PROCESS FOR PREPARING AQUEOUS EMULSIONS OF POLYISOCYANATES

Abstract: Stable aqueous emulsions of polyisocyanates are pre­ pared by gradually adding the latter to an aqueous solution at 1-5% by weight of a polyoxyethylene glycol having an average molecular weight ranging from 350,000 to 600,000, under such conditions, with regard both to stirring and to polyisocyanate feeding rate, as to allow a practically immediate mixing of the polyisocyanate in the water.

Description: This invention relates to a process for preparing aqueous emulsions of polyisocyanates. It is known in the technique . to prepare polyisocyanic emulsions by using surfactants, generally-anionic surfactants,having a molecular weight not higher than 1000-1500, which exhibit in the molecule hydrophobic groups with a structure like the one of polyisocyanate (for example an urethane bond, according to British patent 1,444,933) and hydrophilic groups (for example a polyoxyethylene chain). It is also known to use, for this purpose, anionic surfactants based on hexamethylenediamine (as hydrophobic moiety) and polyoxymethylene (as hydrophilic moiety) optionally modified with polyoxypropylene, according to what is described, for example, in British patent 2,093,760. The present invention relates to a process for preparing aqueous emulsions of polyisocyanates, which differs from the methods of the prior art reported hereinabove, and which permits to obtain generally more stable emulsions. Such -process,which forms the object of the present invention, consists in gradually adding. the polyisocyanate under stirring to a solution at 1-5 < in water of a polyoxyethylene glycol having an average molecular weight ranging from 350,000 to 600,000, but preferably from 400,000 to 500,000. The addition of the polyisocyanate to the aqueous solution of the polyoxyethylene glycol is accomplished in such conditions as to permit a practically immediate mixing of the polyisocyanate with water. This can be achieved by adjusting the addition rate and/or the stirring degree of the solution. For example, if a Cowles stirrer is utilized, the conditions for an immediate mixing occur at an impeller speed of 1800-2200 rpm and at a polyisocyanate feeding rate ranging approximately from about 5G to 60 minute. The temperature of the polyoxyethylene glycol solution is preferably not higher than 30 C, and generally ranges from 10 to 30 C. The polyisocyanates utilizable for the purposes of the present invention may be either hexamethylene diisocyanate, or aromatic, such as 2,4and 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and diphenyl-4,4'-diisocyanate. Particularly suited has proved polymethylene-polyphenylisocyanate having mean functionality of 2,7-2,8, obtained by phosgenation of the polyaminee deriving from the condensation of aniline with formaldehyde. Such product is commercially available under various trade-names, such 3s "Tedimon" 31 (produced by Montepolimeri3, "PaPi" (produced by Up John) and "Hondur bIR" (produced by Mobay). The following examples are given to illustrate the present invention, without being however a limitation thereof. Examples 1-7 Polyoxyethylene glycol having an average molecular weight of 400,000 was added under stirring to water, optionally heated to 600C, until dissolution, in amounts of 0.5%, 1.5s, 2% and 30 by weight, respectively. To these solutiow maintained at 20-25 C there was added polymethylene-polyphenylisocyanate (Tedimon 31) under stirring, supplied by a Cowles-type stirrer, at a speed higher than 2000 rpm. The addition of polyisocyanate was effected at a rate of 50- & g/minute, with polyisocyanate/water weight ratios of 30, 40 and 50,res- pectively. The characteristics of the emulsions so prepared and the ageing time as a function of the concentration of polyoxyethyleneglycol and of polyisocyanate are indicated in Table I and in Table II. The per cent content of iiC0 groups, which remains at acceptable levels even after a 24-hour ageing,is indicative of the applicability of the emulsions. From the data of the tablesit is apparent that the concentration of the polyisocyanate in the emulsion does not substantially affect the stability and applicability of the emulsion. Example 8 An emulsion at 40% of active substance, prepared according to the above described method, - was utilized to impregnate an amount of wooden shavings suitable for the preparation of six three-layer shaving panels; the concentration of polyisocyanate on the dry shaving was of 6% in the inner layer and of 8% in the outer layers. The panels, prepared according to the usual conditions employed also for the ones based on ureic products (15"/mm at a press temperature aound 1600C), were characterized according to DIN 68763 V100 and gave the following results : EMI4.1 <SEP> Panels <SEP> with- <SEP> Panels <SEP> with <SEP> Standard <tb> out <SEP> paraffin <SEP> paraffin <SEP> DIN <SEP> 68763 <tb> values <tb> type <SEP> V <SEP> 100 <tb> Flexural <SEP> strength <SEP> kg/cmê <SEP> 185 <SEP> 190 <SEP> #180 <tb> Tensile <SEP> strength <SEP> " <SEP> 2.2 <SEP> 2.7 <SEP> #1.5 <tb> Swelling <SEP> % <SEP> 9.8 <SEP> 7.5 <SEP> #12 <tb> Density <SEP> g/cm <SEP> 0.63 <SEP> 0.62 <SEP> Thickness <SEP> mm <SEP> 16 <SEP> 16 <SEP> 13-20 <tb> T A B L E 1 STABILITY OF POLYMETHYLENE-POLYPHENYL ISOCYANATE EMULSIONS (AT 40% IN WATER EMI5.1 <tb> <SEP> Emulalon <SEP> character- <SEP> 35 <SEP> Polyoxyothylene <SEP> glycol <SEP> Polyoxyathylana <SEP> glycol <SEP> 15'L <SEP> Po!yoxyathylana <SEP> glycol <SEP> 05 <SEP> Pol)oxyathylana <SEP> gfyco <tb> <SEP> own <tb> <SEP> o <tb> cF4 <SEP> cF4 <SEP> C <SEP> F'4 <SEP> eF4 <tb> urs <SEP> ' <SEP> (sac.) <SEP> (sac.) <SEP> (see.) <tb> <SEP> ¯ <SEP> 100 <SEP> 14tk <SEP> 100 <SEP> O <SEP> 100 <SEP> <tb> <SEP> 2 <SEP> 100 <SEP> g6 <SEP> QQ <tb> <SEP> 3 <SEP> 34 <SEP> > <tb> <SEP> 4 <SEP> 132 <SEP> g4 <SEP> 21 <tb> <SEP> S <SEP> 93 <SEP> 93 <tb> <SEP> 8 <tb> <SEP> tS, <SEP> Q <SEP> ¯ <tb> <SEP> 9 <SEP> 100 <SEP> 93 <SEP> 93 <SEP> 18 <tb> <SEP> g <SEP> 62 <SEP> 31 <tb> <SEP> 10 <SEP> 95 <SEP> ow <tb> <SEP> 11 <tb> <SEP> 12 <SEP> 29 <tb> <SEP> 13 <SEP> o <SEP> 16 <tb> <SEP> o <SEP> ,- > ¯, <tb> <SEP> o <SEP> o <SEP> Ï <SEP> c > <tb> <SEP> 7 <tb> . <SEP> A! <SEP> o <SEP> N <SEP> o <SEP> b <tb> T A B L E 2 STABILITY OF POLYMETHYLENE-POLYPHENYL ISOCYANATE EMULSIONS AT THE SAME CONCENTRATION OF 2% OF POLYOXYETHYLENE GLYCOL ON POLYISOCYANATE EMI6.1 <tb> <SEP> Emul <SEP> Po1yisocyana!H <SEP> 20 <SEP> a <SEP> 50 <SEP> PolyisoeyanateIH2O <SEP> - <SEP> 'to <SEP> polylsceyanatqll <SEP> 20 <SEP> S <SEP> 30 <tb> <SEP> aIonchrabtbnIstioa <SEP> c't <tb> CY <SEP> 2 <SEP> sco <SEP> Visc.a250C <SEP> 2 <SEP> ECO <SEP> Visc.:25eC <SEP> : <SEP> co <SEP> Viec. <SEP> at <SEP> 25C <tb> tima <SEP> (houra) <SEP> c't <SEP> (soc.) <SEP> (see.) <tb> <SEP> (seco) <tb> <SEP> o <SEP> :oo <SEP> 'to <SEP> 100 <SEP> 'tO <SEP> 100 <SEP> 23 <tb> 2 <SEP> g8.7 <SEP> 08.2 <SEP> gg. <tb> 3 <SEP> 34 <SEP> 23 <tb> <SEP> OCS <tb> <SEP> 5 <tb> S <SEP> g3.1 <SEP> 32 <SEP> m <SEP> 90 <tb> <SEP> 4r' <tb> <SEP> 32 <SEP> 93 <SEP> 31 <SEP> 88 <tb> <SEP> 9 <SEP> SB <SEP> 22 <tb> <SEP> 10 <SEP> 5tb.5 <SEP> 32 <SEP> 87 <SEP> 21.5 <tb> <SEP> II <SEP> 32 <SEP> 2S <tb> <SEP> 12 <tb> <SEP> 13 <SEP> 81 <tb> <SEP> 14 <SEP> 89.8 <SEP> 32 <SEP> 81 <SEP> 28 <SEP> 85 <SEP> 20 <tb>

Claims: Claims 1. A process for preparing stable aqueous emulsions of a polyisocyanate which consists in adding the polyisocyanate to an aqueous solution at 1-5 by weight of a polyoxyethylene glycol having an aver age molecular weight ranging from 350,000 to 600,000 in such conditions as to obtain a practically im mediate mixing of the polyisocyanate in water. 2. The process according to claim 1, in which the poly oxyethylene glycol solution has a temperature not higher than 300C. 3. The process according to claims 1 and 2, in which the polyisocyanate is polymethylene-polyphenyliso cyanate having a mean functionaly of 2.7-2.8. 4. The process according to claims 1 through 3,in which the polyoxyethylene glycol has an average molecular weight ranging from 400,000 to 500,000.

Inventors: MANUCRA, FORTUNATO, PALLOZZI, FRANCO, TURCO, PIETRO
Applicants: A.TE.CA. S.R.L.
Application year: 1985
Main classification: C07C118
IPC codes: C07C265, C08L97, C08G18