WO1997007092A1 - Particules de polyisocyanate de dimension et de repartition granulometriques controlees - Google Patents

Particules de polyisocyanate de dimension et de repartition granulometriques controlees Download PDF

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Publication number
WO1997007092A1
WO1997007092A1 PCT/EP1996/003567 EP9603567W WO9707092A1 WO 1997007092 A1 WO1997007092 A1 WO 1997007092A1 EP 9603567 W EP9603567 W EP 9603567W WO 9707092 A1 WO9707092 A1 WO 9707092A1
Authority
WO
WIPO (PCT)
Prior art keywords
particle size
particles
polyisocyanate
particles according
mdi
Prior art date
Application number
PCT/EP1996/003567
Other languages
English (en)
Inventor
Raymond Oliver
Robert James Munro
Mark Lewis Middleton
Joseph Youngblood Stuart
Arend Jan Zeeuw
Original Assignee
Imperial Chemical Industries Plc
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 Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to NZ316485A priority Critical patent/NZ316485A/xx
Priority to MX9801357A priority patent/MX9801357A/es
Priority to EA199800216A priority patent/EA199800216A1/ru
Priority to BR9610226A priority patent/BR9610226A/pt
Priority to PL96325119A priority patent/PL325119A1/xx
Priority to JP9508932A priority patent/JPH11512082A/ja
Priority to AU68727/96A priority patent/AU710055B2/en
Priority to EP96929244A priority patent/EP0846102A1/fr
Publication of WO1997007092A1 publication Critical patent/WO1997007092A1/fr
Priority to NO19980735A priority patent/NO310143B1/no

Links

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

Definitions

  • the present invention relates to 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- 1,5 -diisocyanate (NDI), 1,6-hexamethylene diisocyanate (HDI), p-phenylenediisocyanate (PPDI), trans-cyclohexane-l,4-d ⁇ socyanate (CHDI), isophorone diisocyanate (IPDI) and tetramethylxylene diisocyanates (TMXDI).
  • TDI tolylene diisocyanates
  • MDI diphenylmethane diisocyanates
  • NDI naphthalene- 1,5 -diisocyanate
  • HDI 1,6-hexamethylene diisocyanate
  • One ofthe most important polyisocyanates is MDI.
  • 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.
  • polyisocyanates for example 4,4'-diphenylmethane diisocyanate
  • 4'-diphenylmethane diisocyanate 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 they generate dust.
  • solid polyisocyanate particles can be produced which have a controlled particle size and particle size distribution, and which are chemically virtually identical to the starting material of which they are made.
  • the present invention thus concerns solid polyisocyanate particles having a particle size distribution index of less than 1.5.
  • the particles are substantially free of induced impurities.
  • the term 'induced impurities' includes all reaction products formed through the reaction of isocyanate-groups with isocyanate-reactive groups during the conversion ofthe 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.
  • PSDI particle size distribution index
  • w is the weight ofthe particles with mean diameter D h and the number average particle size being
  • diameter is intended to include the main cross dimension of a particle.
  • Preferred polyisocyanate particles have a PSDI of less than 1.3. Most preferably the PSDI is not more than 1 J .
  • the polyisocyanate particles ofthe present invention may have any shape, but are preferably spheroidal, and most preferably spherical.
  • 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- 1,4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate and p- xylylene-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.
  • '"pure" MD ⁇ 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 dimerize. It is a particular advantage of this invention that “pure MDI” particles according to the invention do not contain any induced dimer groups.
  • the polyisocyanate particles ofthe present invention generally have a diameter of from OJ to 5 mm.
  • the preferred size largely depends on the application of the solid polyisocyanate particles. For most applications a particle size of from 1 to 2.5 mm is preferred, 1.0 to 1.5 mm being even more preferred. Particles having a larger size tend to form 'pop-corns' and are less preferred.
  • the invention also relates to a method for the production of said polyisocyanate particles which comprises subjecting molten polyisocyanates to a , preferably vibrated, prilling treatment.
  • Prilling operations are known from the production of o.a. fertilizers and are described in, for example, EP-A 320.153. Further details on the prilling process can be found in e.g. EP-A 542545, EP-A 569162, EP-A 569163 and EP-A 570119, which are inco ⁇ orated herein by reference.
  • a molten material is caused to flow through at least one nozzle, which is optionally vibrated, to form drops ofthe material which are cooled in a cooling medium to give solid spheres or prills ofthe material.
  • the cooling generally takes place in a tower where the drops fall down in a counter-current flow ofa gas.
  • a plurality of nozzles is used and the size ofthe drops largely depends upon the size and type ofthe nozzles, the nature ofthe material being prilled and the rate of flow of material through the nozzles.
  • the cooling medium is preferably not isocyanate-reactive and may be any inert gas.
  • a preferred gas is nitrogen.
  • the choice of a suitable cooling medium and the cooling temperature depend on the characteristics of the polyisocyanate starting material. For example, in the production of particles from pure MDI a temperature of -20 to -25 °C is preferably employed.
  • the prilled products Compared to other bulk particulate products the prilled products have a very narrow size distribution.
  • the prilling treatment does generally 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.
  • Weight average particle size 1.215 mm
  • Number average particle size 1.11 mm
  • PSDI I.: Table III: Hole size: 520 microns (vibrated)
  • Weight average particle size 1.1 mm
  • Number average particle size 1 04 mm
  • PSDI 1.058 Table IV: Hole size: 1040 microns (vibrated)
  • Weight average particle size 1.92 mm
  • Number average particle size 1.8 mm
  • Flowability ofa range of prilled pure MDI batches was measured by weighing 250 g of frozen prills and pouring it through a funnel into a cylinder of 42 mm diameter.
  • the average flow given in the tables V and VI is the average rate of 4 timed flows of batches of frozen particles.
  • Target Prill Size 1.25 mm % Prill at Target Size Average Flow ⁇ g/secj
  • Table VI shows that for a given particle size the flowability increases with decreasing particle size distribution (the higher the % prill at target size the narrower the particle size distribution).
  • a higher flowability enables quicker and easier drum filling and emptying operations.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Paper (AREA)

Abstract

Particules solides de polyisocyanate présentant un indice de répartition granulométrique inférieur à 1,5, de préférence sensiblement dépourvues d'impuretés induites. Est également décrit un procédé de préparation de ces particules par grelonage.
PCT/EP1996/003567 1995-08-21 1996-08-13 Particules de polyisocyanate de dimension et de repartition granulometriques controlees WO1997007092A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
NZ316485A NZ316485A (en) 1995-08-21 1996-08-13 Polyisocyanate particles of controlled particle size and particle size distribution
MX9801357A MX9801357A (es) 1995-08-21 1996-08-13 Particulas de poliisocianato de tamaño de particula y distribucion de tamaño de particula controlados.
EA199800216A EA199800216A1 (ru) 1995-08-21 1996-08-13 Полиизоцианатные частицы регулируемого размера и распределения частиц по размеру
BR9610226A BR9610226A (pt) 1995-08-21 1996-08-13 Partículas de polisocianato de tamanho de partícula e distribuição de tamanho de partícula controlados
PL96325119A PL325119A1 (en) 1995-08-21 1996-08-13 Polyisocyanate particles of controllable particle size and controllable distribution of dimensions
JP9508932A JPH11512082A (ja) 1995-08-21 1996-08-13 調節された粒子寸法および粒子寸法分布を有するポリイソシアネート粒子
AU68727/96A AU710055B2 (en) 1995-08-21 1996-08-13 Polyisocyanate particles of controlled particle size and particle size distribution
EP96929244A EP0846102A1 (fr) 1995-08-21 1996-08-13 Particules de polyisocyanate de dimension et de repartition granulometriques controlees
NO19980735A NO310143B1 (no) 1995-08-21 1998-02-20 Fremgangsmåte for fremstilling av polyisocyanatpartikler med regulert partikkelstörrelse og partikkelstörrelsesfordeling, samtanvendelse av de oppnådde partiklene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP95113155.6 1995-08-21
EP95113155 1995-08-21

Publications (1)

Publication Number Publication Date
WO1997007092A1 true WO1997007092A1 (fr) 1997-02-27

Family

ID=8219546

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/003567 WO1997007092A1 (fr) 1995-08-21 1996-08-13 Particules de polyisocyanate de dimension et de repartition granulometriques controlees

Country Status (19)

Country Link
EP (1) EP0846102A1 (fr)
JP (1) JPH11512082A (fr)
KR (1) KR19990044037A (fr)
CN (1) CN1077100C (fr)
AR (1) AR003317A1 (fr)
AU (1) AU710055B2 (fr)
BR (1) BR9610226A (fr)
CA (1) CA2227771A1 (fr)
CO (1) CO4560469A1 (fr)
EA (1) EA199800216A1 (fr)
HU (1) HU218736B (fr)
MX (1) MX9801357A (fr)
NO (1) NO310143B1 (fr)
NZ (1) NZ316485A (fr)
PL (1) PL325119A1 (fr)
TR (1) TR199800289T1 (fr)
TW (1) TW412552B (fr)
WO (1) WO1997007092A1 (fr)
ZA (1) ZA967039B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002008173A1 (fr) * 2000-07-20 2002-01-31 Huntsman International Llc Particules de polyisocyanate d'une taille controlee
CN112851904A (zh) * 2019-11-28 2021-05-28 科思创知识产权两合公司 包含固体二异氰酸酯的散料和可由其获得的含氨基甲酸酯基团的预聚物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101236150B (zh) 2007-02-02 2012-09-05 深圳迈瑞生物医疗电子股份有限公司 用于基于流式细胞术的仪器的光电传感器及其照射单元

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1456411A1 (ru) * 1986-12-03 1989-02-07 Предприятие П/Я Г-4302 Способ получени твердого дифенилметан-4,4 @ -диизоцианата
EP0320153A1 (fr) * 1987-12-07 1989-06-14 Imperial Chemical Industries Plc Division controlée de jets de liquide
DD297776A5 (de) * 1988-12-21 1992-01-23 Basf Schwarzheide Gmbh,De Vorrichtung zur strahlenfoermigen zerteilung von geschmolzenen 4,4 diphenylmethandiisocyanat
DD299528A5 (de) * 1988-12-21 1992-04-23 Basf-Schwarzheide Gmbh,De Verfahren zur konditionierung von 4,4-diphenylmethandiisocyanat

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1456411A1 (ru) * 1986-12-03 1989-02-07 Предприятие П/Я Г-4302 Способ получени твердого дифенилметан-4,4 @ -диизоцианата
EP0320153A1 (fr) * 1987-12-07 1989-06-14 Imperial Chemical Industries Plc Division controlée de jets de liquide
DD297776A5 (de) * 1988-12-21 1992-01-23 Basf Schwarzheide Gmbh,De Vorrichtung zur strahlenfoermigen zerteilung von geschmolzenen 4,4 diphenylmethandiisocyanat
DD299528A5 (de) * 1988-12-21 1992-04-23 Basf-Schwarzheide Gmbh,De Verfahren zur konditionierung von 4,4-diphenylmethandiisocyanat

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8947, Derwent World Patents Index; Class A41, AN 89-346361, XP002002062 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002008173A1 (fr) * 2000-07-20 2002-01-31 Huntsman International Llc Particules de polyisocyanate d'une taille controlee
CN112851904A (zh) * 2019-11-28 2021-05-28 科思创知识产权两合公司 包含固体二异氰酸酯的散料和可由其获得的含氨基甲酸酯基团的预聚物
US20210163658A1 (en) * 2019-11-28 2021-06-03 Covestro Intellectual Property Gmbh & Co. Kg Bulk material comprising solid diisocyanates and prepolymers containing urethane groups obtainable therefrom
US11795260B2 (en) * 2019-11-28 2023-10-24 Covestro Intellectual Property Gmbh & Co. Kg Bulk material comprising solid diisocyanates and prepolymers containing urethane groups obtainable therefrom

Also Published As

Publication number Publication date
KR19990044037A (ko) 1999-06-25
MX9801357A (es) 1998-04-30
HU218736B (hu) 2000-11-28
AU710055B2 (en) 1999-09-09
HUP9802378A3 (en) 1999-03-29
TR199800289T1 (xx) 1998-05-21
ZA967039B (en) 1997-02-21
NO980735D0 (no) 1998-02-20
AR003317A1 (es) 1998-07-08
EP0846102A1 (fr) 1998-06-10
NO980735L (no) 1998-02-20
JPH11512082A (ja) 1999-10-19
CN1077100C (zh) 2002-01-02
EA199800216A1 (ru) 1998-08-27
NZ316485A (en) 1999-05-28
CN1200111A (zh) 1998-11-25
TW412552B (en) 2000-11-21
CA2227771A1 (fr) 1997-02-27
PL325119A1 (en) 1998-07-06
AU6872796A (en) 1997-03-12
CO4560469A1 (es) 1998-02-10
NO310143B1 (no) 2001-05-28
BR9610226A (pt) 1999-06-29
HUP9802378A2 (hu) 1999-02-01

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