Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
  • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
• • 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
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • 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
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
  • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers

Definitions

• HIPS high impact polystyrene
• Polymerization occurs a phase separation between the rubber-containing polymer solution and the non-rubber-containing polymer solution.
• the non-rubber-containing polymer solution initially forms a discrete, discontinuous phase.
• phase inversion takes place, i.e. the phase of the non-rubber-containing polymer solution becomes larger and the rubber solution becomes the discontinuous phase, while the non-rubber-containing polymer solution forms the homogeneous phase.
• the rubber solutions prepared by dissolving are in the presence of further monomers and, if appropriate, solvents by known methods of bulk, solvent or Suspension polymerization prepared in a continuous, semi-continuous or batch mode and isolated by known evaporation methods.
• Forms are used, which are dissolved in styrene and / or further monomers and optionally solvents and then fed to the further polymerization process as a rubber solution.
• styrene and / or further monomers and optionally solvents are dissolved in styrene and / or further monomers and optionally solvents and then fed to the further polymerization process as a rubber solution.
• solvents if appropriate, solvents.
• rubbers in solid form is disadvantageous because the production of these soluble rubbers is preferably carried out by solution polymerization, aliphatic and / or aromatic solvents being used as solvents which are inert during the polymerization and which themselves are not polymerization-active, and the solvents may have to be removed by distillation after the polymerization in order to isolate the rubbers formed in solid form.
• Another disadvantage is that rubbers with high cold flow or high stickiness are difficult to process and store.
• an SBR rubber suitable for HIPS production could be obtained by terminating the polymerization either at an initial butadiene in styrene concentration of about 35% by weight, the polymerization being stopped at a butadiene monomer conversion of about 25%, or by increasing the monomer conversion of butadiene to approximately by a high butadiene concentration of approximately 55% by weight
• the disadvantage of the anionic initiators is that styrene-butadiene copolymers (SBR) are formed which, based on the butadiene units, allow only a slight control of the microstructure. By adding modifiers, only the proportion of 1, 2 or 1, 4-trans units can be increased, which leads to an increase in the glass transition temperature of the polymer. It is not possible to produce a high-cis-containing SBR with anionic initiators, in which the 1,4-cis content, based on the butadiene content, is over 40%, preferably over 50%, particularly preferably over 60%.
• Rubber adversely affects the low temperature properties of the material, so that rubbers with low glass transition temperatures are preferred.
• US-A 5096970 and EP-A 304088 describe a process for the preparation of polybutadiene in styrene using catalysts based on neodymium phosphonates, organic aluminum compounds such as di (isobutyl) aluminum hydride (DIBAH). and a halogen-containing Lewis acid, such as ethyl aluminum sesquichloride, described in which butadiene in styrene is converted to a 1,4-cis-polybutadiene without the addition of inert solvents.
• DIBAH di (isobutyl) aluminum hydride
• a halogen-containing Lewis acid such as ethyl aluminum sesquichloride
• a disadvantage of these catalysts in addition to the presence of inert solvents, is that the catalyst activity drops to below 10 g of polymer / mmol of catalyst / h even with a small amount of styrene incorporated, and that the 1,4-cis content of the polymer is based on the polymeric butadiene units decreases significantly with increasing styrene content.
• the rubber is in a matrix of
• SAN Acrylonitrile-styrene copolymers
• the SAN matrix in ABS is incompatible with polystyrene. If, during the polymerization of the diolefins in vinylaromatic solvents, homopolymers of the solvent, such as polystyrene, are formed in addition to the rubber, the incompatibility of the SAN matrix with the homopoly- merized vinyl aromatics to a significant deterioration in the material properties.
• WO 97/38031 and WO 98/07766 describe that styrene-butadiene copolymers or polybutadiene homopolymers are prepared anionically in solution in the presence of inert solvents and for the production of toughened, thermoplastic polystyrene molding compounds and polystyrene-acrylonitrile molding compounds be used. It is disadvantageous that inert solvents are added in the butadiene polymerization, so that the vapors obtained after the degassing, which contain unreacted monomers and solvents, have to be separated and dried in a complex manner in order to reuse them in an anionic polymerization.
• the invention has for its object to develop a process for the production of ABS and HIPS molding compositions by polymerization in rubber-containing solution, which does not meet the above when using suitable catalysts. Has disadvantages and also makes it possible to vary the proportion of styrene units in the dissolved rubber.
• the rubber solutions to be used are obtained by polymerizing conjugated diolefins in vinyl aromatic solvents. In doing so
• the rubber solutions to be used are obtained by polymerizing the diolefins in the presence of catalysts based on rare earth metal compounds and in the presence of vinylaromatic monomers as solvents at temperatures from -30 to 100 ° C., preferably at
• conjugated diolefins e.g. 1,3-butadiene, 1,3-isoprene, 2,3-dimethyl-butadiene, 2,4-hexadiene, 1,3-pentadiene and / or 2-methyl-1,3-pentadiene or mixtures of the monomers mentioned can be used , 1,3-butadiene is preferred.
• conjugated diolefins it is also possible, in addition to the conjugated diolefins, to use other unsaturated compounds, such as ethylene, propene, 1-butene, 1-pentene, 1- Hexene, 1-octene and / or cyclopentene preferably use ethylene, propene, 1-butene, 1-hexene, and or 1-octene, which can be copolymerized with the diolefins mentioned.
• unsaturated compounds such as ethylene, propene, 1-butene, 1-pentene, 1- Hexene, 1-octene and / or cyclopentene preferably use ethylene, propene, 1-butene, 1-hexene, and or 1-octene, which can be copolymerized with the diolefins mentioned.
• the molar ratio of the catalyst components (A) :( B) :( C) can be in the range from 1: 0.01 to 1.99: 0.1 to 1000.
• Component (A) of the catalyst can be used in amounts of 1 ⁇ mol to 10 mmol, based on 100 g of the conjugated diolefins, and the aromatic vinyl compound in amounts of 50 g to 2,000 g, based on 100 g of the conjugated diolefins used become.
• the molar ratio of components (A) :( B) :( C) in the catalyst used is in the range from 1: 0.1 to 1.9: 3 to 500, particularly preferably 1: 0.2 to 1.8: 5 to 100.
• Suitable compounds of the rare earth metals are, in particular, those which are selected from
• Oxygen or nitrogen donor compound
• the compounds of rare earth metals are based in particular on the elements with atomic numbers 21, 39 and 57 to 71.
• Lanthanum, praseodymium or neodymium or a mixture of elements are preferably used as rare earth metals.
• ten of the rare earth metals which contains at least one of the elements lanthanum, praseodymium or neodymium to at least 10 wt .-%.
• Lanthanum or neodymium are very particularly preferably used as rare earth metals, which in turn can be mixed with other rare earth metals.
• the proportion of lanthanum and / or neodymium in such a mixture is particularly preferably at least 30% by weight.
• Suitable alcoholates, phosphonates, phosphinates, phosphates and carboxylates of the rare earth metals or as complex compounds of the rare earth metals with diketones are, in particular, those in which the organic group contained in the compounds in particular straight-chain or branched alkyl radicals having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, neo-pentyl, neo-octyl, neo-decyl or neo-dodecyl .
• Rare earth alcoholates e.g. called:
• phosphinates and rare earth phosphates e.g. called:
• Suitable carboxylates of rare earth metals are:
• Neodymium versatate, neodymium octanoate and / or neodymium naphthenate are very particularly preferably used as compounds of the rare earth metals.
• the above-mentioned compounds of rare earth metals can be used both individually and in a mixture with one another.
• R * to R ° are the same or different or are optionally connected to one another or are condensed on the cyclopentadiene of the formula (I), (II) or (III), and for hydrogen, a Ci - to C30-alkyl group, one C ⁇ to Cl O aryl group, a C ⁇ to C40 alkylaryl group, a C3 to C30 silyl group, where the alkyl groups can either be saturated or mono- or polyunsaturated and can contain heteroatoms such as oxygen, nitrogen or halides .
• the radicals can represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, methylphenyl, cyclohexyl, benzyl, trimethylsilyl or triflourmethyl.
• cyclopentadienes examples include the unsubstituted cyclopentadiene, methyl cyclopentadiene, ethylcyclopentadiene, n-butylcyclopentadiene, tert-butylcyclopentadiene, vinyl cyclopentadiene, Benzylcyclopentadien, Phenylcyclopentadien, Trimefhyl- silylcyclopentadien, 2-Methoxyethylcyclopentadien, 1, 2-dimethylcyclopentadiene, 1, 3- Dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene, tetraphenylcyclopentadiene, tetrabenzylcyclopentadiene, pentamethylcyclopentadiene, pentabenzylcyclopentadiene, ethyl tetramethylcyclopentadiene, trifluoro
• cyclopentadienes can also be used individually or in a mixture with one another.
• Suitable organoaluminum compounds are, in particular, alumoxanes and / or aluminum organyl compounds.
• Aluminum-oxygen compounds which, as is known to the person skilled in the art, are obtained as alumoxanes and are obtained by contacting organoaluminum compounds with condensing components, such as water, and the noncyclic or cyclic compounds of the formula (-Al (R) O- ) contain n , where R can be the same or different and represents a linear or branched alkyl group having 1 to 10 carbon atoms, which can contain heteroatoms, such as oxygen or halogens, and n is determined by the degree of condensation.
• R represents methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-octyl or iso-octyl, particularly preferably methyl, ethyl or iso-butyl.
• alumoxanes are: methylalumoxane, ethylalumoxane and isobutylalumoxane, preferably methylalumoxane and isobutylalumoxane.
• R 10 can be the same or different and can stand for a Ci - to C30-alkyl group, a Cß- to Cio-aryl group, a C7 to C40-alkylaryl group, whereby the alkyl groups can be either saturated or mono- or polyunsaturated and heteroatoms, such as may contain oxygen or nitrogen,
• X represents a hydrogen or a halogen
• d represents a number from 0 to 2.
• organoaluminum compounds of the formula AlR 10 3_ c ⁇ X c ⁇ which can be used are, in particular: tmethylaluminum, tmethylaluminum, Tn-n-propylaluminum,
• the organoaluminum compounds can in turn be used individually or as a mixture with one another.
• This component (D) can be a conjugated diene, which can be the same diene that is later to be polymerized with the catalyst. Butadiene and / or isoprene are preferably used.
• the amount of (D) is preferably 1 to 1000 mol, based on 1 mol of component (A), particularly preferably 1 to 100 mol. 1 to 50 mol, based on 1 mol of component (A), of (D) are very particularly preferably used.
• the catalysts are used in quantities of
• the rubber solution is prepared in the presence of vinylaromatic monomers, in particular in the presence of styrene, ⁇ -methylstyrene, ⁇ -methylstyrene dimer, p-methylstyrene, divinylbenzene and / or other nucleus-substituted alkylstyrenes, preferably with 2 to 6 carbon atoms in the Alkyl radical performed.
• the preparation of the rubber solution in the presence of styrene, ⁇ -methylstyrene, ⁇ -methylstyrene dimer and / or p-methylstyrene as a solvent is very particularly preferably carried out.
• the solvents can be used individually or in a mixture.
• the amount of vinyl aromatic monomers used as solvent is usually 10 to 2,000 parts by weight, preferably 30 to 1,000 parts by weight, very particularly preferably 50 to 500 parts by weight, based on 100 parts by weight of the set monomers.
• the rubber solutions are preferably produced at temperatures from -20 to 90 ° C., very particularly preferably at temperatures from 20 to 80 ° C.
• the production can be carried out without pressure or at elevated pressure (0.1 to 12 bar).
• the production can be carried out continuously or discontinuously, preferably in a continuous manner.
• thermoplastic molding compositions according to the invention are obtained by radical polymerization of a vinylaromatic monomer and an ethylenically unsaturated nitrile monomer or a vinylaromatic
• Rubber solutions are preferably used in which the dissolved styrene-butadiene copolymers have a styrene unit content of 5 to 40 mol%, particularly preferably 10 to 30 mol% and, based on the butadiene content, a 1,2-unit content, ie on pendant vinyl groups, from 2 to 20 mol%, particularly preferably 4 to 15 mol% and a content of 1,4-cis units from 35 to 85 mol%, particularly preferably from 45 to 85 mol% and the glass temperature is below -60 ° C, particularly preferably below -70 ° C.
• Vinylaromatic monomers which alone or optionally together with free-radically polymerized together with ethylenically unsaturated nitrile monomers and thereby form the homogeneous phase (matrix phase) of the molding compositions, are the same as those used to prepare the rubber solution.
• Core-substituted chlorostyrenes can also be used in a mixture with these.
• Ethylenically unsaturated nitrile monomers are preferably acrylonitrile and methacrylonitrile, acrylonitrile is particularly preferred.
• acrylic monomers or maleic acid derivatives such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, tert-butyl (meth) acrylate , Esters of fumaric acid, itaconic acid, maleic anhydride, maleic acid esters, N-substituted maleimides such as advantageously N-cycohexyl- or N-phenyl-maleimide, N-alkylphenyl-maleimide. further acrylic acid, methacrylic acid, fumaric acid, itaconic acid, or their amides.
• the ratio of vinyl aromatic monomers to ethylenically unsaturated nitrile monomers in the ABS molding compositions according to the invention is 60-90% by weight to 40-10% by weight, based on the matrix phase.
• the rubber content in the ABS molding compositions according to the invention is 5-35% by weight, preferably 8-25% by weight, based on the ABS molding composition.
• the rubber content in the HIPS molding compositions according to the invention is 1 to 25% by weight, preferably 3 to 15% by weight, based on the HIPS molding compositions.
• aromatic hydrocarbons such as toluene, ethylbenzene, xylenes and ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone and mixtures of these solvents are suitable as solvents.
• aromatic hydrocarbons such as toluene, ethylbenzene, xylenes and ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone and mixtures of these solvents are suitable as solvents.
• Ethylbenzene, methyl ethyl ketone and acetone and mixtures thereof are preferred.
• the polymerization is advantageously triggered by radical starters, but can also be carried out thermally; the molecular weight of the polymer formed can be adjusted by molecular weight regulators.
• Suitable initiators for radical polymerization are graft-active, in
• peroxides such as peroxycarbonates, peroxydicarbonates, diacyl peroxides, perketals, or dialkyl peroxides and / or azo compounds or mixtures thereof.
• peroxides such as peroxycarbonates, peroxydicarbonates, diacyl peroxides, perketals, or dialkyl peroxides and / or azo compounds or mixtures thereof.
• examples are azodiisobutyronitrile, azoisobutyric acid alkyl ester, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl perneodecanoate, tert-butyl per- (2-ethylhexyl) carbonate.
• These initiators are used in amounts of 0.005 to 1% by weight, based on the monomers.
• molecular weight regulators such as mercaptans, olefins, for example tert-dodecyl mercaptan, n-dodecyl mercaptan, cyclohexene, terpi ⁇ olen, ⁇ -methylstyrene dimer in amounts of 0.05 to 2% by weight, based on the monomers, can be used become.
• the process according to the invention can be carried out batchwise, semi-continuously and continuously.
• the rubber solution, monomers and, if appropriate, solvents can advantageously be polymerized in a continuously charged, mixed and stirred tank reactor with a stationary monomer conversion after the phase inversion in the first stage of more than 10%, and the radical-triggered polymerization in at least one continue in a further stage up to a monomer conversion of 30-90% with mixing in one or more continuously operated stirred kettles in cascade or in a mixing plug flow reactor and / or a combination of both types of reactor. Residual monomers and solvents can be removed using conventional techniques (e.g.
• Propellants and entraining agents e.g. Water vapor
• Water vapor is possible, and can be returned to the process.
• Lubricants can be added.
• the discontinuous and semi-continuous polymerization can be carried out in one or more filled or partially filled stirred tanks connected in series with the rubber solution, monomers and, if appropriate, solvents and polymerization, up to the stated monomer conversion of 30-90%.
• the syrup can be pumped in a circle over both mixing and shearing organs with continuous and discontinuous operation.
• Such loop reactors are state of the art and can be used when setting the
• Particle size of the rubber may be helpful.
• the arrangement is more advantageous of shear organs between two separate reactors to avoid back-mixing, which leads to a broadening of the particle size distribution.
• the average residence time is 1 to 10 hours, preferably 2 to 6 hours.
• the polymerization temperature is 50 to 180 ° C, preferably 70 to 170 ° C.
• the rubber-modified thermoplastic molding compositions according to the invention have rubber particle sizes with a diameter (weight average, dw) of 0.1-10 ⁇ m, preferably 0.1-2 ⁇ m (ABS) or 0.1-10 ⁇ m, preferably 0.2- 6 ⁇ m (HIPS).
• the molding compositions according to the invention can be processed themioplastically into molded parts by extrusion, injection molding, calendering, hollow body blowing, pressing and sintering.
• the solution viscosity of the rubber solutions is measured on a 5% strength by weight solution using a Brookfield viscometer at 25 ° C. (Brookfield RV, Syncro-Lectric, model LVT, spindle 2, speed can be set permanently, depending on viscosity: 6.12 , 30, 60 rpm).
• the conversion is determined by solids determination by evaporation at 200 ° C.
• the rubber content in the end product was determined from the mass balance. Gel contents were determined in acetone as the dispersing medium.
• the Staudinger index of the soluble fraction was determined using dimethylformamide + lg / L LiCl as solvent.
• the particle size and distribution were determined by centrifugation as in US
• the phase structure was examined by dynamic-mechanical measurement of the thrust module characteristics G * (T) at the NPS at a frequency of approx. 1 Hz in the temperature range from -150 to 200 ° C with the RDA II from Rheometrics.
• the glass transition temperature (Tg) of the soft phase and the matrix is determined. Furthermore, the corrected shear modulus at 23 ° C
• the impact strength (a k , Izod) was determined at 23 ° C and -40 ° C according to ISO 180 / 1U, tensile strength, elongation at break, yield stress and modulus of elasticity according to DIN 53 455 and DIN 53 457. The measured values were measured on injection molded molds at a melt temperature of 200 ° C and a mold temperature of 45 ° C.
• the melt volume index (MVI, 220 ° C, 5 kg) was determined according to DIN 53 735.
• the polymerizations were under the exclusion of air and moisture
• Argon performed.
• the isolation of the polymers from the styrenic solution described in individual examples was carried out only for the purpose of characterizing the polymers obtained.
• the polymers can of course also be stored in the styrenic solution without insulation and processed further accordingly.
• the styrene used as solvent for the diene polymerization was stirred under argon over CaH2 at 25 ° C. for 24 h and distilled off at 25 ° C. under reduced pressure.
• the styrene content in the polymer is determined by means of H-NMR spectroscopy, the selectivity of the polybutadiene content (1,4-cis, 1,4-trans and 1,2-content) is determined by means of IR spectroscopy and the determination the molecular weights by means of GPC / light scattering.
• the polymerization was carried out in a 40L steel reactor with anchor stirrer (50 rpm). At room temperature, a solution of trimethyl aluminum (TMA) or tri-iso-butyl aluminum (TIBA) in hexane was added to a solution of butadiene in styrene as a scavenger, the reaction solution was heated to 50 ° C. within 45 min and with the appropriate amount of catalyst solution transferred. During the
• the reaction temperature was kept at 50 ° C. After the reaction time had expired, the polymer solution was transferred to a second reactor (80 L reactor, anchor stirrer, 50 rpm) within 15 minutes and the polymerization was carried out by adding 3,410 g of methyl ethyl ketone with 7.8 g of p-2,5-di-tert.- octyl butylphenol propionate (Irganox 1076, Ciba-Geigy) and 25.5 g of tris (nonylphenyl) phosphite (Irgafos TNPP, Ciba-Geigy). To remove unreacted butadiene, the internal reactor pressure at 50 ° C. was reduced to 200 mbar within 1 h and to 100 mbar within 2 h.
• Solution I consisting of rubber solution, styrene, acrylonitrile, methyl ethyl ketone (MEK), p-2,5-di-tert-butylphenol-propionic acid octyl ester (Irganox 1076, Ciba Geigy) and alpha-methyl styrene dimer (AMSD), with 40 ° C mixed with an anchor stirrer (150 rpm).
• the starter solution II consisting of methyl ethyl ketone and tert-butyl perpivalate (t-BPPIV), is metered in within 4 h.
• metering solution III consisting of methyl ethyl ketone and alpha-methylstyrene dimer, is added in 1-2 minutes, then the stirrer is set to 100 rpm. After metering in of solution II, the mixture is stirred for a further 2 h at 85 ° C., then cooled to RT.
• a solution of octyl p-2,5-di-tert-butylphenol-propionate (Irganox 1076, Ciba Geigy) and dilauryl dithio-propionate (Irganox PS 800, Ciba Geigy) in methyl ethyl ketone is added.
• the solutions are then evaporated and granulated on a ZSK laboratory evaporation screw. The granules were hosed down into standard small bars.
• compositions of the formulations results of the polymerization and characterization of the ABS molding compositions are summarized in the tables below.
• Composition of the recipes (all data in g)
• the rubber solution from Example E is diluted to 6% solids by adding styrene (stabilized). After adding 0.5 parts by weight of Vulkanox MB y and 0.2 parts by weight Parts of ⁇ -methylstyrene dimers, 1 200 g of this solution are flushed with N 2 in a 2 l glass autoclave with a spiral stirrer for 15 minutes. The mixture is heated to 120 ° C. within 1 hour and stirred at this temperature for 4.5 hours (80 rpm). The highly viscous solution obtained is filled into pressure-proof aluminum molds and polymerized according to the following time / temperature program:
• Vacuum degassed For testing, the samples are sprayed on an injection molding machine. The mechanical values are determined on standard small bars.

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