WO2002008173A1 - Particules de polyisocyanate d'une taille controlee - Google Patents

Particules de polyisocyanate d'une taille controlee Download PDF

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Publication number
WO2002008173A1
WO2002008173A1 PCT/EP2001/007365 EP0107365W WO0208173A1 WO 2002008173 A1 WO2002008173 A1 WO 2002008173A1 EP 0107365 W EP0107365 W EP 0107365W WO 0208173 A1 WO0208173 A1 WO 0208173A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyisocyanate
drops
particles
cooling
molten
Prior art date
Application number
PCT/EP2001/007365
Other languages
English (en)
Inventor
David Nigel Crockett
Original Assignee
Huntsman International Llc
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 Huntsman International Llc filed Critical Huntsman International Llc
Priority to AU2001272515A priority Critical patent/AU2001272515A1/en
Publication of WO2002008173A1 publication Critical patent/WO2002008173A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/16—Preparation of derivatives of isocyanic acid by reactions not involving the formation of isocyanate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

Definitions

  • the present invention relates to improved solid particles of polyisocyanates, in particular diisocyanates, and more particularly diphenylmethane diisocyanates (MDI), a method for the production thereof and their use.
  • polyisocyanates in particular diisocyanates, and more particularly diphenylmethane diisocyanates (MDI), a method for the production thereof and their use.
  • MDI diphenylmethane diisocyanates
  • Polyisocyanates are well known in the art and are used extensively as raw materials, for example in the production of polyurethanes.
  • Polyisocyanates cover a broad range of organic compounds having 2 or more isocyanate groups. Such compounds may comprise aromatic and/or aliphatic groups. Examples of polyisocyanates which are widely used include tolylene diisocyanates (TDI), diphenylmethane diisocyanates (MDI), naphthalene-l,5-diisocyanate (NDI), 1,6-hexamethylene diisocyanate (HDI), p- phenylenediisocyanate (PPDI), trans-cyclohexane-l,4-diisocyanate (CHDI), isophorone diisocyanate (IPDI) and tetramethylxylene diisocyanates (TMXDI).One of the most important polyisocyanates is MDI.
  • MDI tolylene diisocyanates
  • MDI diphenylmethane diisocyanates
  • NDI naphthalene-l,5-diisocyanate
  • Modified forms of polyisocyanates are mainly liquefied products such as dimerised or trimerised forms of the polyisocyanates, or reaction products of polyisocyanates with compounds containing isocyanate-reactive groups.
  • Some polyisocyanates for example 4,4 -diphenylmethane diisocyanate, are already available in the form of flakes, but these give rise to problems from a health and safety point of view since dust is formed during manufacture and transportation. The bulk density of the flaked material is low, increasing the cost of transportation to the customer.
  • Finely-divided solid polyisocyanates for example MDI-powders, particularly in binders or adhesives are described in US-A 4569982). These powders are produced by atomising a liquid stream. Hence, the droplets here have a broad particle size distribution, i.e. are polydispersed and have a tendency to coalesce. The result is that such powders generally have a diameter of substantially less than 1 mm, are of irregular shape and have a large size distribution.
  • WO 97/07092 describes a process for preparation of particles by means of a prilling treatment.
  • This technology includes prilling which is normally done in a prilling tower which has to be of considerable height to prill MDI due to the cold temperatures and low heat transfers between the cold gas and liquid isocyanate.
  • the solid polyisocyanate particles produced by the present invention provide a good flowable solid with adequate bulk density and acceptable dust levels .
  • the improved flowability of such particles allows easier and quicker handling for storage or transport, the bulk density achieved with these particles allow transport at a cost comparable to that of solid MDI in drums.
  • the particles have a controlled particle size, are chemically virtually identical to the starting material of which they are made.
  • the polyisocyanate particles of the present invention are beneficial to the customer in that, upon melting before use in reaction processes, the melting time of the polyisocyanate particle is significantly reduced, thereby further reducing the level of induced impurities at the customer
  • the term 'induced impurities' includes all reaction products formed through the reaction of isocyanate-groups with isocyanate-reactive groups during the conversion of the polyisocyanate starting material into particles which were not present in the starting material.
  • reaction products may be urethanes, allophanates, ureas, biurets, amides, carbodiimides or uretonimines, or dimers or trimers of isocyanates.
  • the present invention is directed to a process for the manufacture of polyisocyanate particles comprising the steps of:
  • Polyisocyanate particles according to the invention may be one or more polyisocyanate species, preferably one or a mixture of congeneric species, e.g. oligomers, in particular one species, and can be obtained from any organic polyisocyanate.
  • Useful polyisocyanates may be aliphatic, cycloaliphatic, araliphatic, heterocyclic or aromatic.
  • Suitable polyisocyanates include, for example, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-l,4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate and pxylylene- diisocyanate.
  • Preferred polyisocyanates are aromatic polyisocyanates, for example phenylene diisocyanates, tolylene diisocyanates, 1,5-naphthylene diisocyanate and especially diphenylmethane diisocyanate (MDI) based polyisocyanates like 4,4-MDI, 2,4'-MDI or mixtures thereof and polymeric MDI having an isocyanate functionality of more than 2.
  • MDI diphenylmethane diisocyanate
  • a type of polyisocyanate with which it has been found particularly useful, is "pure" MDI.
  • the term '"pure" MDI is intended to include polyisocyanate compositions comprising at least 85%, preferably at least 95% and most preferably at least 99% by weight of 4,4 -MDI.
  • pure MDI shows a strong tendency to dirnerize. It is a particular advantage of this mvention that “pure MDI” particles according to the invention are free of induced dimer groups.
  • the process defined herein is a “pastillation” or “miciOpastillation” process.
  • “Pastilles” or “micropastilles” of are formed by the solidification of molten droplets.
  • a known drop forming device is described in DE 28 53 054, published on 12th Jun. 1980, owned by Sandvik Conveyor GmbH of Fellbach, Germany.
  • the known device is a rotary drop former comprising outer and inner coaxial cylinders, the outer cylinder being rotatable, and the inner cylinder being stationary.
  • the outer cylinder is perforated over its entire circumference, and those perforations periodically become aligned with a series of openings (or with a slit or a nozzle lip) formed in the inner cylinder.
  • the melt contained inside the inner cylinder drips under pressure through the aligned openings.
  • drops of the melt are formed directly onto a cooling belt to form on the belt a row of drops distributed adjacent to each other across the width of the belt.
  • the drops thus formed on the cooling belt crystallise into solid pellets, or "(micro)pastilles".
  • the cooling belt is a continuous stainless steel conveyor belt. Most conveniently the cooling belt is cooled by spraying a cooling liquid on to the side of the belt opposite that on which droplets are formed. This enables any direct contact between the surfactant paste and the cooling liquid to be avoided.
  • Pastilles made by the process of the invention are generally recognisable by then- surface profile which is generally round, but has a planar surface.
  • the planar surface corresponds to the area of the pastille that has been in direct contact with the cooling belt.
  • the molten droplets may be formed and cooled on a rotating cooling drum, or on a surface such as a rotating disc.
  • a suitable device is a Disc Pastillator for uniform free flowing pastilles manufactured by Goudsche maschinefabriek B. V. of Waddinxveen, The Netherlands. Another device is described in their Dutch patent application NL-A-7 113 934. In all of these devices outer surface of the droplet former and the cooling surface will normally move at the same linear speed so that substantially round uniform droplets are formed. However non-uniform droplets may be formed by driving the outer surface of the droplet former and the cooling surface at different linear speeds.
  • cooling surface it is meant herein that the surface of the belt, drum, or disc is cooled by a cooling fluid.
  • the cooling fluid may be applied to the opposite surface of the belt, drum or disc to the surface on which the droplets are formed.
  • the cooling temperature depends on the characteristics of the polyisocyanate starting material. For example, in the production of particles from pure MDI, a temperature of -10 to -25 °C is preferably employed.
  • the particles of the present invention are in the form of pastilles, preferably hemispherical with a maximum cross section of 2.5 mm to 3.5 mm., and with a height varying between 0.8 to 1.5 mm.
  • Preferred particles of the present invention have bulk densities varying from 0.7 - 0.8 Tonnes/m 3 .
  • diameter is meant the largest cross-sectional dimension of a given particle.
  • Liquid pure MDI at 42 degrees centigrade is caused to flow at a constant rate, through a rotoformer.
  • the rotoformer consists of a static feed chamber (nozzle Bar) located in a heated stator and a rotating outer shell.
  • the outer shell has small holes drilled in it at regular intervals, the number and size of the holes combined with the angular velosity of the outer shell and the feed flow rate determines the size and shape of the Pastilles formed, and hence the pastillation capacity.
  • the rotoformer forms drops of the material which are laid onto a continuous flat steel belt.
  • the Rotoform outer shell and steel belt are run at equal speed.
  • the steel belt is cooled by circulating a cooling medium through a cavity in the leading belt pulley.
  • the pastille size and shape for low dust generation and highest bulk density is 2.5 - 3.5 mm in diameter and 0.8 - 1.0 mm high i.e. hemispherical in shape, and give a bulk density of 0.7 Te/m3
  • Rotoformer is commercially marketed by Sandvik Process Systems GMBH.
  • the particles according to the present invention have a very narrow size distribution.
  • Pastillation treatment generally does not have a detrimental effect on the product quality
  • usual additives such as stabilisers, anti-oxidants or pigments may be added to improve such properties as storage and colour stability or oxidation resistance.
  • the polyisocyanate particles of the present invention can advantageously be used in the production of polyisocyanate polyaddition products, such as foams, elastomers, coatings, adhesives, sealants, encapsulants or binders.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de fabrication de particules de polyisocyanate consistant: (i) à faire fondre le polyisocyanate, (ii) à mettre la pâte fondue de polyisocyanate sous forme de gouttes sur une surface de refroidissement, (iii) à former des pastilles solides par refroidissement des gouttes de pâte fondue, et (iv) à enlever les pastilles solidifiées de la surface de refroidissement.
PCT/EP2001/007365 2000-07-20 2001-06-28 Particules de polyisocyanate d'une taille controlee WO2002008173A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001272515A AU2001272515A1 (en) 2000-07-20 2001-06-28 Polyisocyanate particles of controlled particle size

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP00115635 2000-07-20
EP00115635.5 2000-07-20

Publications (1)

Publication Number Publication Date
WO2002008173A1 true WO2002008173A1 (fr) 2002-01-31

Family

ID=8169309

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/007365 WO2002008173A1 (fr) 2000-07-20 2001-06-28 Particules de polyisocyanate d'une taille controlee

Country Status (2)

Country Link
AU (1) AU2001272515A1 (fr)
WO (1) WO2002008173A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2853054A1 (de) * 1978-12-08 1980-06-12 Sandvik Conveyor Gmbh Vorrichtung zum auspressen von fliessfaehigen massen aus einem behaelter
SU1456411A1 (ru) * 1986-12-03 1989-02-07 Предприятие П/Я Г-4302 Способ получени твердого дифенилметан-4,4 @ -диизоцианата
DD299528A5 (de) * 1988-12-21 1992-04-23 Basf-Schwarzheide Gmbh,De Verfahren zur konditionierung von 4,4-diphenylmethandiisocyanat
WO1997007092A1 (fr) * 1995-08-21 1997-02-27 Imperial Chemical Industries Plc Particules de polyisocyanate de dimension et de repartition granulometriques controlees

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2853054A1 (de) * 1978-12-08 1980-06-12 Sandvik Conveyor Gmbh Vorrichtung zum auspressen von fliessfaehigen massen aus einem behaelter
SU1456411A1 (ru) * 1986-12-03 1989-02-07 Предприятие П/Я Г-4302 Способ получени твердого дифенилметан-4,4 @ -диизоцианата
DD299528A5 (de) * 1988-12-21 1992-04-23 Basf-Schwarzheide Gmbh,De Verfahren zur konditionierung von 4,4-diphenylmethandiisocyanat
WO1997007092A1 (fr) * 1995-08-21 1997-02-27 Imperial Chemical Industries Plc Particules de polyisocyanate de dimension et de repartition granulometriques controlees

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198947, Derwent World Patents Index; Class A41, AN 1989-346361, XP002002062 *

Also Published As

Publication number Publication date
AU2001272515A1 (en) 2002-02-05

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