DE19648029A1 - Metallated carbanions contg. iso-butene and aryl-ethylene units - Google Patents

Abstract

Cpds. of formula (I) are new, in which m = 1-6; n = 1-1500;R<1> = the residue of a m-functional carbocationic initiator; R<2> = phenyl substd. with R<4>, or naphthyl or phenanthryl; R<3>, R<4> = H, Me, OSiR<5>R<6>R<7>, NO2 or OMe; R<5>, R<6> = Me; R<7> = Me or CMe3; M = alkali metal, 0.5(alkaline earth metal), NR<8>R<9>R<10>R<11> or PR<8>R<9>R<10>R<11> R<8>-R<11> = 1-5C alkyl or Ph. Also claimed are (i) solns. of (I) in organic solvents; (ii) a process for the prodn. of (I); (iii) a process for the anionically initiated polymerisation of ethylenic monomers using (I) as initiator; (iv) copolymers obtd. by this process; (v) copolymers contg. 2-block copolymer segment(s) of formula (VII), in which R<21> = H or Me; R<23> = 1-12C alkyl, H, alkali metal, NH4 and/or (alkyl)4N; k = 1-10<4>; (vi) a process for the radical aq. emulsion polymerisation of unsatd. monomers, in which a copolymer (as in iv and v) is added to the reactor before, during and/or after polymerisation.

Description

The present invention relates to anionic polymerization initiators of the general formula I

With
m = an integer from 1 to 6,
n = an integer from 1 to 1500,
R¹ = residue of an m-functional carbocationic initiator,
R²

Naphthyl or phenanthryl,
R³, R⁴ = independently of one another -H, -CH₃,

R⁵, R⁶ = -CH₃,
R⁷ = -CH₃ or -C (CH₃) ₃,

R⁸, R⁹, R¹⁰, R¹¹ = independently of one another C₁- to C₅-alkyl or -C₆H₅ (phenyl).

The present invention further relates to methods of manufacture of compounds of general formula I and their use for anionically initiated polymerization of at least one monomers containing ethylenically unsaturated groups.

The compounds (I) are essentially homo polymers of isobutene. Show homopolymers of isobutene a number of attractive properties. They are hydrophobic as well as stable against thermal and oxidative influences, they prove to be chemically relatively inert (hydrolyze for example not) and have low temperature elasticity tity (they have a low glass transition temperature).

It would therefore be desirable to consider the properties of homopolyeri seeds of isobutene with the properties of homopolymers others have at least one ethylenically unsaturated group transmitting monomers by suitable copolymerization of the isobutene to be able to combine with such monomers. The disadvantage is however, regarding this objective, the fact that Iso buten essentially only carbocationically initiated poly is merisable (short: carbocationic polymerization), while the vast majority of the remaining at least one ethylenically Monomers containing unsaturated groups essentially only after poly different from carbocationic polymerization merization mechanisms can be polymerized. examples for such other polymerization mechanisms are radical initiated polymerization (short: radical polymerization), the anionically initiated polymerization (in short: anionic poly merization) and group transfer polymerization.

That is, copolymers of isobutene are essentially only obtainable by first the isobutene by carbo cationically initiated polymerization and polymerized concluding with the addition of further, at least one ethylenically  monomers containing unsaturated grouping, the chain wax continues with a change in the polymerization mechanism (or polymerized in the reverse order) or isobutene first polymerized separately in a spatially separated manner, which with Iso butene co-polymerizing monomers according to another polymer risk mechanism also spatially separated for itself poly merized and then the spatially separated Polymers via suitable functional groups (e.g. from the polymerization initiators used may originate) or chemically linked with each other through direct implementation.

In all cases, so-called block copolymers of Iso received butens. The term block copolymer stands for Polymers whose molecules consist of linked blocks, the blocks directly or through constitutional units, that are not part of the blocks, are connected to each other and the term block being a section of a polymer molecule means that it consists of several identical constitutional units and at least one constitutional or configurative characteristic does not have that in the immediately adjacent sections occurs. Di-block copolymers accordingly consist of two blocks and we mentioned above block copolymers of isobutene at least one polyisobutene block.

If necessary, different blocks are linked together constitutional units as well as initiator, if necessary Functionalization and demolition remains not taken into account block copolymers symbolize themselves in a simple manner ren that the basic unit of the respective block in angular Place parentheses and add one outside the square bracket number shows how often the basic unit in each Block linked with itself is included. Through the sequence The square brackets can also be used with diblock copolymers the chronological sequence of the block production are reproduced.

Block copolymers have a wide range of applications. This applies in particular when the block copolymer is consti monomeric building blocks are different from one another Solubility in water, d. that is, different from each other Have polarity.

Since isobutene is an essentially non-polar molecule, Block copolymers of isobutene from the aforementioned aspect usually have a special appeal and are suitable for example as amphiphilic surfactants in organic solutions means or water to stabilize the disperse distribution of others dispersed in the aforementioned liquids  Polymers and / or finely divided mineral materials (see e.g. DE-A 19 60 2538, DE-A 19 60 2539, DE-A 19 60 2544, DE-A 19 60 2540). In her capacity as an intermediary between phases that are not compatible with each other is also the one working of block copolymers of isobutene in technical Plastics of interest and last but not least are such blocks copolymers of isobutene due to the special mechanical Properties of the polyisobutene block in substance itself as engineering plastics suitable.

There is therefore an increased need for manufacturing processes of block copolymers of isobutene.

An advantage in this regard is the fact that polyisobutene now routinely on the way of living carbo cationic polymerization is accessible, but form the living carbocationic polymer chain ends in particular interesting starting points for a continuation of the polymerization with other monomers with simultaneous change of the polymerization mechanism.

It is also on the way to living carbocationic poly merization by varying the speed of the start reaction relative to the speed of the growth reaction in simpler Way possible, the molecular mass distribution of the resulting Set polyisobutene specifically (the start reaction takes place in the Compared to the growth reaction very quickly, narrow molecular mass distributions become receive).

A detailed description of the living carbocationic Polymerization of isobutene is found e.g. B. in Table 1 Literature listed:

Table 1

1. JP Kennedy and B. Iván, "Designed Polymers by Carbon Macromolecular Engineering: Theory and Practice", Hanser Publishers, Munich, New York, 1992
2. B. Iván and JP Kennedy, Ind. J. Technol. 31, 183 (1993)
3. B. Iván Makromol. Chem., Macromol. Symp., 75, 181 (1993)
4. M. Sawamoto, Prog. Polym. Sci., 16, 111 (1991)
5. B. Iván, JP Kennedy, and PW Mackey, Polym. Preprints, 31 (2), 215 (1990); ibid, 31 (2), 217 (1990)
6. B. Iván, JP Kennedy, and PW Mackey, in "Polymeric Drugs and Drug Delivery Systems", Eds., RL Dunn and RM Otten brit, ACS Symp. Ser., Vol. 469, Am. Chem. Sol., Washington, DC, 1991, pp. 194; ibid., 1991, pp. 203
7. B. Iván, JP Kennedy, and PW Mackey, US Patent, 5,073,381 (Dec. 17, 1991)
8. JP Kennedy, VSC Chang, RA Smith, and B. Iván, Polym. Bull., 1, 575 (1979)
9. B. Iván, JP Kennedy, J. Polym. Sci., Part A: Chem. Ed., 28, 89 (1990)
10. B. Iván, JP Kennedy, and VSC Chang, J. Polym. Sci., Polym. Chem. Ed., 18, 3177 (1980)
11. T. Kitayama, T. Nishiura, and K. Hatada, Polym. Bull. 26, 513 (1991)
12. T. Nishiura, T. Kitayama, and K. Hatada, Polym. Bull. 27, 615 (1992)
13. WG Ruth, CG Moore, WJ Brittain, J. Si, and JP Kennedy, Polym. Preprint, 34 (1), 479 (1993)
14. JP Kennedy, JL Price, and K. Koshimura, Macromolecules, 24, 6567 (1991)
15. JP Kennedy and M. Hiza, J. Polym. Sci., Polym. Chem. Ed., 21, 3573 (1983)
16. M. Gyor, K. Kitayama, N. Fujimoto, T. Nishiura, and K. Hatada, Polym. Bull. 32, 155 (1994)
17. S. Nemes and JP Kennedy, J. Macromol. Sci.-Chem. A28, 311 (1991)
18. S. Hadjikyriacou, Zs. Fodor, and R. Faust, J. Macromol. Reports, A32, 639 (1995)
19th J. Feldthusen. B. Iván, AHE Müller, and J. Kops, Macro mol. Reports A32, 639 (1995)
20. A. Takacs and R. Faust, Macromolecules, 28, 7266 (1995)
21. J. Feldthusen, B. Iván. AHE Müller, and J. Kops, Macro mol. Symp. Submitted
22. H. Everland, J. Kops, A. Nielsen, and B. Iván, Polym. Bull., 31, 159 (1993)
If, in the further course of this document, reference is made to the literature citations listed in Table 1, this is done as "Ref.No.", whereby No. corresponds to the numerical rank of the literature quotation in Table 1.

As a starter for the living carbocationic polymerization of Isobutene are usually made from an initiator (hereinafter carbo called cationic initiator) and existing coinitiator Initiator systems used, the coinitiator training promotes the carbocation.

Suitable carbocationic initiators are u. a. Links, which have at least one tertiary carbon atom which has a Substi tutors such as B. -Cl, -Br, -J, -OH, -OCH₃ or

has, and thus the potential to form a Carboka carry in themselves. If the carbocationic initiator on meh is able to form a carbocation, is a multifunctional carbocationic itiator (e.g. an initiator of the two such tertiary carbon atoms points = difunctional). Multifunctional carbocationic in itiators are suitable, for example, for the production of polyiso butene molecules in which one of the carbocationic initiator residue corresponding to the functionality of the carbocationic initiator Radially points out the number of polyisobutene blocks. As an example of is a monofunctional carbocationic initiator Called 2-chloro-2,4,4-trimethylpentane. 1,3,5-tris (2-chloro-2-pro pyl) benzene is an example of a trifunctional carboka tional initiator called.

The coinitiators are usually Lewis acids such as TiCl₄ or BCl₃. Often it turns out for the course of living carbo cationic polymerization, the use of a Lewis base such as N, N-dimethylacetamide as beneficial to the charge density of the carbocations carrying the polymerization.  

Usually the living carbocationic polymerization of isobutene under inert gas (e.g. nitrogen atmosphere) and in Solution carried out for which solvents such as n-hexane, methylene chloride loride, chloroform or mixtures thereof are suitable.

By adding suitable demolition agents such. B. leave methanol the polymerization-bearing (le benden) polyisobutene carbocations into an undissociated one Convict condition, reducing their activity and thus their ability ability to continue the carbocationic polymerization is deleted.

Based on the living carbocationic polymerization of the The prior art assigns the following methods to isobutene Production of block copolymers of isobutene.

The living carbocationic polymerization is known from ref. (1) cancel isobutene so that with a tertiary chlorine (Chlorine atom covalently bonded to a tertiary carbon atom; subsequently this form of shortened speech in equivalents applied form) ending polyisobutene (hereinafter for Polyisobutene shortening "PIB" used) is obtained. According to Ref. (8) can do the same by quantitative dehydrochlorination in PIB containing isobutenyl end groups are transferred. Hydrobo the same and subsequent oxidation (Ref. (9), (10)) leads to PIB terminated with primary hydroxyl. Implementation of the same with isobutyrochloride gives isobutyrate-terminated PIB (Ref. (11), (12)). Lithiation of the latter leads according to Ref. (11), (12) to anionically terminated PIB, which turns out to be anio African polymerization initiator is suitable and z. B. for extraction of block copolymers from isobutene and methyl methacrylate has been used.

Ref. (9) additionally discloses the production of allyl termi nated PIB by aborting the living carbocationic poly merization of isobutene with allyltrimethylsilane. Treated the same in a corresponding manner as above, the isobutenyl PIBs with end groups are used in a corresponding manner receive suitable anionic polymerization initiators.

Ref. (13) is directly related to the above. The isobuty rat end groups of the intermediate isobutyrate terminator However, the PIB are converted into O-silyl ketene acetal end groups and via the PIB thus scheduled on the way of Group transfer polymerization Block copolymers from isobutene and methyl methacrylate.  

Ref. (14) relates to the lithiation of tolyl-terminated PIB, that according to Ref. (15) by Friedel-Crafts alkylation of with a tertiary chlorine-terminated PIB is available. By order setting of the resulting anionic polymerisationini tiators with 1,1-diphenylethylene (only one diphenylethylene each molecule is added) becomes a comparatively steric hindrance ter anionic polymerization initiator obtained, also for anionic polymerization of z. B. methyl methacrylate is suitable and thereby to block copolymers of isobutene and Methyl methacrylate leads.

Ref. (17) concerns the conversion of termini with tertiary chlorine PIB by dehydrochlorination and metalation in one Step to anionically terminated PIB, which turns into anionic Polymerization of butadiene is suitable and so to block copolymers of isobutene and butadiene. In Ref. (16) also Polymethyl methacrylate blocks linked with polyisobutene blocks.

What is negative about the aforementioned methods of the prior art is that, based on living carbocationic poly Merisates of carbocationically terminated isobutene obtainable PIB, is a process involving at least one of the following Disadvantages:

• - multi-stage process;
• - The polymerization of different from isobutene Comonomers require extreme reaction conditions;
• - There are mixtures of block copolymers and homo receive polymers.

The object of the present invention was therefore a more advantageous process for the production of block copolymers to provide the seeds of isobutene.

In this regard, it was known from (18) that the living carbo cationic polymerization of isobutene by adding 1,1-diphenylethylene in a simple manner to form carbocationic 2,2-diphenylethyl-terminated PIB can be functionalized (only one 1,1-diphenylethy lenmolekül added) and by the subsequent addition of methanol and then feeding aqueous ammoniacal metha nol to the reaction mixture 1-methoxy-1,1-diphenylethyl-terminated PIB is available. Instead of 1,1-diphenylethylene can also in appropriately substituted 1,1-diphenylethylene used will. Furthermore, another can be used instead of methanol  Alcohol such as benzyl alcohol, ethanol, tert-butanol or an ent speaking thiol can be used to abort. To match in the way can instead of ammonia also a low molecular weight organic amine can be used as a basic agent to the To suppress cleavage of the ether formed.

According to the invention it has now been found that according to standing procedure resulting compounds like that 1-methoxy-1,1-diphenyl-terminated PIB by metalation as well if necessary subsequent quantitative reprecipitation into Have compounds of the general formula (I) transferred, which for their part in an excellent way as initiators for the anio nically initiated polymerization of at least one ethylenically Monomers containing unsaturated groups can be used can what the desired block copolymers of isobutene leads.

It is particularly advantageous that block copolymers which contain practically no homopolymer can be obtained with a favorable design of the process according to the invention. That is, starting from carbocationically terminated PIB obtainable by living carbocationic polymerization of isobutene, block transfer coefficients f of almost 1 can be achieved (f is defined as M _n ^ex / M _n ^th , where M _n ^{ex is} the experimentally determined number average molecular weight of the resulting block copoly merisats and M _n ^{th is} the number average molecular weight of the resulting block copolymer which, starting from carbocationically terminated PIB, can be expected with ideal block transfer).

For the living carbocationically initiated polymerization of isobutene are on the way to the preparation of compounds of general formula I z. B. the following carbocationic initiators are suitable:
Monofunctional carbocation initiators:

Difunctional carbocation initiators:

Trifunctional carbocation initiators:

Tetrafunctional carbocation initiator:

Hexafunctional carbocationic initiators:

with X = -Cl, -Br, -J, -F, -OH, -OCH₃,

and R¹², R¹³ = C₁ to C₄ alkyl and

X is preferably Cl or OH.

Among the aforementioned carbocationic initiators are very cheap:

The sits in the aforementioned carbocationic initiators Substituent X always on a two methyl groups tertiary carbon atom. The initiator effect of these groups is also given when one of the two CH₃ groups by H is replaced.

Carbocationic initiators are also suitable as such Compounds that are in addition to the carbocationic functionality have other functionalities.

The compounds may be mentioned as examples

with R¹⁴ = -F, -OCH₃, -CH₃,

as well as compounds that have a potential allylic carbocation have, e.g. B. (CH₃) ₂-C = C-CH₂-Cl.

Further carbocationic initiators suitable according to the invention can be found in Ref. (1) to (22), especially in Table I. on page 14 ff of ref. (1).

Possible coinitiators are Lewis acids such as the Friedel-Crafts catalysts listed in Römpp Chemie Lexikon, Cm-G, 9th edition (1990), Thieme Verlag, p. 1444, column 2. Particularly preferred Friedel-Crafts catalysts are TiCl₄ and BCl₃. This applies in particular if the aforementioned carbocationic initiators are used and X = Cl. The choice of coinitiator influences in particular the poly dispersity index D of the molecular weight distribution of the resulting PIB. D is defined as M _w / M _n , where M _{w means} the weight average molecular weight. According to ref. (21) is a favorable coinitiator for desired relative M _n values of the PIB from 1000 to 3000 with simultaneous D values from 1 to 1.15 BCl₃. For relative Mg values of the PIB from 4000 to 10000 with a uniform molecular weight distribution at the same time, a two-stage process is recommended according to Ref. (21), in which BCl₃ and TiCl₄ are used as coinitiators in the first stage. The sole use of TiCl₄ usually leads to polydispersity indices 1,2 in the aforementioned molecular weight range. For the desired relative PIB molecular weights <10000, however, TiCl₄ is a particularly favorable coinitiator (cf. Ref. (21)).

As mentioned earlier, the living carbocationic poly merization of isobutene is normally carried out in solution. The aprotic solvent should be chosen in particular so that the PIB desired as a product with its polymerization is still resolving. With increasing target molecular weight PIB therefore requires less polar solvents. The required reduction in the polarity of the solvent is necessary also the aforementioned change from a weaker Lewis acid (BCl₃) to a stronger Lewis acid (TiCl₄).

To carry out living carbocationic polymerization Suitable solvents of isobutene are found, for. B. in Ref. (1) to Ref. (22), especially in Ref. (1), Table I, p. 14 ff.

At this point, CHCl₂ and its mixtures with n-hexane and / or methylcyclohexane and CH₃Cl and its mixtures with n-hexane and / or methylcyclohexane called.

The reaction temperature is usually -70 to -80 ° C. For Deactivation of protic impurities are the reaction mixture often in small amounts proton traps such as di-tert. Butylpyridine added.

According to the invention, m can assume the values 1, 2, 3, 4, 5 or 6.

If m = 1, di-block copolymers (AB) are of isobutene available, which contain a polyisobutene block A. ten. If m = 2, according to the invention are in principle tri-block copolymers of isobutene (BAB) are also available  contain a polyisobutene block A, which, however, by the carbocationic initiator residue is interrupted.

According to the invention, n can be 1 to 30, 10 to 30, 35 to 45, <30 to 1500, <30 to 750, <30 to 500, 40 to 250 or 40 to 100 be. These possible ranges for n are especially then favorable if the above-mentioned di-block copolymers of isobutene of type AB or BAB.

For the functionalization of the le to be carried out according to the invention suitable carbocationic polymerization of isobutene 1,1-Diphenylethylene compounds are those of the general Formula II

among which the 1,1-diphenylethylene, i.e. that is, the connection with R³, R⁴ = H, is particularly preferred. Usually the connection (II) after consumption of the isobutene in the polymerization mixture dissolved form added at once. One chooses as solvent fortunately for the living carbocationic polymer used solvents. For this reaction too step, the reaction temperature is usually -60 to -80 ° C.

Finally, according to the invention, by adding an alcohol such as Methanol, ethanol, tert-butanol, benzyl alcohol or an ent speaking thiol terminated with ether or thioether formation. Methanol is preferably used.

As a rule, the alcohol or thiol becomes the reaction mixture added pre-cooled to its temperature. To split back To avoid the ether formed, the reaction mixture normally use a basic aqueous solution for demolition Deten alcohol or thiols supplied. As base come NH₃ or organic amines into consideration, of which NH₃ in particular Use of methanol as the terminating alcohol is preferred. The Lewis acid used as coinitiator normally falls by the aforementioned measure (which is the possibility of ether cleavage reduces) and is then filtered off.  

The organic phase of the filtrate is separated off, first with basic and then with neutral water for so long washed until the pH of the wash water is in the neutral range lies. Then the organic phase z. B. dried over MgSO₄ (MgSO₄ is added to the organic phase), separated and that 1-alkoxy-1,1-diphenylethyl or 1-alkylthio-1,1-diphenylethyl terminated PIB isolated.

From the isolated intermediates as described above the desired compound (I) by final metalation available.

For this purpose, the intermediate is usually in a solution medium such as tetrahydrofuran, dioxane or dimethoxyethane dissolved. This solution is then preferably added to a reaction vessel leads that the metal (e.g. Li, Na, K, Rb, Cs, Mg, Ca) as Metal mirror or in liquid form (e.g. in the form of an alloy tion) or dispersed in a hydrocarbon. The subsequent metallization usually takes place already satisfactorily at room temperature (25 ° C). The The end of the metallization is ensured by a constant UV Absorption spectrum of the reaction mixture displayed.

Then the organic solution of the Ver filtered off bond (I) and the compound (I) if necessary Removing the solvent used (by distillation) isolated. The metalation is preferably carried out with a potassium / sodium Alloy performed, the weight ratio of K: Na 3 is up to 5: 1 because such alloys are liquid at 25 ° C. Due to the higher reactivity of K relative to Na arises selectively the corresponding K⊕ compound (I). From the same can then z. B. by falling other M⊕ compounds (I) be generated. LiCl addition leads to the corresponding one K⊕ compound (I) containing solution normally to the Li⊕ compound (I) containing solution and KCl precipitates.

The anionic initiator can be selected by suitable choice of M⊕ Control activity of connection (I). With increasing waiter area charge density of M⊕ decreases the initiator activity in the Rule. This enables adaptation to the reactivity of the Monomers to be polymerized ionically. Li⊕ is z. B. preferred M⊕ in the case of the anionically initiated polymers according to the invention sation of methyl methacrylate, while in the case of the corresponding Polymerization of tert-butyl methacrylate K⊕ is preferred. For a use of the compounds (I) according to the invention as In itiator for the anionic polymerization of at least one monomers containing ethylenically unsaturated group must  Compound (I) but not necessarily isolated because Tetrahydrofuran, dioxane or dimethoxyethane also suitable Solvent for the implementation of anionically initiated polymers risks (see e.g. A.H.E. Müller, Makromol. Chem. 182, 2863 (1981)).

The anionic polymerization can be carried out in be done in a known manner. By excluding protic Impurities such as water and O₂ exclusion will be in the Usually designed alive. The reaction temperatures are usually at <-50 ° C.

The anionic polymerization is carried out sequentially (First of all, one type of monomeric building blocks is successive linked together and after consumption of these Monomer type linking to another type of mono continued building blocks), di-, tri- and higher block units of the comonomers are generated.

Detailed illustrations of the sequential anionic poly Merizations can be found e.g. In U.S. 3,251,905; US-A 3 390 207; US-A 3 598 887; U.S.-A 4,219,627; Macromolecules 1994, 27, 4908; Polymer, 1991, Volume 32, Number 12, 2279; Macromolecules 1994, 27, 4615; Macromolecules 1994, 27, 4635 and Macromolecules 1991, 24, 4997). Of course, the one initiated by anionic Polymerization produced polymer block does not necessarily be a homopolymer. By adding appropriate Monomer mixtures are also available in copolymer blocks. Of course, from the living anionic polymer sation in a manner known per se on other initiated wax mechanisms alternately further modifications of the ge Desired copolymer of isobutene can be achieved. P. Rempp, E. Franta, J.E. Herz, Advances in Polymer Science, 1988, p. 164 up to 168 provide an overview of such switching options on other growth mechanisms. By adding a protic Compound can be the living anionic polymerization in itself be canceled in a known manner. Frequently is caused by methanol sentence canceled.

Of course, anionic polymerization Connect polymer-analogous implementations. But also the connection of blocks generated by anionically initiated polymerization on blocks that are mono only by polycondensation or polyaddition other blocks are available (e.g. polyester or polyurethane) is possible, for example, by using a suitable radio tional end group provided anionically generated block polycondensation is added (e.g. R.N. Young, R.P.  Quirk, L.J. Fetters, Advances in Polymer Science, Vol. 56, p. 70, 1984). Corresponding links can also be created via R¹ are chosen if such a carbocationic initiator that, in addition to its carbocationic functionality others suitable for this purpose in a manner known per se has functional groups.

Particularly suitable for a compound (I) Initiated anionic polymerizations are esters from acrylic acid and C₁ to C₁₂ alkanols, esters of methacrylic acid and C₁- bis C₁₂ alkanols, acrylonitrile, vinyl pyridine and substi on the ring tuiert vinylpyridine, acrolein, methacrolein, acrylamide, meth acrylamide, N, N-dialkyl- or N, N-diaryl-acrylamides, N, N-dialkyl- or N, N-diaryl methacrylamides, vinyl ketones of the general Formula (III)

with R¹⁵ = C₁ to C₁₂ alkyl, preferably C₁ to C₄ alkyl, and R¹⁶ = C₁ to C₄ alkyl, phenyl or H,
Compounds of the general formula (IV),

with R¹⁷ = C₁ to C₄ alkyl, phenyl or H,
Compounds of the general formula (V)

with p = 1 to 10,
and the compounds of the general formula (VI)

with R¹⁸ and R¹⁹ independently of one another C₁ to C₄ alkyl, preferably way both -CH₃.

Characteristic of all copolymers of isobutene are obtainable in that a anionic polymerization initiated by a compound (I) an alkyl ester of acrylic or methacrylic acid is, is that these copolymers at least one di-block copo polymer segment of the general formula (VII)

have, with R²¹ = -H or -CH₃,
R²⁰ = C₁ to C₁₂ alkyl,
n = 1 to 1500 and
k = 1 to 10⁴.

Preferably R²⁰ is C₁ to C₃ alkyl and is particularly preferred R²⁰ C₁ to C₄ alkyl, especially methyl, ethyl, n-propyl, iso propyl, n-butyl and tert-butyl. Furthermore, R²¹ is preferably -CH₃.

Copoly obtainable according to the invention are of particular importance merisate of isobutene, which is a di-block copolymer segment of have general formula (VII), wherein R²⁰ is tert-butyl. From tert-butyl acrylate or tert-butyl methacrylate in anionic Polymer blocks built up in polymerized form can namely e.g. B. by selective hydrolysis in dioxane / HCl or dioxane / p-toluene olsulfonic acid in a known manner in the corresponding Polyacrylic acid or polymethacrylic acid blocks are converted.

However, this produces di-block copolymer segments of the general my formula (VIII), which has a pronounced amphiphilic character have, especially when the carboxyl groups subsequently Lich (e.g. with alkali hydroxide (especially KOH or NaOH) and / or ammonium hydroxide):

with R²² = H, alkali metal, ammonium and / or tetraalkylammonium.

Preferred di-block copolymer segments (VII), (VIII) are those with R³ = H and R² = phenyl.

Block copolymers of isobutene obtainable according to the invention usually have no more than six di-block copolymers Segments of the general formula (VII) or (VIII).

Of particular interest are those of the invention block copoly available anionically initiated polymerization merisate of isobutene, which consists exclusively of di-block copoly merisate segments of the general formula (VII) or (VIII) are built.

Such block copolymers have a pronounced amphiphilic character ter and can be used as surfactants in a corresponding manner be set as the amphiphilic block copolymers DE-A 196 02 539, DE-A 196 02 538, DE-A 196 02 540 and the DE-A 196 02 544. This applies in particular to those of the invention according to the available amphiphilic block copolymers of the pre known way to form the aqueous solutions of frozen micelles assets as described in DE-A 196 02 538.

To the amphiphilic block copoly obtainable according to the invention Merisates with a surfactant character therefore belong e.g. B. those who exclusively from di-block copolymer segments of the general Formula (VII) or (VIII) are constructed, where n = 10 to 50 or 10 to 40 or 10 to 30 or 10 to 20, and k at least 50%, or at least 75% or 100% of the respective associated Coefficient is n. N is preferably 35 to 45 and k likewise from 35 to 45. Such block copolymers are suitable themselves as dispersants and protective colloids in the course of the production of aqueous polymer dispersions the method of radical aqueous emulsion polymerization.  

This applies in particular if that which is obtainable according to the invention amphiphilic block copolymer a di-block copolymer AB or is a triblock copolymer BAB.

High molecular weight triblock copolymers BAB with B = polymethyl methacrylate and A = PIB have the properties of a thermoplastic elastomer.  

That is to say, interesting process which is obtainable when the compounds (I) are used according to the invention products are u. a. those of the general formula (IX) or (X):

with n = 10 to 50 and k = 10 to 50.

These compounds (IX), (X) include in particular those with R₃ = H and R² = phenyl.  

Favorable block copolymers obtainable according to the invention are also those resulting formally from the compounds (IX), (X) are available that R²² is replaced by R²⁰, especially if R²⁰ is tert-butyl or methyl. The above applies especially in Case R²¹ = -CH₃.

Otherwise, when using the invention Compounds (I) as initiators for the anionically initiated Polymerization of at least one ethylenically unsaturated Group-containing monomers regularly number average moles achieve molecular weights of up to 3 · 10⁶ (the molecular weight of the anionic initiator is not included).

Finally, it should be noted that the invention Use of the compounds (I) for anionically initiated Polymerization of at least one ethylenically unsaturated Group containing monomers in a simple manner the preparation of block copolymers of isobutene, which essentially no homopolymer contamination and one if necessary Polydispersity index of the molecular weight distribution by 1 point. These block copolymers are suitable as thermoplastics cal elastomers, dispersants, emulsifiers and not ionic or polyelectrolytic surfactants.

Examples

In the following examples, the following were Chemicals and analytical methods used:

• Acros from Acros (purity 99%, used as purchased);
• - aqueous ammonia solution from Aldrich (SN [normal], used as purchased);
• - 1 molar solution of boron trichloride in CH₂Cl₂ from Aldrich (used as purchased);
• - 5-tert-butyl-1,3-dicumyl chloride (generated from 5-tert-butyl- 1,3-dicumyl alcohol by hydrochlorination using gas HCl at 0 ° C (see B. Wang, M.K. Mishra, and J.P. Kennedy, Polym. Bull. 17, 205, (1987)); after evaporation was dried to dryness twice in n-hexane; then the solid pure compound at -18 ° C in Refrigerator stored);  
• - 2-chloro-2,4,4-trimethylpentane (generated from 2,4,4-trimethyl- 1-pentene from Aldrich (99%) by hydrochlorination using gaseous HCl at 0 ° C (see B. Wang, M. K. Mishra, and J.P. Kennedy, Polym. Bull. 17, 205, (1987)); the liquid product was dried by adding CaCl₂ (at -18 ° C in the refrigerator) and immediately before use the required amount under reduced pressure separated by distillation;
• - dichloromethane from Riedel-de Haën (purity 99.8%; was dried by adding CaH₂ and immediately before Use under N₂ atmosphere the required amount separated by distillation; the N₂ atmosphere is essential, to avoid phosgene formation, what polymerization can have an initiating effect);
• N, N-dimethylacetamide from Aldrich (purity 99%, <0.005% water, used as purchased);
• - 1,1-Diphenylethylene from Aldrich (purity 97%, used like bought);
• - 2,6-di-tert-butylpyridine from Aldrich (purity 97%, used as purchased);
• - Isobutene from BASF Aktiengesellschaft (the same from To get rid of oxygen and moisture, it was through a CaSO₄ and # 13 molecular sieve drying column containing Sent from Aldrich ("Labclear filter");
• - Aldrich n-hexane was previously used as Solvent for carbocationic polymerization with 97 wt .-% sulfuric acid added and the mixture Normal pressure kept under reflux for 48 h, so to obtain olefin-free n-hexane; the organic phase was then washed with neutral water (pH ≈ 7) and then dried by adding CaH₂ and immediately before Use the required amount under reduced Pressure separated);
• - Aldrich n-hexane was used for recrystallization purposes sierens or felling used as purchased;
• LiCl from Merck was dried in vacuo at 200 ° C. for 48 h (heated sand bath as heat source) and until use kept under N₂ atmosphere;  
• - Aldrich methanol (purity 99.9%, used as Bought);
• - Methyl methacrylate from Röhm was fractionally distilled and then mixed with CaH₂ in the refrigerator at -18 ° C stored; this was required immediately before use required quantity separated under reduced pressure;
• - N₂ from Messer Griesheim (purity 99.999%) was in advance its use as an inert gas for anionically initiated Polymerizations through three series-connected washes bottles sent with a benzophenone as a blue Color indicator added dispersion of a K / Na Alloy (weight ratio 3 to 5: 1) in toluene were; Color erasure showed the metal consumption by Um setting with O₂ or H₂O;
• - N₂ from Messer Griesheim (purity 99.999%, as an inert gas used for carbocationic polymerization as ge buys);
• - Potassium from Merck (purity <98%, stored in paraffin oil; prior to use in making the K / Na alloy parts tarnished mechanically with hydroxide);
• - Merck sodium (purity <99%, stored in paraffin oil; prior to use in making the K / Na alloy parts tarnished mechanically with hydroxide);
• - K / Na alloy: K and Na were in the weight ratio of 3 to 5: 1 melted under high vacuum; the resulting Alloy was liquid at 25 ° C;
• - Röhm tert-butyl methacrylate was fractionated distilled and after adding CaH₂ in the refrigerator at -18 ° C stored; this was required immediately before use required quantity separated under reduced pressure;
• - Tetrahydrofuran (industrial grade) was successively distilled three times: a) at normal pressure (1 atm) after addition of sodium; b) under reduced pressure (≈ 10 ^-4 mbar) after addition of a K / Na alloy (weight ratio 3 to 5: 1); c) under reduced pressure as in b); the last distillation was carried out immediately before use;
• - Titanium tetrachloride from Aldrich (purity 99.9%, used like bought);
• - SEC (Size Exclusion Chromatography, see Macromol. Rapid Commun. 16, p. 400, 1995): eluent:
  Tetrahydrofuran
  Detectors:
  2 × JASCO-UVIDEC 100 III UV detector with variable wavelength set to 260 nm
  Bischoff RI detector 8110 (refractive index detector)
  Columns:
  1 x 5 µm / 100 Å / 60 cm; 1 × 5 µm / linear: 10² to 10² Å / 60 cm / PSS SDV gel (= poly (styrene / divinyl benzene) gel from Polymer Standards Service GmbH in Mainz;
  Calibration:
  Using PIB and polymethyl methacrylate standards
  1 H NMR:
  200 MHz measuring frequency, CDCl₃ as a solvent.

All examples were under N₂ atmosphere, i.e. H. excluding performed by oxygen and moisture.

example 1

Production of

a) Preparation of 1-methoxy-1,1-diphenyl-3,3,5,5-tetramethyl hexane

For the preparation of compounds (I) according to the invention Isobutene with the lowest possible degree of polymerization contains, for the sake of simplicity, 2-chloro-2,4,4- trimethylpentane as a carbocationic initiator

which already chemically bound the desired isobutene unit contains, whereby the carbocationic polymerization occurs limits the formation of the carbocation.

0.01 mol of 2-chloro-2,4,4-trimethylpentane and 0.01 mol of N, N-dimethylacetamide were added to a solvent of 170 ml of CH₂Cl₂ and 300 ml of n-hexane. The resulting mixture was cooled to -78 ° C and mixed with 0.04 mol TiCl₄, which was dissolved in 30 ml CH₂Cl₂ (which contained 5 · 10 ^-4 mol 2,6-di-tert-butylpyridine) and at - Stirred at 78 ° C for 10 min.

Then the mixture was maintained while maintaining the temperature of -78 ° C a solution of 0.0105 mol 1,1-diphenylethylene in 10 ml of a CH₂Cl₂ / n-hexane mixture (volume ratio 40:60) added.

After stirring the reaction mixture at -78 ° C. for 15 minutes was by adding 30 ml of methanol (which was pre-adjusted to -78 ° C was cooled off) 2 minutes later there was so much solution from SN aqueous ammonia and CH₃OH (volume ratio 1: 4) added that the mixture contained 0.32 mol of ammonia and that Ti precipitated in the form of amine complexes. Then it was filtered to separate the titanium complexes. The organic phase was separated and once with 5N aqueous ammonia and then washed with distilled water until the pH of the Water was 7 to 8. After that the organic phase dried by adding MgSO₄. After drying is complete the organic phase was separated off, the solvent removed and recrystallized once in n-hexane.

It became a pure connection of the structure

receive.

b) metalation of the methoxy compound from a)

500 mg (1.54 · 10 ^-3 mol) of the methoxy compound from a) were dissolved at 25 ° C. in 50 ml of tetrahydrofuran, which contained 2 g of a K / Na alloy (weight ratio 4: 1). After different reaction times (at 25 ° C), 5 ml of the solution was removed and quenched with 2 ml of degassed methanol (the use of non-degassed methanol led to by-products). It was found in these experiments that 95% of the methoxy compound had already converted to the corresponding carbanion after 15 minutes. After 30 min a quantitative metalation to the desired compound I according to the invention was achieved (the experimental detection of the 100% metalation was carried out using 1 H NMR; the -OCH₃ peak at 3.0 ppm had completely disappeared and after termination by means of methanol occurred at 4.0 ppm the peak of the underlying between the phenyl groups -CH unit;. cf. Fig 1 and Fig 2)...

UV spectroscopy provides another means of detecting the end of the metalation. Reaching a stationary UV spectrum (λ _max = 480 nm) indicates the end of the metalation.

Example 2

Means

Initiated anionic polymerization of methyl methacrylate 10 ml of the initiator solution obtainable in Example 1b) were diluted with 40 ml of tetrahydrofuran at 25 ° C. Then, based on the molar amount of K contained therein, a 10-fold molar amount of LiCl was added. The mixture was then stirred at 25 ° C. for 15 minutes and then at -78 ° C. for 10 minutes. Then 1.6 g of methyl methacrylate was added all at once. After 90 minutes of anionically initiated polymerization, the polymerization was terminated by adding 5 ml of methanol
SEC examination of the resulting polymer showed the following values:

M _n = 5500 M _w / M _n = 1.09 f = 0.95 ± 0.05

The associated elugram is shown in FIG. 3.

Example 3 Production of ω-methoxy-ω, ω-diphenylpolyisobutene

As an initiator for the living carbocationic polymerization of Isobutene, 2-chloro-2,4,4-trimethylpentane was also used.

In one with septum, mechanical stirrer and nitrogen supply equipped three-necked flask were 80 ml CH₂Cl₂, 80 ml n-hexane, 0.28 mol N, N-dimethylacetamide and 450 mg 2-chloro-2,4,4-trimethyl Pentane mixed together and cooled to -78 ° C. Means 10 ml of isobutene was added to a needle tip. 5 min later was a solution of 40 ml CH₂Cl₂, 100 ml n-hexane, 6.6 ml TiCl₄ and 0.1 ml of 2,6-di-tert-butylpyridine was added. Another 10 min this was followed by a second addition of 11 ml of isobutene. Again 10 minutes later, a solution of 2.65 ml of 1,1-diphenylethylene, 6 ml of n-hexane and 4 ml of CH₂Cl₂ are added, the color changing the reaction mixture changed from light yellow to dark red. Then the mixture was stirred for 20 min and finally by adding 30 ml Methanol (pre-cooled to -78 ° C) canceled (during all of the previous ones) going reaction steps became a temperature of -78 ° C maintained). 2 min after that, a mixture of 100 ml 5N aqueous ammonia solution and 400 ml of methanol added to To avoid methanol elimination. Subsequently it became similar proceed as in Example 1.

First, the precipitated titanium complexes were filtered off (after filtration, washed with n-hexane). Then the Separated n-hexane phase and initially with 5N aqueous Ammonia solution and then washed with water until the  Water had a pH of 7. Then the organic MgSO₄ phase added and dried for 2 h.

The n-hexane was then removed on a rotary evaporator.

The resulting ω-methoxy-ω, ω-diphenylisobutene was described in a small amount of n-hexane and added twice in acetone falls to separate excess 1,1-diphenylethylene.

Finally, the ω-methoxy-ω, ω-diphenylisobutene formed analyzed by SEC. There was quantitative product formation detects with

M _n = 5800, M _w / M _n = 1.18 and f <0.98 (see Fig. 4).

Example 4 Production of α, ω-bis (methoxydiphenyl) polyisobutene

5-tert.- was used as the difunctional carbocation initiator. Butyl-1,3-dicumyl chloride used.

In one with septum, mechanical stirrer and nitrogen supply equipped three-necked flask were 20 ml of hexane, 20 ml of CH₂Cl₂, 0.095 ml N, N-dimethylacetamide and 287 mg 5-tert-butyl-1,3- dicumyl chloride mixed together and cooled to -78 ° C. Then 3.5 ml of isobutene were added using a needle syringe. 5 min later a solution of 20 ml CH₂Cl₂, 40 ml n-hexane, 2.2 ml TiCl₄ and 0.03 ml of 2,6-di-tert-butylpyridine added. After that 3.5 ml of isobutene were added again. 10 min later a solution of 1.75 ml of 1,1-diphenylethylene, 5 ml n-hexane and 3.4 ml of CH₂Cl₂ added, the color of the Reaction mixture changed from slightly yellow to dark red. Then it was stirred for 15 min and finally by adding 30 ml Methanol (pre-cooled to 78 ° C) canceled (during all of the previous going reaction steps became a temperature of -78 ° C keep right). 2 minutes later a mixture of 32 ml of 5N aqueous ammonia solution and 160 ml of methanol added to Suppress methanol elimination. After that, as in Bei game 3 procedure.

SEC analysis showed quantitative product formation

M _n = 6300, M _w / M _n = 1.12 and f <0.98 (see FIG. 5)

Example 5

Metallization of the α, ω-bis (methoxydiphenyl) polyisobutene from Bei game 4 and thus anionically initiated polymers sation of methyl methacrylate.

1 g of α, ω-bis (methoxydiphenyl) polyisobutene from Example 4 (number of chain ends = 3.2 × 10 ^-4 mol) was dissolved in 20 ml of tetrahydrofuran and the solution was dissolved. Addition of CaH₂ dried. Then it was filtered under N₂. The tetrahydrofuran was then removed in a high vacuum (0 ° C., 24 h).

0.6 g of the modified PIB (number of chain ends = 1.9 ± 10 ^-4 mol) was dissolved in 50 ml of tetrahydrofuran (molar concentration of chain ends = 3.8 · 10 ^-3 mol / l) and the solution in a vessel leads, which contained 2 g K / Na alloy (weight ratio 3 to 5: 1).

After a reaction time of 6 hours at 25 ° C., the mixture was filtered off and the Filtrate 81 mg LiCl added. The mixture was stirred at 25 ° C. for 40 min, then cooled to -78 ° C and 0.014 mol of methyl methacrylate at a time added. After polymerization for 2 hours at -78 ° C., Addition of 10 ml of methanol stopped. After that, the solution removed on the rotary evaporator and the tri- Block copolymer dried under high vacuum.

The yield of tri-block copolymer (BAB) was 2 g and thus corresponded to the theoretically expected value. The molecular weight distribution was monomodal (see. FIG. 6 and FIG. 7) and M _w / M _n was 1.13. M _n was 18,000.

To determine if necessary in the tri-block copolymer containing proportion of homopolymeric modified PIB the 2 g product extracted at 25 ° C for 35 days in n-hexane. The extra The amount of modified PIB was 25 mg. So that's a Block transfer coefficient of almost 1 is shown.

Example 6

Metalation of the ω-methoxy-ω, ω-diphenylpolyisobutene from Bei game 3 and then anionically initiated polymers sation of tert-butyl methacrylate (t-BMA).

The procedure was as in Example 5, the metalation time however, was chosen to be 10 days.

There was no reprecipitation with LiCl.  

The anionic polymerization was carried out under the following conditions gene carried out at -78 ° C in tetrahydrofuran:

Counter ion: K⊕;

molar concentration of anionic initiator: 1.9 × 10 ^-3 mol / l; molar concentration of tert-butyl methacrylate: 0.53 mol / l (4.5 g weight);

Polymerization time: 90 min; Yield: <95% of th. Demolition with methanol.

8 shows the SEC elugram. From this a f-value <0.95 could be estimated with a theoretical value for M _n of 26000.

By selective hydrolysis (e.g. in dioxane / HCl or dioxane / p-toluene olsulfonic acid) is from the obtained PIB-t-BMA di-block copolymer the corresponding PIB-MAS Di- Block copolymer available (MAS = methacrylic acid).

Example 7 Production of ω-methoxy-ω, ω-diphenylpolyisobutene

As an initiator for the living carbocationic polymerization of Isobutene, 2-chloro-2,4,4-trimethylpentane was also used.

In a septum, mechanical stirrer and nitrogen supply equipped three-necked flask were 18 ml of CH₂Cl₂, 0.08 ml of N, N-dimethyl acetamide and 128 mg 2-chloro-2,4,4-trimethylpentane with each other mixed and cooled to -78 ° C. Using a needle syringe fed to the 2 ml isobutene. 5 min later, 18 ml of BCl₃ (as 1 molar solution in CH₂Cl₂) added. Another 10 minutes later was a solution of 0.5 ml of TiCl₄, 54 ml of n-hexane and 0.03 ml 2,6-di-tert-butylpyridine added. Then the poly Merisat solution added another 4 ml of isobutene. 10 minutes after that a solution of 0.76 ml of 1,1-diphenylethylene, 3 ml of n-hexane and 2 ml of CH₂Cl₂ added, the color of the solution being slightly yellow changed to orange. The mixture was then stirred for 25 minutes. Finally was removed using 30 ml of methanol (which had been pre-cooled to -78 ° C) broken (during all previous reaction steps the reaction temperature -78 ° C). A mixture was made 2 minutes later 40 ml of SN aqueous ammonia solution and 160 ml of methanol are added, to avoid methanol elimination. Subsequently, as in Example 3 worked up.  

A mixture consisting of:

80% by weight of methoxydiphenyl-terminated PIB,
15% by weight of 2,2-diphenylvinyl-terminated PIB,
and 5% by weight with tert-chlorine-terminated PIB.

Example 8 Production of α, ω-bis (methoxydiphenyl) polyisobutene

5-tert.- was used as the difunctional carbocation initiator. Butyl-1,3-dicumyl chloride used.

In one with septum, mechanical stirrer and nitrogen supply equipped three-necked flask were 40 ml CH₂Cl₂, 0.185 ml N, N-dimethylacetamide and 575 mg of 5-tert-butyl-1,3-dicumyl chloride mixed together and cooled to -78 ° C. Then by means of 5.5 ml of isobutene are fed to a needle syringe. After stirring for 5 min 40 ml of BCl₃ (as a 1 molar solution in CH₂Cl₂) were added. 10 min then a solution of 1.1 ml of TiCl₄, 120 ml of n-hexane and 0.05 ml of 2,6-di-tert-butylpyridine was added. After that the Polymer solution added a further 8 ml of isobutene. 10 min later a solution of 3.5 ml of 1,1-diphenylethylene was added, 10 ml of n-hexane and 6.7 ml of CH₂Cl₂. The color of the Solution from light yellow to orange. After stirring for 15 min 30 ml of methanol (pre-cooled to -78 ° C) stopped (during all previous reaction steps was the reaction temperature -78 ° C). Two minutes later, a mixture of 80 ml of 5N became more aqueous Ammonia solution and 400 ml of methanol added to methanol to avoid elimination. Then, as in Example 4 worked up.

A mixture consisting of:

75% by weight methoxydiphenyl-terminated PIB,
12% by weight of 2,2-diphenylvinyl-terminated PIB,
and 13 wt% tert-chlorine terminated PIB.

Example 9 Metallation of 1-methoxy-3,3,5,5-tetramethyl-1,1-diphenylhexane with Cs

43 mg (1.33 x 10⁴ mol) of 1-methoxy-3,3,5,5-tetramethyl-1,1-diphenyl hexane was dissolved in 50 ml of tetrahydrofuran. Then was 1 g of Cs was added to the solution. Then the mixture of  Room temperature warmed to 34 ° C. After a reaction time of 60 minutes at 34 ° C the UV absorption spectrum of the reaction gene changed no longer mix what indicated the end of the metallization.

Claims (23)

1. Compounds of the general formula I With
m = an integer from 1 to 6,
n = an integer from 1 to 1500,
R¹ = residue of an m-functional carbocationic initiator,
R² = Naphthyl or phenanthryl,
R³, R⁴ = independently of one another -H, -CH₃, R⁵, R⁶ = -CH₃,
R⁷ = -CH₃ or -C (CH₃) ₃, R⁸, R⁹, R¹⁰, R¹¹ = independently of one another C₁- to C₅-alkyl or -C₆H₅ (phenyl). 2. Compounds of general formula I according to claim 1, with 3. Compounds of the general formula I according to claim 1 or 2, with n = 1 to 30. 4. Compounds of the general formula I according to claim 1 or 2, with n = 10 to 30. 5. Compounds of the general formula I according to claim 1 or 2, with n = 35 to 45. 6. Compounds of the general formula I according to claim 1 or 2, with n = <30 to 1500. 7. Compounds of general formula I according to claim 1 to 6, with m = 1 or 2. 8. Compounds of the general formula I according to claim 1 to 7, with R³ = H and R² = phenyl. 9. Compounds of the general formula I according to claim 1 to 8, with M⊕ = K⊕ or Li⊕.   10. Solutions of compounds of general formula I according to Claims 1 to 9 in organic solvents. 11. A process for the preparation of compounds of the general formula I according to claims 1 to 9, characterized in that isobutene is polymerized by the process of living carbocation-initiated polymerization, the polymerization by adding a compound of the general formula R³, R⁴ = independently of one another -H, -CH₃, R⁵, R⁶ = -CH₃ and R⁷ = -CH₃ or -C (CH₃) ₃
functionalized, then terminated by adding an alcohol or thiol and then metallizing the resulting ether or thioether compound with an alkali metal and / or alkaline earth metal. 12. The method according to claim 11, characterized in that R³ = H and R² = phenyl. 13. The method according to claim 11 or 12, characterized in that methanol is used for demolition. 14. The method according to claim 11 to 13, characterized in that the metalation takes place with a K / Na alloy, the Contains K and Na in a weight ratio of 3 to 5: 1.   15. The method according to claim 11 to 14, characterized in that BCl₃ and / or TiCl₄ as a coinitiator for the living carbocationically initiated polymerization of isobutene is used. 16. Method of anionically initiated polymerization of have at least one ethylenically unsaturated group the monomers, characterized in that as anionic Initiator used a compound according to claims 1 to 9 becomes. 17. The method according to claim 16, characterized in that the at least one ethylenically unsaturated monomer is selected from the group comprising esters of acrylic acid and C₁- to C₁₂-alkanols, esters of methacrylic acid and C₁- to C₁₂-alkanols, acrylonitrile, vinyl pyridine, acrolein , Meth acrolein, acrylamide, methacrylamide, N, N-dialkyl and N, N-dialacryl acrylamide and methacrylamide, Vinyl ketones of the general formula (III) with R¹⁵ = C₁ to C₁₂ alkyl,
and R¹⁶ = C₁ to C₄ alkyl, phenyl or H,
Compounds of the general formula (IV), with R¹⁷ = C₁ to C₄ alkyl, phenyl or H, and
Compounds of the general formula (V) with R⁵, R⁶ = CH₃,
p = 1 to 10 and
R⁷ = -CH₃ or -C (CH₃) ₃. 18. Use of compounds according to claim 1 to 9 as In initiators of an anionically initiated polymerization of we at least one ethylenically unsaturated group Monomers. 19. Copolymers, obtainable by a process according to Claim 16 or 17. 20. Copolymers containing at least one di-block copolymer segment of the general formula (VII) with R² = Naphthyl or phenanthryl,
R³, R⁴ = independently of one another -H, -CH₃, R⁵, R⁶ = -CH₃,
R⁷ = -CH₃, or -C (CH₃) ₃,
R²¹ = -H or -CH₃,
R²³ = C₁ to C₁₂ alkyl, H, alkali metal, ammonium and / or tetraalkylammonium,
k = an integer from 1 to 10⁴ and
n = an integer from 1 to 1500. 21. Copolymers according to claim 19, containing at least one Di-block copolymer segment of the general formula VII with R³ = H and R² = phenyl. 22. Copolymers according to claim 19 to 21, the only from di-block copolymer segments of the general formula VII are built up. 23. Process of radical aqueous emulsion polymerization from at least one ethylenically unsaturated group pointing monomers, characterized in that the poly merization vessel before, during and / or after the radical aqueous emulsion polymerization according to a copolymer Claim 19 to 22 is added.