CN110819281A - Impregnating adhesive composition and preparation method and application thereof - Google Patents
Impregnating adhesive composition and preparation method and application thereof Download PDFInfo
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- CN110819281A CN110819281A CN201911164160.9A CN201911164160A CN110819281A CN 110819281 A CN110819281 A CN 110819281A CN 201911164160 A CN201911164160 A CN 201911164160A CN 110819281 A CN110819281 A CN 110819281A
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention provides an impregnating adhesive composition and a preparation method and application thereof, wherein the impregnating adhesive composition is composed of a component A and a component B, the mass ratio of the component A to the component B is 2: 1-3: 1, and the component A comprises the following components in parts by weight: 50-75 parts of bisphenol F type epoxy resin, 5-15 parts of modified epoxy resin, 5-10 parts of reactive diluent, 10-20 parts of silicon micropowder, 10-18 parts of calcium carbonate, 0.03-0.2 part of graphene and 0.5-1 part of silane coupling agent; the component B comprises: 60-70 parts of amine curing agent, 10-20 parts of silicon micropowder and 10-20 parts of calcium carbonate; wherein, the modified epoxy resin is shown as the following formula I:wherein, R is selected from-CH3OH、‑CH3CH2OH, epoxy value of 0.49-0.52. The impregnating adhesive composition can be used as a primer-free impregnating adhesive and has good dielectric resistanceAnd the coating can be cured at low temperature, is suitable for various application occasions, and has good industrial application prospect.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a dipping glue composition and a preparation method and application thereof.
Background
Engineering structure reinforcement is an emerging industry, which means that when a building or a structural system of the building cannot meet the use requirements, necessary structural modification and reinforcement are carried out on the building or the structural system of the building. In engineering structure reinforcement, the carbon fiber cloth reinforcement technology has the advantages of light weight, high strength, good corrosion resistance, simple and convenient construction operation, no increase of the self weight and the section size of the structure, low requirement on the appearance of the structure, capability of even improving the performance of the structure and the like, and is widely applied to reinforcement of building beams, plates, columns, walls and the like and maintenance and reinforcement of other civil engineering such as bridges, tunnels, chimneys, silos and the like. The carbon fiber cloth reinforcing technology usually adopts a matched adhesive to paste the carbon fiber cloth on the surface of a structure, and plays the roles of structure reinforcement and earthquake resistance reinforcement.
In the carbon fiber cloth reinforcing technology, an adhesive is a tie for connecting a structural substrate to be reinforced and the carbon fiber cloth, the impregnation glue has good and bad impregnation effects on the substrate and the carbon fiber cloth, the performance of the impregnation glue is good and bad, and the strength of the bonding capacity often determines the success or failure of the carbon fiber cloth reinforcing construction.
The construction temperature of the carbon fiber resin widely used in the engineering at present is 5-35 ℃, the air temperature is lower than 5 ℃ in the actual construction, the fluidity of the resin is poor, the permeability is weak, the curing time is long, the construction is inconvenient, and the engineering quality is difficult to ensure. Chinese patent CN106928891A mentions that the low-temperature curing type high-strength adhesive prepared by adopting-SH group modified amine curing agent can be cured at low temperature (-15 ℃) to normal temperature, can reach higher crosslinking density without post-curing, and has little smell and no brittle fracture at low temperature. But the resin contains-SH groups, still has certain odor, has longer curing time, contains flexible chain segments and has poorer resistance to wet heat aging; in addition, the conventional carbon fiber impregnating adhesive is generally composed of a primer, a repair adhesive and an impregnating adhesive, and the three adhesives are applied in sequence in construction, so that the construction can be completed in a long time. Compared with the conventional carbon fiber impregnating adhesive, the primer-free impregnating adhesive can well shorten the construction steps and the construction time and improve the construction efficiency; finally, conventional impregnating compounds have poor dielectric resistance, especially in special applications such as acid-base salt dielectric environments.
In view of the above, there is a need in the art for a new type of impregnating adhesive that solves the problems of the prior art.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides an impregnating adhesive composition, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an impregnating adhesive composition which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2: 1-3: 1, and the component A comprises the following components in parts by weight: 50-75 parts of bisphenol F type epoxy resin, 5-15 parts of modified epoxy resin, 5-10 parts of reactive diluent, 10-20 parts of silicon micropowder, 10-18 parts of calcium carbonate, 0.03-0.2 part of graphene and 0.5-1 part of silane coupling agent; the component B comprises: 60-70 parts of amine curing agent, 10-20 parts of silicon micropowder and 10-20 parts of calcium carbonate; wherein, the modified epoxy resin is shown as the following formula I:
wherein, R is selected from-CH3OH、-CH3CH2OH, epoxy value of 0.49-0.52.
According to an embodiment of the present invention, the a component further includes a bisphenol a type epoxy resin, wherein the bisphenol a type epoxy resin is not more than 10 parts by weight.
According to one embodiment of the present invention, the epoxy value of the bisphenol A type epoxy resin is 0.48 to 0.51; the epoxy value of the bisphenol F type epoxy resin is 0.56-0.65.
According to one embodiment of the invention, the amine curing agent is a non-thiol amine curing agent.
According to one embodiment of the present invention, the silane coupling agent is selected from one or more of gamma-epoxypropyletherpropyltriethoxysilane, gamma-aminopropyltriethoxysilane; the reactive diluent is selected from one or more of benzyl glycidyl ether, carbon dodecyl to tetradecyl glycidyl ether, ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether and butyl glycidyl ether.
According to one embodiment of the present invention, the number of graphene layers is 1 to 50.
According to one embodiment of the present invention, the fine silica powder is an active fine silica powder having a mesh size of 400 to 2500; the calcium carbonate is active calcium carbonate with 1000 meshes to 1500 meshes.
The invention provides a preparation method of the impregnating compound composition, which comprises the following steps:
preparing a component A: mixing an active diluent, a silane coupling agent and graphene to obtain graphene slurry; uniformly mixing the modified epoxy resin, the silicon micropowder and the calcium carbonate in vacuum, and then adding the bisphenol F type epoxy resin and the graphene slurry to uniformly mix to obtain a component A;
preparing a component B: uniformly mixing 15-30% of modified fatty amine curing agent, silicon micropowder and calcium carbonate under vacuum, and then adding the rest amine curing agent for uniform mixing to obtain a component B;
and uniformly stirring the prepared component A and the component B to obtain the impregnating compound composition.
According to one embodiment of the invention, the preparation method further comprises the step of preparing the component A, wherein the component A is obtained by uniformly mixing the modified epoxy resin, the bisphenol A epoxy resin, the silica micropowder and the calcium carbonate in vacuum, and then adding the bisphenol F epoxy resin and the graphene slurry to be uniformly mixed.
The invention also provides an application of the impregnating compound composition as a primer-free impregnating compound.
According to the technical scheme, the invention has the beneficial effects that:
the impregnating compound composition provided by the invention can be used as a primer-free impregnating compound, and compared with a conventional impregnating compound, the impregnating compound composition can well shorten construction steps and time and improve construction efficiency; the modified epoxy resin is adopted to replace the traditional epoxy resin, and the bisphenol F type epoxy resin is combined, so that the impregnating adhesive can be quickly cured at low temperature; in addition, the graphene component is added into the composition, so that the composition has excellent medium resistance and can improve the flexibility and the impact resistance of the adhesive. In a word, the impregnating compound composition disclosed by the invention is used as a primer-free impregnating adhesive, can meet various related requirements of GB50728, ensures the stability of the structure, is used for reinforcing construction in cooperation with carbon fibers in a low-temperature environment, has good bonding strength and medium resistance to most of metal and nonmetal building materials, can be suitable for various application occasions, and has good industrial application prospects.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides an impregnating adhesive composition which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2: 1-3: 1, and the component A comprises the following components in parts by weight: 50-75 parts of bisphenol F type epoxy resin, 5-15 parts of modified epoxy resin, 5-10 parts of reactive diluent, 10-20 parts of silicon micropowder, 10-18 parts of calcium carbonate, 0.03-0.2 part of graphene and 0.5-1 part of silane coupling agent; the component B comprises: 60-70 parts of amine curing agent, 10-20 parts of silicon micropowder and 10-20 parts of calcium carbonate;
wherein, the modified epoxy resin is shown as the following formula I:
wherein, R is selected from-CH3OH、-CH3CH2OH, epoxy value of 0.49-0.52.
The modified epoxy resin is an epoxy resin having a ring-opening activity much higher than that of a conventional epoxy resin, and is commercially available or can be prepared by a method conventional in the art. With the radical R as-CH3The synthesis route of the OH modified epoxy resin is as follows: adding bisphenol A, methanol, formaldehyde and sodium hydroxide into a reactor, carrying out reflux reaction for 20 minutes, then adding epoxy chloropropane, carrying out reflux dropwise addition on a sodium hydroxide solution, filtering to remove salt after the reaction is finished, washing with water, and distilling out unreacted epoxy chloropropane to obtain the modified epoxy resin.
According to the invention, as mentioned above, most of the existing impregnating adhesives are composed of the primer, the repair adhesive and the impregnating adhesive, and the three adhesives are applied in sequence in construction, so that the construction can be completed in a long time; in addition, the medium resistance of the common impregnating adhesive is poor, the durability of the common impregnating adhesive is poor in special occasions such as an acid-base salt medium environment, and in actual construction, if the temperature is too low, the fluidity, the permeability and the curing time of the resin are poor, so that the construction is inconvenient, and the engineering quality is difficult to guarantee.
The inventors of the present invention have found that the use of two resins, a bisphenol F type epoxy resin and a modified epoxy resin, can improve the disadvantages of the conventional epoxy resin, such as epoxy resin E51, that the viscosity increases at low temperature and is easily crystallized, the epoxy adhesive is not easily cured at low temperature, and the toughness of the cured product is poor. The modified epoxy resin provided by the invention contains hydroxymethyl or hydroxyethyl, is epoxy resin with ring-opening activity much higher than that of common epoxy resin, and can be quickly cured at low temperature due to high activity when being used for epoxy resin impregnating adhesive; in addition, the curing speed can be improved, the impact resistance and the fracture toughness of a cured product after curing are obviously improved, the properties of the cured product of the epoxy resin, such as the flexural modulus and the like, are not influenced, and more importantly, the epoxy resin can be normally cured at the low temperature of-15-0 ℃ and in a humid environment. The impregnating compound composition can be used as a primer-free impregnating compound, and compared with the conventional impregnating compound, the impregnating compound composition can well shorten the construction steps and time and improve the construction efficiency.
In some embodiments, the amine curing agent is a non-thiol amine curing agent, i.e., a thiol-free amine curing agent, for example, the amine curing agent can be MH-222 and MH2218 of Changshanend aviation chemical, JH-5280 of Shenzhen Jia Di Da chemical, J-004R of Jindao Qishi, LT-45 of Changzhou mountain peak chemical, or a combination thereof, but the invention is not limited thereto. Because the composition does not contain-SH group modified amine curing agent, the irritant odor caused by sulfydryl can be avoided, and the composition can be used as a novel environment-friendly primer-free impregnating adhesive.
In some embodiments, the epoxy value of the bisphenol F epoxy resin is 0.56-0.65. In some embodiments, the a component may also add a bisphenol a type epoxy resin, wherein the bisphenol a type epoxy resin does not exceed 10 parts by weight. The product effectiveness is ensured, and meanwhile, the cost of the product can be reduced by adding part of bisphenol A epoxy resin. Preferably, the epoxy value of the bisphenol A epoxy resin is 0.48 to 0.51.
In some embodiments, the silane coupling agent in component a is selected from one or two of gamma-epoxypropyletherpropyltriethoxysilane (KH-560), gamma-aminopropyltriethoxysilane (KH-550), preferably gamma-epoxypropyletherpropyltriethoxysilane, and the reactive diluent is selected from one or more of benzyl glycidyl ether (692), carboxydodecyl to tetradecyl glycidyl ether (748), ethylene glycol diglycidyl ether (669), 1, 4-butanediol diglycidyl ether (622), and butyl glycidyl ether (501).
In some embodiments, the graphene in the component a may be single-layer graphene or multi-layer graphene, and the number of layers may be 2 to 50. The graphene can form a labyrinth shielding structure in the adhesive layer due to a two-dimensional honeycomb lattice structure formed by specific carbon six-membered rings of the graphene, can be used for obstructing erosion media, solves the problem that common cured materials are poor in chemical medium resistance, has excellent medium resistance, and effectively reduces the internal stress of the adhesive layer, consumes the fracture energy and further improves the flexibility and the impact resistance of the adhesive by dividing the adhesive layer into a plurality of small regions by the lamellar structure of the graphene.
In some embodiments, the silica fume is 400-2500 mesh active silica fume, and the calcium carbonate is 1000-1500 mesh active calcium carbonate. As known to those skilled in the art, the active silica micropowder refers to active silica micropowder modified by a surface modifier, and has the functions of reinforcing and reducing the product cost; the active calcium carbonate is modified by a surface modifier, and has the effects of reinforcing, reducing the product cost and improving the construction performance of the product.
In addition, 2-4 parts of thixotropic agent, such as hydrophilic fumed silica, can be added into the component B to improve the thixotropic property of the impregnating compound composition.
The invention also provides a preparation method of the impregnating compound composition, which comprises the following steps:
preparing a component A: mixing an active diluent, a silane coupling agent and graphene to obtain graphene slurry; uniformly mixing modified epoxy resin, silicon micropowder and calcium carbonate under vacuum, generally, vacuum mixing and stirring for 20 minutes until the mixture is uniform, then adding the bisphenol F type epoxy resin and the graphene slurry, and uniformly mixing, generally, stirring for about 10 minutes to obtain a component A;
preparing a component B: uniformly mixing a part of amine curing agent, such as 15-30% of modified fatty amine curing agent, silicon micropowder and the calcium carbonate under vacuum, generally, mixing and stirring under vacuum for 20 minutes until the mixture is uniform, then adding the rest of the amine curing agent, and uniformly mixing, generally, stirring for about 10 minutes to obtain a component B; the mode of adding the powder materials step by step is beneficial to improving the dispersibility of the powder materials such as silicon micropowder, calcium carbonate, gas-phase silicon dioxide and the like in the composition.
And uniformly stirring the prepared component A and the component B to obtain the impregnating compound composition.
In some embodiments, further comprising: in the process of preparing the component A, the modified epoxy resin, the bisphenol A epoxy resin, the silica micropowder and the calcium carbonate are uniformly mixed under vacuum, and then the bisphenol F epoxy resin and the graphene slurry are added and uniformly mixed to obtain the component A.
The impregnating adhesive composition has the advantages that the adhesive viscosity changes little compared with the normal temperature in the low-temperature (-15-5 ℃) environment, the self viscosity is small, the infiltrating permeability with carbon fiber is good, the thixotropy is good, and the low-temperature and normal-temperature construction manufacturability is good. The adhesive provided by the invention has the advantages that the defects of low-temperature resistance of the conventional carbon fiber impregnating adhesive are overcome, the adhesive can be cured at low temperature (-15 ℃) to normal temperature, the curing speed is high at low temperature, the odor is small, the toxicity is extremely low, the toughness is good, the low-temperature embrittlement is avoided, and the good structure can be maintained after curing.
The invention will be further illustrated by the following specific examples, but the invention is not limited thereto. Unless otherwise specified, the experimental procedures used in the following examples are all conventional. Materials, reagents and the like used in the following examples are commercially available.
Preparation example 1
This preparation example is intended to illustrate the preparation of the modified epoxy resin of the present invention.
Adding 228g of bisphenol A, 90g of methanol, 36g of formaldehyde and 24g of sodium hydroxide into a reactor, carrying out reflux reaction at 65 ℃ for 20 minutes, then adding 200g of epoxy chloropropane, carrying out reflux dropwise addition on 400g of 10% sodium hydroxide solution, filtering to remove salt after the reaction is finished, washing with water, and distilling out unreacted epoxy chloropropane to obtain the modified epoxy resin.
Example 1
This example illustrates the preparation of an impregnating adhesive composition according to the invention.
Preparation of the component A: mixing 8 parts of C-dodecyl-tetradecyl glycidyl ether (748), 1 part of gamma-epoxypropyl ether propyl triethoxysilane (KH-560) and 0.1 part of graphene to obtain graphene slurry; 5 parts of bisphenol A epoxy resin, 5 parts of the modified epoxy resin of preparation example 1, 15 parts of active silica micropowder and 15 parts of active calcium carbonate are vacuumized, mixed and stirred for 20 minutes until uniform, and then 65 parts of bisphenol F epoxy resin and graphene slurry are added and mixed and stirred for 10 minutes.
Preparation of the component B: the preparation method comprises the following steps of vacuumizing, mixing and stirring 14 parts of amine curing agent MH-222 (Changsha new chemical industry), 16 parts of active silica micropowder, 17 parts of active calcium carbonate and 2 parts of hydrophilic fumed silica for 20 minutes until the mixture is uniform, and then adding 20 parts of amine curing agent MH-222 (Changsha new chemical industry), 20 parts of amine curing agent JH-5280 (Shenzhen Jia Dida chemical industry) and 14 parts of amine curing agent LT-45 (Changzhou mountain peak chemical industry) to mix and stir for 10 minutes.
Mixing the component A and the component B according to the mass ratio of 3:1, uniformly mixing to obtain the impregnating adhesive composition.
Example 2
This example illustrates the preparation of an impregnating adhesive composition according to the invention.
Preparation of the component A: mixing 8 parts of active diluent, 1 part of coupling agent and 0.15 part of graphene to obtain graphene slurry; 7 parts of the modified epoxy resin of preparation example 1, 18 parts of active silica micropowder and 12 parts of active calcium carbonate are vacuumized, mixed and stirred for 20 minutes until uniform, and then 68 parts of bisphenol F epoxy resin and graphene slurry are added and mixed and stirred for 10 minutes.
Preparation of the component B: 16 parts of amine curing agent JH-5280 (Shenzhen Jia Di Da chemical industry), 13 parts of active silica micropowder, 20 parts of active calcium carbonate and 2 parts of hydrophilic fumed silica are vacuumized, mixed and stirred for 20 minutes until the mixture is uniform, and then 45 parts of amine curing agent MH-222 (Changshanen Shendao chemical industry) are added and mixed and stirred for 10 minutes.
Mixing the component A and the component B according to the mass ratio of 2:1, uniformly mixing to obtain the impregnating adhesive composition.
Example 3
This example illustrates the preparation of an impregnating adhesive composition according to the invention.
Preparation of the component A: mixing 10 parts of active diluent, 0.5 part of coupling agent and 0.2 part of graphene to obtain graphene slurry; 13 parts of modified epoxy resin, 18 parts of active silica micropowder and 12 parts of active calcium carbonate in preparation example 1 are vacuumized, mixed and stirred for 20 minutes until uniform, and then 65 parts of bisphenol F epoxy resin and graphene slurry are added and mixed and stirred for 10 minutes.
Preparation of the component B: 14 parts of JH-5280, 13 parts of active silica powder, 20 parts of active calcium carbonate and 1.5 parts of hydrophilic fumed silica are vacuumized, mixed and stirred for 20 minutes until the mixture is uniform, and then 4 parts of amine curing agent MH-222 (Changsha Xingdao chemical industry) and 10 parts of amine curing agent MH-2218 (Changsha Xingdao chemical industry) are added and mixed and stirred for 10 minutes.
Mixing the component A and the component B according to the mass ratio of 3:1, uniformly mixing to obtain the impregnating adhesive composition.
Comparative example 1
And the preparation of the component A, namely mixing and stirring 80 parts of bisphenol F type epoxy resin, 10 parts of active diluent and 0.5 part of coupling agent for 5 minutes, then adding 18 parts of active silica micropowder and 12 parts of active calcium carbonate, vacuumizing, mixing and stirring for 20 minutes until the components are uniformly stirred.
And B, preparing the component B, namely vacuumizing and mixing 30 parts of thiol amine curing agent, 13 parts of active silica powder, 20 parts of active calcium carbonate and 1.5 parts of hydrophilic fumed silica for 20 minutes until the components are uniform, and then adding 50 parts of modified amine curing agent, mixing and stirring for 10 minutes.
Mixing the component A and the component B according to the mass ratio of 3:1, uniformly mixing to obtain the impregnating adhesive composition.
Test example 1
The impregnating compound compositions of the examples 1-3 and the comparative example 1 and the commercially available carbon fiber impregnating compound (manufacturer: Shibida; purchased in 2017) were subjected to performance detection according to the relevant requirements of GB50728, and the detection data are shown in Table 1.
TABLE 1
From table 1, it can be seen that the impregnating compound compositions of the present invention have better performance than the commercial impregnating compound or the comparative example 1 in terms of overall performance, and the gel time is better than the thiol-based impregnating compound and the commercial impregnating compound of the comparative example 1 in terms of gel time and the gel performance of the products of the examples 1, 2 and 3 of the present invention at a low temperature of-15 ℃.
Test example 2
The construction time comparisons for the dip gum compositions of example 1 and comparative example 1 and for a commercially available carbon fiber dip gum (manufacturer: shibida; available in 2017) are shown in table 2 below.
TABLE 2
As can be seen from Table 2, compared with the commercially available impregnating compound, the impregnating compound of the present invention saves time relatively, has simple process, and can shorten the construction steps and time and improve the construction efficiency.
Test example 3
The impregnating size compositions of example 1 and comparative example 1 and a commercially available carbon fiber impregnating size (manufacturer: shibida; purchased in 2017) were subjected to a medium resistance test. The results are shown in Table 3. Firstly, tinplate is used as an experimental base material, and the impregnating adhesives are uniformly coated on the surface of the tinplate respectively to ensure that no gap exists on the surface. After the coated tinplate was soaked in a 5% sulfuric acid solution for 30 days, the surface was observed for the presence of bubbling and peeling of the gum layer. It can be seen that the impregnating glue of the present invention has no bubbles on the surface and no peeling of the glue layer, while the other two glues either have peeling of the glue layer or have bubbles. Further, a stainless steel is used as a base material to prepare a tensile-shear test piece, and the reduction rate of tensile-shear strength is tested after 60 days at 60 ℃ and 95% humidity. It can be seen that the reduction in tensile shear strength of the dip-coated adhesives of the present invention is low relative to the other two groups of adhesives, which also indicates that the dip-coated adhesive compositions have good media resistance.
TABLE 3
In conclusion, the impregnating adhesive composition can be used as a primer-free impregnating adhesive, and compared with the conventional impregnating adhesive, the impregnating adhesive composition can well shorten the construction steps and time and improve the construction efficiency; the impregnating adhesive can be rapidly cured at low temperature, has excellent medium resistance due to the addition of the graphene component, and can also improve the flexibility and impact resistance of the adhesive. The adhesive can meet various related requirements of GB50728 when used as a prime coat-free dipping adhesive, ensures the stability of the structure, has good bonding strength and medium resistance to most of metal and nonmetal building materials, can be suitable for various application occasions, and has good industrial application prospect.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
1. The impregnating adhesive composition is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 2: 1-3: 1, and the impregnating adhesive composition comprises the components A and B in parts by weight,
the component A comprises: 50-75 parts of bisphenol F type epoxy resin, 5-15 parts of modified epoxy resin, 5-10 parts of reactive diluent, 10-20 parts of silicon micropowder, 10-18 parts of calcium carbonate, 0.03-0.2 part of graphene and 0.5-1 part of silane coupling agent;
the component B comprises: 60-70 parts of amine curing agent, 10-20 parts of silicon micropowder and 10-20 parts of calcium carbonate;
wherein, the modified epoxy resin is shown as the following formula I:
wherein, R is selected from-CH3OH、-CH3CH2OH, epoxy value of 0.49-0.52.
2. The impregnating adhesive composition of claim 1, wherein said a-component further comprises a bisphenol a epoxy resin, wherein said bisphenol a epoxy resin is present in an amount of not more than 10 parts by weight.
3. The impregnating compound composition according to claim 2, wherein the epoxy value of the bisphenol a type epoxy resin is 0.48 to 0.51; the epoxy value of the bisphenol F type epoxy resin is 0.56-0.65.
4. The impregnating gel composition of claim 1, wherein said amine curing agent is a non-thiol amine curing agent.
5. The impregnation glue composition of claim 1, wherein said silane coupling agent is selected from one or more of gamma-epoxypropyletherpropyltriethoxysilane, gamma-aminopropyltriethoxysilane; the reactive diluent is selected from one or more of benzyl glycidyl ether, carbon dodecyl-tetradecyl glycidyl ether, ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether and butyl glycidyl ether.
6. The impregnating compound composition according to claim 1, wherein the number of graphene layers is 1-50.
7. The impregnating compound composition according to claim 1, wherein the silica micropowder is an active silica micropowder of 400 to 2500 meshes; the calcium carbonate is active calcium carbonate with 1000 meshes-1500 meshes.
8. A method of preparing the impregnating compound composition of any one of claims 1 to 7, comprising:
preparing a component A: mixing the active diluent, the silane coupling agent and the graphene to obtain graphene slurry; uniformly mixing the modified epoxy resin, the silica micropowder and the calcium carbonate in vacuum, and then adding the bisphenol F type epoxy resin and the graphene slurry to uniformly mix to obtain a component A;
preparing a component B: uniformly mixing 15-30% of the modified fatty amine curing agent, the silicon micropowder and the calcium carbonate under vacuum, and then adding the rest of the amine curing agent for uniform mixing to obtain a component B;
and uniformly stirring the prepared component A and the prepared component B to obtain the impregnating compound composition.
9. The preparation method of claim 8, further comprising the step of preparing the component A, wherein the modified epoxy resin, the bisphenol A epoxy resin, the silica powder and the calcium carbonate are uniformly mixed under vacuum, and then the bisphenol F epoxy resin and the graphene slurry are added and uniformly mixed to obtain the component A.
10. Use of the impregnating compound composition according to any one of claims 1 to 7 as a primer-free impregnating compound.
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| CN111995977A (en) * | 2020-09-03 | 2020-11-27 | 广西大学 | Summer slow-setting type high-performance structural adhesive and preparation method thereof |
| CN112898928A (en) * | 2021-02-05 | 2021-06-04 | 南京曼卡特科技有限公司 | Underwater type impregnating adhesive |
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| CN112898928A (en) * | 2021-02-05 | 2021-06-04 | 南京曼卡特科技有限公司 | Underwater type impregnating adhesive |
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