DE1906257A1 - Process for the production of ethylene homopolymers and copolymers - Google Patents

Description

DR. ELISABETH JUNG, DR. VOLKER VOSSIUS. DIPL.-ING. GERHARD COLDEWEY

PATENT LAWYERS MDNCHEN 23 - S 1 E G E S T H ASSE 26 - TEL EFON 345067 ■ TE LEG R AM M-AD HESSE: INVENT / M ONCH EN

U.Z .: E o53 (Be / Vo) February 7, 1969

POS-16 639 ■.

SUMITOMO CHEMICAL COMPANY, Ltd.

Osaka, Japan

"Process for the production of ethylene homopolymers and copolymer! seeds

Priority: February 8 , 1968, Japan, No. 8o58 / 68

The invention relates to a method for producing Ethylene homo- and copolymer! Seeds using a new one Polymerization catalyst. The invention also relates to the new catalyst for use in the process.

Many catalysts are already used for the polymerization of ethylene! known, such as the so-called Ziegler-Natta catalysts, the catalysts proposed by Phillips Petroleum Co. and Standard Oil Co. and according to their own proposal

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POfTtCHfCK ACCOUNT: MÖNCHEN KH7 »- IANK ACCOUNT: GERMAN IANK A. O. MÖNCHEN. LIOPOLO8T «. 71. KTO. Nile. HVSIM

Catalysts containing vanediura phosphorus compounds which a compound obtained by reacting a vanadium alkoxide obtained with a phosphoric acid or a phosphoric acid ester as well as containing an organoaluminum compound, with which polyethylene can be produced in a particularly smooth manner.

Since the known catalysts in terms of their activity, Lifespan and effect when used in solvents not necessarily satisfactory, there is a need for a manufacturing process for ethylene homo- and co-polymer * sabe with the help of better catalysts.

It has been found that reaction products of certain other Vanadium compounds instead of vanadium alkoxides with phosphoric acids or phosphoric acid esters together with organoaluminum compounds as a catalyst result in particular advantages.

The process according to the invention for the production of ethylene homo- and copolymer seeds by polymerizing ethylene alone or together with at least one other olefin or diolefin in an amount not exceeding about 1 ο MoI .- ^ in the presence of a Catalyst made from a vanadium-phosphorus compound and an organoaluminum compound is characterized by the fact that one a catalyst used as a vanadium-phosphorus compound a compound, which by reacting a vanadium compound alt at least one halogen atom and / or at least one acetyl *

0098177J772

acef.onat.gruppe _f die an. Vanadium are bound with a shoe phosphoric acid aer general formula I.

(K ¹ O) _1n P (O) (OH) ₃ ^ (I)

in which R denotes a hydrogen radical and nt has the value ο, 1, 2 or 3 »at, or a mixture of two or more such compounds, and as organoaluminum ¹ one of the general formula II

ο
in which R an AXkylgx-group, 1 a hydrogen atom _ff an alkoxy

gnxppe or * denotes a halogen atom and η denotes the value o, 1, 2 or 3 hat, ex-j-tbäJ +.

The catalyst used according to the invention has the following advantages

1) The vanadium-phosphorus compound can be easily and with high Yield can be produced. It can also be in either liquid or solid form can be obtained by the Reaction conditions can be changed, and therefore can be in the most suitable form either as a solution or in the form of a suspension be used in a fine distribution in a solvent in the process.

2) The catalyst has a considerably higher activity ala a catalyst made from vanadium tetrachloride and an organoeruminum compoundj, as it is used as a common Ziegler catalyst.

3) The activity of the catalyst will be during the polymerization

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• 19Ö6257

Maintained for a long time, the unit of quantity of polymer formed is large, and the amount of catalyst components contained in the polymer, especially components from the transition metal compounds, is so small that the polymer is discolored by esters the catalyst components is largely avoided.

4} The catalyst results in a polymer that is more beautiful in shape a slurry of the reaction i8ch precipitates as a Product made using a common vanadium compound and an organoalurainiura compound as a catalyst-obtained .'-- " wirdj so that the polymer yield, based on the used Solvent amount, is higher and the _Äi5hylenp: olymeris'ation v / can be carried out more economically *

The vanadium compound used to produce the vanadium-phosphorus compound as part of the catalyst used according to the invention is a compound whose vanadium atom is directly linked to at least one HBlog atom or at least one acetylacetonate group or both at least one halogen atom and with at least one acetylacetonate group. Examples of such Vanadium compounds are vanadium oxychloride-di-n-amyloxide fflOGl ( On-Am) «7»

, Vanadium Oxydichloriä-

mono-n-butoxide //OClgfo-n-Bu),./, vanadium oxydibromide mono-isopropoxide ^ 0Br ₂ (OI-PrJJ ^ ₁ vanadium cytrichloride, vanadium oxytribromide, vanadium tetrachloride, vanadiurate tetrabromide, vanadium tetraiodoyl oxide,

009 8 17/1772 _gÄ0

(OEt) 2 »EtOH ^, vanadivundichlorid-ariso-amyloxid ^ onyl alcoholate

(Oi-Am) ₂ ^ i-AmOHT ", vanadium oxydichloride, vanadium trir chloride, Vanadivunoxydiacetylacetonat ^ tTO (ac ac) ^ J wtä vanadium triacetylacetonate ^ (acacKJ ^, where in the given formulas Am the amyl group, Bu the butyl group, Pr the propyl group, Et denotes the ethy group and acac denotes the acetylacetonate group.

As the phosphoric acids, the connection for the preparation of vanadium-phosphorus Ϊ used as a component of the catalyst used in the invention, for example, orthophosphoric acid _# Pyrophosphoreäure, metaphosphoric acid, polyphosphoric acids and Phoephorsäureanhydrid come into question. Examples of phosphoric acid esters that can be used are phosphoric acid monoethyl ester, phosphoric acid monoethyl ester, phosphoric acid diethyl ester, phosphoric acid mono-n-butyl ester, phosphoric acid di-isobutyl ester, phosphoric acid

rn- odex r ■

acid mondf-isoamyl ester, phosphoric acid dihexyl ester, phosphoric acid di-n-octyl ester, Phosphoric acid dilauryl ester, phosphoric acid monostearyl ester, Diallyl phosphorate, diphenyl phosphorate, Phosphoric acid monophenyl ester, phosphoric acid triethyl ester, Tri-n-butyl phosphoric acid and triphenyl phosphoric acid.

The first component of that used according to the invention Catalyst β used Vanadium-Phosphorverbiiidiir.g is through Implementation of 0.1 to 1 mol, vorsugsweiee 0.5 to 2 hols Phosphoric acid and / or the phosphoric acid ester »per mole of

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Vanadium compound? manufactured, wabea. Also, there are more different phosphoric acids or esters (depending on which can be used, the reaction can take place in the absence of a reaction medium; however, because of the need to stir the reaction mixture or remove the heat of reaction, the reaction in durehaufuhren presence eiiiea solvent. Preferred solvents are Kohlenwasaerstoffe and alcohols such as hexane, heptane, Cyelohexan, _{Benaol? t} fll toluene xylene, ethanol ,, butanol, amyl alcohol and octyl alcohol.

pie implementation between the vanadium compound and the phosphorus » , acid and / or the phosphoric acid ester can be used at binary temperature between ~ 8o ° C and 15o ° C. Are preferred however, reaction temperatures between 2o ° C and 13o ° C,

The reaction product can be used without separating off the solvent can be used or it can be removed from the solvent by evaporation being freed to dryness, it usually represents a viscous liquid or solid powder.

As an organoaluminum compound for the production of the invention The catalyst used is preferably a compound whose general formula II H is an alkyl group having 1 to 8 carbon atoms · If the group X of the general form in is an alkoxy group, becomes an alkoxy group with 1 to 8 carbon atoms preferred. If X is a halogen atom, it becomes chlorine, bromine or iodine as a halogen atom preferred·' -

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- - SAD ORIGINAL

Examples of organoaluminum compounds are trimethylaluminum, "Triäitliylaluminium, TrAisobutylaluininium, Trihexylali" nin.iura, Diföthylaluiainiuramonoehlor id "ionoäthylaluminium ~ · _r dichloriö AthylalurainiiiMeesquichloriö, Isobutylaluminiumdi ·?.."Chlorine; _p * fl Äthvlaluttiiniiundibromid, DIAE ^ hylaluiainiumhydrid and D \ ä + "hylalustiriiuniäthoxid These connections can also be used as ftcfminithR by two or more connections.

The polymer? -Dr.

wnter-berüaksiohtigiaag the shape and size of the reactor, dee type of reaction and the Katalyisavoj .- 'konseitti'atioh selected. The Ethylenei.TUspeioung; takes place at a pressure of 1 bit 300 kg / cm, vorKUgKweisG 1 to 50 kg / om «, .- The polymerization know switjchen -5o ° C and 15o ° G «It is common However, a temperature between 10 ° O and 100 ° C was used.

In order to improve the penetration of the catalyst and the polymer obtained and to dissipate the heat of polymerisation, the polymerisation is preferably carried out in the presence of an inert solvent. Examples of useful solvents are conventional hydrocarbon solvents and halogenated hydrocarbons, such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, Ββηκοί, toluene, xylene, xthylbenaol, chlorobenzene and dichlorobenzene. These solvents are used either alone or as a mixture.

The amount of the catalyst components used may vary depending on

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ORIGINAL

the type and amount of the solvent used and the desired polymerisation time ¹ as well as the corresponding polymerisation! Onconditions, such as reaction temperature and pressure, are usually and preferably used, however, for every 1,000 parts by weight of solvent, about 0.01 to 1 parts by weight of the vanadium phosphorus compound and about 0.01 to 8 parts by weight of the organoaluminum compound are used.

According to the process according to the invention, not only ethylene homopolymers but also copolymers of ethylene with other olefins or diolefins are obtained. Examples of monomers that are sierΐ with ethylene he / indungo? Emäß copolymer!, Are propylene, butene-1 and Ruxen ~ l e_le olefins and butadiene, isoprene, hexadiene, Cyclooctaüien and dicyclopentadiene as diolefins These monomers grazing such _s copolymerized that Λ their amount in the copolymer is not more than about 10 mol. The ethylene copolymers have improved physical properties and are easier to process.,

If the polymerization is carried out in the presence of hydrogen, in this way the average molecular weight of the polymer obtained can be regulated.

The polymer produced according to the invention can be dried from the solvent and dried immediately; will. If desired, however, characterize the polymer ₉ naohdem it optionally separated from LöBuagfiraittel ia _s are freed from KaLalys & torrüokständea ₉ by the Kata ^ satorrUckstfinde by adding

009817/177 2

of an alcohol such as methanol, propanol or butenol, soluble be made. The residue-free polymer is isolated and then dried. The manufactured according to the invention Homo- and copolymers have excellent properties, especially high mechanical strength, high softening point, high melting point and low Embrittlement points can therefore be achieved by blow molding, injection molding, extrusion and compression molding using powder are processed. '

The method of the invention is carried out by the following Examples explained in more detail.

Example 1

3s86 g vanadium tetrachloride wurdsi 4 _f 2o g of dibutyl phosphate in 1oo ml of benzene mixed "and the mixture was reacted for 4 hours at 8o ° C. After the benzene had been distilled off, the reaction product was dried at 100 ° C. for 5 hours and gave 7.1 g of a brown-black viscous mass which was used as the first catalyst component.

A 1 liter autoclave with electromagnetic stirring was evacuated and flushed with nitrogen and 500 ml of n-heptane were introduced. 30 mg of the first catalyst component and 0.62 g of ethylaluminum sesquichloride as the second catalyst component were placed in the autoclave. Subsequently was. Ethylene under a pressure of 5 kg / om on AEEN pressed autoclave and reacted for 2 hours at 7o ° C "lVechd" workup viuvten 2o g polyethylene weiies

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"* *""'"'' BAQ '.ORIGINAL

- 1o

powder received. The polymer had a viscosity number of 15 »5 dl / g» measured with an Ostwald viscometer in xylene at 12o ° C.

It became ethylene under the same conditions as according to

Example 1 polymerized, but the ethylene pressure 12 kg / cm and additionally hydrogen was injected at a pressure of 9 kg / em «Bs litter 31, ο g polyethylene obtained.

For comparison purposes, the experiment was repeated »where as Catalyst a mixture of 3o mg of vanadium tetrachloride and 0.62 g of ethylaluminum sesquiehloride was used. The polyethylene yield was only 13 »ο g,

Example β

3ρ46 g Vanadiuraoxytriehlorid was mixed with 3 ₉ o8 g phosphoric acid diethyl ester in 100 ml of heptane and the mixture reacted for 2 hours at 100 ° C. After the heptane had been distilled off, the product obtained was dried for 30 minutes at 50 ° C. Yield 5.9o g of a vanadium-phosphorus compound.

Using 3o mg of the reaction product obtained as the first catalyst component and 0.64 g of Ithylaliuainiumdir Chloride as the second KataLysatorkoaponetite was polymerized according to Example 1 under an ethylene pressure of 12 kg / cm and a hydrogen pressure of 9 kg / om ² polymerisitrt. Auebeutt 21 g Polyäthyleii.

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11 -

The viscosity number of the polyethylene was 1.7 dl / g.

Bgiggigl 4

It was 8.5 g of vanadium dichloride-di-isoamyloxid- ^ soaioylalkoholtit mixed with 5.3 g of triphenyl phosphoric acid in 100 ml of benzene and the mixture reacted at 80 ° C. for 1 hour. After this Dist-iliating the benzene, the residue was 4 hours

ο yield /

Dried 100 ° C./ "11.5 g of a vanadium-phosphorus compound. G

3o mg of the reaction product and 0.57 g of triethylalurainiura were placed in an autoclave as the catalyst components and according to Example 1, ethylene under a pressure of 1 kg / cm impressed and polymerized. Yield 1.3 g of polyethylene. The viscosity number of the polyethylene was 15. o dl / g.

8.53 g of vanadium oxydiacetylacetonate was mixed with 7 »5 g of phosphoric acid di-n-octyl ester mixed in 100 ml of benzene and the mixture reacted at 80 ° C. for 1 hour. After distilling off the Benzene, the residue was dried at 100 ° C. for 1 hour. Spoil 15.1 g of a vanadium-phosphorus compound.

Using 3o mg of the vanadium-phosphorus compound and 0.61 g of diethylaluminum monochloride as catalyst components ethylene was polymerized according to Example 1, an ethylene pressure of 1 kg / cm was used. Yield 1.7 β polyethylene. The viscosity number of the polyethylene was 14.9 dl / g.

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1 1 II * ■ I * I »

- 12 -

Example 6 _@ '

6.56 g ν8ηΕο1υπ2θΧ ^ ο1ι1θΓί £ ΐ-αΐ-ι> -6ϋ37ΐοχία were mixed with ο.90 g phosphoric acid in a liquid mixture of 50 ml benzene and

became/

15o ml »amyl vermiseht, and reacting the Gemisoh / o hours at 125 ⁰ C. After distilling off the solvent and drying the residue for four hours at 100 ° C, 5.9 g of a vanadium-phosphorus compound was obtained «· _

Using 3o mg of the reaction product and ©, 62 g Ethyl aluminum sesquichloride was used as a catalyst component Ethylene polymerized according to Example 1, with the ethylene pressure 2

Was 12 kg / cm and hydrogen under a pressure of 9 kg / cm was pressed, yield 64 g of polyethylene, the viscosity The number of polyethylene was 1.29 d2 / g «

Example 7

Using the same catalyst as in Example 6, a polymerization of ethylene was carried out according to Example 1, but initially Io g of propylene was added to the autoclave and worked under an ethylene pressure of 15 kg / cm ² and a hydrogen pressure of 6 kg / cm 41 »3 g of a powdery copolymer of ethylene and propylene with a viscosity number of 1.64 dl / g were obtained.

From the absorption of the copolymer la infrared spectrum at 1378 cm "it was found that 9» 3 methyl groups in the copolymer 1 000 carbon atoms each.

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Claims (12)

gat enJ b-an s P r 1 · Process for the production of ethylene homo- and copolymers by polymerizing ethylene alone or together with at least one other olefin or diolefin in an amount of at most about 10 mol, - ?? in the presence of a catalyst composed of a vanadium-phosphorus compound and an organoaluminum compound, characterized in that a catalyst is used which, as the vanadium-phosphorus compound, is a compound which is obtained by reacting a vanadium compound with a few halogen atoms and / or at least one acetylaoetonate group are bound to vanadium, with a phosphoric acid or a phosphoric acid ester of the general formula (R ¹ O) _a P (O) (OH) _3-10 in which R denotes a hydrocarbon radical and m has the value 0, 1, 2 or 3, or a mixture of two or more such compounds, and an organoaluminum compound of the general formula in which R is an alley group, a web β er β toff atom, an alkoxy group or a halogen atom and η has the value o, 1, 2 or 3 contains. 2. The method according to claim 1 »thereby gektnnntiohn β t that ethylene is copolymerized together with propylene, butene-1" or hexene-1. 009817/1772 w. 14 - 3. The method according to claim 1 "or 2, characterized ge character- ises that one sur preparation of Vanaditua-RIOB phorverbindung as Vanadiumverbin & ung Vana & iumoxyehlorid-di-narayloxid, vanadium oxydichloride, mono-n-butoxide, Vanadiumoxydibromid-Mono 'i-propoxide , Vanadium oxytrichloride, vanadium oxytrichloride, vanadium tetrachloride, vanadiim tetrabroiBid, vanadium tetraiodide, vanadium dichloride diethoxyethanolate vanadium dichloride dt-iso-ainyloxid ^ yladiadiyl alcoholate, vanadium tylacetone, vanadium aiocyanate, vanadium acetylacetone, vanadium acid acetylacetone, vanadium acetylacetone, vanadium acetylacetone, vanadium acetylacetone, vanadium acid acetylacetone, vanadium acetylacetone, vanadium acid acetylacetone. 4.Verfahr s according to claim 1 to 3 _f characterized ge k e η η is characterized in that for the preparation of the vanadium-phosphorus compound ale phosphoric acid or phosphoric acid ester orthophosphoric acid, pyrophoaphoric acid, metapheaporic acid, poly phosphoric acid, phoephoroic anhydride, mono-phosphoric acid, mono-phosphoric acid, phosphoric acid mono-phosphoric ester, phosphoric acid mono-phosphoric acid -iÄutyl-ester, Bioephoreäuredi-Isobutyiester »Phosphoreäurejaono-isoaylester, Ihosphorsäuremonp-n-amyleater, Biosphorsäuredifeexylester, i octyl Phosphorsäurtdilaurylseter, aryleeter, PSiosphorsäurediallyleater used Hiosphoraäurediphenylester _s, Fhosphoreäuremonophenylester, Phosphorsäuratriäthylester, Hiosphoreäuretri-n-buty! ester, Shosphorsäuretripfeesiyleeter or a mixture of several such compounds. 5. The method according to claim 1 to 4, characterized in that g ® k β η η - that one for the production of Venedlum » 009817/1772 O phosphorus compound, 1 to 1o mol of the phosphoric acid or the Pho3phorsäureesters "or a mixture of such Verbindlangen used per mole of the Vanadiuraverbindung and the reaction is carried out at a temperature of -80 ⁰ C to l5o ° C. 6. The method according to claim 1 to 5, characterized in that the organoaluminum compound Triiae thy! aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, Diethyl aluminum monochloride, monoethyl aluminum dichloride, Xthylaluminum sesquichloride, isobutylaluminum dichloride, ethylalurainium dibromide, diethyl aluminum hydride, diethyl aluminum ethoxide or a mixture of several of these compounds is used. 7. The method according to claim 1 to 6, characterized in that g e k e η η 2eieh.net, that the polymerization is carried out in an inert solvent. 8. The method according to claim 7, characterized in that that one per 1000 parts by weight of solvent o, oo1 to ( To parts by weight of the vanadium-baophosphorus compound and ο, οί up 100 parts by weight of the organoaluminum compound used. 9. The method according to claim 7 to 8, characterized ge k e η η, that the inert solvent used is a hydrocarbon or a halogenated hydrocarbon used. 10. The method according to claim 9, characterized in that the inert solvent is fentane, hexane, 0098 17/1772 bath Heptane, octane, cyclohexene, methylcyclohexane, benzene, Toluene, xylene, ethylbenzene, chlorobenzene or dichlorobenzene are used. 11. The method according to claim 1 to 1o, characterized in that the polymerization at a temperature of -5o ^c C to 15o ° C and an ethylene pressure of 1 to 3oo leg / cm ^{2 is} carried out. 12. Catalyst for use in the process of claim 1 to 11, characterized in that he has the Reaction product of a vanadium compound with at least a halogen atom and / or at least one acetylacetonate group, which are bonded en vanadium, with a phosphoric acid or a phosphoric acid ester of the general formula (R ¹ O) _m P (O) (0H) ₃ _ _m in which R denotes a hydrocarbon radical and m den Has the value 0, 1, 2 or 3, or a mixture of two or more such compounds as well as an organoaluminum compound of the general formula m the R is an alkyl group, X is a hydrogen atom, a Is alkoxy group or a halogen atom and η is the value o, 1, 2 or 3 contains. 009817/1772