SE455101B - Rigid, hardened, solid polyurethane product based on an ammonia or amininitiated polyether polyol, an organic polyisocyanate, and a liquid modifier compound and preparation process - Google Patents

Description

The present invention is obtained by: mixing and reacting (A) ammonia or an amine-initiated polyether polyol having an equivalent weight of from 50 to less than 250, preferably from SO to 200, with (B) an organic polyisocyanate containing an aromatic cyclic ring in the presence of (C) a liquid modifier compound having a boiling point above 150 ° C selected from esters of carboxylic acids and mixtures thereof; wherein components (A) and (B) are present in such amounts that an NCO; OH ratio of from 0.8 to 1.5 is provided, preferably from 0.9 to 1.2 and most preferably from 0.95 to 1, 05, and component (C) is used in an amount of from 5% to 60%, preferably 15-40% by weight, based on the total weight of (A), (B) and (C).

Suitable amine-initiated polyether polyols used as component (A) in the present invention include, for example, those prepared by reacting an alkylene oxide with ammonia or an amine having 3-8 active hydrogen atoms.

Suitable amines include, for example, ammonia, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopropane, 1,6-diamino-hexane, diethylenetriamine, triethylenediamine, tetraethylenepentamine, pentaethylenehexamine and mixtures thereof.

Suitable alkylene oxides include, for example, ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, epichlorohydrin, epibromohydrin, epiodiodhydrin and mixtures thereof.

Suitable organic polyisocyanates used as component (B) in the present invention include, for example, any organic polyisocyanate having two or more NCO groups per molecule and no other substituents capable of reacting with the hydroxy groups of the amine-initiated polyoxyalkylene compounds used as component (C). The isocyanate groups need not be substituted in the aromatic ring. Suitable such polyisocyanates include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p, p'-diphenylmethane diisocyanate, p-phenylene diisocyanate, hydrogenated methylene diphenyl diisocyanate, naphthalene diisocyanate, dianisidin diphenylene isocyanate and dianisidin diphenyl isocyanate. for ll 455 101 or more polyisocyanates.

Other organic isocyanates which are suitably used and which are to be included in the term organic polyisocyanate include isocyanate-terminated prepolymers prepared from the aforementioned polyols and the above-mentioned isocyanates.

Suitable esters of a carboxylic acid used as component (C) in the present invention include those esters prepared from mono- and polycarboxylic acids having 1 to 20 carbon atoms, for example, phthalic, adipic, acetoneacetic, formic, acetic, abietic acids , and wherein the ester moiety contains 1-20 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, eicosyl as long as the carboxylic acid ester has a boiling point above 150 ° C and constitutes a liquid at room temperature.

These acid esters can be prepared by condensation of an acid having 1 to 20 carbon atoms with a saturated or unsaturated aliphatic alcohol having 1 to 20 carbon atoms, with the proviso that the ester product is a liquid and has a boiling point> 150 ° C.

The term "Liquid modifier boiling above 150 ° C" includes eutectic mixtures of the previously described groups of compounds which form solids at atmospheric pressure but the eutectic mixtures constitute a liquid at room temperature and atmospheric pressure having boiling points above 150 ° C. The definition also includes the solid compounds of the previously described groups which are dissolved in a liquid compound of any of the previously described groups of compounds having boiling points above 150 ° C wherein the resulting solution constitutes a liquid under standard conditions regarding temperature and pressure and which have boiling points at atmospheric pressures above 150 ° C.

Other compounds including inert fillers, for example sand, microballoons, glass fibers, asbestos, aluminum granules and silicon carbide powder, coloring agents such as pigments and dyes including, for example, chromium oxide, ferric oxide and mixtures thereof may be used in the compositions of the present invention. Suitable materials from which suitable molds for casting the compositions of the present invention can be prepared include polymers, for example, polyethylene, polypropylene, their copolymers and the like, polyurethanes, polysiloxane elastomers, polyethylene terephthalate, cured polyepoxides and mixtures thereof.

It is preferred to use relatively thin-walled molds or molds which have low heat capacity or thermal conductivity.

Heavy molds made of materials with relatively high thermal conductivity, such as aluminum, copper, iron or steel can give rise to hardening problems, ie. the reactants may not be easily removed from the mold unless the mold is preheated to 50-90 ° C, especially when casting relatively thin sections. However, materials with high thermal conductivity, such as copper or aluminum, can be used as thin-walled molds without preheating if the heat capacity of the mold is relatively low compared to the amount of heat released during casting.

The compositions of the present invention are suitable as, but not limited to, such uses as a casting material for making bearing surfaces, annular spacers, game pieces, decorative objects, furniture or furniture components gears or other machine parts, threaded protective plugs and housings.

In some cases, a mixture of components (A) and (B) is so incompatible that the reaction takes place very slowly (ie solidification requires more than 10 minutes). When this occurs, a modifying compound having a high dielectric constant determined at 20 ° C and a frequency of 1x10 4 cycles per second is greater than 4 and preferably greater than 8, for example ethyl acetoacetate and dimethyl phthalate are particularly suitable by making the mixture compatible. . These compounds help to make components (A) and (B) more compatible in that they can be mixed and will react rapidly and give a fast curing solid which is removable from the mold in less than 5 minutes.

The modifiable miscibility compounds are used in an amount in the range of 45- 101% of the total weight of components (A), (B) and (C) and such amounts are included as part of the total amount of component (C). ) which are present in the composition.

In each of the examples and comparative experiments, all the components except the polyisocyanate were thoroughly mixed together and then the polyisocyanate was rapidly mixed into the mixture and immediately poured into a polyethylene mold or a polyethylene terephthalate bowl.

The compositions, curing times and mold removal times and properties of the products are reported in the following table. 455 191 .CUUCHEÜCNHD H WÜUÜUCNHQ UmUMCN% UOwH> HO @ ECM MUHHQCOOÛ UÜÜ CWHM WÜU # mÉ CÜUHE ¥ _ wm> m vsmu fi mu cm w fl> ~ eo \ mg mmm "uwnummm wu um ww wm ww wm ww wm. N .xm wcmumnøm ummw Ummumw fwwmmm .xmmo om A om om mm o om m mm <m .xm xumumm zoo @@ mmm> m mm.ø |||| 11 cwmam om 4 om mm xww fl wm Hoxo fl umm m> 0um m fl m fl IHHQ SUO mU®H> M © W iu fi mw .mwïmäw 3.0 11 mm I cwm fi om <mm 4 4 Mmwäë Hmïåcå fi ëëmuw fl mw mEu \ @ cwëuom mc fl c fi wuw Emuw mms Emuw mha Emma mw fi nu xwmumw uw mmc » The aminitiated polyols used as component (A) in the previous example and comparative experiments were as follows: Type A was an aminoerylethanolamine reacted with a molybene oxide with propylene oxide. of about 1.3 with a hydroxy equivalent weight of about 72.

Type B was the reaction product of diethylenetriamine with propylene oxide in a molar ratio of about 1.5 and having an OH equivalent weight of about 76.

The polyisocyanates used as component (B) in the previous example and comparative experiments were as follows: Type A was an 80/20 mixture of the 2,4- / 2,6-isomers of toluene diisocyanate with an NCO equivalent weight of about 87.

Type B was a dimerized diphenylmethane diisocyanate having an average functionality of about 2.25 and an NCO equivalent weight of about 144.

The modifiers used as component (C) in the previous example and comparative experiments were as follows: Type C was dioctyl phthalate.

Claims (6)

455 101 8 PATENT CLAIMS f 1. l. Rigid, fast-cured, solid polyurethane product with a density of at least lg / cm3, produced without the use of a catalyst or externally applied heat, suitable for example as a casting material for the production of bearing surfaces, annular spacers, game pieces, decorative objects , furniture or furniture components, gears or other machine parts and threaded protective plugs or covers, characterized in that it is obtained as a result of mixing, in addition to any inert additives, the components consisting of (A) an ammonia- or aminitiated polyether polyol having an OH equivalent of from 50 to less than 250; F: EÉÉV <2. (l) .I (s) an organic polyisocyanate containing an aromatic '1 p; ng and fx (_)) a liquid modifier compound having a boiling point above'OOC selected from esters of carboxylic acids, J | a \ * a arí mmmonenü fl na ( A) and (B) are present in such amounts that the NCO: OH ratio is from 0.8 to 1.5 and component (C) is used in an amount of 5-60% of the total weight of the components (ä), (B) and (C). Polyurethane product according to claim 1, characterized in that components (A) and (B) are present in such amounts that the NCO: OH ratio is from about 0.90: 1 to about 1.2: 1 and component (C ) are present in an amount of from about 15% to about HO% by weight of the total weight of components (A), (B) and (C). A polyurethane product according to claim 2, characterized in that components (A) and (B) are present in such amounts that the NCO: OH ratio is from about 0.95: 1 to about 1.05: 1. Product according to one of Claims 1 to 3, characterized in that component (C) consists of dioctyl phthalate. A product according to any one of claims 1 to 3, characterized in that component (C) is ethyl acetate (acetate). A process for the preparation of solid polyurethane products according to claim 1, characterized in that (A) an ammonia- or amine-initiated polyether polyol having an OH equivalent weight of from So to less than 250 is mixed; (E) an organic polyisocyanate containing an aromatic ring and (C) a liquid modifier compound having a boiling point above 150 ° C selected from esters of carboxylic acids, the reaction mixture will rapidly cure and the components (A) and (B) there are present E such amounts that the NCO: OH ratio is from 0.8 to 1.5 and component (C) is used in an amount of from 5 to 60% of the total weight of the components (A), ( B) and (C).