WO1981000259A1 - Procede et dispositif pour la fabrication en continu de polymethanes - Google Patents

Procede et dispositif pour la fabrication en continu de polymethanes Download PDF

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Publication number
WO1981000259A1
WO1981000259A1 PCT/CH1980/000086 CH8000086W WO8100259A1 WO 1981000259 A1 WO1981000259 A1 WO 1981000259A1 CH 8000086 W CH8000086 W CH 8000086W WO 8100259 A1 WO8100259 A1 WO 8100259A1
Authority
WO
WIPO (PCT)
Prior art keywords
kneading
screw
mixing
endless screw
reaction
Prior art date
Application number
PCT/CH1980/000086
Other languages
German (de)
English (en)
Inventor
I Stojanovic
P Schimanski
Original Assignee
Buss Ag
Iroquois Chem Gmbh
I Stojanovic
P Schimanski
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 Buss Ag, Iroquois Chem Gmbh, I Stojanovic, P Schimanski filed Critical Buss Ag
Publication of WO1981000259A1 publication Critical patent/WO1981000259A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • 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
    • B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
    • B29C48/38—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in the same barrel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands

Definitions

  • the present invention relates to a method and a device according to the preceding claims. This is intended to avoid an untargeted crosslinking of the individual components during the addition polymerization, as a result of which the material properties would be adversely affected and incorrectly polymerized, jelly particles could also occur.
  • Recipes, types of manufacture and use of polyurethanes are known from publications, for example from the plastics handbook. Volume VII, Vieweg-Höchtlen, Carl-Hanser Verlag. However, these • deal primarily with batch production using the casting process or on mixing rolling mills.
  • a short-chain diol is added as a so-called chain extender to the reaction between the long-chain bi-functional polyol and isocyanate
  • chain extender preferably an diol, for example 1,4-butanediol
  • the distribution of the soft and hard segments in the chains is not carried out in the desired manner, and in extreme cases this can even lead to the formation of linear non-elastic polyurethanes if large amounts of the diisocyanate are consumed in the reaction with butanediol alone.
  • the inventive method and the device for this have the features listed in the characterizing part of claims 1 and 2.
  • the object of the invention was to overcome the difficulties and disadvantages described above and describes a successful process in which the individual reaction components are separated into the screw housing of a single-shaft mixing and kneading machine, as described, for example, in DE PS 20 56 611 has been described, injected. f OMPI - 3 -
  • This mixing and kneading machine has an intensive mixing effect, both in the axial and in the radial direction, with clear backmixing between the individual kneading stages, which represent a progressive reactor cascade.
  • This mixing effect is caused by the interaction of the individual worm wings and the knuckle teeth.
  • the reaction progresses gradually in individual sections of the snail shell with a smooth transition.
  • the individual reaction components can be adjusted individually or partially with reaction adaptation. premixed or even pre-reacted injected.
  • fillers, extenders, colorants and auxiliaries can be added and kneaded homogeneously during or after the reaction.
  • the melt is preferably discharged through a thread nozzle into a cooling bath and then granulated.
  • Fig. 2 shows three different kneading chicanes, which in the
  • Inner wall of the housing of the mixing and kneading machine can be used / ÜRE-AT? "
  • OMPI Fig. 3 shows the mixing and kneading machine in side view
  • Fig. 4 is a front view of the flanged Trans ferschnecke.
  • the shaft of the mixing and kneading machine 16 is driven by the motor 1 by means of V-belts 15 and the gear 14.
  • the housing of the machine 16 is equipped with kneading chicanes over its entire length without an inlet connection. Kneading teeth 27 can be used, which are secured against rotation with the pin 28 in the housing wall, or kneading bolts 25, 26.
  • the machine is equipped with 126 bolts 26 and three bolts 25; the latter are pierced and are used to inject the reaction components.
  • the bolts 25 can be used in any A number and at optimally chosen points instead of the bolts 26.
  • the individual bolts form a cascade of 129 intermeshing processing chambers in the known To interact with the rotating and simultaneously reciprocating screw blades.
  • the product is mixed intensively, kneaded and divided by the screw wing edge. A smaller part is pushed back into the previous chamber, the larger part is pushed into the next subsequent chamber.
  • the edges of the screw blades brush the inside wall of the housing and past the bolt, which in turn wipes the screw blades, so that the process is self-cleaning
  • the reactants an isocyanate 6, a polyol 7, which can be an unbranched or slightly branched polyester mixture, and a so-called chain extender are preheated in the boilers 9 provided with a heating jacket.
  • the individual components are pumped by means of metering pumps 17 through heated pipelines 18 to the mixing and kneading machine 16 and injected through the bolts 25 into the kneading chambers.
  • the kneader housing has a length of 12 L / D from the first injection point.
  • the average residence time of the components when passing through the 129 kneading cascades is 3-4 minutes. Due to the inclination of the screw blades, the excellent longitudinal and transverse mixing effect with partial recirculation is overlaid by a dominant plug flow in the exit direction, which means that the residence time can be shortened by increasing the speed.
  • Kneader housing and shaft can be heated or cooled, which enables the temperature of the strongly exothermic reaction to be controlled.
  • the mixture of the isocyanate with the polyol begins at 1 after one L / D length and is continued until close to 3 at three L / D lengths; the reaction already begins.
  • the chain extender is now added and takes part in the reaction, which is already quite advanced shortly after 5 at five L / D.
  • the material is processed over a further seven L / D lengths in order to mature the reaction at a temperature.
  • the resulting highly viscous melt is then ejected into a short transfer screw 19 with drive 20.
  • the screw conveyor 19 builds up a uniform delivery pressure in order to push the melt through a right-angled thread nozzle 21 into a water bath 22.
  • the threads drawn through the water bath are then cut into a granulator 23.
  • degassing the melt can be advantageous.
  • a degassing nozzle 24 is provided on the kneader housing, which is closed by an insert when not in use.
  • OMPI still had a medium viscosity.
  • the liquid di- isoc.yanate was injected through a kneading pin, the ratio between the premix and the diisocyanate was kept at approx. 2.4: 1.
  • the worm shaft and the three separately heatable housing zones were heated to 178 ° C. After the onset of the reaction, the product temperature rose briefly to 182 ° C. and then decreased again.
  • the screw speed in the reaction kneader was 85 rpm and was tempered to 70 ° C., so that the viscous product could be knocked off hot immediately after leaving the multi-hole nozzle plate and quickly cooled in a conveying air stream.
  • a polyurethane was continuously prepared from three individual metered components.
  • the drilled kneading pins were inserted into the reactor housing as follows in accordance with the recipe.
  • a long-chain polyol mixture with a relative molecular weight of about 16O0 to 50 ° C was premelted and injected into the reactor at zero D.
  • the three zones of the reactor housing were tempered at 120 ° C., then 100 ° C. and 60 ° C., the screw shaft at 100 ° C.
  • the production temperature jumped to 120 ° C and then at 4 D to 140 ° C, before slowly falling again.
  • the screw speed was kept at 40 rpm and 4.2 kg / h of product was produced.
  • the method disclosed above offers numerous advantages; For example, the installation of pierced kneading pins at freely selected locations, which can be found on the circumference or length of the reactor housing, enables a very good adaptation to the known recipes. This also makes it possible to shorten the length of the reaction zones.
  • the large number of successive reactor stages in a cascade brings about thorough mixing and advantageous homogenization of the reaction.
  • the speed and the shear rate in the kneading reactor can be selected so that the reaction product is not overheated and thermally damaged.
  • the worm shaft consists of a shaft core with slid-on screw wing bushes, which are interchangeable.
  • the screw wing geometry can . be selected so that the speed can be regulated independently of the throughput, and the reactor remains filled.
  • the reaction products in granular form have the same excellent properties as could previously only be achieved using the pouring method; they are free of jellyfish or nodules.
  • the reactor can also be used at high temperatures without modification.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Le procede doit permettre la polyaddition et la fabrication en continu de polymethanes avec la granulation consecutive, qui soit propre a l'usinage sur des extrudeuses, des presses et des boudineuses. Cela est obtenu par l'injection dans le boitier d'une machine a vis sans fin (16), en des points choisis (25), avec des pompes de dosage (17), des differents constituants (6, 7, 8) prealablement chauffes. La machine a vis sans fin (16) est a axe unique et sert de reacteur en cascade. Sa construction est particuliere: les filets de la vis sans fin sont interrompus et l'arbre rotatif accomplit simultanement un mouvement de va-et-vient, de sorte que des chevilles (25, 25) ou des dents (27) disposees a l'interieur du boitier de la vis sans fin puissent penetrer entre les ailettes de la vis, par les lacunes, pour diviser, malaxer et melanger de facon intensive le materiau transporte. A la sortie de la machine a vis sans fin (16), le polymerisat penetre dans une courte vis de transfert (19) puis ressort par une buse a plusieurs trous (21) ou il est decoupe pour former le granulat.
PCT/CH1980/000086 1979-07-13 1980-07-14 Procede et dispositif pour la fabrication en continu de polymethanes WO1981000259A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH652879 1979-07-13
CH6528/79 1979-07-13

Publications (1)

Publication Number Publication Date
WO1981000259A1 true WO1981000259A1 (fr) 1981-02-05

Family

ID=4311014

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CH1980/000086 WO1981000259A1 (fr) 1979-07-13 1980-07-14 Procede et dispositif pour la fabrication en continu de polymethanes

Country Status (5)

Country Link
EP (1) EP0032142A1 (fr)
BE (1) BE884296A (fr)
DE (1) DE3049740D2 (fr)
IT (1) IT1132527B (fr)
WO (1) WO1981000259A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2678627A1 (fr) * 1991-07-04 1993-01-08 Hennecke Gmbh Maschf Procede de fabrication de polyurethannes elastomeriques, en particulier sous forme de semelles de chaussures.
EP1110691A2 (fr) * 1999-12-21 2001-06-27 General Electric Company Mélange de compositions de silicone chargé
EP1110696A2 (fr) * 1999-12-21 2001-06-27 General Electric Company Procédé continu de préparation de compositions silicone
WO2002011975A1 (fr) * 2000-08-03 2002-02-14 Ranier Limited Production d'un polyurethanne de precision
US6417312B1 (en) 1995-06-07 2002-07-09 Bayer Aktiengesellschaft Thermoplastic polyurethane elastomers
DE102006038197A1 (de) * 2006-08-16 2008-02-21 Kraussmaffei Technologies Gmbh Vorrichtung und Verfahren zur Verarbeitung von Duroplasten
WO2017032615A1 (fr) * 2015-08-26 2017-03-02 Kraussmaffei Technologies Gmbh Procédé de moulage par injection d'un mélange à base de résine réactive et machine correspondante
DE102010025995B4 (de) 2010-07-04 2023-01-26 Entex Rust & Mitschke Gmbh Herstellung thermoplastischer Polyurethane in einem Extruder

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1401613A (fr) * 1963-06-17 1965-06-04 Celanese Corp Appareil à cisailler et à mélanger des matières
FR2072814A5 (fr) * 1969-12-03 1971-09-24 Upjohn Co
FR2214719A1 (fr) * 1973-01-19 1974-08-19 Bayer Ag
DE2549372A1 (de) * 1975-11-04 1977-05-05 Bayer Ag Verfahren zur kontinuierlichen herstellung von polyurethanen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1401613A (fr) * 1963-06-17 1965-06-04 Celanese Corp Appareil à cisailler et à mélanger des matières
FR2072814A5 (fr) * 1969-12-03 1971-09-24 Upjohn Co
FR2214719A1 (fr) * 1973-01-19 1974-08-19 Bayer Ag
DE2549372A1 (de) * 1975-11-04 1977-05-05 Bayer Ag Verfahren zur kontinuierlichen herstellung von polyurethanen

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2678627A1 (fr) * 1991-07-04 1993-01-08 Hennecke Gmbh Maschf Procede de fabrication de polyurethannes elastomeriques, en particulier sous forme de semelles de chaussures.
US6417312B1 (en) 1995-06-07 2002-07-09 Bayer Aktiengesellschaft Thermoplastic polyurethane elastomers
EP1110691A2 (fr) * 1999-12-21 2001-06-27 General Electric Company Mélange de compositions de silicone chargé
EP1110696A2 (fr) * 1999-12-21 2001-06-27 General Electric Company Procédé continu de préparation de compositions silicone
EP1110696A3 (fr) * 1999-12-21 2001-11-21 General Electric Company Procédé continu de préparation de compositions silicone
EP1110691A3 (fr) * 1999-12-21 2002-03-20 General Electric Company Mélange de compositions de silicone chargé
WO2002011975A1 (fr) * 2000-08-03 2002-02-14 Ranier Limited Production d'un polyurethanne de precision
EP1935622A1 (fr) * 2000-08-03 2008-06-25 Ranier Limited Fabrication précise de polyuréthane
US8784712B2 (en) 2000-08-03 2014-07-22 Ranier Limited Precision polyurethane manufacture
DE102006038197A1 (de) * 2006-08-16 2008-02-21 Kraussmaffei Technologies Gmbh Vorrichtung und Verfahren zur Verarbeitung von Duroplasten
DE102010025995B4 (de) 2010-07-04 2023-01-26 Entex Rust & Mitschke Gmbh Herstellung thermoplastischer Polyurethane in einem Extruder
WO2017032615A1 (fr) * 2015-08-26 2017-03-02 Kraussmaffei Technologies Gmbh Procédé de moulage par injection d'un mélange à base de résine réactive et machine correspondante

Also Published As

Publication number Publication date
BE884296A (fr) 1980-11-03
IT8023403A0 (it) 1980-07-11
EP0032142A1 (fr) 1981-07-22
DE3049740D2 (en) 1982-02-11
IT1132527B (it) 1986-07-02

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