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United States Patent (19) 11 Patent Number: 4,697,009 Deschler Et Al

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United States Patent (19) 11 Patent Number: 4,697,009 Deschler Et Al United States Patent (19) 11 Patent Number: 4,697,009 Deschler et al. (45) Date of Patent: Sep. 29, 1987 54 N-SILYLPROPYL-N'-ACYL-UREAS AND 58 Field of Search ........................ 556/421; 544/229; PROCESS FOR THER PRODUCTION 546/14: 548/110; 260/239 BC; 556/414; 540/487 75) Inventors: Ulrich Deschler; Peter Kleinschmit, 56) References Cited both of Hanau; Rudolf Michel, Freigericht, all of Fed. Rep. of U.S. PATENT DOCUMENTS Germany 2,857,430 10/1958 Applegath et al. ............. 556/421 X 2,907,782 10/1959 Pike ..................................... 556/421 73 Assignee: Degussa Aktiengesellschaft, 3,793,253 2/1974 Quiring et al. ... ... 556/421 X Frankfurt am Main, Fed. Rep. of 3,803,194 4/1974 Golitz et al. .................... 556/42 X Germany 3,856,756 12/1974 Wagner et al. ................. 556/421 X Primary Examiner-Paul F. Shaver 21 Appl. No.: 875,867 Attorney, Agent, or Firm-Cushman, Darby & Cushman 22 Filed: Jun. 18, 1986 57 ABSTRACT The invention is directed to N-silylpropyl-N'-acyl ureas 30 Foreign Application Priority Data and their production from an alkali cyanate, a 3-halo propylsilane and in a given case, a cyclic acidamide. By Jul. 6, 1985 IDE Fed. Rep. of Germany ....... 352.425 heating the compounds of the invention the blocked 5) Int. Cl. ................................................ C07F 7/10 isocyanate function can be set free. 52 U.S. Cl. .................................... 540/487; 556/414; 556/421; 544/229; 546/14: 548/110 16 Claims, 3 Drawing Figures U.S. Patent Sep. 29, 1987 Sheet 1 of 3 4,697,009 (z+w)/92° oQtz,oºgOOººO972OO2 4,697,009 1. 2 attainable time-space yields are unsatisfactory for an N-SILYLPROPYL-N'-ACYL-UREAS AND industrial process. PROCESS FOR THER PRODUCTION The same is true for the process for the production of 3-isocyanatopropylsilanes by gas phase esterification of BACKGROUND OF THE INVENTION 5 3-isocyanatopropyltrichlorosilane with alcohols (Ben The invention is directed to N-silylpropyl-N'-acyl nett U.S. Pat. No. 3,651,117) in which the simulta ureas, a process of their production and the setting free neously undesired side reaction of the isocyanate group of the blocked isocyanate function. with the alcohol can be suppressed only through an Silanes of the general structure I have large scale significance as coupling agents in material systems 10 industrially expensive procedure. which consist of an inorganic and an organic phase, as The invention is directed to hydrolyzable silanes well as for the modification of OH functional surfaces: having a blocked isocyanate function and a process for their direct production in high yields. (RO)3Si-CH2-CH2-CH2-X (I) Simultaneously the isocyanate group should quite 15 easily be set free by thermolysis. (R4 = CH3, C2H5) The most important functional groups include: SUMMARY OF THE INVENTION X=NH2, -S4- (Si 69), -SH, -Cl, -O- The present invention is directed to N-silylpropyl-N'- CO-C(CH3)=CH2 and 20 acyl-ureas of the formula: -O-CH2-CH-CH2 N / O (III) O A-C-NH-CH6-Si(CH3)(OR)3- The isocyanate function (X=-NCO) represents a 25 particularly valuable functional group: in which On the one hand it can be reacted with numerous x is 0, 1, or 2 H-acidic, monomeric materials (amines, alcohols, ox R is C1-C6 alkyl, straight chain or branched, (2'- imes, and many others) with the formation of newer methoxy)ethyl, aryl, preferably phenyl functional silanes, on the other hand it can also react 30 A is with polymeric resins and rubbers in mutual binding. In contrast to the advantage of the multifold chemical activity there is the disadvantage of the high toxicity of Rl O II the isocyanate group and the cumbersome synthesis of -N-C-R2 the silane (II) in practice (Hedaya U.S. Pat. No. 35 4,130,576): where R is C1-C6 alkyl, straight chain or branched, (RO)3Si-C3H6-NCO (II) R2 is hydrogen, C1-C6 alkyl, straight chain or branched, O In industry therefore there are frequently employed A is blocked alkyl and aryl isocyanates: (Z. W. Wicks, Progr. Org. Coat. Volume 9, (1981) pages 3-28. CH2-D As blocking agents for the non-silyl containing or / ganic isocyanates there are used, e.g. alcohols (espe m-N cially phenols), A-dicarbonyl compounds, lactams or oximes. Blocked isocyanates on the one hand are usable 45 CO-(CH2) from aqueous systems and on the other hand relatively inexpensive procedures are sufficient for safely han where y is 1, 2, or 3 and D is -CH2-, >NR1. dling them because of their comparatively low toxicity. These compounds for example, can be applied to In Berger U.S. Pat. No. 3,994,951 there is described a glass fibers from-aqueous solution, which fibers are hydrolyzable silane from which the isocyanate function 50 designed to be worked into synthetic resins. After ther is set free at a temperature of 160° C. which silane is O-methyl-N-trimethoxysilyl-propyl-urethane. mal and/or catalytic treatment the cross-linking can be This compound, however, is little'suited for use as an carried out via the then set free isocyanate. coupling agent in filler reinforced polymer systems for A further subject matter of the invention is a process the reason that the thermolysis only proceeds at rela 55 for the production of compounds of formula (III) by tively high temperatures and the byproduct methanol mixing in an aprotic, polar organic solvent equimolar (flash point: 11 C) formed makes it necessary to take amounts of an alkali cyanate (e.g. sodium cyanate or corresponding safety precautions. potassium cyanate), a 3-halopropyl silane of the for The thermolysis of O-methyl-N-trimethoxysilylpro mula: pyl urethane can only be carried out in good yields if 60 there is used very slow thermolysis. The cause of this X-C3H6-Si(CH3)(OR)3. (IV) must be that the thermolysis byproduct methanol is more volatile than the desired 3-isocyanatopropyltrime and a compound of the formula: thoxysilane, so that in the distillative separation of the 65 latter silane from the thermolysis sump the recombina O (V) tion of methanol and 3-isocyantopropyltrimethoxysi I lane in the gas phase can only be prevented if this sepa R2-C-NH-R1 or ration is carried out comparatively slowly. The thus 4,697,009 3 4. -continued phenylacetamide, N-methylcapronic acid amide, N CH-D (VI) methyllaurylamide, N-methyloleylamide, N-methylpal / mitylamide, N-methylstearylamide, N-methylbenza HN N mide, N-methyltolylamide, cyclic: CO-(CH2) 2-pyrrolidone, 1-N-methyl-hexahydro-1,4-diazepi none of the formula preferably in this sequence, wherein R, R, R2, D, x, and y are as defined above and X is Cl, Br, or I, subse CH-CO quently reacting them with each other at elevated tem M perature, after the end of the reaction and cooling the 10 CH3-N reaction mixture to room temperature filtering off the N / precipitated alkali halide and distilling off the solvent (CH2)3 from the filtrate. The desired product remains behind and can be used 2-piperidone and especially e-caprolactam. without further purification. 15 The desired N-acyl ureas are obtained according to The reactants can be quickly mixed together at room the process of the invention in high yield. temperature, without fear of starting a reaction. Members of this new class of compounds are yellow The reaction is carried out at a temperature of oils as crude products. 100-140° C. within 1-8 hours, preferably 100°-130' C. They can be decomposed thermally at temperatures within 4 hours under a protective gas atmosphere. As of 2135 C. for example according to the following protective gases there are especially suitable nitrogen equation (2) in which case the decomposition tempera and argon. ture can be lowered still further through the addition of In using the preferably employed cyclic amides the catalytic amounts of dibutyltin dilaurate. reaction proceeds according to the following scheme: 25 CH2-D (1) / (RO)3Si-CH6-C1 + KOCN + HN N CO-(CH2) 30 CH2-D / (RO)Si-CH6-NH-CO-N - KC N 35 CO-(CH2) CO-(CH2) As solvents there are suitable N,N-dimethylforma There are formed 3-isocyantopropylsilanes of the timide, N,N-dimethylacetamide, N,N,N',N'-tetramethyl formula urea, N,N,N',N'-tetramethylenediamine, N-methylpyr rolidone, dimethylsulfoxide, hexamethylphosphoric OCN-C3H6-Si(CH3)xOR)3 (VII) . acid triamide. Especially preferred is N,N-dimethylfor mamide. The thermolysis of the compounds of the invention Per mole of silane employed there is used 250-400 ml preferably takes place in a vacuum distillation apparatus of solvent, preferably 300 ml. 45 at pressures of 100 to 6500 Pa, preferably of 200 to 2000 As alkali cyanates there can be used sodium cyanate Pa and a sump temperature between 130' and 160 C. and especially potassium cyanate. Thereby it has been found favorable that, in contrast Suitable silanes are: 3-chloropropyltrimethoxysilane, to the process according to Berger U.S. Pat. No. 3-chloropropyltriethoxysilane, 3-chloropropyltri-i- 3,494,951, the boiling point of the blocking agent as a propoxysilane, 3-chloropropyltri-n-propoxysilane, 3 50 rule is above that of the isocyanatopropylsilane, so that chloropropyltri-t-butoxysilane, 3-chloropropyltri(2'- there does not occur a recombination of the materials in methoxy)ethoxysilane, 3-chloropropyldimethoxyme the gas phase above the distillation sump. thylsilane, 3-chloropropyldiethoxymethylsilane, 3 The thermolysis temperature can be lowered through chloropropylmethoxydimethylsilane, 3-chloropropyle addition of catalytic amounts of dibutyltin dilaurate, thoxydimethylsilane, 3-chloropropyltriphenoxysilane 55 and the corresponding Br- and I-substituted analogous especially 0.5 to 5 mole% based on the acylurea, so that compounds, e.g.
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