DE494169T1 - METHOD FOR THE PRODUCTION OF HEAT-CURABLE POLYURETHANE-TYPE COMPOSITIONS REINFORCED WITH FILLERS AND THE COMPOSITIONS BASED THEREOF. - Google Patents

Claims (22)

091-46.105DeEP-Ru(SF)-Bk EP 90913356.3 Claims 1. Process for the preparation of filler-containing thermosetting compounds of the polyurethane type by condensation of the constituents of the desired compound in the presence of a powdered filler, characterized in that the filler is predispersed with the aid of a stabilizing agent in an organic phase compatible with the desired thermosetting compound during its formation reaction, the filler then being in the form of a homogeneous and stable suspension and the suspension thus prepared then being added to the reaction mixture before, during or after the addition of at least one of the constituents of the desired thermosetting compound. 2. Process according to claim 1, characterized in that the liquid organic phase is selected from symmetrical or asymmetrical aliphatic, aromatic, cyclic, branched or unbranched dialkyl phthalates or glycol derivatives, which are used alone or in admixture. 3· Process according to claim 1 or 2, characterized in that the liquid organic phase is preferably selected from dioctyl phthalate, dibutyl phthalate, dinonyl phthalate, didecyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, mixed octyl, butyl and decyl phthalates, benzyl phthalate, cyclohexyl phthalate, methoxyethyl phthalate, methoxybutyl phthalate, butoxyethyl phthalate and other substituents based on glycols. 4· Process according to claim 1, characterized in that the liquid organic phase is selected from esters of organic or inorganic mono- or polybasic acids of the alkyl adipate and alkyl sebacate type and the diesters of C o-mono-, di- or triethylene glycol and glycerin of the trimellitate, azelate, abietate, citrates, mellitate, stearate, oleate, palmitate, ricinoleate, myristate, benzoate and pelargonate type. 5· Process according to claim 1, characterized in that the liquid organic phase is selected from mono- or polyalkyl phosphates, aryl phosphates and phosphates of glycol derivatives and preferably from trioctyl phosphate, tricresyl phosphate, octyldicresyl phosphate and other alkylaryl phosphates. 6. Process according to claim 1, characterized in that the liquid organic phase is selected from polyesters and preferably from ethylene glycol polyadipates, propylene glycol polyadipates, ethylene glycol polysebacates and
Propylene glycol polysebacates is selected. 7· Process according to one of claims 1 to 6, characterized in that the stabilizing agent of the filler has the following formula R (A) _m (B) _n X ₅ which has at least one free acid function and wherein: X is a carboxyl, phosphinic acid _, phosphonic acid, phosphoric acid, sulfonic acid or sulfuric acid residue, A ethylene oxide and B propylene oxide, where 0 ^(m + n) < 24, and R is an alkyl radical, aryl radical or alkylaryl radical, a radical of a saturated or unsaturated heterocycle having 5 to 28 carbon atoms and preferably 8 to 24 carbon atoms or a radical of a steroid. 8. Process according to claim 7, characterized in that when X has several acid functions, at least one of these is free, the others being in salt form or esterified with an alcohol of formula R'-OH in which R ¹ is a hydrocarbon chain having 1 to 4 carbon atoms and one of the groups selected from those defined for R. 9- Process according to claim 7, characterized in that R has at least one of the following functional groups: halogen, -OH, -COOH, -COOR, ~ ^N 0 ₂ ' ~ ^NH 2' -CONH ₂ , CN, phosphinic acid, phosphonic acid, phosphoric acid, sulfonic acid, sulfuric acid. 10. Process according to claim 8, characterized in that the radical R ¹ is identical to the radical R. 11. Process according to one of claims 1 to 10, characterized in that at least one auxiliary agent is added to the reaction mixture, which is selected from reaction catalysts, surfactants, thermal and photochemical stabilizers, lubricants, plasticizers which are not used in the preparation of the suspension of the filler, antistatic agents, fire retardants, metal passivation agents and blowing agents. 12. Process according to one of claims 1 to 11, characterized in that the powdery filler to be predispersed in the liquid organic phase is selected from inorganic and/or synthetic powdery substances, in particular from calcium carbonate, zinc carbonate, dolomite, lime, magnesium oxide, aluminum trihydroxide, silica, clays, kaolin, talc, mica, zinc oxide, iron oxide, antimony oxide, titanium oxide, glass fibers and glass beads, wollastonite, red phosphorus, various pigments, which can be used alone or in a mixture. 13« Process according to one of claims 1 to 12, characterized in that the powdery filler to be predispersed in the organic phase is selected from organic powdery substances of natural and/or synthetic origin, in particular dyes, carbon black, starch, cellulose fibers and cellulose flour, carbon fibers and melamine powder, which can be used alone or in a mixture. -s- 14· Process according to claims 12 and 13, characterized in that the powdered filler is a combination of powdered inorganic substances of natural or synthetic origin· 15· Process according to one of claims 1 to 14, characterized in that the powdery substances forming the filler have a particle size between 0.01 and 300 μιη and preferably between 0.1 and 100 μιη· 16. Process according to one of claims 1 to 15, characterized in that the homogeneous and stable suspension of the filler is composed, in relation to the total mass, essentially as follows: a) 20 to 80 wt. % and preferably 40 to 70 wt. %
Filler, b) 79.9 to 18.4 wt. % and preferably 59.5 to
28.9 wt. % liquid organic phase, c) 0.1 to 1.6 wt. % and preferably 0.5 to
1.1 % by weight stabilizing agent. 17· Process according to one of claims 1 to 16, characterized in that polyol, which can be used in the preparation of the desired thermosetting compound, is introduced into the homogeneous and stable suspension of the filler. 18. Process according to one of claims 1 to 17, characterized in that the Brookfield viscosity of the homogeneous and stable suspension of the filler between 500 and 2000 mPa-s and preferably between 600 and 1600 mPa-s, measured at ambient temperature. 19· Process according to one of claims 1 to 18, characterized in that the homogeneous and stable suspension of the filler is introduced into the reaction mixture in the form of a premix with the polyol and is subsequently processed in this form with the other components of the desired polyurethane, all components being used in the required amounts and proportions. 20. Process according to one of claims 1 to 18, characterized in that the homogeneous and stable suspension of the filler is used simultaneously with the various components of the desired polyurethane, all components being used in the required amounts and proportions. 21. Process according to one of claims 1 to 18, characterized in that the homogeneous and stable suspension of the filler is added to the reaction mixture after all the components of the desired polyurethane have been premixed, all the components being used in the required amounts and proportions. 22. Process according to one of claims 1 to 21, characterized in that the homogeneous and stable suspension of the filler is added to the composition of the desired polyurethane compound in an amount of from 1 to 100 % by weight and preferably from 10 to 50 % by weight, based on the polyol used. 23· Process according to one of claims 1 to 22, characterized in that it is applied to the techniques known for the preparation of thermosetting compounds based on polyurethane. 24· Filler in suspension in a liquid organic phase with the aid of a stabilizing agent, used for the preparation of filler-containing thermosetting compounds based on polyurethane according to one of claims 1 to 23, characterized in that the liquid organic phase is compatible with at least one of the constituents of the desired thermosetting compound and remains compatible with this compound during its formation reaction. 25· Filler-containing thermosetting compounds of the polyurethane type, obtained according to one of claims 1 to 24-