PL191849B1 - Novel silylcarbamates and method of obtaining them - Google Patents

Abstract

New general silylcarbamates Formula 1 where R is methyl (CH3) "(ROUSiCH2CH2CH2NHC (O) ZCH2CH = CH2 ethy or betamethoxyethyl Z - atom oxygen or an imino group, and n takes values 0, 1 or 2.

Description

The subject of the invention is new silylcarbamates and a method of their preparation by modification of 3-isopropyltrisubstituted silanes.

3-isopropyltrisubstituted silanes with an isocyanate group (-N = C = O) constitute a group of compounds whose use is intensively increasing and varied. The isocyanate group -N = C = O present in these compounds contains a very reactive cumulative double bond between heteroatoms, thanks to which they constitute an intermediate for the preparation of a number of new organofunctional silane derivatives with a wide variety of specialized applications, mainly as coupling and cross-linking agents.

An example is the reaction of an isocyanate group with organic compounds containing active hydrogen, i.e. with alcohols, glycols or amines. Most often for this purpose, the reaction of an isocyanate group with a hydroxyl group is used. For example, 3-isocyanatopropyltrimethoxysilane when reacted with tetrahydroxybenzophenone forms a compound used as an ultraviolet ray absorber [French Patent No. 2,483,421]. The compound obtained by reacting isocyanatopropyltrimethoxysilane with hydroxybutyl vinyl ether [Japanese Patent No. 04,235,993] is also used for the same purpose. The products of the interaction of the -NCO group with the -OH group are also fungal and bactericidal compounds formed in the reaction of isocyanatosilane with pentachlorohydroxybenzene [US Patent No. 4,339,581]. As a result of the interaction of the isocyanate group with the -NH group, anti-seaweed compounds are formed [Japanese Patent Specification No. 05 170 777].

The reaction of isocyanatosilanes with hydroxybenzophenone produces an organosilicon compound used as a component of weatherproof coatings [Japanese Patent No. 06 299 088]. Among the extensive group of new silane adhesion promoters, the reaction products of isocyanatopropyltrialkoxysilanes with 2-hydroxyethyl acrylate [European Patent No. 298,734], with bis (2-hydroxyethyl) amine [Czech Patent No. 196,941], with aminopropyltriethoxysilane [US patent application] can be mentioned. 86 05 798 (1986)], t-butanol [European Patent No. 476,564], benzoic acid derivatives [Japanese Patent No. 04 310 953] with diamines [Japanese Patent No. 61,112,086], with dichlorophenyldimethylurea [Japanese Patent Specification No. 05 171 046], with (hydroxyethylamino) anthraquinone [Japanese Patent No. 05 178 995]. For most of the above processes, various catalysts were used, such as triethylamine, methylmorpholine, tetramethylenediamine, 1,4-diazobicycloacetate, as well as various complex organometallic compounds of tin (II) and tin (IV), e.g. derivatives of higher carboxylic acids and dialkyl tin (II) and tin (IV) i.e. octenate laurate or tin (II) acetate, dibutyltin (IV) dilaurate, dibutyltin (IV) maleate. The reactions were carried out both without and in solvents, e.g. toluene, tetrahydrofuran, diethyl ether.

The subject of the invention are new isocyanatosilane derivatives containing an allyl group, silylcarbamates of the general formula I, in which R is a methyl, ethyl or betamethoxyethyl group, Z - an oxygen atom or an imino group, and n takes the values 0 or 2.

The essence of the invention is also a process for the preparation of silyl carbamates of the general formula I in which R, Z and n are as defined above. According to the invention, they are obtained by catalytic reaction of a 3-isocyanatopropyl trisubstituted silane of the general formula II, wherein R and n are as defined above, with allyl alcohol or allylamine in which dibutyl tin oxide is used as the catalyst. The reaction is carried out in a polar solvent that does not react with the reactants and the reaction product, preferably tetrahydrofuran, at a temperature of 323-373 K.

The compounds according to the invention contain an allyl group which, due to its reactivity and specific properties, offers much wider application possibilities for isocyanate derivatives. The catalyst used is a relatively simple organometallic tin compound, readily available and cheaper than those used so far. Moreover, its use allows to obtain 100% conversion of the starting silane and the yield of the final product above 95%, which could not be achieved with the methods known to date.

The compounds according to the invention, like the previously known 3-isopropyltrisubstituted silanes with an isocyanate group (-N = C = O), can be used as excellent adhesion promoters. They are an excellent link between inorganic materials and organic or organosilicon polymers. These substances, when applied to an inorganic surface, bind with it through chemical bonds, while maintaining an active allyl group.

PL 191 849 B1

As a result of polyaddition of polyhydrogen siloxanes or radical processes, it is possible to immobilize polysiloxanes or organic polymers on the surfaces of organic materials.

The following examples illustrate the invention.

P r z k ł a d I

30 cm of dried and freshly distilled tetrahydrofuran (THF), 9.28 g of dried allyl alcohol and 73 mg of dibutyl tin oxide were placed in a 100 cc ^{two-neck rounded flask equipped with a thermometer, magnetic stirrer, reflux condenser and gas inlet cap.} . The contents of the flask were heated to 333 K to activate the catalyst, heating was continued for 45 min while stirring the contents of the flask with a stirrer. After the activation was completed, 30 g of 3-isocyanatopropyltrimethoxysilane were introduced into the system. The process was carried out for 1 h at 333 K, obtaining 100% conversion of the starting silane. Solvent and excess allyl alcohol were evaporated from the cooled mixture. The product content of the mixture was above 98%. Vacuum distillation of the product was performed, not exceeding 373 K under a vacuum of 0.5-1 mmHg, as the ester obtained is cracked at a higher temperature. Pure product allyl 3- (trimethoxysilyl) propylcarbamate was obtained after distillation with a final yield of 95%.

¹ H NMR a bcde fgh (CH3O) 3SiCH2CH2CH2NHC (O) OCH2CH = CH2 d (ppm) = 0.63 ((b) 2H, t); 1.62 ((c) 2H, Apr); 3.15 ((d) 2H, q);

3.56 ((a) 9H, s); 4.54 ((f) 2H, d); 5.22 ((h) 1H, dd);

5.31 ((h) 1H, dd); 5.54 ((e) 1H, shs); 5.95 ((g) 1H, m) ¹³ CNMR a bcd e fgh (CHsO) 3SiCH2CH2CH2NHC (O) OCH2CH = CH2 d (ppm) = 5.92 (b); 22.78 (c); 42.8 (d); 50.01 (a); 64.81 (f); 116.73 (h); 132.88 (g); 156.82 (e)

P r z x l a d II

The process was carried out analogously to method I, except that 3-isocyanatopropylmethyldiethoxysilane (31 g) was used instead of 3-isocyanatopropyltrimethoxysilane. Allyl 3- (dimethylethoxysilyl) propylcarbamate was obtained in a final yield of 91%.

¹ H NMR abc defg hij (CH3) 2 (CHsCH2O) SiCH2CH2CH2NHC (O) OCH2CH = CH2 d (ppm) = 0.21 ((a), 6H, s) 0.78 ((d) 2H, t); 1.25 ((b) 3H, t); 1.82 ((e) 2H, Apr);

3.25 ((f) 2H, q); 3.95 ((c) 2H, q); 4.64 ((h) 2H, d);

5.32 ((j) 1H, dd); 5.41 ((j) 1H, dd); 5.59 ((g) 1H, shs); 6.05 ((i) 1H, m) ¹³ CNMR abc def g hij

CH3 (CHsCH2O) 2SiCH2CH2CH2NHC (O) OCH2CH = CH2 d (ppm) = - 0.12 (a); 14.31 (d); 24.75 (e); 28.54 (b); 43.5 (f); 52.83 (c); 68.71 (h);

119,730); 139.88 (i); 156.82 (g)

P r z x l a d III

Similarly, 28 g of 3-isocyanatopropyl dimethyl (b-methoxyethoxy) silane derivative with allyl alcohol was obtained, resulting in 89% of allyl 3- (dimethyl (b-methoxyethoxysilyl) propyl carbamate) after distillation of the reaction mixture.

¹ H NMR a bcd efgh ijk (CH3) 2 (CHsOCH2CH2O) SiCH2CH2CH2NHC (O) OCH2CH = CH2 d (ppm) = 0.19 ((a), 6H, s) 0.82 ((e) 2H, t); 1.86 ((f) 2H Apr);

3.25 ((g) 2H, q); 3.42 ((b) 2H, s); 3.54 ((c) 2H, t) 3.95 ((d) 2H, t);

4.64 ((i) 2H, d); 5.32 ((k) 1H, dd); 5.41 ((k) 1H, dd);

5.59 ((h) 1H, shs); 6.05 ((j) 1H, m)

PL 191 849 B1 ¹³ cnmr abcd efgh ijk

CH3 (CH3OCH2CH2O) 2SiCH2CH2CH2NHC (O) OCH2CH = CH2 d (ppm) = - 0.13 (a); 14.31l (e); 24.75 (f); 43.5 (g); 59.81 (c) 62.51 (b); 68.71 (i);

74.76 (d); 120.76 (k); 140.73 (j); 158.74 (h)

P r x l a d IV

Analogously to method I, the reaction between 3-isocyanatopropyltrimethoxysilane (30 g) and allylamine (9.12 g) was carried out to obtain pure product 3- (N-allylureido) propyltrimethoxysilane after distillation of the reaction mixture, with a yield of 94%.

¹ H NMR a bcde fghk (CH3O) 3SiCH2CH2CH2NHC (O) NHCH2CH = CH2 d (ppm) = 0.65 ((b) 2H, t); 1.66 ((c) 2H, Apr); 3.18 ((d) 2H, q);

3.59 ((a) 9H, s); 5.1 ((g) 2H, wp); 5.38 ((k) 1H, dd);

5.45 ((k) 1H, dd); 5.62 ((e) 1H, shs); 58.81 ((f) 1H, w S) 6.15 ((h) 1H, m) ¹³ CNMR a bcd e fgh (CH3O) 3SiCH2CH2CH2NHC (O) NHCH2CH = CH2 d (ppm) = 5.95 (b); 22.86 (c); 43.9 (d); 50.83 (a); 68.93 (f); 121.83 (h); 142.64 (g); 171.92 (e)

Claims (2)

1. New silylcarbamates of general formula I, in which R is a methyl, ethyl or betamethoxyethyl group, Z - an oxygen atom or an imino group, and n takes the values 0, 1 or 2. 2. The method of obtaining new silylcarbamates of the general formula I, in which R is a methyl, ethyl or betamethoxyethyl group, Z - an oxygen atom or an imino group, and n takes the value 0 or 2, characterized in that the 3-isocyanatopropyl trisubstituted silane of the general formula 2 in which R and n are as defined above, is reacted with allyl alcohol or allylamine in the presence of dibutyltin oxide as the catalyst, the reaction being carried out in a polar solvent which does not react with the reactants and the reaction product, preferably tetrahydrofuran, at a temperature of 323 - 373 K.