DE2257221A1 - PROCESS FOR THE PRODUCTION OF ALPHAOLEFIN POLYMERS - Google Patents

Description

Dr. Werner Haßler _ .., "-., _O. ", "« No _o

PATENT ADVERTISER Ludenscheid, November 21, 1972-8

588 LÖDENSCHEID A 72 165

Asenberg 30 P.O. Box 1704

Applicant: Mitsubishi Petrochemical Company Limited 3-1, Marunouchi 2-Chome, Chiyoda-Ku, Tokyo, Japan.

Process for Making % -olefin Polymers The invention relates to the production of % -olefin polymers.

The field of application of the invention is the production of ^Λ ν-olefin polymers by a solvent-free process in which no non-reactive solvent is used. The aim of this process is the production of OC -olefin polymers of high crystallinity using a special Ziegler catalyst.

The polymerization of propylene using a Ziegler catalyst or a Ziegler- ^ Natta catalyst takes place usually after the precipitation polymerization, where a non-reactive Solvent, for example a hydrocarbon, is used, so that the polymer is obtained in a slurry. Among the most widely used manufacturing processes is a treatment stage - to remove the catalyst residue, a treatment stage to extract the atactic Polymers and a treatment step required to recover and purify a large proportion of the solvent; these treatment stages are determined by the demands of the customers in terms of mechanical, physical and chemical properties of the polymer formed accordingly

__ ■ 309822/1074

of the desired quality. Bring these levels of treatment various disadvantages such as a complexity of the course of the process with it, whereby the economy of the process management is adversely affected.

For this purpose, the solvent-free polymerization, namely ¹ the gas-phase polymerization or the polymerization in the solvent-free liquid phase, brings about a solution. Because the difficulties mentioned can be completely eliminated if the catalyst used has a high activity or a high yield, so that the removal of the catalyst residue is unnecessary, and if the catalyst used has a high specificity for a polymer of high crystallinity, the meets customer requirements without the need for a treatment step to extract the atactic polymer.

The previously known solvent-free polymerization processes however, are not entirely satisfactory. The catalyst used is not without problems. Because in In some cases where the catalyst has a high activity, the stereospecificity of the polymer formed is low.

Titanium trichloride is obtained by reducing titanium tetrachloride. Suitable reducing agents are: hydrogen; reducing metals such as titanium, aluminum or silicon; Metal hydrides such as aluminum hydride or silicon hydride; organometallic Compounds such as organoaluminum compounds.

Titanium trichloride occurs in three modifications, in Ö ^ ß-shape and / -form according to the respective crystal shape. Usually the crystal form of titanium trichloride becomes different depending on the type of reducing agent and the reducing conditions. If the reduction with Hydrogen, with metallic titanium, with silicon hydride or the like takes place, one obtains ^ '- titanium trichloride. If the

= - 3-na.fi '?? / Ulli _

Reduction is carried out at a low temperature with an organoaluminum compound or the like, β-titanium trichloride is obtained. It is known that grinding titanium trichloride increases the activity for the catalytic polymerization of Λ - olefins increase significantly. In most cases, titanium trichloride is used as a polymerization catalyst in industrial applications eiiE activation treatment such as milling. TiCl, of the AA grade is a titanium trichloride, which by reduction with metallic aluminum obtained from titanium tetrachloride and activated by grinding. .Although it is known that the effective The surface of the catalyst is increased by grinding and that the titanium trichloride is brought into an amorphous state is, but the reasons for the increase in catalyst activity are still largely unknown.

The use of halogenated hydrocarbons to various Purposes in the polymerization of <V-olefins under The use of a Ziegler catalyst is known. Such an application of halogenated hydrocarbons where the same mixed with titanium trichloride and ground to improve the crystallinity of the polyolefins is in the Japanese Publication Nos. 24272/1964 and No. 23503/1969.

The titanium trichloride is ground in each case. In the first proposal, a halogenated aromatic hydrocarbon is present during the milling process. According to the second proposal, a halogenated aromatic hydrocarbon is introduced after the grinding of the titanium trichloride in order to eliminate a reduction in the polymerization yield due to the presence of the halogenated hydrocarbon during the grinding process. Both publications relate to precipitation polymerization, where the polymerization takes place in a solvent. According to German Offenlegungsschrift 2,052,525, disclosed on 28 April 1971 y -Titantrichlorid obtained by reduction of titanium tetrachloride with aluminum. This titanium component is carefully

3 0.9.8.2 Il 107 A

ground in the presence of a halogenated hydrocarbon until there is no longer a * V-shape or λ- shape in the structure. The resulting titanium composition is then extracted using a solvent such as an aromatic hydrocarbon and used as a titanium component for a Ziegler catalyst in precipitation polymerization or solvent-free polymerization. An essential feature of this process is that the titanium trichloride is present in> form before milling and that solvent extraction takes place after milling.

The object of the invention is to provide a solvent-free A polymerisation process which produces a polymer which can be used essentially without post-treatment.

This object is achieved according to the invention in that a / V-olefin in the substantial absence of one Polymerization solvent is exposed to the action of a catalyst system, which by combining a solid Composition obtained by grinding, ^ - titanium trichloride in Presence of a halogenated hydrocarbon is obtained, and an organoaluminum compound.

Characterized in that according to the invention a solid, which by j mixing and grinding a special titanium trichloride, namely a & -Titanium trichloride with a halogenated hydrogen is used as a component of a Ziegler catalyst, and that solvent-free polymerization, preferably gas phase polymerization, is used, is obtained a polymer with high stereospecificity in a high yield based on the catalyst.

The use of a (Dtf titanium trichloride and the grinding of the same with a halogenated hydrocarbon, both are critical Features within the scope of the invention. If namely titanium trichloride by fleduction of titanium tetrachloride with metallic A] umi-

nium is prepared and is therefore present in> form, is not missing only the favorable influence of milling with a halogenated hydrocarbon, but in some cases it shows namely the comparative examples 22, 23, - 24 a catalyst effectiveness, which is inferior to a catalyst obtained by grinding titanium trichloride alone. No additional beneficial effect can be demonstrated if the halogenated hydrocarbon is only used as an additive is used in the preparation of the catalyst slurry before the polymerization, as in the comparative examples 4- to 21 show. The favorable influence of the invention is also not present in the precipitation polymerization, as in the comparative example 23 reveals.

In the following detailed description, all important measures within the scope of the invention are dealt with »

1. Ziegler catalyst .

1). Titanium component

^ -Titanium trichloride is used. When the titanium trichloride normally produced by reducing titanium tetrachloride, a reducing agent must be used that gives. ^ - titanium trichloride, so Hydrogen, metallic titanium or a hydrogenated silicon compound. If possibly titanium trichloride another modification may be present in a mixed state depending on the manufacture, An admixture of titanium trichloride of different crystal forms in small proportions is permissible as long as the beneficial influence remains within the scope of the invention.

The. ^ - modification of titanium trichloride can be given by ' Detect X-ray diffraction. Then, namely, very intense diffraction lines can be found at diffraction angles h

ο ρ prove that the lattice constants 2.72 A, 5 »85 A,

3-09822 / 1074 .

ο ο
1.77 A, 2.12 A etc. Various examples of halogenated hydrocarbons suitable for co-milling with the C-titanium trichloride are enumerated below. The beneficial influence of joint milling with bc -titanium trichloride can be seen essentially with all halogenated hydrocarbons. These hydrocarbons should preferably contain a Cy to Cg hydrocarbon radical. The following hydrocarbons are particularly suitable:

(1) Halogenated aliphatic hydrocarbons. Carbon tetrachloride, chloroform, dichloromethane, Ethyl chloride, 1,2-dichloroethane, (1,1 ', 2,2') - tetrachloroethane, hexachloroethane, (1,1 ', 2,2') - tetrabromoethane, ^ ropylchlorid,

(( 1,3), (1,2)) -dichloropropane, (1,2,3) -trichloropropane, (1,3) -dibromopropane, butyl chloride, C (1,4), (1,2), ( 1,3), (2,3) J-dichlorobutane, (1,2) -dichloroisobutane, (1,2,3,4) -tetrabromobutane, pentyl chloride, (1,5) -dichloropentane, (1,6) - Dichloro

hexane.

(2) Halogenated unsaturated hydrocarbons. Tetrachlorethylene, (1,2) -dibromoethylene, allyl chloride, allyl bromide, (1,3) -dichloropropene, (1,3) -Uichlorobutene-2, (1,4) -Dichlorobutene-2, 1,3-hexachlorobutadiene, hexachlorocyclopentadiene.

(3) Halogenated aromatic hydrocarbons, including compounds where a halogenated Hydrocarbon residue is attached to an aromatic ring.

Hexachlorobenzene, benzyl chloride, benzotrichloride.

The proportion of the respective halogenated hydrocarbon which is mixed with the titanium trichloride and ground, can be selected within wide limits where an influence of the grinding can be proven. This share

depends to some extent on the kind of halogenated hydrocarbon. The molar ratio of the halogenated The hydrocarbon over the titanium trichloride normally lies between 0.01 and 1.0. Individual examples are in. given in the following table.

Table 1

halogenated
Hydrocarbon

(A) / Ti ₃ (molar ratio)

preferred area

₃ (molar ratio)

Carbon tetrachloride ° ⁰²

Chloroform 0.02

Dichloromethane 0.02

(1,2) -Dichloroethane 0.03 (1,1 ', 2,2') - Tetrachloroethane or Oi

Hexachloroethane 0.01

Tetrachlorethylene 0.03 (1.1 ', 2.2') - tetrabromoethane or oil.

(1,2) -Dibromoethylene '0.03 -

(1, '2) -Dichloropropane 0.05 -

(1,3) -Dichloropropane 0.05-

(1,3) -Dibromopropane 0.01-

Allyl chloride 0.05 -

(1,3) -Dichloropropene 0.05 -

Allyl bromide 0.03 -

(1,4 -) - dichlorobutane 0.01-

Hexachlorobutadiene-1,3 0.01-

(1,2,3,4) -Tetrabromobutane 0.01-

(1.5) -Dichloropentane 0.01-

Hexachlorocyclopentadiene 0.01 -

- 0.3

- 0.7

- 1.0

- 1.0

- 0.5

- 0.3

-

-

-

-

■

■

0.5

0.5 0.7

0.5 0 ·. 0.7 0.20 O.O5 O.O5 O.O5 O.O5 O.O3 0.02 O.O5 O.O5 0.05 0.10 0.10 0.05 Ö.1Ö 0.10 0.05 0.05 0.05 - 0.02 O.O5 0.02 -

- 0.20

- O.ifO

- O.5O

- O.5O

- 0.20

- 0.20

- 0.40

- 0.20

- O.5O

- .0.50

- ΟΛΟ O.3O 0.50

0.50 0.40 O.3O 0.20

o.4o

0.10

(1,6) -Dichlorhexane 0.05-1 ° 0.10-

Hexachlorobenzene 0.01-0.7

Benzyl chloride 0.01-0.7 ° '° ⁵ "°' ⁵ °

If you have two or more halogenated compounds at If mixing and milling are used in combination, it will be advisable to separately determine the optimum ratios in such cases measured.

The co-grinding of the titanium trichloride and the halogenated hydrocarbon is carried out by a known method, the j delivers the desired result. A grinding process can be used where grinding takes place in a protective gas atmosphere. You can use a grinding device such as a vibrating mill, a drum mill or a hammer mill, in which a protective gas atmosphere can be sustained by argon, helium or nitrogen. In all cases it is important to be careful ensure that the protective gas atmosphere does not contain any polar substances such as water, oxygen or similar substances, which act as a catalyst poison ^ because the grist is very active,

The grinding time depends on the particular dialing method and the Grinding conditions. In a vibrating mill, the optimal grinding time depends on the combination of process conditions such as the amount of balls used, the amount of ground material used, the ball diameter, the vibration frequency and the vibration amplitude. The milling time can of course be changed by changing the milling conditions shorten that an increase in the grinding speed and the grinding efficiency adjusts ^ by, for example The number of balls increased, the use of the ground material reduced or the vibration frequency and / or vibration

■ - 9 amplitude increased.

The optimal combination of these grinding conditions can easily be determined through experiments. In connection with this, it should be mentioned that when using a 3ch.wingmuh.le with a tight fitting Pot for batch operation a modified titanium trichloride can be obtained with very improved catalytic efficiency for a continuous milling time of 100 hours can.

The obtained pesticide composition, i.e. the modified one Titanium trichloride is transferred from the mill into a vessel under a protective gas atmosphere and can be used as a component a Ziegler catalyst can be used. This modified titanium trichloride can be used by removing it from the mill placed in a drying chamber under an argon atmosphere and. at the same time in a solid state or as a suspension in one non-reactive liquid medium, e.g. dried and deaerated heptane is combined with an organoaluminum compound, so that one has a high efficiency catalyst for the polymerization of ^. "- olefins.

2). Organoaluminum compounds.

A compound of the general formula AIR X ₇ . insert. R denotes a hydrocarbon radical, in particular an alkyl radical, especially a lower alkyl radical up to 6 carbon atoms or a cycloalkyl radical, especially a lower cycloalkyl radical up to 6 carbon atoms; X is hydrogen or halogen, especially chlorine; ⁿ = 1; 1 »5; 2; 3 · Individual examples of such organoaluminum compounds are trialkyl aluminum, namely tri-lower alkyl aluminum, for example trimethyl aluminum, triethyl aluminum or trisobutyl aluminum; Dialkyl aluminum halides, namely di-lower alkyl aluminum halides, e.g.

225722Γ

Dimethyl, diethyl or dibutyl aluminum monochlorides; Alkyl aluminum sesquichlorides, namely, lower alkyl aluminum sesquichloride, e.g., ethyl aluminum sesquichloride. Under a low

alkyl radical is understood here to be a C ₁ to C ^ radical. Part II b

the organoaluminum compound used is normally between 0.05 and 50 parts by weight, preferably between 1 and 20 parts by weight of the mixed and ground solid composition described. The yield of the highly crystalline polymer can be increased even further by carrying out the polymerization in the presence of a cycloheptatriene compound which is used in addition to the catalyst constituents mentioned.

3). Cycloheptatriene compounds. ·,

The cycloheptatriene compounds useful in the context of the invention can be divided into different groups. One can have two or more of these compounds from one group or from different groups together. Then it goes without saying the optimal proportions and other process parameters differ.

Tropylium salts and tropylium complexes

Tropylium salts and tropylium complexes are carbenium salts of Cycloheptatrienes. They can be broken down into the following

Prepare known working methods:

C ₇ H ₈ + PCl ₅ - £ -> C ₇ H ₇ Cl + HCl + PCl ₅

described in Dokl.akad. Nauk, USSR, r ^ 3, p. 339 (1957)

θ Θ ® Θ

C ₇ H ₇ Hl + MCl _n > C ₇ H ₇ MCl _{n + 1}

with MCl _n as Lewis acid, M as Fe, Al, Ti, P, 8b, As, Sn etc. and with η as the valency of M, described in J. Chem. Soc.,

1961.JL232O.

Specific examples of tropylium salts of this type are given below indicated where the tropylium residue is indicated by the symbol T. is. '

TF, T Cl, T Br, TI, TI ₃ , T ClO ₄ , TBF ₄ , it £ & θ Θ β ί 'θ ΐ fr. TB Cl ₄ , T Al Cl ₄ , T Al Br ₄ , T Fe Cl ₄ , T Ti Cl ₅ ,

2 © 2 θ β- θ (t θ Ct ⁵ C- & θ (T) ^ Sn Cl ₆ , T Sb Cl ₆ , T Zn Cl ₅ ,. TP Cl ₆ , T As Cl ₆ ,

& 6
T Bi Cl ₆ . ■

In addition to these salts with an unsubstituted tropylium the rest come salts with a halogen-substituted, alkyl-substituted one (especially lower alkyl-substituted), alkoxy-substituted (especially lower-alkoxy-substituted), aryl-substituted (especially phenyl-substituted) tropilium radical and benzene derivatives with condensed benzene rings. Individual examples of such substituted tropylium salts are the following:

(± C- (± L- s ν p £ 2 e (+ θ

(± C- (± L- s ν p £ 2 e ( CH. - T Br, CH ₃ - T ClO ₄ , / CH ₃ - Tj ^ FtCl _6. , Ph - T

(+ <' θ 6J t (± 1C- CH ₃ 0 - T ClO ₄ , Cl - T' ClO ₄ , Br-T ClO ₄ ,

with CH ₃ - T, Ph-T, Cl-T, Br-T each as a methyl-substituted, phenyl-substituted, chlorine-substituted,] bromine-substituted tropylium radical:

x V «I °

309: 8 2 ^ / 107

- 12 -

Λ \\ ^2θ

^l ^ ^Μ PtCl,

CH.

τ, \

ι? χν

/ ^C A

ClO,

ClO,

- 13 - · Cycloheptatriene derivatives These derivatives can be represented by the general formula

with A as hydrogen (i.e. unsubstituted), as halogen, Alkyl radical, aryl radical, aralkyl radical (whereby in all cases the ATkyl radical or alkyl moiety includes a cycloalkyl radical with 1 to 20 carbon atoms, in particular a C ^ - to Cg-alkyl radical, as well as a phenyl radical and a naphthyl radical instead of the Aryl radical or the Arylahteils) or as a condensed benzene radical, the two carbon atoms with the cycloheptatriene ring has in common. ·

One class of the radical Y comprises monovalent polar radicals to which at least one T, S or O atom is bonded. By the name monovalent residues should exclude polar residues which are bonded to a carbon atom of the cycloheptatriene by a double bond, for example a = O radical;

Within the polar group, the N, S and O atoms are below Formation of bonding groups present, namely as an amino radical, as an amide radical, as an imide radical, as an isocyanate radical, as Nitrile residue, as nitro residue, as nitroso residue, as keto residue, as Aldehyde residue, as a carboxyl residue, as a carboxylate residue, as an ether residue, as a hydroxyl residue, as a thioalkoxy residue or as a thioether residue Residues can be attached directly to the cyclohepta- • ^ rienring be bound; they can also be via other radicals, for example a C 1 - to C ^ Q hydrocarbon radical with the cycloheptatriene ring be connected.

Another class of the radical Y comprises organic radicals, in particular hydrocarbon radicals, the benzene-like C-C multiple bonds contain, such as a cyclopentadienyl radical, a.

81

Cycloheptatrienyl radical, an ethynyl radical, a vinyl radical, a Allyl radical and mono- and polyhalogenated derivatives of these hydrocarbon radicals and other hydrocarbon radicals ".

The subscripts a and b are integers that meet the constraint a + b ^ 7 and usually have a value of 2 or less have, in particular the value (1).

These compounds are easily synthesized by introducing the desired residues into compounds which are obtained from nucleophilic substances. A large part of these compounds is known. Among such cycloheptatriene compounds those with a polar residue are preferable. Individual examples are given below. >

NO,

ο 5 2

/ "- V ¹

\\ - + ~ τ Jz ^1N > etc. ι. ^ ^^ 1 ^

/ - V-NHCR
O

NHC C, H, _, etc. II ^b 5/0

NHC CH-

V-,

■ N

17th

^r \

SB U!

NS.

SCAl

5;

CH

COOR, ■ 'COR' CH (C00R)

OCR

CR _? CIIO ι \

CsC-P;

^CR

CE - CR J X

3,9277,77 2 "^" P T

CR ΠΝ

_O
2 >

Ar (OH) η (

A fr, V- oh

/ Yl / >

CIL

CH.

HO t.

(ο)

“ ^X

Etc.] ; | \

CH-CR

! IO - ³ X- Ar (OCR)

CHC, l! O

CH,

- \

/ { O) - OC CH,

OC CH O

O) OC CH ₃ , etc.) j \ | \.

Ar (OH) 1 (OCR).

CH

_ / θ V OH, etc.);

ΧΊ /

7 Ar (OR)

CO CH

3098227TO74

WÖV

etc. J.

OCH

OCH.

OCH

OCH

\\ Jf- Ar (OH) I (OR);

m /

OCH

OCiL

OCH.

etc. J,

-ArNR.

N- N (CH ₃ ) ₂ , etc / '!

CH_

² I t)

, Etc.

309022 / 10T4

The substitution position can be used within each of these compounds on the cycloheptatriene nucleus can be selected as desired. Similar connections can also be used where an alkyl radical, an aryl radical, an aralkyl radical are each bonded to the cycloheptatriene ring and similar compounds with a condensed benzene ring.

In the formulas mentioned, R denotes a hydrogen atom or a C ₁ to C ₂₀ hydrocarbon. If several radicals R are given, they can be different or the same; they can also be coupled to one another to form a ring. Ar means an aryl radical. The letters 1, m, η are whole numbers that meet the following constraints:

1 + m + 1 η + 1

Λ (maximum number of aryl residues, di ^ e on one / - matical nucleus are substitutable).

aro-

X means a halogen atom, ρ is an integer, ρ Γ> 2.

Among the compounds mentioned, the following are particularly effective:

-λ, .NR.

"Λ

NO,

R has the same meaning as above; preferable-is a C, - to C / iQ residue, H or a Me thy! Rest. Individual examples are N dimethylcycloheptatriene, p-tropyl-N ^ N'-dimethylaniline, ■ Tropylacetylacetone, Tropylchlorcyclopenten, Methyltropylthioäther, Ditropyl, tropylcyclopentadiene, tropyl methoxyethyl ether.

Tropolone and its derivatives

Tropolone and its derivatives can be broken down into the following represent general formulas:

Y'a'-jf Λ = 0, · Y'a'-jf ") = °. ^Va '4

(0H) _b , (0H ') _b , (OCR') _b ,

Here, R ¹ denotes a C ^ - to CpQ hydrocarbon radical or a hydrocarbon radical with an alkoxy group or a hydrocarbylamino group attached to it. Y ¹ denotes a Gy, - to CpQ hydrocarbon radical, - a halogen or a substituent Y of the type described above for the cycloheptatriene derivatives. A 'and b' are integers which satisfy the secondary condition a '+ b' ^ 6; usually they have a value of 2 or less, preferably the value (1).

Individual examples of these connections are as follows:

= 0, f) = 0,

OC CH

Among these compounds, the compound is particularly effective:

R has the same meaning as above; however, is a C ^ - bis Preferred C ^ Q hydrocarbon radical, H or methyl radical. Individual examples are tropolone and ninokitiol.

Tropone and its derivatives

Tropone and its derivatives can be expressed by the general formula _γΙ , _η

= 0

represent with Y '' meaning A or Y and with η as an integer <C 6. An example of a particularly effective one Compound is tropon.

j Compounds according to Dutch patent specification No. 6,902,197

In this patent, cycloheptatriene-1,3,5 and alkyl, aryl and alkoxy derivatives with a C ₁ - to C ^ -alkyl or alkoxy radical are mentioned. This cycloheptatriene and its derivatives can be used successfully in the context of the invention. Individual examples are cycloheptatriene, methoxycycloheptatriene, methylcycloheptatriene, dimethylcycloheptatriene.

4). Catalyst preparation

The catalyst system, which essentially consists of a combination of the two above-mentioned indispensable components can be made by mixing these two ingredients in

Presence or absence of a non-reactive dispersant be prepared. The preparation is preferably carried out in a protective gas atmosphere. The preparation takes place in one step or in stages. In some cases, a cycloheptatriene compound is incorporated at the same time. For example, you can first use a modified titanium trichloride and mix a cycloheptatriene compound with one another and then, after a certain period of time, an organoaluminum compound to mix.

An example of the mixing sequence is organoaluminum compound, modified titanium trichloride, cycloheptatriene compound. In ! Depending on the type of cycloheptatriene compound I however, a certain additional sequence may be necessary. ' Tropon and its derivatives must, for example, first with the organoaluminum Compound mixed and then introduced into the polymerization system, or they must be separated from the titanium trichloride component and the organoaluminum compound are introduced into the polymerization system.

For the preparation of the catalyst you can use different Use working methods, e.g. moistening, grinding of all ingredients before mixing or after mixing, Grinding with other ingredients.

The proportion of the cycloheptatriene compound can be selected according to the desired effect. A useful portion the cycloheptatriene compound is 0.001 in a molar ratio. to 10, preferably 0.01 to 10, of the halogenated titanium, It ΐημβ must be observed that an excessive proportion of the cycloheptatriene compound for'die polymerization is a hindrance.

2. Gas phase polymerization

A catalyst system of the type described is particularly effective for a solvent-free polymerization of OC -r olefins,

so if an unreactive solvent is essentially is missing. This also applies in addition to the case where no non-reactive solvent is present at all is the case where a polymerization solvent is present in a minor proportion, e.g., 5% by weight of the polymer is, which is insufficient to state that the polymer formed is in a sludge state. Accordingly the use of a modified titanium trichloride falls under the basic idea of the invention when the titanium trichloride prepared by wet milling and with a organoaluminum compound is combined to form a catalyst, this catalyst in a small amount Amount of an organic solvent is suspended. A polymerization solvent is not intended to be an all-in-one monomer be liquid phase.

An exemplary polymerization system within the scope of the invention is a process procedure in which a gaseous monomer is exposed to the action of a solid catalyst under polymerization conditions, so that gas-phase polymerization takes place. Another procedure is such that a liquefied monomer is used as the polymerization medium , this is the solvent-free process operating in the liquid phase.

The polymerization conditions, particularly temperature and pressure, can be appropriately selected . In general, the polymerization temperature is between 50 and 120 ° C., preferably between 65 and 100 ° C. The polymerization pressure is between atmospheric pressure and 100 atm, preferably between 25 and 60 atm.

The polymerized polymer is obtained as a finished product, without it being necessary to separate off the catalyst. In addition, the polymer obtained can be used within operations without the need to develop

30äö22 / 107

removal of the catalyst reagent "exists

The invention is applicable to ίί-olefins, namely ethylene, Propylene, butene-1 and the like, each individually or as mixtures. The most common polymerization systems are homopolymerization, propylene polymerization and interpolymerization of propylene and ethylene, the ethylene content based on the ethylene-propylene mixed polymer between 3 and 30 mol% is between 1 and 10 mole percent based on the monomer.

3. Individual examples

Example 1. Preparation of the titanium component. A stainless steel vessel with a capacity of 0.7 l is used with 600 ml (bulk volume), stainless steel balls with a diameter of 12.7 mm. There is a joint grinding of 30 g Gcl titanium trichloride (titanium trichloride that is produced by reduction is obtained with metallic titanium) and 5 »02 ml of 1,5-dichloropentane (DCP) (molar ratio DCP / TiCl, = 0.2) during one Duration of 50 minutes in an argon atmosphere after the ■ Container has been sealed in a drying chamber. The vibrating mill is operated with a vibration amplitude of 3 »5 mm, whereby the drive is carried out by a motor that runs at a speed of 1,410 revolutions / minute.

After completion of the milling process, the resulting dry and free flowing pesticide composition is taken out and divided into a number of sufficiently large parts within the drying chamber. Then using dried and deaerated heptane solvent 100 ml of a slurry of the titanium component containing 1.829 g of the solid composition contains, prepared in an argon atmosphere and used for a polymerization experiment.

Examples 2-31 · Preparation of the titanium component.

The preparation of other solid catalyst components are given in Table 2. Unless otherwise stated, are

the conditions are the same as in example 1.

3 VTS B TZ t TOTtr

- E.g. Mill product (A) ml TiCl ₃
(B)
(S) ' AWAY
(MoI-
behaves
nis) meal
duration
-(H) Concentration of
Solids
slurry
(g / ml) * "" Y_ j. ■ -, _π jj ί. ^. χ. ■ ι_ί ·· solid component
. * Concentration of the solid slurry = - heptane i 2
3 halogenated hydrocarbons
material 0.9 ^
1.9 30th
Il 0.05
0.10 85
72 O.OI319
O.OI327 i
hä 1
P.
CT ¹ ΓΟ
φ vn
M.
MI
φ
IY)
κ>
Cn
-J k C Cl ₄ 0.80 Il 0.05 50 0.01258 Γθ
K) 5 CHCl ₃ . 2.5 Il 0.20 Il O.OII26 Oi 6th
7th CH ₂ Cl ₂ 1.02
2.05 If
M. O.O5
0.10 Il
M. 0.017 ^
0.0215 ^ OC 8th
9 Cl ₂ CH-CHCl ₂ 1.15 (g)
2.30 (g) Il
ti Ο.Ο25
0.050 ti
ti O.OI81I -
0.021 ^ 0
• 1 i N
IS. 10
11 Cl C-CCl ₃ 1.98
3.96 Il
Il 0.10
0.20 It
Il 0.01506;
'0.0204.0 12th Cl ₂ C = CCl ₂ 1.13, Il O.O5 Il 0.02205 13th
Ik Br ₂ CH-CHBr ₂ 1.6
3.22 Il
Il 0.10
0.20 ; i
Jl 0.013 ^ 8
0.01593 BrCH = CHBr

ON VO rH OJ VD OJ OJ OJ LA H rH VO t-. H H O
VO H OJ OJ O Ha IA (N OO ON r- \ J- L ^ - LA O
OJ cc rH cc CC IA rH LA [N PQ " OJ O (N O CiI LA O OJ VO ON Ü ON H J- CC Ü J- O ^ KN. VO LA VO OJ LA <- { OJ υ
rH VO VO ON K \ J- H H O rH I. PQ r- \ r- \ rH H cc H O Cr; U rH r-l H H rH . H O O I. OJ O IN O O O O O O d O O O O O O O •
O •
O cc O rH d O d d I ' O r OJ d d O O d O Sn. -E = = = E. = K E. rc E. = E. E. E. OO E. U O O O LA OJ ο O O O O O ο Il O OJ LA O IA OJ LA O H OJ rH OJ OJ rH OJ OJ
cc H d OJ O r-H O O
* O
• OJ
• d •
■ o d d d O d O d E. cn d d d
> O O O - r E. E. O E. E. = E. E. E. LA I. bO ON ON OO VO J- OO OJ OJ J " OD OJ CO VO ΓΛ CJN ON ON rH VO VO OJ H J- LA O VO IN
• LA
• VO
• H Ha • ΚΛ ΓΑ H OJ H ΓΑ Kn O H LA. U
pn OJ rH rc Ü O O! O Ti H I. J r- \ • -% U O U = r cj VO pq
OJ "Y H O
Il PQ
CC V r \ cc O H Ü A. OJ O I. / ^x I. cc O « ^ U. H H CJ. PQ > O O (ijv H CC VD TpU ir, υ O\ ijj O ο OJ 3f II Il ^ OJ ! C j] O U S. O oj
CC 3 OJ
r-t O r ^ O O O PQ CJ LA OO ON O OJ J- VO CJ ON rH rH H OJ OJ OJ OJ OJ IN OJ

309822/1074

ο co co

Tabel

30th Cl ^l Cl
Cl __ / V_ Cl
\ J
Cl ^ ^S C1 5.53 (g) 30th , οαο 50 0.01378 31 • / V-GH ₂ Cl 2.23 I! 0.10 Il 0.01319 - comparison
example 1 - 75 - 72 O.O3A21

Comparative Example 2. Polymerization.

A 1-1 autoclave with an inductive drive for stirring blades of anchor-like shape is filled with 20.0 g of polypropylene powder as a dispersion medium for the catalyst. This powder contains 96.9 % polymer which is insoluble in boiling heptane (II) and 1.1 % polymer which is soluble in boiling ethyl ether (ES); Then, after the interior of the autoclave has been evacuated, the above-mentioned starting material is dried at a temperature of 80 to 90 ° C. for about one hour. The inside of the autoclave is then filled with propylene.

1.4-2 ml of a 25% by weight heptane solution of 0.296 g of Al Et ^ (Et = ethyl residue) is added. Five minutes later, while continuing to stir the contents, add 1.41 ml of titanium slurry according to comparative example 1 (20 mg TiCl, and accordingly a weight ratio AlEt, / TiCl, - 14.8) by means of a Measuring pipette filled into the autoclave. After the catalyst has completely dispersed, it becomes propylene, which is anhydrous and cleaned by means of a molecular sieve, filled into the autoclave so that the polymerization begins. the The reaction temperature is 85 ° G, the pressure 35 kp / cm, the The polymerization time is 2 hours, the stirring speed is 500 revolutions per minute. These reaction conditions are kept constant throughout the entire duration of the polymerization.

When the polymerization is complete, the remaining propylene is drained off. 124.5 g of polymer are obtained as a white powder. If you subtract the amount of 20.0 g that was initially used as a dispersant in the catalyst, that does Weight of the polymer produced by the polymerization from 104.5 g. This gives a yield of 5,200 g Polymer / g TiCl ,.

309822/1074

Extraction of this polymer in boiling heptane and ethyl ether gives the values II = 88.3%, E, S. = 6.8%. Accordingly, after subtracting the dispersant for the polymer formed, the values II = 86.6 % and ES ₄ = are obtained

7.9%.

Examples 32 to 64. Polymerization.

Any of the catalyst compositions of Examples 1 to 31 above will be used used for a polymerization under the working conditions of Comparative Example 2. The polymerization results after correction for the dispersant are given in Table 3 below.

309822/1074

Solids on
slurry (A) ml - 30 -
Tabel B / A
Weight
Ver
holds-
nis 2257221 II
% IT
%
7.9
1.9 at
game Ex. * 1 1.41 AlEt ₃ (B)
(G) 14.8 Polymers
yield
per (A) * 2
(s / g) 86.6 6.7
2.7 Cf.
Ex. 2 Cf.
example
1 1.09 0.296 Il 52OO 94, Q 7.4 at
game ^ example 1 1.52
1.51 π Il
dd 9000 90.0
93.6 6.9 it 33
" y * "2
3 1.59 Il
" It 4900
4800 88.0 3.3
3.5 π 35 I.78 It 58OO 88.0 5.1
2.9 "36 M 5 1.15
0.93 " Il
dd 6200 93.4
92.1 4.9
3.4 "37
38 »6
7th 1.10
0.93 ti
It dd
Il 6100
3 ^ 00 90.6
94.4 3.7 "39-
4o ,, 8th
9 1.33
O.98 Il
It Il
Il 64oo
4700 92.4
92.5 z '.' k "41
concentration camp 11 0.91 Il
It Il 4600
4500 91.5 3.5
2.7 "43 »12 1.48
I.26 Il Il
ti 48oo 9O.5
93.3 3.3 45 .. 13
14th 1.70
1.57 Il
It Il
It 5000
7300 91.9
93. k 5Λ "46
47 M 15
16 I.36 Il
Il It 8700
7600 92.7 2.9 "48 "17th 1.48 ti Il 5900 91.O 8.3
4.2 "if9 ¹¹ 18 1.24 Il Il 6500 94.2 6.8
2.0 "5o 11 ig 1.29
1.19 ti dd
Il 6300 88.7
91.5 4.8
3.7 "51
52 .. 20
21 1.33
1.14 It
11 It
It 6100
63OO 89. "
94.6 2.7 "53
5 ^ .. 22
23 1.21
I.25 Il
It dd
ti 8300
45OO 30.7:
91.9 5.3
2.7 "55
56 ,. 24
25th 1-.99 Il '
It It 6300 '
49OO 93.3 5.0 "57 »26 1.02
1.43 Il It
It 5100 «9.7
94.7 3.5 "5Ö
59 "27
28 1.34 Il
It Il 6800
7000 89.8 2.0 "60 Il 29 1.45 dd It 6OOO 93.O • 1 example, according to which the solids composition herge
represents is.
* 2 Polymer yield based on the solids composition "61 "30 1.52 ti • I 7700 94.9 »62 "31 ti 6100

309822/1074

Examples 63-82. Polymerization.

AlEtpCl is used instead of AlEt ^ as the organoaluminum component for the polymerisation. The polymerization is carried out according to the process conditions of Comparative Example 2. MO mg titanium component, 0.2 g AlEt ₀ Cl, weight ratio Al / Ti = 5, temperature 90 C, pressure 35 kp / cm, polymerization time 2 hours, addition of 1000 cnr Ho (normal conditions) in the initial phase of polymerization.

The test results after correction for the dispersant are given in Table 4. The 'comparative example 3 refers based on the polymerization using titanium trichloride, without the presence of a halogenated hydrocarbon is ground.

309822/1074,

Table 4

Solids
slurry
(A) Polymer
yield
per (A) -
(g / g) 1.1.
% F ^Ο Λ
% MI
% Cf. 3
Ex. Cf. _ χ 2100 88.0 7.3 - Ex. -63 Example - 3 25OO 95.9 2.5 12.8 -Gk
-65 - 6
_ 7 2600
I5OO 95.0
9 ^ .2 2.5
2.8 17.6
6.1 -66 . 9 29OO 90.0 ^ l ¹¹ -67 "-10 26OO 90. k k.7 21.0 -68 "-12 I9OO 95.9 2.1 I5.O "-69
"-70 -13
" -Ik 2100
23OO 93.1
97.1 3.2
2.0 - "-71 "-16 3100 96.2 1.7 8.5 ¹¹ -72 "-17 25OO 96.5 1.8 2.6 -73 "-18 2800 92.7 3.9 17.5 " -7k "-21 2200 95.0 3.0 -75 it _23 23OO 96.I 2.k 3Λ ¹¹ -76
μ _ ₇₇ "-2'f
"-25 25OO
2700 9 ^ .6
91.5 3.'4
2.9 10.2
10.3 "-78 "-26 ik) o 95.0 2.7 25.Ο -79 " - 1 ΐβοο 95.8 3.0 - "-80
"-81 "-"> 7
- c- f
¹¹ -28 2600
2200 91. ^
95.5 3.7
2.3 52.5
16.3 -82 -31 1900 94.8 2.3 -

309822/1074

Example 83.

Following the procedure of Example 1, tY titanium trichloride is produced by reducing titanium tetrachloride with metallic titanium. This £ i -titanium trichloride is ground together with 1,2-dichloropropane in a vibrating mill. The grinding process takes place with an amount of 60 g ft titanium chloride, 8.00 ml 1,2-dichloropropane, molar ratio 1,2-dichloropropane: TiCl ^ = 0.20, grinding time? 2 hours, the other working conditions as in the example 1.

Having a muddy titanium component that has the solid composition contains, is prepared, a polymerization according to the procedure of Example 63 is carried out. The • test results are corrected for the dispersant. A yield based on the solids composition is obtained (g polymer / g solids composition) of 3,300, 1.1, = 97.0%, E.S. = 1.6%, M.I. = 30.5-

Example 84.

With the sludge titanium component of Example 83, a polymerization at a temperature of 75 ° C, a pressure of 25 kp / cm during a polymerization time of 3 hours, otherwise carried out under the conditions of Example 83 .

After correcting for the dispersant, the measured values obtained are a yield of 2900 g polymer / g solid composition, 1.1. = 98.2%, E.S. = 1.0% ', M.I. = 8.0.

Example 85.

A 2-1 autoclave is used with 30 g of polypropylene as a dispersant filled according to comparative example 2. Then 0.96 ml of a 25 volume% solution of triethyl

309822/1074

aluminum in heptane, 1.09 ml of a slurry of the titanium component of Example 1 in heptane, weight ratio AlEt * / titanium component = 10 and 0.5 ml of a heptane solution which Methoxyethyltropylether ((j) OCH-CH-- OCH,)

in an amount corresponding to a weight ratio to the titanium component of 0.5 successively in the specified order added so that a catalyst is obtained. The propylene is then polymerized. The polymerization takes place at a temperature of 95 ° C, a pressure of 40 kp / cm for a period of 3 hours. After the end of the polymerization, 313 g of polymer are obtained as a white powder.

After correcting for the dispersant, the following measured values are obtained: Yield 14 100 g polymer / g solids composition, 1.1. = 98.0%, ES = 0.9 %; the Il-Vert is unusually high.

Comparative Examples 4-21. Polymerization.

So that the critical importance of the joint grinding process for a full development of the improved catalyst efficiency within the meaning of the invention can be recognized, the following comparative examples will now show that the increase in the catalyst efficiency by joint grinding is much greater than an increase in a process where the halogenated hydrocarbon is only used as an additive; the substances CCl ^, Cl ₂ CH-CHCl ₂ , Cl ₅ C-CCl, ^ Br ₂ CH-CHBr ₂ , CH ₀ CH-CH ₂ Br, Cl (CH ₂ ) ^ Cl, are used as examples.

Using the slurry of the ground titanium chloride of Comparative Example 1, the organoaluminum compound and the required amount of the halogenated hydrocarbon diluted in heptane, each of them is separately introduced into an autoclave, whereby the polymerization catalyst is obtained. The polymerization takes place using AlEl ₅ and AlEt ₂ Cl as aluminum

309822/1074

organic connection. The polymerization conditions correspond The test results are after correction for the Dispersants given in Tables 5 and 6.

309822/10

Tabel

ro, ro i

(A)
Titanium-
trichloride
mg (B)
AlEt ₅
mg (C)
halogenated egg
Hydrocarbon
material Β / Α
¹ wt.
■
hold. G / A
MoI-
ver
hold. Folymerer
yield
per TiCl ₂
(A)
(ε / ε) II
% Eo
'% Example "57 (20) * 296 Cl ₂ CK-CHCl ₂ (Ik. 8) · 0.050 (6,100) * 93. k 3.3 Comp. - _ 4
Example
- 5th ti
It It
It ? l Il
Il 0.050
0.10 7,900
8,300 0 0
00 CN
00 00 9Λ
8.5 Example- ^ O (") *. ti Cl C-ClCl ( H )· 0.050 (^, 700) * 2.9 Cf. _ ζ
example
- 7th "1
11 If
It Il if
ti 0.050
0.10 7.100
5,900 87.2
86.1 8.6
9.1 Example- ^ 3 (") * Il Br ₂ CH-CHBr ₂ (») * 0.050 (^ f, 800) * 91.5 3.7 Cf. _ β
example
- 9 It
ti ; t
It Il Il
If 0.050
0.10 7,600
7.300 86.2
. 86.1 8.6
8.0 Example_ 52 (") * It CH ₂ = CH-CH ₂ Br (") · 0.20 (6,300) * 91.5 Verprl.
Example - ¹⁰
Il
- 11 Il
"1 I!
Il Il It
Il 0.10
0.20 7,800
7,200 86.2
86.7 7.8
7.9

* The weight of the Ti component is the weight of the total solid composition,

Tabel

CD CO »Ο Κ»

ι (A)
? itan-
trichloride
mg CB)
AlEt ₅
mg (C)
halogenating
ter coals
hydrogen B / A
Weight, -
Relationship
nis C / A
MoI-
ver
holds-
nis Polymer
spoil
Dro TiCl ^
(A) ³
Cr / k) II
% IT
% Example - 63 (2β) 200 CCIi ₊ (5) * 0.10 (2,500) * 95.9 2.5 VeigL.Bsp. _ 2.2
- 13 Il
It M.
11 Il It
Il 0.10
0.20 2,200
2,000 87.7
88.1 7.1
6.7 Example - ^ (H) * Il Cl ₂ CH-CHCl ₂ (") * ■ To (2,600) 95.0 2.5 See Ex. - 3A-
dd
- 15 Il
Il Il
It 11 H
Il 0.050
0.10 2,300
2.100 88.9 -
88.2 6.0
6.3 Example - 68 (H) * Il Br ₂ CHrCHBr ₂ . (V) * 0.050 (1,900) * 95.9 2.1 See Ex. - 16
- "■ · - 17 H
Il Il
Il H Il
ti 0.050
0.10 2,000
1,600 90.6
90.0 5 «^
5.7 Example - 7 ^. (") Il
\ CH ₂ = CH-CH ₂ Br- (") * 0.20 (2,200) * 95.0 3.0 Cf. Ex. - l8
'"- 19 Il
Il . Il
Il Il Il
Il 0.10
0.20 2,200
2.100 87.6
86.1 ■ 7.1 ·
7.8 Example - 75 Il Il Cl (CH ₂ ) ^ Cl (H) * 0.20 (2,300) * 96.1 See Ex. ± 20
-21 it
H Il
Il Il • It
• II 0.10
0.20 2.100
2,200 86.9
87.5 8.1
6.8

to fetch!

• * The weight of the Ti component is the weight of the total solid composition.

Comparative Examples 22, 23, 24. Polymerization.

The process according to the invention for improving the stereospecificity of the polymerization of Λ-olefins is, in contrast to known processes, extremely critical of the crystal form of the titanium trichloride used. A marked improvement in the catalyst efficiency is shown only when CC titanium trichloride is used, which is obtained by reducing titanium tetrachloride with Hp, with metallic titanium, with a hydrogenated silicon compound or the like. This is shown with the following comparative examples 22, 23 and 24-.

In the preparation of the titanium component in these comparative examples, an unground titanium trichloride is used, that from Toho Titanium Company, Japati, by reduction made of titanium tetrachloride with metallic aluminum. CCIy, and are used as halogenated hydrocarbons

Cl Cl

used. Apart from the change in the grinding treatment, the procedure corresponds to Example 1 above.

The polymerization takes place according to Comparative Example 2. The measurement results are after correction for the dispersant given in Table 7.

309822/1074

Table 7

Example 33 grinding together Additional ver
ratio
(Mol-Ver
ratio) meal
duration
(H) Polymerization 1.1
% Ε.ί
% · f
j : See Ex22
! "23 halogens
nier
Coals
water
material 0.05 85 Polymers made of
Interpret
(g / s) ■ 90 6.7 Example 61 CCl ^ 0.05
Il k8.
72 4900 82.6
82.9 10.6
9.9 See Ex ^ Il 0.10 50 2200 '
1800 93.0 3.5 Cl .. Cl
Cl- / -y Cl
Cl ^ Cl Il Il 7700 73.2 15Λ H 1500

Like a comparison of the above examples and the comparative examples shows, has a solid composition that by co-grinding titanium trichloride with a halogenated hydrocarbon is substantially increased Effectiveness in the stereospecific polymerization of Λ-olefins as a catalyst produced by grinding titanium trichloride is prepared on its own. This can be seen clearly from Tables 3 and 4.

In addition, a catalyst system using a solid composition according to the invention is superior to a catalyst system which is prepared by adding a halogenated hydrocarbon alone as an additive, for example in the context of the known process using CH ₂ = CH-CH ₂ Br. This results clearly from Tables 5 and 6 for different halogenated hydrocarbons.

According to the process of the invention, there is also a

3.0-982 2 / '107 4

partial influence in some other cases, depending on the type of titanium trichloride used. Apparently these different phenomena cannot be predicted or expected from the prior art.

Comparative Example 25 · Precipitation Polymerization.

A 1-1 Widmer apparatus is successively filled with 500 ml. dried and deaerated heptane, filled with 0.37 6 triethylaluminum and with 0.050 g of a solid titanium component according to Example (Al / Ti = 7 4- in the weight ratio), so that a catalyst is obtained. The sludgy catalyst is filled into a 1-1 autoclave, the interior of which is filled with propylene. The polymerization takes place at a temperature of 85 ° C and
2 hours.

85 C and a pressure of U- kp / cm for a period of

The total amount of polymer formed is 88.5 6. Of this, 76.9 6 are insoluble in the solvent and 11.6 g are soluble. Accordingly, the yield based on the solids composition is 1,800 g polypropylene / g solids composition, Extraction in boiling heptane gave a residue within the portion insoluble in the solvent of 91 »3%. This gives a value I.I. = 79.3%

309822/10 7 4

Claims (14)

- 4-1 patents claims: A process for the preparation of bC- -olefin polymers, characterized in that a ¹ X -olefin is exposed to the action of a catalyst system, essentially in the absence of a polymerization solvent, which is obtained by combining a solid composition obtained by grinding # -titanium trichloride in the presence of a halogenated Hydrocarbon, and an organoaluminum compound has been prepared. 2. The method according to claim 1, characterized in that the molar ratio of the halogenated hydrocarbon to the Titanium trichloride is chosen between 0.01 and 1.0. 3. The method according to claim 1 or 2, characterized in that the hydrocarbon radical of the halogenated hydrocarbon ^ substance is a Gy, - to Cg radical. 4. The method according to claim 3 »characterized in that the hydrocarbon radical is a saturated aliphatic Gy, - to Cg radical. 5. The method according to claim 3 _5, characterized in that the hydrocarbon _{radical is an unsaturated C x} , - to Cg radical. 6. The method according to claim 3 * 'characterized in that the hydrocarbon residue is an aromatic Gy, - to Cg-Eest. 7. The method according to any one of claims 1 to 6, characterized in that that the halogen radical of the halogenated hydrocarbon is chlorine, bromine and / or iodine. 8. The method according to any one of claims 1 to 7 »characterized in that an organoaluminum compound of the general formula Al ^R _n ^X 3_ _n is used, with R as a hydrocarbon residue, X as hydrogen or halogen and η as 1; 1.5; 309822/1074 2 or 3 9. The method according to claim 8, characterized in that as R is an alkyl radical having 6 or fewer carbon atoms and as X chlorine is used. 10. The method according to claim 8, characterized in that as R is a cycloalkyl radical having 6 or fewer carbon atoms and is used as X chlorine. 11. The method according to any one of claims 1 to 10, characterized in that ethylene, propylene and / or butene-1 is used as! X -olefin. 12. The method according to claim 11, characterized in that the ÖC-olef in a mixture of ethylene and propylene with an ethylene content between 1 and 30 mol% of the total amount (ethylene + propylene) is used. 13. Method according to one of Claims 1 to 12, characterized in that that the catalyst system contains 0.001 to 10 moles of a cycloheptatriene compound per mole of titanium trichloride. 14. The method according to claim 13, characterized in that at least one of the following is used as the cycloheptatriene compound Connections is used: Tropylium salts, tropylium complexes, cycloheptatriene derivatives the formula: with A as hydrogen, halogen, C, - to CoQ-alkyl radical, aryl radical, Aralkyl radical with a C ^ - to C2Q-alkyl portion, alkaryl radical with a C ^ - to Coq- alkyl moiety, fused benzene rings, the have two carbon atoms in common with the cycloheptatriene ring; with Y as a monovalent residue of at least one of the elements 309822/1074 N, S and O as a non-benzene-like, unsaturated hydrocarbon radical or as a non-benzene-like, unsaturated halogenated hydrocarbon radical;
Tropolone of the formula: Y'a ¹ - o (OH)- Y'a ¹ (OR) b ' Y'a ' (OCR '), II 0 with R 'as a C ^ - to C ₂₀ hydrocarbon residue, as an alkoxylated hydrocarbon residue with a C ^ - to C ₂₀ ^ hydrocarbon portion or as a hydrocarbonated, aminated hydrocarbon _{residue with a C 1} - to C ₂₀ hydrocarbon residue, with Y as halogen and with a 'andb' as whole numbers that ^{meet the secondary condition a 1} + b '<£ 6 -,
Tropons of the formula: ~. ο 309822/1074 with Y ¹ 'as the Gubstituent A and / or Y ₁ with η as a positive integer that satisfies the constraint n ^ 6; Cycloheptatriene, an alkylated cycloheptatriene with a C, - to C-alkyl portion, an alkoxylated cycloheptatriene with a C, - to C ^ -alkyl portion and an arylated cycloheptatriene. 309822/1074