DE1745393A1 - Multi-component copolymers and processes for their manufacture - Google Patents

Description

DR.ELISABETH JUNQ 1 7 / C O Q Q DR. VOLKER VOSSIUS '' ^ ⁰ ^ " PATENT LAWYERS Munich 23 - Siegesstrasse 26

Phone; 345Q62

ff June 6, 1967

Poe .1135-Sumi tcmo

Sumitomo Chemical Company, Ltd., Osaka / Japan

Multicomponent copolymers and methods of making them

Priority: June 6, 1966, Japan, Annelde-Hr. 36745/66

The invention relates to copolymers consisting of several components which are built up from at least three-component components, and a method for their production. The invention-geoäfien alternating, consisting of several constituent copolymers of at least 3 monomers, consisting of (A) at least one (1) terminally ethylenically unsaturated compound, (2) internally olefinic compound, (3) PcIy en compound with 30 or fewer carbon atoms, (4 ) acetylene! see compounds or (5) carbonyl or thiocarbonyl compounds as monomer A, and (B) at least

109837/1244

atene consist of a conjugierfcen Vipylroonoiaeren, the cu the monomers belonging to the groups (A) and the monomers belonging to the group (B) essentially alternating are bound by using (I) an organoaluminum halide or boron halides or elnea mixtures of at least 2 compounds from the group of organometallic halides, Organometallic compounds and metal halides ^ _ where the metal consists of aluminum or boron, or (II) durei a complex of the eur group (B) belonging conjugated ver bond coordinated with an organometallic halide component has been received.

In particular, the invention relates to new alternating, Copolymers built up from several Beatand parts, which contain at least 4ne 3 monomeric units, the outer (A) at least one monomer of group A, wosu

(1) ends continuously ethylenic unsaturated compounds of the general formal

1 2
wherein R and H have the meaning given below

beaitsen,

(2) Internal olefinic bond compounds the general formula:

4 R ⁶

* H ^ R vs. c

R * - 0 * C ^ ₅ or HC «C - JT

wherein IU, R ^, Hr and R _{6 are} those given below

* Meaning baaitaon,

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(3) polyene compounds with up to 30 carbon atoms, the at least one carbon-carbon double bond contain at least two waeaeratoff atoms »

(4) aoetylenic compounds of the general formula;

R ⁷ O s CR ⁸

t ft
where R ^f and R have the meanings given below, and

(5) Carbonyl or thiocarbony! Compounds of the general Formula:

R ¹¹ c N

r9 _ _c _ γ. _R 10 _or R ¹¹ - c - N - R ¹⁰

i!

in which R ^, R, R ¹¹ , Z and Y have the meaning given below, include and

(B) connected to a conjugated linkage to all monoomers B the general Vorotlx

R ¹ OH «0 -

in which R, R and Q ignore the meaning given below, and in which the Honoaeran of groups A and B are bound alternately. The invention bef "U3T eioh further old · a" method for producing * "ines WM several Beetandteilen existing Cοpolymeren, wherein the Toretehend listed nindeatens 3 monomers from the groups

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A and B with (I) an organoaluminum halide or boron halide or a mixture of at least two compounds from the group of organometallic halides, organometallic compounds and metal halides ^ being the metal from Aluminum or boron, or with (II) an organometallic halide component are brought into contact, which via a complex formation process by mixing an organic Connection of a metal of the groups lib, IHb or P ITb of the perlodic system in the presence of at least the conjugated Compound of group B with a halide of a metal of groups IHb or IVb of the periodic table and Contact was received.

Hach's own older proposals were copolymers and Process for their production by means of a complex polymerization obtained, whereby conjugated monomers with nitrile, Carbonyl or thiocarbonyl groups in conjugated positions see double bonds with unsaturated compounds, such as olefins, halogen olefins, olefins with internal double bonds, Polyenes, aoetylenes, unsaturated ethers of carbonic acids or H-, O- or S-containing unsaturated nonconjugated compounds Compounds using catalyst components, which contain aluminum or boron, are copolymerized. These methods generally involve alternating ones Copolymers obtained and they are therefore compared to usual Copolynerieationeumsetaungen ale specific reactions considered.

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It is now shown that the above copolymerization is detrimental on more was part amöiiomerayeteme are applicable and are very successful for the production of alternating Mehrbestaildtoilscopolymers prove, in which the selected from the above two groups several ingredients are essentially older are bound only by the two groups.

The object of the present invention is shown in an alternating, composed of several components Oopolymer, in which at least three components from the above listed groups in a practically alternating arrangement half of the two types of groups bound • ind.

Another object of the invention is to provide a new method for dividing those listed above Copolyesters using a «β catalyst.,

Next «Objects and Advantages of the Present Invention result from the following description.

The copolymer according to the invention from (A) reduced one of the monomers

(1) There are permanently methylene unsaturated compounds of the general formulas

CH ₂

R ¹

1 2

where H and H are hydrogen atoms or β Ln halogen atoms, a carbon dioxide residue with 1-20

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an ihalo-containing hydrocarbon radical of 1-20 Carbon atoms or with substituting groups thereon mean

(2) Compounds with an internal olefinic bond the general formula

H ⁶

⁵ - HC - O ^ ₅ or HO »CR ⁵

H'

P wherein R ⁵ and R ^{4 are} hydrocarbon radicals with 1-20 carbon atoms, halogen-containing hydrocarbon radicals with 1-20 carbon atoms or with substituting groups, H is a Waeeeretoffatoe or a Kohlemraeeeratoffreet with 1-20 carbon atoms, a halogen-containing carbon atoms with 1-20 carbon atoms or with Substituting groups and R a hydrocarbon radical with 1-20 carbon atoms, a halogen-containing carbon waeeeretoffreet with 1-20 carbon atoms or with subordinate groups »

"(9) Pole bonds with up to 90 carbon atoms, the

"If there is at least one carbon-carbon double bond with contain at least 2 hydrogen atoms, (4) aoetyleuieohen compounds of the general formula:

R ⁷ O s CR ⁸

7th
where R is a Waeeeretoffatom or a Kohl entrasser stoffroot with 1-20 carbon atoms or with substituting groups and H oin Wasseret off atom or one, a

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polymerizable unsaturated group-containing hydrocarbon re at with 1-20 carbon atoms and (5) carbonyl or thioearbonyl compounds of the general formula

c - Y - R ¹⁰ or R ¹¹ -CN

I S

_ c - Y - R ¹⁰ or R ¹¹ -CNR ¹⁰

I S

where R ^{9 is} a group R ¹² -, R ¹² O-, R ¹² S- or R and Z is an oxygen or sulfur atom, Y is an Λ oxygen or sulfur atom or a group HR- and R is a carbon radical containing a polymerizable unsaturated bond with 2 -20 carbon atoms or with substituting groups, R is an organic one

12th

ftyollBchen radical with 1-20 carbon atoms, R a hydrocarbon radical old 1-20 carbon atoms or with substituting groups and R, R and R mean carbon water radicals old 1 _r 20 carbon atoms or with substituting groups, and from

(B) at least one conjugated compound as Monomereθ Β the general formula

B ¹ OH «C-Q
before R ¹ and R hydrocarbon radicals with 1-20 carbon

Contains halo · hydrocarbons with 1-20 coals off atoms, «la halogen atom or« in hydrogen atom mean

However, at least one of the radicals B and H is a hydrogen «Ton let, while Q is a nitrile group or a group of the formula

means in which Y * halogen atoms or hydrogen atoms or the groupings 2Iff, ZR, ZTlIe, KH ¹ R "or R, Z and Z oxygen or sulfur atom, R an organic Feet with 1-20 carbon atoms, R * and R" Wasseretoffatome or organic radicals ait 1-20 carbon atoms, including dee case, no R ¹ and R "each other in another part rla attached to nitrogen atom eind _t and Ke represent the monovalent part of an element of groups X to III de" Periodic Table or an ammonium group, built alnd.

The present invention is further concerned with adit a process for the production of a Hehrbeetaadteilaoοpolymer en, where at least 3 monomers, each selected from the groups A and B listed above, with (1) an organoaluminium halide or boron halide of general formula

where I is aluminum or boron, B "is generally an organic radical, X is a halogenated and a« la «is 1-2, or a Gemleoh of broken two connections of the all-

e ^

common formula

(a) BV _n X _3-11 , (b) M'R ^ j and (c)

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nor in M, M ¹ and M "aluminum or boron, R" ^f and R ^{IV are} generally organic best, X and X ^{1 are} halogen atoms and η is a number from 1-2, or with

(2) contacted an organometallic halide reactant be, which after a complex formation process, by mixing and contacting at least in the presence of oonjugated compound of Group B listed above

(a) an organic compound of a metal from groups lib, HIb or IVb of the periodic table with %

(b) a halide of a metal from groups IHb or IVb of the Periodic Table, where at least one of the compounds (a) or (b) is a boron or aluminum compound became.

In the process according to the invention, the copolymerization can also be carried out in the presence of oxygen or an organic peroxide.

Due to the present invention, it becomes possible to even obtain a au "more components constructed Oopolymeres in atm case au where in the described Komplexpolyaerieation to form an alternating copolymer of the monomers of group A and the eonjuglerten compound of group B are not each direction of these monomers one and more monomers of group A or several monomers of group B are used. On the other hand, the copolymerization of four or more constituents can sometimes be carried out if the two types of monomers are each in the form

109337/1244

Several monomers used clay «ground. When the multi-bed part coopolymeriaation under which conditions of alternate copolymer formation is carried out generally the monomers of group A alternating with the monomers of group B. For example see the ternary copolymerization of 2 monomers of group B with one) monomer of group A a copolymer, which 50 mol-jt of units of the monomer of group A enter holds. The mutual ratio of the monomers of group B varies depending on the Mononertusaisneneetsung and therefore, it can be appropriately selected to obtain any copolymer.

On the other hand, the same applies to the Pall au, where 2 or more monomers of group A are copolymerized and a halogen-containing olefin or a carbonyl group-containing Monomeree can b.B. introduced in the desired ratio will. Furthermore, the addition of a suitable amount of a diene compound supports the present invention copolymers are available that are curable with sulfur and an appropriate ability to react.

Thus the present invention is of great importance insofar as ais production of copolymers with any Properties using 3 or more monomers is possible despite the fact that it is used in the ttbllohen complex polymerization was not possible, the Zuaam * alternating copolymers obtained in the 4ee

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desired way to change Eu.

On the other hand, such procedural measures never "in the usual complexo-polymerisation using of 2 monomers that an aluminum or boron compound is required for all Katalyeatorbeοtendteil iet, a conjugated compound -be coordinated with a catalyst component should avoid a polar solvent and the Application clay oxygen or an organic peroxide aur accelerated TJmeerung, also on the present complex polymerization applicable using 3 or more monomers.

You unsaturated compounds with terminal ethylene groups, the group of the -ιate used according to the invention Forming monomers of group A can be given by the general formula

R ¹

Ί 2

reproduce, where R and R balogen atoms such as chlorine, bromine, Iodine or fluorine or carbon dioxide-free or halogen-containing Hydrocarbon residues are. Old hydrocarbon residues are alkyl, Arjl, AraUcyl-, Alkylaryl-, Cycloalkylgruppem or groups of this type substituted with halogens and groups derived herefrom can also be used be used.

Examples of such compounds are olefins such as ethylene, propylene, butene-1, isobutene, hexene-1, heptene-1,

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2-methylbutene-1, 2-methylpentene-1, 4-Methylyenten-1, Ootadeoen-1, 4-phenylbutene-1 _r styrene, α-Methyletyrol, α-butylstyrene, p-methylstyrene, Vinyloyclobutan "vinylcyclohexane, isopropenyl benzene, vinyl naphthalene and Allylbenzene and halogen-containing olefinically unsaturated compounds, never vinyl chloride, vinyl bromide, allyl chloride, allylbroaid, allyl iodide, 4-chlorobutene-1, 3-chlorobutene-1, 3-bromopene-1, p-chlorostyrene, p-iodatyrene, 4-chlorovinylcyclohexane, p -Chlorallylbehzol, 2,4-Diohlor8tyrol, 2,4-Difluororetyrol, 4-Chloro-1-viny! Naphthalin, Vinylidenchlorid, Vinylidenbroaid, 2-chloropropene-1, 1-bromo-chloroethylene, 2-Chloroallylchlorid, Methallylchlorid and 1,1 -bis- (p-chlorophenyl) ethylene.

Until the second group of honors of group A-forming compounds are old with internal olefinic bonds, never see from the general Foxsel results, sfrelf «oh in 1,2-3 division or three ethylenically substituted in 1,2,2-position Unsaturated carbon dioxide or helium-containing unsaturated Hydrocarbons and other linear and cyolic olefins.

As such bonds, those of the general Jorml, noria H ⁵ «ad E ⁴ alkyl, aryl, aralkyl, alkylaryl or oyoloalkyl groups, H * a hydrogen atom or the carbon hydrogen radical listed above, and B a group corresponding to the raw water radical listed above , prevent.

As connections of the. general formula

**
HC \ * 0 - B ⁵

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Not only do they have monocyclic * compounds but also polyolieohe compounds and cyclic compounds with Bridge bond used «earth.

Examples of such compounds are butene-2, 2-methylbutene-2, hexene-2, hexene ·?, 2-methylpentene-S, heptene-2, oetadeeen-2, γ -methallyl chloride, 1,5-biochloropentene-2, 1 - Ailoro-3-ethylbutene-2, i-chloromethylbutene-2, 8-ethyl- • tyrene, 4-phenylbutene-2, α, β-dimethylstyrene, β, fi-methylstyrene, 1,1-diphenyl propene-1 , Stilbene, a-methylstilbene, α-methyl-p-ohloretyrol, a-chloromethyletyrene, a-propenylnaphthalene, I-cyolohexylpropene-I, cyelopentene, oycloheptene, i- ^ ethyloyclobutene-i, 4-chloroyolohexene »indene, 3« srominden, 3-Setnylinden, Dihydronaphthalin, Aoenaphthylen, Iforbornen, 5-Kethylnorbornen, 5-Fhenylnorbornen, 5-Cnlornorbornen, 5,6-Diohlornorbornen, 7-Chlornorbornen _f 2-Hethylnorbornen _t ) f-? Enohen, Bornethylnorbornen, 5-chlorenomhen, Bornethylnorbornen. a-pinene "ad hyrtenyl chloride.

The third group of dl · Monoaeren Group A forming Polyenrerbindtingen "lad in aUgeaeinen polyoltfini- ■ oh · compounds such _as]>} iene trienes and tetraenes where a PoffittplHi nindeatene old aiadeatene 2 Waaaeretoff-: atoaen required iet. Such · polyene can tituesten old halogen or other sub, "the Polyoeri- _{(organization} nioht heanen substituted" one.

Examples of such compounds are 1,3-butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, i, 4-hexadiene,

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BATH

1,5-hexadiene, 2,3-dimethyl-1,3-butadiene, 11-ethyl-1,11-tridecadiene, myrcene, 1,3,5-hexatriene, 2-chloro-1 _f 3-butadiene, 3- i "luoro-1,4-hexadiene, p-di vinyl benzene, p-isopropenylstyrene, diallyloyolohexane, trivinylcyclohexane, 4" »vinylcyclohexene-1,2-methylallylcyclopenten-i, 3-allylindene, 4,7,8,9-tetrahydroindene , Bioyolo- (4,2,0) -octadiene-2,7, powders, 1,3-cyclopentadiene, 5-chloro-i, 3-pentadiene, 1,5-cyolooctadiene, 1,3,5-cycloheptatriene, A2 , 2 '~ bioyolopentenyl, dicyclopentadiene, 2,5-horbornadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, $ -Ieopropenyl-2 »norbornene _f 2-vinyl-1,4-endomethylene 1,2,3,4,5, 5a, 8,8a ~ ootohydronaphthalene, idaones and dipentene.

The acetylenic compounds which form the fourth group of the monomers of the group Δ can be given by the general formula E ⁷ OS CB ⁸ «. In the above formula, R denotes a waeeeretoff atom or a Koblenwaeeeretoffreet with 1-20 carbon atoms, optionally with substituting groups, for example a saturated or saturated kotaeovaststoffgruppe, alkyl, alkenyl, alkynyl, aryl, aralkyl, armolkenyl -, alkylaryl, alkenylaryl, oyoloalkyl or oyoloalkeayl groups, whether these groups carry halogen atoms or other inert substituents. R ⁸ denotes "la Waeeeretoffatoa or a polymerizable hydrocarbon group with 1 * 20 carbon atoms, or a polymerizable hydrocarbon group with 1-20 carbon atoms, which can be substituted by a halogen atom or another inert Oubetituemten, for example a group" with a double bond from Vinyl-,

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Vinylidene or vinyl type.

Examples of the above compounds are acetylene, methylacetylene, ethyl acetylene, 1-hexyne, phenylaoetylene, Cyclonexylacetylene, vinyl acetylene, divinylacetylene. Hexen-1-yn-4, butenylmethylaoetylene, allyläthylacetylen » Allylcyolohexylacetylene and allyl (p-chlorophenyl) acetylene.

The carbonyl or thiccarbonyl compounds forming the fifth group of monomers of group A correspond the general formulas

η ♦ * r% \ t

H ⁹ - C - Y - R ¹⁰ or R ¹¹ - C - N - R ^'10 .

Il Il

Z Z

In the above JS formulas, R * denotes a grouping R -, P ² O-, RS- or R * H ¹ * H-, where the ^{carbon dioxide free P 12} , R ¹⁵ and R ^{14 are} alkyl, aryl, aralkyl, alkylaryl , Cycloalkyl or cyclic carbons connected to one another by bridging bonds denote ra * e «retoffgroup« »n. These groups can eubewituiert AUOH ", and swsr with substituents * which sees the Copolyaerieationerealction hemen. In addition, carbon atoms or halogen atoms are often used. T β divides a Saueratoff- or 8ohulfur * tom or

«C IC

a group -BB ' ⁷ , in which B ^{7 has} the same meaning as the radicals R * and R. Z represents an oxygen or sulfur atom. B represents a polymerizable, unsaturated bond-containing hydrocarbon group having 2-20 carbon atoms. Ale polymerizable unsaturated

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Bond in this red becomes a vinyl or vinylidene group a vinylene group is preferably used at some point. In particular, a hydrocarbon radical is very often with a Viny! group and in many cases let the The radical H is the vinyl group itself. In addition, allyl or iopropenyl groups are also frequently used. As substituents halogens in particular come into consideration for the hydrocarbon radicals. Furthermore, substituents can be present, which contain a hetero atom which the copolymerization reaction does not bother, but such a position is necessary, that there is no conjugation with the unsaturated Bond occurs. R denotes an organic ring radical with 1-20 carbon atoms, which is not only made up of a sole material can exist, but can also contain other heteroatoms, in particular oxygen, sulfur or nitrogen atoms. For example, the groupings > 0 «0 |> 0 * 8, -0-, -S- or> -H-R ale part of the ring is present MiA. On the other hand, there is also a polycyclic structure «Öglioh.

Kare, the non-conjugated ^ unsaturated compounds generally have a bond type of the following type

-CYH ¹⁰

Ii

If the compounds meet the above condition, the reactivities of the monomers are similar and will be not essential because of the types of the other parts of the molecule

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17A5393

~ 17 -

influenced. Examples of such compounds are given below brought.

All representatives for unsaturated oxygen or sulfur compounds the unsaturated esters of carboxylic acids, toiolcarboxylic acids, thiocarboxylic acids, dithiocarboxylic acids, Carbonic acid, thi ο! Carbonic acid, thionic carbonic acid, di thiocarbonic acid, Xrithiocarbonic acid, carbamic acid, thiolcarbamic acid, Shioncarbaadna acid and dithiocarbamic acid are listed. He are representatives of unsaturated nitrogen compounds unsaturated cyclic amine compounds and compounds those unsaturated hydrocarbon groups on nitrogen atoms are bound, never 2.B. Carboxamides, thiolcarboxamides, Carbamates, thiol carbamates, thion carbamates, dithiocarbamates, Urea compounds and thiourea ▼ compounds should be mentioned.

Have di · unsaturated oyoliaohen iodine compounds dl · allgeMeln «Jormtl

11 -0-i.

woeu sB Laot «M _t Dloarbonaänreisidt, Dithiooarbonaäureimide, Oxaeolidone and Alkylenureas belong. These compounds can also be substituted by halogen or similar groups.

Examples of the above compounds are vinyl formate, vinyl acetate, vinyl propionate, vinyl pelargonate,

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BATH

Vinyl-2-ethyl-hexanecarboxylate, vinylotearate, Xthylvinyicxo'i.at, vinyl chloroacetate, vinyl thiol acetate, vinyl benzoate. Vinyl cyclohexanoarboxylate, vinyl norbornane-2-carboxylate, allyl acetate, allyl laurate, allylcyolobutanoarboxylate, 2-chloroallyl acetate, iopropenyl acetate, oc-methallyl acetate, 1-propenyl acetate, 1-Ieobutenylbutyrate, 1-ieobutenylbutyrate 0-methylcarbonylate, ethyl carbonate, vinylcarbonyl-O-vinylcarbonyl-vinylcarbonyl-O-vinylcarbonylate, O-vinylcarbonyl-O-vinylcarbonylate, allylcyolobutanoarboxylate, allylcyolobutanoarboxylate vinylthicncarbonate, phenylvinyltrithlooarbonate, O-vinyl-H, K-dimethylcarbamate, S-vinyl-If, B-diethylthiolcarbanate, O-allyl-Π, N-dimethylthionecarbamate, S-Iaopropeuyl-N, N-dietbyldithioarbaaatamide, H ± nyldithioarbaaat, H ± nyldithioarbaaat, Allyl-N-methylpropionic acid amide, H-vinylbeneeamide, Η-vinylthioacetamide, H-vinylurothane (H-vinyl-O-ethylcarbamate), 5-ethyl-H-vinyl-methylcarbamate, N-linyl-S-pheüyl-thioD.carbamate, N-vinyl-O-ethylthionoarbaaat, H-vinyl-H-ethyl-S-ethyldithiooarbamate, IT-ethyl-li-tinyl urea,!, H-diethyl-N-vinyl-N-ethyl urea, H-phenyl-H-vinylthio urea, H-vinylcarbamyl chloride, I-vinyl-S-ethyl-thiocaibaiiQrlohlorid, H-vinylpyrrolidon, I-vinylplpvrldon, I-vinylomoprolaotane, I-vinylb "rnet" ineäur "ljnd _# 1-Tiaylphthali ^ .d, -lllylbemeteinfliureiald, I-Ieoprop ^ aylphtballald, V-TlnjloxasolidlAon, I-Allyl-5- ^ thyloxj «oll * laea, I-Tinyldlelycoll ^ Ld, I-Vinyläthylenharnetoff, V-Ittaxojl-Ihametyletoff.

In the foregoing, items & fi of the invention have been incorporated Group A monomers shown in detail. Particularly preferred compounds of these monomers

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summarized below:

(a) Unsaturated hydrocarbon compounds and the like halogen-substituted compounds, i.e. terminally ethylenic unsaturated carbon dioxide, 1,2- or 1,2,2-substituted Ethylenically unsaturated hydrocarbons, polyenically unsaturated Hydrocarbons and halogen substitution modules of these connections.

(b) Unsaturated oxygen or sulfur compound from the Group of unsaturated esters of carboxylic acids, unsaturated carbonates, unsaturated carbonates and such compounds, in which a rope or all of the oxygen atoms are replaced by sulfur atoms.

(o) Unsaturated nitrogen compounds from the group of unsaturated carboxamides, unsaturated carbamates, unsaturated urea compounds and such compounds, in which some or all of the oxygen atoms are replaced by sulfur atoms. . .

Furthermore, these monomers Ib generally have one

low e- * ert near the Price-Alfrey's Q- »- Sehtma, the one Reactivity index for the monomers and those ■ Has an e-value of 0.5 or below, especially one negative zeal will produce very favorable results.

The monomers used according to the invention Group 'B are compounds old nitrile, carbonyl or thiocarbony groups in conjugated position with double bonds and let jsioh by the 'general formula

1 * 9837/1244

- 20 -

H ¹ CH β 0 - Q

reproduce, in which Q is a nitric group or a group -C - Y, where T ^f and Z ¹ denote the ζ meaning given above.

The usual hydrocarbon radicals are avoided and groups derived therefrom can also be used. Examples of this are alkyl and aryl * -, aralkyl, alkylaryl and cyoloalkyl groups · Furthermore, all halogen substituents chlorine, brob, iodine or fluorine can be used. Me means the monovalent portion of a bee tea of groups I-III of the periodic table or an ammonium group »· Ser-like elements uafaeeen sB lithium, Matrlum, potassium, rubidium, calcium, copper, silver, beryllium, calcium, strontium, barium, magnesium, sink, cadmium, mercury, boron, aluminum and gallium Metals of groups I-III the periodic table by Me *, that the monovalent · for Me of a weight element is Me '/ 2 and that · let the trivalent Eleaentee Ks * / 3 · Bs thus corresponds to "CH-C- Z ^ gMe * la lall elnee bivalent elements

and (CH ₂ = CH-C- Z4 ^ Me ^f in the case of a trivalent electrolyte.

109137/1244

Of these, the monovalent salts, ie the salts of the elements of group I and the ammonium ales, are particularly preferred. The fact that the grouping KH ¹ H "also includes the case where R ¹ and R" are each bound to positions other than the stickatoffatesi means "that here we are looking for morpholine-. Pyrrolidine or piperidine groups are included, ie

CH ₂ -CH ₂ ^ 2-? ^H 2> ^0H 2- ^CH 2 _v

-FC> 0, -H <I or -I \> CH ₉ . XJH ₂ -0H ₂ ^XN CH ₂ -CH ₂ ^x CHg-CH ₂ < ^&

Of the above compounds are listed here acrylonitrile, the aorylates, acrylamides, Η-substituted acrylamides, aoryloy halides, acrolein and vinyl ketones, as well as compounds in which some or all of the oxygen atoms of these oxygen-containing compounds are replaced by sulfur atoms, and alolohe compounds in which the hydrogen atoms in the carbon-carbon double bonds in the "- or f-position are substituted by hydrocarbon groups, halogen-containing carbon hydrogen groups or halogens, particularly if both R ¹ and R are hydrogen atoms," the above compounds are aorylnitrile unc compounds of acrylic acid or thioacrylic acid ·. These compounds include the aorylatt, thiol acrylate, thione aorylate, £ 1thioacrylate, acrylamide, thio aorylamide, Η-substituted acrylamide, K-substituted arylaoide,-substituted aorylane _t M, ir-di-substituted acrylamides, Ι, ϊ-disubstituted thio aorylaoide, Aoryloyl halide, thioacryloyl halide,

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~ 22 -

Aoryleic acid, thiolacrylaic acid, thionaaryleic acid, dithioacrylaMure, Salt these acids, acroleins, and vinyl ketones.

If neither R nooh H ¹¹ hydrogen atoms occur, one of the two rods can also consist of a hydrocarbon radical, a halogen-containing carbon atom or a halogen atom, or one of these leading groups with other inert substances in the carbon atom. Ale Kohlenwaseeretoffreete can be used at best alkyl, aryl, alkyl Ax · '"alkylaryl or Oyoloalkylgruppen. Since halogen used aleolohea or any substituent also includes chlorine, bron, iodine or fluorine, these compounds also include x-substituted and B-substituted aorylnitriles and compounds of aeroyl ethanoic acid and thioacrylic acid

Beiepiele for voratehenden compounds Bind "ethylaorylet, Ithylaorylat, a-Butylaorylat _f n-Anylacrylat, Ootadeoylaorylat, Allylaorylat, o-tolnolaorylat, Bansylacrylat, Cyolohexylaorylat, 2-Ohlorllthylaorylat, β-Chlorallylacrylat, Methyltnioaorylat, Xthylthioaorylat, Hethylthlonaorylat, Methylditaioaorylatr Aorylawld, Thioaorylamld, "-Metnylacrylanld, In-Butylaorylanid, V-2-lthyllMzylaorylaaid," -stearylacrylanid, I-Oyelohea ^ laorylaadd, I-foluylaorylanld, I-Äethylthioa "rylanid _v I, M>I> inatfcyUorylanid, -e-a-4l- Aerylylnorjholin, Aorylylsyrrelldln, 1,1-SlMthyl- «aoaorylanld, Aoryloyloalorid, AoryloylAroaid, Thioaeryloylehlorid« Aorylatore, fhldewsryleätir ·, Ihionaorylaflarn ·, Bithioacrylataliat, Sloryloryuna «.

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Aluminum aorylate, AtuEoniuisaerylate, acrolein, methyl vinyl ketone, Ethyl vinyl ketone and ethyl vinyl ketone. Voiterhin belong to the α- or Ε-substituted conjugated vinyl compounds Methylraethaerylate, ethylnothacrylate, butyl rivet baorylate, Octadecyl methacrylate, ben3yl methacrylate, phenyl methacrylate, Toluyl methacrylate, cyclohexylraethacrylate, 2-chloroethyl methacrylate, Äetlyrlthiolnethacrylat, Äthylthiolmethacrylat, Ethyl-o-ethyl aorylate, xthyl-a-liutyl acrylate, Methyl-a-cycloheotyl aorylate, methyl-ot-phenyl acrylate, methyl - «- chloroorylate, methyl-α-broaacrylate, methyl - «- (p-chlorophenyl) -aorylate, tfethacrylaaid, I-ithylaethacrylamid, H-Oyclohexylmethacrylaeid, I, I-J) ieethyl »etheorylamid, Hethacrylylpiperidin, α-X thy! acrylamide, a-Chloracrylaaid, a-Chleraethylacxylamid, Methacryloyl chloride, α-chloro-ayloyl chloride, α-ethyl methacryloylochloride, itothaoxylaic acid, thioluethaoryl acid, liatrium methaorylate, Zinc ethaerylate, aluminum methaorylate, ammonium a-fluoroacrylate, Methaoroleln, Methieopropenylketon, 1-Chlor « butenyl ethyl ketone, methacrylonitrile, a-ethyl acrylonitrile, α-Cyolohexylacrylnitril, «-Chloraorylnitrll, oc-Chlormethylacrylnitril, Xthylorotonate, phenylorotonate, crotonainide, Crotonoyl chloride, Crtrtoni-Iril, methyl cinnanate, butyloinnamate, Chlornethylciimeaftt, cinnaenitrile, methyl-ß-ethyl acrylate and methyl ß-ohloreettylaorylate.

The catalyst bed parts that can be used in connection with the invention are (1) compounds of the general formulas MR ^ ¹ JC _3-11 , * · 1 ** ₃ or Μ «Χ · ₅ » in which M, M ¹ and H "aluminum or Boron, R "'and R Common organic residues,

109837/1244

X and X * halogen atoms and η any number from 1-2 mean, or (2) (a) organic compounds of metals of groups lib, HIb or IYb of the periodic system and (b) Halides of metals of groups IHb or IVb dee Periodic table.

In the aluminum or boron compounds of the general formulas MR ^IM _n X _5-n , M ^f R ^IV ₅ or Μ »Χ« ₅ , the radicals R " ¹ and R ^{IV are} preferably formed from hydrocarbon radicals with 1-20 carbon atoms groups derived therefrom and having inert substituents in these radicals can also be effectively used. The preferred groups are, for example, alkyl, alkenyl, aryl, aralkyl, alkylaryl or cycloalkyl groups. Methyl, ethyl and propyl are particular examples -, butyl, hexyl, octyl, decyl, dodecyl, stearyl, phenyl, toluyl, haphthyl, beneyl, cyclopentadienyl and cyolohexyl groups. All groups X and X ^f are chlorine, bromine, iodine or fluorine is used.

Example "eind following these links: Under dl · compounds of the general formula MR"_'n X _3-n falleniMethylaluainiu ^ dichloride, Xthylaluniniumdlohlorld, Iiobutylaluminiuadiohlorld, Hexylalumlniumdiehlorld, Dodeoylaluniniuadiohlorid, PhenylalualniumdichlorId, Cyclohezylalumlniuadiohlorld, Methylalumlniumdibromid, Xthylalumlniuadljodld, Allylalualnluadlohlorld, IthylaluminiumsesquiChlorid, Athylalu "! nluwsesqulbromid, Ethylaluelniumsesqulfluorid, Methylaluminiumsesquichlorid, Diethylaluminiue- .. Chloride, Dl & thylaluainiumfluorid, Ithylphenylaluminiuechlorid,

101837/1244

Dicyolohexylaluminum chloride, methyl boron dichloride, ethyl boron dichloride, ethyl boron iodide, butyl boron dichloride, hexyl boron dichloride, dodecyl boron dichloride, phenyl boron dichloride, benzyl boron dichloride, boron boron, diboron boron, dibloboronylboron, di-boron boron, di-boron boron, di-chloro-boron, di-boron, di-boron-boron, di-dichloro-boron, di-boron-boron, di-chloro-boron, di-boron-boron, di-dichloro-boron, di-dichloro-boryl chloride, The compounds of the general formula M'R ^ include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, iridecylaluminum, ^ O? Tricyolohexyl boron. The compounds of the general formula M "X ^f include aluminum trichloride, aluminum tribromide, aluminum triiodide, partially fluorinated aluminum chloride, boron triochloride, boron trifluoride, boron tribroadide and boron triiodide.

Diethylene organieohen compounds of metals of groups Hb, IIIb or IVb de · Periodeneyat · * · that gesäfi dea gate !! • constricting process al · Beetendteil · de · catalyst (2) ä used "ground, eind those dl · contain zinc, oadaiua, mercury, boron, aluniniun, oalliua, indium, thallium, oreraaniue, tin or lead as metal constituents. In particular, the metal compounds of zinc, boron, aluminum and tin are to be used. The usual hydrocarbon groups or derivatives derived therefrom can preferably be incorporated as organic groups. Particularly effective *

1 * 9137/1244

same compounds are those with alkyl, alkenyl, aryl, aralkyl, alkylaryl and cycloalkyl groups. The metals are also used in the case where the compounds have groups other than the organic groups. Special Organometal! compounds are valuable in general Formula:

^{Ά Λ} JT pn

where M " ^{1 is} a metal from groups lib, IUb or IVb of the periodic table, H is a hydrocarbon group with 1-20 carbon atoms or a group derived therefrom, X ^{n is} a halogen atom, ρ is the valency of the metal and η is a popular" * "M - ▼ on 1 bie ρ mean. In general, the compounds are particularly effective if η * p. If necessary kunaen "" oh organic compounds of the metals of groups ZXb, ZZIb or ZYb of the periodic table "are used"

w Examples of the above compounds are

Ditthyleink, Ithyleinkohlorid, Diethylcadmiua, Diethylmercury, Diphenylqueekeilber, triethyl boron, tributyl boron, Trioyolohexylboron, Ithylborbromld, Triäthylalusinium, IrI-bu ty! aluminum, irlheiqflalaminium, irioyolohexylaluminium, . Vinyl diethyl aluminum, diethyl aluminum chloride, ethyl aluminum sesquiohlorid, Xthylaluminumdichlorid, TrimethylfAlliua, Triethylindium, Tetraätylgermanium, Tetramethylinn, Tetraäthylinn, TetraisobutylBinn, Dimethyldiäthylainn, Tetra-

• ·

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phenyltin, tetrabenzyltin, diethyldiphonyltin, tristhyltin chloride, Diethyl zimidiochloride, ethyltin trichloride, Tetraethyl lead, dietraethyl lead, dimethyl diethyl lead and Triethyl lead chloride.

On the other hand, the metal halides used are halides of metals from groups IHb or IVb of the periodic table. Examples are the compounds of boron, aluminum, gallium, indium, thallium, germanium, tin or lead. The halogens that can be used are chlorine, bromine, μ iodine or fluorine. All such metal halides can also be used with groups other than halogens. Particularly preferred metal halides in the present process are compounds of the general formula:

wherein H is a metal from group HIb or IVb of the Ferioden-

VI

systems, R is a hydrocarbon group with 1-20 carbon atoms or a group derived therefrom, q the valency of the metals and m any number of 1 to q. In general, very favorable results are obtained »if μ» q. If necessary, can also Halides of other metals of groups HIb or IVb des Periodic table can be used.

Examples of methods according to the invention are valuable Metal halides are: boron triochloride, boron trifluoride, boron tribroedd, Boron triiodide, ethyl boron dichloride, diethyl boron chloride, Aluminum trichloride, aluminum tribromide, aluminum triiodide,

109837/1244

^BATH ORIGINAL

_r partially fluorinated Alurainiumchlorid, Athylaluminiumdiehlorid, methylaluminum, ÄthylaluminiumseaquiChlorid, Diäthylaluiainiumchlorid, gallium trichloride, Galliumdiehlorid, germanium tetrachloride, tin tetrachloride, Zinntetrabroinid, Zinntetrajodid, Äthyleinntrichlorid, MethylBinn.tr ichlorid, phenyltin, dimethyltin, Diäirhylzinndiohlorid, SiIsobuty! tin dichloride, Triäthylzlnnchlorid, lead tetrachloride and Diäthylbleidichlorid.

If the catalyst (2) is a combination of one Organo bond of a metal from groups lib, IHb or IVb of the periodic table and a halide of a metal from groups IHb or IVb of the periodic table are used, «Ground the organometallic compound and the metal halide used without prior rental. See mixing this up Compounds are eumindeet in the presence of a conjugation Durable vinyl facing. In particular, favorable results are obtained when the conjugated vinyl compound and since «metal halide are previously deformed, whereupon the Sugabe of the organo-metal connection is made.

The organic used in the present processes Peroxides are generally organic compounds with peroxide bonds and hlersu belong s.B. Diacyl peroxides, ketone peroxides, Aldehyde peroxides, xtherperoacides, hydroperoxides,

Dinydroearbyl peroxides, persaureneaters, dihydrocarbyl percarbonates and percarbonates. Examples of such compounds are bencoyl peroxide, lauroyl peroxide, 2,4-dichloro

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benzoyl peroxide, 4-chlorobenzoyl peroxide, acetyl peroxide, stearoyl peroxide, phthaloyl peroxide, methyl ethyl ketone peroxide, gyolohexanone peroxide, t-butyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide. Di-t-butyl peroxide, dioiunyl peroxide, t-butylcunyl peroxide, t-butyl perbenzoate, t-butyl perisobutyrate, t-butyl peracetate, t-butyl peroxypivaleate, phenyl percarbanate, diisopropyl * pero carbonate and t-butyl perieopropyl carbonate. However, the peroxides which can be used according to the invention are not limited to the % of the above compounds. If there is such a tendency that the higher the rate of radical decomposition of these peroxides, the greater their acceleration effect.

In the practice of the present invention, the Katalysatorbeetandteile in the desired proportions, "can be ingeaetst, but a ratio of 0.005 is 10 * ₉ MoI particular 0.02-1.5 mol je'Hol conjugierten the compound of group B h & btvorsugt IFIG. In general terms, favorable brines are obtained when the halogen-containing metal compound is used practically in a mquiaolar manganese for conjugated use. Of course, it is also aUglioh, di · metal compound la excess or below used in smaller amounts, FIf jedooh the halogen-containing metal compound is used B in an excessively low Verhiltnis to the oonjugierten compound of Group ^1, there are some Vttlle where the PoIynerisationsaktivitat is greatly reduced . It is therefore

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17A5393

Not very favorable if the concentration of this metal compound is made excessively low. At relatively low concentrations of the halogen-containing metal compounds, it is generally effective if the polymerization is carried out, in particular in the presence of an organic peroxide or of oxygen. They effect dee organic peroxide or dee oxygen is observed at Soloh low temperatures such as -76 ⁰ C. These ingredients give sufficient

fc high potency even when in relatively small amount be used. For example, an acceleration effect becomes observe what organic peroxide or oxygen there is in a quantity of about 0.01-5.5 *, based on the conjugated Connection, is applied. Bs is of course possible, these compounds also at higher or lower concentrations use su. Generally speaking, favorable results are obtained when the metal compound contains halogens contacted with the ooajuglerten connection and in complex form * Is transferred before Al Sugase 4 organic per-

Ψ oxji * or d ·· SsjMMftrtoff · takes place. Di · Katalyeatorbeetandtttlle kffuMtt MMii M de "Moaoaergesdsoh sugeMtst will".

The .Poljaerlsatlonrteaperattzr came gewttnsohtenfalle in a tes9 * raturb "r" ioh swleo] i «a such a low temperature wi · -15O ⁰ O to a s" o high temperature such values chosen +100 ⁰ C.

Diethylene Oopolymerlsationsreaktion gemaB the present invention proceeds rapidly swlbst toi eiemlich low temperature door off worau · look sohlie8en IaJt ₉ DA8 the Iktivierunge-

10M37 / 1J44 BADOR ₁ Q ₁ NAt '

energy of the geeasit reactions becomes very low.

The method according to the invention can either be corresponding a polymerization in the measure in the liquid Monomers or in the presence of customary inert solvents are carried out. These solvents include the common hydrocarbons and halogenated hydrocarbon compounds. Examples are propane, butane, pentane. Hexane * heptane, octane, ligxoin, petroleum ether, other mixed solvents from the petroleum group, benzene, toluene, xylene, Cyclohexane, Methylcyclohexane, Methylend.icb3.prid, EthylenendiChlorid, Ir i chlorothy len, tetrachlorethylene, butyl chloride, Chlorobenzene and bromobenzene are listed, tile already above are compounds that form stable complexes Form catalyst bed parts, not desirable as a solvent.

Haoh the completion of the polymerization reaction the top treatments according to the usual cleaning methods and (tewimmae dei polymerization products β durohgejTUhrt. Examples of how can alcohol treatments, alcohol salesmure treatments, Saleetture water treatments, alkali treatments and the like or those in conventional polyaeration processes using Lewie acids or Catalysts of the Ziegler-Iatta type applied hair treatment process can be used in the desired manner. It is also used in processes but separation and recovery the catalyst components from the polymerization

109137/1244

^BA ^ original

to use the product without the catalyst components EOTO being depleted, for which purpose compounds that are capable of forming complexes with it are added.

The following examples illustrate the present invention furthermore »without this limiting the invention.

example 1

Sin has been ml with stirrer equipped 300 aiaeautoklav old flushed nitrogen and charged old 62 ml of toluene and 0.125 amol Bensoylperosyd and cooled to -78 ⁰ C. In this reaction vessel, 200 μl of methyl acrylate, 100 mmol of propylene and 100 μl of vinyl chloride were added in this form and liquefied. Furthermore, a solution of 100 waste oil ethyl aluminum sesquiehloride (AlXt ₁ 5Cl ₁ ^) in 38 ml of toluene was sugegebes. The temperature was then raised to ⁰ ° C. and the polymerization was carried out for 5 hours with stirring. The unreacted gas was sucked off and the contents were placed in the heating vessel in a large amount of methanol. Then the deposited solid was · grilndlioh old methanol washed and la vacuum dried at 40 ⁰ O to obtain 9.2 g of a white solid Oopolyaeren were obtained. The result of the Bleaentaranalyee the Oopolymeren was Ot 60.16 Jt ₉ Ht 8.26 J (, 01 £ 6.87. The amount of methyl aorylate determined according to the Salftmgsrerfahren was 52.4, based on the copolymer, which from the halogen determination.

109137/1244

The amount of vinyl chloride determined was 13.1 moles and the amount of propylene 3415 S

Example 2

Dae same Reaktionegefäß as charged in Example 1 with 30 ml of toluene and 40 iriMol tin tetrachloride under nitrogen "and at -78 ⁰ C 40 mmol of methyl methacrylate Bugegeben. To the reaction vessel was added me 40 mmol Triäthylalunjinium, 100 mmol isobutylene and 100 mmol of vinyl acetate and the temperature to 29 ⁰ O homogeneously mixed compounds. After raising the mixture was treated nourishing two hours wherein Stickstoffgae was injected with a content of 5 # oxygen, wherein 1.31 g of a ternary copolymer was obtained.

Example 3 _v

Under nitrogen, the same as HeaktionsgefäB was charged in Example 1 with 62 ml of toluene and 0.125 mmol Beneoyiperoxyd and cooled to -78 ⁰ O. In the Beaktiona- i gefttB me 100 "Mol Methylaorylat, 100 mmol acrylonitrile, vinylidene chloride fiOO mmol and 200 mmol Xthylalumini'umeeeqiuichlorid added (as a solution in 38 ml toluene) in this order, and the temperature increased to O ⁰ C. The monomer mixture was polymerized for 5 hours while stirring, 1.34 g of tine ternary copolymer being obtained. The deaentar analysis values of the copolymer were: C 38.19 *, Hi 3.65 ^, Ns 3.41 $ and Cl: 44.48 £. The salary

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17A5393

on the respective monomers, calculated from the chlorine content, the Brgebnleeen des Vevseifungeverfahrene and the Analyeenirerte of nitrogen was 52.6 Hol-ft of vinylidene chloride, 27.0 oil methyl aerylate and 20.4 hol acrylonitrile.

If the polymerization under the same conditions never above, but with 200 mmol of ethyl boron dichloride Instead of ithylaluminum chloride and benzoyl peroxide was used, a tern & res copolymer was also used obtain.

Example 4

A 200 ml four-shark flask was evacuated and flushed with nitrogen. The flask was basobiokt with 75 ml of toluene, 100 mol of methyl acrylate and 100 mol of acrylonitrile under nitrogen. Then at -7S ⁰ C 100 mHoI XthylaluainlumseaquiohlordLd (contained in 25 ml toluene) were etst. After raising the temperature to ⁰ ° C., 200 mmol of etyrene were added while listening and the bed parts were reassigned for 2 hours. The light yellow, homogeneous and transparent reaction flux obtained was treated in the same way as in Example 1, 12.94 g of a white, solid oopolyera being obtained. The fundamental solar viscosity of this copolymer "" measured in acetone solution at 30 ⁰ O, amounts to 6.77 dl / g. Based on the presence of carbonyl, htril and phenyl groups, it was confirmed that the copolymer is part of a tertiary copolymer.

109837/1244

example 5

Under nitrogen, the same flask vi ± e in Example 4 with 50 al of n-heptane, 50 mmol Methylthiolaorylat and 50 mmol Ä-Äthylaorylamid beaohickt was cooled to -78 ⁰ C and further treated with 100 mmol Bortrichierid. 50 mmol of diethylink were then added to the flask. After increasing the temperature to 25 ⁰ O, 200 mmol of styrene were further cugesetst. The monomer mixture was polymerized for 2 hours with stirring to obtain 5.33 g of a ternary copolymer.

Example 6

Under nitrogen the same Heakticneeföß Ίβ in Example 1 was besohiokt with 15 ml of toluene and 0.125 mMcl of benzoyl peroxide. Haoh cooling dee Xclbene to -78 ⁰ C were added 250 mmoles Methyla '■ *% and 500 mmol of propylene was added and liquefied. The flask was further charged with 25 mMcl ethylaluminium / cesquichloride and the temperature increased to ⁰ ° C. Then 25 mmol of dicyclopentadiene was added while stirring and the monomer mixture was polymerized for 5 hours, whereby 17.35 g of a white solid copolymer was obtained. This copolymer gelled and became insoluble during the treatment.

Venn polymerization at 0 ⁰ C using the same moaoaergemiaohes was performed as above, but instead of Divinylbeneol Dioyolopentadien used Xthylaluminiumseeq.uichlorid the final züge-

10S837 / 1244

BATH ORIGINAL

was given, so that the order of addition of the ingredients was changed, 9.55 g of θineβ white copolymers were obtained.

Furthermore, a ternary copolymer, which by using butadiene instead of! ^. cyclopentadiene was obtained, a Jodeahl of 146.

Example 7

Sticketoff under the same reaction vessel was cooled as in Example 1 to -78 ⁰ C and ml with 20, 50 and 80 Alfol DiäthylaluBiniuiochlorid mtfol acrylonitrile-heptane n charged. 50 millimoles of isoprene and 200 millimoles of α-methyletyrene were introduced into the reaction vessel. After increasing the temperature to ⁰ ° C., the monomer mixture was polymerized for 1 hour, 3.16 g of a ternary copolymer being obtained.

Example 8

The same reaction vessel as in Example 1 was charged with 15 al toluene under nitrogen. Vaohdea the ReaktionagefEß was cooled to -78 ⁰ C were added 0.125 mHol Benaoylperoxyd, 500 alfol'Propylen, 250 Alfol methyl acrylate and eye give 100 Alfol 1,5-Oyoloootadien. The mixture was then mixed with 25 amoles of ethylaluminium chloride-eeequiohloride, while stirring uniformly. The temperature was increased to ⁰ ° C and the Wonoasrgeaisoh set for 5 hours. AnsohlisBsnd words the reaction liquid old methanol treated, which

109937/1244

17A5393

Phenyl-S-naphthylamine contained all stabilizers, with 11-48 g of a ternary copolymer ** with an iodine cream. 6.4- were obtained. From this Jodaahl and from the analysis of the ester group content it was found that dl *? The total volume of the copolymer was 1.8 mol- # cycloootadiene, 56.4- mol- # methyl aorylate and 41.9 mol- # propylene. 1 part of stearic acid, 5 parts of zinc white, 50 parts of HAP carbon black, 1.5 parts of sulfur, 1 to 5 parts of tetramethylthiuramide sulfide and 0.5 part of mercaptobenzothia oil were added to 100 parts of the oopclynserea the mixture cured at 160 C and 50 kg / cm for 40 minutes, a vulcanized product with a? Tensile strength of 114 kg / on ² and a tensile strength of 500 i> was obtained.

If the polymer! Aation under the same conditions as above, but using isobutylene instead of of propylene, 34.45 g of a ternary copolymer was obtained.

i Example 9

The polyeerieation was carried out under the same conditions carried out as in example β, but 4-vinylcyclohöxen used instead of oyoloootadiene, where «in ternärβa Copolyaere · bit of an iodine steel of 4t3 was obtained that was curable well with sulfur.

109837/1244

Beiepial 10

under nitrogen, a four-neck flask of 200 ml alt 500 al n-heptane, 20 mmol aluminum chloride and 20 mmol Trihexylaluainium charged and the compounds mixed homogeneously. After cooling the flask to -78 ° C 40 oMol ethyl acrylate added. Furthermore, 50 mmol 2-butene and 50 alfol phenylacetylene added and the monomer Reacted for 8 hours with stirring, with 2.05 g of ternary copolymers are obtained.

101137/1244

Claims (1)

Claims 1.) Aue of several alternating components Copolymer containing at least 5 monomer units, clie (A) nindeetena one of the monomeric compounds (1) terminal ethylenic unsaturated compounds of the general formula: CH 1 2 before H and R Waaeer et off atoms or halogen atoms, Kohlenwaeeeretoffreate with 1-20 carbon atoms, Kohlenwaseeratof. - ^ q with 1-20 carbon atoms or ¹ such groupings with further substituents, (2) compounds with an internal olefinic bond of the general formula: E ⁶ E ³ - HO · C <e or HC «0 - R ⁵ where R * and R * carbons * aa «eratoffreBeBe with 1-20 carbon atoms, halo-containing coals ^ aeeeretoffreete with 1-2C Carbon atoms or such groups with further subs tuenten, R a Vasaeretoffatom, a Kohlenwaeseretoffreet with 1-20 carbon atoms, a halogen-containing carbon 100837/1244 hydrogen radicals with 1-20 carbon atoms or such radicals with other substituents and Jr a cyclic hydrocarbon radical with 1-20 carbon atoms, the heat of a halogen-containing carbon hydrogen ring with 1-20 carbon atoms or such groups with further substituents, (3) Polyene compounds with up to 30 carbon atoms which have at least one carbon-carbon double bond have at least swel hydrogen atoms, (4) aoetylenisehe compounds of the general formula: H ⁷ C β CH ⁸ where H 'is a hydrogen atom, a hydrocarbon residue with 1-20 carbon atoms or one such group with further Substitusntsn and R is a hydrogen atom, a, containing a polymerizable * unsaturated group Hydrocarbon radical with 1-20 carbon atoms or one Group with further substituents »mean, or (5) Carbonyl or ihiooarbonyl compounds of the general Goal opinion ⁹ - O - T - T - R ¹⁰ or R ¹¹ - 0 - I - R ¹⁰ wherein R ^{9 is} a grouping R ¹² -, R ¹² O-, R ¹² S- or S ¹ V ⁴ H-, 2 is an oxygen or sulfur atom, T is a Sausretoff or sulfur atom or a grouping -IR ¹⁵ , R is a one 109837/1244 17453S3 Hydrogen radical containing polymeric unsaturated bonds with 2-20 carbon atoms odo.T such a Group with further substituents, H a crgani- 12 see a cyclic bed with 1-20 carbon atoms, E one Hydrocarbon rust with 1-20 carbon atoms or one such heat with substituting groups and P .. P. 15 uxid R hydrocarbon radicals with 1-20 carbon atoms, such radicals with substituting groups or hydrogen atoms mean, as Monomerea A and (B) at least one monomeric conjugierten ¹ Ve: nindung of the general formula!: R ¹¹
R ¹ CH -CQ where R and R Eohlemfaeserstoffreste with 1 ~ 2O carbon atoms * »0 - Y» mean, where T ^{1 is} a grouping Z ^, 2 R, S ² Ks, IR ^ R ¹ ·, R or «in halogen or hydrogen 12th
atom, 2 and t oxygen or sulfur atoms, R an organic residue with 1-20 carbon atoms, R * uM B ^{! l} Waeseretoff atoms or organic residues with 1-20 carbon atoms, eiÄSof the Pallee, where R ⁽ and R "to others Places than are bound to the nitrogen atom, and Me den 108837/1244 monovalent portion of a sienente of groups I to III represent the period equations or an ammonium group, exist as monomersQ B, the monomers of the groups A and B are essentially alternately connected. 2) copolymers according to claim 1, characterized in that dafi daa group A monomers (A) an unsaturated hydrocarbon or an F halogen-substituted derivative thereof from the group of terminally ethylenically unsaturated hydrocarbons, the 1,2- or 1,2,2-substituted ethylenically unsaturated Hydrocarbons, polyenically unsaturated coal « substances or acetylenically unsaturated carbon mass substances, (b) an unsaturated oxygen or Schiefelver- ~ binding to the group of unsaturated carboxylic acids, unsaturated carbonates, unsaturated carbamates and such · compounds in which a fur or the whole the hydrogen atoms are replaced by sulfur atoms, or (o) unsaturated nitrogen compounds from the group the unsaturated carboxamides, the unsaturated carbamates, the unsaturated urea compounds and such compounds, wherein one or all of the oxygen atoms is replaced by a sulfur atom and these monomers measured up to 0.5 according to the Brice-Alfrey-Qe scheme
and the monomer of group B ₉ that of a compound with • * a litrile, carbonyl or thiocarbony group in conju- 109837/1244 clearer position ssu a carbon-carbon double bond, from the group of acrylonitrile, acrylates, acrylamides, M * -substituted acrylamides, acryloyl halides, acrolein or vinyl ketones or such compounds in which some or all of the oxygen atoms are replaced by sulfur atoms, or such compounds in which the hydrogen atoms of the carbon-carbon double bonds in the a- or fi-position of the compounds are replaced by carbon atoms, halogen-containing Koalenwasceratoffgruppen or halogen atoms. ™ 3.) Copolymer * according to Anepruoh 1 or 2, consisting of monomers of group A and monomers of group B ₁ , the monomers of group A and the monomers of group B being alternately connected. 4 ·) OopoljMir ·· naoh claim 1 or 2, defeating from a monomer belonging to group A and two monomers belonging to group B, where the "monomers" of group A and the monomers of group B are connected alternately. 5. Process for the production of an Oopoljmeren consisting of several constituents, characterized in that at least three monomers from groups A and B listed in Claims 1 to 4 are included
(1) an · «Organo-tallhalogsnid of the general Vomel: 109837/1244 where H is aluminum or boron, R " ^{1 is} a customary organic radical, X is a halogen atom and η is any number from 1-2, or with a mixture of at least 2 compounds of the general formulas MR » ¹ J ₁ X _5-11 , M« R ^IV ₅ or M ¹¹ X ¹ ₃ where M, M "and M" aluminum or boron, R "'and R ^{IV are} customary organic radicals" X and X * halogen atoms and η are any number of tone 1-2, or with (2) fine-contact with an organometallic halide component, which after a complex formation process by mixing and contacting at least in the presence of the conjugated Termination of group B of the monomers, (a) an organic termination of a metal of groups Hb, IIIb and ITb of the periodic table with (b) a halide of a metal of groups XIIb or ITb of the periodic table dice, where at least one of these compounds (a) usA (b) sns consists of an aluminum or boron compound. 6.) Terfskren neon Anspruoh 5, thereby marked, dsJ the copolymerization is carried out in the presence of oxygen or organic peroxides. 7 ") Peat oven according to claim 5 or 6, since the copolymerization is carried out at temperatures in the range from -15O ⁰ O to +100 ⁰ O. 109837/1244 B.) Method according to Anopruch 5 Die 7, characterized in that that the catalyst is used in an amount of 0.003-10 moles per mole of the monomers of group B, 9.) The method according to claim 5 bia 8, characterized in that the copolymerization is carried out in a liquid i-iono-mexdiit in a Kohlenwaeseratoff or a halogenated hydrocarbon as a solvent. 109837/1244