• 专利附录
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    • 专利摘要:
    The present invention relates to the use of homo and heterometallic polymers with the ligand 1,3,5-triaza-7-phosphatedmantanofosphine (pta) and 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo [3.3 .1] nonane) (dmopta), as epoxy resin additives. These additives, previous dissolution or suspension, improve and modify the properties of the resins, giving them new properties such as color, electrical and magnetic conductivity, heat and fire resistance, flexibility, different curing time, among other properties. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2627009A1
    申请号:ES201600099
    申请日:2016-01-26
    公开日:2017-07-26
    发明作者:Antonio Manuel Romerosa Nievas；Manuel Serrano Ruiz；Franco SCALAMBRA；Pablo Antonio LORENZO LUIS
    申请人:Universidad de La Laguna；Universidad de Almeria；
    IPC主号:
    专利说明:

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    DESCRIPTION
    Additive epoxy resins by homo and heterometallic polymer complexes with
    1.3.5- triaza-7-phosphaadamantanophosphine (PTA) and 3,7-dimethyl-1,3,7-triaza-5-phosphabiciclo [3.3.1] nonane) (dmoPTA).
    Field of the Invention
    The present invention relates to new additives for epoxy resins. The present invention relates to the use of furnace and heterometal polymers with the ligand
    1.3.5- triaza-7-phosphamamantanophosphine and its derivatives as epoxy resin additives. The present invention relates to the dissolution, emulsion and / or suspension of the additives indicated in the epoxy resin. This invention relates to the modification of the properties of epoxy resins by means of the indicated additives. These additives prior to dissolution or suspension improve and modify the properties of the resins, giving them new properties such as color, electrical and magnetic conductivity, thermal resistance, flexibility, different curing time, among other properties.
    Background of the invention
    Resin is called any solid or semi-solid organic compound, with an undefined melting point, which undergoes the polymerization process generates a three-dimensional total cross-linking between its chains; This process is commonly called curing. Among the most used resins for their versatility, hardness and durability, epoxy or epoxy resins stand out. These types of resins are thermosetting polymers that are obtained from the reaction between epichlorohydrin and a polyhydroxy compound, usually diphenol propane (Bisphenol A), although phenolformaldehyde monomers (such as Bisphenol F) can also be used. The reaction between Bisphenol A and epichlorohydrin in the presence of NaOH gives rise to the diglynyl ether compound of Bisphenol A, which carries two epoxy reactive groups in each molecule. This molecule constitutes the epoxy resin of lower molecular weight and lower viscosity than has been obtained so far. On the other hand, epoxy resins are capable of reacting actively with other functional groups such as amides, amines, organic acids, anhydrides and phenolic resins; These compounds are usually identified in the industry as "hardeners." The reaction between the epoxy resin and the hardener results in polymerization, in this case called "curing." Tertiary and some secondary amines catalyze the polymerization of epoxy resins at room temperature, in the presence of OH groups that are either present in the epoxy resin or are generated during the reaction. These amnenic type hardeners must be polyfunctional to react with several epoxy molecules and produce reticulation of the final polymer. Primary amines are difunctional against epoxy resin, this provides a very high degree of crosslinking. Therefore, the final mechanical, chemical and thermal behavior of the resins is conditioned by the development of the curing process and the level of final curing will largely depend on the process time and temperature, the type of curing agent, etc. . Complete curing occurs in infinite time, so the resin has active sites that can react making it especially susceptible to different chemical agents and UV radiation. This fact, which apparently could be a problem, allows to have chemical anchor positions of molecules that can give the resin particular properties. Both dyes and protectors against UV radiation, passing through compounds with particular magnetic or optical properties. The extensive and general use of resins has demanded that additives have been sought to improve or adapt their properties to the demands of their utilization, but also for the purpose, for example, of hiding their
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    composition to potential competitors. Therefore, having suitable additives to provide resins with those properties that make them suitable for an application remains of special importance, especially considering that there are not many soluble or compatible compounds with epoxy resins and that they also provide them improved properties
    Description of the invention
    The invention provides a method for modifying the properties of epoxy resins by using heterometal polymers of general formula [(CpRuXRuCp) (L) 2 (L ') 2-p- (MY2)] n (M = transition metal; X = CN-, SON ', pyrazole, pyrazine, 4,4'-bipyridine; L, L' = PTA, dmoPTA) (PTA = 1,3,5-triaza-7-phosphatedmantane; dmoPTA = 3,7-dimethyl -1,3,7-triaza-5 phosphabiciclo [3.3.1] nonane)).
    The use of these compounds as epoxy resin additives is an object of the invention.
    The object of the invention is the use of these compounds as epoxy resin additives that provide improved properties thereof.
    The object of the invention is the use of these compounds as epoxy resin additives that provide new properties to them.
    The object of the invention is the use of these compounds as epoxy resin additives that hide their composition.
    The object of the invention is the use of these compounds as epoxy resin additives by dissolution, emulsion and / or suspension therein.
    The furnace and heteropolymeric complexes (from now on polymer polymers) of general formula [(CpRuXRuCp) (L) 2 (L ') 2-p- (MY2)] n (M = transition metal; X = ON-, SON-, pyrazole, pyrazine, 4A'-bipyridine; L, L '= PTA, dmoPTA) (PTA = 1,3,5-triaza-7- phosphaadamantane; dmoPTA = 3,7-dimethyl-1,3,7- triaza-5-phosphabiciclo [3.3.1] -nonane)) are stable both in solid state and in solution, dissolving many of them in water and polar solvents. In water, some of these polymers behave like gels, changing their volume depending on the temperature and conditions of the solution. The distribution of various types of metals in specific positions means that each type of polymer-metal has different properties, such as optical and magnetic, which can be modulated according to not only the metal but also its position in the chain and X groups that bridge between the atoms of Ru. Epoxy resins react with amino groups such as those of the PTA or dmoPTA ligand resulting in a stable chemical bond. This bond allows the polymeric metalmembers to form a natural and stable part in the composition of the polymer obtained when the resin is reacted with the hardener to give rise to the final crosslinked polymer. The polymer-metallic ones will be distributed homogeneously within the formed reticulum when the polymerization takes place contributing its properties. Since the bond with the epoxy part of the polymer is covalent, the stability of the union would be very high, supporting the various conditions of use of the epoxy polymer, in many cases preventing the polymer from decomposing at high temperatures or reacting with external agents such as oxygen from the air, burning. The additivation would be stable in time as well! as the properties that contribute to the resin. This fact makes these additives very convenient when the epoxy polymer has to be used in extreme conditions such as in aeronautics. The strength of the link between the polymer
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    Metallic and epoxy avoid possible leaching by any type of solvent, which would make the additive epoxy polymer stable to immersion in solvents.
    Polymeric metal is incorporated into the uncured epoxy resin or in any of its components prior to mixing. The addition of the additive to the epoxy resin components can be done immediately before mixing or previously. This last possibility allows to prepare a stable hardener-additive system that can be stored and used when convenient. The concentration of the additive is arranged in the range of 0.001 M to 1 M and under temperature conditions between 10 ° C and 100 ° C and under a pressure between 0.5 and 100 atmospheres, with or without agitation. Curing times vary between 3 and 100 hours under oxidizing atmosphere, such as air, or inert. The metal polymer is stable against oxidizing gases such as O2 and Cl2. Preferably, the concentration range will be between 0.01 and 0.1 M, the temperature range from 20 ° C to 50 ° C and the pressure between 1 and 5 atmospheres.
    Preferred Realization Modes
    Example 1
    The commercial 2,2-bis [4- (2,3 epoxy propoxy) phenyl] propane epoxy resin (10 gl is mixed with the polymer-metal [(CpRu-CN-RuCp) (PTA) 2 (PTA) 2-p - (NiCI3)] n (0.1 g) and once homogenized, the commercial amine 4,4'-diamino-diphenyl methane (6 g) is added, stirring the mixture until complete homogenization. it has acquired the appropriate consistency to withstand the pressure of the fingers without deforming while at 24 hours a hardness close to 90% of the maximum is achieved.The additive cured polymer has similar hardness and flexibility to the non-additive but shows a stable orange color Over time (150 days) even in strong sunlight, besides being paramagnetic, treatment with water or organic solvents such as acetone does not eliminate the additive.
    Example 2
    The commercial 2,2-bis [4- (2,3-epoxypropoxy) phenyl] propane epoxy resin (10 g) is mixed with the 4,4'-diamino-diphenyl methane amine (6 gl and the polymer-metal polymer [ (CpRu-CN-RuCp) (PTA) 2 (PTA) 2-p- (NiCI3)] n (0.1 g), stirring the mixture until complete
    homogenization As in the previous case, after 6 hours in the air the orange mixture has enough consisting to withstand the pressure of the fingers without deforming while at 24 hours the hardness close to 90% is achieved.
    Example 3
    To the 2,2-bis [4- (2,3 epoxypropoxy) phenyl] propane epoxy resin 3 g of a previously prepared polymer suspension [(CpRu-CN-RuCp) (PTA) 2 (PTA) 2 is added ) 2-p- (NiCl3)] n (0.1 gl and the 4,4'-diamino-diphenyl-methane amine (6 g). The obtained mixture is homogenized and allowed to cure.
    Example 4
    Similar to the previous example to the 4,4 '- (propane-2,2-diyl) diphenol (8 g) epoxy resin, 5 g of a previously prepared polymer mixture [(CpRu-CN-RuCp) (PTA) is added ) 2 (PTA) 2-p- (CdCI3)] n (0.3 g) and the 4,4'-diamino-phenyl methane amine (6 g). The whole is mixed in the air and allowed to cure. The polymer obtained is colorless and resists yellowing by direct sunlight for 2 months.
    Example 5
    The 2,2-bis [4- (2,3-epoxy-propoxy) phenyl] propane epoxy resin (10 g) is mixed with the 4,4'-diamino-diphenyl methane amine (6 g) and the polymer- metallic [(CpRu-CN-5 RuCp) (PTA) 2 (PTA) 2-p- (Au (CN) 4)] n (0.1 g). It is obtained by mixing all the
    components a polymer cured about 90% after 24 hours, bright yellow that darkens in two weeks under solar radiation to a red color, which remains stable over time.
    10 Example 6
    The 4,4'- (propane-2,2-diyl) diphenol resin (4 gl is mixed with a suspension of 4,4'-diamino-diphenyl methane (6 g) and [(CpRu-CN-RuCp) ( PTA) 2 (PTA) 2-p- (Au (CN) 4)] n (0.8 g) It is homogenized and allowed to cure.The yellow polymer obtained at 24 hours is more flexible than that which would be obtained without additive .
    权利要求:
    Claims (9)
    [1]
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    1. Procedure for the additivation of epoxy resins by means of furnace and heterometal polymers of general formula [(CpRuXRuCp) (L) 2 (L ') 2-p- (MY2)] n (M = transition metal; X = CN-, SCN-, pyrazole, pyrazine, 4,4'-bipyridine; L, L '= PTA, dmoPTA) (PTA =
    1.3.5-triaza-7-phosphaadamantane; dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabiciclo
    [3.3.1) nonane)).
    [2]
    2. Procedure for the additivation of the epoxy resin / hardener mixture by means of metal-polymeric polymers of general formula [(CpRuXRuCp) (L) 2 (L ') 2-p- (MY2)] n (M = transition metal; X = CN ", SCN", pyrazole, pyrazine, 4,4'-bipyridine; L, L '= PTA, dmoPTA) (PTA =
    1.3.5-triaza-7-phosphaadamantane; dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabiciclo
    [3.3.1] nonane)).
    [3]
    3. Procedure for the additivation of epoxy resins in which the additive is previously added to the amine hardener. the additives are made of polymeric metal of general formula [(CpRuXRuCp) (L) 2 (L ') 2-p- (MY2)] n (M = transition metal; X = CN-, SCN-, pyrazole, pyrazine , 4,4'-bipyridine; L, L '= PTA, dmoPTA) (PTA = 1,3,5-triaza-7- phosphaadamantane; dmoPTA = 3,7-dimethyl-1,3,7-triaza-5- phosphabiciclo [3.3.1] nonane)).
    [4]
    4. Method according to the preceding claims to obtain epoxy-polymeric polymers-additives with metal-polymers.
    [5]
    5. Method according to claims 1 to 3 to obtain epoxy polymeric polymers additive with metal polymers that do not lose their additives in counting with organic and inorganic solvents.
    [6]
    6. Method according to claims 1 to 3 to obtain epoxy polymeric polymers added with metal polymers in a temperature range between 10 and 100 ° C.
    [7]
    7. Method according to claims 1 to 3 to obtain epoxidic polymers added with metal polymers in a pressure range between 0.5 and 1 00 atmospheres.
    [8]
    8. Method according to claims 1 to 3 to obtain epoxy-additive polymers with metal polymers in a concentration range of additive in the concentration range 0.001 M to 1 M.
    [9]
    9. Method according to claims 1 to 3 to obtain epoxy-polymerized polymers with metal polymers under any type of oxidizing or inert atmosphere.
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    同族专利:
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    ES2627009B2|2018-01-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4082723A|1975-10-09|1978-04-04|Hoechst Aktiengesellschaft|Aza-adamantane compound stabilizers for organic polymer compositions|
    US4168260A|1977-01-20|1979-09-18|Hoechst Aktiengesellschaft|N-substituted triaza-adamantanyl ureas as stabilizers for thermoplastic materials|
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    ES201600099A|ES2627009B2|2016-01-26|2016-01-26|Additive epoxy resins by homo and heteromethalic polymer complexes with 1,3,5-triaza-7-phosphaadamantanophosphineand 3,7-dimethyl-1,3,7-triaza-5-phosphabiciclo [3.3.1] nonane |ES201600099A| ES2627009B2|2016-01-26|2016-01-26|Additive epoxy resins by homo and heteromethalic polymer complexes with 1,3,5-triaza-7-phosphaadamantanophosphineand 3,7-dimethyl-1,3,7-triaza-5-phosphabiciclo [3.3.1] nonane |
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