FR2530642A1 - PROCESS FOR THE PREPARATION OF MULTIFUNCTIONAL POLYMERIZATION INITIATORS - Google Patents

Abstract

A.PROCEDE FOR THE PREPARATION OF MULTIFUNCTIONAL POLYMERIZATION INITIATORS. B. CHARACTERIZED IN THAT DIVINYL-BENZENE, O, M OR P, OR A MIXTURE OF DIVINYLBENZENE IS REACTED WITH A MONO, DI OR TRILITHIUM ORGANOLITHIUM COMPOUND, AT 268 TO 303K, WITH A HYDROCARBON OR HYDROCARBIDE- ETHER BY MAINTAINING THE APPROPRIATE MOLAR RATIO BETWEEN THE VINYL GROUPS AND THE ORGANO-LITHIUM COMPOUND. C. PROCEDURE APPLICABLE TO THE PREPARATION OF MULTIFUNCTIONAL POLYMERIZATION INITIATORS.

Description

Process for the preparation of polymer initiators

multifunctional

  The invention relates to a process for the preparation of lithium-containing polymerization initiators which have an average functionality greater than 2 and

  which are suitable for the preparation of homo and copoly-

  telechelic mothers of polymerizable monomers

  anionic, in particular conjugated dienes and

  substituted aromatic compounds on a vinyl group.

  The synthesis of branched polymers in the form of a star and polymers carrying a function at the end of the chain,

  In the event of anionic polymerization,

  organo-alkaline units with superior functionality.

  Since the so-called telechelic polymers are low molecular weight products with an average molar mass of 1000 to 10,000, the initiators used for their preparation must also have low molar masses. It is preferred to use lithium initiators for the polymerization reactions because they

  have various advantages over other

  organo-alkali, for example higher resistance

  increased storage stability and the possibility of

  high temperature implementation.

  However, most bi-functional and multifunctional organo- lithium are insoluble in hydrocarbons, that is, they are used exclusively in strongly polar solvents. If the polymerization is carried out with initiators of this type, containing, for example, ether, secondary reactions such as

  chain breaks, chain transfers or

  This is due to a more or less pronounced decrease in the content of active Li-C bonds, which leads to a loss of functionality, higher molecular weights of polymers,

  larger molar masses and at a reduced efficiency.

the initiator.

  It is known to prepare polymeric initiators

  containing lithium, soluble in hydro-

  carbides, by reaction of divinylbenzene with monolithic alkyls, in particular butyllithium, within a

  Inert organic solvent For these metallurgical reactions

  In general, m-divinylbenzene is used because it has a lower tendency to polymerize than the other isomers of divinylbenzene.

  Plaste und Kautschuk 26 (1976) 5, pp. 263-264; Compt.

  Makes Heb Sessions Acad Sci, Ser C 283 (1976) 4, pages 123-125, as well as patents U S 3,725,368,

  3 862 251 and DE-OS 2 063 64, organic initiators

  Lithium were prepared by reacting m-divinylbenzene with alkyl iithium compounds in a molar ratio

  of 1: 2, in the presence or absence of tertiary amines.

  Nevertheless, in all cases, only

  dilithiated poses Li initiators with functionality

  higher can not be obtained by this route.

  Multifunctional Li initiators have been prepared according to DE-AS 2 003 384 and U S patents.

  3,644,322 and 3,787,510, by reaction of alkyl compounds.

  lithium with divinylbenzene, in a molar ratio of I: 0.1 to 1: 2, in the presence of solubilizing monomers,

  such as conjugated dienes, or monovinyl compounds

  aromatics, the molar ratio between alkyl lithium and

  the solubilizing monomer being from 1: 2 to 1: 5

  However, the disadvantage of the solvents is that they require, for their solubilization, the addition of polymerizable monomers during the synthesis of the initiator, so that it also has a high molar mass, and therefore can not be used for the synthesis of low molecular weight polymers In addition, the functionality of multilithied initiators can be controlled only by

  the number of vinyl groups of the polyvinyl aromatic compound

  tic, that is to say by an excess of polyvinyl aromatic compound, which creates a risk of crosslinking of

  initiator, i.e. gel formation.

  According to German Offenlegungsschrift No. 2,427,955, the reaction of divinyl-

  benzene with the organo-alkaline compound is carried out in very

  high dilution The organo-alkaline polyfunctional compounds

  The resulting macrogels are insoluble and unusable as an initiator for the anionic polymerizations. ,

except under certain conditions.

  Soluble crosslinked products of the microgel type are obtained according to DE-OS 2 427 955 only when

  the concentration of divinylbenzene in the reaction mixture

  In this concentration zone, the solubility of the initiator is a function of the molar ratio between divinylbenzene and

  monolithic compound, this ratio must be 0.5-20: 1.

  The higher the molar ratio of divinylbenzene to the low molecular weight organo-alkaline compound, the higher the

  the concentration of divinylbenzene in the reaction mixture

  should be lowered In fact, when the report

  molar increases, the number of metal-alkali

  carbon per molecule of the reaction product also increases

  as well as the molar mass and the degree of

this product.

  As a result, a molar ratio of divinylbenzene to the monoalkaline compound of 0.5: 1 represents the possible lower limit. The upper limit is determined by the concentration of divinylbenzene within the reaction mixture.

  occurs, for a defined concentration, a cross-linking

  partial or total intermolecular formation, with formation of insoluble macrogels. The upper limit of the molar ratio is, for example for a 2.5% solution,

  at 2: 1, and for a solution at 1.25%, at 6.7: 1.

  The known method according to the state of the art

  the following disadvantages, which do not allow

  its use for the synthesis of polymer initiators

  anionic release of monomers to low molecular weight telechelic polymers:

  because of the low concentration imposed on divinyl-

  benzene, only low initiator solutions are obtained;

  for the synthesis of organo-alkaline poly-

  functional, it is still necessary to have an excess of divinylbenzene relative to the monometallic compound, because of which all the initiators are more or less strongly crosslinked, which considerably limits their solubility in hydrocarbon solvents; the initiators themselves have relatively high molar masses (for example 2,800, 265,000 and 320,000), so can not be used for

  the synthesis of low molecular weight polymers.

  DE-OS 2 408 696 describes the production of organo-trilithine polymerization initiators, by reaction of a divinylaromatic compound, for example diisopropylbenzene or divinylbenzene, with an organo-monolithic compound, for example sec-butyllithium , with formation of a mono-adduct and subsequent reaction of this mono-adduct which still contains a free vinyl group, with an organo-dilithium compound, and formation of an organo-trilithine compound Synthesis requires low temperatures, in particular temperatures between 243 and 273 K To carry out the second reaction step (reaction of the monoadduct with the organodilithium compound), it is necessary to use tertiary amines, the ratio

  molar amine on C-Li being 0.5 4: 1.

  According to DE-OS Nos. 2,427,955 and 2,521,200, when divinylbenzene is reacted with alkyl lithium in a molar ratio where vinyl groups exist

  free, micro-shaped products are formed

  gel or macrogel In the process according to DE-OS 2,408 v 696, it is also necessary to count in the 1st reaction stage, using divinylbenzene,

  the appearance of crosslinked reaction products

  that diisopropenyl-benzene is used, there is no risk of crosslinking, because this product is significantly less reactive than divinylbenzene and its "ceiling temperature" is lower But the important cost of

  synthesis of diisopropylbenzene precludes any application

industrial cation.

  The method according to DE-OS 2,408,696 has the further disadvantage of only allowing the production of trilithic compounds, and that their synthesis requires several reaction steps.

  known dilithium compounds, it is also possible to obtain

  However, initiators and polymers having a functionality greater than 3 can not be obtained. Polymers of this type are however necessary for the preparation of crosslinked products having a high crosslinking density.

  and good physical and mechanical properties.

  The object of the invention is to prepare organo

  unbranched, low molecular weight multifunctional lithium from accessible raw materials,

  which allow the synthesis of polymers and copolymers

  res-blocks of low to medium molar mass, in which case the polymers carry, after the reaction with

  appropriate electrophilic reagents, functional groups

  terminals, have a high functionality

  and a narrow distribution of molar masses.

  The convenients of the known processes will have to be avoided.

  The invention must therefore propose a method of prepa-

  of multifunctional polymerization initiators for the anionic polymerization of conjugated dienes or for the copolymerization of these dienes with vinyl aromatic monomers into living polymers, the requirements

above being fulfilled.

  For this purpose, the invention proposes a method

  in that the divinylbenzene is reacted with a mono-, di or trilithic organolithium compound at a

  temperature of 268 to 303 K in a hydrocarbon solvent

  or a hydrocarbon-ether mixture According to the invention

  divinylbenzene is introduced as a solution.

  hydrocarbon solution, in a solution of the organo-

  mono-, di or trilithium lithium in a hydrocarbon, an ether or a hydrocarbon-ether mixture, in the space

from 15 to 60 minutes.

  Suitable hydrocarbon solvents are the hy-

  aliphatic or aromatic hydrocarbons, aromatic hydrocarbons such as benzene or toluene being used

  The appropriate ethereal solvents are preferably

  by aliphatic or cycloaliphatic ethers such as diethyl ether, methyl tertiary butyl ether or

tetrahydrofuran.

  To make the organolithium more reactive, one can

  add tertiary amines, especially triethyl-

  amine and dimethylaniline or their mixtures, the ratio

  molar lithium: amine to be 1: 1 1.5.

  In the reaction of o-, m or p-divinylbenzene or mixtures thereof with an organo-monolithium compound, in particular with an alkylmonolithium compound,

  preferably normal, secondary butyllithium or isobutane

  tyllithium, the molar ratio divinylbenzene: alkyl

  lithium amounts to N: N + 1, N being a higher number

or equal to 2.

  The concentration of divinylbenzene does not represent a remarkable magnitude here.

  soluble, polyfunctional organolithiums with

  centers of divinylbenzene as weak as they are

  The ratio of isomers of divinylbenzene to each other, when using their mixtures, is also not imperative; nevertheless, mixtures which can be isolated from the mixture of

  Technical divinylbenzenes after alkylation of benzene.

  The initiators according to the invention are organophosphorus

  low molecular weight lithium, linear, non-linear

  The number of lithium atoms per initiator molecule is determined by the molar ratio of divinylbenzene to the alkyl lithium compound and corresponds to the number N + 1. The functionality of these initiators is

control so on demand.

  In the reaction of organo-monolithium with a

  a technical mixture of divinylbenzenes, generally

  ranging from: a) 10 to 70% by weight of divinylbenzene b) 80 to 30% by weight of ethylstyrene and

  c) about 10% by weight of diethylbenzene.

  The molar ratio of vinyl groups in divinylbenzene

  technique (from divinylbenzene and ethyl-

  styrene) to the alkyl-lithium compound is 1.1 2: 1 The concentration of divinylbenzene is not, here either, a remarkable size Whether concentrations

  low or high in divinylbenzene, we always get

  days of polyfunctional organolithium, soluble,

low molecular weight.

  The degree of metallation of the initiator is

  molar ratio of vinyl groups: alkyl lithium

and is between 2 and 4.5.

  It is advantageous to use mixtures of divinyl-

  benzene which results from the alkylation of benzene and which contains approximately: 70% by weight of divinylbenzene, 40% by weight of ethylstyrene and

  about 10% by weight of diethylbenzene.

  The reaction of the organolithium di or trilithine with divinylbenzene in a hydrocarbon solvent, ether, or hydrocarbon-ether mixture is carried out with a molar ratio of vinyl groups in divinylbenzene

  that is, technical divinylbenzene to the di-

or trilithea of 1-: 1 10.

  The organodilithiums used for the preparation of

  The organolithium compounds with high functionality according to the invention are, for example, dilithiated adducts.

  conjugated dienes, for example butadiene or iso-

  prene, or a dilithiumalkane, for example dilithium

  butane A suitable organo-trilithium is the reaction product of divinylbenzene and sec-butyllithium,

in a molar ratio of 2: 3.

  Divinylbenzene can be used in the form of pure o, m or p isomer, or in the form of a mixture of these isomers Depending on the metallation agent used (di or trilithium compound) and the molar ratio of the vinyl groups to the metallation agent, we get

  either pure tetra or hexalithic compounds or mixtures

  of these compounds and di or trilithic compounds.

  The higher-functionality pure lithium initiators are obtained with molar-group ratios

  vinyl: metallation agent 1: 1.

  In addition to the pure isomers of divinylbenzene or

  mixtures, it is also advantageous to implement

  The technical mixtures of divinylbenzenes mentioned above are used to obtain high functionality organolithium polymerization initiators. By respecting the molar ratio vinyl groups: metallation agent, mixtures of tetra or dilithium compounds, or mixtures of hexa compounds or trilithyes

  Initiator mixtures of this type have important

  in the preparation of polymers with

  because low-functioning polymer chains

  lity act in crosslinking reactions as chain extenders, with the same chemical structure

of the polymer chain.

  The initiators according to the invention have average molar masses of less than 500 and are therefore

  particularly suitable for the synthesis of poly-

  mothers of low molecular weight

  higher functionality are insoluble

  in the reaction medium They can therefore be isolated

  However, they can also be used in suspension form for subsequent reactions, or converted into a soluble form by addition of

polymerizable monomers.

  The initiators mentioned have been used according to the invention for the anionic polymerization of conjugated dienes, or the copolymerization of these dienes with vinylaromatic monomers, into living polymers.

  with subsequent functionalization.

  Monomers that can be polymerized in advance

  of these initiators are conjugated dienes such as butadiene-1,3 or isoprene, as well as

  vinyl-substituted aromatics, such as styrene, alpha-

  For the synthesis of copolymers, it is nevertheless possible to use, as comonomer, all the other monomers capable of anionic polymerization. The polymerization is carried out under the conditions which are known for the anionic polymerizations in solution with alkali metal organometallic initiators.

  aliphatic, cycloaliphatic and aromatic hydrocarbons

  such as n-hexane, n-heptane, ben-

  zenic, cyclohexane, benzene or toluene The polymerization is conducted at a temperature of 198 to

  423 K, preferably 273 to 323 K, under atmospheric pressure.

  higher pressure The duration of the

  reaction is usually 1 to 3 hours.

  The quantities of initiator to be used are determined

  born by the desired molar mass because it is a

  stoichiometric polymerization The heterogeneous initiators

  genes are transformed into a soluble form using polymerizable monomers, so that the solution

  of polymer is soluble during the polymerization.

  It is surprising to see that this does not result in

  dispersed distribution of the molar mass The polydis-

  Persistence of the polymers Mw amounts on average to 1.1 to 1.4.

  The active chain ends of the living polymers obtained can be reacted in known manner with electrophilic end-group reagents, such as carbon dioxide, alkylene oxides, epichlorohydrin or gamma-butyrolactone, so that can be very advantageously obtained from

telechelic polymers.

  During the polymerization reaction, no side reaction occurs, so that depending on the functionality of the active polymer,

  telechelic polymers with high functionality

  The functionality of the polymers corresponds to that of the initiator. These polymers can be cured simply by

  with a bifunctional crosslinking agent.

  The method according to the invention makes it possible to eliminate

  disadvantages of the known methods, namely the inaccessibility

  low molecular weight lithium initiators

  high functionality, low initiator efficiency, limited molecular weight adjustment capability, dispersion of molecular weight distribution, and low functionality of polymeric products. The resulting polymers are star-shaped polymers, which have a lower viscosity than linear polymers, which facilitates shaping

of the polymer.

  The invention will be better understood with the help of examples

non-limitative plies below.

Example 1 -

  In a 500-milliliter flask was placed 61.5 ml of a 0.98 molar secondary butyllithium solution.

  in benzene, 4 ml of triethylamine, 4 ml of dimethyl

  Aniline and 50 ml of benzene A solution of 5.7 ml of p-divinylbenzene (DVB) was introduced into this mixture over a period of 30 minutes, with stirring at 2980 K.

  in 20 ml of benzene from a dosing funnel.

  After the addition of DVB was complete, the

  still for 2 hours at 2981 K. A homogeneous initiator solution, colored in dark red, whose degree of metallation was

  has been determined by functionalization with ethylene oxide.

  After hydrolysis of the reaction product with 30 ml of water, the solution was centrifuged, and the solvent was removed from the organic phase in a rotary evaporator.

  empty, at 323 K The molar mass was determined, at

  extraction of DVB oligomers isolated by osmosis, at vapor pressure, in benzene, and the hydroxyl content, by acidimetric determination The product had a molar mass Mn of 550 and a hydroxyl content of 9.58%,

  which corresponds to a functionality of 3.1.

  In a solution of 30 millimoles of this initia-

  trilithium, 600 ml of benzene were introduced under an argon atmosphere, and to the homogeneous solution was added,

  within 2 hours, 90 g of 1,3-bentadiene.

  polymerization temperature was 298 K After the end of the polymerization, it was functionalized at 2789 K

  with 7.9 g of ethylene oxide and hydrolysed with water.

  The isolated polymer had an average molecular weight, determined by osmosis at vapor pressure, of 3100 (theory: 3000) and a hydroxyl content of 1.67% by weight.

  weight, which gives a functionality of 3.04.

  The proportion of polybutadiene-1,4 amounted to 57 mol%, that of polybutadiene-l, 2 to 34 mol%,

  and that of divinylbenzene at 9 mol%.

Example 2:

  To a mixture of 20 ml of a 1,4-molar benzene solution of sec-butyllithium (28 millimoles), with 5 ml of triethylamine and 30 ml of benzene, a solution of 21 millimoles of m-DVB was added dropwise. in 20 ml of benzene at 278 K, with stirring, in 15 minutes stirring was continued for 2 hours at 278 K The homogeneous reaction solution was

treated as in Example 1.

  The isolated product had an average molecular weight Mn of 750 and a hydroxyl content of 9.52% II.

shows a functionality of 4.2.

  14 millimoles of this tetralithium initiator and 400 ml of toluene were placed in a flask under an argon atmosphere. To this solution, 56 g of 1,3-butadiene were added over 1 hour to 308 K.

  end of the butadiene addition, stirring was

  followed for another half an hour, then the polymeric

  was quenched with 4.9 g of ethylene oxide, and

finally, it was hydrolysed with water.

  100% polybu-

  liquid tadiene with an average molar mass of 3900 and a microstructure of 57 mol% in -1.4 structure,

  39 mole% in structure-1, 2 and a divinylbenzo content

  zeol of 4 mol% The molar mass calculated from

  monomer / initiator ratio was 4000.

  The hydroxyl content determined by acid

  dimetric was 1.726% by weight, which corresponds to

at a functionality of 3.96.

Example 3

  In a 500 ml flask, 61.5 ml of a

* 0.98 molar solution of sec-butyllithium in the ben-

  zeen, 4 ml of triethylamine and 4 ml of dimethylaniline and 50 ml of benzene. A solution of 20 millimoles of a mixture was introduced dropwise into this mixture within 30 minutes, with stirring, at 298 K. of divinylbenzenes (DVB) m and p, in 20 ml of benzene, with the aid of a dosing ampoule After the end of the addition of DVB, stirring was continued for another 2 hours at 298 K. obtained a homogeneous initiator solution, dark red, the degree of metallation was determined by functionalizing with

  ethylene oxide After hydrolysis of the reaction product

  with 30 ml of water, the solution was centrifuged and -

  the solvent removed from the organic phase in an evaporation

  Vacuum rotator at 323 K On the isolated DVB oligomer,

  the molar mass was determined by osmosis at

  The product has an average molecular weight Mn of 760 and a hydroxyl content of

  6.75%, which corresponds to a functionality of 302.

  Using a benzene solution of 16 millimoles of trilithic compound, dissolved in 400 ml of benzene, 472 g of 1,3-butadiene were polymerized in 2 hours. The living polymer then reacted with 4.22 g. oxide

  ethylene and the resulting gel was hydrolyzed with water.

  A terminal hydroxyl polybutadiene with an average molecular weight of 4600 (theory: 4500) and an OH content of 1.085% by weight was obtained in 100% yield; this results in a functionality of 2, 94 The

  polymer had a microstructure of poly-

  butadiene-l, 4 of 61 mol%, and product-l, 2 of 39%

  Molar The polydispersity U = MW was 1.15.

mn

Example 4

  In a 750 ml flask equipped with a stirrer, a thermometer, a measuring funnel and an introduction of argon, 40 millimoles of sec-butyllithium were placed in 80 ml of benzene, and 6 To this was added, with stirring, to 278 K, 7.03 g of a technical divinylbenzene mixture consisting of 57.2% by weight of divinylbenzene, 33% by weight ethylstyrene and 9.8% by weight of diethylbenzene,

  dissolved in 40 ml of benzene within 15 minutes.

  Stirring was continued for another 2 hours at 278 K. A clear red solution was formed. This solution was functionalized with 44 millimoles of oxide.

  of ethylene, to determine the metallation.

  After hydrolysis with water, separation of the aqueous phase and removal of the solvent in a rotary evaporator under vacuum, the functionalized initiator was

subject to analysis.

  I 1 exhibited a molar mass, determined by osmosis at vapor pressure, of 920 and a

  OH 7.8%; this results in a feature of 4.22.

  1 g of this initiator solution and 300 ml of benzene were placed in a flask under an argon atmosphere. 40 g of butadiene were introduced into this solution within one hour at 3080 K. the reaction, the stirring was continued for another half-hour, then the polymerization was stopped by 44 millimoles of ethylene oxide. Then, it was hydrolysed with 50 ml of water, the aqueous phase was separated and we have

  removed the solvent in a rotary evaporator under vacuum.

  A polybutadiene with a yield of 100% is obtained

  liquid with a molar mass of 4900 and a micro-

  structure with proportions of 50 mole% -1,4 product, 32 mole-1,2 product and a DVB content of 18 mole X. The hydroxyl content, determined by acidimetric titration is 1.42% in weight, which corresponds

to a functionality of 4.1.

Example 5

  To 63 millimoles of iso-butyllithium, dissolved in 100 ml of toluene, 7.03 g was added dropwise.

  of the divinylbenzene mixture of Example 4

  in 40 ml of toluene The reaction time was minutes, the temperature of 2980 K After the end of

  reaction, the product was reacted with 76 milli-

  The molar ratio of vinyl: butyl lithium groups was 1.25: 1. The average molecular weight of the functional initiator was 450, moles of ethylene oxide and the result was treated as in Example 4. the OH content is 8.5% by weight.

functionality of 2.25.

  To the solution of this initiator in 140 ml of toluene was added under argon atmosphere 400 ml of toluene, and to this homogeneous solution was added under

  one hour, 63 g of isoprene. The polymerization temperature

  was 2730 K After the end of the polymerisation,

2530642 -

  it was functionalized with 76 millimoles of ethylene oxide

  and treated according to Example 4.

  Isolated polyisoprene had a molar mass

  average of 2600 and an OH content of 1.41% by weight.

  This results in a functionality of 2.15 molar mass

Theoretical was 2700.

Example 6

  Example 4 was reproduced with this difference that 80 millimoles of n-butyllithium were used and

  15.42 g of a technical mixture of divinylbenzene containing

  51.8% by weight of divinylbenzene, 30.7% by weight

  of ethylstyrene and 17.5% by weight of diethylbenzene.

  By osmosis at the vapor pressure, the average molar mass of the functionalized initiator was determined; it amounted to 850 The hydroxide content was

  8.84% by weight, and the functionality of 4.42.

  With the aid of this initiator dissolved in 750 ml of

  benzene, 60 g of butane were polymerized one after the other.

  diene and 40 g of styrene, in the space of 2 hours, at 323 K, then functionalized with 88 millimoles

  of ethylene oxide and treated in the usual manner.

  The block copolymer obtained consisted of

  74.5 mol% butadiene and 25.5 mol% styrene.

  The molar mass amounted to 5400 and the functionality to 4.3, corresponding to an OH content of 1.35% by weight.

Example 7

  In a 750 ml flask equipped with an agitator, a

  thermometer, a dosing bulb and a supply of ar-

  400 ml of a once-molar solution of a dilithiated butadiene adduct containing 2

  monomer per molecule, in a toluene / tetrahydro-

  drofurane (85: 15 ratio by volume) 21.6 g (0.2 moles) of m-divinylbenzene dissolved in 100 ml of toluene were introduced dropwise over 30 minutes at 268 K. Stirring was continued for a further hour. During the time of addition and stirring, the tetralithium compound formed precipitated. The suspension was functionalized with 1 mole of ethylene oxide with stirring to determine the degree of metallation After hydrolysis with water, separation of

  aqueous phase and removal of the solvent in the evaporation

  rotary actuator, the functionalized initiator has

submitted for analysis.

  It had a mean molar mass, determined by osmosis at vapor pressure, of 480 and an OH content of 13.46%; this results in a functionality of 3.8.

Example 8

  In a solution of 0.24 moles of dilithiumbutane in 300 ml of methyl tert-butyl ether, a technical mixture of divinylbenzenes containing 30 mole% of ethylstyrene and 60 mole% of divinylbenzene, dissolved in 150 ml of benzene in space

  60 minutes, at 303 K The molar ratio of dilithium

  tane: vinyl groups in the technical mixture of DVB was 1: 1 In clear, colorless solution, it

  has appeared a yellowish precipitate.

  The initiator was hydrolysed and treated as in

Example 7.

  The average molar mass of the functional initiator

  nalis was 340, with an OH content of 16.5%.

  corresponds to an average functionality of 3.3.

Example 9

  Example 7 was repeated with the difference that instead of the dilithium compound, 0.4 mol of a trilithine adduct of m-divinylbenzene and sec-butyllithium was placed in the flask in 200 ml of benzene. , and one

  was added dropwise at 278 K, 0.2 mole of p-divinyl

  benzene The functionalized initiator had an average molar mass of 830, an OH content of 11.8% and

a feature of 5.75.

Example 10

  38.5 millimoles of a tetralithic initiator, obtained from 77 millimoles of a dilithium-oligoisoprene containing on average 2 units of isoprene per molecule, and 38.5 millimoles of m-divinylbenzene, suspended in

  1.5 l of a toluene / tetrahydrofuran mixture (volume ratio

  95: 5) were placed in a protected 2.5 l flask, and 155 g of 1,3-butadiene were charged to

  273 K The polymer solution was homogeneous after introduction

  The polymerization was terminated after 2 hours. Then, millimoles of ethylene oxide were added with stirring, and the solution was immediately set to give a solid white gel. This gel was broken by hydrolysis. with 50 ml of water, after which the

solution became liquid again.

  The aqueous phase was separated, with the Li OH formed,

  of the toluene solution, by centrifugation with

  toluene, 1.55 g of di-tert-butyl-

  cresol, and then the solvent was removed in a rotary evaporator under vacuum. A fluid polymer having an average molecular weight Mn = 4400 (theory: 4380) was obtained,

  and a functionality of F = 3.8 The microstructure deter-

  NMR spectroscopy was 90% polybutary

  diene-1, 2 and 10% polybutadiene-1,4.

Example 11

  To a suspension of 30 millimoles of a hexalithic initiator, which was obtained by reaction of 30 millimoles of a mixture of m / p-divinylbenzene with 90 millimoles of a

  trilithic compound, which is the reaction product of the

  butyl lithium with p-divinylbenzene in a report

  molar ratio of 3: 2, 600 ml of benzene were added under argon.

  then, within 2 hours, 135 g of butadiene-

  1.3 The polymerization temperature was 2980 K.

  After the end of the polymerization, we functionalized

  at 278 K with 216 millimoles of ethylene oxide and

  lysed with water After removal of the solvent, the polybutary

  The isolated diene had a molar mass, determined by osmosis at vapor pressure, of 3700 (theory: 3715) and an OH content of 2.67% by weight, from which it resulted.

  a functionality of 5.8 The proportion of polybutadiene-

  1.4 was 69 mole%, that of polybutadiene-1.2

31 mole%.

Example 12

  millimoles of a hexalithied initiator, prepared

  from 20 millimoles of m-divinylbenzene and 60 milliliters

  moles of a trilithic compound, obtained from

  Butyl lithium and m-divinylbenzene in a molar ratio of 3: 2, in benzene, and 600 ml of toluene, were introduced into a flask under argon. To this suspension, was added in 1.5 hours. one after the other, g of butadiene and 40 g of styrene After the end of the introduction of styrene, the stirring was continued for a further half hour, then the living polymer

  has been functionalized with gaseous carbon dioxide.

  The carboxylate formed is then converted using gaseous HC 1 to hexacarboxylic acid. The excess HC 1 is

  neutralized with Na 2 CO 3 and the alkali metal salt is

  After removal of the solvent, the yield is

was 100%.

  The resulting butadiene / styrene block copolymer

  had an average molar mass Mn = 4200 and a function

of 5.98.

Example 13

  To an initiator, prepared from 4 g of a technical mixture of divinylbenzene consisting of 60.3% by weight of divinylbenzene (18 millimoles), 30.3% by weight of ethylstyrene (9 millimoles) and 9.4% by weight of

  diethylbenzene (2.9 millimoles), and 75 millimoles of

  dilithiumbutane in 100 ml of methyl tert-butyl ether was added, under argon, 500 ml of benzene and, with stirring, in the course of 2.5 hours at 298 K, 210 g of butadiene-1,3 After completion of the polymerization, the mixture was cooled to 278 K and 180 millimoles of ethylene oxide was added. The white gel formed was hydrolyzed with

  ml of water, the aqueous solution was separated and the

  The liquid polybutadiene thus obtained had a molar mass Mn of 4050 (theory: 4000), and a functionality of 2.47 (theory: 2.5). of polybutadiene-1, 2 was 45 mol%, that of polybutadiene-1,4

moles%.

Example 14

  To an initiator suspension which was obtained by reacting 40 millimoles of m-divinylbenzene with 160 millimoles of a trilithium compound prepared from sec-butyllithium and m-divinylbenzene in a molar ratio of 3: 2, in 200 ml of benzene, 500 ml of benzene were added, followed by 240 g of butadiene within 2 hours. The temperature of the polymerization was 308 KA for the solution of the living polybutadiene, 0.57 was then added. mole of ethylene oxide, 278 K The aleoolate formed was hydrolysed with 100 ml

  of water The aqueous phase and soil of Li were

  fugés. After removing the solvent from the organic phase in a rotary evaporator under vacuum, a liquid polybutadiene with an average molecular weight of 2700 and a functionality of 3.95 was obtained (theory: 4.0). The polymer contained 65 mole% of structure in-1,4 and 35

moles% of structure in -1,2.

Example 15

  100 g of butadiene-1,3 were polymerized with an initiator which was obtained from 4 g of a technical mixture of divinylbenzenes consisting of 60.3% by weight

  divinylbenzene (18 millimoles), 30.3% by weight of ethyl

  styrene (9 millimoles) and 9.4% by weight of diethylbenzoate

  zene, and 54 millimoles of the trilithic compound of Example 14, in 400 ml of toluene within 2 hours, at 323 K. After this, 35 g of styrene were added over a period of 30 hours. 1 hour Then we functionalized with 194 millimoles of ethylene oxide and treated as

in example 14.

  The isolated butadiene / styrene copolymer had an average molecular weight of 3500 and an average functionality of 3.9 (theory: 4.0). The molar composition amounted to 85% butadiene and 15% styrene.

100%.

  The text adduct expression means binding

of addition.

RE V E N D I C AT IO N S

  1) Process for the preparation of poly-initiators

  multifunctional merification, by metallation of divinyl-

  benzene for the anionic polymerization of conjugated dienes

  or the copolymerization of these dienes with mono-

  vinyl-aromatic mothers, made of living polymers, and

  subsequent generation with electrophilic reagents

  the process characterized in that the divinylbenzene ortho-, meta or para-, pure, or a mixture is reacted

  of these compounds, or a technical mixture of divinylbenzines

  zenes, with a mono-, di or trilithium organo-lithium compound, at 268 to 303 K, in the course of 15 to 60 minutes, optionally in the presence of a tertiary amine, in a hydrocarbon or a hydrocarbon / ether mixture, maintaining a molar ratio between the vinyl groups,

  in the technical mixture of divinylbenzenes, and the

  organolithium compound, from 1 to 2: 1 to 10, or a molar ratio of pure divinylbenzene to the monolithic organolithium compound, N: N + 1, N being greater than or equal to 2, and the organolithium compound di as well as trilithy, of

  1: 2 to 10, and a lithium to tertiary amine molar ratio of

  from 1: 1 to 1.5, the polymerization being conducted at

a temperature of 198 to 423 K.

  2) Process according to claim 1, characterized in that the technical mixture of divinylgenzenes present

a composition of: -

  at 70% by weight of divinylbenzene at 30% by weight of ethylstyrene and

  about 10% by weight of diethylbenzene.

  3) Method according to one of claims 1 and 2,

  characterized in that the molar ratio between the groups

  In the reaction of the technical mixture of divinylbenzene, the vinyl compound in the vinylaromatic compound and the organolithium compound is a monolithic compound of 1.1 to 2: 1 compound dilithium, 1 to 1 to 10

trilithic compound, 1: 1 to 10.

  4) Process according to any one of the claims

  1 to 3, characterized in that the organic compound

  monolithic lithium is an alkyl-lithiated compound, particularly an n-, sec- or iso-butyllithium, the compound

  dilithiated organo-lithium is a dilithiated adduct of butadiene

  diene or isoprene, which contains from 1 to 7 units of diene per molecule, or dilithiumbutane, the trilithium organo-lithium compound being a reaction product of

  divinylbenzene and secondary butyllithium, in one.

molar ratio of 2: 3.

   Process according to any one of Claims 1 to 4, characterized in that the hydrocarbon is benzene or toluene, the ether being diethyl ether,

  methyl tert-butyl ether or tetrahydrofuran.

  6) Process according to any one of the claims

  1 to 5, characterized in that, as tertiary amine, triethylamine, dimethylaniline or their

mixed.

  7) Process according to any one of the claims

  1 to 6, characterized in that the temperature of

  polymerization amounts to 273 K at 323 K.