EP1718686A1 - Procede ameliore de production de polystyrene resistant aux chocs - Google Patents

Procede ameliore de production de polystyrene resistant aux chocs

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Publication number
EP1718686A1
EP1718686A1 EP05715346A EP05715346A EP1718686A1 EP 1718686 A1 EP1718686 A1 EP 1718686A1 EP 05715346 A EP05715346 A EP 05715346A EP 05715346 A EP05715346 A EP 05715346A EP 1718686 A1 EP1718686 A1 EP 1718686A1
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EP
European Patent Office
Prior art keywords
stage
styrene
alkali metal
organyl
aluminum
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EP05715346A
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German (de)
English (en)
Inventor
Philippe Desbois
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes

Definitions

  • the invention relates to a process for the preparation of impact-resistant polystyrene from diene monomers and styrene monomers by anionic polymerization, wherein
  • the invention also relates to the impact-resistant polystyrene obtainable by the process mentioned, the use of impact-resistant polystyrene for the production of moldings, foils, fibers and foams, and the moldings, foils, fibers and foams made from the impact-resistant polystyrene.
  • Impact-resistant polystyrene contains e.g. Polybutadiene rubber or styrene-butadiene block rubber, dispersed in a polystyrene hard matrix, and can be produced by various polymerization processes, for example by radical or anionic polymerization.
  • the anionic polymerization of styrene and / or butadiene is described for example in WO 98/07765 and WO 98/07766.
  • the polymers obtained by anionic polymerization have several advantages over the products obtained by free radical means, i.a. lower residual monomer and oligomer contents. Radical and anionic polymerization are fundamentally different. In radical polymerization, the reaction proceeds via free radicals and e.g. peroxidic initiators are used, whereas the anionic polymerization proceeds via "living" carbanions and, for example, alkali metal organanyl compounds are used as initiators.
  • the anionic polymerization is preferably carried out with a chain terminating agent, e.g. a protic substance such as water or alcohol.
  • the anionic polymerization proceeds much faster and leads to higher sales than the radical polymerization.
  • the temperature control of the exothermic reaction is difficult due to the high speed. This can be done by using so-called retarders (such as Al, Zn or Mg organyl compounds) fertilize), which reduce the reaction rate.
  • retarders such as Al, Zn or Mg organyl compounds
  • the viscosity of the reaction mixture generally increases rapidly during the anionic rubber production, as a result of which undesirable hot spots can form in the reactor and the reaction mixture is difficult to handle.
  • polymerization is generally carried out in an inert solvent, for example hydrocarbons such as toluene or Cyclohexane, thus limiting the increase in viscosity.
  • the rubber solution obtained which is usually produced in batches, is then usually stored temporarily in a buffer tank and finally in a second, e.g. continuously operated reactor transferred, mixed with styrene monomer and the mixture polymerized to HIPS, see e.g. the older, not previously published patent applications DE Az. 10250280.3 and DE Az. 10316266.6 and the examples on page 11 line 28 to page 12 line 6 of DE-A 102 18 161.
  • the task was to remedy the disadvantages described.
  • the object was to provide an alternative method for producing impact-resistant polystyrene that has improved economy.
  • the handling of the rubber solution should be easier in the process.
  • the rubber solution should have a lower viscosity and be easier to pump.
  • a rubber solution is prepared in stage 1) from the diene monomers, or from the diene monomers and the styrene monomers, using an alkali metal organyl as initiator and with the use of a solvent.
  • Suitable diene monomers are all polymerizable dienes, in particular 1,3-butadiene (short: butadiene), 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene, isoprene, piperylene or mixtures thereof. Butadiene is preferred.
  • All vinylaromatic monomers are suitable as styrene monomers, for example styrene, ⁇ -methylstyrene, p-methylstyrene, ethylstyrene, tert-butylstyrene, vinylstyrene, vinyltoluene, 1,2-diphenylethylene, 1,1-diphenylethylene or mixtures thereof.
  • Styrene is particularly preferably used.
  • styrene is used as the styrene monomer and butadiene is used as the diene monomer. Mixtures of these monomers can also be used.
  • Additional comonomers can also be used, for example in a proportion of 0 to 50, preferably 0 to 30 and particularly preferably 0 to 15% by weight, based on the total amount of the monomers used in stage 1).
  • acrylates in particular C 1-12 alkyl acrylates such as n- or tert-butyl acrylate or 2-ethylhexyl acrylate, and the corresponding methacrylates, such as methyl methacrylate (MMA), are suitable.
  • Epoxides such as ethylene oxide or propylene oxide are also suitable.
  • Other suitable comonomers are mentioned in DE-A 196 33626 on page 3, lines 5-50 under M1 to M10.
  • organyles are the organometallic compounds of the elements mentioned with at least one metal-carbon ⁇ bond, in particular the alkyl or aryl compounds.
  • the metal organyls can also contain hydrogen, halogen or organic radicals bound via heteroatoms, such as alcoholates or phenolates, on the metal. The latter can be obtained, for example, by whole or partial hydrolysis, alcoholysis or aminolysis.
  • Suitable alkali metal organyls are, in particular, mono-, bi- or multifunctional alkali metal alkyls, aryls or aralkyls, but no alkali metal hydrides such as lithium hydride, sodium hydride or potassium hydride).
  • An alkali metal organyl is preferably a lithium organyl, ie an organolithium compound.
  • Geeginets are e.g.
  • Sec-butyllithium is preferably used.
  • styrene and the alkali metal organyl form an oligomeric polystyrene-alkali metal compound composed of polystyryl anion and alkali metal cation and that the polymerization takes place on the polystyryl anion. Accordingly, a compound [polystyryl] e Li ⁇ is probably formed from styrene and lithium organyl.
  • Living means that if the monomer is added again, the polymerization reaction would start again without the need to add polymerization initiator again.
  • the required amount of alkali metal organyl depends, among other things. the desired molecular weight (molar mass) of the polymer to be produced, the type and amount of aluminum organyl used (see below) and the polymerization temperature. In general, 0.0001 to 10, preferably 0.001 to 1 and particularly preferably 0.01 to 0.2 mol% of alkali metal organyl, based on the total amount of the monomers used in stage 1), are used. Several alkali metal organyls can also be used.
  • the polymerization is carried out in the presence of a solvent.
  • Suitable solvents are e.g. aliphatic, isocyclic or aromatic hydrocarbons or hydrocarbon mixtures, such as benzene, toluene, ethylbenzene, xylene, cumene, hexane, heptane, octane or cyclohexane.
  • Solvents with a boiling point above 75 ° C. are preferably used, for example ethylbenzene, toluene or cyclohexane. Ethylbenzene is particularly preferred.
  • the solvent is later removed during degassing and can be collected, cleaned and reused.
  • polar compounds or Lewis bases can also be used in the production of the rubber in stage 1) and / or the hard matrix in stage 2).
  • all additives known in the literature for anionic polymerization are suitable. They generally contain at least one O, N, S or P atom that has a lone pair of electrons.
  • Preferred are ethers and amines, e.g. Tetrahydrofuran (THF), diethyl ether, tetrahydropyran, dioxane, crown ether, alkylene glycol dialkyl ether, e.g.
  • the Lewis bases act as an activator and in many cases increase the conversion of the polymerization reaction or increase the reaction rate. If they are added before or during the rubber polymerization, they are also able to control the proportions of the various vinyl linkages in the butadiene or isoprene polymer, and thus to influence the microstructure of the rubber. In particular, in the case of the styrene-butadiene block copolymers, the polybutadiene and the polyisoprene, the content of 1,2-vinyl linkages in the polybutadiene or polyisoprene can be controlled.
  • the Lewis bases increase the reaction rate, their amount is expediently such that the reaction rate of the entire batch is lower than in a batch which is carried out without adding the retarding components.
  • Lewis bases can be added before or after the rubber synthesis.
  • stage 2 It may be advantageous to dilute the rubber solution obtained with styrene monomer before stage 2).
  • the styrene monomers already mentioned are suitable for this, in particular styrene.
  • stage 1) the solids content of the solution can be precisely adjusted by dilution with styrene.
  • the other polymerization conditions for example temperature, pressure and polymerization time, are usually chosen to be similar to the anionic polymerization processes of styrene and diene monomers known to those skilled in the art.
  • stage 1) is usually not terminated after the polymerization by adding a chain terminator such as water or alcohol.
  • the reaction can be "frozen” by adding a molar excess, based on the initiator, of aluminum organyl.
  • Stage 1) of the process according to the invention can be carried out batchwise or continuously, in any pressure- and temperature-resistant reactor, it being possible in principle to use backmixing or non-backmixing reactors (ie reactors with stirred tank or tubular reactor behavior).
  • backmixing or non-backmixing reactors ie reactors with stirred tank or tubular reactor behavior.
  • the process leads to polymers with high or low molecular weight.
  • stirred tanks, tower reactors, loop reactors and tubular reactors or tube bundle reactors with or without internals are suitable. Internals can be static or movable internals.
  • the polymerization can be carried out in one or more stages. In stage 1), polymerization is preferably carried out batchwise, for example in a stirred kettle. Further details on the design of the reactors and the operating conditions can be found in the documents WO 98/07765 and WO 98/07766, to which reference is expressly made here.
  • a reaction mixture which contains the rubber polymer dissolved in an inert solvent.
  • rubber polymers are, for example, homopolymers such as polybutadiene (PB) and polyisoprene (PI), and copolymers such as styrene-butadiene block copolymers (S-B polymers).
  • PB polybutadiene
  • PI polyisoprene
  • S-B polymers copolymers
  • the rubber is preferably selected from polybutadiene and styrene-butadiene block copolymers.
  • the block structure is essentially created by first anionically polymerizing styrene alone, which creates a styrene block. After the styrene monomers have been consumed, the monomer is changed by adding monomeric butadiene and anionically polymerizing to a butadiene block polymer (so-called sequential polymerization).
  • the resulting two-block polymer S-B can be polymerized by renewed monomer change on styrene to a three-block polymer S-B-S, if desired.
  • the two styrene blocks can be of the same size (same molecular weight, ie symmetrical structure S B-S ⁇ ) or different sizes (different molecular weight, ie asymmetrical structure S r BS 2 ).
  • S B-S ⁇ same molecular weight
  • S r BS 2 different sizes
  • block sequences SSB or SS 2 -B, or SBB or S-B ⁇ -B 2 are also possible.
  • the indices for the block sizes are given above.
  • the block sizes depend, for example, on the amounts of monomers used and the polymerization conditions.
  • the block copolymers mentioned can have a linear structure (described above). However, branched or star-shaped structures are also possible and are preferred for some applications. Trains t. Branched block copolymers are obtained in a known manner, for example by grafting polymeric "side branches" onto a main polymer chain.
  • Star-shaped block copolymers are formed, for example, by reacting the living anionic chain ends with an at least bifunctional coupling agent.
  • an at least bifunctional coupling agent are described, for example, in US Pat. Nos. 3,985,030, 3,280,084, 3,635,554 and 4,091,053.
  • Epoxidized glycerides for example epoxidized linseed oil or soybean oil
  • silicon halides such as SiCl 4 or divinylbenzene
  • polyfunctional aldehydes, ketones, esters, anhydrides or epoxides are preferred.
  • Dichlorodialkylsilanes, dialdehydes such as terephthalaldehyde and esters such as ethyl formate are also particularly suitable for dimerization.
  • symmetrical or asymmetrical star structures can be produced, ie the individual star branches can be the same or different, in particular contain different blocks S, B, B / S or different block sequences. Further details on star-shaped block copolymers can be found, for example, in WO 00/58380.
  • the monomer names styrene and butadiene used above are also examples of other vinyl aromatics and dienes.
  • an aluminum organyl and an alkali metal hydride are added to the rubber solution obtained in stage 1) after stage 1) and before stage 2).
  • Aluminum organyls which can be used are those of the formula R JS Al, where the radicals R independently of one another are hydrogen, halogen, C 1-20 alkyl or C 6-2 o-aryl.
  • Preferred aluminum organyls are the aluminum trialkyls such as triethyl aluminum (TEA), tri-isobutyl aluminum (TIBA), tri-n-butyl aluminum, tri-isopropyl aluminum, tri-n-hexylaluminium, and dialkylaluminium hydrides such as diethylaluminium hydride (DEAH) or Di-isobutyl aluminum hydride (DIBAH).
  • TEA or TIBA are particularly preferably used, particularly preferably TEA.
  • Aluminum organyls which can be used are those which result from partial or complete hydrolysis, alcoholysis, aminolysis or oxidation of alkyl or arylaluminum compounds. Examples are diethyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl (2,6-di-tert-butyl-4-methyl-phenoxy) aluminum (CAS No. 56252-56-3), methylaluminoxane , isobutylated methylaluminoxane, isobutylaluminoxane, tetraisobutyldialuminoxane or bis (diisobutyl) aluminum oxide.
  • organyles of magnesium and / or zinc can be used.
  • Suitable magnesium organyls are those of the formula R 2 Mg, where the radicals R have the meaning given above.
  • Dialkyl magnesium compounds, in particular the ethyl, propyl, butyl, hexyl or octyl compounds available as commercial products, are preferably used. Is particularly preferred the hydrocarbon soluble (n-butyl) (s-butyl) magnesium is used.
  • Zinc ganyls which can be used are those of the formula R 2 Zn, where the radicals R have the meaning indicated above.
  • Preferred zinc organyls are dialkyl zinc compounds, in particular with ethyl, propyl, butyl, hexyl or octyl as the alkyl radical. Diethyl zinc is particularly preferred. If magnesium and / or zinc organyl are also used, "aluminum organyl” in the following stands for aluminum, magnesium and zinc organyl.
  • Suitable alkali metal hydrides are e.g. Lithium hydride, sodium hydride or potassium hydride, preferably sodium hydride.
  • the required amount of aluminum organyl depends, among other things. depending on the type and amount of the alkali metal organyl used, and on the viscosity of the rubber solution. Usually 0.0001 to 10, preferably 0.001 to 5 and particularly 0.01 to 2 mol% of aluminum organyl are used, based on the total amount of the monomers used in stage 1). It goes without saying that several aluminum, magnesium or Zinc organyle can be used.
  • the required amount of alkali metal hydride depends, among other things. depending on the type and amount of the aluminum organyl used, and on the viscosity of the rubber solution. Usually 0.0001 to 10, preferably 0.001 to 5 and especially 0.01 to 2 mol% of alkali metal hydride are used, based on the total amount of the monomers used in stage 1). It goes without saying that several alkali metal hydrides can also be used.
  • the aluminum organyls and alkali metal hydrides are only added after the polymerization of the diene monomers, or diene monomers and styrene monomers, ie added to the solution of the finished rubber. Accordingly, the aluminum compounds do not act as retarders, as in the methods of the prior art (additives which are reduced by the rate of polymerization and which thus control the polymerization of the rubber monomers). Surprisingly, it was found that the viscosity of the rubber solution is significantly reduced by adding the aluminum organyls after the polymerization.
  • the aluminum organyl may at least partially destroy the dimeric lithium complexes that are present in the rubber solution after the polymerization, as a result of which the viscosity drops.
  • the aluminum organyls stabilize the living polymer chains.
  • the aluminum organyles apparently prevent thermal degradation of the living chains when the rubber is transferred to the second reactor, which is preferably carried out at elevated temperature, see below.
  • the aluminum organyl and alkali metal hydride can be added separately, or preferably together.
  • the aluminum organyl and the alkali metal hydride - and also the alkali metal organyl initiator - can be used as such, or preferably dissolved or suspended in an inert solvent or suspending agent, for example ethylbenzene, cyclohexane or toluene.
  • Mineral oil for example, is suitable as a suspending agent for the alkali metal hydride.
  • stages 1) and 2) of the process according to the invention are carried out in different reactors, aluminum organyl and alkali metal hydride are preferably added to the rubber solution in the first reactor, particularly preferably before the solution is transferred to the second reactor. If the solution is temporarily stored in a buffer tank, it is preferred to add aluminum organyl and alkali metal hydride before transfer to the buffer tank.
  • a mixture is preferably prepared in advance from aluminum organyl and alkali metal hydride, which is then added to the rubber solution.
  • This mixture particularly preferably additionally contains styrene or other styrene monomers.
  • This mixture is preferably prepared using a solvent or suspending agent.
  • Inert hydrocarbons more specifically aliphatic, cycloaliphatic or aromatic hydrocarbons, such as cyclohexane, methylcyclohexane, pentane, hexane, heptane, isooctane, benzene, toluene, xylene, ethylbenzene, decalin or paraffin oil, or mixtures thereof, are particularly suitable.
  • Ethylbenzene is particularly preferred.
  • the mixture for example, solvent, styrene and the alkali metal hydride can be introduced, and then the aluminum organyl can be added. It is advantageous to let this mixture ripen (age) for a certain time afterwards, for example 2 minutes to 24 hours. The aging process is presumably due to complex formation of the metal compounds, which is slower than the mixing process.
  • the mixing of the components can be carried out in any mixing unit, preferably in those that can be charged with inert gas.
  • stirred reactors with anchor stirrers or shaking vessels are suitable. Tubes with static mixing elements are particularly suitable for continuous production.
  • the ripening can also take place in a stirred tank with a continuous flow or in a pipe section, the volume of which, together with the flow rate, determines the ripening time.
  • the molar ratios of aluminum organyl, alkali metal organyl (initiator) and alkali metal hydride which are present after stage 1) and before stage 2) can vary.
  • the molar ratio of aluminum organyl to alkali metal organyl in stage 1) is usually 10 to 1000, preferably 20 to 500 and in particular 50 to 200 mol% of aluminum minium from the aluminum organyl, based on the amount of alkali metal from the alkali metal organyl initiator.
  • the molar ratio of aluminum organyl to alkali metal hydride after stage 1) and before stage 2) is usually 10 to 200, preferably 20 to 200 and in particular 50 to 150 mol% of alkali metal from the alkali metal hydride, based on the amount of aluminum from the aluminum organyl.
  • the molar ratio of aluminum organyl to the sum of all alkali metal compounds, ie alkali metal organyl and alkali metal hydride is generally 5 to 500, preferably 10 to 300 and in particular 20 to 100 mol% of aluminum from the aluminum organyl , based on the total amount of alkali metal (sum of the alkali metal organyl initiator and the alkali metal hydride).
  • stage 2 of the process according to the invention styrene monomer is added to the rubber solution obtained and the mixture obtained is polymerized anionically to give the impact-resistant polystyrene.
  • Suitable styrene monomers have already been mentioned above.
  • Styrene or ⁇ -methylstyrene is preferably used, particularly preferably styrene.
  • stage 2 The styrene monomer added in stage 2) - and possibly the styrene monomer which was already added in stage 1) to dilute the rubber solution - is polymerized anionically to form the HIPS in the presence of the rubber.
  • stage 2 In addition to the styrene monomers, further comonomers, as already mentioned, can be used in stage 2). Their proportion is generally 0 to 50, preferably 0 to 30 and particularly preferably 0 to 15% by weight, based on the total amount of the monomers used in stage 2).
  • the anionic polymerization in stage 2) takes place in a manner known per se.
  • Suitable initiators are the alkali metal organyls, alkali metal hydrides and mixtures thereof, as have already been mentioned above.
  • Preferred alkali metal compounds have already been mentioned.
  • a particularly preferred alkali metal organyl is sec-butyllithium, and a particularly preferred alkali metal hydride is sodium hydride.
  • step 1) If the polymerization was stopped in step 1), it must be initiated again in step 2) with alkali metal organyl or hydride. If it was not stopped in step 1) (this is preferred), depending on the desired molecular weight of the polymer, alkali metal organyl or hydride can be added again, but this need not be the case. However, alkali metal organyl or hydride is preferably added again in stage 1), in stage 2), even without termination of the polymerization. The amount of alkali metal hydride or organyl required in stage 2) depends, inter alia, on the desired molecular weight (molar mass) of the polymer to be produced, on the type and amount of the aluminum organyl used and on the polymerization temperature.
  • alkali metal hydride or -organyl 0.0001 to 10, preferably 0.001 to 1 and particularly preferably 0.01 to 0.2 mol% of alkali metal hydride or -organyl is generally used, based on the total amount of the in steps 2) Monomers used. Several alkali metal hydrides or organyls can also be used.
  • An aluminum organyl is preferably used in stage 2). Suitable and preferred aluminum organyls have already been described. Particularly preferred aluminum organyls are TIBA and TEA, in particular TEA.
  • magnesium and / or zinc organyls can also be used. If magnesium and / or zinc organyl are also used, "aluminum organyl” in the following stands for aluminum, magnesium and zinc organyl.
  • the aluminum organyl is added in stage 2) before the polymerization and acts as a retarder, thus serving to control the reaction.
  • the amount of aluminum organyl required in stage 2) depends, among other things. depending on the type and amount of the alkali metal organyls or hydrides used in stages 1) and 2) of the process, and on the polymerization temperature. If aluminum organyl is used, its amount is usually 0.0001 to 10, preferably 0.001 to 5 and particularly 0.01 to 2 mol% of aluminum organyl, based on the total amount of the monomers used in stage 2). It goes without saying that several aluminum organyles can also be used.
  • the alkali metal organyls, hydrides or aluminum organyls used in stage 1) or stage 2) can be identical or different from one another.
  • the molar ratios of aluminum organyl, alkali metal organyl and alkali metal hydride present in stage 2) of the process according to the invention can vary.
  • the molar ratio of aluminum organyl to alkali metal hydride in stage 2) is usually 0.2: 1 to 5: 1, preferably 0.5: 1 to 1.5: 1, calculated as the molar ratio Al / Madrid
  • the molar ratio of aluminum organyl to the sum of all alkali metal compounds, i.e. alkali metal organyl and alkali metal hydride, is generally 0.1 in stage 2) : 1 to 5: 1, in particular 0.5: 1 to 1.5: 1, calculated as a molar ratio
  • the order of addition of styrene monomer, aluminum organyl and alkali metal hydride and / or alkali metal organyl in stage 2) is preferably chosen such that the styrene monomer is metered in after or together with the aluminum organyl and the alkali metal hydride or organyl in order to prevent premature polymerization of the styrene monomers. If the components are added one after the other, one can, for example, first add the aluminum organyl, then the alkali metal hydride or organyl, and finally the styrene monomer.
  • Aluminum organyl and alkali metal hydride and / or alkali metal organyl are preferably added as a mixture, which is prepared in advance as has already been described above.
  • An inert solvent can be added again in stage 2). Suitable solvents have already been mentioned. However, no further solvent is preferably added, so that in the subsequent workup, only the solvent added in the rubber synthesis in stage 1) has to be removed again.
  • Polymerization is usually carried out in stage 2) at 50 to 250, preferably 75 to 200 and particularly preferably 80 to 180 ° C.
  • stage 1) applies to pressure and duration of polymerization.
  • Stage 2) of the process can be carried out batchwise or continuously in any pressure- and temperature-resistant reactor, as has already been described in stage 1). Polymerization is preferably carried out continuously in stage 2), for example in a tower reactor or tubular reactor.
  • polymerization is carried out batchwise in stage 1) and continuously in stage 2). It goes without saying that in both stages, instead of a single reactor, a plurality of reactors can be used.
  • stage 1) the rubber can be polymerized in a cascade of stirred tanks and / or the matrix in stage 2) in several tower or tube reactors connected in series.
  • the polymerization reaction is terminated by adding a chain terminator which irreversibly terminates the living polymer chain ends.
  • chain terminator which irreversibly terminates the living polymer chain ends.
  • All proton-active substances and Lewis acids can be considered as chain terminators. Suitable are, for example, water (preferred), and -CC 10 alcohols such as methanol, ethanol, isopropanol, n-propanol and the butanols.
  • Aliphatic and aromatic carboxylic acids such as 2-ethylhexane are also suitable. acid, and phenols.
  • Inorganic acids such as carbonic acid (solution of CO 2 in water) and boric acid can also be used.
  • the terminating agent can either be used as such, or in the form of a terminating agent mixture containing the chain terminating agent, mineral oil (see below for this) and, if appropriate, a customary emulsifier. Due to its surface-active properties, the emulsifier stabilizes the mixture of the polar chain terminator and the non-polar polymer solution.
  • the reaction mixture is generally worked up, for example by means of degassing.
  • the desired impact-resistant polystyrene contains, for example, the auxiliaries and accompanying substances used in the polymerization and demolition, and possibly unreacted monomers (so-called residual monomers), and, if appropriate, oligomers or low-molecular-weight polymers as undesired by-products of the polymerization.
  • the degassing for example by means of conventional degassing devices such as degassing extruders, partial evaporators, continuous degassers or vacuum pots, removes residual monomers and oligomers, and in particular the solvent added in stage 1).
  • HIPS impact-resistant polystyrene
  • Styrene-butadiene two-block copolymers S-B with a styrene content of 1 to 80, preferably 5 to 50 wt .-%.
  • the molecular weights Mw for the styrene block S are preferably 1000 to 200,000, in particular 5000 to 100,000 and for the butadiene block B 20,000 to 300,000, in particular 50,000 to 150,000,
  • the molecular weights Mw for the first styrene block S 1 are preferably 1,000 to 150,000, in particular 5,000 to 100,000, for the butadiene block B 20,000 to 300,000, in particular 50,000 to 150,000 and for the second styrene block S 2 1,000 to 150,000, in particular 5,000 to 100,000.
  • the weight-average Mw are given in g / mol,
  • the weight-average molecular weight Mw of the hard matrix is generally 50,000 to 300,000, preferably 100,000 to 250,000 g / mol.
  • the invention also relates to the impact-resistant polystyrene (HIPS) obtainable by the polymerization process.
  • HIPS impact-resistant polystyrene
  • a mineral oil e.g. White oil
  • a mineral oil e.g. 0.1 to 10
  • a 0.5 to 5 wt .-% added, whereby the mechanical properties are improved, in particular the elongation at break increases.
  • an antioxidant or a stabilizer against the action of light in short: light stabilizer, or a mixture thereof, in amounts of, for example, 0.01 to 0.3, preferably 0.02 to 0.2,% by weight. -% used.
  • light stabilizer a stabilizer against the action of light
  • additives increase the resistance of the polymer to air and oxygen, or to UV radiation, and thus increase the weathering and aging resistance of the polymer.
  • the quantities given relate to the polymer obtained.
  • the polymers can contain further additives or processing aids, e.g. Lubricants or mold release agents, colorants such as Pigments or dyes, flame retardants, fibrous and powdery fillers or reinforcing agents or antistatic agents, as well as other additives or their mixtures.
  • the individual additives are used in the usual amounts, so that further details are not necessary.
  • the additives can be added, for example, during the processing of the polymer melt, and / or the solid polymer (e.g. polymer granulate) according to known mixing processes, for example with melting in an extruder, Banbury mixer, kneader, roller mill or calender.
  • Shaped articles including semifinished products, films, fibers and foams of all kinds can be produced from the impact-resistant polystyrenes according to the invention.
  • the invention accordingly also relates to the use of the impact-resistant polystyrene according to the invention for the production of moldings, films, fibers and foams, and to the moldings, films, fibers and foams obtainable from the impact-resistant polystyrene.
  • the process according to the invention is more economical than the processes of the prior art.
  • the rubber solution can be easily rather handle, especially pump around better.
  • the viscosity of the rubber solution is significantly lower, although no more solvent was used than in the methods of the prior art.
  • Triisobutylaluminum (TIBA) as a 20% by weight solution in toluene, finished solution from Crompton
  • Irganox®1076 octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS 2082-79-3), from Ciba Specialty Chemicals
  • Tables 1 and 2 list the individual values of the variables y1 to y3.
  • the rubber solution obtained had a solids content (FG) of x13% by weight. It was diluted by adding x14 kg of styrene. A rubber solution with a solids content of x15% by weight was obtained. It was temporarily stored in a buffer tank.
  • the polymer had a monomodal distribution.
  • the residual monomer content of butadiene determined by gas chromatography was less than 10 ppm (w).
  • the weight average molecular weight Mw was determined by GPC as described above and was x16 kg / mol.
  • Table 1 summarizes the individual values of the variables x1 to x16.
  • Table 1 Rubber production: Variables y1 to y3 and x1 to x16 (meaning FG solid content)
  • example K4 is a homopolybutadiene.
  • the Hl PS production (polymerisation of the matrix) was carried out continuously as described below, for which purpose the rubber solution was continuously removed from the buffer tank.
  • a double-walled 50 1 stirred kettle with standard anchor stirrer was used.
  • the reactor was designed for an absolute pressure of 25 bar and was tempered with a heat transfer medium and by means of evaporative cooling for isothermal reaction control.
  • the reaction mixture was either fed into a stirred 29 l tower reactor or into a tubular reactor 7 m long and 500 mm in diameter (x21), which was provided with two heating zones of the same size, the first zone at 140 ° C. and the second zone was maintained at 180 ° C reactor wall temperature.
  • the discharge from the tower reactor was mixed with x22 g / h of water and then with x23 g / h of an additive mixture I, which had previously been prepared from x24 g of Irganox® 1076 and x25 kg of mineral oil Winog® 70, then passed through a mixer and finally through a pipe section heated to 250 C C passed.
  • the reaction mixture for degassing was then conveyed via a pressure control valve into a partial evaporator operated at x26 ° C and expanded into a vacuum pot operated at 10 mbar absolute pressure and x27 ° C.
  • the polymer melt obtained was discharged with a screw conveyor and then mixed with x28 g / h of an additive mixture II which had previously been prepared from x29 g of Irganox® 1076 and x30 kg of mineral oil Winog®70, then passed through a mixer and granulated. The turnover was quantitative.
  • the HIPS obtained had the following residual monomer contents, which were determined as already described: styrene less than 5 ppm (w), ethylbenzene less than 5 ppm (w).
  • Table 2 summarizes the individual values of the variables x17 to x30.
  • Table 2 HIPS production: Variables x17 to x32 (it means Ro. Rohr, FG solids content)

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un procédé permettant de produire du polystyrène résistant aux chocs, à partir de monomères diéniques et de monomères styréniques, par polymérisation anionique. Selon ledit procédé, il est prévu : 1) dans une étape 1), de produire une solution de caoutchouc, à partir des monomères diéniques et des monomères styréniques, avec un organyle métallique alcalin comme initiateur et en co-utilisation d'un solvant, puis 2), dans une seconde étape 2), la solution de caoutchouc est ajoutée au monomère styrénique et le mélange obtenu est polymérisé par voie anionique en polystyrène résistant aux chocs. Un aluminium organyle et un hydrure métallique alcalin sont ajoutés à la solution de caoutchouc, après l'étape 1) et avant l'étape 2).
EP05715346A 2004-02-18 2005-02-16 Procede ameliore de production de polystyrene resistant aux chocs Withdrawn EP1718686A1 (fr)

Applications Claiming Priority (2)

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DE102004008199A DE102004008199A1 (de) 2004-02-18 2004-02-18 Verbessertes Verfahren zur Herstellung von schlagzähem Polystyrol
PCT/EP2005/001535 WO2005082959A1 (fr) 2004-02-18 2005-02-16 Procede ameliore de production de polystyrene resistant aux chocs

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EP1892255B1 (fr) * 2005-06-15 2012-08-01 Nippon Soda Co., Ltd. Polymère d' acide acrylique
CN101868482A (zh) * 2007-09-13 2010-10-20 陶氏环球技术公司 含杂原子的乙烯类单体的聚合
ITMI20072324A1 (it) * 2007-12-12 2009-06-13 Polimeri Europa Spa Procedimento semi-continuo integrato per la produzione di (co)polimeri vinilaromatici antiurto mediante polimerizzazione in sequenza anionica/radicalica
CN101628959A (zh) * 2008-07-15 2010-01-20 中国石油化工集团公司 一种可发泡苯乙烯属单体-二烯烃共聚物、其制备方法和用途
TWI486367B (zh) 2012-05-30 2015-06-01 Nippon Soda Co 聚胺甲酸酯
MX2018012248A (es) 2016-04-05 2019-05-30 Albemarle Corp Proceso y catalizador de hidruro salino soluble en hidrocarburos para polimerizacion de transferencia de cadena anionica iniciada por hidruro salino mediada por hidrogeno y composiciones de distribucion de polimero producidas a partir de este.

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US6444762B1 (en) * 1996-08-19 2002-09-03 Basf Aktiengesellschaft Anionic polymerization process
US6983182B2 (en) * 1998-04-10 2006-01-03 Wisconsin Alumni Research Foundation Time resolved computed tomography angiography
US6593430B1 (en) * 1999-03-27 2003-07-15 Basf Aktiengesellschaft Transparent, impact-resistant polystyrene on a styrene-butadiene block copolymer basis
DE10022504A1 (de) 2000-05-10 2001-11-15 Basf Ag Anionisch polymerisiertes, schlagzähes Polystyrol mit Kapselteilchenmorphologie
DE10218161A1 (de) * 2002-04-23 2003-11-13 Basf Ag Initiatorzusammensetzung und Verfahren zur anionischen Polymerisation
DE10250280A1 (de) 2002-10-28 2004-05-13 Basf Ag Verfahren zur anionischen Polymerisation von schlagzähem Polystyrol
DE10316266A1 (de) 2003-04-08 2004-10-28 Basf Ag Verbessertes Verfahren zur anionischen Polymerisation von Styrol- und Dienmonomeren

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DE102004008199A1 (de) 2005-09-01
US20070161763A1 (en) 2007-07-12
US7368504B2 (en) 2008-05-06
WO2005082959A1 (fr) 2005-09-09
JP2007523977A (ja) 2007-08-23

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