NO310143B1 - Process for Preparation of Controlled Particle Size and Particle Size Distribution of Polyisocyanate Particles, Using the Particles Obtained - Google Patents
Process for Preparation of Controlled Particle Size and Particle Size Distribution of Polyisocyanate Particles, Using the Particles Obtained Download PDFInfo
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- NO310143B1 NO310143B1 NO19980735A NO980735A NO310143B1 NO 310143 B1 NO310143 B1 NO 310143B1 NO 19980735 A NO19980735 A NO 19980735A NO 980735 A NO980735 A NO 980735A NO 310143 B1 NO310143 B1 NO 310143B1
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- polyisocyanate
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- diisocyanate
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- 239000002245 particle Substances 0.000 title claims description 46
- 239000005056 polyisocyanate Substances 0.000 title claims description 39
- 229920001228 polyisocyanate Polymers 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 20
- 238000009826 distribution Methods 0.000 title claims description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002826 coolant Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000007858 starting material Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical class O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical class N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 241000482268 Zea mays subsp. mays Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
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)
Description
Foreliggende oppfinnelse angår en fremgangsmåte for fremstilling av faste partikler av polyisocyanat, spesielt diisocyanater, og mer spesielt difenylmetan-diisocyanater (MDI), samt anvendelse av samme. The present invention relates to a method for producing solid particles of polyisocyanate, in particular diisocyanates, and more particularly diphenylmethane diisocyanates (MDI), as well as the use of the same.
Polyisocyanater er velkjent innenfor fagområdet, og anvendes i stor ut-strekning som råmaterialer, eksempelvis i fremstilling av polyuretaner. Polyisocyanates are well known in the field, and are used to a large extent as raw materials, for example in the production of polyurethanes.
Polyisocyanater dekker et stort område av organiske fobindelser med to eller flere isocyanatgrupper. Slike forbindelser kan omfatte aromatiske og/eller alifatiske grupper. Eksempler på polyisocyanater som finner vid anvendelse omfatter tolylen-diisocyanater (TDI), difenylmetan-diisocyanater (MDI), naftalen-1,5-diisocyanat (NDI), 1,6-heksametylen-diisocyanat (HDI), p-fenylen-diisocyanat (PPDI), trans-cykloheksan-1,4-diisocyanat (CHDI), isoforon-diisocyanat (IPDI) og tetrametylxylen-diisocyanater (TMXDI). Polyisocyanates cover a large range of organic compounds with two or more isocyanate groups. Such compounds may comprise aromatic and/or aliphatic groups. Examples of widely used polyisocyanates include tolylene diisocyanates (TDI), diphenylmethane diisocyanates (MDI), naphthalene-1,5-diisocyanate (NDI), 1,6-hexamethylene diisocyanate (HDI), p-phenylene diisocyanate ( PPDI), trans-cyclohexane-1,4-diisocyanate (CHDI), isophorone diisocyanate (IPDI) and tetramethylxylene diisocyanates (TMXDI).
Ett av de viktigste polyisocyanater er MDI. One of the most important polyisocyanates is MDI.
Fqt å oppnå tilfredsstillende lagringsstabilitet og viderebearbeiding, håndte-rings- og reaksjonsegenskaper, er det gjennomført modifikasjoner på isocyanat-typene. In order to achieve satisfactory storage stability and further processing, handling and reaction properties, modifications have been made to the isocyanate types.
Modifiserte former av polyisocyanater er hovedsakelig flytendegjorte produkter, så som dimeriserte eller trimeriserte former av polyisocyanater, eller reaksjonsprodukter av polyisocyanater med forbindelser som inneholder isocyanatreaktive grupper. Modified forms of polyisocyanates are mainly liquefied products, such as dimerized or trimerized forms of polyisocyanates, or reaction products of polyisocyanates with compounds containing isocyanate-reactive groups.
Enkelte polyisocyanater, f.eks. 4,4-difenylmetan-diisocyanat, er allerede tilgjengelige i form av flak, men disse skaper problemer sett fra et helsemessig synspunkt og fra et sikkerhetssynspunkt ettersom de genererer støv. Certain polyisocyanates, e.g. 4,4-diphenylmethane diisocyanate, are already available in the form of flakes, but these create problems from a health point of view and from a safety point of view as they generate dust.
Også kjent er anvendelsen av findelte, faste polyisocyanater, f.eks. MDI-pulvere, spesielt i bindemidler eller adhesiver (se f.eks. US-A-4 569 982). Disse pulvere fremstilles ved at en flytende strøm atomiseres. Dråpene har således en bred partikkelstørrelsesfordeling, dvs. at de er polydisperse og har en tendens til å klumpe seg sammen. Resultatet er at slike pulvere vanligvis har en diameter på i hovedsak mindre enn 1 mm, har en uregelmessig form og en vid størrelsesforde-ling. Also known is the use of finely divided, solid polyisocyanates, e.g. MDI powders, especially in binders or adhesives (see, eg, US-A-4,569,982). These powders are produced by atomizing a liquid stream. The drops thus have a broad particle size distribution, i.e. they are polydisperse and tend to clump together. The result is that such powders usually have a diameter of essentially less than 1 mm, have an irregular shape and a wide size distribution.
I SU-A 1 456 411 beskrives en fremgangsmåte for fremstilling av faste sfæriske granuler av 4,4'-MDI ved at smeltet produkt helles dråpevist i vann og avkjø-les, hvoretter dråpene blir faste og danner faste granuler. SU-A 1 456 411 describes a method for producing solid spherical granules of 4,4'-MDI by pouring the molten product drop by drop into water and cooling, after which the drops become solid and form solid granules.
Fremgangsmåten resulterer imidlertid i dannelse av ureagrupper på grunn av reaksjonen med vann og tilstedeværelsen av betydelige mengder 4,4'-MDI-dimerer, som er skadelige med hensyn til produktkvaliteten. However, the process results in the formation of urea groups due to the reaction with water and the presence of significant amounts of 4,4'-MDI dimers, which are detrimental to product quality.
Det har nå blitt funnet at det kan fremstilles faste polyisocyanatpartikler som har en regulert partikkelstørrelse og partikkelstørrelsesfordeling, og som kjemisk sett er praktisk talt identisk med utgangsmaterialet som de er laget av. It has now been found that solid polyisocyanate particles can be produced which have a controlled particle size and particle size distribution, and which are chemically practically identical to the starting material from which they are made.
Spesielt er strømbarheten for slike partikler mye bedre, noe som tillater lettere og hurtigere håndtering i lagrings- og transportsammenheng. Støvgenere-ring av disse partikler er dessuten betydelig redusert og er under akseptabelt nivå. In particular, the flowability of such particles is much better, which allows easier and faster handling in the context of storage and transport. Dust generation by these particles is also significantly reduced and is below an acceptable level.
Foreliggende oppfinnelse angår følgelig en fremgangsmåte for fremstilling av polyisocyanatpartikler som har en partikkelstørrelsesfordelingsindeks på mindre enn 1,5 som er i det vesentlige frie for innførte urenheter, kjennetegnet ved at den omfatter at minst ett smeltet polyisocyanat underkastes en prillingsbehandling, hvor det smeltede polyisocyanatet bringes til å strømme gjennom minst én dyse for å danne dråper som avkjøles i et kjølemedium som ikke er isocyanatreaktivt. The present invention therefore relates to a method for the production of polyisocyanate particles which have a particle size distribution index of less than 1.5 which are essentially free of introduced impurities, characterized in that it comprises subjecting at least one molten polyisocyanate to a prilling treatment, where the molten polyisocyanate is brought to to flow through at least one nozzle to form droplets which are cooled in a coolant which is not isocyanate reactive.
Betegnelsen "innførte urenheter" omfatter alle reaksjonsprodukter dannet under reaksjonen av isocyanatgruppene med isocyanatreaktive grupper under omdannelse av polyisocyanatutgangsmaterialet til partikler som ikke var til stede i utgangsmaterialet. The term "introduced impurities" includes all reaction products formed during the reaction of the isocyanate groups with isocyanate-reactive groups during conversion of the polyisocyanate starting material into particles that were not present in the starting material.
Slike reaksjonsprodukter kan være uretaner, allofanater, urea-typer, biure-ter, amider, karbodiimider eller uretoniminer, eller dimerer eller trimerer av isocya-nater. Such reaction products can be urethanes, allophanates, urea types, biurets, amides, carbodiimides or uretonimines, or dimers or trimers of isocyanates.
Partikkelstørrelses-fordelingsindeksen (PSDI) er forholdet mellom den vektmidlere partikkelstørrelse og den antallsmidlere partikkelstørrelse, idet den vektmidlere partikkelstørrelse er The particle size distribution index (PSDI) is the ratio between the weight average particle size and the number average particle size, the weight average particle size being
hvor w-\ er vekten av partikler med midlere diameter Dj, og den antallsmidlere partikkelstørrelse er where w-\ is the weight of particles with average diameter Dj, and the number average particle size is
hvor ni er antall partikler med midlere diameter Dj. where nine is the number of particles with average diameter Dj.
Betegnelsen diameter slik den anvendes her, er ment å omfatte hoved-tverrsnittet av en partikkel. The term diameter as used here is intended to include the main cross-section of a particle.
Fortrinnsvis har polyisocyanatpartikler en PSDI på mindre enn 1,3. Mest foretrukket er PSDI ikke mer enn 1,1. Preferably, polyisocyanate particles have a PSDI of less than 1.3. Most preferably, the PSDI is no more than 1.1.
Polyisocyanatpartiklene fremstilt ifølge foreliggende oppfinnelse kan ha hvilken som helst form, men er fortrinnsvis sfæroidale, og mest foretrukket sfæriske. The polyisocyanate particles produced according to the present invention can have any shape, but are preferably spheroidal, and most preferably spherical.
Polyisocyanatpartikler fremstilt i henhold til oppfinnelsen kan være én eller flere typer av polyisocyanater, fortrinnsvis én eller en blanding av beslektede typer, f.eks. oligomerer, spesielt én type, og kan oppnås fra hvilket som helst organisk polyisocyanat. Polyisocyanate particles produced according to the invention can be one or more types of polyisocyanates, preferably one or a mixture of related types, e.g. oligomers, particularly one type, and can be obtained from any organic polyisocyanate.
Anvendbare polyisocyanater kan være alifatiske, cykloalifatiske, aralifatiske, heterocykliske eller aromatiske. Useful polyisocyanates can be aliphatic, cycloaliphatic, araliphatic, heterocyclic or aromatic.
Egnede polyisocyanater omfatter f.eks. heksametylen-diisocyanat, isoforon-diisocyanat, cykloheksan-1,4-diisocyanat, dicykloheksylmetan-4,4-diisocyanat og p-xylylen-diisocyanat. Suitable polyisocyanates include e.g. hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate and p-xylylene diisocyanate.
Foretrukne polyisocyanater er aromatisks polyisocyanater, f.eks. fenylen-diisocyanater, tolylen-diisocyanatér, 1,5-naftylen-diisocyanat og spesielt difenylmetan-diisocyanat (MDI)-baserte polyisocyanater så som 4,4-MDI, 2,4'-MDI eller blandinger derav og polymere MDI med en isocyanatfunksjonalitet på mer enn 2. Preferred polyisocyanates are aromatic polyisocyanates, e.g. phenylene diisocyanates, tolylene diisocyanates, 1,5-naphthylene diisocyanate and especially diphenylmethane diisocyanate (MDI)-based polyisocyanates such as 4,4-MDI, 2,4'-MDI or mixtures thereof and polymeric MDI with an isocyanate functionality of more than 2.
En type polyisocyanater som har blitt funnet å være spesielt nyttig, er "rent" One type of polyisocyanate that has been found to be particularly useful is "pure"
MDI. MDI.
Betegnelsen '"rent" MDI' er ment å inkludere polyisocyanat-blandinger som omfatter minst 85 vekt%, fortrinnsvis minst 95 vekt% og mest foretrukket minst 99 vekt% 4,4'-MDI. The term "pure" MDI is intended to include polyisocyanate mixtures comprising at least 85% by weight, preferably at least 95% by weight and most preferably at least 99% by weight of 4,4'-MDI.
Generelt viser "rent MDI" en sterk tendens til å dimerisere. Det er spesielt fordelaktig for denne oppfinnelse at "rene MDI"-partikler i henhold til oppfinnelsen ikke inneholder noen innførte dimergrupper. In general, "pure MDI" shows a strong tendency to dimerize. It is particularly advantageous for this invention that "pure MDI" particles according to the invention do not contain any introduced dimer groups.
Polyisocyanatpartikler fremstilt ifølge foreliggende oppfinnelse har generelt en diameter på fra 0,1 til 5 mm. Den foretrukne størrelse avhenger i stor grad av hva de faste polyisocyanatpartikler skal anvendes til. For de fleste anvendelser er en partikkelstørrelse fra 1 til 2,5 mm foretrukket. Enda mer foretrukket er 1,0 til 1,5 mm. Partikler med en større størrelse har tilbøyelighet til å danne "pop-corn" og er mindre å foretrekke. Polyisocyanate particles produced according to the present invention generally have a diameter of from 0.1 to 5 mm. The preferred size largely depends on what the solid polyisocyanate particles are to be used for. For most applications, a particle size of 1 to 2.5 mm is preferred. Even more preferred is 1.0 to 1.5 mm. Particles of a larger size have a tendency to form "pop-corn" and are less preferred.
Det å anvende prilling er kjent fra fremstilling av fremfor alt gjødselproduk-ter, og beskrives f.eks. i EP-A-320 153. Ytterligere detaljer når det gjelder prilleprosessen er å finne i f.eks. EP-A-542 545, EP-A-569 162, EP-A-569 163 og EP-A-570 119. The use of prilling is known from the production of above all fertilizer products, and is described e.g. in EP-A-320 153. Further details regarding the priming process can be found in e.g. EP-A-542 545, EP-A-569 162, EP-A-569 163 and EP-A-570 119.
I prilleoperasjonen får man et smeltet materiale til å strømme gjennom minst én dyse, som eventuelt vibreres, for å danne dråper av materialet, som avkjøles i et kjølemedium slik at det dannes faste sfærer eller priller av materialet. In the beading operation, a molten material is caused to flow through at least one nozzle, which may be vibrated, to form droplets of the material, which are cooled in a cooling medium so that solid spheres or beads of the material are formed.
Avkjølingen finner vanligvis sted i et tårn hvor dråpene faller ned i en mot-strøms strøm av en gass. Det anvendes vanligvis flere dyser, og størrelsen på dråpene avhenger for det meste av størrelsen og typen av dysene, arten av materialet som prilles og strømningshastigheten for materialet gjennom dysene. The cooling usually takes place in a tower where the droplets fall in a counter-current flow of a gas. Several nozzles are usually used, and the size of the droplets depends mostly on the size and type of the nozzles, the nature of the material being prilled and the flow rate of the material through the nozzles.
Avkjølingsmediet er fortrinnsvis ikke isocyanat-reaktivt, og kan være enhver inert gass. En foretrukket gass er nitrogen. Valget av egnet kjølemedium og avkjø-lingstemperatur avhenger av karakteristikkene for polyisocyanat-utgangsmaterialet. I fremstillingen av partikler fra rent MDI anvendes eksempelvis fortrinnsvis en temperatur på -20°C til -25 °C. The cooling medium is preferably not isocyanate-reactive, and can be any inert gas. A preferred gas is nitrogen. The choice of a suitable cooling medium and cooling temperature depends on the characteristics of the polyisocyanate starting material. In the production of particles from pure MDI, for example, a temperature of -20°C to -25°C is preferably used.
Sammenlignet med andre volumprodukter i partikkelform har de prillede produkter en svært smal størrelsesfordeling. Compared to other volume products in particle form, the prilled products have a very narrow size distribution.
Selv om prillebehandlingen generelt ikke har en skadelig effekt på produktkvaliteten, kan vanlige additiver, så som stabilisatorer, anti-oksydanter eller pig-menter, tilsettes for å forbedre slike egenskaper som lagrings- og farvestabilitet eller oksydasjonsmotstand. Although the pilling treatment generally does not have a detrimental effect on product quality, common additives, such as stabilizers, anti-oxidants or pigments, may be added to improve such properties as storage and color stability or oxidation resistance.
Polyisocyanatpartiklene ifølge foreliggende oppfinnelse kan med fordel anvendes ved fremstilling av polyisocyanat-polyaddisjonsprodukter, så som skum-typer, elastomerer, belegg, adhesiver, forseglingsmidler, innkapslingsmidler og bindemidler. The polyisocyanate particles according to the present invention can be advantageously used in the production of polyisocyanate-polyaddition products, such as foam types, elastomers, coatings, adhesives, sealing agents, encapsulating agents and binders.
EKSEMPLER EXAMPLES
Eksempler 1-4 Examples 1-4
Fire satser priller av rent MDI ble fremstilt i et pilot-skala-prilletåm ved hjelp av fremgangsmåten beskrevet i EP-A-320 153, men her modifisert for å oppfylle kravene for 4,4-MDI-fremstilling. Tilførselshastigheten for smeiten var 25 kg/time, og avkjølingsmediet var flytende nitrogen. Det ble anvendt maksimalt en 6-hulls plate. Four batches of prills of pure MDI were prepared in a pilot-scale prillet plant using the method described in EP-A-320 153, but here modified to meet the requirements for 4,4-MDI production. The feed rate for the smelt was 25 kg/hour, and the cooling medium was liquid nitrogen. A maximum of one 6-hole plate was used.
En prøve ble tatt fra hver sats, og PSDI ble beregnet. Resultatene er vist i tabeller l-IV. A sample was taken from each batch and the PSDI was calculated. The results are shown in Tables 1-IV.
Eksempler 5-6 Examples 5-6
Strømbarheten for en rekke prillede satser av rent MDI ble målt ved å veie opp 250 g frosne priller og helle disse gjennom en trakt inn i en sylinder med 42 mm diameter. Gjennomsnittlig strømning angitt i tabeller V og VI er gjennomsnitts-hastigheten på 4 ganger strømning av satser av frosne partikler. The flowability of a number of prilled batches of pure MDI was measured by weighing out 250 g of frozen prills and pouring these through a funnel into a 42 mm diameter cylinder. The average flow given in Tables V and VI is the average rate of 4 times the flow of batches of frozen particles.
Som det kan sees i ovenstående tabell V, så øker strømbarheten vesentlig med mindre partikkelstørrelse. As can be seen in the above table V, flowability increases significantly with smaller particle size.
Tabell VI viser at for en gitt partikkelstørrelse så øker strømbarheten med minskende partikkelstørrelsesfordeling (desto høyere prosent prill med målgitt størrelse, jo smalere partikkelstørrelsesfordeling). Table VI shows that for a given particle size, the flowability increases with decreasing particle size distribution (the higher the percentage prill with the target size, the narrower the particle size distribution).
En høyere strømbarhet gjør fylling og tømming av fat lettere og hurtigere. A higher flowability makes filling and emptying barrels easier and faster.
Eksempel 7 Example 7
Det ble gjennomført en kjemisk analyse for en sats av priller av rent MDI og en sats av flytende utgangsmateriale av rent MDI for å vise at prilleprosessen ikke endrer MDI-utgangsmaterialet kjemisk. A chemical analysis was carried out for a batch of pure MDI prills and a batch of pure MDI liquid feedstock to show that the prilling process does not chemically alter the MDI feedstock.
Den kjemiske analyse viser liten eller ingen forskjell mellom priller av rent MDI og det flytende MDI-utgangsmateriale. Prilleprosessen endrer således ikke MDI-utgangsmaterialet kjemisk. The chemical analysis shows little or no difference between pellets of pure MDI and the liquid MDI starting material. The prilling process thus does not chemically change the MDI starting material.
Gasskromatogrammene som man fikk av prillene og det flytende MDI viste seg å være identiske, noe som indikerer at prillingsprosessen ikke fører inn ytterligere urenheter i utgangsmaterialet. The gas chromatograms obtained from the prills and the liquid MDI were found to be identical, indicating that the prilling process does not introduce additional impurities into the starting material.
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Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95113155 | 1995-08-21 | ||
| PCT/EP1996/003567 WO1997007092A1 (en) | 1995-08-21 | 1996-08-13 | Polyisocyanate particles of controlled particle size and particle size distribution |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO980735L NO980735L (en) | 1998-02-20 |
| NO980735D0 NO980735D0 (en) | 1998-02-20 |
| NO310143B1 true NO310143B1 (en) | 2001-05-28 |
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| NO19980735A NO310143B1 (en) | 1995-08-21 | 1998-02-20 | Process for Preparation of Controlled Particle Size and Particle Size Distribution of Polyisocyanate Particles, Using the Particles Obtained |
Country Status (19)
| Country | Link |
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| EP (1) | EP0846102A1 (en) |
| JP (1) | JPH11512082A (en) |
| KR (1) | KR19990044037A (en) |
| CN (1) | CN1077100C (en) |
| AR (1) | AR003317A1 (en) |
| AU (1) | AU710055B2 (en) |
| BR (1) | BR9610226A (en) |
| CA (1) | CA2227771A1 (en) |
| CO (1) | CO4560469A1 (en) |
| EA (1) | EA199800216A1 (en) |
| HU (1) | HU218736B (en) |
| MX (1) | MX9801357A (en) |
| NO (1) | NO310143B1 (en) |
| NZ (1) | NZ316485A (en) |
| PL (1) | PL325119A1 (en) |
| TR (1) | TR199800289T1 (en) |
| TW (1) | TW412552B (en) |
| WO (1) | WO1997007092A1 (en) |
| ZA (1) | ZA967039B (en) |
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| AU2001272515A1 (en) * | 2000-07-20 | 2002-02-05 | Huntsman International, Llc | Polyisocyanate particles of controlled particle size |
| CN101236150B (en) | 2007-02-02 | 2012-09-05 | 深圳迈瑞生物医疗电子股份有限公司 | Stream type cell technique instrument opto-electronic sensor and its irradiation unit |
| EP3828213A1 (en) * | 2019-11-28 | 2021-06-02 | Covestro Deutschland AG | Bulk material containing solid diisocyanates and urethane group-containing prepolymers obtainable therefrom |
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| SU1456411A1 (en) * | 1986-12-03 | 1989-02-07 | Предприятие П/Я Г-4302 | Method of producing hard diphenylmethane-4,4ъ-diisocyanate |
| GB8728564D0 (en) * | 1987-12-07 | 1988-01-13 | Ici Plc | Controlled break-up of liquid jets |
| DD299528A5 (en) * | 1988-12-21 | 1992-04-23 | Basf-Schwarzheide Gmbh,De | METHOD FOR CONDITIONING 4,4-DIPHENYL METHANDIISOCYANATE |
| DD297776A5 (en) * | 1988-12-21 | 1992-01-23 | Basf Schwarzheide Gmbh,De | DEVICE FOR IRRADIATED DISPERSION OF MELTED 4,4-DIPHENYL METHANDIISOCYANATE |
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1996
- 1996-08-13 HU HU9802378A patent/HU218736B/en not_active IP Right Cessation
- 1996-08-13 EA EA199800216A patent/EA199800216A1/en unknown
- 1996-08-13 PL PL96325119A patent/PL325119A1/en unknown
- 1996-08-13 MX MX9801357A patent/MX9801357A/en unknown
- 1996-08-13 TR TR1998/00289T patent/TR199800289T1/en unknown
- 1996-08-13 EP EP96929244A patent/EP0846102A1/en not_active Ceased
- 1996-08-13 KR KR1019980701269A patent/KR19990044037A/en not_active Application Discontinuation
- 1996-08-13 NZ NZ316485A patent/NZ316485A/en unknown
- 1996-08-13 JP JP9508932A patent/JPH11512082A/en not_active Ceased
- 1996-08-13 WO PCT/EP1996/003567 patent/WO1997007092A1/en not_active Application Discontinuation
- 1996-08-13 CN CN96197745A patent/CN1077100C/en not_active Expired - Fee Related
- 1996-08-13 CA CA002227771A patent/CA2227771A1/en not_active Abandoned
- 1996-08-13 AU AU68727/96A patent/AU710055B2/en not_active Ceased
- 1996-08-13 BR BR9610226A patent/BR9610226A/en not_active Application Discontinuation
- 1996-08-19 ZA ZA9607039A patent/ZA967039B/en unknown
- 1996-08-20 CO CO96044000A patent/CO4560469A1/en unknown
- 1996-08-21 AR ARP960104063A patent/AR003317A1/en not_active Application Discontinuation
- 1996-10-16 TW TW085112617A patent/TW412552B/en not_active IP Right Cessation
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Also Published As
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| ZA967039B (en) | 1997-02-21 |
| MX9801357A (en) | 1998-04-30 |
| PL325119A1 (en) | 1998-07-06 |
| CO4560469A1 (en) | 1998-02-10 |
| EA199800216A1 (en) | 1998-08-27 |
| HUP9802378A2 (en) | 1999-02-01 |
| AU6872796A (en) | 1997-03-12 |
| TR199800289T1 (en) | 1998-05-21 |
| NO980735L (en) | 1998-02-20 |
| CN1077100C (en) | 2002-01-02 |
| TW412552B (en) | 2000-11-21 |
| BR9610226A (en) | 1999-06-29 |
| NZ316485A (en) | 1999-05-28 |
| EP0846102A1 (en) | 1998-06-10 |
| HUP9802378A3 (en) | 1999-03-29 |
| HU218736B (en) | 2000-11-28 |
| KR19990044037A (en) | 1999-06-25 |
| CN1200111A (en) | 1998-11-25 |
| JPH11512082A (en) | 1999-10-19 |
| AU710055B2 (en) | 1999-09-09 |
| AR003317A1 (en) | 1998-07-08 |
| NO980735D0 (en) | 1998-02-20 |
| WO1997007092A1 (en) | 1997-02-27 |
| CA2227771A1 (en) | 1997-02-27 |
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