MXPA96005594A - Polymers finished in oximino-silano and elastomeros formados de el - Google Patents

Abstract

Oximinosilane-terminated polymers, which, when cured at room temperature, become stable elastomers. The former has a hydrolysable ketoximino-silyl group at each end of each molecule and are prepared by the reaction of a hydroxyl-terminated liquid polymer with an organic diisocyanate, to produce an isocyanate-terminated pre-polymer. The resulting prepolymer is then converted into a mercaptan-terminated polymer, by reaction with a mercaptoalcohol or by reaction with an olefinic alkylene alcohol or amine, to yield an olefin-terminated polymer, which is then reacted with a dimercaptan . When the mercaptan-terminated polymer is reacted with a vinyl-oximino-silane or a vinylalkoxy-oximinosilane, a liquid polymer terminated in silane is obtained. Such polymers have improved elongation, moisture resistance, tensile strength and tear properties in adhesive, coating and sealant formulations

Description

POLYMERS FINISHED IN OXIMINO-SILANO AND THE ELASTOMERS FORMED OF THEM BACKGROUND OF THE INVENTION Field of the Invention This invention relates to polymers terminated in oximinosilane, which are cured at room temperature to become stable elastomers. They have improved physical properties, such as elongation, moisture resistance, variable cure regimes, and resistance to stress and tear in various formulations. These polymers are used as adhesives, coatings and sealants. Description of the Prior Art It is known in the art that the cure of the liquid polymers terminated in isocyanate and mercaptan require amines to form disulfides that form urea / urethanes or peroxides. Both urethane and mercapto type polymers are commonly used in two component sealing systems, where the mixing of the main polymer component with a catalyst or reactive curing component is essentially before use. The incorporation of the oximosilanes in these liquid polymers has the advantage of cure vulcanization by moisture, due to the extreme reactivity of the oximosilanes with moisture. The wet cure at room temperature of the oximosilane-terminated polymers eliminates the need for the handling of toxic isocyanates and peroxides. In the silicone sealant industry, polysiloxanes, which have hydrolysable silicon end groups, are often used in one-component sealant formulations. When exposed to the atmosphere, the polymer is subjected to a rapid vulcanization with atmospheric humidity. Due to the high cost of polysiloxane polymers, it is convenient to use low cost organic polymers, such as polyethers, polyesters and polysulfides, such as the polymer backbone. Among commercially available liquid polymers, silane-terminated polymers are the most convenient, due to the ease of their cure with atmospheric moisture and their low odor and toxicity. However, these silane-terminated polymers are of limited use due to their poor physical properties, such as low tensile and tear strengths. Therefore, it is convenient to produce organic liquid polymers that upon curing become elastomeric materials with characteristics of fast curing regimes, hydrolytic stability, good elongation, and high resistance to stress and tear. U.A. Patent No. 3,317,461 discloses polysulfides terminated in oximosilane, obtained by the reaction of a mercaptan-terminated polysulfide with a silane having hydrolyzable groups and at least one olefinic double bond. These polymers, when cured, do not have a high resistance to stress and tear, due to the lack of urethane groups. The patent of E. U. A., No. 4,960,844 discloses silane-capped polymers, with urethane groups in the polymer chain. Hydrolyzable groups attached to the silicon atom are alkoxy groups with lower alkyl groups. The silane-terminated polymers of this invention are readily cured at room temperature, in the presence of normal moisture, to a hydrolytically stable solid elastomer, which has high resistance to stress and tearing and low compression. Catalyst is not required for healing to take place, although a wide variety of catalysts, known in the art, can be used to decrease cure times. An object of the invention is to provide an organic liquid polymer with terminal blockage with ketoximes containing silanes, such as hydrolysable groups which can be cured at room temperature in a rubber-like elastomer or a rubbery adhesive when exposed to moisture. COMPENDIUM OF THE INVENTION the invention supplies polymers terminated in oximinosilanes, which have the formula: which has an average molecular weight of at least about 600; wherein R is an organic polymer containing a polyether, polythioether or polyester skeleton; R1 is a divalent organic radical; R2 is an alkylene group, having at least 3 carbon atoms; X is O or NR6, where R6 is hydrogen or a monovalent group of lower alkyl; And it is sulfur or S-R7-S, where R7 is an alkylene-thioether having 4 to 12 carbon atoms, an alkylene having 2 to 10 carbon atoms or a substituted cyclohexyl ring group, having the formula: CH 3 R3 is an alkyl radical with 1 to 7 carbon atoms or an alkoxy radical with 1 to 6 carbon atoms and R4 and R5 are, independently, an alkyl radical, saturated, straight or branched chain, with 1 to 7 carbon atoms , such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and amyl, or R4 and R5, taken together form a cyclic group, p is 2 to 3, m is 0 to 2, n is 1 to 3, and the sum of m and n is 3. The invention also provides a method for the production of the above polymers terminated in oximinosilane. A pre-polymer is formed by the reaction of a hydroxyl-terminated polymer with an organic diisocyanate, to produce an isocyanate-terminated polymer. The isocyanate-terminated polyol is reacted with an olefinic alcohol or an amine, in which the olefinic group is separated by at least one carbon atom, to give an olefin-terminated polyether polyol. The olefin-terminated prepolymer is then reacted with a dimercaptan and a vinyloxime-silane. The invention further provides a method for the production of the above oxyximilane-terminated polymers, by reacting the isocyanate-terminated polyol with a mercapto alcohol, to produce a mercapto-terminated polymer, and then reacting with a vinyl oxysilane. The invention also provides a sealant, coating, sealant, foam or adhesive composition, which comprises the above oximinosilane-terminated polymer, in admixture with a plasticizer, filler and a moisture scavenger, as well as an adhesion promoter, catalyst , rheology modifier and / or optional interleaver. DETAILED DESCRIPTION OF THE PREFERRED MODALITY The invention encompasses organic polymers, which have a hydrolyzable ketoximino-allyl group, at each end of each molecule, as shown in the formula described above, the ketoximino-silane terminated polymers are prepared by forming a polymer or Isocyanate-terminated prepolymer, which has the general formula: R [0 - C - NH - R1 - N = C = 0] p »? 0 where R, R1 and p have the same meanings above, by the reaction of a hydroxyl-terminated polymer with an organic diisocyanate. In the preferred embodiment, the polymeric backbone, represented as R in the general formula, can be for example hydroxyl terminated propylene oxide polyols, polybutylene oxide glycol polyols, polytetramethylene glycol polyols, polyester polyols, polyols of polythioethers, polyalkylene glycol copolymer polyols, and polyalkylene glycol polyester copolymer polyols. These hydroxyl-terminated polyols are reacted with organic diisocyanates, followed by a method known in the prior art. Examples of organic diisocyanates are toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate and isophorone diisocyanate. The pre-polymers can be converted into mercaptan-terminated polymers by 1) the reaction with a mercapto-alcohol, in which the mercapto and hydroxyl groups are separated by at least two methylene groups or 2) by reacting with an alkylene olefinic alcohol of an amine of at least three carbon atoms, in which the olefin group is separated from the hydroxyl or the amine by at least 1 carbon atom. The resulting olefin-terminated polymer then reacts with a dimercaptan, in which the mercaptan functionality is separated by alkyols, alkylene ethers, alkylene thioethers, alkylene esters and substituted cyclohexyl rings, to give finished mercaptan polymers. Hydrogen sulfide can also be used to obtain the mercaptan-terminated polymer using at least 1 mole of each equivalent of the olefin polymer to ensure that all olefin functionality is terminated with the mercaptan groups. Due to their greater availability, the preferred dimercaptans are 1,2-ethanedithiol, 1,6-hexane-dithiol, 1,10-decane-dithiol, 2-mercaptoethyl ether, 2-mercaptoethyl sulfide, glycol acetate dimercapto, propionate. of glycol dimercapto, p-menthane-2,9-dithiol and ethylcyclohexane-dithiol. Preferred mercapto alcohols are 2-mercaptoethanol, 3-mercapto-1-propanol. The reactions described above are disclosed in the patents of U. U.A., Nos. 3,923,748, 4,366,307 and 4,960,844, the disclosure of which is incorporated herein by reference. The radical initiated coupling reaction between the olefinic compound, ie the olefin-terminated polymer, and an organic compound with 2 to 4, but at least 2, mercaptan groups, will supply the mercaptan-terminated polymer, as described in the following equation: p [R7- (SH) 2-4] + R- [0-C-NH-R1-NH-C-X-CH2-C = C] 'Pp - »II II O 0 R- [0-C-NH-R1-NH-C-X-CH2-C = C-S-R7- (SH) -3] II II The previous direct reaction is catalyzed by 0.1 to 1. 0% by weight of radical initiators, such as organic peroxides or azo-bis-alkyl-nitriles. The reaction temperature is maintained between 55 and 120ac, with a preferred range being between 55 and 85se.

When the mercaptan-terminated polymer is reacted with a vinyl-oximino-silane, vinylaxyloxy-silane, vinylaryloximino-silane, vinylalkylalkoxy-oxysino-silane, vinylalkoxyoxy-silane or vinylarylalkoxy-oxoxy-silane, a silane-terminated polymer is obtained, which is preferably a liquid and preferably has a molecular weight of about 1200 to 100,000. This is also a radical-initiated addition reaction between the mercaptan group of the polymer and the olefin group of the vinyl-trynosilane. The preferred silane has the formula: R4 I H2C = CH-Si- (0-N = C) n I I (R3) m R5 in which R3, R4, R5, and n have the definitions indicated above. The ketoximino-silane terminated liquid polymers of the present invention are different from those of the prior art in that they have urethane groups and the sulfur atoms are separated by just 2 or more carbon atoms in the polymer backbone and also due to when less a group of faster hydrolysable ketoximino neutral, attached to the silicone atom. In the formulation of an adhesive, coating, foam or sealant composition, the oxymylosilane-terminated polymers can be used alone, but, more preferably, they are mixed with additives known in the art for the preparation of such compositions of adhesives, sealants and coatings . These compositions include, but are not limited to, plasticizers, fillers, reinforcing agents, moisture scavengers, rheology modifiers, dyes, UV light stabilizers, fungicides, mildewis, antimicrobial agents, antioxidants, polymers, crosslinkers coupling, adhesion promoters and catalysts, thixotropic agents, flame retardants thermal and electrically conductive fillers, blowing agents, surfactants, heat stabilizers, solvents, etc. to adjust the composition to an application specifically desired. They can usually be added at any stage of the mixing operation, but care must be taken to add them under anhydrous conditions, to avoid introducing additional moisture. In the preparation of the adhesive composition, As the coating, foam or sealant, the amount of polymer to be used in this invention ranges from more than 5 to about 90 weight percent of the total composition, but preferably ranges from 15 to 60 weight percent of the total composition.

The polymer can be used to create a foam by those skilled in the art, through the use of a low-boiling liquid or other suitable blowing agent, an example of which is 1,1-dichloro-1-fluoroethane, in combination with a surfactant, such as a foam stabilizer. The composition may contain a filler, which may be a reinforcing silica filler, an i-reinforcer filler, a non-reinforcing filler, or mixtures thereof. Examples of reinforced silica fillers are fumed silica and precipitated silica. Examples of useful silica fillers are described in the patents of U. U.A., Nos. 3,837,878, 2,938,009, 3,004,859 and 3,635,743, which are incorporated by reference. The amounts of the reinforcing filler vary from 0 to about 50 weight percent of the total composition, preferably from 0 to 14 weight percent and more preferably from 2 to 8 weight percent. The use of the reinforcing fillers imparts an increased strength to the tension of the cured composition, as well as providing a thixotropic character to the uncured composition. A non-reinforcing or semi-reinforcing filler can also be used at levels up to 75%. These fillers include, for example, calcium carbonate and ground quartz. Other semi-reinforcement fillers or extension fillings, which are known in the art, can be used.

They include, but are not limited to, silica airgel, diatomaceous earth, iron oxide, titanium oxide, aluminum oxide, zirconium silicate, calcined clay, magnesium oxide, talc, wollastonite, hydrated alumina, and carbon black. The total amount of all fillers in the composition varies from 0 to 60%, and preferably from 6 to 55% by weight, of the overall composition. Methyl tris- (methyl-ethyl-ketoximino) -silane, tris- (methyl-ethyl-ketoximino) -vinyl silane and tetrakis- (methyl-ethyl-ketoximino) silane are predominantly commercially used oxime silanes. as crosslinkers in oxime RTV compounds and used to accelerate healing. Equally useful as interleavers are the silanes described in U.A. Patent No. 3,189,576 and are incorporated herein by reference. The interlayer may be present in an amount of about 0 to 10 weight percent of the total composition, however 3 to 7 weight percent is preferred and more preferred is 3 to 6 weight percent. The tetrafunctional alkoxy ketoxime silanes described in U.S. Patent Nos. 4,657,967 and 4,973,623 can also be used as crosslinkers and are incorporated herein by reference, U.S. Patent No. 4,705,877 describes ketoximino-silanes substituted with aminohydrocarbyl as coupling agents and are incorporated herein by reference.

Additionally, known in the art are organofunctional silanes as adhesion promoters, including, but not limited to, gamma-aminopropyltriethoxy-silane and gamma-aminopropyltrimethoxy-silane, as described in U.S. Patent No. 4,720,530. Other adhesion promoters may include 3-glycidoxypropyltrimethoxysilane or gamma-mercaptopropyltrimethoxysilane. The amount of the adhesion promoter can vary from about 0 to 5.0 weight percent of the total composition. Preferably 0.5 to 1.5 weight percent of the total composition is used. The composition may also contain an optional catalyst, which accelerates the polymer reaction. Examples of catalysts include, but are not limited to, organic tin carboxylates, such as dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioctoate, dibutyl tin maleate, dialkyl tin hexoates, dioctyl dilaurate. tin, zinc octanoate, lead octanoate, cobalt naphthenate, amines, such as diamine, and titanates. The preferred catalyst is dibutyltin dilaurate. The levels of use of the catalyst can vary from 0 to 2.0 percent by weight of the total composition, preferably from 0.05 to about 1 percent and more preferably from 0.2 to 0.5 percent by weight.

The composition may also contain an optional plasticizer to improve the properties of the extrusion of the composition and to modify the modulus of the cured composition. They include phthalates, adiptaos and aromatic hydrocarbons. Suitable plasticizers include dibutyl phthalate, dioctyl phthalate, triaryl phosphate and their analogues. The plastifizer is added in an amount ranging from 0 to 50 weight percent, based on the general composition, preferably 10 to 30. percent by weight. The preferred viscosity of the plasticizer ranges from about 100 to 1000 cps, at a temperature of 25 ° C. Common stabilizers of UV light include the families of benzophenones and benzotriazoles of hydroxyphenyl, which comprise the benzotriazole monomers of hydroxyphenyl and the dimers. The benzotriazole monomers of hydroxyphenyl "" "are disclosed in the patents of E. U. A., Nos. 3,204,896, ,097,041, 4,943,637 and 5,104,991. The 2-hydroxy-2-alkoxybenzophenones are useful as absorbers of the UV radiation and as light stabilizers. The patents of E. U. A., Nos. 3,399,237 and 3,310,525 show compounds having benzophenone functional groups. The UV light stability of such materials is improved by mixing the polymer with about 0.1 to 5%, based on the weight of the asymmetric dimer polymer composition of this invention. Moisture scrubbers are preferably present in an amount from 0 to about 5% by weight of the composition. Suitable moisture scrubbers include, not exclusively, trifunctional or greater oximinosilanes, molecular sieves and other moisture reactive materials. The rheology modifiers are preferably present in an amount of 0 to 5% by weight of the composition. Suitable rheology modifiers include, but are not limited to smectite clay, fumed silica, castor oil, castor and fiber fence. Preferred colorants for this invention are pigments and dyes. Examples of dyes are titanium dioxide, carbon black, silica, zinc oxide and clay. They are preferably present in an amount ranging from about 5 to 10%, based on the weight of the solids in the layer. The composition may also contain an optional bacteriostat / fungistat. The most preferred compound is acetoxy-dimethoxydioxide. They are present in an amount of about 0.001 to 1.0% by weight of the composition. Useful solvents for forming the coating compositions include essentially any inert organic solvent, which is a solvent for the other components of the composition. The solvents can be ethers, ketones, hydrocarbons and halocarbons, among others. The amount of the solvent can be determined by experienced technicians, depending on the end use. The other optional components may be present in an amount ranging from about 0 to 10 percent, based on the total composition. The composition of the present invention can be used in the form of a curing composition at room temperature, of a component, which is produced by mixing the components, described above, and various additives, in the absence of moisture and stored in a container closed, which is impervious to moisture. The composition is cured to an elastomer by exposure to atmospheric moisture at the time of use, when the package is opened. The following non-limiting examples serve to illustrate the invention. EXAMPLE 1 To 2000 grams (0.5 mole) of the polyoxypropylene diol, which has a molecular weight of 4000, 74.5 grams were added (1.0 mol) of toluene diisocyanate. The reaction was carried out in the presence of nitrogen, in a reaction kettle of 3 liters, equipped with a mechanical agitator and three-neck cap. The mixture was heated at 800C for 1-2 hours, in the presence of 2.26 grams of a DABCO catalyst solution (24% in toluene). To the pre-polymer, obtained above, 58.1 g (1.0 mol) of allyl alcohol was mixed, in the presence of 9.3 grams of the DABCO solution and heated to 800 C for 1-2 hours, with continuous stirring. The termination of the reaction was characterized by the disappearance of the -NCO peak in the IR spectrum and the GPC chromatography. To the olefin-terminated polymer, obtained above, 94.2 g (1.0 mol) of 1,2-ethanedithiol and 4.65 g of azo-bis-isobutyronitrile were added and heated to 80-95 ° C for two hours, with slow stirring, to prevent swirling. The mercapto content of the polymer was confirmed by the iodometric titration and the equivalent weight of mercaptan was calculated. To the mercaptan polymer thus obtained, 267.5 g of the ethyl-vinyl bis (2-butanone-oxime) -silane (1.05 mol, 95% test) and 5.18 g of azo-bis-isobutyronitrile initiator and the mixture were added. it was heated at 80-952C for 2 hours, with continuous stirring. A nitrogen blanket was maintained through the reaction. The molecular weight of the polymer, in different stages, was determined by GPC chromatography. Therefore, the final polymer, sensitive to moisture, was stored in a closed vessel flooded with nitrogen. The viscosity of the polymer varies between 900 and 1100 poises at 232C (90,000 to 110,000 cps).

EXAMPLE 2 An olefin-terminated polymer was prepared following the procedure described in Example 1. The prepolymer was obtained from 1,100 grams of polypropylene glycol-polyol with a hydroxyl number of 28.8, 96 grams of toluene diisocyanate and 0.30 gram of DABCO . The olefin-terminated polymer was prepared by reacting the prepolymer with 33.6 grams of allyl alcohol and 1.20 grams of DABCO. To the above polymer, 102.0 grams of ethylcyclohexydimercaptan and 2.4 grams of azo-bis-isobutyronitrile were added and heated for 4 hours at 80 ° C, to give a mercaptan-terminated polymer, which was then reacted with 147 grams of bis (2). -butanone oxime) -methylenyl vinyl ester and 3.0 grams of azo-bis-isobutyronitrile (radical initiator) at 80 ° C, for 4 hours, to give a polymer terminated in oxime-silane. EXAMPLE 3 An olefin-terminated polymer was prepared according to the procedure described in Example 1. 1300 grams of polypropylene glycol polyol, with a hydroxyl number of 28.8, 130.5 grams of toluene diisocyanate and 0.36 grams of the DABCO catalyst, they were heated at 80 ° C for 1 1/2 hours, to give an isocyanate-terminated polymer, which was converted to an olefin-terminated polymer by reaction with 43.6 grams of allyl alcohol and 1.26 grams of DABC catalyst, at 80 ° C, for 4 hours. hours. To the above polymer, 178.8 grams of ethene bis- (3-mercaptopropionate) and 3.0 grams of azo-bis-isobutyronitrile were added and heated at 80ac, for 4 hours, to give a mercapto-terminated polymer, which was then Reacted with 191 grams of the methyl-vinyl bis- (2-butanone-oxime) -silane and 3.4 grams of the azo-bis-isobutyronitrile, at 80 ° C., for 4 hours, to give a polymer terminated in oxime-silane. EXAMPLE 4 The 2,4-toluene diisocyanate (0.123 mol, 21.46 g), which has 20% 2,6-toluene diisocyanate, ie TDI 80/20, and 0.33 g of a 24% solution of DABCO, they were added to the polybutylene oxide, which has a molecular weight of 4878 (300 g, 0.0615 mol) under a nitrogen atmosphere. The mixture was heated at 80 ° C for 1-2 hours. Allyl alcohol (7.15 g, 0.123 mol, 99%) and 1.31 g of a DABCO solution was added to the above mixture and was stirred at 80 ° C for 1-2 hours, with continuous stir. To the polymer thus obtained was added (146 g, 0.123 mol, 99%) 1,2-ethanedithiol and 0.51 g of azo-bis-isobutyronitrile, and heated for 2 hours at 80-900C. Finally (32.9 g, 0.1292 mol, 95%) methyl- (2-butanone-oxime) -silane methyl vinyl and 0.56 g of AIBN were added to the mercaptan polymer and heated for 2 hours at 80-90ac. The polymer, in different stages, was characterized by the IR spectrum, GPC chromatography and volumetric titration. The viscosity of the silyl-terminated polymer is 100,000 cps at 24ac. EXAMPLE 5 To 300 g (0.14465 mol) of the propylene oxide-pentanediol and polyester-polyol, 50.4 g (0.2983 mol) of toluene diisocyanate and 0.37 g of a DABCO catalyst solution were added. The polyester polyol used had a molecular weight of 2074 and a hydroxyl number of 54.1. The mixture was heated at 80 ° C for 1-2 hours in a nitrogen atmosphere. Allyl alcohol (16.8 g, 0.2893 mol, 99%) and 1.5 g of a DABCO solution was added and heated for 1-2 hours at 80 ° C, with continuous stir. 27.3 g (0.2893 mol, 99%) of 1,2-ethanedithiol and 0.59 g of AIBN were added to the olefin-terminated polymer and radical coupling was carried out at 80-90 ° C for 2 hours, with slow stir . To the mercaptan polymer thus obtained, 77.4 g (0.3037 mol, 95%) of the methyl (ethyl) bis (2-butanone-oxime) -silane were added and heated for 2 hours at 80-90ac. The polymer was characterized in different stages by the IR spectrum and the GPC chromatography and the content of -SH in the mercaptan-terminated polymer was determined by the volumetric titration. The viscosity of the silyl-terminated polymer is 140,000 cps at 24ac.

EXAMPLE 6 297.1 g (0.102 mol) of polytetramethylene glycol, which has a molecular weight of 2914 and a hydroxyl number of 385, were melted at 60ac and mixed to obtain a homogeneous liquid and 356 g (0.204 mol) of toluene diisocyanate and 0.35 g of a DABCO solution were added, a ratio of 80:20. The reaction was brought to 80 ° C for 1-2 hours in a nitrogen atmosphere. To this pre-polymer were added 11.9 g (0.204 mol) of allyl alcohol and 1.45 g of a DABCO solution. The product was encouraged at 80 ° C, with continuous agitation, for 1-2 hours. The allyl-terminated polymer thus obtained was reacted with 19.2 g (0.2040 mol) of 1,2-ethane-dimercaptan and 0.55 g of the initiator AIBN. The reaction temperature was maintained between 80-90ac for 2 hours. Finally, 54.5 g (0.2142 mol) of the methyl-vinyl bis- (2-butanone-oxime) -silane, 95% test, and 0.52 g of AIBN were added and reacted at 80-90ac for 2 hours. The finished polymer in silyl, thus obtained, is highly viscous (1 million cps, at 24.5ac). EXAMPLE 7 A polyethylene glycol, 300 g (0.15 mol), having a hydroxyl number of 56 and a molecular weight of 2000, was reacted with 52.4 g (0.30 mol) of toluene diisocyanate in the presence of 0.37 g of the DABCO solution at 80ac, for 1-2 hours. The pre-polymer, thus obtained, was reacted with 17.4 g (0.30 mol) of allyl alcohol, in the presence of 1.5 g of the DABCO catalyst solution for -12 hours. 28.3 g (0.30 mol) of 1,2-ethanedithiol, and 0.15% by weight of AIBN were added, and slowly stirred for 2 hours, at 80-90 ° C. To this mercaptan-terminated polymer was added 93.5 g (0.367 mol, 95% test) of the methyl-vinyl bis- (2-butanone-oxime) -silane and 0.15% by weight of AIBN, and was reacted at 80.degree. 90ac for 2 hours to obtain an oxime-terminated polymer having a viscosity of 220,000 cps, at 23ac. The nitrogen atmosphere was maintained throughout the reaction process. Comparison of the Cure Regime The cure rate for identical polymers was compared with various types of silane endcapping. He The polymer terminated in mercaptan, prepared in Example 1, was divided into three reactors, designated A, B and C. polymer in reactor A was topped with methyl-vinyl bis (methoxy) -silane, polymer B was topped with methyl-vinyl bis (ethoxy) -silane and the polymer in reactor C was was topped with the methyl-vinyl bis (2-butanone-oxime) -silane, as described in Example 1 for ketoximino-silane. The topped polymers were prepared as sealants, to compare physical properties, such as cure rates and strength, for the following formulations and methods.

Formulation 1 COMPONENTS% WEIGHT Polyether Polymer of Example 1 30.00 Di-octyl phthalate 24.50 CaC03 42.90 Tri (2-butanone-oxime) -methylamine 2.00 Amino-propyl-triethoxy-silane 0.50 Dibutyltin dilaurate 0.1 Formulation 2 COMPONENTS% BY WEIGHT Polyether Polymer of Example 1 30.00 Di-octyl phthalate 24.50 CaC03 43.00 Tri (2-butanone-oxime) -silane methyl 2.00 Amino-propyl-triethoxy-silane 0.50 To a double planetary mixer, under vacuum, the polymer and the plasticizer were added. and mixed under vacuum. Precipitated calcium carbonate was added and mixed under vacuum. To the mixture were added ethylimino-silane and amino propyltriethoxy-silane (available as OSI A-1100). The mixture was carried out under vacuum. The mixture was then discharged into tubes for storage and further evaluation.

The sealant was produced from each polymer, using the formulas and methods in Table 1. Cure times, cure rates and mechanical properties were measured and listed in Table 1. Sealer, prepared in formulation 1 or 2, with the polymer topped with ethoxy-silane failed to cure. TABLE 1 MECHANICAL PROPERTIES In the following examples, a number of other polymer backbones were evaluated as starting materials for the silane addition methods and the properties are provided as follows.

Formulation 3 COMPONENTS% BY WEIGHT Polyester polymer of Example 5 30.00 Aromatic hydrocarbon oil 24.50 CaC03 43.00 Tri (2-butanone-oxime) -methylamine 2.00 A-1100 0.50 To a double planetary mixer, under vacuum, 30 parts by weight of the polymer and 24.5 parts by weight of the plasticizer were added. and mixed for 2 to 5 minutes under vacuum. Precipitated calcium carbonate was added and mixed for 15 to 20 minutes under vacuum. The methyloxyminosilane was added to the mixture. The mixing took place for approximately five minutes, under vacuum. The mixture was then discharged into tubes for storage and further evaluation.

Formulation 4 COMPONENTS% BY WEIGHT Polymer of Example 7 30.00 Alkyl aryl phosphate ester. 24.50 CaC03 43.00 Tri (2-butanone-oxime) -methylamine 2.00 A-1100 0.50 To a double planetary mixer, under vacuum, 30 parts by weight of the polymer and 24.5 parts by weight of the plasticizer were added. and mixed for 2 to 5 minutes under vacuum. Precipitated calcium carbonate was added and mixed for 15 to 20 minutes under vacuum. The methyloxyminosilane and the A-1100 were added to the mixture. The mixing took place for approximately five minutes under vacuum. The mixture was then discharged into tubes for storage and further evaluation.

TABLE 2 MECHANICAL PROPERTIES Formulation 5 To 50 parts by weight of the polymer of Example 6, 50 parts by weight of a modified cumene-indole resin (softening point, ASTM E-28 Ring and Ball method, ooac) was added at a temperature between 150 and 200ac. The mixture was prepared as a polypropylene sheet and allowed to cool. This leaf was cured for 15 days at room temperature, after which it was exposed to Ioac for 6 hours, followed by an additional 9 days at room temperature. The tensile properties are as follows: tensile strength: 15 n / mm2; Lengthening: 790%; Hardness (Shore A): 17.

Formulation 6 COMPONENTS% WEIGHT Polyether polymer of Example 2 40.00 Di-octyl phthalate 14.50 CaC03 43.00 Tri (2-butanone-oxime) -silane methyl 2.00 A-1100 0.50 To a double planetary mixer, under vacuum, 40 parts by weight of the polymer and 14.5 parts by weight of the plasticizer were added. and mixed for 2 to 5 minutes under vacuum. Precipitated calcium carbonate was added and mixed for 15 to 20 minutes under vacuum. Methyloxyminosilane and A-1100 were added to the mixture. The mixing took place for approximately five minutes under vacuum. The mixture was then discharged into tubes for storage and further evaluation. Sealant slats were applied to the glass and aluminum substrates and allowed to cure at ambient conditions for 7 days. The adhesion test consists of making an initial cut with a shaving knife to the adhesive interface of the substrate. A manual 45th and 90th force was applied and the failure mode was visually evaluated. The adhesion was classified on a scale from 1 to 6, with 1 representing no adhesion and 6 is a cohesive failure at both angles of the tensile force. The samples were then exposed to boiling water for 15 days and retested using the same method. The sample consistently exhibited a cohesive failure at a tensile force of 45a and a cohesive failure at a 90a traction.

Formulation 7 COMPONENTS% WEIGHT Polyether Polymer of Example 3 30.00 Di-octyl phthalate 24.50 CaC03 43.00 Tri (2-butanone-oxime) -silane methyl 2.00 A-1100 0.50 To a double planetary mixer, under vacuum, 40 parts by weight of the polymer and 14.5 parts by weight of the plasticizer were added. and mixed for 2 to 5 minutes under vacuum. Precipitated calcium carbonate was added and mixed for 15 to 20 minutes under vacuum. Methyloxyminosilane and A-1100 were added to the mixture. The mixing took place for approximately five minutes under vacuum. The mixture was then discharged into tubes for storage and further evaluation. The sample was cured for 7 days at room temperature and the tensile properties were determined according to DIN 53504 type s2 and Shore A hardness by the ASTM C-661 standard.

Formulation 8 COMPONENTS% WEIGHT Polymer of Example 1 30.00 Di-octyl phthalate 24.00 CaCO3 43.00 Moisture scrubber: Oxazolidine (Angus Chemical) 3.00 3-ethyl-2-methyl-2- (3-methylbutyl) - 1,3- oxazolidine To a double planetary mixer, under vacuum, the polymer and di-octyl phthalate were added. This was mixed for 2 to 5 minutes under vacuum. Precipitated calcium carbonate was added and mixed for 15 to 20 minutes under vacuum. Then the moisture scrubber was added to the mixture. The mixing took place for approximately five minutes under vacuum. The mixture was then discharged into tubes for storage and further evaluation. The sealant of each composition was produced and the mechanical properties were measured and listed in the following Table 3.

TABLE 3 Formulation 9 COMPONENTS% WEIGHT Polyether polymer of Example 1 49.50 Di-octyl phthalate 9.90 Hydrated alumina precipitate 24.75 Titanium dioxide 14.85 A-1100 0.99 Solvent Component Parts per hundred parts of the mixture: Methyl chloroform 40 To 49.5 g of the polymer 9.9 g of dioctyl phthalate were added and combined at medium speed with a high-cut dispersion sheet. To this mixture, 24.75 g of alumina trihydrate and 14.85 g of titanium dioxide were combined at medium cutting for 5 minutes, using a high cut blade. 0.99 g of the amino-ethoxy silane were added and mixed for 1 minute at medium speed. Approximately 40 parts per hundred methyl chloroform were added to the mixture to obtain a viscosity with flowability. The aluminum sheet cleaned with hexane was coated with the mixture to a uniform thickness. The surface was tack-free between 120 and 140 minutes after application. A sheet with a thickness of 3,175 mm of coating was prepared by molding the compound in a mold. Time of lack of tack 120-150 minutes Resistance to tension 3.6 N / mm2 Lengthening 260% Shore hardness A 42 Bending approves, no cracks EXAMPLE 8 A 1-liter, three-necked reaction flask equipped with an overhead stirrer, thermometer and addition funnel was charged with 17.5 grams of toluene diisocyanate (0.10M) and heated to 80-90ac. The polypropylene oxide diol was added slowly, with an average molecular weight of 4000, (200 g, 0.05M). The reaction mixture was refluxed at 80-90ac for 2-4 hours and the progress of condensation was monitored by infrared spectroscopy. The 2-mercaptoethanol (7.8 g, 0.10M) was slowly added to the reaction mixture and refluxed at 90-100ac until the infrared spectrum of the pot sample showed no absorption of the isocyanate at 2265 cm -1. The methyl-vinyl bis (methylethyl ketoximino) -silane (31.3 g, 0.10M) and the AIBN (460 mg) were added to the mercapto-terminated polyol and refluxed at 85-90ac for 3 hours, to give a liquid polyol polymer terminated on oxime-silane. EXAMPLE 9 Example 8 was repeated, except that 3-mercaptopropanol (92 g, 0.10M) was used. Similar results were noted. Formulation 10 COMPONENT% BY WEIGHT Polymer of Example 8 or 9 30.00 Di-octyl phthalate 24.50 CaC03 43.00 Tri (2-butanone-oxime) -silane methyl 2.00 A-1100 0.50 To a double planetary mixer, under vacuum, 30.0 parts by weight of the polymer and 24.5 parts by weight of the plasticizer were added. This was mixed for 2 to 5 minutes under vacuum. Precipitated calcium carbonate was added and mixed for 15 to 20 minutes under vacuum. The methyloxyminosilane and the amino propyltrimethoxysilane were then added to the mixture (Available as A-1110, from Union Carbide). The mixing took place for approximately five minutes under vacuum. The mixture was then discharged into tubes for storage and further evaluation, with the following results. TABLE 4

Claims (10)

1. CLAIMS 1. A polymer finished in oximinosilane, which has the formula: and having an average molecular weight of at least 1,200; wherein R is an organic polymer containing a polyether, polythioether or polyester skeleton; R1 is a bivalent organic radical; R2 is an alkylene group, having at least 2 carbon atoms; X is O or NR6, where R6 is hydrogen or a monovalent group of lower alkyl; Y is sulfur or S-R7-S, where R7 is an alkylene thioether having from 4 to 12 carbon atoms, an alkylene having 2 to 10 carbon atoms or a substituted cyclohexyl ring group, having the formula : CH3 R3 is an alkyl radical with 1 to 7 carbon atoms or an alkoxy radical with 1 to 6 carbon atoms and R4 and R5 are, independently, a straight or branched chain saturated alkyl radical with 1 to 7 carbon atoms, or R4 and R5 taken together form a cyclic group, p is from 2 to 3, m is from 0 to 2, n is from 1 to 3, and the sum of m and n is 3.
2. 2. The polymer terminated in oximinosilane, according to claim 1, wherein R is a hydroxyl-terminated polymer selected from the group consisting of polypropylene oxide polyols, polybutylene oxide glycol polyols, polytetramethylene glycol polyols, polyester polyols, polyols of polythioethers, polyalkylene glycol copolymer polyols, and polyalkylene glycol polyester copolymer polyols.
3. 3. The oximinosilane-terminated polymer according to claim 1, which is a liquid having a molecular weight in the range of about 1,200 to 100,000.
4. 4. A composition comprising: a) the oximinosilane-terminated polymer according to claim 1, in an amount of about 5 to 90% by weight of the composition; b) a moisture scavenger, in an amount from 0 to about 5% by weight of the composition; c) a plasticizer, in an amount from 0 to about 50% by weight of the composition; and d) a filler, in an amount from 0 to about 75% by weight of the composition. ? A method for the production of oximinosilane-terminated polymers, which have the formula: and having an average molecular weight of at least 1,200; wherein R is an organic polymer containing a polyether, polythioether or polyester skeleton; R1 is a bivalent organic radical; R2 is an alkylene group, having at least 3 carbon atoms; X is O or NR6, where R6 is hydrogen or a monovalent group of lower alkyl; Y is sulfur or S-R7-S, where R7 is an alkylene thioether having from 4 to 12 carbon atoms, an alkylene having 2 to 10 carbon atoms or a substituted cyclohexyl ring group, having the formula : "10 R3 is an alkyl radical with 1 to 7 carbon atoms or an alkoxy radical with 1 to 6 carbon atoms and R4 and R ^ are, independently, a saturated alkyl radical, straight or branched chain, with 1 to 7 carbon atoms; carbon, or R4 and R5 taken together, form a cyclic group, p is from 2 to 3, m is from 0 to 2, n is from 1 to 3, and the sum of m and n is 3; this method comprises: a) reacting an isocyanate-terminated polymer, having the general formula: R [0-C-NH-R1-N = C = 0] p II O with an olefin alcohol or amine, in which the olefin group is separated by at least one carbon atom, to give an olefin-terminated polyether polyol; b) reacting the olefin-terminated polymer with a dimercaptan, in which the mercaptan functionality is separated by an alkylene, alkylene ether, thioether of 15 alkylene, alkylene ester or substituted cyclohexyl rings, to give a mercaptan-terminated polymer; and c) reacting the finished mercaptan polymer with a component selected from the group consisting of 20 vinyl oximino-silane, vinylalkyl-oximino-silane, vinylaryloxyamino-silane and vinylarylalkoxyoxyimino-silane. 6. The method according to claim 5, wherein R is a hydroxyl-terminated polymer, selected from the group consisting of polypropylene oxide polyols, 25 polybutylene oxide glycol polyols, polytetramethylene glycol polyols, polyester polyols, polythioether polyols, polyalkylene glycol copolymer polyols, and polyalkylene glycol polyester copolymer polyols. The method according to claim 5, wherein the dimercaptans are selected from the group consisting of 1,2-ethanedithiol, 1,6-hexane-dithiol, 1,10-decane-dithiol, 2-mercaptoethyl ether, 2 -mercaptoethylsulfide, glycol acetate-dimercapto, glycol-dimercapto propionate, p-menthane-2,9-dithiol, bis- (3-mercapto-propionate) of ethylene and ethylcyclohexane-dithiol. 8. The method according to claim 5, wherein the vinylloxy silane or the vinylalkoxyoximino silane has the formula: R4 I H2C = CH-Si- (0-N = C) n I I (R3) m R5 9. A method for the production of oximinosilane-terminated polymers, having the formula: P and having an average molecular weight of at least 1,200; wherein R is an organic polymer containing a polyether, polythioether or polyester skeleton; R1 is a bivalent organic radical; R2 is an alkylene group, having at least 2 carbon atoms; X is O or NR6, where R6 is hydrogen or a monovalent group of lower alkyl; Y is sulfur or S-R7-S, where R7 is an alkylene thioether having from 4 to 12 carbon atoms, an alkylene having 2 to 10 carbon atoms or a substituted cyclohexyl ring group, having the formula : CHs R3 is an alkyl radical with 1 to 7 carbon atoms or an alkoxy radical with 1 to 6 carbon atoms and R4 and R5 are, independently, a straight or branched chain saturated alkyl radical with 1 to 7 carbon atoms, or R4 and R5 taken together, form a cyclic group, p is from 2 to 3, m is from 0 to 2, n is from 1 to 3, and the sum of m and n is 3; this method comprises: a) reacting an isocyanate-terminated polymer, having the general formula: R [0-C-NH-R1-N = C = 0] p II O with a mercapto alcohol, in which the mercaptan and hydroxy groups are separated by at least two methylene groups, to produce a "-" "polymer" "terminated in mercaptan, and b) reacting the finished mercaptan polymer with one component selected from the group consisting of vinyl oximinosilane, vinyl alkyl siloxane silane, vinylaryloximino silane, vinylalkylalkoxyoximino silane, vinylalkoxyoximino silane and vinylaryl alkoxyoximino silane. 10. The method according to claim 9, wherein R is a hydroxyl-terminated polymer selected from the group consisting of polypropylene oxide polyols, polybutylene oxide glycol polyols, polytetramethylene glycol polyols, polyester polyols, polyols of polythioether, polyalkylene glycol copolymer polyols, and polyalkylene glycol-polyester copolymer polyols.