in a vial with a stopper.^pgovernment^s mixing the slurry. it changed color from colorless to yellow-green. After bubbling ethylene through the solution, a white-colored polymer precipitated within 30 sec and the solution was heated. 0.13 g of polyethylene was obtained.

Example XIV. In this example, the active catalyst was obtained by reacting 45 mm -is / J: entamethylcyclopopeitadienyl / diroethylcyckoid with 30 mg of tri-n-yl-carbamecarbaine undecylhydride in 5 cm? teluenu^fiolce this one ^kor^kiem. A solution <5r denounced the color from colorless to yellow. When ethylene is passed through the solution for 30 seconds. the solution heated the sieves as the polymer sieve added.

Example XV. In this example, the active catalyst was prepared by suspending 80 mg bis / amentam ^ tylocyclopcmtaeicnyl / dimetho <y^Γrkomu and 90 mg ris / 7,8edicarbamddel <arorano / aobr.lttnm / II^l/ N,^,N-^dęietyloamil^andęiwwe^gow 5 ern? toluene^fIolce bay ^kor^kiem. The solution has changed color from yellow to orange-purple, and excreted the strain. After passing ethylene through the solution within 30 sec, the solution turns dark purple and becomes a viscous sieve when the heat screens are significantly pronounced. The vial was opened and the solid and solid precipitated with ethanol. These ingredients were washed with a 10% aqueous sodium chloride solution, ethanol, acetone and hexane. 0.41 g of polyethylene was obtained.

Example XVI. In this example, an active catalyst was prepared by reacting 40 mg bęs / ίentamtylcyclopentadienyl / dimethyl-Zirconium with 45 mg ris / 7,8-dikarr Inedearborano / z ^^e.a ^ ee ^ l.ai^ml^l>^/ N, N-^dime^cyloanil^andęiwwe^gow KJ cm? toluene in a vial with a stopper. While the ethylene was passed through the solution, the mixture was solid hot sieve in miart as formed by the polymer sieve. The Fiolkt was opened and its content was diluted with acetone, filtered and dried. 0.33 g of separated polymer was obtained.

Example XVII. In this example, the active catalyst was prepared by reacting 40 mg of hand / pcntaiethylcyclopcntadienyl / dimethocarbon with 45 mg bis / 7.8 dearcarbaum^e^ ek^rrΓ8ro / n^ml8nu / I^/AND/ ^tri^mNo.^atutylrⁱⁱmy family ³⁰ cn? 'toluene in tolMe o^kΓ^AGLabout^ecmne^jcapped cap. Ethylene was bubbled through the solution for 1 minute. The solution became hot as a mite, as the polymer precipitated out of it. The kolbt was opened and its contents were diluted with acetone. The solid polymer was filtered off, washed with acetone and dried. 0.48 g of separated polymer was obtained.

Example XVIII. In this example, the active catalyst was prepared by suspending 100 mg of Bis / methylcyclopentaeienyl dihydrate / cyprom and 180 mg of Bis / 7.8-dicarb ^ medekaboramo / ^^ Ηθ ^ / ΙΙ¹/ tr^{/ m}nrbutyla^andittlmniwego in DO cm? toluene in tolMe o^andrągło^denmeJ at^je^mties 25⁰ cm? ^ ^ ik for the^gagreement^sm tart. et^slinen bar^bI will open through the solution within 10 minotes. The colbt was opened and the contents poured into hexane, filtered and dried. 2.98 g of polymer were obtained.

Example XIX. In this example, the active catalyst was prepared by suspending 105 mg of hand / _^-1,3-bis / tricethylsilyl / cyclocmnaed Cenyl 7 dimethyl zirconium and 90 mg bis / 7.8^diaarbaunde^cand^rrΓano / Koba^raanu^{to me/}I / NN-Umtyloanili.NEW in 50 cn? toluene in a circular form^kol^bnot with capacity ¹⁰⁰ you, with this rubber bag. et^ylen rrrrcto^{wrmc through}solution within 10 minutes. The flask was opened and its contents poured into ethanols and then evaporated. 2.7 g of polymer were obtained.

Example XX. In this example, the active catalyst was prepared by mixing 50 mg bis / cyclopcntaeienyl / dylctyl zirconium and 90 mg ris / 7,8ediaarrInedek8bcrrno / aobrltrin

159 193/111 / N, N-dimethylanilini (in a 50 cm v v 1.00 cm round bottom flask), crumble over this with a rubber stopper. When ethylene is passed through the solution for 1 minute, no signs of reaction have been observed, after which significant after 10 minutes, the flask was opened and its contents were diluted with ethanol and evaporated, 1.9 g of polymer was obtained.

Example XXI. In this example, ethylene was polymerized by reacting 69 mg bis / cyclopent8-dienyl / dimethiohafnium with 90 mg bis / 7,8-dikaΓbaundekabb8no / cobiltθnuiIII / N, N-UmethylaniUnUwej in⁵⁰ cn? -toluene in IrolMe the bottom of the bay tortok.^pWHO. passing ethylene through the solution after about 30 sec, turbidity was observed and the solution was warming up. After 10 minutes, the solution was poured into acetone, after which the polymer was filtered off and dried. Unocwy polyethylene with a capacity of 2.2 g was obtained.

Example XXII. In this example, ethylene was polymerized by reacting 50 mg bis / trirκϊtyOo3iliCocyclopoI «ntadinnyio / diπetyiohaί'nu with 45 mg bis / 7,8-dicarbanradekaborane / cobal tanu / III / NN-dtostylani. the flow of vial in this torture.^PWhen ethylene was passed through the solution, a polymer formed and the mixture warmed up. After 1 minute, the vial was opened and its contents were diluted with acetone and filtered. Linear polyethylene was obtained with a yield of 0.35 g.

Example XXIII. In this example, ethylene and 1-butene were copolymerized in toluene as a diluent by adding this mixture under a nitrogen atmosphere to a stainless steel autoclave^dexternal with a capacity of 1 dm ^ u^psculpture^dpreamplifier^hnitrogen containing 4 °⁰ cn? s / c^hego^,oxygen-free toluene, ³5 cm? toluene solution containing the totalizer obtained in situ from 50 mg bis / cyclopentadienyl / dimethyl zirconium and 45 mg bis ^. e-dktorbaun^dekaboi8bn / cobalt^bflax^onII / NN-dimethylanine. To a /^tabout^andlaw / todano ²⁰⁰ en? l-^butenu^,and then ethylene was injected under 0.84 MPa. The contents of the autoclave were stirred at 50 ° C for 30 minutes, after which the autoclave was cooled and degassed. The contents of the autoclave were dried in an air stream. An amount of 44.7 g of polymer was obtained. The melting point of the polymer was 117 ° and the analysis by means of an attachment spectroscopy (1R) showed the presence of about 17 ethyl branches per 1000 carbon atoms.

Example XXIV. In this example, ethylene and 1-butene copolymeric acid were kept in a thiacnine diluent by adding the mixture under a nitrogen atmosphere to a stainless steel autoclave,

3 with a capacity of 1 dm, previously purged with nitrogen and containing 400 cm of dry toluene containing no tylene and. ⁵0 cm? totoene solution of a totalizator containing⁷⁰ m^gbds / cykOoicntθdienylo / dilIctyiohbfna and 45 mg bis / 7,8-dicarbaundekiborabo / iobilalnuiaII / ^N,^N-^dthem^cylianil^andn^andiwc^gi. To autoltava was added ²° 0 cm IL-totenu, and the following^Epethylene was not injected at 0.84 MFa. The contents of the reactor were stirred at 50 ° C for 20 minutes, then the autoclave was cooled and degassed. The autoclave contents were dried in a povidt stream. A polymer was obtained with 75.1 g. The melting temperature of the polymer was equal

109 ° C, and analysis by means of an IR spectroscope showed the presence of about 29 branches of etytes per 1000 carbon atoms.

Example XXV. In this example, ethylene polymers were reacted by reacting 66 mg l-blsCcykiipintad Cenylttyaib-3 - dimethyosiacckliobutane with 88 mg bis / 7.8-^ditobbanndckαbiΓano / kobalt8bn /^andII / N^N-^dimtylianiUn^andand ate^gand in 25 cm? toluene in toltde dead-end closed with a stopper. Dark solution when ethylene is passed through. After 10 minutes, the flask was opened and its contents were diluted with ethanol. The polymer was filtered off, washed with ethanol and acetone and then dried. Polyethylene was obtained with a yield of 0.09 g.

Example XXVI. In this example, the ethylene polymers were named by reacting 61 mg of 1-bisCckliocinαodCinyio / cyi0ina-3-dimethylsaccykibutane with 87 rog bis / 7, - ditorbanndekabi ^ 110 ^^ 31 ^ 1- ^ 11 /^N,^N-^dimtylibniUniiwe ^gthat ²⁰ cm? tolien in^kolbi.e was dizzy with a stopper. When ethylene is passed through the solution, the polymer precipitates and 3am of solution warms up. After 10 minutes, the vial was opened and its contents were diluted with ethanol. The precipitate was filtered off, punctured with ethanol and dried. Polyethylene was obtained with a yield of 1.41 g.

Example XXVII. In this example, ethylene was polymerized by reacting 82 mg of 1-bis / cyclopentadienyl / haf ra-3-dimethylsilylcyclobutane with 88 mg bis / 7,8-dicarbaund^andborane^aboutkkłoltanu /^atIl / N, N-^dimtyllanilin^lester ^{in 20} cm? toluene in^kol^bie round circular stopper. By passing ethylene through the solution, a polymer precipitated and the solution itself was heated. After 5 minutes, the flask was opened and its contents were diluted with ethanol. The polymer was filtered off, usually with ethanol and dried. Polyethylene was obtained with a yield of 1.54 g.

Example XXVIII. In this example, ethylene was polymerized by reaction of 67 mg bis / cyclopentiethyl // 2,3-dimethyl-1,3-Uutadίnyl / zirconium with 88-Zil-3-rba / o-dicarbonate / cobalt / u / III / N, N-dimethylanilyl in 5⁰ cm? ^ luene in a -PuteUe with a stopper. Ethylene was passed through a solution that was getting warmer and warmer. After 15 minutes, the bottle was opened, and its contents were diluted with ethanol. The polymer was filtered off, washed with ethanol and dried. A polymer was obtained with a yield of 1.67 g.

Example XIII. In this example, ethylene pollmerase reacting 40 mg bis / cyclopeotadienl. III / 2,3-diratyl-1,3-Uruladione / hafn / with 43 mg bis / 7, θ-dikarl / ondekBbora "ro / kotaltara.^N^ ^ DimtyloaniUn acid ⁱⁿ 5 ° cm³ toluenes in a bottle with this ^kor^kiem. Ethylene was passed through a solution which became cloudy within 30 sec. After 20 minutes, the bottle was opened and its contents were diluted with ethanol. The solid polymer was filtered off, washed with ethanol and dried. A polymer was obtained with a yield of 0.43 g.

Example XXX. In this example, polymethylene ethylene reacting 55 mg / J »otαmαyllcykⁿabout^lFri.^aboutadiet [^aboutlo^lTETRAM^tyll- 'J? -ethylene-? -c^sntadienylo aza ^ / ^ u feoylocyrk ^{from 4}5 m^gbis / 7,8-dⁿcarba / o^delnbrrano / ^ kntl^rαflax /^/II / ^N, N^dthem^tyloanil^aboutnlwte^gthat ²⁰ cm? toluene in a round-bottomed flask with a stopper. By passing ethylene through the solution, a polymer began to form almost immediately, while a large amount of heat was released. After 5 minutes, the flask was opened and its contents were diluted with ethanol. The precipitate was filtered off, washed with acetone and dried. Polyethylene was obtained with a yield of 0.55 g.

Example IXCI. In this example, the ethylene polyether was reacted by reacting 80 mg / ptotamylcyclopope Oadzhenol / tttΓamttylycyclopopta Zitnyll / tt! Nzylohαfnu with 60 mg bis / 7.8dik^andΓba / Sun^tnboΓlno^0laboutⁿl^rtanu^0/II / ^N,^N-ⁿJakers^llanilani^ln^lthose^gabout ^{in 50} cm? toluene in a closed Puttate. Ethylene was bubbled through the solution for 10 minutes. The polymer precipitated and the solution warmed up. The bottle was opened and its contents were diluted with ethanol.

The solid polymer was filtered off, washed with acetone and dried. 0.92 g polyethylene was obtained.

Example I5KII. In this example, ethylene was polymerized by reacting 0.42 g ris / trimethylsillloCklloennaadtonesOodimethyohohnone with 0.08 g ris / 7.8zdicarb / healing / rtltano / kolrltano /^/II / N, tt-dimethylanilide in 1 (5 cm 5 toluene. Part^ścut these^gabout solution /^0,4 cm ?? injected at 300 MPa into an autoclave containing ethylene compressed at 150 M ^ a, heated to 16O⁰C. After 5 seconds, the autoclave was overjoyed. 2.1 g of polyethylene with a weight average molecular weight of 144,000 and a molecular weight distribution of 2.9 was obtained.

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