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CN-121975471-A - Flame-retardant adhesive and preparation method thereof

CN121975471ACN 121975471 ACN121975471 ACN 121975471ACN-121975471-A

Abstract

The invention relates to the technical field of adhesives, and relates to a flame-retardant adhesive and a preparation method thereof. The flame-retardant adhesive comprises, by weight, 60-80 parts of silicon-phosphorus co-modified epoxy resin, 1.5-3.5 parts of polychloroprene, 1.6-3.2 parts of carbon nine petroleum resin, 1.2-3.2 parts of phenolic resin, 1.3-3.1 parts of hydrogenated rosin, 11.0-13.0 parts of emulsifying agent, 0.05-0.15 parts of magnesium oxide, 15-22 parts of composite flame-retardant filler, 76.3-83.6 parts of diluent, 3-8 parts of toughening agent, 10-15 parts of curing agent and 0.5-2 parts of accelerator, wherein the composite flame-retardant filler is micro-nano composite particles with a core-shell structure, the core is modified ammonium polyphosphate, the shell is porous nano silicon dioxide wrapping the core-shell structure, and the shell is loaded with carbon nano tubes and layered double hydroxide nano sheets. According to the flame-retardant adhesive provided by the invention, the flame retardance of the adhesive is improved, and the resin is endowed with good flame retardance through the synergistic modification of silicon and phosphorus.

Inventors

  • ZHANG ZHICHENG
  • ZHANG JINGYAN

Assignees

  • 河北霆兴化工产品有限公司

Dates

Publication Date
20260505
Application Date
20260320

Claims (10)

  1. 1. The flame-retardant adhesive is characterized by comprising, by weight, 60-80 parts of silicon-phosphorus co-modified epoxy resin, 1.5-3.5 parts of polychloroprene, 1.6-3.2 parts of carbon nine petroleum resin, 1.2-3.2 parts of phenolic resin, 1.3-3.1 parts of hydrogenated rosin, 11.0-13.0 parts of emulsifier, 0.05-0.15 part of magnesium oxide, 15-22 parts of composite flame-retardant filler, 76.3-83.6 parts of diluent, 3-8 parts of toughening agent, 10-15 parts of curing agent and 0.5-2 parts of accelerator; The composite flame-retardant filler is a micro-nano composite particle with a core-shell structure, the core of the composite flame-retardant filler is modified ammonium polyphosphate, the shell of the composite flame-retardant filler is porous nano silicon dioxide wrapping the core-shell structure, and carbon nano tubes and layered double hydroxide nano sheets are loaded in the shell.
  2. 2. The flame-retardant adhesive according to claim 1, wherein the preparation method of the silicon-phosphorus co-modified epoxy resin comprises the steps of heating the epoxy resin to 90-100 ℃ under the protection of nitrogen, slowly adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, maintaining the temperature at 100-110 ℃ for 3-4 hours to obtain a phosphorus modified epoxy resin intermediate, cooling the phosphorus modified epoxy resin intermediate to 70-80 ℃, adding a silane coupling agent, and stirring and mixing at 500-800rpm for 0.5-1 hour until the mixture is uniform, thereby obtaining the silicon-phosphorus co-modified epoxy resin.
  3. 3. The flame retardant adhesive according to claim 2, wherein the epoxy resin, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and silane coupling agent are used in a ratio of 90-110g:9-11g:1.5-2.5g.
  4. 4. The flame retardant adhesive of claim 1, wherein the method for preparing the composite flame retardant filler comprises: (1) Dispersing ammonium polyphosphate in hot water, adding melamine and formaldehyde, reacting for 2-3 hours at the pH value of 4-5 and the temperature of 65-75 ℃, and filtering, washing and drying after the reaction is finished to obtain MAPP microspheres coated with melamine-formaldehyde resin on the surfaces; (2) Adding the MAPP microsphere into a mixed solvent of ethanol and water, performing ultrasonic dispersion, adding ammonia water as a catalyst, adding a mixed solution of tetraethoxysilane and ethanol under mechanical stirring, reacting for 8-9h at 35-40 ℃, and performing centrifugal separation, washing and drying after the reaction is finished to obtain a MAPP@SiO 2 intermediate; (3) Dispersing carboxylated carbon nano tube CNTs-COOH and aluminum magnesium hydrotalcite in N, N-dimethylformamide, performing ultrasonic treatment to form uniform dispersion liquid, impregnating a MAPP@SiO 2 intermediate with the dispersion liquid for 0.5-2h under vacuum of-0.05 to-0.08 MPa, performing heat treatment on the mixture at 110-120 ℃ for 5-6h after impregnation, and filtering, washing and drying after the reaction is finished to obtain the composite flame retardant filler.
  5. 5. The flame retardant adhesive according to claim 4, wherein in the step (1), the ammonium polyphosphate, melamine and formaldehyde are added in the form of 37wt% aqueous solution at a ratio of 100g:20-30g:40-60 g.
  6. 6. The flame-retardant adhesive according to claim 4, wherein in the step (2), the dosage ratio of the MAPP microsphere, the mixed solvent, the ammonia water, the ethyl orthosilicate and the ethanol is 20g:360-440mL:8-12mL:6-10mL:30-50mL, and the volume ratio of the ethanol to the water in the mixed solvent is 4:1.
  7. 7. The flame retardant adhesive according to claim 4, wherein in the step (3), the dosage ratio of CNTs-COOH, aluminum magnesium hydrotalcite, N-dimethylformamide, MAPP@SiO 2 intermediate is 1-3g:3-5g:400mL:20g.
  8. 8. The flame-retardant adhesive according to claim 1, wherein the emulsifier is Span-80, the diluent comprises xylene, cyclohexane, methyl ester and benzyl glycidyl ether mixed according to the weight ratio of 45.5-46.5:11.5-13.6:3.6-5.7:15.7-17.8, the toughening agent is carboxyl-terminated liquid nitrile rubber CTBN, the curing agent is superfine micronized dicyandiamide, and the accelerator is 4,4' -methylenebis (phenyldimethylurea).
  9. 9. A method of preparing the flame retardant adhesive of any one of claims 1-8, comprising the steps of: Mixing the silicon-phosphorus co-modified epoxy resin, the diluent, the polychloroprene, the carbon nine petroleum resin, the phenolic resin, the hydrogenated rosin, the emulsifier, the magnesium oxide and the toughening agent according to the formula amount, stirring and mixing for 30-45min at the stirring speed of 40-50 ℃ and 300-500 rpm, adding the compound flame retardant filler according to the formula amount, after the adding, raising the stirring speed to 2000-2500 rpm, continuously shearing and dispersing for 40-60min at the high speed of 40-50 ℃, cooling to below 30 ℃, slowly adding the curing agent and the accelerating agent according to the formula amount at the mild stirring speed of 300-500 rpm, continuously stirring for 20-30min, and transferring to vacuum defoaming equipment to obtain the flame retardant adhesive.
  10. 10. The method for preparing the flame-retardant adhesive according to claim 9, wherein the vacuum defoaming condition is that the defoaming treatment is carried out for 15-25min under the conditions of vacuum degree of-0.08 to-0.09 MPa and temperature of 25-35 ℃.

Description

Flame-retardant adhesive and preparation method thereof Technical Field The invention relates to the technical field of adhesives, in particular to a flame-retardant adhesive and a preparation method thereof. Background The flame-retardant adhesive can effectively prevent or delay the spread of flame when a fire disaster occurs, reduce fire disaster loss and ensure the life and property safety of personnel. However, the existing flame-retardant adhesive still has a plurality of defects in flame retardant performance, storage stability and the like, and is difficult to meet the increasingly severe application requirements. Most of the existing flame-retardant adhesives adopt a single flame-retardant mechanism, such as adding an inorganic flame retardant or performing simple chemical modification to improve the flame retardant property. This single flame retardant approach often makes it difficult to achieve the desired flame retardant effect in the face of complex fire environments. In the process of preparing a flame-retardant adhesive by a physical blending method, poor compatibility between a flame-retardant filler and an adhesive matrix is a common problem. Because the surface properties of the filler and the matrix are different, good interface bonding is difficult to form between the filler and the matrix, so that the filler is easy to agglomerate in the matrix to form larger particles. The rheological property of the adhesive can be affected, so that the problems of flowing, uneven smearing and the like occur in the construction process, and the interaction between the flame-retardant filler and the matrix can be reduced, thereby affecting the exertion of the flame-retardant effect. In addition, the aggregation of the filler can also cause stress concentration in the adhesive, and the mechanical property and the adhesive property of the adhesive are reduced. Based on the above, the invention provides a flame-retardant adhesive and a preparation method thereof. Disclosure of Invention The flame-retardant adhesive and the preparation method thereof provided by the invention have the advantages that the flame retardant property of the adhesive is improved, the resin is endowed with good flame retardance through the synergistic modification of silicon and phosphorus, the composite flame-retardant filler realizes the synergistic effect of various flame retardant mechanisms, the storage stability of the adhesive is improved, the problem of filler dispersion is solved through the modification of silicon and phosphorus, and the composite flame-retardant filler and the resin stably interact to prevent phase separation and sedimentation. The technical scheme of the invention is as follows: The invention provides a flame-retardant adhesive, which comprises, by weight, 60-80 parts of silicon-phosphorus co-modified epoxy resin, 1.5-3.5 parts of polychloroprene, 1.6-3.2 parts of carbon nine petroleum resin, 1.2-3.2 parts of phenolic resin, 1.3-3.1 parts of hydrogenated rosin, 11.0-13.0 parts of emulsifier, 0.05-0.15 parts of magnesium oxide, 15-22 parts of composite flame-retardant filler, 76.3-83.6 parts of diluent, 3-8 parts of flexibilizer, 10-15 parts of curing agent and 0.5-2 parts of accelerator; The composite flame-retardant filler is a micro-nano composite particle with a core-shell structure, the core of the composite flame-retardant filler is modified ammonium polyphosphate, the shell of the composite flame-retardant filler is porous nano silicon dioxide wrapping the core-shell structure, and carbon nano tubes and layered double hydroxide nano sheets are loaded in the shell. The preparation method of the silicon-phosphorus co-modified epoxy resin comprises the steps of heating the epoxy resin to 90-100 ℃ under the protection of nitrogen, then slowly adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, maintaining the temperature at 100-110 ℃ for 3-4 hours to obtain a phosphorus modified epoxy resin intermediate, cooling the phosphorus modified epoxy resin intermediate to 70-80 ℃, adding a silane coupling agent, and stirring and mixing for 0.5-1 hour at 500-800rpm until the mixture is uniform, thus obtaining the silicon-phosphorus co-modified epoxy resin. As a further technical scheme, the dosage ratio of the epoxy resin, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the silane coupling agent is 90-110g:9-11g:1.5-2.5g. As a further technical scheme, the preparation method of the composite flame retardant filler comprises the following steps: (1) Dispersing ammonium polyphosphate in hot water, adding melamine and formaldehyde, reacting for 2-3 hours at the pH value of 4-5 and the temperature of 65-75 ℃, and filtering, washing and drying after the reaction is finished to obtain MAPP microspheres coated with melamine-formaldehyde resin on the surfaces; (2) Adding the MAPP microsphere into a mixed solvent of ethanol and water, performing ultrasonic dispersion, adding ammonia water as a cat