Classifications

• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
  • C08F212/10—Styrene with nitriles
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/42—Nitriles
  • C08F220/44—Acrylonitrile
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/04—Anhydrides, e.g. cyclic anhydrides
  • C08F222/06—Maleic anhydride
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/04—Anhydrides, e.g. cyclic anhydrides
  • C08F222/06—Maleic anhydride
  • C08F222/08—Maleic anhydride with vinyl aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles

Definitions

• the present invention relates to processes for the preparation of copolymers A) comprising A1) one or more vinylaromatic monomers, A2) one or more vinyl cyanides and A3) one or more dicarboxylic acid anhydrides by bulk or solution polymerization.
• the present invention relates to the copolymers A), thermoplastic
• Molding compositions comprising the copolymers A), the use of the copolymers A) and of the thermoplastic molding compositions and the moldings, films, fibers and foams obtainable from the copolymers A) and the thermoplastic molding compositions.
• Anhydride-containing vinyl aromatic-vinyl cyanide copolymers as such, for example styrene-acrylonitrile-maleic anhydride copolymers, and processes for their preparation are known.
• polymers based on styrene, acrylonitrile and maleic anhydride which are prepared by a special continuous bulk polymerization in several process stages in the presence of polymerization initiators.
• the residual monomer contents of the polymers are reduced by applying a vacuum or introducing inert gas to contents of less than 0.5% by weight.
• EP 0 001 625 A1 are ua.a. special terpolymers of styrene, acrylonitrile and maleic anhydride. Their preparation is carried out by continuous bulk polymerization in the presence of a radical-decomposing initiator. In subsequent process steps, the residual monomer contents are reduced to less than 0.1% by weight by evaporating or blowing in inert gas.
• EP 0 433 71 1 A2 describes special processes for the preparation of terpolymers based on styrene, acrylonitrile and maleic anhydride, in which the reaction of the monomers takes place in bulk without the addition of solvents or diluents.
• the polymerization is initiated thermally without the addition of chemical initiators. In subsequent process stages, residual monomers can be separated off.
• DE 100 58 302 A1 discloses stabilized styrene copolymers containing vinylaromatic monomers and one or more comonomers.
• the preparation of the styrene copolymers is carried out in particular in bulk or in solution.
• the polymerization can be initiated by the addition of chemical initiators or thermal initiation.
• low molecular weight compounds within the meaning of this invention are defined as compounds having an average molecular weight M w (weight average) of 10,000 g / mol or less, determined by gel permeation chromatography at 35 ° C. with three polystyrene gel columns connected in series from the company Polymer Laboratories with tetrahydrofuran as eluent (calibration with polystyrene standard) using the UV detector signal].
• copolymers A) based on vinylaromatic monomers, vinyl cyanides and dicarboxylic acid anhydrides were found, thermoplastic molding compositions containing these copolymers A), the uses of these copolymers A) or of these thermoplastic molding compositions, and moldings, films, fibers and foams comprising these copolymers A) or these thermoplastic molding compositions.
• Suitable components A1) are all vinylaromatic monomers known to the person skilled in the art and described in the prior art, for example DE 100 58 302 A1; Styrene, ⁇ -methylstyrene, p-methylstyrene, t-butylstyrene, vinylnaphthalene or mixtures thereof are preferably used; Styrene is particularly preferably used.
• Suitable components A2) are all vinyl cyanides known to the person skilled in the art and described in the prior art, for example DT 25 40 517 A1; Preference is given to using acrylonitrile, methacrylonitrile or mixtures thereof; Acrylonitrile is particularly preferably used.
• Suitable components A3) are all dicarboxylic anhydrides known to the person skilled in the art and described in the prior art; Preference is given to using maleic anhydride, methylmaleic anhydride, itaconic anhydride or mixtures thereof; Particular preference is given to using maleic anhydride.
• component A4) of the copolymers A) according to the invention it is possible to use further monomers which are copolymerizable with the components A1), A2) and A3) and different from these.
• the copolymers A) are particularly preferably styrene-acrylonitrile-maleic anhydride copolymers.
• copolymers A) usually contain
• component A4 0 to 25 wt .-%, preferably 0 to 15 wt .-%, particularly preferably 0 to 10 wt .-%, of component A4), wherein the wt .-% each on the total weight of components A1), A2), A3) and A4) and together give 100% by weight.
• the preparation of the copolymers A) is carried out by bulk or solution polymerization, but preferably as a solution polymerization in the presence of an organic solvent, for example cyclohexane, ethylbenzene or dimethyl sulfoxide, preferably ethylbenzene.
• an organic solvent for example cyclohexane, ethylbenzene or dimethyl sulfoxide, preferably ethylbenzene.
• the initiation of the polymerization reaction can in principle be effected by adding chemical polymerization initiators, as described, for example, in DE 100 58 302 A1; Preferably, however, the initiation takes place purely thermally, ie without the addition of a polymerization initiator.
• the preparation can be carried out in a batch or semibatch process, but preferably a continuous process is carried out.
• the process is carried out continuously under steady-state conditions; under steady-state conditions means: the concentrations of all the reactants and the composition of the copolymers A) formed remain practically constant over the duration of the reaction (information on the relationship between monomer and polymer composition and on stationary reaction can be found in particular EP 0 001 625 A1 and DT 25 40 517 A1).
• Suitable process parameters such as pressure, temperature, residence times, etc., suitable apparatus for carrying out the method and suitable metered flow of the monomers, if any of the solvents, if any of the initiators and optionally other polymerization additives are known in the art and described in the prior art.
• the water may either be added separately to the polymerization mixture, but it may also be added to one of the metered monomer streams or, if present, solvent streams.
• the water is preferably added in the form of a mixture with component A2) to the polymerization mixture.
• the workup of the polymerization mixture and the isolation of the copolymers A) can be carried out by methods known in the art and described in the prior art, for example by separation of low molecular weight compounds by applying a vacuum or stripping with inert gas.
• copolymers A) prepared by the processes according to the invention in the presence of said amounts of water in the polymerization mixture differ from copolymers prepared without the presence of said amounts of water in the polymerization mixture, but otherwise comparable processes in that they have a lower intrinsic color, have a higher melt stability and / or lower residual contents of low molecular weight compounds.
• the copolymers A) according to the invention can be further copolymerized with other thermoplastic polymers B), for example styrene-acrylonitrile copolymers (SAN), polyamide (PA), polyisocyanate ly (meth) acrylates (PMMA) or polycarbonates (PC), with rubbers C), for example polybutadiene or acrylate rubbers, with particulate or fibrous fillers or reinforcing materials D), in particular glass fibers, and / or with plastic additives E), for example heat - or UV stabilizers, lubricants, flame retardants, antistatic agents, dyes or pigments etc, are processed into thermoplastic molding compositions.
• thermoplastic polymers B for example styrene-acrylonitrile copolymers (SAN), polyamide (PA), polyisocyanate ly (meth) acrylates (PMMA) or polycarbonates (PC), with rubbers C), for example polybutadiene or acrylate rubbers, with particulate or fibrous fillers
• thermoplastic molding compositions comprise 1 to 95% by weight of copolymers A), 5 to 99% by weight of one or more thermoplastic polymers B) other than component A),
• thermoplastic molding compositions from the individual components are known in the art and described in the prior art.
• novel copolymers A) and the thermoplastic molding compositions comprising the copolymers A) can be prepared by processes known to the person skilled in the art and described in the prior art, for example by injection molding, pressing, calendering or by extrusion, shaped bodies, films, fibers and foams.
• acrylonitrile from Fluka Riedel-de Haen (Sigma-Aldrich) was used as component A2-i.
• commercially available maleic anhydride from Fluka Riedel-de Haen (Sigma-Aldrich) was used as component A3-i.
• the viscosity number VZ was determined at 25 ° C using a 0.5 wt .-% solution of the respective copolymer in dimethylformamide according to DIN 53726.
• Yellow index (Yellowness Index) or Yellowness Index Yl was determined according to ASTM D 1925 on injection molded panels (dimensions: 60 mm x 60 mm x 2 mm, melt temperature during injection molding 240 ° C, mold temperature during injection molding 60 ° C).
• the melt viscosity ⁇ of the copolymers was determined using a high-pressure capillary rheometer (Rheograph 2003) from Göttfert at a shear rate of 55 Hz at a measurement temperature of 300 ° C. after every 5 min ( ⁇ 5 ) and 30 min ( ⁇ 30 ) determined.
• the measure of the melt stability is calculated by dividing in each case the absolute difference of the melt viscosities after 30 min and after 5 min to the melt viscosity after 5 min and multiplying by 100%: / ⁇ 5 .
• Weight fraction of the compounds having an average molecular weight M w (weight average, determined by GPC) of 10000 g / mol or less, based on the total weight of the copolymers, determined by gel permeation chromatography at 35 ° C with three successive polystyrene gel columns from Polymer Laboratories with tetrahydrofuran as mobile phase (calibration with polystyrene standard) using the UV detector signal.
• Examples marked with “V” are comparative examples; in the comparative examples in which no water was metered in, the
• the examples demonstrate the lower intrinsic color, the higher melt stability and the lower residual contents of low molecular weight compounds of the copolymers A) prepared according to the invention.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2005
  • 2005-11-16 DE DE102005055080A patent/DE102005055080A1/de not_active Withdrawn
• 2006
  • 2006-11-10 US US12/093,004 patent/US20080300333A1/en not_active Abandoned
  • 2006-11-10 KR KR1020087014204A patent/KR20080076940A/ko not_active Application Discontinuation
  • 2006-11-10 WO PCT/EP2006/068331 patent/WO2007057351A1/de active Application Filing
  • 2006-11-10 EP EP06829972A patent/EP1954731A1/de not_active Withdrawn

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