Patent Application
20060084777
This application is a continuation of international application PCT EP2004/050898, filed May 24, 2004, which claims priority to EP 03013241.9, filed Jun. 12, 2003, both of which applications are hereby incorporated by reference.
The present invention is related to a process for preparing a polyisocyanurate polyurethane material. More specifically, the present invention is related to a process for preparing a polyisocyanurate polyurethane material using a polyether polyol having a high oxyethylene content and a polyisocyanate having a high diphenylmethane diisocyanate (MDI) content.
The preparation of polyurethane materials having a low and a high hardblock content from polyols having a high oxyethylene content, polyisocyanates comprising at least 85% by weight of 4,4′-MDI or a variant thereof and water are the subject of WO 02/06370 and WO 98/00450. The materials made are polyurethane elastomers. Further, it has been discussed in EP 608626 to produce shape memory polyurethane foams by reacting a polyisocyanate comprising a high amount of 4,4′-MDI and a polyol with a high oxyethylene content with water. WO 02/10249 discusses a process for preparing a polyurethane material having a high hard block content by reacting an MDI, a polyol having a high oxyethylene content and a cross-linker/chain extender. These citations do not disclose a process for making a polyisocyanurate polyurethane material by reacting a polyisocyanate and a polyol at a high NCO-index and in the presence of a trimerisation catalyst.
Processes for making polyisocyanurate polyurethane materials by reacting polyisocyanates and polyols at a high index in the presence of a trimerisation catalyst, as such, have been widely described. See e.g. EP 922063 and WO 00/29459, WO 02/00752, EP 1173495, EP 745627, EP 587317, U.S. Pat. No. 4,247,656, U.S. Pat. No. 4,129,697, DE 10145458, U.S. Pat. No. 4,661,533, U.S. Pat. No. 4,424,288 and GB 1433642.
Surprisingly, we have found a novel class of polyisocyanurate polyurethane materials prepared from certain MDI-based polyisocyanates and certain polyols having a high oxyethylene content. The invention allows for the production of materials having a high modulus, a high impact-, temperature- and flammability resistance, a short demould time and a high green strength. In particular, the materials can be advantageously produced according to the reaction injection moulding (RIM) process.
Further, the process is suitable to make reinforced materials by using fillers like organic particles and mineral particles like nanoclay particles, BaSO4 and CaCO3 and/or fibers like glass fibers, natural fibers like flax, hemp and sisal fibers, synthetic fibers like polyamides (Kevlar™ products) and polyethylene (Spectra™ products). Such materials exhibit a good thermal stability.
Still further, the ingredients used to make the materials are easily processable and exhibit excellent curing characteristics allowing for short demould times. Still further, the materials obtained show lower levels of residual NCO groups in infra-red analysis compared to materials made from high amounts of polyols having a high level of oxypropylene groups at the same NCO-index. The materials according to the present invention show a higher impact and are less brittle.
Therefore, the present invention is concerned with a process for preparing a polyisocyanurate polyurethane material which process comprises reacting a polyisocyanate and an isocyanate-reactive composition wherein the reaction is conducted at an isocyanate index of 150 to 1500, the polyisocyanate consists of a) 80-100% by weight of diphenylmethane diisocyanate comprising at least 40%, preferably at least 60% and most preferably at least 85% by weight of 4,4′-diphenylmethane diisocyanate and/or a variant of said diphenylmethane diisocyanate which variant is liquid at 25° C. and has an NCO value of at least 20% by weight (polyisocyanate a), and b) 20-0% by weight of another polyisocyanate (polyisocyanate b), and wherein the isocyanate-reactive composition consists of a) 80-100% by weight of a polyether polyol having an average nominal functionality of 2-6, an average equivalent weight of 150-1000, an average molecular weight of 600-5000, an oxyethylene (EO) content of 75-100% by weight, and b) an 20-0% by weight of one or more other isocyanate-reactive compounds excluding water, the amount of polyol a) and compound b) being calculated on the total amount of this polyol a) and compound b).
The present invention is concerned with a process for preparing a polyisocyanurate polyurethane material which process comprises reacting a polyisocyanate and an isocyanate-reactive composition wherein the reaction is conducted at an isocyanate index of 150 to 1500, the polyisocyanate consists of a) 80-100% by weight of diphenylmethane diisocyanate comprising at least 40%, preferably at least 60% and most preferably at least 85% by weight of 4,4′-diphenylmethane diisocyanate and/or a variant of said diphenylmethane diisocyanate which variant is liquid at 25° C. and has an NCO value of at least 20% by weight (polyisocyanate a), and b) 20-0% by weight of another polyisocyanate (polyisocyanate b), and wherein the isocyanate-reactive composition consists of a) 80-100% by weight of a polyether polyol having an average nominal functionality of 2-6, an average equivalent weight of 150-1000, an average molecular weight of 600-5000, an oxyethylene (EO) content of 75-100% by weight, and b) an 20-0% by weight of one or more other isocyanate-reactive compounds excluding water, the amount of polyol a) and compound b) being calculated on the total amount of this polyol a) and compound b).
In the context of the present invention the following terms have the following meaning:
Preferably, the polyisocyanate a) is selected from 1) a diphenylmethane diisocyanate comprising at least 40%, preferably at least 60% and most preferably at least 85% by weight of 4,4′-diphenylmethane diisocyanate and the following preferred variants of such diphenylmethane diisocyanate; 2) a carbodiimide and/or uretonimine modified variant of polyisocyanate 1), the, variant having an NCO value of 20% by weight or more; 3) a urethane modified variant of polyisocyanate 1), the variant having an NCO value of 20% by weight or more and being the reaction product of an excess of polyisocyanate 1) and of a polyol having an average nominal hydroxyl functionality of 2-4 and an average molecular weight of at most 1000; 4) a prepolymer having an NCO value of 20% by weight or more and which is the reaction product of an excess of any of the aforementioned polyisocyanates 1-3) and of a polyol having an average nominal functionality of 2-6, an average molecular weight of 2000-12000 and preferably an hydroxyl value of 15 to 60 mg KOH/g, and 5) mixtures of any of the aforementioned polyisocyanates. Polyisocyanates 1) and 2) and mixtures thereof are preferred as polyisocyanate a).
Polyisocyanate 1) comprises at least 40% by weight of 4,4′-MDI. Such polyisocyanates are known in the art and include pure 4,4′-MDI and isomeric mixtures of 4,4′-MDI and up to 60% by weight of 2,4′-MDI and 2,2′-MDI.
It is to be noted that the amount of 2,2′-MDI in the isomeric mixtures is rather at an impurity level and in general will not exceed 2% by weight, the remainder being 4,4′-MDI and 2,4′-MDI. Polyisocyanates as these are known in the art and commercially available; for example Suprasec™ MPR isocyanate ex Huntsman Polyurethanes, which is a business of Huntsman International LLC (who owns the Suprasec trademark).
The carbodiimide and/or uretonimine modified variants of the above polyisocyanate 1) are also known in the art and commercially available; e.g. Suprasec 2020 isocyanate, ex Huntsman Polyurethanes.
Urethane modified variants of the above polyisocyanate 1) are also known in the art, see e.g. The ICI Polyurethanes Book by G. Woods 1990, 2nd edition, pages 32-35. Aforementioned prepolymers of polyisocyanate 1) having an NCO value of 20% by weight or more are also known in the art. Preferably the polyol used for making these prepolymers is selected from polyester polyols and polyether polyols and especially from polyoxyethylene polyoxypropylene polyols having an average nominal functionality of 2-4, an average molecular weight of 2500-8000, and preferably an hydroxyl value of 15-60 mg KOH/g and preferably either an oxyethylene content of 5-25% by weight, which oxyethylene preferably is at the end of the polymer chains, or an oxyethylene content of 50-90% by weight, which oxyethylene preferably is randomly distributed over the polymer chains.
Mixtures of the aforementioned polyisocyanates may be used as well, see e.g. The ICI Polyurethanes Book by G. Woods 1990, 2nd edition pages 32-35. An example of such a commercially available polyisocyanate is Suprasec 2021 isocyanate ex Huntsman Polyurethanes.
The other polyisocyanate b) may be chosen from aliphatic, cycloaliphatic, araliphatic and, preferably, aromatic polyisocyanates, such as toluene diisocyanate in the form of its 2,4 and 2,6-isomers and mixtures thereof and mixtures of diphenylmethane diisocyanates (MDI) and oligomers thereof having an isocyanate functionality greater than 2 known in the art as “crude” or polymeric MDI (polymethylene polyphenylene polyisocyanates). Mixtures of toluene diisocyanate and polymethylene polyphenylene polyisocyanates may be used as well.
When polyisocyanates are used which have an NCO functionality of more than 2, the amount of such polyisocyanate used is such that the average NCO functionality of the total polyisocyanate used in the present invention is 2.0-2.2 preferably.
Polyether polyol a) having a high EO content is selected from those having an EO content of 75-100% by weight calculated on the weight of the polyether polyol. These polyether polyols may contain other oxyalkylene groups like oxypropylene and/or oxybutylene groups. These polyols have an average nominal functionality of 2-6 and more preferably of 2-4, an average equivalent weight of 150-1000 and a molecular weight of 600-5000, preferably of 600-3000. If the polyol contains oxyethylene groups and another oxyalkylene group like oxypropylene, the polyol may be of the type of a random distribution, a block copolymer distribution or a combination thereof. Mixtures of polyols may be used. Methods to prepare such polyols are known and such polyols are commercially available; examples are Caradol™ 3602 polyol from Shell, Lupranol™ polyol 9205 from BASF, Daltocel F526 polyol ex Huntsman Polyurethanes (Daltocel is a trademark of Huntsman International LLC) and G2005 ex Uniqema. Preferably they are used in an amount of 90-100% by weight.
The other isocyanate-reactive compounds b), which may be used in an amount of 0-20% by weight and preferably of 0-10% by weight, may be selected from chain extenders, cross-linkers, polyether polyamines, polyester polyols and polyether polyols (different from the above described ones) having a molecular weight of more than 500 and in particular from such other polyether polyols, which may be selected from polyoxypropylene polyols, polyoxyethylene polyoxypropylene polyols having an oxyethylene content of less than 75% by weight and polyoxyethylene polyoxypropylene polyols having a primary hydroxyl content of less than 70%. Preferred polyoxyethylene polyoxypropylene polyols are those having an oxyethylene content of 5-30% and preferably 10-25% by weight, wherein all the oxyethylene groups are at the end of the polymer chains (so-called EO-capped polyols) and those having an oxyethylene content of 60-90% by weight and having all oxyethylene groups and oxypropylene groups randomly distributed and a primary hydroxyl content of 20-60%, calculated on the number of primary and secondary hydroxyl groups in the polyol. Preferably, these other polyether polyols have an average nominal functionality of 2-6, more preferably 2-4 and an average molecular weight of 2000-10000, more preferably of 2500-8000.
The isocyanate-reactive chain extenders, which have a functionality of 2, may be selected from amines, amino-alcohols and polyols; preferably polyols are used. Further, the chain extenders may be aromatic, cycloaliphatic, araliphatic and aliphatic; preferably aliphatic ones are used. The chain extenders have a molecular weight of 500 or less. Most preferred are aliphatic diols having a molecular weight of 62-500, such as ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 1,2-hexanediol, 3-methylpentane-1,5-diol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol and tripropylene glycol, and aromatic diols and propoxylated and/or ethoxylated products thereof. The cross-linkers are isocyanate-reactive compounds having an average molecular weight of 500 or less and a functionality of 3-8. Examples of such cross-linkers are glycerol, trimethylolpropane, pentaerythritol, sucrose, sorbitol, mono-, di- and triethanolamine, ethylenediamine, toluenediamine, diethyltoluene diamine, polyoxyethylene polyols having an average nominal functionality of 3-8 and an average molecular weight of 500 or less like ethoxylated glycerol, trimethylol propane, pentaerythritol, sucrose and sorbitol having said molecular weight, and polyether diamines and triamines having an average molecular weight of 500 or less; most preferred cross-linkers are the polyol cross-linkers.
Still further, the other isocyanate-reactive compounds may be selected from polyesters, polyesteramides, polythioethers, polycarbonates, polyacetals, polyolefins or polysiloxanes. Polyester polyols which may be used include hydroxyl-terminated reaction products of dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol or cyclohexane dimethanol or mixtures of such dihydric alcohols, and dicarboxylic acids or their ester-forming derivatives, for example succinic, glutaric and adipic acids or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl terephthalate or mixtures thereof. Polythioether polyols, which may be used, include products obtained by condensing thiodiglycol either alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, amino-alcohols or aminocarboxylic acids. Polycarbonate polyols which may be used include products obtained by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol or teraethylene glycol with diaryl carbonates, for example diphenyl carbonate, or with phosgene. Polyacetal polyols which may be used include those prepared by reacting glycols such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Suitable polyacetals may also be prepared by polymerising cyclic acetals. Suitable polyolefin polyols include hydroxy-terminated butadiene homo- and copolymers and suitable polysiloxane polyols include polydimethylsiloxane diols.
Mixtures of the aforementioned other isocyanate-reactive compounds may be used as well. Preferably, the other isocyanate-reactive compounds are polyols selected from the above preferred ones.
The polyols may comprise dispersions or solutions of addition or condensation polymers in polyols of the types described above. Such modified polyols, often referred to as “polymer polyols” have been fully described in the prior art and include products obtained by the in situ polymerisation of one or more vinyl monomers, for example styrene and/or acrylonitrile, in the above polyether polyols, or by the in situ reaction between a polyisocyanate and an amino- and/or hydroxy-functional compound, such as triethanolamine, in the above polyol. Polyoxyalkylene polyols containing from 1 to 50% of dispersed polymer are particularly useful. Particle sizes of the dispersed polymer of less than 50 microns are preferred.
Still further, the following optional ingredients may be used: catalysts enhancing the formation of urethane bonds like tin catalysts like tin octoate and dibutyltindilaurate, tertiary amine catalysts like triethylenediamine and imidazoles like dimethylimidazole and other catalysts like maleate esters and acetate esters; surfactants; foam stabilisers like siloxane-oxyalkylene copolymers; fire retardants; smoke suppressants; UV-stabilizers; colorants; microbial inhibitors; organic and inorganic fillers, impact modifiers, plasticizers and internal mould release agents. Further external mould release agents may be used in the process according to the present invention.
Any compound that catalyses the isocyanate trimerisation reaction (isocyanurate-formation) can be used as trimerisation catalyst in the process according to the present invention, such as tertiary amines, triazines and most preferably metal salt trimerisation catalysts.
Examples of suitable metal salt trimerisation catalysts are alkali metal salts of organic carboxylic acids. Preferred alkali metals are potassium and sodium, and preferred carboxylic acids are acetic acid and 2-ethylhexanoic acid.
Most preferred metal salt trimerisation catalysts are potassium acetate (commercially available as Polycat 46 catalyst from Air Products and Catalyst LB from Huntsman Polyurethanes) and potassium 2-ethylhexanoate (commercially available as Dabco K15 catalyst from Air Products). Two or more different metal salt trimerisation catalysts can be used in the process of the present invention.
The metal salt trimerisation catalyst is generally used in an amount of up to 5% by weight based on the isocyanate-reactive composition, preferably 0.1 to 3% by weight. It may occur that the polyol used in the process according to the present invention still contains metal salt from its preparation which may then be used as the trimerisation catalyst or as part of the trimerisation catalyst.
The polyurethane material may be a solid or blown (microcellular) material. Microcellular materials are obtained by conducting the reaction in the presence of a blowing agent, like hydrocarbons, hydrofluorocarbons, hydrochlorofluoro-carbons, gases like N2 and CO2, and water. Most preferably water is used as the blowing agent. The amount of blowing agent will depend on the desired density. The amount of water will be less than 5, preferably less than 3 and most preferably less than 1% by weight; calculated on the weight of the isocyanate-reactive composition. Density reduction may also be achieved by the incorporation of expanded or expandable microspheres like Expancel microspheres or hollow glass microbeads.
The reaction to prepare the material is conducted at an NCO index of 150-1500. The density of the materials is higher than 100 kg/m3.
The materials are preferably made in a mould. The process may be conducted in any type of mould known in the art. Examples of such moulds are the moulds commercially used for making shoe parts like soccer shoes and ski- and skate boots, automotive parts, like arm-rests, door panels and back-shelves. Preferably, the reaction is conducted in a closed mould. The ingredients used for making the material are fed into the mould at a temperature of from ambient temperature up to 80° C., the mould being kept at a temperature of from ambient temperature up to 150° C. during the process. Demoulding time is relatively short despite the fact that preferably no isocyanate-reactive compounds, containing reactive amine groups, are used; depending on the amount of catalyst demould times may be below 10 minutes, preferably below 5 minutes, more preferably below 3 minutes and most preferably below 1 minute.
The moulding process may be conducted according to the reaction injection moulding (RIM) process and the cast moulding process. The process may also be conducted according to the RRIM (reinforced RIM) and SRIM (structural RIM) process.
In general, the isocyanate-reactive ingredients and catalysts may be pre-mixed, optionally together with the optional ingredients, before being brought into contact with the polyisocyanate.
The materials according to the invention are particularly suitable for use in applications where high stiffness, non-brittle, high impact resistant and low density materials are desirable, like soccer shoe soles and ski-boots, and automotive parts like arm-rests, doorpanels, back-shelves and sun visors.
The present invention is illustrated by the following examples.
Suprasec 2020 isocyanate* and Daltocel F526 polyol** were dispensed into a mould (dispensing machine Krauss Maffei Comet 2020 high pressure piston machine, output was 300 g/s). The mould was a steel mould having dimensions 30×60×0.3 cm and mounted in a Battenfeld press. The temperature of the chemicals and of the mould was 35 and 85° C., respectively. Before use, the mould was treated with Acmos 35-5015 mould release agent. Demould time was 60 seconds. The amounts (in parts by weight) used and the physical properties of the polyisocyanurate polyurethane parts are given in below table.
*A uretonimine/carbodiimide-modified 4,4′-MDI having an NCO-content of 29.3% by weight and a uretonimine/carbodiimide content of about 27% by weight obtainable from Huntsman Polyurethanes. Suprasec is a trademark of Huntsman International LLC.
**A glycerol-initiated polyoxyethylene polyol having an OH-value of 140 mg KOH/g obtainable from Huntsman Polyurethanes. Daltocel is a trademark of Huntsman International LLC.
***mixed in Daltocel F526.
****Daltocel F526 contains enough Na/K-salt catalyst from its production; no additional catalyst needed.
| Number | Date | Country | Kind |
|---|---|---|---|
| 03013241.9 | Jun 2003 | EP | regional |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/EP04/50898 | May 2004 | US |
| Child | 11292398 | Dec 2005 | US |
