CN112029463A - Epoxy modified phenyl hydrogen-containing silicone oil, composite epoxy adhesive and preparation method thereof - Google Patents
Epoxy modified phenyl hydrogen-containing silicone oil, composite epoxy adhesive and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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Abstract
The invention discloses epoxy modified phenyl hydrogen-containing silicone oil, a composite epoxy adhesive and a preparation method thereof. The epoxy modified phenyl silicone oil is epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil. The composite epoxy adhesive comprises A, B components, wherein the A component comprises bisphenol A epoxy resin, epoxy modified phenyl silicone oil, first nano silicon dioxide and an epoxy-containing silane coupling agent; wherein the epoxy modified phenyl silicone oil is epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil; the component B is a cured composition of an epoxy adhesive. The epoxy modified phenyl hydrogen-containing silicone oil and the bisphenol A epoxy resin have good compatibility, and after the epoxy modified phenyl hydrogen-containing silicone oil and the bisphenol A epoxy resin are used in an epoxy adhesive, the adhesive force of an adhesive layer formed by curing the epoxy adhesive is strong, and the toughness and the high temperature resistance are excellent. The composite epoxy adhesive contains the epoxy modified phenyl hydrogen-containing silicone oil, and the adhesive layer of the composite epoxy adhesive has high adhesive force and excellent toughness and high temperature resistance.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to epoxy modified phenyl hydrogen-containing silicone oil, a composite epoxy adhesive and a preparation method thereof.
Background
The epoxy resin has the characteristics of excellent adhesive property, mechanical property, good chemical stability resistance and the like, and is an important adhesive material in the field of sealant. However, after the epoxy resin is cured and ring-opened, a dense three-dimensional network structure can be formed, so that the cured product has the defects of high brittleness, easiness in cracking, high internal stress and the like, and the epoxy resin is limited to be widely applied to the field of sealants.
The organic silicon polymer has the outstanding advantages of low surface energy, good flexibility, good high temperature resistance and the like, can reduce the internal stress of the epoxy resin and increase the heat resistance of the epoxy resin when used for modifying the epoxy resin, and is an effective method for toughening and modifying the epoxy resin at high temperature. However, the compatibility between the silicone polymer and the epoxy resin is poor, and the silicone polymer and the epoxy resin are difficult to achieve the purpose of improving the performance of the epoxy resin by a direct blending method.
At present, the organosilicon modified epoxy method is mainly to introduce organosilicon chain segments by the reaction of active end groups of polysiloxane macromolecules, such as hydroxyl, amino, alkoxy and the like, with epoxy groups and hydroxyl groups in epoxy resin.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a composite epoxy adhesive and a preparation method thereof, so as to solve the technical problems that the compatibility of an organic silicon polymer and epoxy resin is poor or the adhesive property of organic silicon modified epoxy resin is reduced in the existing epoxy adhesive.
In order to achieve the above object, according to one aspect of the present invention, there is provided a composite epoxy adhesive. The composite epoxy adhesive comprises A, B components, wherein the A component comprises bisphenol A epoxy resin, epoxy modified phenyl silicone oil, first nano silicon dioxide and an epoxy-containing silane coupling agent; wherein the epoxy modified phenyl silicone oil is epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil;
the component B is a cured composition of an epoxy adhesive.
In another aspect of the invention, a preparation method of the composite epoxy adhesive is provided. The preparation method of the composite epoxy adhesive comprises the following steps:
measuring each component according to the formula of the component A contained in the composite epoxy adhesive;
measuring each component according to the formula of the component B contained in the composite epoxy adhesive;
measuring and mixing all the components of the component A to obtain the component A;
and (3) measuring all the components of the component B, and mixing to obtain the component B.
In another aspect of the invention, a modified phenyl hydrogen-containing silicone oil is provided. The modified phenyl hydrogen-containing silicone oil is prepared by the following steps:
dissolving phenyl hydrogen-containing silicone oil, epoxy-terminated allyl polyether and a catalyst in a reaction solvent, reacting for 10-15 hours at the temperature of 100-120 ℃, and performing post-purification treatment.
Compared with the prior art, the invention has the following technical effects:
because the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil contained in the composite epoxy adhesive is modified by the epoxy-terminated allyl polyether, the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil has good compatibility with bisphenol A epoxy resin, can fully and uniformly mix the two components, and overcomes the problem of poor compatibility of the traditional organic silicon polymer and the epoxy resin; the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil contains epoxy functional groups, and after the epoxy functional groups are compounded and blended with bisphenol A epoxy resin, the composite epoxy adhesive is endowed with strong adhesive force, and the curing time is short; meanwhile, the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil belongs to a modified organic silicon polymer, and endows the composite epoxy adhesive curing bonding layer with excellent toughness and high-temperature resistance. On the basis, the nano silicon dioxide contained in the composite epoxy adhesive can effectively cooperate with epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil to achieve the synergistic effects of toughening and improving high temperature resistance, and the contained silane coupling agent can enable the nano silicon dioxide and other components to have excellent compatibility, so that the components of the composite epoxy adhesive are uniformly dispersed, and a dispersion system and adhesive performance are stable. Therefore, the composite epoxy adhesive disclosed by the embodiment of the invention has good compatibility among all components, and the cured adhesive layer has excellent adhesive strength, toughness and high-temperature resistance.
According to the preparation method of the composite epoxy adhesive, the components are respectively prepared according to A, B components according to the components and the content of the composite epoxy adhesive, so that on one hand, the prepared composite epoxy adhesive has good compatibility among the components, stable dispersion system and excellent adhesive property, toughness and high temperature resistance; on the other hand, the raw materials for preparing the nano-crystalline silicon are easy to obtain, and the preparation method is simple and convenient to operate, easy to control, pollution-free, mild in production conditions and convenient for industrialization.
The epoxy modified phenyl hydrogen-containing silicone oil is modified by epoxy-terminated allyl polyether, so that the epoxy modified phenyl hydrogen-containing silicone oil has good compatibility with bisphenol A epoxy resin, and the two components can be fully and uniformly mixed; the epoxy modified phenyl hydrogen-containing silicone oil contains epoxy functional groups, and after the epoxy functional groups are compounded and blended with bisphenol A epoxy resin, the epoxy adhesive is endowed with strong adhesive force and short curing time for curing the adhesive layer; in addition, the epoxy modified phenyl hydrogen-containing silicone oil belongs to a modified organic silicon polymer, and endows the epoxy adhesive with excellent toughness and high temperature resistance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a process flow diagram of a preparation method of the composite epoxy adhesive according to the embodiment of the invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
On one hand, the embodiment of the invention provides epoxy modified phenyl hydrogen-containing silicone oil. The epoxy modified phenyl hydrogen-containing silicone oil is epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil. Thus, the epoxy modified phenyl hydrogen-containing silicone oil in the embodiment of the invention is modified by epoxy-terminated allyl polyether, so that the epoxy modified phenyl hydrogen-containing silicone oil has good compatibility with bisphenol A epoxy resin, and the two components can be fully and uniformly mixed; in addition, the epoxy modified phenyl hydrogen-containing silicone oil contains epoxy functional groups, and after the epoxy modified phenyl hydrogen-containing silicone oil is compounded and blended with bisphenol A epoxy resin, the epoxy adhesive is endowed with strong adhesive force and short curing time for curing the adhesive layer; in addition, the epoxy modified phenyl hydrogen-containing silicone oil in the embodiment of the invention belongs to a modified organic silicon polymer, and endows the epoxy adhesive curing bonding layer with excellent toughness and high temperature resistance.
In one embodiment, the epoxy modified phenyl hydrogen-containing silicone oil is prepared by a method comprising the following steps:
dissolving phenyl hydrogen-containing silicone oil, epoxy-terminated allyl polyether and a catalyst in a reaction solvent, reacting at 100-120 ℃, specifically 110 ℃ for 10-15 hours, specifically 12 hours, and performing post-purification treatment.
At the temperature, the epoxy-terminated allyl polyether can modify the phenyl hydrogen-containing silicone oil under the action of the catalyst to generate the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil, and the yield and the reaction rate of a target product are improved.
In a preferred embodiment, the phenyl hydrogen-containing silicone oil, the epoxy-terminated allyl polyether and the catalyst are mixed according to a mass ratio of 100: (100-120) a proportion of (0.3-0.8) solvent in the reaction solvent; and/or the mass concentration of the phenyl hydrogen-containing silicone oil solvent in the reaction solvent is 1.7-1.8 g/ml. By controlling and adjusting the proportion and concentration of each reactant, the reaction efficiency is improved, and the yield of the target product is improved.
In a specific embodiment, the reaction solvent is at least one of toluene, benzene, and xylene. Through the selection of the reaction solvent, the reaction efficiency can be improved, the generation of byproducts is reduced, the yield of target products is improved, and the subsequent purification steps are simplified.
In another embodiment, the catalyst is preferably at least one of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and chloroplatinic acid. Through the selection of the catalyst, the reaction efficiency can be improved, and the reaction condition requirements can be reduced.
In another embodiment, the phenyl hydrogen-containing silicone oil comprises terminal hydrogen-containing phenyl hydrogen-containing silicone oil, wherein the number average molecular weight of the terminal hydrogen-containing phenyl hydrogen-containing silicone oil is 1300-1700, preferably 1500. And/or the number average molecular weight of the epoxy-terminated allyl polyether is 700-. By selecting the phenyl hydrogen-containing silicone oil and/or the epoxy-terminated allyl polyether, the compatibility of the generated epoxy modified phenyl hydrogen-containing silicone oil, specifically the compatibility of the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil and the bisphenol A epoxy resin can be further optimized, the adhesive force, toughness and high temperature resistance of the epoxy adhesive formed by compounding and blending the epoxy modified phenyl hydrogen-containing silicone oil and the bisphenol A epoxy resin are improved, and the curing time of the epoxy adhesive is shortened.
On the other hand, the epoxy-modified phenyl hydrogen-containing silicone oil is based on the epoxy-modified phenyl hydrogen-containing silicone oil described above. The embodiment of the invention also provides the composite epoxy adhesive. The composite epoxy adhesive includes A, B components.
The component A contained in the composite epoxy adhesive comprises bisphenol A type epoxy resin, epoxy modified phenyl silicone oil, first nano silicon dioxide and an epoxy-containing silane coupling agent, wherein the epoxy modified phenyl silicone oil is epoxy modified phenyl silicone oil, namely epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil in the embodiment of the invention. Thus, the component A contains the epoxy modified phenyl silicone oil disclosed in the embodiment of the invention, and the epoxy modified phenyl silicone oil, namely the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil, has good compatibility with the bisphenol A epoxy resin, so that the two components can be fully and uniformly mixed, and the problem of poor compatibility of the traditional organic silicon polymer and the epoxy resin is solved; and the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil contains epoxy functional groups, and after the epoxy functional groups are compounded and blended with the bisphenol A epoxy resin, the adhesive force of an adhesive layer formed by mixing and curing the component A and the component B is strong, and the curing time is short. In addition, the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil belongs to a modified organic silicon polymer, and endows the composite epoxy adhesive curing bonding layer of the embodiment of the invention with excellent toughness and high temperature resistance. On the basis, the nano silicon dioxide contained in the component A can effectively cooperate with the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil to achieve the synergistic effects of toughening and improving high temperature resistance, and the contained silane coupling agent can enable the nano silicon dioxide and other components to have excellent compatibility, so that the components formed by mixing the component A, the component A and the component B are uniformly dispersed, and a dispersion system and bonding performance are stable.
In one embodiment, the mass ratio of the bisphenol a epoxy resin, the epoxy modified phenyl silicone oil, the nano silica and the epoxy-containing silane coupling agent in the component a is 1: (0.2-0.4): (0.02-0.08): (0.03-0.08). By adjusting and optimizing the content ratio of each component in the component A, the compatibility among the components can be improved, the dispersion uniformity of each component is improved, and the stability of a component A dispersion system is improved; on the basis, the bonding layer formed by mixing and curing the component A and the component B in the content ratio has stronger bonding force, better toughness and better high-temperature resistance.
In a specific embodiment, the bisphenol a type epoxy resin may be a bisphenol a type epoxy resin commonly used for epoxy adhesives, and preferably includes at least one of E44, E51, and E55. The optimized bisphenol A epoxy resin can enhance the synergistic effect with the epoxy modified phenyl silicone oil in the embodiment of the invention, improve the compatibility of the bisphenol A epoxy resin and the epoxy modified phenyl silicone oil, and improve the binding power, the toughness and the high temperature resistance of the composite epoxy adhesive.
The epoxy silane coupling agent is at least one of KH560, KH561 and KH 563. The preferable epoxy silane coupling agent contains epoxy functional groups, and has a synergistic effect with the epoxy modified phenyl silicone oil in the embodiment of the invention, so that the compatibility with bisphenol A epoxy resin is improved, and the adhesive force of the composite epoxy adhesive is improved; in addition, the compatibility between the contained first nano-silica and other components of the A component can be improved, and the dispersion uniformity between the first nano-silica and other components and the stability of the A component dispersion system can be improved.
The particle size of the first nanometer silicon dioxide is 50-150 nm, and the particle size is the same or different. The first nanometer silicon dioxide with the optimized particle size range has the advantages of surface effect, volume effect, quantum effect, high temperature resistance, no toxicity, no pollution and the like which are peculiar to nanometer materials, and can be uniformly dispersed in the component A, more importantly, the first nanometer silicon dioxide can play a role in synergism with epoxy modified phenyl silicone oil in the embodiment of the invention, and the binding power and the high temperature resistance of the composite epoxy adhesive are improved.
The B component contained in the composite epoxy adhesive may be a conventional curing composition contained in an epoxy adhesive. In one embodiment, the component B comprises polyether amine, second nano-silica, an amino-containing silane coupling agent and a curing accelerator. The component B containing the component and the component A have good compatibility, and can improve the curing effect of the composite epoxy adhesive, such as the adhesive strength, the heat property and other properties of an adhesive layer formed by curing the composite epoxy adhesive, and can also shorten the curing time of the composite epoxy adhesive.
In further embodiments, the ratio of the polyetheramine, nanosilica, aminosilane-containing coupling agent, curing accelerator in the B component is 1: (0.02-0.08): (0.03-0.08): (0.05-0.1). By adjusting and optimizing the content ratio of each component in the component B, the compatibility among the components can be improved, the dispersion uniformity of each component can be improved, the stability of a component B dispersion system is improved, the compatibility with the component A is improved, the performances of bonding strength, heat property and the like of a bonding layer formed by curing the composite epoxy adhesive are improved, and the curing time of the composite epoxy adhesive is shortened.
In a specific embodiment, the polyetheramine may be a polyetheramine commonly used for epoxy adhesives, preferably comprising a mixture of a polyetheramine having a number average molecular weight of 300-. Wherein, the mass ratio of the polyether amine with the number average molecular weight of 300-500), specifically 400, to the polyether amine with the number average molecular weight of 1500-2500, specifically 2000, is 1: (0.4-0.5). The preferred polyetheramine can react with the component A, shorten the curing time and improve the toughness and the bonding strength of a bonding layer formed by curing.
The silane coupling agent containing amino comprises at least one of KH550, KH602, KH791 and KH 792. The preferable amino-containing silane coupling agent can improve the compatibility with other components of the B component, particularly the second nano-silica, and improve the dispersion uniformity among the components contained in the B component and the stability of a B component dispersion system.
The particle size of the second nanometer silicon dioxide is 50-150 nm, and the particle size is the same or different. The second nano silicon dioxide in the preferable particle size range has the advantages of surface effect, volume effect, quantum effect, high temperature resistance, no toxicity, no pollution and the like which are peculiar to nano materials, and can be uniformly dispersed in the component B, more importantly, the second nano silicon dioxide can play a role in synergism with the component A, and the adhesive force and the high temperature resistance of the composite epoxy adhesive are improved.
The curing accelerator can be a curing accelerator commonly used for epoxy adhesives, such as at least one of DMP-10, DMP-20 and DMP-30.
Therefore, the A, B components contained in the composite epoxy adhesive in the embodiments have good compatibility, the A, B component dispersion system is uniformly dispersed and stable, and the A, B component mixed and cured forms a bonding layer with high bonding strength, excellent toughness and high temperature resistance, safety and environmental protection.
In addition, the composite epoxy adhesive in each of the above embodiments is provided with the a component and the B component separately before use, for example, in a shelf-life product, the a component and the B component are separately provided. When the composite epoxy adhesive is used, the component A and the component B are mixed to form a mixture for adhesive use. In one embodiment, the composite epoxy adhesive is prepared by mixing (1.2-1.8) a component A and a component B in a mass ratio of: 1, the component A and the component B are mixed and then cured and bonded, the functions of the components are fully exerted by adjusting the mixing ratio of the component A and the component B, and the bonding strength of the bonding layer formed by curing the composite epoxy adhesive is improved, the bonding layer is high in toughness and high-temperature resistance, and is safe and environment-friendly. Among them, the mixing treatment conditions of the component a or the component B are preferably: and mechanically stirring and dispersing for 60-90 minutes at the temperature of 20-30 ℃ at the speed of 300-500 rpm, so that all the components are fully and uniformly mixed, and the bonding strength and the bonding performance stability of the composite epoxy adhesive are improved. The curing may be carried out at a curing temperature conventional for epoxy adhesives, such as preferably at 80 ℃.
Correspondingly, based on the composite epoxy adhesive, the embodiment of the invention also provides a preparation method of the composite epoxy adhesive. The process flow of the preparation method of the composite epoxy adhesive is shown in figure 1, and the preparation method comprises the following steps:
s01: measuring each component according to the formula of the component A contained in the composite epoxy adhesive;
s02: measuring each component according to the formula of the component B contained in the composite epoxy adhesive;
s03: measuring and mixing all the components of the component A to obtain the component A;
s04: and (3) measuring all the components of the component B, and mixing to obtain the component B.
Wherein the composite epoxy adhesive in the steps S01 and S02 is the composite epoxy adhesive described above. Therefore, the formulation of the a component in the step S01 is as the formulation of the a component of the composite epoxy adhesive described above, and includes the bisphenol a type epoxy resin, the epoxy-modified phenyl silicone oil, the first nano silica, and the epoxy group-containing silane coupling agent. Similarly, the formulation of the component B in the step S02 is the formulation of the component B of the composite epoxy adhesive, such as including the polyetheramine, the second nano-silica, the amino-containing silane coupling agent, and the curing accelerator. For the sake of economy, the description of the formula of the component a in the step S01 and the formula of the component B in the step S02 will not be repeated herein.
The mixing process in step S03 and step S04 may be a mixing process commonly used in the binder preparation process, and may be a mechanical stirring process as long as the mixing process can uniformly mix the components within the scope disclosed in the embodiments of the present invention.
In addition, the step S01 and the step S02 do not have a requirement on the priority, and the step S03 and the step S04 do not have a requirement on the priority.
Therefore, according to the preparation method of the composite epoxy adhesive provided by the embodiment of the invention, the components are respectively prepared according to A, B components according to the components and content of the composite epoxy adhesive, so that on one hand, the prepared composite epoxy adhesive has good compatibility among the components, stable dispersion system and excellent adhesive property, toughness and high temperature resistance; on the other hand, the raw materials for preparing the nano-crystalline silicon are easy to obtain, and the preparation method is simple and convenient to operate, easy to control, pollution-free, mild in production conditions and convenient for industrialization.
The embodiments of the present invention have been repeated several times, and the present invention will be further described in detail with reference to a part of the test results, which will be described in detail with reference to the specific embodiments.
1. Epoxy modified phenyl hydrogen-containing silicone oil and preparation method embodiment thereof
Example 11
The embodiment provides epoxy modified phenyl hydrogen-containing silicone oil and a preparation method thereof.
The epoxy modified phenyl hydrogen-containing silicone oil is amino silicone oil modified phenyl hydrogen-containing silicone oil.
The preparation method of the epoxy modified phenyl hydrogen-containing silicone oil comprises the following steps:
100g of phenyl hydrogen silicone oil with molecular weight of 1500, 110 g of epoxy-terminated allyl polyether with molecular weight of 800 and 50g of toluene are added into a three-neck flask at 25 ℃, mixed evenly under vigorous stirring, then 0.5 g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane is added, the temperature is raised to 110 ℃ and the stirring state is kept for 12 hours. Naturally cooling, and distilling at 80 ℃ under reduced pressure to remove toluene to obtain the epoxy modified phenyl silicone oil product.
Example 12
The embodiment provides epoxy modified phenyl hydrogen-containing silicone oil and a preparation method thereof.
The epoxy modified phenyl hydrogen-containing silicone oil is amino silicone oil modified phenyl hydrogen-containing silicone oil.
The preparation method of the epoxy modified phenyl hydrogen-containing silicone oil comprises the following steps:
100g of phenyl hydrogen silicone oil with molecular weight of 1500, 120 g of epoxy-terminated allyl polyether with molecular weight of 800 and 50g of toluene are added into a three-neck flask at 25 ℃, mixed evenly under vigorous stirring, then 0.8 g of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane is added, the temperature is raised to 100 ℃ and the stirring state is kept for 12 hours. Naturally cooling, and distilling at 80 ℃ under reduced pressure to remove toluene to obtain the epoxy modified phenyl silicone oil product.
2. Embodiment of composite epoxy adhesive and preparation method thereof
Example 21
The embodiment provides a composite epoxy adhesive and a preparation method thereof.
The composite epoxy adhesive comprises a component A and a component B. Wherein the content of the first and second substances,
the component A comprises: 100g of E51 epoxy resin, 40g of epoxy modified phenyl silicone oil provided in example 11, 8g of nano silicon dioxide, and KH-5608 g of silane coupling agent;
the component B comprises: polyether amine D400100 g, polyether amine D200050 g, curing accelerator DMP-3015g, nano silicon dioxide 12g and silane coupling agent KH-55012 g.
The preparation method of the composite epoxy adhesive comprises the following steps:
s21. preparation of the component A: the following materials were added in sequence to the dispersion mixer: 100g of E51 epoxy resin, 40g of the epoxy-modified phenyl silicone oil prepared in example 1, were dispersed for 60 minutes with mechanical stirring at a speed of 300 revolutions per minute. Adding 8g of nano silicon dioxide and 8g of silane coupling agent KH-560 in 3 batches (the mass of each batch is the same) in the stirring process, continuously stirring, and mechanically stirring and dispersing for 90 minutes at the speed of 400 revolutions per minute to prepare a component A;
s22.B component preparation: the following materials were added in sequence to the dispersion mixer: 100g of polyetheramine D400, 50g of polyetheramine D2000 and 15g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 12g of nano-silica and 12g of silane coupling agent KH-550 are added in 3 batches (the mass of each batch is the same) during stirring, stirring is continued, and mechanical stirring and dispersion are carried out at the speed of 400 revolutions per minute for 90 minutes, so that a component B is prepared.
The curing ratio of the A component to the B component is 1.7: 1, the curing condition is heating at 80 ℃ for 1 hour.
Example 22
The embodiment provides a composite epoxy adhesive and a preparation method thereof.
The composite epoxy adhesive comprises a component A and a component B. Wherein the content of the first and second substances,
the component A comprises: 80g of E55 epoxy resin, 20g of epoxy modified phenyl silicone oil provided in example 11, 2g of nano silicon dioxide and KH-5603 g of silane coupling agent;
the component B comprises: polyetheramine D400100 g, polyetheramine D200040 g, curing accelerator DMP-307g, nano silicon dioxide 2.8g and silane coupling agent KH-5504.2 g.
The preparation method of the composite epoxy adhesive comprises the following steps:
s21. preparation of the component A: the following materials were added in sequence to the dispersion mixer: 80g of E55 epoxy resin, 20g of E44 epoxy resin, 20g of the epoxy-modified phenyl silicone oil prepared in example 1 were dispersed by mechanical stirring at 300 rpm for 60 minutes. Adding 2g of nano silicon dioxide and 3g of silane coupling agent KH-560 in 3 batches (the mass of each batch is the same) in the stirring process, continuously stirring, and mechanically stirring and dispersing for 90 minutes at the speed of 400 revolutions per minute to obtain a component A;
s22.B component preparation: the following materials were added in sequence to the dispersion mixer: 100g of polyetheramine D400, 40g of polyetheramine D2000 and 7g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 2.8g of nano silica and 4.2g of silane coupling agent KH-550 are added in 3 batches (the mass of each batch is the same) during stirring, stirring is continued, and mechanical stirring and dispersion are carried out at the speed of 400 revolutions per minute for 90 minutes. Preparing the component B.
The curing ratio of the A component to the B component is 1.2: 1, the curing condition is heating at 80 ℃ for 1 hour.
Example 23
The embodiment provides a composite epoxy adhesive and a preparation method thereof.
The composite epoxy adhesive comprises a component A and a component B. Wherein the content of the first and second substances,
the component A comprises: 80g of E55 epoxy resin, 20g of E44 epoxy resin, 40g of epoxy modified phenyl silicone oil provided in example 11, 6g of nano silicon dioxide and KH-5606 g of silane coupling agent;
the component B comprises: polyether amine D400100 g, polyether amine D200050 g, curing accelerator DMP-3015g, nano silicon dioxide 12g and silane coupling agent KH-55012 g.
The preparation method of the composite epoxy adhesive comprises the following steps:
s21. preparation of the component A: the following materials were added in sequence to the dispersion mixer: 80g of E55 epoxy resin, 20g of E44 epoxy resin, 40g of the epoxy-modified phenyl silicone oil prepared in example 1 were dispersed by mechanical stirring at 300 rpm for 60 minutes. Adding 6g of nano silicon dioxide and 6g of silane coupling agent KH-560 in 3 batches (the mass of each batch is the same) in the stirring process, continuously stirring, and mechanically stirring and dispersing for 90 minutes at the speed of 400 revolutions per minute to obtain a component A;
s22.B component preparation: the following materials were added in sequence to the dispersion mixer: 100g of polyetheramine D400, 50g of polyetheramine D2000 and 15g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 12g of nano-silica and 12g of silane coupling agent KH-550 are added in 3 batches (the mass of each batch is the same) during stirring, stirring is continued, and mechanical stirring is carried out at the speed of 400 revolutions per minute for 90 minutes. Preparing the component B.
The curing ratio of the component A to the component B is 1.3: 1, the curing condition is heating at 80 ℃ for 1 hour.
Example 24
The embodiment provides a composite epoxy adhesive and a preparation method thereof.
The composite epoxy adhesive comprises a component A and a component B. Wherein the content of the first and second substances,
the component A comprises: 60g of E55 epoxy resin, 40g of E44 epoxy resin, 35g of epoxy modified phenyl silicone oil provided in example 11, 6g of nano silicon dioxide and KH-5606 g of silane coupling agent;
the component B comprises: polyether amine D400100 g, polyether amine D200050 g, curing accelerator DMP-3012g, nano silicon dioxide 9g and silane coupling agent KH-5509 g.
The preparation method of the composite epoxy adhesive comprises the following steps:
s21. preparation of the component A: the following materials were added in sequence to the dispersion mixer: 60g of E55 epoxy resin, 40g of E44 epoxy resin, 35g of the epoxy-modified phenyl silicone oil prepared in example 1 were dispersed for 60 minutes with mechanical stirring at 300 revolutions per minute. Adding 6g of nano silicon dioxide and 6g of silane coupling agent KH-560 in 3 batches (the mass of each batch is the same) in the stirring process, continuously stirring, and mechanically stirring and dispersing for 90 minutes at the speed of 400 revolutions per minute to obtain a component A;
s22.B component preparation: the following materials were added in sequence to the dispersion mixer: 100g of polyetheramine D400, 50g of polyetheramine D2000 and 12g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 9g of nano-silica and 9g of silane coupling agent KH-550 are added in 3 batches (the mass of each batch is the same) during stirring, stirring is continued, and mechanical stirring is carried out at the speed of 400 revolutions per minute for 90 minutes. Preparing the component B.
The curing ratio of the A component to the B component is 1.5: 1, the curing condition is heating at 80 ℃ for 1 hour.
Example 25
The embodiment provides a composite epoxy adhesive and a preparation method thereof.
The composite epoxy adhesive comprises a component A and a component B. Wherein the content of the first and second substances,
the component A comprises: 50g of E55 epoxy resin, 50g of E44 epoxy resin, 35g of epoxy modified phenyl silicone oil provided in example 11, 6g of nano silicon dioxide and KH-5606 g of silane coupling agent;
the component B comprises: polyether amine D400100 g, polyether amine D200045 g, curing accelerator DMP-3011.6g, nano silicon dioxide 8.7g and silane coupling agent KH-5508.7 g.
The preparation method of the composite epoxy adhesive comprises the following steps:
s21. preparation of the component A: the following materials were added in sequence to the dispersion mixer: 50g of E55 epoxy resin, 50g of E44 epoxy resin, 35g of the epoxy-modified phenyl silicone oil prepared in example 1 were dispersed for 60 minutes with mechanical stirring at 300 revolutions per minute. Adding 6g of nano silicon dioxide and 6g of silane coupling agent KH-560 in 3 batches (the mass of each batch is the same) in the stirring process, continuously stirring, and mechanically stirring and dispersing for 90 minutes at the speed of 400 revolutions per minute to obtain a component A;
s22.B component preparation: the following materials were added in sequence to the dispersion mixer: 100g of polyetheramine D400, 45g of polyetheramine D2000 and 11.6g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 8.7g of nano silica and 8.7g of silane coupling agent KH-550 are added in 3 batches (the mass of each batch is the same) during stirring, stirring is continued, and mechanical stirring and dispersion are carried out at the speed of 400 revolutions per minute for 90 minutes. Preparing the component B.
The curing ratio of the A component to the B component is 1.8: 1, the curing condition is heating at 80 ℃ for 1 hour.
Example 26
The embodiment provides a composite epoxy adhesive and a preparation method thereof.
The composite epoxy adhesive comprises a component A and a component B. Wherein the content of the first and second substances,
the component A comprises: 60g of E55 epoxy resin, 40g of E44 epoxy resin, 35g of epoxy modified phenyl silicone oil provided in example 11, 6g of nano silicon dioxide and KH-5606 g of silane coupling agent;
the component B comprises: polyether amine D400100 g, polyether amine D200050 g, curing accelerator DMP-3012g, nano silicon dioxide 10g and silane coupling agent KH-55010 g.
The preparation method of the composite epoxy adhesive comprises the following steps:
s21. preparation of the component A: the following materials were added in sequence to the dispersion mixer: 60g of E55 epoxy resin, 40g of E44 epoxy resin, 35g of the epoxy-modified phenyl silicone oil prepared in example 1 were dispersed for 60 minutes with mechanical stirring at 300 revolutions per minute. Adding 6g of nano silicon dioxide and 6g of silane coupling agent KH-560 in 3 batches (the mass of each batch is the same) in the stirring process, continuously stirring, and mechanically stirring and dispersing for 90 minutes at the speed of 400 revolutions per minute to obtain a component A;
s22.B component preparation: the following materials were added in sequence to the dispersion mixer: 100g of polyetheramine D400, 50g of polyetheramine D2000 and 12g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 10g of nano-silica and 10g of silane coupling agent KH-550 are added in 3 batches (the mass of each batch is the same) during stirring, stirring is continued, and mechanical stirring is carried out at the speed of 400 revolutions per minute for 90 minutes. The prepared finished product is the component B.
The curing ratio of the A component to the B component is 1.6: 1, the curing condition is heating at 80 ℃ for 1 hour.
Example 27
The embodiment provides a composite epoxy adhesive and a preparation method thereof.
The composite epoxy adhesive comprises a component A and a component B. Wherein the content of the first and second substances,
the component A comprises: 60g of E55 epoxy resin, 40g of E44 epoxy resin, 35g of epoxy modified phenyl silicone oil provided in example 11, 6g of nano silicon dioxide and KH-5616 g of silane coupling agent;
the component B comprises: polyether amine D400100 g, polyether amine D200050 g, curing accelerator DMP-3012g, nano silicon dioxide 9g and silane coupling agent KH-6029 g.
The preparation method of the composite epoxy adhesive comprises the following steps:
s21. preparation of the component A: the following materials were added in sequence to the dispersion mixer: 60g of E55 epoxy resin, 40g of E44 epoxy resin, 35g of the epoxy-modified phenyl silicone oil prepared in example 1 were dispersed for 60 minutes with mechanical stirring at 300 revolutions per minute. 6g of nano silicon dioxide and 6g of silane coupling agent KH-561 are added in 3 batches (the mass of each batch is the same) in the stirring process, the stirring is continued, and the mechanical stirring is carried out at the speed of 400 r/min for 90 minutes to obtain the final component A.
S22.B component preparation: the following materials were added in sequence to the dispersion mixer: 100g of polyetheramine D400, 50g of polyetheramine D2000 and 12g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 9g of nano-silica and 9g of silane coupling agent KH-602 are added in 3 batches (the mass of each batch is the same) during stirring, stirring is continued, and mechanical stirring is carried out at the speed of 400 revolutions per minute for 90 minutes. The prepared finished product is the component B.
The curing ratio of the A component to the B component is 1.6: 1, the curing condition is heating at 80 ℃ for 1 hour.
Comparative example 1
The comparative example provides a composite epoxy adhesive and a preparation method thereof.
The composite epoxy adhesive comprises a component A and a component B. Wherein the content of the first and second substances,
the component A comprises: 80g of E55 epoxy resin and 20g of E44 epoxy resin;
the component B comprises: polyetheramine D400100 g, polyetheramine D200050 g and curing accelerator DMP-3015 g.
The preparation method of the composite epoxy adhesive comprises the following steps:
s21. preparation of the component A: the following materials were added in sequence to the dispersion mixer: 80g of E55 epoxy resin and 20g of E44 epoxy resin were dispersed for 90 minutes with mechanical stirring at 300 revolutions per minute. Obtaining a component A;
s22.B component preparation: the following materials were added in sequence to the dispersion mixer: 100g of polyetheramine D400, 50g of polyetheramine D2000 and 15g of curing accelerator DMP-30 were dispersed for 90 minutes with mechanical stirring at 300 revolutions per minute. Preparing the component B.
The curing ratio of the A component to the B component is 1.2: 1, the curing condition is heating at 80 ℃ for 1 hour.
And (3) testing the relevant performance of the composite epoxy adhesive:
each of the composite epoxy adhesives provided in examples 21 to 27 and comparative example 1 described above was subjected to the performance tests shown in table 1 below. The specific test method comprises the following steps:
the elongation at break of the samples obtained in the examples and comparative examples was measured by a universal tensile machine in accordance with GB/T GB1040-1992, and the test specimens were dumbbell-shaped and the tensile rate was 5 mm/min. The shear strength of PET bonded PET was tested using a universal tensile tester. The glass transition temperature of the product is tested by Differential Scanning Calorimetry (DSC), and the temperature rise speed is 5 ℃/min under the nitrogen atmosphere.
The relevant performance tests are shown in table 1 below:
TABLE 1
| Sample (I) | Elongation at Break (%) | Shear strength (MPa) | Glass transition temperature (Tg,. degree.C.) |
| Comparative example | 10.29 | 24.68 | 130 |
| Example 21 | 25.87 | 27.12 | 195 |
| Example 22 | 24.88 | 28.39 | 190 |
| Example 23 | 25.19 | 27.56 | 192 |
| Example 24 | 26.87 | 26.87 | 209 |
| Example 25 | 26.31 | 24.51 | 198 |
| Example 26 | 27.12 | 26.13 | 215 |
| Example 27 | 26.52 | 25.39 | 203 |
The performance test result in table 1 shows that the composite epoxy adhesive provided by the embodiment of the invention has the characteristics of strong adhesive force, good toughness and excellent high temperature resistance by adding the epoxy modified phenyl silicone oil, and is a toughened high temperature resistant epoxy adhesive material with excellent performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The composite epoxy adhesive is characterized by comprising A, B components, wherein the A component comprises bisphenol A epoxy resin, epoxy modified phenyl silicone oil, first nano silicon dioxide and an epoxy-containing silane coupling agent; wherein the epoxy modified phenyl silicone oil is epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil;
the component B is a cured composition of an epoxy adhesive.
2. The composite epoxy adhesive according to claim 1, wherein the bisphenol a epoxy resin, the epoxy modified phenyl silicone oil, the nano silica, and the epoxy group-containing silane coupling agent in the component a are present in a mass ratio of 1: (0.2-0.4): (0.02-0.08): (0.03-0.08);
the component B comprises polyether amine, second nano silicon dioxide, an amino-containing silane coupling agent and a curing accelerator, wherein the weight ratio of the polyether amine to the nano silicon dioxide to the amino-containing silane coupling agent to the curing accelerator is 1: (0.02-0.08): (0.03-0.08): (0.05-0.1).
3. The composite epoxy adhesive of claim 1, wherein: the epoxy-terminated allyl polyether modified phenyl hydrogen-containing silicone oil is prepared by the following steps:
dissolving phenyl hydrogen-containing silicone oil, epoxy-terminated allyl polyether and a catalyst in a reaction solvent, reacting for 10-15 hours at the temperature of 100-120 ℃, and performing post-purification treatment.
4. A composite epoxy adhesive according to claim 3, wherein: the phenyl hydrogen-containing silicone oil, the epoxy-terminated allyl polyether and the catalyst are prepared from the following raw materials in a mass ratio of 100: (100-120) a proportion of (0.3-0.8) solvent in the reaction solvent; and/or
The mass concentration of the phenyl hydrogen-containing silicone oil solvent in the reaction solvent is 1.7-1.8 g/ml; and/or
The reaction solvent is at least one of toluene, benzene and xylene; and/or
The phenyl hydrogen-containing silicone oil is end hydrogen-containing phenyl hydrogen-containing silicone oil, and the number average molecular weight of the end hydrogen-containing phenyl hydrogen-containing silicone oil is 1300-1700; and/or
The number average molecular weight of the epoxy-terminated allyl polyether is 700-1000.
5. The composite epoxy adhesive according to any one of claims 1 to 4, wherein: the bisphenol A epoxy resin includes at least one of E44, E51, and E55; and/or
The epoxy-containing silane coupling agent is at least one of KH560, KH561 and KH 563; and/or
The particle size of the first nano silicon dioxide is 50-150 nm.
6. The composite epoxy adhesive according to any one of claims 2 to 4, wherein: the polyether amine comprises a mixture of polyether amine with the number average molecular weight of 300-500 and polyether amine with the number average molecular weight of 1500-2500; and/or
The amino-containing silane coupling agent is at least one of KH550, KH602, KH791 and KH 792; and/or
The curing accelerator is at least one of DMP-10, DMP-20 and DMP-30; and/or
The particle size of the second nano silicon dioxide is 50-150 nm; and/or
The composite epoxy adhesive is prepared from a component A and a component B according to the mass ratio of (1.2-1.8): 1, mixing the component A and the component B, and curing and bonding.
7. The composite epoxy adhesive of claim 6, wherein: the mass ratio of the polyether amine with the number average molecular weight of 300-500 to the polyether amine with the number average molecular weight of 1500-2500 is 1: (0.4-0.5).
8. A preparation method of a composite epoxy adhesive comprises the following steps:
measuring the components according to the formula of the component A contained in the compound epoxy adhesive of any one of claims 1 to 7;
measuring each component according to the formula of the component B contained in the compound epoxy adhesive of any one of claims 1 to 7;
measuring and mixing all the components of the component A to obtain the component A;
and (3) measuring all the components of the component B, and mixing to obtain the component B.
9. The epoxy modified phenyl hydrogen-containing silicone oil is prepared by the following steps:
dissolving phenyl hydrogen-containing silicone oil, epoxy-terminated allyl polyether and a catalyst in a reaction solvent, reacting for 10-15 hours at the temperature of 100-120 ℃, and performing post-purification treatment.
10. The epoxy-modified phenyl hydrogen-containing silicone oil according to claim 9, characterized in that: the phenyl hydrogen-containing silicone oil, the epoxy-terminated allyl polyether and the catalyst are prepared from the following raw materials in a mass ratio of 100: (100-120) a proportion of (0.3-0.8) solvent in the reaction solvent; and/or
The mass concentration of the phenyl hydrogen-containing silicone oil solvent in the reaction solvent is 1.7-1.8 g/ml; and/or
The reaction solvent is at least one of toluene, benzene and xylene; and/or
The number average molecular weight of the phenyl hydrogen-containing silicone oil at the end is 1300-1700; and/or
The number average molecular weight of the epoxy-terminated allyl polyether is 700-1000; and/or
The catalyst is preferably at least one of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and chloroplatinic acid.
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| CN114262528A (en) * | 2021-12-07 | 2022-04-01 | 中国科学院深圳先进技术研究院 | Surface modification method and application of silicon dioxide |
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