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WO1996018666A1 - Procede pour preparer des matieres de moulage en polystyrene modifie pour resister aux chocs - Google Patents

Procede pour preparer des matieres de moulage en polystyrene modifie pour resister aux chocs Download PDF

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Publication number
WO1996018666A1
WO1996018666A1 PCT/EP1995/004810 EP9504810W WO9618666A1 WO 1996018666 A1 WO1996018666 A1 WO 1996018666A1 EP 9504810 W EP9504810 W EP 9504810W WO 9618666 A1 WO9618666 A1 WO 9618666A1
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WO
WIPO (PCT)
Prior art keywords
rubber
styrene
block
molding composition
mixture
Prior art date
Application number
PCT/EP1995/004810
Other languages
German (de)
English (en)
Inventor
Wolfgang Loth
Volker Warzelhan
Hermann Gausepohl
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to JP8518233A priority Critical patent/JPH10510567A/ja
Priority to EP95941686A priority patent/EP0797603A1/fr
Publication of WO1996018666A1 publication Critical patent/WO1996018666A1/fr

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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
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers

Definitions

  • the invention relates to a process for the preparation of impact-modified polystyrene (polyvinylaromatic) molding compositions by continuous anionic polymerization of styrene monomers in the presence of a rubber in a single reaction zone.
  • the radical polymerization has the disadvantage that volatile constituents (residual monomer and low molecular weight oligomers) remain in the molding compositions despite the sometimes complex degassing processes and lead to complaints because of the smell and physiological concerns or lower the softening point.
  • the object is achieved in that, in a process of the type mentioned, the polymerization is carried out above the phase inversion point by continuously feeding a styrene solution containing rubber to a reaction mixture whose polymer content is above the phase inversion point and a styrene rubber Butadiene block rubber or a mixture of a styrene-butadiene block rubber with a polybutadiene rubber is used, the styrene content of which, based on the total amount of the rubber or rubber mixture used, is between 10 and 90% by weight.
  • the block copolymers themselves contain 5 to 95, preferably 15 to 85% by weight of units of diene and correspondingly 95 to 5, preferably 85 to 15% by weight of styrene.
  • phase inversion and phase inversion point is described in detail in the specialist literature (cf., for example, GE Molau and H. Keskula; J. Polym. Sei. Al, 1595 (1966) or Angew. Makromol. Chemie 58/59, 175 (1977)).
  • phase inversion also takes place in anionic polymerization, provided that the composition of the reaction mixture of styrene monomer, rubber and styrene polymer corresponds to the conditions in free-radical polymerization.
  • Suitable block rubbers are styrene-butadiene block rubbers which have blocks or block sequences of the structure (SB) n , n being an integer from 1 or more, preferably 1 to 10, and S being a styrene polymer block or generally a polymer block a vinyl aromatic compound and B represents a poly (buta) diene block and linear block copolymers of the type S-BS and BSB.
  • styrene it is also possible to use alpha-methylstyrene, p-methylstyrene, t-butylstyrene or 1,1-diphenylethylene or blocks composed of mixtures of the monomers mentioned.
  • Suitable as component B are polymers, in particular of butadiene, furthermore 2, 3-dimethylbutadiene, isoprene, piperylene or 1,3-hexadiene and mixtures thereof.
  • the transitions between the blocks can be both sharply separated and smeared.
  • the total molecular weight of the block copolymers can be in the range from 50,000 to 500,000, preferably between 100,000 and 350,000, measured by means of gel permeation. tion chromatography (GPC) as value M p (peak aximum) using calibration standards based on polystyrene.
  • GPC tion chromatography
  • M p peak aximum
  • block copolymers which contain blocks of randomly distributed styrene and butadiene units, such (S / B) blocks being both in addition to and instead of S and of B blocks of the type mentioned above. This type of block copolymer can be used to produce impact-resistant and at the same time transparent molding compounds.
  • translucency or transparency is dispensed with, it is also possible to use mixtures of polydienes and block copolymers instead of the pure block copolymers, provided that the polymer is composed of the same monomer unit as the soft component block in the block copolymer. Accordingly, the hard component of the block copolymer should be polymerized with the same monomer unit as the matrix of the molding compound.
  • the block rubbers or the mixtures of polydienes and block rubbers are used in such an amount that the diene content in the end product is in the range from 2 to 50, preferably from 4 to 35,% by weight.
  • the block rubbers or mixtures of polydienes and block rubbers mentioned are dispersed in the thermoplastic molding composition in the form of small particles (average diameter 0.1 to 15 ⁇ m), while the coherent phase (the matrix) is composed of styrene polymers.
  • All anionically polymerizable aromatic vinyl compounds are suitable as styrene polymers for the matrix.
  • examples include styrene, alpha-methylstyrene, vinyltoluene, vinylxylene, t-butylstyrene, vinylnaphthalene and 1,1-diphenylethylene and mixtures thereof.
  • Suitable solvents are, for example, cyclohexane, methylcyclohexane, benzene, toluene, ethylbenzene or xylene.
  • the polymerization is initiated by means of organometallic compounds, as is customary in the case of a polymerization which proceeds according to the anionic mechanism.
  • organometallic compounds Compounds of alkali metals, in particular lithium, are preferred.
  • initiators are methyl lithium, ethyl lithium, propyllithium, n-butyllithium, sec-butyllithium and tert-butyllithium.
  • the organometallic compound is generally added as a solution in a hydrocarbon. The dosage depends on the desired molecular weight of the polymer, but is generally in the range from 0.002 to 5 mol% by weight, if it is based on the monomers.
  • polar, aprotic solvents can be added as cosolvents.
  • Diethyl ether, diisopropyl ether, diethylene glycol dimethyl ether, diethylene glycol di-butyl ether or, in particular, tetrahydrofuran are suitable, for example.
  • the polar cosolvent is generally added to the nonpolar solvent in a small amount of about 0.5 to 5% by volume.
  • Tetrahydrofuran (THF) is particularly preferred in an amount of 0.1 to 0.3% by volume.
  • the polymerization temperature can be between 0 and 130 ° C. Temperatures of 50 to 90 ° C. are preferred. Appropriately under isothermal conditions, i.e. H. polymerized essentially at constant temperature.
  • Stirred vessels with anchor or cross-bar stirrers are suitable as the polymerization reactor, the heat of polymerization being removed via external heat exchangers or by evaporative cooling.
  • loop reactors are also suitable, which can be designed as tube bundle reactors or so-called static mixers (tube sections with internals made of sheet metal strip fabrics or the like).
  • the polymer solution emerging from the reactor is expediently likewise passed over a static mixer which, on the one hand, serves as a short residence time zone in order to allow traces of residual monomers to react and, on the other hand, is used if the relevant active compound has been added immediately beforehand, the living Break off chain ends and, if necessary, add additives such as lubricants, antistatic antioxidants, UV stabilizers, flame retardants, fillers etc. or to add z. B. to mix in peroxides, which cause crosslinking of the rubber particles during subsequent heating (as occurs in the downstream degassing zone).
  • additives such as lubricants, antistatic antioxidants, UV stabilizers, flame retardants, fillers etc.
  • Proton-active substances such as carboxylic acids, alcohols, phenols, thio compounds, sulfonic or phosphonic acids, mineral acids and in particular water and carbon dioxide serve as means for terminating the chain ends.
  • thermoplastic molding compositions do not contain any oligomers (dimers and trimers of the phenyltetraline derivative type).
  • oligomers dimers and trimers of the phenyltetraline derivative type.
  • the molding compositions obtained by the process of this invention can be processed by the known methods for processing thermoplastics, for example by extrusion, injection molding, Ka ⁇ country Center, blow molding, pressing or sintering; especially be ⁇ be vorzugt made of the process of the invention molding compounds made her ⁇ moldings by injection molding.
  • the molding compositions can also be used for blending with other contractual polymers.
  • the impact-resistant polystyrene molding compositions prepared by this process are particularly suitable for blending with polyphenylene ether and for the production of flame-retardant products, the usual halogen and phosphorus compounds and phosphazenes or triazenes (for example melamine) being suitable as flame retardants are gnet.
  • the solvents used in the following examples were dried over aluminum oxide.
  • the monomers used were i. V., the 1,1-diphenylethylene used was distilled over n-butyl lithium.
  • a styrene-butadiene two-block rubber with a molecular weight M n of 180,000 was dissolved in cyclohexane, so that a 20% solution was obtained.
  • the impurities were removed with a 1% solution of sec-butyllithium in cyclohexane and with
  • Rubber solution in 1 1 cyclohexane and 110 ml of a 1% by weight solution of sec. Butyllithium in cyclohexane were continuously fed to a 10 1 reactor and polymerized at 80 ° C. The conversion was 99.5% by weight.
  • the polymer solution was continuously discharged from the reactor and fed to a degassing extruder on which the polymer solution degassed at 220 ° C. by means of a static mixer, in which an excess of carbon dioxide was added to the polymer solution (based on the initiator used) has been.
  • the rubber from Example 1 was hydrogenated as follows.
  • the 10% hydrogenated rubber was dissolved in methylcyclohexane. After titration of the impurities, 100 parts of the solution were mixed with 90 parts of styrene. This mixture was pumped into the reactor at a rate of 5 l / h and 1% by weight sec. Butyllithium solution was added with the addition of 80 ml / h

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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)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un procédé pour préparer des matières de moulage en polystyrène modifié pour résister aux chocs, par polymérisation anionique continue de monomères de styrène en présence d'un caoutchouc dans une seule zone de réaction. Dans ce procédé, une solution de styrène contenant comme caoutchouc un caoutchouc séquencé de styrène-butadiène ou bien un mélange d'un caoutchouc séquencé de styrène-butadiène avec un caoutchouc de polybutadiène dont la teneur en styrène, par rapport au caoutchouc ou au mélange de caoutchoucs est comprise entre 10 et 90 % en poids, est acheminée à un mélange de réaction dont la teneur en polymère est supérieure au point d'inversion de phase. L'invention concerne également une matière de moulage produite selon ce procédé et son utilisation pour la fabrication de feuilles et de corps moulés.
PCT/EP1995/004810 1994-12-17 1995-12-07 Procede pour preparer des matieres de moulage en polystyrene modifie pour resister aux chocs WO1996018666A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP8518233A JPH10510567A (ja) 1994-12-17 1995-12-07 耐衝撃性に変性されたポリスチレン成形材料の製法
EP95941686A EP0797603A1 (fr) 1994-12-17 1995-12-07 Procede pour preparer des matieres de moulage en polystyrene modifie pour resister aux chocs

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4445139.3 1994-12-17
DE19944445139 DE4445139A1 (de) 1994-12-17 1994-12-17 Verfahren zur Herstellung von schlagzäh modifizierten Polystyrol-Formmassen

Publications (1)

Publication Number Publication Date
WO1996018666A1 true WO1996018666A1 (fr) 1996-06-20

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Application Number Title Priority Date Filing Date
PCT/EP1995/004810 WO1996018666A1 (fr) 1994-12-17 1995-12-07 Procede pour preparer des matieres de moulage en polystyrene modifie pour resister aux chocs

Country Status (4)

Country Link
EP (1) EP0797603A1 (fr)
JP (1) JPH10510567A (fr)
DE (1) DE4445139A1 (fr)
WO (1) WO1996018666A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998031721A1 (fr) * 1997-01-21 1998-07-23 Basf Aktiengesellschaft Procede de production continue de matieres de moulage thermoplastiques
WO1999067308A1 (fr) * 1998-06-24 1999-12-29 Basf Aktiengesellschaft Polystyrene resistant aux chocs a rigidite et tenacite elevees
US6825271B2 (en) 2000-05-10 2004-11-30 Basf Aktiengesellschaft Anionically polymerized, impact-resistant polystyrene with capsule particle morphology

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998045369A1 (fr) * 1997-04-04 1998-10-15 Basf Aktiengesellschaft Matiere de moulage thermoplastique modifiee de maniere a resister aux chocs
DE19715821A1 (de) * 1997-04-16 1998-10-22 Basf Ag Thermoplastische Formmasse
JP3476382B2 (ja) * 1999-04-06 2003-12-10 日本エラストマー株式会社 ゴム状重合体組成物及びその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903202A (en) * 1973-09-19 1975-09-02 Monsanto Co Continuous mass polymerization process for polyblends
DE2632235B2 (de) * 1975-07-21 1981-02-26 Asahi Kasei Kogyo K.K., Osaka (Japan) Verfahren zur Herstellung von schlagzähen Polystyrolen
WO1985002406A1 (fr) * 1983-11-23 1985-06-06 The Dow Chemical Company Polymeres de composes aromatiques de monovinylidene renforces par du caoutchouc, possedant un equilibre unique de proprietes de lustre et de resistance physique, et leur procede de preparation
EP0417310A1 (fr) * 1989-03-10 1991-03-20 Nippon Steel Chemical Co. Ltd. Production de resine styrenique modifiee par du caoutchouc
US5017660A (en) * 1987-08-04 1991-05-21 Asahi Kasei Kogyo Kabushiki Kaisha Selectively, partially hydrogenated polymer and rubber composition and impact resistant styrenic resin containing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903202A (en) * 1973-09-19 1975-09-02 Monsanto Co Continuous mass polymerization process for polyblends
DE2632235B2 (de) * 1975-07-21 1981-02-26 Asahi Kasei Kogyo K.K., Osaka (Japan) Verfahren zur Herstellung von schlagzähen Polystyrolen
WO1985002406A1 (fr) * 1983-11-23 1985-06-06 The Dow Chemical Company Polymeres de composes aromatiques de monovinylidene renforces par du caoutchouc, possedant un equilibre unique de proprietes de lustre et de resistance physique, et leur procede de preparation
US5017660A (en) * 1987-08-04 1991-05-21 Asahi Kasei Kogyo Kabushiki Kaisha Selectively, partially hydrogenated polymer and rubber composition and impact resistant styrenic resin containing the same
EP0417310A1 (fr) * 1989-03-10 1991-03-20 Nippon Steel Chemical Co. Ltd. Production de resine styrenique modifiee par du caoutchouc

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998031721A1 (fr) * 1997-01-21 1998-07-23 Basf Aktiengesellschaft Procede de production continue de matieres de moulage thermoplastiques
WO1999067308A1 (fr) * 1998-06-24 1999-12-29 Basf Aktiengesellschaft Polystyrene resistant aux chocs a rigidite et tenacite elevees
US6410654B1 (en) 1998-06-24 2002-06-25 Basf Aktiengesellschaft Highly rigid, high-tenacity impact-resistant polystyrene
US6825271B2 (en) 2000-05-10 2004-11-30 Basf Aktiengesellschaft Anionically polymerized, impact-resistant polystyrene with capsule particle morphology

Also Published As

Publication number Publication date
EP0797603A1 (fr) 1997-10-01
DE4445139A1 (de) 1996-06-20
JPH10510567A (ja) 1998-10-13

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