PT87571B - PROCESS FOR THE PREPARATION OF RIGID POLYMERIC FOAMS DERIVED FROM POLY-ISOCYANATE COMPOSITIONS OF POLYPHENYLENE POLYMETHYLENE - Google Patents

PROCESS FOR THE PREPARATION OF RIGID POLYMERIC FOAMS DERIVED FROM POLY-ISOCYANATE COMPOSITIONS OF POLYPHENYLENE POLYMETHYLENE Download PDF

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PT87571B
PT87571B PT87571A PT8757188A PT87571B PT 87571 B PT87571 B PT 87571B PT 87571 A PT87571 A PT 87571A PT 8757188 A PT8757188 A PT 8757188A PT 87571 B PT87571 B PT 87571B
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PT87571A (en
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Berend Eling
Q Dueber
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Ici Plc
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    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal 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
    • C08G18/70—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

A method is claimed for prepn. of rigid foams comprising reacting under foam forming conditions: a) a polymethylene polyphenyl polyisocyanate compsn. (I) contg. not more than 20 (pref. less than 15)wt. % diisocyanates and not more than 20 (pref. less than 10)wt. % polyisocyanates contg. more than 5 NCO gps. per mol.; with b) a polyfunctional active H cpd. Pref. the reaction is carried out wtih greater than a stoichiometric amount of (I) in the presence of a trimerisation catalyst. Also claimed is a polyisocyanate compsn. contg. 0-20 wt. % diisocyanate, 40-80 wt. % triisocyanate, 5-25 wt. % tetra/pentaisocyanate and not more than 20 wt. % polyisocyanate, and wherein the NCO value is 32-33.3 wt. %.

Description

Memória descritivaDescription

A presente invenção refere-se a espumas rígidas e especialmente a espumas rígidas poliméricas deriva das de determinadas composições de poli-isocianato de poli -metileno poli-fenilo.The present invention relates to rigid foams and especially to polymeric rigid foams derived from certain polyphenylene polyphenylene polyisocyanate compositions.

As composições de poli-isocianato de po li-metileno poli-fenilo são fabricadas industrialmente por fosgenação de misturas de poli-aminas obtidas por condensação ácida da anilina e formaldeido. As misturas de poli-iso cianato que alcançaram maior importância comercial obtiveram -se de cerca de 30% a cerca de 70% em peso de di-isocianato de difenil-metano juntamente com várias quantidades do referido tri- a penta- e poli-isocianatos superiores de poli-fenileno ligado a metileno sendo as composições actuais larga1Poly-methylene polyphenyl polyisocyanate compositions are manufactured industrially by phosgenation of polyamine mixtures obtained by acid condensation of aniline and formaldehyde. The mixtures of polyisocyanate that achieved the greatest commercial importance were obtained from about 30% to about 70% by weight of diphenylmethane diisocyanate together with various amounts of said tri-penta- and polyisocyanates higher polyethylene bonds linked to methylene, the current compositions being wide1

mente dependentes de proporção anilina/formaldeído iniciais.dependent on initial aniline / formaldehyde ratio.

Tais composições utilizaram-se em fórmu lações de base iso-cianato de muitos tipos e especialmente na produção de espumas rígidas de poli-uretano e poli-isocia nurato como descrito, por exemplo, nas especificações das Pa tentes do Reino Unido 848671, 874430, 1146661, 1184893 e 1223415.Such compositions have been used in iso-cyanate based formulations of many types and especially in the production of rigid polyurethane and polyisocyanurate foams as described, for example, in the specifications of United Kingdom Patents 848671, 874430, 1146661, 1184893 and 1223415.

Verificou-se que se podem fazer espumas rígidas superiores a partir de misturas de poli-isocianato de poli-metileno-poli-fenilo tendo teores reduzidos de di-iso cianatos e poli-isocianatos de elevado peso molecular e correspondente aumento do conteúdo de tri- a penta-isocianatos. Em particular, verificou-se que as espumas poli-isocianuradas com propriedades ao fogo melhoradas, como medidas pelo índice de oxigénio, e espumas de poli-uretano com propriedades de superfície melhoradas, especialmente friabilidade superficial baixa, podem preparar-se a partir das misturas referidas.It has been found that superior rigid foams can be made from poly-methylene-poly-phenyl polyisocyanate mixtures having reduced levels of high molecular weight diisocyanates and polyisocyanates and a corresponding increase in the content of trihydrates. pentaisocyanates. In particular, it has been found that polyisocyanurated foams with improved fire properties, as measured by the oxygen index, and polyurethane foams with improved surface properties, especially low surface friability, can be prepared from mixtures. referred to.

Assim, a invenção proporciona um método para a preparação de espumas rígidas consistindo da reacção duma composição de poli-isocianato de poli-metileno-poli-fenilo com um composto de hidrogénio activo poli-funcional,sob condições de formação de espuma, contendo a composição de pjo li-isocianato não mais do que 20% em peso de di-isocianatos e não mais que 20% em peso de poli-isocianatos contendo mais de 5 grupos de isocianato por molécula.Thus, the invention provides a method for the preparation of rigid foams consisting of the reaction of a poly-methylene-poly-phenyl polyisocyanate composition with a polyfunctional active hydrogen compound, under foaming conditions, containing the composition no more than 20% by weight of diisocyanates and no more than 20% by weight of polyisocyanates containing more than 5 isocyanate groups per molecule.

As composições típicas de poli-isociana to, para utilização no método da invenção contêm:Typical polyisocyanate compositions for use in the method of the invention contain:

- 20% di-isocianatos de di-fenil-metano- 20% di-phenyl-methane diisocyanates

- 80% tri-isocianatos de di-metileno tri-fenileno- 80% di-methylene tri-phenylene triisocyanates

- 25% tetra- e penta-isocianatos de poli-metileno poli-fenileno e- 25% polymethylene polyphenylene tetra- and pentaisocyanates and

- 20% poli-isocianatos superiores de poli-metileno poli-fenileno numa base de peso.- 20% higher polyisocyanates of polymethylene polyphenylene on a weight basis.

As composições de poli-isocianato preferenciais para utilização no método da invenção têm um valor de NCO que varia de 32 - 33,3 por cento em peso, o que constí tui composições novas as quais são também assunto específico desta invenção.Preferred polyisocyanate compositions for use in the method of the invention have an NCO value ranging from 32 - 33.3 weight percent, which constitutes new compositions which are also a specific subject of this invention.

É preferencial que o conteúdo de di-isocianato de composição de poli-isocianato seja inferior a 15% em peso. É também preferencial que o conteúdo de poli-isocia natos tendo 6 ou mais grupos NCO, seja inferior a 10% em peso. As composições adequadas têm, de preferência uma viscosidade menor do que 1000 mPa.s a 252C.It is preferred that the diisocyanate content of the polyisocyanate composition is less than 15% by weight. It is also preferred that the content of polyisociety born having 6 or more NCO groups, is less than 10% by weight. Suitable compositions preferably have a viscosity of less than 1000 mPa.s at 25 ° C.

As misturas de poli-isocianatos que devem ser utilizadas, de acordo com esta invenção e os métodos para a sua preparação foram descritas na técnica anterior, por exemplo, na DE - OS 3245678 e EP 133 538. Em geral, as mistu ras preparam-se por processos de extracção do solvente a partir das misturas de polimetileno-poli-fenilo poli-amina origi nais, antes das fosgenação ou a partir dos correspondentes p£ li-isocianatos de poli-metileno-poli-fenilo.The mixtures of polyisocyanates which are to be used according to this invention and the methods for their preparation have been described in the prior art, for example, in DE - OS 3245678 and EP 133 538. In general, mixtures are prepared by solvent extraction processes from the original polymethylene-polyphenyl polyamine mixtures, prior to phosgenation or from the corresponding polyethylene polyphenyl p-isocyanates.

Qualquer excesso de di-isocianato pode então remover-se por destilação.Any excess diisocyanate can then be removed by distillation.

Em particular, DE 3245678 descreve um método para obter uma composição de poli-isocianato por fosge nação de uma fracção de poli-amina que contenha pelo menos 94% em peso de tri-aminas. A fracção de poli-amina obtêm-se da destilação duma fraccional mistura contendo di e poli-feni leno poli-metileno poli-amina que resulta da condensação ácida de anilina e formaldeído.In particular, DE 3245678 describes a method for obtaining a polyisocyanate composition by phosgene a polyamine fraction which contains at least 94% by weight of triamine. The polyamine fraction is obtained from the distillation of a fractional mixture containing di and polyphenylene polymethylene polyamine which results from the acid condensation of aniline and formaldehyde.

Os compostos de hidrogénio activo poli-funcional que se devem utilizar no método da invenção, incluem polióis, poli-aminas e água que, respectivamente reagem com poli-isocianatos formando produtos de poli-uretano e de poli-ureias. 0 poli-isocianato pode reagir com compostos de hidrogénio activo em quantidades aproximadamente estequiométricas (NCO índice 100) ou, alternativamente índices NCO supe riores, por exemplo, 500 ou 1000 ou ainda superiores, pode empregar-se conjuntamente com catalizadores de trimerização para formar então produtos de poli-isocianurato modificado.The polyfunctional active hydrogen compounds which are to be used in the method of the invention, include polyols, polyamines and water which, respectively, react with polyisocyanates to form polyurethane and polyurea products. The polyisocyanate can react with active hydrogen compounds in approximately stoichiometric amounts (NCO index 100) or, alternatively higher NCO indices, for example, 500 or 1000 or even higher, can be used in conjunction with trimerization catalysts to form then modified polyisocyanurate products.

Os polióis adequados e as poli-aminas incluem os materiais convencionais utilizados ou propostos pa ra serem utilizados no fabrico de espumas rígidas de poli-ure tano, de poli-ureia e de poli-isocianuratos.Suitable polyols and polyamines include conventional materials used or proposed to be used in the manufacture of rigid polyurethane, polyurea and polyisocyanurate foams.

Geralmente os polióis adequados têm dois ou mais grupos hidroxilo e pesos moleculares de 62 a 1500, sendo a funcionalidade e o peso molecular apropriado quer para as espumas de poli-uretano ou de poli-isocianurato, seleccionados de forma conhecida.Generally, suitable polyols have two or more hydroxyl groups and molecular weights from 62 to 1500, with functionality and molecular weight being appropriate for both polyurethane or polyisocyanurate foams, selected in a known manner.

Exemplos de tais polióis incluem o glicol de etileno, glicerol, tri-metilolpropano, tri-etanolamina e os seus produtos de oxi-alquilação de peso molecular inferior. As alcanol-aminas tais como a mono-etanol amina podem também utilizar-se. Outros polióis adequados incluem produtos de oxi-alquilação de peso molecular inferior do sorbitol, sacarose e poli-aminas aromáticas tais como tolileno di-amina e polimetileno poli-fenil poli-amina como, bis-fenóis e po li-éter e polióis de poli-éster.Examples of such polyols include ethylene glycol, glycerol, tri-methylolpropane, tri-ethanolamine and their lower molecular weight oxyalkyl products. Alkanol-amines such as mono-ethanol-amine can also be used. Other suitable polyols include lower molecular weight oxyalkyl products of sorbitol, sucrose and aromatic polyamines such as tolylene diamine and polymethylene polyphenyl polyamine such as bisphenols and polyether ether and polyols. -ester.

As poli-aminas adequadas, geralmente têm dois ou mais grupos amino primários ou secundários e pesos moleculares de 60 a 1500.Suitable polyamines generally have two or more primary or secondary amino groups and molecular weights of 60 to 1500.

Podem utilizar-se misturas de polióis e/ /ou poli-aminas e/ou água.Mixtures of polyols and / or polyamines and / or water can be used.

A composição de poli-isocianato e o composto de hidrogénio activo poli-funcional podem reagir sob condições de formação de espuma convencionais. Em geral, isto envolve a preparação duma mistura de reacção que contêm um agente de sopro em adição ao poli-isocianato e composto de hidrogénio activo.The polyisocyanate composition and the polyfunctional active hydrogen compound can react under conventional foaming conditions. In general, this involves preparing a reaction mixture that contains a blowing agent in addition to the polyisocyanate and active hydrogen compound.

Tais misturas de reacção podem também conter outros ingredientes convencionais, por exemplo, catalizadores, tensio-activos, retardadores de chama e catalizado res de trimerização.Such reaction mixtures can also contain other conventional ingredients, for example, catalysts, surfactants, flame retardants and trimerization catalysts.

Os agentes de sopro adequados incluem H quidos voláteis inertes, especialmente alcanos halogenados tais como tri-cloro-fiuoro-metano e di-cloro-di-fluoro-metano.Suitable blowing agents include inert volatile H liquids, especially halogenated alkanes such as tri-chloro-fluoro-methane and dichloro-fluoro-methane.

Nalguns casos, a água pode empregar-se como um agente de S£ pro em adição a, ou em vez do, líquido inerte.In some cases, water can be used as an agent of S pro in addition to, or instead of, the inert liquid.

Os tensio-activos adequados para a pre paração da espuma incluem copolímeros de siloxano-oxi-alqui leno e agentes tensio-activos não iónicos convencionais. Os catalizadores adequados para a preparação de espumas de poli-uretano e poli-ureia incluem as aminas terciárias usuais e compostos de estanho enquanto os catalizadores de trimeri. zação necessários para espumas de poli-isocianurato incluem metal alcalino e hidróxidos de metal alcalino terroso alcóxidos e alcanoatos. Os catalizadores particularmente adequa dos para a produção de espumas de poli-isocianurato incluem misturas de um sal da fórmula:Suitable surfactants for the preparation of foam include siloxane-oxyalkylene copolymers and conventional nonionic surfactants. Suitable catalysts for the preparation of polyurethane and polyurea foams include the usual tertiary amines and tin compounds as the trimeri catalysts. Necessary uses for polyisocyanurate foams include alkali metal and alkaline earth metal hydroxides, alkoxides and alkanoates. Catalysts particularly suitable for the production of polyisocyanurate foams include mixtures of a salt of the formula:

R1- C - COO M+ e um sal da fórmula:R 1 - C - COO M + and a salt of the formula:

ondeWhere

M representa um metal alcalino ou tetra-alquil-amónio,M represents an alkali metal or tetraalkylammonium,

Q representa um metal do grupo II A ou zinco e 12 3Q represents a group II A metal or zinc and 12 3

R , R e R que podem ser o mesmo ou diferente, re presentam hidrogénio, alquilo inferior, ciclo-al^ quilo, fenilo ou alquil-fenilo.R, R and R which may be the same or different, represent hydrogen, lower alkyl, cycloalkyl, phenyl or alkyl-phenyl.

ίί

Tais catalizadores sao em particular, preferenciais, quando o índice de isocianato é superior a 500.Such catalysts are in particular preferred when the isocyanate index is greater than 500.

As espumas podem preparar-se utilizando qualquer das técnicas de fabricação e mistura convencional. Assim, técnicas de aspersão ou moldagem ou processos de laminação podem utilizar-se como desejado. A reduzida friabi. lidade superficial das espumas de poli-uretano é particular mente valiosa nos processos de laminação , visto que a adesão entre a espuma e os materiais de contacto é significatí. vamente melhorada.Foams can be prepared using any conventional manufacturing and mixing techniques. Thus, spraying or molding techniques or lamination processes can be used as desired. The reduced friabi. The surface quality of polyurethane foams is particularly valuable in lamination processes, since the adhesion between the foam and the contact materials is significant. improved.

A invenção é ilustrada mas não limitada pelos exemplos seguintes, nos quais todas as partes são em peso.The invention is illustrated but not limited to the following examples, in which all parts are by weight.

Exemplo 1Example 1

Fizeram-se duas espumas no a partir da seguinte formulação:Two foams were made from the following formulation:

Glicerol oxipropilatado (0H=540) 38,Oxypropylated glycerol (0H = 540) 38,

Silicone fluido DC-193 (DOW Chemical) 0 Ν,Ν-Dimetil-ciclo-hexil-amina 1,Fluid silicone DC-193 (DOW Chemical) 0 Ν, Ν-Dimethyl-cyclohexyl-amine 1,

Dilaurato de dibutil-estanho 0,Dibutyltin dilaurate 0,

Tri-cloro-fluoro-metano 13,Tri-chloro-fluoro-methane 13,

Poli-isocianato 1 47.Polyisocyanate 1 47.

Poli-isocianato 2 de poli-ureta1 36.8 ,5 0.5Poly-ureta1 polyisocyanate 2 36.8, 5 0.5

1.01.0

015 0.015015 0.015

13.013.0

48.7 poli-isocianato 1 era uma composição de poli-isocianato de poli-metileno-poli-fenilo tendo um valor de NCO de 33.0 e que continha 16% em peso de di-iso cianato de 6% em peso de poli-isocianatos com um peso molecu lar superior a 650.48.7 polyisocyanate 1 was a polymethylene-polyphenyl polyisocyanate composition having an NCO value of 33.0 and containing 16% by weight of 6% by weight of polyisocyanates with a molecular weight greater than 650.

O poli-isocianato 2 era uma composição de poli-isocianato de poli-metileno-poli-fenilo convencional tendo um valor de NCO de 30.6 e que continha 50% em peso de di-isocianato.Polyisocyanate 2 was a conventional polymethylene-polyphenyl polyisocyanate composition having an NCO value of 30.6 and containing 50% by weight of diisocyanate.

Mostrcu-se, por exame táctil, que a friabilidade superficial da espuma 1 era menor que o da espuma 2.Tactile examination showed that the surface friability of foam 1 was less than that of foam 2.

Exemplos 2Examples 2

Prepararam-se espumas de poli-isocianu rato a partir das seguintes formulações:Polyisocyanurate foams were prepared from the following formulations:

A THE B B G G Glicol de poli-propileno 425 Polypropylene glycol 425 18.9 18.9 12.7 12.7 7.90 7.90 Silicone fluido DC-193 Fluid silicone DC-193 0.35 0.35 0.35 0.35 0.35 0.35 (DOW Chemical) (DOW Chemical) Acetato de potássio (50%) Potassium acetate (50%) Solução de glicol de etileno Ethylene glycol solution 0.45 0.45 0.30 0.30 0.30 0.30 N,N-di-metil-ciclo-hexil-amina N, N-di-methyl-cyclohexyl-amine 1.00 1.00 0.30 0.30 0.30 0.30 Tri-cloro-fluoro-metano Tri-chloro-fluoro-methane 10.00 10.00 10.00 10.00 10.00 10.00 Poli-isocianato 1 Polyisocyanate 1 69.9 69.9 77.5 77.5 88.1 88.1

Prepararam-se então três espumas corres pondentes a partir das mesmas formulações excepto que o Poli -isocianato 1 foi substituído pelo Poli-isocianato 2 (como no exemplo 1).Three corresponding foams were then prepared from the same formulations except that Polyisocyanate 1 was replaced by Polyisocyanate 2 (as in example 1).

As seis espumas rígidas de poli-isocianurato assim obtidas foram submetidas ao teste do Índice de Oxigénio (ASTM 2863) tendo dado os seguintes resultados:The six rigid polyisocyanurate foams thus obtained were subjected to the Oxygen Index test (ASTM 2863) having given the following results:

Poli-isocianato 1Polyisocyanate 1

Poli-isocianato 2 (como no Exemplo 1)Polyisocyanate 2 (as in Example 1)

A THE B B C Ç 23.4 23.4 25.0 25.0 27.0 27.0 23.8 23.8 25.7 25.7 28.0 28.0

Claims (6)

- lê Processo para a preparação de espumas rí gidas caracterizado por se fazer reagir uma composição de poli-isocianato de polimetileno polifenílico com um composto hi drogeno-activo polífuncional sob condições de formação de espuma, não contendo a composição de poli-isocianato mais do que 20% em peso de diisocianatos e não mais do que 20% em peso de poli-isocianatos que contém mais do que 5 grupos de isocianato por molécula.- reads Process for the preparation of rigid foams characterized by reacting a polyphenyl polyethylene polyisocyanate composition with a polyfunctional hydrogenoactive compound under foaming conditions, containing no more than the polyisocyanate composition 20% by weight of diisocyanates and not more than 20% by weight of polyisocyanates containing more than 5 isocyanate groups per molecule. -- 2§ Processo de acordo com a reivindicação 1, caracterizado por a composição poli-isocianato conter entre 0 e 20% em peso de diisocianatos de difenilmetano, entre 40 e 80% em peso de triisocianatos de dimetileno, trifenileno en tre 5 e 25% em peso de tetra e penta-isocianatos de polimetileno polifenileno e entre 0 e 20% em peso de poli-isocianatos de polimetileno polifenileno elevados.Process according to claim 1, characterized in that the polyisocyanate composition contains between 0 and 20% by weight of diphenylmethane diisocyanates, between 40 and 80% by weight of dimethylene, triphenylene triisocyanates between 5 and 25% in weight of polymethylene polyethylene tetra and pentaisocyanates and between 0 and 20% by weight of high polyphenylene polyphenylene polyisocyanates. -- 3ê Processo de acordo com as reivindicações3ê Process according to the claims 1-2, caracterizado por o conteúdo de NGO da composição de poliisocianato estar compreendido entre 32 e 33,3% em peso.1-2, characterized in that the NGO content of the polyisocyanate composition is between 32 and 33.3% by weight. -- 4ê Processo de acordo com as reivindicações 1 ou 2, caracterizado por a composição de poli-isocianato con ter menos do que 15% em peso de diisocianatos.Process according to claim 1 or 2, characterized in that the polyisocyanate composition contains less than 15% by weight of diisocyanates. -- 5ê Processo de acordo com qualquer das reivindicações anteriores caracterizado por a composição de poli, isocianatos conter menos do que 10% em peso de poliisocianatos que contêm mais do que 5 grupos isocianato por molécula.Process according to any of the preceding claims, characterized in that the polyisocyanate composition contains less than 10% by weight of polyisocyanates containing more than 5 isocyanate groups per molecule. 6<â Processo de acordo com qualquer das reivindicações anteriores, caracterizado por a composições de po li-isocianato ter uma viscosidade inferior a 1000 mPa.s a 252C.Process according to one of the preceding claims, characterized in that the polyisocyanate compositions have a viscosity of less than 1000 mPa.s at 25 ° C. - 7ê Processo de acordo com qualquer das reivindicações anteriores, caracterizado por o composto hidrogeno-activo polifuncional ser um poliol, uma poliamida, água ou uma mistura de um ou mais destes.7. A process according to any of the preceding claims, characterized in that the polyfunctional hydrogen-active compound is a polyol, a polyamide, water or a mixture of one or more of these. - 8ê Processo de acordo com qualquer das reivindicações anteriores, caracterizado por a composição de poliisocianato ser usada numa quantidade superior â quantidade estequeomêtrica em associação com um catalizador de trimerização.Process according to one of the preceding claims, characterized in that the polyisocyanate composition is used in an amount greater than the stoichiometric amount in association with a trimerization catalyst. _ 9a __ 9a _ Processo de acordo com a reivindicação 8, caracterizado por o catalizador consistir numa mistura de um sal da fórmulaProcess according to claim 8, characterized in that the catalyst consists of a mixture of a salt of the formula R - C - COOR - C - COO R~ e de um sal da fórmulaR ~ and a salt of the formula R - C - COOR - C - COO R~ >++ em queR ~> ++ where M representa um metal alcalino ou tetra-alquil-amónio,M represents an alkali metal or tetraalkylammonium, Q representa um metal do grupo IIA ou zinco eQ represents a group IIA metal or zinc and 12 312 3 R ,R e R , que podem ser iguais ou diferentes repre sentam hidrogénio, alquilo inferior,ciclo-alquilo, fenilo ou alquil-fenilo.R, R and R, which may be the same or different, represent hydrogen, lower alkyl, cycloalkyl, phenyl or alkyl phenyl. - 10a Processo de acordo com a reivindicação 9, caracterizado por o Índice de NCO ser superior a 500.10. A process according to claim 9, characterized in that the NCO Index is greater than 500. - lia Processo de acordo com a reivindicação- read Process according to claim I, caracterizado por o conteúdo de diisocianato estar compreendido entre 0 e 20% em peso, o conteúdo de triisociana to estar compreendido entre 40 e 80% em peso, o conteúdo de tetra e penta-isocianato estar compreendido entre 5 e 25% em peso e um conteúdo de poli-isocianato inferior a 20% em peso e por o valor de NCO estar compreendido entre 32 e 33,3%, em peso.I, characterized in that the content of diisocyanate is between 0 and 20% by weight, the content of triisocyanate is between 40 and 80% by weight, the content of tetra and penta-isocyanate is between 5 and 25% by weight and a polyisocyanate content of less than 20% by weight and because the NCO value is between 32 and 33.3% by weight. - 12§ Processo de acordo com a reivindicação- 12§ Process according to claim II, caracterizado por o conteúdo em diisocianato ser inferior a 15% em peso.II, characterized in that the diisocyanate content is less than 15% by weight. - 13ê Processo de acordo com a reivindicação 11 ou 12 caracterizado por o conteúdo de poliisocianato que contem mais do que 5 grupos isocianato por molécula ser in ferior a 10% em peso.13. A process according to claim 11 or 12, characterized in that the polyisocyanate content containing more than 5 isocyanate groups per molecule is less than 10% by weight. - 14ã Processo de acordo com qualquer das reivindicações de 11 a 13 caracterizado por a viscosidade da composição ser inferior a 1000 mPa.s a 25° CProcess according to one of Claims 11 to 13, characterized in that the viscosity of the composition is less than 1000 mPa.s at 25 ° C A requerente declara que o primeiro pedi do desta patente foi apresentado no Reino Unido em 26 de Maio de 1987, sob o n°. 8712364.The applicant declares that the first application for this patent was filed in the United Kingdom on 26 May 1987, under no. 8712364.
PT87571A 1987-05-26 1988-05-25 PROCESS FOR THE PREPARATION OF RIGID POLYMERIC FOAMS DERIVED FROM POLY-ISOCYANATE COMPOSITIONS OF POLYPHENYLENE POLYMETHYLENE PT87571B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB878712364A GB8712364D0 (en) 1987-05-26 1987-05-26 Rigid foams

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PT87571A PT87571A (en) 1989-05-31
PT87571B true PT87571B (en) 1992-12-31

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KR (1) KR970002520B1 (en)
AT (1) ATE94182T1 (en)
CA (1) CA1322816C (en)
DK (1) DK289088A (en)
FI (1) FI882485A (en)
GB (1) GB8712364D0 (en)
HK (1) HK1001692A1 (en)
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NO882283D0 (en) 1988-05-25
GB8712364D0 (en) 1987-07-01
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DK289088A (en) 1988-11-27
DK289088D0 (en) 1988-05-26
HK1001692A1 (en) 1998-07-03
PT87571A (en) 1989-05-31
FI882485A0 (en) 1988-05-26
KR880014023A (en) 1988-12-22
FI882485A (en) 1988-11-27
CA1322816C (en) 1993-10-05
ATE94182T1 (en) 1993-09-15
NO882283L (en) 1988-11-28
NZ224659A (en) 1990-08-28

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