MXPA96004336A - Composition for the preparation of rapid hardened desilicone fillers, which may amreosula - Google Patents

Abstract

The present invention relates to a set of components for preparing fast hardening silicones putties crosslinking aminosilanes, consisting of: A) 100 parts by weight of a diorganopolysiloxane terminator at least bifunctional, which is composed of a straight or branched chain of repeating units of the formula: and which contains at least two terminal groups Z, wherein Z is independently -H, -OH, -OR1ó-SiR3 (NR4R5) 2 and R1 and R2 are independently a saturated or unsaturated hydrocarbon radical, optionally substituted with halogen or cyano groups; B) 0.1 to 20 parts by weight of an aminosilane crosslinker of the formula R3y-Si- (NR4R5) 4-y wherein y = 0 or 1, R3 is hydrogen or a monovalent hydrocarbon or oxyhydrocarbon radical saturated or unsaturated, and R4 and R5 are independently selected from the group consisting of hydrogen and an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, saturated or unsaturated, with 1 - carbon atoms, optionally substituted with halogen or cyano groups, C) 0.1 to 20 parts by weight of an inorganic or organic compound capable of reacting with an amine for formars, and D) 0 to 20 parts by weight of ag

Description

COMPOSITION FOR THE PROCESS L.1 A M U L I S C H I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I II "assembly or kit of components for the preparation of quick hardening silicone mastics, which can be crosslinked at 1 year, and which consists of diorganopolic compounds with terminals at least bi tune tonal, crosslinking agents for the l? arasi Ios as well as eventually also filling materials, suitable additives, pigments, dyes, agents that protect against oxidation, heat and light, and solvents and rebonding agents and the use of these materials as adhesives and as materials i mol These types of organopolyses, which are also known as single-component silicone rubbers that vulcanize in trio, usually cross-link at room temperature with absorption of water from the surrounding atmosphere. To form polymers with the elasticity of rubber, quality of chain extenders and as a reticulators, we use ami nosi 1-year bi-tuneal or poly-4 compounds. unites i onal s, which by reaction with pol i si I oxano, or by hydrolysis, release amines, thereby initiating the formation of a macromol reticulation cu I r. After they have hardened, this type of mastics are characterized by their good self-adhesion properties on the surfaces * 3 of the most diverse materials, and by an inalbility in general high with respect to the influence of temperature, light, humidity, as well as the attack of chemical products. The hardening of these mixtures of polynucleotides that consist of a single component and that take place at room temperature with moisture absorption, takes place relatively slowly, since the water necessary for the reaction has to be spread inside the mass in gas torma from the 1 ? surrounding atmosphere, bs therefore the speed of the hardening decreases continuously inside the mass as the reaction progresses, in the case of a ba to relative humidity of the environment, or in the case of a disadvantageous relationship between the surface and the volume of If the silicone mass, the reaction can become very slow or, as is the case in spaces sealed with steam, it can stop completely. The various application possibilities such as glues or sellers that offer these silicones When hardening with the humidity of the environment, they are limited especially in relation to their use in industrial manufacturing, due to the slowness of the hardening. Even when silicone rubber systems are known that consist of two components that harden quickly at room temperature or only at higher temperatures, they can often not be used due to their poor self-adherence or due to their altered depending on the temperature it is comparatively low. However, if silicones are used that only harden in a very slow way or the influence of the humidity of the environment, in order to ensure the hardening, it is necessary to have large intermediate stores for the sealed or glued pieces, due to the short and work intervals that are required for reasons of economy, it is also necessary to add or dampen these intermediate stores adi cially. Circumstantially, it may be the case that a large number of pieces are manufactured, before it results It is possible to carry out the tests with respect to the integrity and functionality of the same, in practice it is not possible to carry out extensive surface sticking between diffusion-tight surfaces using silicas which harden with the humidity of the medium.

B environment, as well as it is not possible with them the production of molded bodies in closed molds. To the well-known putties that contain at the same time and which harden with the humidity of the environment, water is added to it in its liquid form., a certain acceleration of the hardening compared to the crosslinking is achieved by the humidity of the environment, however, this crosslinking agent does not provide finished products with properties of i? material such as those obtained with the crosslinking carried out purely with the humidity of the environment. Rather, they result in masses which, in the long run, remain considerably softer, have a poor self-adhesion, and still remain sponged for a long time with the resulting amine as a product of detachment from cross-linking. Therefore, the odor of the amine, which usually suffers as quite unpleasant, does not fade for a correspondingly long time. Similar results are obtained, that is, only an intimate acceleration of the hardening, coupled with comparatively poorer properties of the materials and an amine odor that is maintained for a long time, if water is added in the form of salts containing water of crystallization, or in substance substances whose surface is deliberately moistened. The task proposed by the invention therefore consists in providing masses of adhesives and adhesives based on mixtures of polymers that can crosslink together, and these must harden within a certain period of time. reduced, that is, within a few minutes to within a few hours. Additionally, the hardening must be independent of the humidity of the environment, that is, it must be able to happen even in areas or molds sealed hermetically to steam. For this, the typical characteristics of the vulcanizates hitherto known, which should also be retained substantially, should also be preserved.

They are the result of cross-linking due to humidity in the environment, such as self-adhesion, mechanical properties and inalterability. The task proposed by the invention is solved with the characteristics of the clause Or principal, and is perfected by those of the secondary clauses, these mixtures are characterized in that they contain at least the following components: A) 1UÜ parts by weight of a diorganopol i if 1 oxano terminator at least bituncional, being that the organopol i if I oxano is composed of a linear or branched chain of repetitive units of formula A kl - ?-OR- R? Luy, as represented below using the case of a linear chain as an example, ends with functional terminal groups. 1 * 0? I Rl ^ -? -U) _ - b? - K * k¿ Here: kl, R2: meaning hydrocarbon residues, saturated or unsaturated, possibly substituted with halogen or cyan groups ^ ¿i means -H, -üH, -ÜRl and - Si k- ^ Nk -3) 2? k3: means hydrogen or hydrocarbon residue or ox i h i monovalent saturated or unsaturated hydrocarbon, with 1 - Ib carbon atoms. R4, R: signify hydrogen and / or aliphatic hydrocarbon residue, saturated or unsaturated, with 1 - Ib carbon atoms, possibly Lu substituted with halogen or cyan groups. b > ? l to 20 parts by weight of a re ti cient of am i nos of general formula Ib K3y-t > ? - < Nk4kt? > 4-y where y • U and 1, while R3, k4 and kb have the meaning indicated above. •.? L)? L to 20 parts by weight of an inorganic or organic compound, which reacts with amines under formation of s I is. ü) ü to 20 parts by weight of water.

As an example of the residues R1 and R2 of component A, mention may be made of any saturated alkyl residues, such as methyl, ethyl, n-propyl, isopropyl, octyl, dodecyl, octadecyl, but also cyclic, such as b-cyclopentyl and cyclohexyl. In addition, aliphatic or unsaturated aliphatic residues such as vinyl, villous, openten and oocycline, and also aromatics such as phenyl or natyl, and aryl or substituted residues can be used. fát i canten te, as for example í? benzyl or toluyl. The residues R1 and R2 can be inside a polysiloxane of the same or different composition. It is also possible to mix poly i if branched and unbranched 1 oxanes of the composition described above and of different chain length. From Preferred ID are used if 1 oxanes terminated in hydroxyl groups, so-called dih i di di organopol i si Ioxanos alpha, omega, with residues met i 1 o and fen i 1 o.

The waste mentioned can also be 0 used in the form substituted with halogen or with cyano. The corresponding examples are residues 1, 1, 1-tr i f 1 uortolu i 1, be ta-c i anoet i 1 o u o-, m- or p-chloro eni lo.

B The viscosity of di-organopoli if 1-oxanes is preferably within the range of OUO to 330000 Pa. Bn component b can be used in addition b compounds of formula Kd2-S? - < NR4 - > 5) 2 who serve as trainers in the chain of 1U pol i si I oxanos employees. The residue R3, if not hydrogen, can have the same composition as the residues R1 and R2. Preferably, simple alkyl residues, such as methyl or ethyl, are used. * 3 The residues R4 and R5 can have the same composition as the residues R1, R2 or R3, one of the two residues also consisting of one hydrogen atom. Preferably, organoamines are used, which are obtained, for example, by reactions of -u met i i orosi Ios with primary, aliphatic or cyclic amines, especially with sec-but i 1 amine or cyclohexamine. Suitable carboxylic or mineral acids, such as, for example, those which are suitable for component C, are suitable.

T > formic, acetic, citric, tartaric, oxalic acids, hydrochloric, sulfuric and phosphoric, and also the acid salts, as for example the bi-carbonated phosphates and the bi-carbonated sulfates of the ammonium, alkaline and lime-free metals, optionally also in combination. If these substances are used in a form containing water of crystallization, in some cases the addition of component D to the mixture can be dispensed with. It is for this reason that, for example, oxalic acid dihydrate is preferably used. Component D can be added to the mixture both in liquid form and also bound as water of crystallization, for example as sodium sulphate decahydrate, or enclosed in zeolites, and also absorbed on the surface of filling materials, as per 13 example calcium carbonate. The addition of component D is preferably carried out in combination with component C, bound as water of crystallization in the dihydrate of oxalic acid. To mixtures that include components A to --U D can be added other substances to obtain specific properties. We mention here especially the coloring pigments and soluble coloring substances, stabilizers against oxidation and the effects of heat, dispersants, catalysts of the 3 reaction, fungicides, adhesion promoting agents, solvents, retarders of 1 to 1, softeners (preferably silicone oils, but also based on hydrocarbons), reinforcing fillers, such as silicic acids highly dispersed or precipitated, graphite, carbon black, as well as also passive fillers, such as, for example, calcium carbonate, silicates, quartz flour, glass and carbon fibers, earth of particles (earth of infusoria) , metal powders, metal oxides, l? powders of synthetic materials as well as hollow balls of glass or of synthetic materials. The mixtures that include the components A to D are not unalterable when they are stored. That is why the components C and D, necessary to accelerate the reaction, are added to the mixture of the components A and B in a suitable form just before use, preferably pasted in silicone oils or mixed with polymers. If the hardening of the mixtures that -u include the components A to D is carried out at elevated temperature, thereby achieving an additional acceleration of the crosslinking reaction. The present invention also relates to a process for the preparation of a mixture of Is it made of glue, or respectively of a mouldable mass, based on diorganopol i if 1 oxanos of at least bifunctional termination and reticulators of ami nosi 1 years, which is characterized 3 A) 100 parts by weight of a diorganopol t si 1 oxano of this nature, in which this is composed of a linear or branched chain of repeating units of formula 1U Rl -Yes-0- R2 13 according to the following formula kl k U < -Si-0) n - Si- Z R2 R2 -.3 which is valid for the exceptional case of linear chains, terminates in terminal groups? and in which: kl, R2: means hydrocarbon residues, saturated or unsaturated, optionally substituted with halogen or cyano groups 2: means -H, -OH, -ORÍ and -SÍR3 < NR4R5 > 2 R3: hydrogen or hydrocarbon residue l? monohydric saturated or unsaturated monocarboxycarbonate, with 1 - Ib "carbon atoms, HA, R5: mean hydrogen and / or aliphatic hydrocarbon residue, saturated or unsaturated, with 1 - 13 13 atoms carbon, possibly substituted with halogen or cyan groups, they intermingle with ? B > 0.1 to 20 parts by weight of a representative of the i and i years of general formula k3y-Si- < NR4R5) 4-y B being y = 0 and 1, while R3, R4 and R5 have the meaning indicated above, 3 as well as optionally also with coloring pigments or soluble coloring substances, stabilizers against oxidation and the effects of heat, dipers, reaction catalysts, fungicides, adhesion promoting agents, solvents, light retardants 1 , softeners (preferably iconic silicone oils, but also hydrocarbon-based softeners), as well as active, reinforcing fillers, such as highly dispersed or precipitated silicas, graphite, carbon black, 13 as well as passive fillers, such as calcium carbonate, silicates, quartz flour, glass and carbon fibers, diatomaceous earth (infusoria earth), metal powders, metal oxides, synthetic powders as well as balls Or hollows of idrio or synthetic materials, and just before use, are added Or 0.1 to 20 parts by weight of an inorganic compound? organic, which reacts with amines under formation of 2b salts, and D) O to 20 parts by weight of water.

The mixtures according to the invention adhere on their own to glass, ceramic, wood, concrete, plaster, metal and synthetic materials. This is why they are conveniently used as seals or adhesives, but they are also suitable as protective coatings for electrical insulations, such as insulating fish or fusible masses for electrical and electronic components, but also as molding compounds for the production of molds. and other shaped parts, which are conveniently made of elastomers. The following is explained in more detail 13 Invention by means of examples. EXAMPLE 1 100 parts by weight of a component I consisting of 100 parts by weight of an alpha, omega-dihydroxine dimet i 1 pol i si 1 oxano with a viscosity of 20,000 mPa. ß parts by weight of an al, omega-bi s- (r ime 111 if 1 i 1) d? me 111 pol i -si 1 oxane with a viscosity of ¿B 100 mPa. the 13 parts by weight of a highly dispersed silicic acid with a specific surface area according to BET of approximately 110 m ^ g. 51 parts by weight of a calcium carbonate filler. ? parts by weight of tr i s- (c icl ohex i 1 ami no) met i 1 if 1 anus are mixed homogeneously at room temperature, with 20 parts by weight of a component II, consisting of 80 parts by weight from one to the fa, omega-bi s (tr imet i 1 si 1 i 1) d? me ti 1 pol i -si 1 oxane with a viscosity of 1000 mPa. 9 parts by weight of a highly dispersed silicic acid with a specific surface area according to BET of approximately 110 m2 / g 10 parts by weight of an oxalic acid dihydrate with a fineness of << 10 um. The mixture obtained from the components reaches a Shore-A hardness of 22 'in 60 minutes, at room temperature and to the exclusion of moisture from the environment, while both components alone (without mixing them together) are preserved under these conditions as unalterable pastes during storage.

If, in component II described above, the oxalic acid dihydrate is replaced by aqueous solutions at 20V. of sulfuric, hydrochloric or phosphoric acid, then hardening occurs a few minutes after mixing with component 1. EXAMPLE 2 For comparison purposes, respectively, 100 parts by weight of a mixture consisting of 100 parts by weight of an alpha, or anhydride, and 1 polymer with a viscosity of 80,000 mPa, 41 parts by weight, weight of a al fa, omega-bi s-13 < r i e t i 1 if I i 1) d? me 11 pol i -si 1 oxane with a viscosity of 100 mPa. or parts by weight of a silicic acid to the dispersed atom with a specific surface area according to BET of about 130 m2 / ga - U 123 parts by weight of a calcium carbonate filler. 12 parts by weight of tr i s- < c icl ohex i 1 ami no) me t i 1 s and 1 year are mixed at room temperature in one case B with 2 parts by weight of glass oxalic acid dihydrate ftno, and in another case with O.o parts by weight of water, and stored under the exclusion of moisture from the environment. The mixture with the oxalic acid already after 3 3 hours has a Shore-A hardness of 13"Shore-A, and only emits a slight amine smell, while the mixture that only contains water does not show a Shore-A hardness measurable, even after 24 hours have elapsed, and is very soft and sticky, in addition to a strong amine odor. 13 -.or 3

Claims (14)

1. Cl ausu I 1. Okit set of components for the preparation of masi l of the l if you are based on diorganopol i if 1 oxanos with terminals at least bi tonal fun, reticulators aminosi 1 years, as well as eventually also filling materials, suitable additives and pigments, characterized in that it contains the following components: A) 100 parts by weight of a diorganopol i si 1 oxano of lv termination at least bi functional, being that this diorganopol i si loxane is composed by a linear or branched chain of repetitive units of formula ib Rl -Yes-0- R2 u and contains at least two terminal groups 2. in which i 2? means -H, -OH, -ORl and -SiR3 < NR4R5 > 2 Rl, R 2: means hydrocarbon residues, saturated or unsaturated, optionally substituted with halogen or cyclic groups 3 B) 0.1 to 20 parts by weight of an amylosin reticulator 1 years of general formula R3y-Si- (NR4R5) 4-y I1- »where y« 0 and 1, with R3: which means hydrogen or hydrocarbon residue or ox i h i drocar saturated or unsaturated monovalent bureau, and R4, R5: - meaning hydrogen and / or residue 13 aliphatic hydrocarbon, saturated or unsaturated, with 1 - 15 carbon atoms, optionally substituted with halogen or cyano groups. -u OR 0.1 to 20 parts by weight of an inorganic or organic compound, which reacts with amides under salt formation. D) 0 to 20 parts by weight of water. 3 2. Assembly or kit of components according to clause 1, characterized in that component B also contains compounds of formula 3 R32-Si- < NR4R5) 2, with R3: which means hydrogen or hydrocarbon residue or ox ihi saturated monovalent or unsaturated hydrocarbon, and R4, R5: meaning hydrogen and / or residue i "aliphatic hydrocarbon, c icl oal i fát i co or harmonic, saturated or unsaturated, with 1 - 13 carbon atoms, optionally substituted with halogen or cyan groups.> 3. Assembly or kit of components in accordance with clauses 1 to 2, which is characterized as Component C contains organic or inorganic acids, or acid salts 4. Compound or kit of components in accordance with clauses 1 to 3, characterized in that Component C is contained in the form of crysalization water. 3. Assembly or kit of components in accordance with clauses 1 to 4, which is characterized as 3 component D is used for the water of crystallization of hydrated substances, or the water absorbed in zeolites or silica gels or on surfaces of filling materials, or. Assembly or kit of components in accordance with the 3 clauses 1 to 5, characterized in that in one of the components AD are additionally contained coloring pigments or soluble coloring substances, stabilizers against oxidation and the effects of heat , dispersants, reaction catalysts, fungicides, adhesion promoting agents, solvents, retarders of amorphous properties, softeners (preferably silicone oils, but also hydrocarbon-based softeners), as well as fillers 13 active, reinforcing, such as highly dispersed or precipitated silicas, graphite, carbon black, as well as passive fillers, such as calcium carbonate, silicates, quartz flour, glass or carbon fibers , earth of di a tome s (land of infusoria), metallic powders, metal oxides, synthetic powders as well as hollow balls of glass or of synthetic materials, 7. Set or kit of components in accordance with the 3 clauses 1 a or, which is characterized because as a component of organopol i si 1 oxano A is used a di i drox i di organopol i si 1 oxano-al fa, omega. 8. Procedure for the preparation of a diorganopol i-b based glue or dye-based glue mix and aminosi reticulators 1 year, which is characterized in that the components A and B according to clause 1 are mixed to form a first premix, and the components C and D are mixed together to form a second premix and, just prior to use, both premixes are bonded together Form the effective mix of paint and glue. 9. Procedure in accordance with clause 8, characterized in that compounds of formula ib R32-Si- (NR4R5) 2 are intermixed with the first premix in addition. wherein R3, R4 and Rb have the meaning mentioned above. 10. Procedure in accordance with clause 8 or 9, characterized in that, as component C, a compound is used according to clause 3 or 4, and as a component D a mixture according to clause 3 is used. sul to 4 or 5. 3 11. Procedure in accordance with clause 8 to 10, which is characterized by the fact that components C and / or D are bound (optionally) in combination with substances of clause 6, and because eventually 3 a softener is added based on whether the plates or a polimeric polymer of diorganopol and 1 oxano in accordance with 1 to clause 1. 12. Procedure in accordance with clause 8 to 11, which is characterized in that employs a 1 u di h i drox i di organopol i si 1 o ano-a 1 f a, omega. 13. The use of mixtures made with the set or kit of components according to clause 1 to 7, in quality of sellers or adhesives. 14. The use of mixtures made with the whole or Ib k i t of components according to clause 1 to 7, in quality of moldable masses. or ..3 EXTRACT The present invention relates to a set or kit of components for the preparation of fast-hardening silicone sealants, which can be cross-linked for 1 to 1 years, and which consists of diorganopolides and crosslinking agents for the ani-llanos. and, eventually, filling materials, suitable additives, pigments, dyes, agents that l? they protect against oxidation, heat and light, and solvents and rebonding agents containing water and, as a crosslinking agent, a compound that reacts with the amines to form a salt. The invention also relates to the use of these silicone materials as adhesives and as molded masses. U ¿b