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WO1998031721A1 - Procede de production continue de matieres de moulage thermoplastiques - Google Patents

Procede de production continue de matieres de moulage thermoplastiques Download PDF

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Publication number
WO1998031721A1
WO1998031721A1 PCT/EP1998/000065 EP9800065W WO9831721A1 WO 1998031721 A1 WO1998031721 A1 WO 1998031721A1 EP 9800065 W EP9800065 W EP 9800065W WO 9831721 A1 WO9831721 A1 WO 9831721A1
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WO
WIPO (PCT)
Prior art keywords
reaction zone
rubber
heat exchanger
reaction
impact
Prior art date
Application number
PCT/EP1998/000065
Other languages
German (de)
English (en)
Inventor
Wolfgang Fischer
Michael BAUMGÄRTEL
Hermann Gausepohl
Norbert Hasenbein
Rolf Kick
Wolfgang Loth
Volker Warzelhan
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 AU58622/98A priority Critical patent/AU5862298A/en
Publication of WO1998031721A1 publication Critical patent/WO1998031721A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/242—Tubular reactors in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00101—Reflux columns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00103—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger separate from the reactor

Definitions

  • the invention relates to a process for the continuous production of impact-modified, thermoplastic molding compositions which contain a rubber-elastic soft phase dispersed in a vinylaromatic hard matrix, and to a device for producing impact-modified, thermoplastic molding compositions.
  • phase inversion grafting reactions also occur on the polybutadiene, which together with the stirring intensity and the viscosity influence the setting of the disperse soft phase.
  • the polystyrene matrix is built up in the subsequent main polymerization.
  • the separately produced rubber has to be comminuted and dissolved in a complex manner and the polybutadiene rubber solution thus obtained has to be filtered in styrene before the polymerization in order to remove gel particles.
  • the block rubber thus produced must either be purified by precipitation or else the solvent and other volatile substances, in particular monomeric butadiene, must be distilled off.
  • the monomer butadiene which, due to the residence time spectrum in stirred tanks, can only be reduced in quantity by long post-polymerization times after the monomers have been added, would then radical polymerization of styrene lead to crosslinking. Due to the high solution viscosity, only relatively dilute rubber solutions can be handled, which means high solvent consumption, cleaning and energy expenditure.
  • the object of the invention was to provide a continuous process for the preparation of impact-modified molding compositions with a low residual monomer content. Only monomeric feedstocks should be used in the process and high space-time yields should be made possible. Furthermore, a device for carrying out the method should be provided.
  • thermoplastic molding compositions which contain a rubbery soft phase disperse distribution in a vinyl aromatic resin matrix, found, which is marked in characterized ⁇ distinguished, is carried out that the entire process in at least three reac ⁇ tion zones, wherein
  • the rubber required for the formation of the soft phase is polymerized anionically, essentially without backmixing, until complete conversion in solution,
  • the rubber is fed directly or after the addition of a stopping or coupling agent to a second reaction zone R2, in which the addition of an amount sufficient for the phase inversion of vinyl aromatic monomer and further anionic initiator is polymerized at least until the phase inversion and
  • a third reaction zone R3 with as much vinyl aromatic monomer as is required to form the impact-modified thermoplastic molding composition the polymerization is carried out anionically.
  • the first reaction zone R1 for the production of the rubber component for the soft phase is shown schematically in FIG. 1. It essentially consists of N temperature-controlled mixer sections (1), N tube reactors (2) and N-1 heat exchangers (3) which are connected in series, where N is an integer> 1 and is advantageously between 2 and 8.
  • the mixing sections can be designed, for example, as pipes which contain static mixers in order to promote radial mixing. So-called Kenics mixers or SMR reactors or so-called SMX or SMXL mixers as are marketed by Sulzer or in Chem. Eng. Techn. 13 (1990) pages 214-220.
  • the tubular reactors (2) can optionally also contain mixing elements.
  • the temperature-controlled mixer section and the tubular reactor can also be implemented as one unit. For example, a shell-and-tube heat exchanger or an SMR reactor can be used as the heat exchanger. After the last tubular reactor, before entering the second reaction zone R2, an inlet (7) is provided for a chain termination or coupling agent.
  • the second reaction zone R2 is designed as a temperature-controllable backmixing unit. It can be designed, for example, as a stirred tank with a heat exchanger or as a circulation reactor with static mixers. A hydraulically filled circuit reactor can be particularly advantageous when the reaction mass has higher viscosities.
  • the hard phase usually polystyrene, is polymerized until phase inversion and the desired morphology and particle size of the rubber-elastic phase are set.
  • the necessary shear conditions are elements through the selected static mixing ⁇ and the flow rate of the polymerization - mass by adjusting the circulation ratio in the case of use of a circulation reactor, or by selecting suitable stirrer and the stirrer speed in the case of a stirred tank, preserver - technical th Detailed. embodiments of the reactors so ⁇ as the morphology and properties of the rubber-modified polystyrene is found of Industrial Chemistry, VCH, Weinheim 1993, pages 484 to A. True, manual - 489th
  • the third reaction zone R3 consists of the same elements and has the same structure as the first reaction zone. You can just ⁇ if consist of repetitive structures. Usually there is also no heat exchanger following the last tubular reactor and the reaction energy released can advantageously be used to remove the solvent. It contains at least one inlet 10 for metering the styrenic monomer and one inlet 11 for the chain terminator. The number of tubular reactors, heat exchangers and inlets depends on the desired temperature profile and the desired final temperature.
  • the initiator solution, the solvent and the vinyl aromatic monomer or diene monomer are fed to the first tubular reactor via the mixer section. Further comonomers can be metered in via the further mixing sections. If necessary, further initiator solution or solvent can also be metered in.
  • the number N of tubular reactors depends on the structure and composition of the desired rubber. The reaction in the tubular reactors is essentially adiabatic, that is to say without targeted heat exchange and essentially without backmixing. In technical systems, however, a slight heat exchange with the environment and slight backmixing in limited areas can never be completely ruled out.
  • the temperature of the mixing sections, the metering of the monomers so ⁇ as the amount of solvent are selected so that the temperature in the tubular reactors is not above 200 ° C, preferably not rise above 150 ° C and the reaction at the end of each tubular reactor na ⁇ hezu is complete.
  • the temperature of the mixing sections is advantageously set so that the reaction mixture has a temperature of 30 ° C. to 60 ° C., preferably 40 ° C. to 55 ° C., when it enters the tubular reactor.
  • the reaction mixture is cooled to 20 ° C. to 70 ° C., preferably to 30 ° C. to 60 ° C., via the heat exchanger (3). After the last tubular reactor in reaction zone 1, there is usually no cooling.
  • a chain terminating or coupling agent can optionally be metered in via inlet 7 in order to terminate the chain ends or to link them to form multi-block or star polymers.
  • the rubber solution can, however, also be fed directly to reaction zone 2 without termination.
  • Their concentration can vary within wide limits. It is only limited by the solution viscosity. Because of the economy of the process, the highest possible concentration is desirable. In general, the concentration of the rubber solution before entering the second reaction zone is 5-60% by weight, preferably 10-45% by weight.
  • S is a block of vinyl aromatic monomer, preferably styrene 0 B is a polydiene block, preferably of butadiene or isoprene,
  • X is an m-functional coupling agent or m- functional ⁇ In itiator.
  • Block length of each individual block and the block sequences can be adjusted to the individual mixing sections via the initiator quantity, the monomer quantity and the metering method.
  • Blocks S can also contain alkadiene monomers, blocks B also vinyl aromatic monomers in statistical order.
  • Statistical incorporation is achieved, for example, by adding small amounts of Lewis bases such as dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, alkali metal salts of primary, secondary and tertiary alcohols and tertiary amines such as pyridine and tributylamine. These are usually used in concentrations 5 from 0.1 to 5 vol .-% based on the initiator used, such as alkoxides used in Kaliumtetrahydrolinoleat 3-20 volume per ⁇ producers.
  • the starting materials and process conditions are preferably chosen such that a 1,2-vinyl content in the diene block of less than 30% by weight, based on the diene block, results.
  • the average molecular weights Mw of the blocks are generally in the range of 1,000 to 500,000, preferably in the Be ⁇ ranging from 20,000 to 300,000 g / mol.
  • the total content of vinyl aromatic monomer ⁇ is in the range of 3 to 85 wt -.%, Preferably between 10 and 60 wt -.%, And most forthcoming
  • the glass transition temperatures of the rubber-elastic blocks are below -20 ° C, preferably below -40 ° C.
  • the rubber solution produced in the first 40 reaction zone is fed continuously to the second reaction zone, and further styrenic monomer and initiator are fed in via feeds 8 and 9, in flow rates as are necessary to achieve phase inversion.
  • polymerization is usually carried out at temperatures from 50 to 120 ° C., preferably from 60 to 45 100 ° C.
  • the reaction mass from zone 2 fed to the third reaction zone is heated to 20 to 70 ° C., preferably 30 to 60 ° C. Additional styrenic monomer and optionally further initiator are metered in via feed 10.
  • the reaction mixture is polymerized in the tubular reactor without heat removal to complete conversion.
  • the polymerization solution can be worked up in a known manner in degassing extruders or degassing evaporators at temperatures of usually 190 to 320 ° C.
  • the solvent obtained here is expediently returned to the process after distillation and appropriate drying.
  • Preferred monomers are styrene, ⁇ -methylstyrene, p-methylstyrene, ethylstyrene, tert. -Butylstyrene, vinyltoluene, 1, 1-diphenylethylene and butadiene, isoprene, dimethylbutadiene, pentadiene-1, 3 or hexadienes-1, 3 or mixtures thereof.
  • the usual mono-, bi- or multifunctional alkali metal alkyls or aryls are used as initiators.
  • Advantageously - organolithium compounds are used, such as ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert. -Butyl-, phenyl-, hexyldiphenyl-, hexamethylenedi-, butadienyl- or isopropenyllithium.
  • the amount of initiator required results from the desired molecular weight and is generally in the range from 0.0002 to 5 mol percent, based on the amount of monomer.
  • Suitable chain terminators are proton-active substances or Lewis acids such as water, alcohols, aliphatic and aromatic carboxylic acids or their salts, and inorganic acids such as carbonic acid or boric acid.
  • Polyfunctional compounds such as polyfunctional aldehydes, ketones, esters, anhydrides or epoxides can be used to couple the rubbers.
  • the customary anionically polymerizable vinyl aromatic monomers which meet the usual purity requirements, such as, in particular, the absence of polar substances, can be used as the monomer for the preparation of the hard phase.
  • Styrene, ⁇ -methylstyrene, p-methylstyrene, ethylstyrene, tert are preferred.
  • -Butylstyrene, vinyltoluene, 1, 1-diphenylethylene or mixtures thereof are used.
  • the organization for the anionic Polymeri ⁇ conventional aliphatic, cycloaliphatic or aromatic hydrocarbons having 4 to 12 carbon atoms such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, isooctane, benzene, alkylbenzenes such as toluene, xylene, ethylbenzene or decalin or suitable mixtures.
  • the solvent must of course have the high purity required for the process. To remove proton-active substances, they can be dried, for example, over aluminum oxide or molecular sieve and distilled before use.
  • the solvent from the process is preferably reused after condensation and the cleaning mentioned.
  • customary auxiliaries and additives such as lubricants, stabilizers or mold release agents can be added to the molding composition.
  • the device described is also suitable for producing other multi-phase molding compositions.
  • the polymer forming the soft phase is synthesized in reaction zone 1 and mixed in reaction zone 2 with further monomer or monomer mixtures which form the polymer of the hard phase and polymerized until phase inversion.
  • the polymerization is completed in the third reaction zone.
  • FIG. 1 An arrangement as shown in FIG. 1 was used for the examples, four tube reactors (2a, 2b, 2c, 2d) each having a length of 500 mm (DN 32-SMXL mixer from Sulzer) being used in the unit designated as reaction zone R1 ) were used, each of which had a temperature-controllable premixer (la, lb, lc, ld) each 350 mm long (DN 15 SMX mixer from Sulzer) with the corresponding feeds for monomers (feeds 1,4,5,6 ), Solvent (inlet 2) and initiator (inlet 3) upstream and in the case of tube reactors 2a to 2c each have a heat exchanger (3a, 3b, 3c), each consisting of a tube bundle with 3 DN 15 tubes and a length of 1000 mm, were downstream.
  • a 10 1 stirred tank was used, which was equipped with an anchor stirrer and reflux condenser and the inlets for chain terminating or coupling agents (inlet 7), monomers (in
  • the reaction zone R3 consisting of a heat exchanger (3d) consisting of a 1000 mm long tube bundle with 3 DN 15 tubes, two 300 mm long mixers (le and lf) (DN 25 SMX mixer from Sulzer) with inlet 10 (for Monomers) or 11 (for chain terminating agent) and a 400 mm long, interposed tubular reactor (2e) (DN 50 SMXL mixer from Sulzer) was connected via a gear pump to the boiler outlet valve of the stirred reactor of reaction zone 2.
  • the total reaction volume of the arrangement was approximately 9.9 1, divided into 3.5 1 in reaction zone 1, 5 1 in reaction zone 2 (fill level of the stirred tank) and 1.4 1 in reaction zone 3.
  • a degassing extruder was installed downstream of the arrangement.
  • the monomers and solvents used for the polymerization were dried over A1 2 0 3 (ethylbenzene) or molecular sieve (butadiene) and distilled (styrene, ethylbenzene) before use.
  • a 1.2% solution of sec-butyllithium in n-hexane / ethylbenzene (10/90% by weight) was used as the initiator.
  • the molar masses Mp (peak maximum) of the styrene matrix were determined by means of gel permeation chromatography (GPC) against narrowly distributed polystyrene standards.
  • the notched impact strength was determined on notched standard bodies in accordance with DIN 53453.
  • the yield stress was determined on test specimens produced according to ISO 3167 according to DIN 53455.
  • Examples 1-3 were carried out in the apparatus described above using the process parameters listed in Table 1.
  • the examples show, in particular, low residual monomer contents and very high space-time yields, which are between 0.08 and 0.2 kg / (hx 1) in the technical plants usually used for the production of impact-resistant polystyrene.
  • Table 1

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé de production continue de matières de moulage thermoplastiques modifiées à résistance élevée aux chocs, qui contiennent une phase molle caoutchouteuse répartie de manière dispersée dans une matrice dure vinylaromatique. Dans une première zone de réaction, le caoutchouc requis pour la formation de la phase molle est polymérisé en solution de manière anionique sensiblement sans remélange jusqu'à réaction complète. Le caoutchouc est acheminé directement ou après adjonction d'un agent de réaction de rupture ou un agent de copulation, jusqu'à une deuxième zone de réaction où il est polymérisé sous apport d'une quantité suffisante, pour l'inversion de phase, de monomère vinylaromatique et d'un autre initiateur anionique. La polymérisation est parachevée de manière anionique, dans une troisième zone de réaction, avec la quantité de monomère vinylaromatique requise pour obtenir une matière de moulage thermoplastique modifiée à résistance élevée aux chocs.
PCT/EP1998/000065 1997-01-21 1998-01-08 Procede de production continue de matieres de moulage thermoplastiques WO1998031721A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58622/98A AU5862298A (en) 1997-01-21 1998-01-08 Continuous process for producing thermoplastic moulding compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997101865 DE19701865A1 (de) 1997-01-21 1997-01-21 Kontinuierliches Verfahren zur Herstellung von thermoplastischen Formmassen
DE19701865.3 1997-01-21

Publications (1)

Publication Number Publication Date
WO1998031721A1 true WO1998031721A1 (fr) 1998-07-23

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PCT/EP1998/000065 WO1998031721A1 (fr) 1997-01-21 1998-01-08 Procede de production continue de matieres de moulage thermoplastiques

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AU (1) AU5862298A (fr)
DE (1) DE19701865A1 (fr)
TW (1) TW363975B (fr)
WO (1) WO1998031721A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999067308A1 (fr) * 1998-06-24 1999-12-29 Basf Aktiengesellschaft Polystyrene resistant aux chocs a rigidite et tenacite elevees
US6448353B1 (en) 2000-02-08 2002-09-10 3M Innovative Properties Company Continuous process for the production of controlled architecture materials

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19804912A1 (de) 1998-02-07 1999-08-12 Basf Ag Kontinuierliches Verfahren zur Herstellung thermoplastischer Formmassen
DE10152116A1 (de) * 2001-10-23 2003-04-30 Basf Ag Verfahren zur kontinuierlichen anionischen Polymerisation von schlagzähem Polystyrol

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1013205A (en) * 1963-01-16 1965-12-15 Monsanto Co Polymerization processes
US3723575A (en) * 1971-04-14 1973-03-27 Firestone Tire & Rubber Co Method of producing graft polymers
US4153647A (en) * 1977-06-15 1979-05-08 Glukhovskoi Vladimir S Process for producing-impact polystyrene
US5096970A (en) * 1987-08-19 1992-03-17 Asahi Kasei Kogyo Kabushiki Kaisha Prepolymerization process for producing a conjugated diene compound prepolymer solution
WO1996018666A1 (fr) * 1994-12-17 1996-06-20 Basf Aktiengesellschaft Procede pour preparer des matieres de moulage en polystyrene modifie pour resister aux chocs

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1013205A (en) * 1963-01-16 1965-12-15 Monsanto Co Polymerization processes
US3723575A (en) * 1971-04-14 1973-03-27 Firestone Tire & Rubber Co Method of producing graft polymers
US4153647A (en) * 1977-06-15 1979-05-08 Glukhovskoi Vladimir S Process for producing-impact polystyrene
US5096970A (en) * 1987-08-19 1992-03-17 Asahi Kasei Kogyo Kabushiki Kaisha Prepolymerization process for producing a conjugated diene compound prepolymer solution
WO1996018666A1 (fr) * 1994-12-17 1996-06-20 Basf Aktiengesellschaft Procede pour preparer des matieres de moulage en polystyrene modifie pour resister aux chocs

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US6448353B1 (en) 2000-02-08 2002-09-10 3M Innovative Properties Company Continuous process for the production of controlled architecture materials

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Publication number Publication date
TW363975B (en) 1999-07-11
DE19701865A1 (de) 1998-07-23
AU5862298A (en) 1998-08-07

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