DE1172429B - Process for the polymerization of monomers having at least one polymerizable, olefinically unsaturated double bond or of mixtures of such monomers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Kl .: C 08 f;

C08d

German KL: 39 c- 25/01

Number: 1172429

File number: B 44363 IV d / 39 c

Filing date: April 18, 1957

Opening day: June 18, 1964

It is already known, ethylene under pressure with the help of catalysts made of aluminum chloride, titanium tetrachloride and polymerize aluminum powder. It is also known from ethylene and α-olefins thereby producing polymers that these monomers in the presence of an organometallic Compounds of metals of groups I, II and III of the periodic table and compounds of Metals from IV. To VI. The catalyst formed by the side group of the periodic table polymerizes. ίο

It has now been found that polymers with improved and new properties are obtained if one monomers with at least one polymerizable olefinically unsaturated double bond or Mixtures of these polymerized in the presence of a catalyst consisting of at least one by a Metal of groups I to IV of the Periodic Table of metalized hydrocarbon compounds (component 1) and at least one compound of the Friedel-Crafts type (component 2 [b]) and one the catalyst-modifying polar compound (component 2 [a]) and / or a carrier or carrier mixture (Component 3) exists.

Catalyst systems consisting of components (1) and (2 [b]) with a component (3) result in the polymerization of monomers or monomer mixtures, polymers that differ in terms of their physical properties differ from those obtained by polymerisation of polymers Monomers or mixtures of monomers in the presence of catalyst systems, which also have the Component (2 [a]) contain, are obtained.

For the polymerization of dienes or polar monomers, preferably in the absence of olefins, is preferably used as component (1) monometalated in inert hydrocarbon solvents (which does not involve the organometallic compound of the catalyst during its manufacture or use metal exchange) insoluble metal hydrocarbon compounds of alkali and Alkaline earth metals, thez. B. sodium, potassium, rubidium cesium, calcium, strontium and barium, or Mixtures of these.

The components (2 [b]) and / or (2 [a]) making up the catalyst systems can be mixed with the component (1) react, form complexes or attach to them and thereby metalated organic Compounds give rise to the metal substituents or metal complex substituents, the whole or are partially different from those of component (1) which are used to form the catalyst systems to be used.

Process for the polymerization of monomers
with at least one polymerizable olefinically unsaturated double bond or of
Mixtures of such monomers

Applicant:

Dr. Oliver Wallis Burke jun.,

Grosse Pointe Park, Me. (V. St. A.)

Representative:

Dipl.-Chem. Dr. rer. nat. H. Kainer,

Patent attorney, Heidelberg, Steubenstr. 22-24

Named as inventor:

Oskar E. H. Klopfer, Clawson, Mich.,

Oliver Wallis Burke jun.,

Grosse Pointe Park, Me. (V. St. A.)

Claimed priority:

V. St. v. America dated April 25, 1956 (580 642), February 19, 1957
(641 046 and 641047)

When the component (2 [b]) is used to prepare the catalyst, it is particularly desirable to use at least one compound of the Friedel-Crafts type, the metal of which in different Valence levels can occur.

Furthermore, the order in which the components from groups (1), (2 [a]) and (2 [b]) are added, an influence on the structure of those formed in the metalated catalyst mixture Have complex substituents. The order can also change the nature of the presence of these catalysts affect the polymers produced.

The above-described catalyst systems enable the production of polymers from olefins, Vinyl or diene monomers or from mixtures of monomers. Here are new polymers with receive new and valuable properties, e.g. B. Polyolefins with improved elastic properties or crystalline structure.

For the preparation of the catalyst to be used according to the invention and for the preparation No protection is sought for the catalyst components at this point.

409 600/419

3 4

Component (1) f) Unsaturated hydrocarbons with aromatic

Substituents such as those given above with aro-

The oils that were substituted for the production of the new catalysts, mathematical hydrocarbons, were used Component (1) consists of one or fine, such as vinylethylene, isopropenylbenzene, «-Me-

several metalated hydrocarbon compounds. 5 thylstyrene, including poly- \ -methylstyrenes

The metals of these metalated hydrocarbons - the di-, tri- and tetramers, the vinyl toluenes,

compounds from groups I, II, III and IV can be diphenylethylene;

of the periodic table. From group I.

this includes lithium, sodium, potassium, rubidium, g) acetylene hydrocarbons, their homologues Cesium, copper and silver, from Group II beryllium, io and the cyclic and aromatic acetylenes. Magnesium, calcium, strontium, zinc, cadmium

and mercury, from group III boron, aluminum, these listed, which form metal compounds-

Scandium, ytterbium, lanthanum, the metals of the hydrocarbons can optionally contain further rare earths, gallium, indium, and thallium, carry substituents provided that these do not Group IV titanium, zirconium, thorium, germanium, 15 the catalytic effect of the catalysis tin to be produced, Lead into consideration. affect goals.

If the catalyst component (1) consists of a For the preparation of the organometallic compounds

Hydrocarbon metal compound consists of the metals of groups I, II and III of the periodic Metal from groups I, II, III and IV of the Periodic Table are organic halides with metals see system, including the group of rare 20 implemented in a known manner. The ones used here Earth metals. If the catalyst component is organic halides, halogen-substituted ones can be used if, on the other hand, an organometallic halide, its metal will be organic hydrocarbons, the coals of which are made of groups II, III and IV and the rare hydrogen radicals above as components of the Or-earth metal group chosen. ganometallverbindungen were called. You can

The organometallic halide compounds can be substituted by two or more halides. Superior Metals can only have one halogen atom, although in the examples generally the mono- or tetravalent metals, on the other hand, two or three substituted halides can be used Halogen atoms and a hydrocarbon radical or two, three, four and even five times one or two halogen atoms and two hydrocarbons substituted water are used. Have scraps of fabric. 30 The substitution can also take place in such a way that residual

As halogens, fluorine, chlorine, bromine and iodine are present in the compounds into consideration. or that in these unsaturated compounds

The halogen atoms of the organometallic halides will result. Nevertheless, such compounds can be replaced by hydrogen, for example still effective as a catalyst component (1), for example by reaction with a metal hydride 35
[Component (3)] such as sodium hydride. Component (2 [a])

In addition, they can be exchanged for polar groups, e.g. B. by reaction with alkali The catalyst-modifying polar vermetall Compounds containing the compo-compounds are as complexes or as complex components (2 [a]). 40 sculptors applied. They close the complexes

The hydrocarbon component of the non-poly-forming organic donor compounds, the sour meres metallized component (1) can consist of a substance and / or N and / or sulfur and / or selenium Remainder consist of a hydrocarbon and / or tellurium and / or halogens and contain is derived from the following groups: less than 32, preferably less than 18 carbon

Containing 45 atoms of matter, a. In certain cases you can

a) Paraffin hydrocarbons, such as methane, ethane, also formed from the monomers of these classes Propane, butane, isobutane, pentane, isopentane, polymers can be used. Such donor compounds in hexane, the isohexanes; fertilize include organic acids, amino acids,

b) Hydrocarbons of the olefin type, such as ethylene, ^KetOn ^ ^Dike ! TV Ι ^ ΐ ^ 'Λο ^' _t ^E i ^te \ ^Ket ° "Propylene, the butenes, isobutenes, the pentenes; dfe ⁵ ° f ^er ^ ^Ath _M ^er ; ^{A Ikc} £ ^O _t ^le 'P ^ nole ureas, nurse, isopentenes, the hexenes, the isohexenes: ^{amides' N "nle'. 1} ^ ⁰ "" ^nd N.troso connections,

^r thioethers, oxythioethers, mercaptans, mercaptoethers,

c) the cycloparaffin and cycloolefin hydrocarbon thiophenols, sulfones and the sulfur substances mentioned, such as cyclopropane, cyclobutane, cyclopentane, compounds analogous selenium and tellurium compounds Cyclopentene, cyclohexane, cyclohexene, isopropyl 55 and halides. Furthermore, the modicyclohexenterpen as well as their derivatives; fying polar compounds from oxygen

d) Aromatic hydrocarbons, such as benzene, or nitrogen-containing free radicals generate-alkylbenzenes, biphenyl, alkylbiphenyl, other substances such as alkiper oxides, or azo-polyphenyls, including the naphthalenes. ^{bl "üun} g ^s öestenen

Azonaphthalenes such as methylnaphthalene; ^6o . ^SoI ° ^hey donor compounds include continued

^r jr j _ene J ₆ J. _o b _s compounds listed one, in

e) the hydrocarbons of the paraffin type with aro- which the active hydrogen, such as. B. in alcohols, matic substituents including the above phenols, mercaptans, thiophenols and enols listed paraffins, those with the above-mentioned forming ketones, etc. by a suitable metal th aromatic hydrocarbons, such as To- 65, which was selected from the metals, luene, xylenes, isopropylbenzenes, mesitylene, ethyl the as substituents of component (1) or the benzenes, ethyltoluenes, ethylxylenes, alkylpoly component (2 [b]) can be used. pre-condition phenols, alkylnaphthalenes, are substituted. is, however, that the metal with the metal compounds,

5 6

those in the other catalyst components or cobalt, nickel into consideration. The liquid or low-melting oxygens which are catalytically compatible are particularly advantageously used in the other catalyst component. halides such as VOBr ₃ , VOCl ₃ , CrO ₂ Cl ₂ .

These complex-forming, oxygen and / or nitrogen particularly active catalysts are obtained

substance and / or sulfur-containing donor agent 5 if the catalyst component (1) with at least In certain cases, bonds can be a Friedelals consisting of an oxyhalide alone the catalyst-modifying polar Ver Crafts component (2 [b]) and with at least one bond (2 [a]) can be used. other Friedel-Crafts component (2 [b]) implemented

Furthermore, these complex-forming donor will be.

Compounds with one or more metalated io The active Friedel-Crafts catalysts polymeri-hydrocarbon - Metal halide compounds, if necessary, together with supporting ones be bound complex, e.g. B. with the mixed Friedel-Crafts catalysts olefins, vinyl and diene-alkyl and / or aryl metal halide, including hydrocarbons and mixtures thereof. If the the fluorine, chlorine, bromine and iodine metal alkyl or supporting Friedel-Crafts catalysts alone -aryl compounds. The hydrocarbon components 15 or in connection with catalyst component (1) These complexing compounds can be used to derive the resulting catalysts usually not very active from the same hydrocarbons as those of the generators. It is therefore Component (1). As metals for such complexing- recommended at least a small amount of The compounds include both the alkali and one or more of the active Friedel-Crafts alkaline earth metals as well as the metals of the other 20 type compounds together with these auxiliaries below Friedel-Crafts compounds mentioned by Friedel-Crafts type compounds to use Component (2 [b]) and lead into consideration. active catalysts with the catalyst component (l)

Furthermore, this complex-forming donor can be obtained.

Compounds with one or more of the following If polymerizable diene hydrocarbons

the Friedel-Crafts compounds of 25 described by the catalysts of the invention polymeric component (2 [b]) are bound to be complexed in order to be ized and these catalysts from the alkali component (2 [a]) to form. metallized hydrocarbons are produced,

Like the order of addition of the catalyst, it is not necessary to have a component content Compounds based on the nature of the catalyst and of (2 [b]) to use. One can, however, for such formed polymer is of influence, so also 30 polymerizations a proportion of component (2 [b]) found that a better catalyst is obtained, use the one based on the amount of if the complex formation of component (2 [a]) alkali metal of the metalated hydrocarbon, before the reaction with the other catalyst contains a stoichiometric amount of halogen, components as if one were plexing the grain in order to produce the physical properties in situ, in the presence of components (1) 35 to change the diene polymer. So you can get through and / or (2 [b]). Selection of Friedel-Crafts compounds and the

Each of the catalyst-modifying polar carriers, the degree of branching, the ratio of compounds (2 [a]) _5, the oxygen and / or nitrogen 1: 2 and 1: 4 polymerization and the ratio of substance and / or sulfur, can alone or in the cis and trans configuration in a 1: 4 polymer combination. 40 control the station. By suitable choice of

If the Friedel-Crafts component (2 [b]) is in catalyst components, one can thus practically a lower oxidation state, then complete cis-1: ^ -polymerization and practical the modifying polar component (2 [a]) can achieve complete trans-1: ^ polymerization, an oxidizing agent, e.g. B. a peroxide. Is the molecular weights of the new catalysts

on the other hand the component (2 [b]) in a higher 45 sators formed polymers are except by the Oxidation state, then the component temperature and the amount of applied Lö- (2 [a]) a reducing agent, for example an amine, solvent also by the polymerization initiator use. Activity of the catalyst influenced, which by the

Alkali metal content of the metalated catalyst is component (2 [b]) 50. When dienes and olefins are copolymers

be used, small amounts of

The compounds that are used here as such of the Friedel bonds of the Friedel-Crafts type of metals, the Crafts-type are designated, which one to the high-valued can occur and which during position of the catalyst system according to the preceding transition of the oxidation state, in the case of underlying Invention used not only include the 55 mixer instability or in the reaction with the acidic chlorides, generally called Friedel-Crafts metal of the multi-metalated hydrocarbon compounds are known, but also the reactive component (1) effectively initiates the copolymerization Halides, oxyhalides and halide conductors.

complexes with halogen acids of metals in the polymerization of olefins and olefin

Groups Ib to VIII of the Periodic Table. 60 mixes it is desirable to have at least one From group Ib come copper and silver, a small proportion of a compound from Friedel-Craftsvon Group II magnesium, zinc, cadmium and type with a metal that has several valence mercury, of group III boron, aluminum, gallic stages occurs, use to initiate the to obtain from group IV titanium, zirconium, thallium, polymerisation or interpolymerisation tin, Hafnium, lead, from Group V vanadium, 65 lighter. The remaining compound from Friedel niobium, Tantalum, antimony and bismuth, of Group VI Crafts-type can be made from a metal that is only one Chromium, molybdenum, tungsten, uranium and tellurium, of valence level, or of one metal that contains several Group VII manganese and group VIII iron, forms valence levels, but not for themselves

The polymerization initiator is, although it is metallized with all or part of the metal components Component (1) react and improve the catalyst system can be prepared. It was found that the Friedel-Crafts compounds, which metals with two or more valence levels and can initiate the polymerizations, often in the solvent and / or the one used Monomers are soluble. These compounds also initiate the polymerization in places that are far from the catalyst surface, and result in mixed polymers of the non-oriented or oriented type. If only oriented polymers are desired, one can use of components (2 [a]) to reduce the solubility of the initiating metal component of the polyvalent metals predominantly achieve an oriented surface contact polymerization, which gives oriented or so-called crystalline polymers. In this way a practically complete, oriented polymerization, e.g. B. of propylene can be achieved.

If, on the other hand, the Friedel-Crafts compound of the polyvalent metal in that is not reactive hydrocarbon solvent or is readily soluble in the monomer to be polymerized and this component (2 [b]) is greater than that required for complexation with catalyst component (1) Amount used and no catalyst component (2 [a]) is added, this can Catalyst non-oriented polymers, e.g. B. a non-crystalline polypropylene.

By using mixtures of these components, each of them can be used to achieve special desired properties, optimal mixtures of oriented and non-oriented polymers are produced will. Furthermore, by a suitable

ίο Friedel-Crafts connection, e.g. B. vanadium chloride Polymer of partially crystalline nature, e.g. B. a partially crystalline propylene obtained which has elastic properties and, in part, the tensile strength of the crystalline type.

It has been found that very active fine-grain Friedel-Crafts chlorides are produced by heating the metals of groups IV, V, VI and VII and iron alloys of such metals in the chlorine stream, optionally after Reduction, obtained after treatment with metal powder, metal hydrides, carbides and hydrogen can be. In some cases, such halides can be mixed with oxygen, water and organic Compounds with active hydrogens such as alcohol are treated. Table A shows typical

as iron alloys, which are suitable for manufacturing the Friedel-Crafts-type chlorides from which the catalysts of the present invention have been established.

Table A Iron alloys

Elemental composition,
% Fe-W Fe-V Fe-Mn Fe-Mo Fe-Cr Fe-Cb W. 81.02 V - 62.0 - - - - Mn 0.13 - 78.6 - - - Mon 0.70 - - 62.6 - - Cr - - - 71.23 - Cb - - - - - 57.36 C. 0.51 - 6.38 - 0.4 0.35 Si 0.17 - 1.38 0.56 0.57 6.47

For certain catalysts of this invention, mixed Friedel-Crafts type compounds are highest desirable. These are made by combining metals and alloys in the desired ratio and halogenating them at an elevated temperature in a very inexpensive manner.

Component (3)

The carrier component of the catalyst systems according to the invention can be composed of metals, metal hydrides and compounds of metals from Groups I to VIII of the Periodic Table. from Group I comes in particular lithium, sodium, potassium and copper, from group II beryllium, Magnesium, calcium, strontium, barium, zinc and cadmium, from group III boron and aluminum, the Rare earth metals, from Group IV carbon, silicon, titanium, zirconium, and tin, from Group V Vanadium, tantalum, antimony and bismuth, from group VI chromium, molybdenum and tungsten, from group VII Manganese and rhenium and, from Group VIII, iron and, in certain cases, cobalt and nickel. The carrier must of course be in the monomers to be polymerized and in the optionally used hydrocarbon solvents or diluents be practically insoluble. if If the carrier is in finely divided form, it is advantageous if it is dissolved in water and acids or alkalis is readily soluble so that it can be easily removed from the polymer. The soluble carriers have the advantage that they can be added to pills, sticks or others with or without the addition of a binder Moldings can be pressed and that they are sintered and made porous in the desired manner can be used to ensure an adequate surface finish. The carrier body formed can then with one or more of the components (1), (2 [a]) and (2 [b]) in liquid, dissolved or in vapor form and surface treated in the appropriate order. The Friedel Crafts type component (2 [b]) can be sublimed onto the carrier bodies formed or applied from the solution by drying. the Carrier bodies must of course be able to withstand dry temperatures.

9 10

The metalated component (1) can either be formed from catalyst components, e.g. B. in

be preformed, or it can be applied to the carrier body trap of the sodium chloride resulting transmetallic

as a liquid or a solution, depending on the solution used.

Compound, can be applied, or it can be in situ. Furthermore, the metalated catalysts

are formed on the support surface. The Modi- 5 wholly or partially in the presence of the polymeric

Factor components (2 [a]) will be formed in suitable monomers. The ones with these

applied in a non-complexed form metalated catalysts catalyzed polymer

and selected from materials that can be used as liquids, sations can either be discontinuous or con-

Vapors or applied as solutions are run continuously.

can. If a component (2 [a]) is not in an io For the preparation of the catalyst and for the

these forms can be used, so they can lead to the polymerizations are suitable

can also be formed in situ on the carrier. applied thinners, e.g. B. paraffin hydrocarbons, Cycloparaffin hydrocarbons and

,. _{,,,, Λ} , "aromatic hydrocarbons and their halo-

The compounds of the metals to be used _{15 generated derivatives} (provided that these derivatives

exist _n ^ _{t d} j _e catalyst formation and the polymer

., ".", Disrupt the station process). For example, as

a) exan of salts of the aforesaid metals with salt _{LosungsmitteI propane) Butail) H,} heptane, Okb "n components from the groups II _t i _soo ktan, cyclohexane, methylcyclohexane, benzene, to VIII of the Periodic Table from group II _{ao toluene; χ lol and} chlorobenzene used come from group III borates and are zincates

Aluminates, from group IV carbonates, silicates, if "polymerisation takes place at low temperatures,

Titanates, zirconates, stannates, stannites, plumbates _{, methyl chloride can be} used as a diluent and plumbites, from group V nitrates, nitrites can be used

Phosphate vanadates, arsenates, arsenites _{anti-a5 The} 'temperature range for carrying out the months and Antimonite from Group VI sulfates, polymerization ranges from about -65 to 250 ⁰ C, sulfites, chromates, molybdates, tungstates Where _vorzU Se g _S, by -65 to 150 ⁰ C. Pressures of lenate and tellurate from group VII the halo atmospheric pressure up to 200 kg / cm ² or higher, gemde, the oxysaurhalogemde unless they are _preferably those of the order of magnitude of the component (2 [b ]) are contained and _3o atmospheric pressure up to 35 kg / cm ² , the manganates, from group VIII ferrates, ferrites can be used

and complex compounds including the- _The polymerization should be carried out with the exclusion of water

those of cobalt and nickel in consideration. _{and exclusion of} oxygen, carbon monoxide and

Carbon dioxide can also be carried out. Sometimes is

",. ",,, ^, Χ", 35 the addition of traces of oxygen advantageous,

b) the hydroxides of group I, e.g. B. of lithium, such as sodium and potassium, and is used, _{for example, in the high-pressure polyethylene process.} Small amounts of oxygen can

,, _ _,. _X " _DD . optionally by adding hydrogen

c) the oxides of groups I to VIII, preferably _{rendered harmless to the} polymerization system in their lower oxidation state, _{are destroyed}

be turned. From group I come especially _{in the} polymerization processes with the help of

_other lithium oxide, potassium oxide, sodium oxide according to catalysts can be used in counter-

and copper oxide, from Group II beryllium oxide, was _{a suitable} diluent, e.g. B. one

Magnesmmoxy <l · Calcmmoxyd Strontium Oxide Hydrocarbon diluent.

Barium oxide, Zmkoxyd, cadmium oxide and _{45 to this case, and the m} j _{ymerisierende Mono.}

Mercury oxide from group III, boron oxide, aluminum _{itself is the} diluent.

_{The diene monomers used} here include miniumoxide and the oxides of the metals

rare earths, from group IV silica, _butadiene) i _SO p _re n, pentene, 2,3-dimethylbutadiene,

Titanium oxide Zirconium oxide, Zmnoxyd, thorium- ₂ , 3-dimethylpentadiene-1,3, 3,3,4-dimethylpentadiene-1,3,

oxide and lead oxides, from group V vanadium _{50 2 4} _ _dim ethylpentadiene - 1,3, 2 - neopentyl butadiene,

oxides, tantalum oxides, the arsenic oxides antimony ₂ , 3,4-trimethylpentadiene-1,3, hexadiene-1,3, 2-ethyl

oxide and bismuth oxide, from group VI chromium _butaciien- 1,3,2-phenylbutadiene, 2,3-diphenylbutadiene,

oxide, and tungsten oxides Molybdanoxyde from _C yclohexadien-l, 3, cycloheptadiene-l, 3, Dimethyltoluol

Group VII manganese oxides and rhenium oxides and _other polymerizable methyl, ethyl, propyl,

from group VIII iron oxides, cobalt oxides and _{55 isopropyl} substituted butadienes, pentadienes, hexa-

Nicke oxides and the mixed oxides of these dienes _{and cyclodienes} , heptadienes, octadienes, hexa-

Metals into consideration. _trienej heptatrienes and octatrienes, such as hexadiene-2,4,

Hexatriene-1,3,5, octatriene-2,4,6, octadiene-1,3, octa-

Finally, the support can be made of carbon or diene-2,4, myrcene.

a carrier for catalytic substances, as in 6o is preferably used because of its lightness the petroleum industry and chemical polymerisability and good yields industry is applied. The polymer 1,3-dienes formed above, the 4 to 8 coals carried Carriers can contain atoms alone or in combination.

be used. You can continue to use in the form of vinyl compounds, aryl and alkyl

synthetic or naturally occurring mineral 65 aryl-substituted olefins are used, such as styrene,

be applied. The insoluble carrier vinyltoluenes, «-Methylstyrene,« -Methylvinyltoluenes,

{Component (3)] can be prepared by itself or completely ethyl, propyl, isopropyl, butyl and isobutyl, mono-

'or partly only in situ by reaction of the other and polysubstituted styrenes and a-methylstyrenes,

11 12

Vinylbiphenyls, vinylnaphthalenes, allylbenzene, allyl- metric amount of other metal halides of

toluene, allylnaphthalene, stilbene, methylstilbenes, indene, metals of groups I and II and treatment

2,2-Diphenylethylene, triphenylethylene, phenylsubsti- these compounds with a Friedel-Crafts type

tuated propylenes and butadienes. Link.

In addition to the aryl-substituted olefins grain 5 It has been found that a finished, from the

men halogenated aryl-substituted olefins, such as mono-, catalyst components (1), (2 [b]) and (3) with or

di-, tri- and tetrachloro- and bromine-substituted aryl, without component (2 [a]) produced according to the invention

and alkaryl olefins, styrenes, the vinyl toluenes, vinyl appropriate catalyst often by further addition

ethyl-, propyl-, isopropylbenzenes and naphthalenes, monometalated hydrocarbon compounds (Ka-

into consideration. io catalyst component (1) can be activated,

Preference is given to using aryl olefins, which, especially when these monometalated hydrocarbons

2 to 6 carbon atoms in addition to the aryl or substance compound with a group I metal Contain alkaryl and whose alkyl radical is metalated.

Alkaryl group preferably consists of 1 to 4 carbon atoms. The olefins include ethylene, propylene, butene-1, 50 to 6O ⁰ C. Ethyl, propyl, isopropyl, and according to catalysts, a higher or lower butyl and isobutyl-substituted 4 to 6 carbon temperature can also be used.
"-Olefins containing hydrogen, such as. B. 3-Me- 20 The monomer pressures used are relatively thylbutene-1, 3,3-dimethylbutene-l, 2,3,3-trimethyl- low, but this does not mean the use of higher butene-1, 2,2,3 , 3-TetramethyIbuten-l, 2,4,4-trimethyl pressure excludes. If one wishes to work in a solution-pentene-1 and certain 2-olefins such as 2-methylbutene-2, agent-free system, a. Preference is given to using -olefins which are applied from pressures which reduce the monomers

3 to 6 carbon atoms are built up, and 25 liquid. So you can use the Kataly-Ethylenes described here, because of their easy polymerizability and satoren for example in the plants of the Ethylender good yields of polymers. use high pressure method.

Preferred halogenated olefins are. The catalyst is derived from the polymer in

Fluorine, chlorine or mixed fluorine-chlorine and in a known manner by washing with alcohol, water

some examples are bromine substituted olefins, preferred or both, the soluble salt forming acid

contain halogenated olefins with 2 to 6 carbon, in most cases hydrochloric acid

atoms, used. is suitable removed. For metal connections, which

Furthermore, acetylenes, and in particular, can dissolve more easily in aqueous alkalis, becomes a

polymeric acetylenes of low molecular weight, alkaline solution, e.g. B. caustic soda or aqueous

z. B. the dimers, trimers and tetramers of ammonia 35 used.

Acetylene with or without other olefins as well as partially to counteract the polymers during deformation

Protecting hydrogenated products of this low molecular weight acetoxyoxidation is the addition of a few tenths

lenpolymers and copolymers, as monomers in percent, e.g. B. 0.2 percent by weight, based on the

the polymerization according to the invention uses polymers, an antioxidant, e.g. B. Ditert.-

will. 40 butyl-p-cresol is recommended.

It has been found that halogen-containing monomers amyl sodium, xylene sodium and the sodium

Instead of hydrocarbon monomers, a compound of the trimer of λ-methylstyrene can be used

are applied and with a solid catalyst according to various methods known per se

system can be polymerized, provided that they are produced.

45 Most of the examples are in tabular form

containing monomers react in such a way that arranged. The letters according to the amount of

the polymerization is prevented. Although some added components show the order

of these catalysts Halogenkohlenwasserstoffabspal- the addition in the relevant examples.

You can still get polymers where solid substances are mixed with other solid substances

of valuable properties. At 50, it proves very useful to the product

Grind the halocarbon and halocarbons for a few hours with a ball mill until material monomers close chlorine-containing monomers, the reaction of the solid material is complete.
such as vinyl and vinylidene chloride, trichlorethylene, The examples given here were in bomb tetrachlorethylene, fluoroolefins such as vinyl fluoride, Vi- tubes, which were moved in a water bath with constant Temnylidenfluorid, Trifiuorchloräthylen, Tetrafluoräthy- 55 temperature, or len in a pressure autoclave, Hexafluorobutadiene; chlorine- and fluorine-substituted ones carried out with a stirring device,
vinyl aromatic and vinylidene aromatic monomers. It is important that solvents and reactants B. dichlorostyrene and fluorostyrene, vinylchlorotoluene components are free of moisture and air and chlorine- and fluorine-substituted «-Methylstyren, is kept away during the reactions. The interweaving of the substitution both in the alkyl ratio and in the ratio of the catalyst to the one to be polymerized in the aromatic group can have taken place. Monomers, that is the yield of polymers,

These halogen monomers mentioned above must be based on the catalyst, is not important,

be compatible with the catalyst and allowed to use it If small amounts of the polymer without special

be prepared with a loss of its catalyst activity

disturb. 65 considerable proportion of the catalyst in the container

For example, very active catalysts are surface-activated. It has been found that obtained by reacting a hydrocarbon using a continuous polymerization sodium compound with less than the stoichiometric system, the catalyst requirement is reduced to 10% or less

can reduce the need for small laboratory approaches.

In the tables, the polymerization time is not necessarily the reaction time, but the time which elapses between the introduction of the monomers and isolation of the polymers.

example 1

This example shows the polymerization of monochlorostyrene. In a pressure vessel made of glass with a Capacity of 1 1 were 250 ml of dry pentane, 30 g of anhydrous, freshly sublimed aluminum chloride, 10 g of titanium tetrachloride, 5 g of triethylaluminum in 2 ml of dry pentane and 0.1 g of aluminum powder given. After shaking, a dark brown precipitate settled out, which was more solid Catalyst was used. To this solid catalyst, 75 g of monochlorostyrene was added. The bottle was then placed in a polymerization box at 60 ° C and rotated in it overnight. It was then opened, 250 ml of water and 5 ml of concentrated hydrochloric acid were added and the bottle Shaken until the catalyst was decomposed. After removing the water and pentane, the Product dried. 73.5 g of polymer were obtained.

Example 2

This example shows the polymerization of 1-trifluoromethyl-1,2-dichloroethylene with a solid catalyst to be used according to the invention. The polymerization was carried out as described in Example 1, except that monochlorostyrene was used instead l-trifluoromethyl-l ^ -dichlorethylene. Approximately one third of the monomer polymerized under the conditions used. One received 12.4 g of liquid polymer.

B e i s ρ i e 1 3

This example shows the polymerization of vinylidene chloride with the solid catalyst system. the Polymerization was carried out in the same way as in Example 1, except that instead of 75 g monochlorostyrene 75 g vinylidene chloride used. 55 g of a semisolid polymer were obtained.

The polymer thus obtained is for the production of hot water coils and pipes and for others Suitable for uses where resistance to boiling water is required will.

Example 5

This example shows the polymerization of trifluorochloroethylene. It was worked according to Example 4 ίο. 5 g of a liquid polymer were obtained.

Example 6

This example shows the polymerization of tetrafluoroethylene using a solid catalyst. In this example, the polymerization was carried out in a closed sealed tube at 50 ^° C. using a catalyst according to Example 1, but using 1.5 g of triethylaluminum, 3 g of titanium tetrachloride, 0.2 g of AlCl ₃ , 0.02 g of aluminum and 10 ml of pentane carried out. A yield of 6% of polytetrafluoroethylene was obtained.

B e i s ρ i e 1 7

This example shows the polymerization of vinylidene fluoride using an organometallic heterogeneous, solid catalyst system. The polymerization was carried out in the same way as in Example 5, however, using vinylidene fluoride, which is carried out in the reaction mixture for 5 hours was initiated. After removing the catalyst residue with dilute hydrochloric acid and evaporation of the pentane, 20 g of a liquid polymer was obtained.

Example 8 Example 4

This example shows the polymerization of vinyl chloride.

1 liter of dry hexane was placed in a reaction vessel of approx. 41 cm, equipped with a mixer, reflux condenser and heating mantle. With constant stirring, the following were added in the following order: 30 g of anhydrous aluminum chloride, 10 g of titanium tetrachloride, 0.1 g of aluminum powder and 8.5 g of aluminum triisobutyl. The mixture was heated for ¹ hour under reflux _J2. Then, without further heating, vinyl chloride gas was bubbled into the stirred mixture for 4 hours under atmospheric pressure. The resulting product was washed with alcohol, hydrochloric acid and water and, after drying, gave 21 g of vinyl chloride polymer with a Vicat softening point of 126 ^° C.

This example shows the polymerization of an allyl acrylic phosphate monomer (phosphoresin monomer der Victor Chm. Co., Monomer E-3490 [see p. USA. Patent 2,425,765]) with the aid of a solid described here Catalyst.

An aluminum triethyl - titanium chloride - aluminum chloride, aluminum metal combination, as in the example 1, was used in the same manner and in the same amount of Example 1 with the Exception that 25 g of phosphoresin monomer were used instead of chlorostyrene. After 2 hours During the polymerization time, the bottle was opened and the contents treated as in Example 1. Man received 20.6 g of a solid greenish white polymer.

Example 9

This example illustrates the polymerization of polar monomers with those of the invention catalysts to be used. A ball mill was filled with 500 ml of pentane, 10 g of sodium amyl and the charged corresponding molar amount of sodium chloride. 5.4 g of anhydrous were then added Aluminum chloride was added and the mixture was ground for 4 hours. Then 2 g of titanium tetrachloride were added. The catalyst was placed in a pressure vessel, which was charged with 50 g of methyl methacrylate. The pressure vessel was then left to stand overnight. The yield of polymethyl methacrylate was> 88% based on the monomer used.

Further exemplary embodiments are compiled in the tables below.

15 16

Table I.
Examples of the catalyst components (1), alkaryl metalated compounds

10

11

example
13th

14th

15th

catalyst

Component (1) - Monometalated Compound

Monometallic compounds

o-xylene, g

m-xylene, g

p-xylene, g

Mixed xylenes, g

Mesitylene, g

Dimethylnaphthalene, g

Λ-methylstyrene trimers **, g

Metallic connection
Amyl sodium (in pentane), g

solvent
Pentane, ml

Metallic conditions
Time, hours

Temperature, ⁰ C

Component (2 [b]) - Friedel-Craft compounds
Aluminum chloride, g

Titanium tetrachloride, g

Ball mill the catalysts, hours

Catalyst component (3)
Sodium chloride

Monomers
Propylene, kg / cm ²

Butadiene, g

Ethylene, kg / cm ² .

Polymerization conditions

Temperature, ⁰ C

Time, hours, ***

10.6b *

10.6b

9.4a 200a

5 50

4,4c l, 0d

2c 5.8

2.1 e

9.4a 200a

5 50

4,4c l, 0d

2c 5.8

2.1 e

10.6 b

12.0b

9.4 a 9.4 a

220a 220

3
65

4,4c
l, 0d

2c

5 65

4.4 c l, 0d

2c

; 5.8 j 5.8 2.1 e! 2.1c

30 16

30 12

15.6b

9.4a a

8 50

4,4c l, 0d

2c 5.8

2.1c

35b 9.4a a

8 50

4,4c l, 0d

2c 5.8

: 30

! 16

30 16

55 16

35c

70 16

* The letters a, b, c in this and the following tables indicate the order in which the components are added. ** A product from Dow Chemical Co. called Resin 276-V2. *** The time given in this table is not the reaction time, but the time in which the polymer was isolated.

Table II
Examples of the catalyst component (1), monometalated compounds

17th

Example 20

21

22nd

catalyst

Component (1) - Monometalated Compound Preparation of prepolymer for easy metallation
Monomers

Vinyl toluene (Dow) *, g

Vinyl toluene (cyanamide) **, g

Isoprene, g

12b

12b

12b

b

10b

* According to information, vinyl toluene from Dow Chemikal Co. contains 65 to 70% m-methylstyrene and 30 to 35% p-methylstyrene. ** The vinyltoluene the American Cyanamid Company includes, according to 66 ° / ₀ p-methyl styrene and 33 ° / ₀ o-methyl styrene, and 1% methyl styrene.

Tabel!! (Continuation)

18th

17th

18th

example
I 20

21

catalyst

Pre-polymerizing and / or metallizing compound

Amyl sodium (in pentane), g

solvent
Pentane, ml

Pre-polymerizing and / or metallizing conditions

Time, hours

Temperature, ⁰ C

Yield, g

Component (2 [b]) —Friedel-Crafts compounds

Aluminum chloride (sublimed), g

Titanium tetrachloride

Ball mill the catalysts, hours

Catalyst component (3)
Sodium chloride, g

Monomers

Ethylene, kg / cm ²

Propylene, g

Polymerization conditions

Temperature, ⁰ C

Time, hours

9.4 a 400 a

12 28

4.5

4,5c 1, Od

24c 5.8

60Oe

30 16

9.4 a 9.4a 9.4a 3 9.4 a 220 a 220 a 220 a 650 a 12th 16 12th 12th 28 60 28 28 12th 12th 12th 25th 4.5 c 4.4 c l, 0d 3.2c 3.2c l, 0d 12c 2c 5.8 5.8 5.8 5.8 35e 35d 35e 35f 19d 59 e 45 45 48 40 16 16 12th

9.4a 200 a

12 28 10

4.4 c l, 0d

16c 5.8

35e

55 12

Table III Examples of the catalyst component (2 [b]) Group IV - Friedel-Crafts compounds

23

25th

example
27

28

29

30th

Component (1) - Monometalated Compound

Metallized mixture
p-xylene monosodium
(in pentane), g

«-Methylstyrene trimeremosodium (in pentane), g

solvent
Pentane, ml

Component (2 [b]) - Friedel-Crafts compound
titanium
Titanium tetrachloride, g

zirconium
Zirconium tetrachloride, g ...

solvent
Pentane, ml

Catalyst component (3)
Sodium chloride

13a

300 a

13a

400 a

5.8 bj i 50b I 95 b

I ]

5.8! 5.8

13a

400 a

4.7 b

64b

13a

a

4.7b

95b

5.8 5.8

13a 13a 38a 400 a 400 a 400 a 4.7 b 4.7 b 4.7 b 64 b 64b 64b 5.8 5.8 5.8

38 a

a

4.7 b

64b

600/419

19th

Table III (continued)

23

example

26 I 27

28

29

Monomers

Ethylene, kg / cm ²

Propylene, kg / cm ²

Butadiene, g

Isobutylene, g

Isoprene, g

Polymerization conditions

Temperature, ⁰ C

Time, hours

* Added in grams.

2.1c

30 16

7.7C

15c

52
16

7.7c * 5.5c * lic

15c i

52
16

15c

52 16

52 16

Table IV Examples of elastic fabrics

50 16

32

example

33 I 34

35

catalyst

Component (1) - Monometalated compound Metallized compound

p-xylene monosodium (in pentane) g

solvent
Pentane, ml

Component (2 [b]) - Friedel-Crafts compound titanium tetrachloride, g

Component (3)
Sodium chloride

solvent
Pentane, ml

6.5a 13a

13a

13a i 13a

200a 400a 400a 400a

3.2b

400a

6.4b 6.4b ^! 6.4b! 6.4b

5Qi co CQ CQ

, 0 J, ö 3.0 ι J, ö

32b! 94b; 94b: 64b 64b

Monomers
Isobutylene, g
Ethylene, g ..
Propylene, g.
Isoprene, g ..
Butadiene, g.

Polymerization conditions

Temperature, ⁰ C

Time, hours

76 c

142.5c j 142.5c ■ 75c 7.5 c

7.5c: 5c

53
16

53
16

50 16

70c HOc

53 16

13a

400 a

9.6 b

5.8

94 b

142.5c 7.5c

53 16

Table V Examples of the catalyst component (2 [b]) Group V - Friedel-Crafts compounds

37 example
38 39 catalyst Component (1) - Monometalated Compound
Metallized connection
p-xylene monosodium (in pentane), g 6.5 a 3.2 a Monosodium compound of the trimer of «-Methyl-
styrene (in pentane), g 38a solvent
Pentane, ml 400 a 200 a 100a

Table V (continued)

example
37 I 38 2.2b
5.8
50b
28 c
30th
16 39 Component (2 [b]) - Friedel-Crafts compounds
Vanadium
Vanadium chloride (VCl ₅ )
Catalyst component (3)
Sodium chloride
solvent
Pentane, ml 5.8
100b
2.1c
30th
1.5 2.9
50 b
2.1c
30th
2.5 Monomers
Ethylene, kg / cm ²
Propylene, kg / cm
Polymerization conditions
Temperature, ⁰ C
Time, hours

Table VI Examples of the catalyst component (2 [b]) Group VIa - Friedel-Crafts compounds

40 example
41 I 42 13a
200 a
5.8
2.1
30th
16 catalyst
Component (1) - Monometalated Compound
Metallized connection
p-xylene monosodium
(in pentane with sodium chloride), g
solvent
Pentane, ml 13a
200a
1.29b
5.8
2.1 e
30th
16 13a
200a
5.8
2.1 e
30th
16 Component (2 [b]) - Friedel-Crafts compounds
chrome
Chromyl chloride
Catalyst component (3)
Sodium chloride
Monomer
Ethylene, kg / cm ²
Polymerization conditions
Temperature, ⁰ C
Time, hours

Table VII Examples of the polar compounds modifying the catalyst component (2 [a])

43 44 example
45 [46 6.4a
2.3 d 47 48 catalyst
Component (1) - Monometalated Compound
Metallized connections
p-xylene monosodium
(in pentane with sodium chloride), g 6.4a
2.3 d 6.4 a
2.3 d 6.4a
2.3 d 6.4 a
2.3 d 6.4 a
2.3 d Amyl sodium
(in pentane with sodium chloride), g

23

Table VII (continued)

24

43

44

example
45 46

47

Component (2 [a]) - catalyst-modifying polar compound

Diisopropyl ketone, g

N-phenyl-N'-cyclohexyl-p-phenylenediamine, g

Pyridine, g

Diethyl carbonate, g

Butyraldehyde, g

Morpholine, g

solvent
Pentane, ml

Component (2 [b]) - Friedel-Crafts compounds
Titanium tetrachloride, g

Monomer
Propylene, kg / cm ²

Polymerization conditions

Temperature, ⁰ C

Time, hours

Yield, g

1,4c

3.3 c

a

4.7 b

2.8 e

4.7 b

30th 30th 30th 16 16 16 14th 21.5 8.3

1.0c

3.0c

0.9 c

700a 700a> 700a 700a

700 a

4.7b j 4.7b '4.7b j 4.7b

2.8e I 2.8e! 2.8e j 2.8e 2.8e

30th
16
6.4

30 16 8.4

Table VIII Examples of the polar compounds modifying the catalyst component (2 [a])

, 50 example 52 j 53 49 21.2 I 51 21.2 I.
21.2 21.2 18.8 21.2 18.8 18.8 18.8 700 a 18.8 700 a 700 a 700 a 3 700 a 3 3 3 50 3 50 50 50 50

catalyst

Component (1) - Monometalated Compound Monometalable mixture p-xylene, g

Metallating compound amyl sodium
(in pentane with sodium chloride), g

solvent
Pentane, ml

Metallic conditions time, hours

Temperature, ⁰ C

Component (2 [a]) - catalyst-modifying polar compound

Ethyl etherate of aluminum chloride (ratio 1: 1 mol), g

Ethyl ether

Component (2 [b]) - Friedel-Crafts compounds
Titanium tetrachloride, g

Monomers
Propylene, kg / cm ²

Polymerization conditions

Temperature, ⁰ C

Time, hours

9.4 c

2.8 d

14.8d

9.4 c

2.8 f

30th
24

4.8 d

9.5c

2.8 f

30th
24

7.2

4.7 c

2.8f

30th
24

6.9 d

4.7 c

2.8 f

30 24

25 26

Table IX
Examples of the polar compounds modifying the catalyst components

54

Example 55 I 56

catalyst

Component (1) - Monometalated Compound Monometalable Compounds p-xylene, g

oc-methylstyrene trimers

Metallic connection
Amyl sodium (in pentane with sodium chloride), g ...

solvent
Pentane, ml

Metallic conditions

Time, hours

Temperature, ° C

Component (2 [a]) - catalyst-modifying polar compound

Ethyl etherate of aluminum chloride, g

Ethyl etherate of titanium tetrachloride, g

Component (2 [b]) - Friedel-Crafts compound titanium tetrachloride, g

Monomer

Ethylene, kg / cm ²

Propylene, kg / cm ²

Polymerization conditions

Temperature, ° C

Time, hours

70b
18.8a
700a

6.9 d

4.7 c
e

21b

18.8a
700a

2
60

2.9 d

9.5c
e

50
16

21b

18.8 a
a

2
60

6.9 d

4.7 c
4.2e

50
16

21b

11.6a a

2 60

24.2 c

2.8 e

30 16

Table X
Examples of the catalyst component (1) of Groups 1 and II

59 example 61 58 60 18.8 a 6.4 a 6.4 a 2.1b 6.4a 4.5 b 5.2b 4b 4b 250 a 4b 250 a 250 a 200 a 2.2b 2.3 b 2.3 c 1.0c 5.8 ■■■ 4.7 2.9 4.7

62

catalyst

Component (1) - Monometalated Compound Metallic Compounds Group I and II Monosodium compound of the methylstyrene trimers (in pentane), g

p-xylene monosodium (in pentane), g

p-xylene monopotassium (in pentane), g

Lithium chloride, g

Cadmium chloride, g

Barium chloride, g

Ball mill grinding, hours

solvent
Pentane, ml

Component (2 [b]) - Friedel-Crafts compound

AlCl ₃

Ferrp vanadium chloride, g

TiCl ₄

Component (3)
Sodium chloride

7.2a

a

2.4 c 2.9 '

409 500/419

Table X (continued)

28

58

59

example
60

61

solvent
Pentane, ml.

Monomers
Ethylene, kg / cm ² .
Propylene, kg / cm ²

Butadiene, g

Isoprene, g

Polymerization conditions

Temperature, ⁰ C

Time, hours

lOOd

60
16

40d

60 30

b

50
16

b

2.1c

30th

Table XI
Examples of the catalyst component (1) from groups I and II

28c

45 16

63 74A

example

I 65

Attempt no.
B 75

66 58B

catalyst

Component (1) - Metalated Component Metalated Compound Group I

Amyl sodium (in pentane), g

Amylbarium (in pentane), g

p-xylene potassium (in pentane), g

solvent
Pentane, ml

Component (2 [b]) - Friedel-Crafts-type compound

Titanium tetrachloride, g

Ferrovanadium chloride, g

Zinc chloride, g

Chromyl chloride, g

solvent
Pentane, ml

Milling in the ball mill, hour component (3)

Sodium chloride

Potassium chloride

Monomer

Ethylene, g

Propylene, kg / cm ²
Butadiene, g

Polymerization conditions

Temperature, ⁰ C

Time, hours

Yield,%

Test results
Physical state, * .. softening temperature, ⁰ C tensile strength, kg / cm ² ... extensibility,%

* EL = elastic; PL = plastic.

9.4a

300a

1.05 c

5.1 d 0.65 b

15c

5.8

14d

30th

100

PL

155
301
500

9.4a

a

1.05 c

5.1b
0.65 b

15c

5.8

2.1 d

Tbsp

28.8 a
a

2 B
20b

14.8
c

30th

16

100

Tbsp

13.9a

a

5b

45 b

10.9

300c

30th

100

PL

205

186.2

300

Table XII

Examples of the catalyst components (2 [b]) Group V — Friedel-Crafts component with (2 [a]) modifying

polar connection

* PL = plastic.

catalyst

Component (1) - Metallized connection Metallized and metallized connection Amyl sodium (in pentane with sodium chloride), g.

solvent
Pentane, ml

Metallable connection

Component (2 [a]) - catalyst-modifying polar compound
Ethyl etherate of titanium tetrachloride (1: 1 molar ratio), g

Component (2 [bJ) - Friedel-Crafts type compound
Titanium tetrachloride, g

Monomer
Propylene, kg / cm ²

Polymerization conditions

Temperature, ⁰ C

Time, hours

Yield,%

Test values

Physical condition *

Softening temperature, ⁰ C

Tensile strength, kg / cm ²

Extensibility,%

Table XIII

catalyst

Component (1) - Metallized compound

Metallized connection
Amyl sodium (in pentane), g

solvent
Pentane, ml

Component (2 [b]) - Friedel-Crafts-type compound
Vanadium chloride (VCl ₄ ) g

Component (3)
Sodium chloride

solvent
Pentane, ml

Example 67

Attempt no.,

K-VII

36-2

18.8a a

24.4 b

9.5b 2.1c

30 24 12

PL 140 238 125

Example 68

Attempt no.,

K-VIII

54b

9.4a a

6.4

5.8

50b

Table XIII (continued)

Monomer
Ethylene, kg / cm ²

Polymerization conditions

Temperature, ⁰ C

Time, hours

Yield,%

Test results

Softening temperature, ⁰ C 195

Tensile Strength, kg / cm ² 381.5

Extensibility,% 450

Table XIV Examples of Catalyst Component (2 [b]) Group VIa - Friedel-Crafts Compounds

Example 68

Trial No., K-VIII

54b

2.1c

1.5 100

Example 69

Attempt no.,

K-VII

53 b

catalyst

Component (1) - Metalated compound amyl sodium (in pentane), g

solvent
Pentane, ml

Component (2 [b]) - Friedel-Crafts-type compounds
chrome
Chromyl chloride, g

Component (3)
Sodium chloride

Monomer
Ethylene, kg / cm ²

Polymerization conditions

Temperature, ⁰ C

Time, hours

Yield,%

Test values

Softening temperature, ^c C Tensile strength, kg / cm ² Extensibility,%

4.7 a 400a

1.29 b 2.9

2.1 e

30th
16
42

190

310.8 380

Examples of newer Table XV
Polymer and copolymer game 72 73 9.4a catalyst
Component (1) - Metallized
(in pentane)
Amyl sodium, g link 8a Aluminum triisobutyl Be
70 ι 71 I.
I.
I.
j
j
9.4a 9.4a

33

Table XV (continued)

70 Example I 72

73

Diluents

Pentane, ml

Component (2 [b]) - Friedel-Crafts compounds

Titanium tetrachloride, g

BF ₃ etherate

Component (3)
Sodium chloride

Monomer

Vinyl chloride

Styrene

Λ-methylstyrene

Vinyl toluene (Dow)

Vinyl toluene (Am. Cyan.)

Polymerization conditions

Temperature, ⁰ C

Time, hours

Yield,%

Test data
Vicat melting point, ⁰ C

590 a 1.6b

5.8

100c

22 16 81

97 a
1.6b

5.8

100c

590 a 1.6b

5.8

50c 50 c

22 16 60

38Oa

1.9c 8b *

30d

22 6 10 **

100 ***

* Allowed to react 1 hour after adding BF _{3 ether before adding titanium tetrachloride.}

** Chlorine analysis shows that the polymer formed was polyvinyl chloride; Yield can be increased to 40% by stirring will.

*** For comparison, the rigid polyvinyl chloride produced today has a Vicat melting point of 90 °.

Table XVI Polymers from Mixed -olefins

catalyst

Component (1) - Metalated compound (in pentane)
Amyl sodium, g

Diluents

Pentane, ml

Component (2 [b])
Titanium tetrachloride, g

Component (3)
Sodium chloride

Monomer

Propylene, g

Isobutylene, g

Polymerization conditions

Temperature, ⁰ C

Time, hours

Yield,%

Test data

Deformation temperature ^{, 0 C}

Tensile strength, kg / cm ²

Extensibility,%

example

9.4a
590 a
1.6b

10c
10c

22nd
16
38

110

73.2
175

409 600/419

Table XVII

Polymers of an α-olefin and / or a vinyl hydrocarbon monomer and / or a diene monomer

example
76

77

catalyst

Component (1) - Metallized compound
(in pentane)
Amyl sodium, g

Diluents
Pentane, ml

Component (2 [b])
Titanium tetrachloride, g

Component (3)
Sodium chloride

Monomer, g

Ethylene

Isobutylene

Isoprene

Butadiene

Vinyl toluene (Dow)

Styrene

Polymerization conditions

Temperature, ° C

Time, hours

Yield,%

Test data

Deformation temperature, ° C

Vicat melting point, ⁰ C

* The product was a vulcanizable polymer.

Claims (1)

Claim: 45 Process for the polymerization of monomers with at least one polymerizable olefinic unsaturated double bond or mixtures of such monomers, characterized in that that the polymerization takes place in the presence of such a catalyst, which consists of at least one by a metal of I. to IV. Group of the Periodic Table Metalated 9.4 a 9.4 a 9.4 a 590a 590a 590 a 1.6b 1.6b 1.6b 10c 10c lOc 10c 10c 10c lOc 10c 10c 22nd 22nd 22nd 16 16 16 90 90 66 86 Hydrocarbon compound (component 1) and at least one compound of the Friedel-Crafts type (Component 2 [b]) and a polar compound that modifies the catalyst (component 2 [a]) and / or a carrier or carrier mixture (component 3). Documents considered: Belgian patent laid out documents No. 538 782. 409 600/419 6.64 © Bundesdruckerei Berlin