EP0812310A1 - Nouveaux composes diamino et polyamino destines a la preparation de materiaux a base de polyurethanne - Google Patents

Nouveaux composes diamino et polyamino destines a la preparation de materiaux a base de polyurethanne

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Publication number
EP0812310A1
EP0812310A1 EP96902935A EP96902935A EP0812310A1 EP 0812310 A1 EP0812310 A1 EP 0812310A1 EP 96902935 A EP96902935 A EP 96902935A EP 96902935 A EP96902935 A EP 96902935A EP 0812310 A1 EP0812310 A1 EP 0812310A1
Authority
EP
European Patent Office
Prior art keywords
polyisocyanate
integer
compound
polyol
preparing
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP96902935A
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German (de)
English (en)
Inventor
Guy Leon Jean Ghislain Biesmans
Gonda Van Essche
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
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 Ltd filed Critical Imperial Chemical Industries Ltd
Priority to EP96902935A priority Critical patent/EP0812310A1/fr
Publication of EP0812310A1 publication Critical patent/EP0812310A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/50—Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/16—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
    • 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5066—Polyethers having heteroatoms other than oxygen having nitrogen having halogens in addition to nitrogen
    • 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
    • C08G18/773—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur halogens
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0091—Aerogels; Xerogels
    • 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
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate groups

Definitions

  • the present invention relates to novel di- and polyamino compounds that can be used for preparing polyols and polyisocyanates, which in turn can be used in the synthesis of polyurethane materials.
  • the present invention relates also to the polyols, polyisocyanates and polyurethane materials obtained by using said compound.
  • polyurethane materials of a cellular or non- cellular, flexible or rigid nature by reacting organic polyisocyanates having two or more isocyanate groups per molecule with compounds containing a plurality of isocyanate reactive groups, for example polyols and polyamines, in the presence, where required, of other components such as blowing agents, cross-linking agents, catalysts and surfactants.
  • These polyurethane materials may take the form of adhesives, coatings, elastomers, fibres, films, foams, thermoplastics, powders, xerogels, aerogels and the like.
  • Polyols for use in preparing polyurethanes are usually prepared by reacting an initiator compound having a plurality of active hydrogen atoms (alcohols or amines) with an alkylene oxide (usually propylene oxide).
  • a suitable initiator compound is diammodiphenylmethane (methylenedianiline) .
  • Polyamines for use in preparing polyurethanes are obtained by converting the hydroxyl end-groups of the polyols to amino end-groups.
  • Organic polyisocyanates for use in preparing polyurethanes are conventionally manufactured by reacting phosgene with the corresponding organic polyamines.
  • the starting materials for diisocyanatodiphenylmethane (MDI) and its homologues are the mixtures of isomers and homologues of dia ⁇ nodiphenylmethane that are formed by the condensation reaction of formaldehyde and aniline.
  • a problem encountered when preparing polyurethane or polyisocyanurate aerogels is the limited solubility of known organic polyisocyanates in CO_ and/or hydro (chloro) fluorocarbons, especially at pressures below 100 bar.
  • novel polyamino compounds suitable for use in the preparation of polyols and polyisocyanates, and thus also polyurethane materials.
  • the polyisocyanates derived from these novel polyamino compounds have a higher solubility in C0_ and hydro(chloro) fluorocarbons than the conventional polyisocyanates and dissolve (cyclo) alkanes better than the conventional polyisocyanates.
  • n, n' and n" each independently represent an integer of from 0 to 4 , at least one of n, n' and n" not being equal to 0; m represents an integer of from 0 to 8, preferably from 0 to 4; and wherein the amino substituents are situated in ortho, meta or para position with regard to the methylene substituent; with the exception of bis (2, 3, 5, 6-tetrafluoro-4-am ⁇ nophenyl)methane and bis (3-fluoro-4-am ⁇ nophenyl)methane.
  • m 1
  • Preferred compound according to formula (I) for use in the preparation of polyurethane materials are compound (1.1) and compound (1.9) .
  • the compounds according to formula (I) are obtained by the acid condensation of the corresponding fluorinated aniline(s) and formaldehyde.
  • Two different fluorinated anilines may be used and also a mixture of a fluorinated aniline and a non- luorinated aniline. Methods for performing this reaction are known in the art. When two different fluorinated anilines are used mixtures of different compounds according to formula (I) are obtained.
  • Compounds according to formula (I) are useful in the preparation of polyurethane based materials. They can be used as such and have the function of, for example, amme chain extenders (especially in flexible foam applications) or they can be converted into polyols and/or polyisocyanates which in turn can be converted into polyurethane based materials.
  • the present invention also provides polyol compositions obtainable by oxyalkylation of a compound of formula (I) and optionally a second initiator.
  • the polyol compositions according to the present invention may contain oxyalkylene units derived from propylene oxide, ethylene oxide and butylene oxide. These oxyalkylene units may be partially or fully fluorinated. When both propylene and ethylene oxides are employed in the oxyalkylation, they may be reacted either simultaneously or sequentially with the compound according to formula (I). It is preferred that the ethylene oxide content does not exceed 70 * of the total alkylene oxide units on a molar basis.
  • another initiator may be used in the formation of the polyol compositions according to the present invention.
  • Suitable co-initiators include: water and polyols, for example ethylene glycol, propylene glycol and their oligomers, glycerol, t ⁇ methylolpropane, triethanolamine, pentaerythritol, sorbitol and sucrose; polyamines, for example ethylene diamine, tolylene diarmne, diaminodiphenylmethane and polymethylene polyphenylene polyamines; and ammoalcohols, for example ethanolamine, triisopropanolamine and diethanolamine; and mixtures of such initiators.
  • polyols for example ethylene glycol, propylene glycol and their oligomers, glycerol, t ⁇ methylolpropane, triethanolamine, pentaerythritol, sorbitol and sucrose
  • polyamines for example ethylene diamine, tolylene diarmne, diaminodiphenylmethane and polymethylene polypheny
  • Polyols having hydroxyl values in the range 30 to 680 mg KOH/g can be prepared, preferably in the range 30 to 620 mg KOH/g and more preferably in the range 300 to 500 mg KOH/g.
  • the method for making the polyol compositions according to the present invention basically follows prior art modes of making polyether polyols.
  • the oxyalkylation is performed in the presence of ionic catalysts as known in the art.
  • the amount of catalyst utilised may vary over a wide weight percentage based on tne weight of the initiator(s) .
  • an amount of catalyst ranging from about 0.01 to about 5 weight - is employed, based on the weight of the initiator. More often, the amount employed is 0.1-2 -, and most often 0.3-1 ⁇ .
  • the amount of alkylene oxide added to the compound of formula (I) and the optional co-initiator may range over a wide range of about 1-100 moles of alkylene oxide per mole of initiator. More often, 1-50 moles of alkylene oxide are reacted per mole of initiator.
  • the temperature of reaction may range from about 50°C to about 200 C C, and is preferably from 80°C to 150°C.
  • the polyols should have average hydroxyl numbers in the range from 300 to 880 mg KOH/g, especially in the range from 300 to 500 mg KOH/g, and a hydroxyl functionality in the range from 2 to 8, especially m the range from 3 to 6, preferably 4.
  • tne polyols should have a molecular weight in the range from 1000 to 10000, preferably from 3000 to 7500, and a number average functionality in the range from 2 to 4.
  • the present invention also provides polyisocyanate compositions obtainable by phosgenation cf compounds of formula (I) .
  • n, n', n" and m have the meanings as defined above.
  • Preferre ⁇ compounds according to formula (II) are bis (3, 5-d ⁇ fluoro-4- lsocyana opher.yl methane (compound II.1) and bis .2, 3, 5, 6-tetrafluoro-4- lsocyanatopher. l methane (compound II. Si .
  • the phosgenation can take place both continuously and discontmuously.
  • the phosgenation car take place in two steps according to the well-known cold/hot phosgenation principle or in one step according to the hot phosgenation principle.
  • solvents include aliphatic, cycloaliphatic and aromatic hydrocarbons, halogenated hydrocarbons, nitro-substituted hydrocarbons, aliphatic-aromatic ethers, aromatic ethers, carboxylic acid esters, carboxylic acid nitriles, sulfone, phosphoric acid halogenide and phosphoric acid ester. Chlorobenzene and ortho dichlorobenzene have been generally accepted as the most commonly used solvents.
  • phosgenation can take place at normal or slightly elevated pressure.
  • the phosgene is added to the composition in an amount of 1 to 10 times, in particular 1.05 to 6 times the stoichiometric amount.
  • Catalysts such as dimethylformamide and acid acceptors such as pyridme can accelerate the phosgenation. Further processing of the reaction mixture after the phosgenation involves the recovery of gaseous substances (hydrogen chloride and excess of phosgene) and multistage distillation to separate the solvent. The isocyanate itself can then be recovered by means of extraction, crystallisation, distillation or sublimation.
  • the isocyanates according to formula (II) can be post-reacted; they can be trimerised, urea-modified, allophonate-modified, biuret-modified or they can be prepolyme ⁇ sed (i.e. reacted with polyols, etc.). In any of these forms they can then be used in the preparation of polyurethane based materials.
  • the polyol compositions and polyisocyanate compositions resulting from compounds according to formula (I) can be used in a conventional manner in order to prepare polyurethane materials.
  • the polyurethane materials can be solid (e.g. elastomers) or they can be cellular.
  • the polyurethane material can be in the form of rigid foams, flexible foams, self-skinning foams, elastomers, thermoplastic polyurethane (TPU) , powders, xerogels, aerogels or as coatings, adhesives, sealants and binders.
  • polyurethane materials as used herein is meant to also include urethane-modifled polyisocyanurate materials, polyisocyanurate materials, polyurea materials, polyallophanate materials and polybiuret materials.
  • polyurethane preparation involves reacting a polyol composition with an organic polyisocyanate in the presence of a foaming agent in the case of polyurethane foam preparation, and usually, catalysts, surfactants and other known additives.
  • a polyol composition according to the present invention may be reacted with a conventional polyisocyanate composition, or a polyisocyanate composition according to the present invention may be reacted with a conventional polyol composition. Alternatively a polyol composition according to the present invention may be reacted with a polyisocyanate composition according to the present invention.
  • polyol composition used may comprise a mixture of different types of polyols, including conventional polyols and polyols according to the present invention; similarly the polyisocyanate composition used may comprise a mixture of different types of polyisocyanates, including conventional polyisocyanates and polyisocyanates according to the invention.
  • polyisocyanates for use in the polyurethane forming process include aliphatic, cycloaliphatic, araliphatic and aromatic polyisocyanates as proposed in the literature.
  • aromatic diisocyanates such as tolylene and diphenylmethane dnsocyanate in the well known pure, modified and crude forms, in particular the so-called MDI variants and the mixtures of diphenylmethane dnsocyanate(s) and oligomers thereof known in the art as "crude” or "polymeric" MDI.
  • the polyisocyanates used in the polyurethane forming process can be in the form of a prepolymer, or in the form of a trimerised isocyanate or a modified (urea, allophonate, biuret) isocyanate.
  • Preferred polyisocyanates for the preparation of rigid polyurethane foams are those having an average nominal functionality of 2.4-3.0 and in particular of 2.4-2.9.
  • Preferred polyisocyanates for the preparation of flexible and integral skin foams and for microcellular elastomers are those having an average nominal functionality of 2.0 to 2.4.
  • MDI based polyurethane prepolymers and semi- or quasi- prepolymers having an NCO value of 5 to 31 - by weight may be used.
  • Foaming agents which may be used include carbon dioxide-evolving compounds such as water and inert low boiling compounds having a boiling point of above -70 C C at atmospheric pressure.
  • Suitable inert blowing agents include those well known and described in the art, for example, hydrocarbons, dialkyl ethers, alkyl alkanoates, aliphatic and cycloaliphatic hydrofluorocarbons, hydrochiorofluoroca bons, chlorofluorocarbons, hy ⁇ rochlorocarbons and fluorine-containing ethers.
  • Catalysts include the usual tertiary amines, tin compounds and metal salts of carboxylic acids whilst useful surfactants include siloxane-oxyalkylene copolymers and conventional non-ionic types. Other useful additives include fire-retardants, for example, tr ⁇ s-2-chloroethyl phosphate and dimethyl methylphosphonate.
  • the known one-shot full prepolymer or semi-prepolymer techniques may be used together with conventional mixing methods and the foams and elastomers may be prepared in the form of mouldings, cavity fillings, sprayed foam, frothed foam, slabstock foam or laminates with other materials such as hardboard, plasterboard, plastics, paper or metals.
  • the compounds according to formula (I) are used as chain extenders in the polyurethane forming process they are conveniently added to the pre- blended polyol formulation in an amount of from 0.1 to 20 parts by weight based on the total polyol composition.
  • the compounds according to the invention may be used as chain extenders either as the sole isocyanate-reactive ingredient (apart from water in case water is used as blowing agent) or together with other isocyanate-reactive ingredients, like other chain extenders and high molecular weight polyol m relatively small amounts.
  • Polyisocyanate compositions according to the present invention are especially useful for preparing polyurethane base ⁇ aerogels according to the process described in WO 95/03358 (incorporated herein by reference) and polyurethane based porous materials according to the processes described in WO 95/00530 (incorporated herein by reference).
  • these materials are prepared by dissolving an organic polyisocyanate (usually in an amount of 1 to 25 * by weight) in a suitable solvent tsuch as a hydrofluorocarbon) .
  • a suitable trimerisation catalyst is added hereto in a weight ratio isocyanate/catalyst of between 3 and 5000 (preferably between 5 and 1000 and most preferably between 10 and 500) and the mixture is thoroughly mixed. Thereafter it is left in a quiescent state until a sol-gel is obtained which is dried by super critical drying in case of an aerogel or by flash-off (sudden release of pressure) in case of a powder.
  • a 250 ml 3-necked flask was fitted with a reflux condenser, an addition funnel and a nitrogen gas flow.
  • 0.426 moles (54.95 g) of 2,6- difluoroanilme and 50 ml of t-butanol were charged into the flask and heated to 50°C under mechanical stirring.
  • 0.20 moles (20.0 g) of a 30 % aqueous solution of formaldehyde was added dropwise and stirred magnetically for hour at 50°C.
  • the mixture was allowed to cool to room temperature and transferred to a Parr-reactor where 0.18 mole (18.5 g) of hydrochloric acid, 35 % in 60 ml t-butanol, was fed at 40°C.
  • Polyurethane foams were prepared from the formulations indicated in Table 3 below. Various properties of the obtained foams were measured; the results are also given in Table 3.
  • DALTOLAC XR 159 being a polyether polyol available from Imperial Chemical
  • DALTOLAC XR 144 being a polyether polyol available from Imperial Chemical
  • DALTOLAC R 130 being a polyether polyol available from Imperial Chemical
  • DALTOLAC R 170 being a polyether polyol available from Imperial Chemical Industries;
  • DALTOCEL F 455 being a polyether polyol available from Imperial Chemical
  • DALTOLAC XR 124 being a polyether polyol available from Imperial Chemical
  • NIAX Al being a catalyst available from Union Carbide
  • SFC being a catalyst available from Imperial Chemical Industries
  • TEGOSTAB B 8423 being a surfactant available from Goldschmidt
  • RS 201 being a surfactant available from Union Carbide
  • L 6900 being a surfactant available from Union Carbide
  • DESMORAPID PV being a catalyst available from Bayer
  • SUPRASEC DNR being polymeric MDI available from Imperial Chemical
  • ISO being a mixture of SUPRASEC DNR and 2 r by weight of compound II.1.
  • DALTOLAC, DALTOCEL and SUPRASEC are trademarks of Imperial Chemical Industries.
  • reaction mixture was left in a quiscent state. After 3 hours gelation occurred and after 24 hours a solid gel was obtained which was supercritically dried. A white hard matrix of medium elasticity having a density of 137 kg / , a surface area of 473 m /g and a pore size of 21.9 nm, was obtained.
  • This example shows that by using a fluorinated polyisocyanate lower density aerogel/powders are obtained.
  • Example 1 was repeated using 0.341 mole of 2,6-difluoroaniline and 0.085 mole 2, -difluoroaniline. 26 g of a mixture of different species with as main component compound 1.3 was formed.
  • Example 1 was repeated using 0.21 mole 2,6-d ⁇ fluoroan ⁇ line and 0.21 mole 2, 5-difluoroan ⁇ lme to give compound 1.4.
  • the ratio between 2,5/2,6 and 2,5/2,5 coupling was 2.4/1. Traces of 2,6/2,6 coupling adducts were found as well.
  • Example 1 was repeated with 0.21 mole aniline and 0.21 mole 2,6- difluoroamline.
  • Product 1.5 was formed but contained highly insoluble polymeric species.
  • Example 1 was repeate ⁇ with 0.42 mole 2, 3, 6-tr ⁇ fluoroan ⁇ l ⁇ ne. The yield of compound 1.7 was 40-.
  • Example 1 was repeated using 0.42 mole 2, 3, 5, 6-tetrafluoroanil ⁇ ne to give compound 1.9 with 45- yield.
  • Example 4 was repeated employing mixtures of compound II.1 and SUPRASEC DNR (available from Imperial Chemical Industries) in weight ratio of 1/99, 5/95 and 10/9C. The results obtained on the final aerogel are given in Table 4. Table 4
  • Example 4 was repeated using a mixture of compound II.9 and SUPRASEC DNR (weight ratio 5/95) employing a solvent mixture of dichloromethane and acetone in a weight ratio of 90/10.
  • the final aerogel had a density of 118 kg/rn ⁇ and a specific surface area of 430 ⁇ r/g.

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

Abstract

L'invention se rapporte à des composés de diaminodiphénylméthane fluoré et à la conversion de ces composés en polyols et polyisocyanates, qui peuvent à leur tour être utilisés dans la préparation d'aérogels, de poudres et de mousses de polyuréthanne.
EP96902935A 1995-02-27 1996-01-23 Nouveaux composes diamino et polyamino destines a la preparation de materiaux a base de polyurethanne Withdrawn EP0812310A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96902935A EP0812310A1 (fr) 1995-02-27 1996-01-23 Nouveaux composes diamino et polyamino destines a la preparation de materiaux a base de polyurethanne

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP95200474 1995-02-27
EP95200474 1995-02-27
EP96902935A EP0812310A1 (fr) 1995-02-27 1996-01-23 Nouveaux composes diamino et polyamino destines a la preparation de materiaux a base de polyurethanne
PCT/EP1996/000340 WO1996026915A1 (fr) 1995-02-27 1996-01-23 Nouveaux composes diamino et polyamino destines a la preparation de materiaux a base de polyurethanne

Publications (1)

Publication Number Publication Date
EP0812310A1 true EP0812310A1 (fr) 1997-12-17

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EP (1) EP0812310A1 (fr)
JP (1) JPH11501621A (fr)
WO (1) WO1996026915A1 (fr)

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US9328190B2 (en) * 2006-01-18 2016-05-03 Invista North America S.A.R.L. Non-textile polymer compositions and methods
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