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CN-121991621-A - Modified polyurea adhesive and preparation method thereof

CN121991621ACN 121991621 ACN121991621 ACN 121991621ACN-121991621-A

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to a modified polyurea adhesive and a preparation method thereof. The polyurea adhesive comprises, by weight, 40-45 parts of polyether diamine, 30-40 parts of isocyanate, 10-15 parts of polyol, 8-10 parts of functionalized nano calcium carbonate, 2-8 parts of chain extender, 0.01-0.02 part of catalyst and 0.1-0.5 part of antioxidant, wherein the functionalized nano calcium carbonate is added to modify the polyurea adhesive to improve the comprehensive performance of the polyurea adhesive, so that the peeling strength, mechanical property and antibacterial property of the polyurea adhesive are enhanced.

Inventors

  • CHEN YU
  • ZHOU HENG
  • SHEN DI
  • GUO YUJIAO

Assignees

  • 浙江澳宇新材料科技有限公司

Dates

Publication Date
20260508
Application Date
20260326

Claims (10)

  1. 1. A modified polyurea adhesive is characterized by comprising, by weight, 40-45 parts of polyether diamine, 30-40 parts of isocyanate, 10-15 parts of polyol, 8-10 parts of functionalized nano calcium carbonate, 2-8 parts of chain extender, 0.01-0.02 part of catalyst and 0.1-0.5 part of antioxidant; the preparation method of the functionalized nano calcium carbonate comprises the following steps: S1, adding nano calcium carbonate into a reaction solvent, uniformly stirring, adding dopamine hydrochloride, adjusting the pH value to 8.5-8.6, and stirring and reacting for 20-22 hours at room temperature to obtain modified nano calcium carbonate; S2, adding modified nano calcium carbonate into 50-60wt% ethanol solution, uniformly stirring, adding magnolol derivative and triethylamine, placing at 70-80 ℃, and stirring and reacting for 5-6h to obtain the functional nano calcium carbonate.
  2. 2. The modified polyurea adhesive according to claim 1, wherein the mass ratio of the nano calcium carbonate to the reaction solvent in the step S1 is 1:20-25, the concentration of dopamine hydrochloride in the reaction solvent is 3-4mg/mL, the reaction solvent is Tris-HCL buffer solution, and the concentration of the Tris-HCl buffer solution is 12-15mmol/L.
  3. 3. The modified polyurea adhesive of claim 1, wherein the modified nano calcium carbonate, magnolol derivative, and triethylamine in step S2 are 1:0.2-0.3:0.04-0.05.
  4. 4. The modified polyurea adhesive of claim 1, wherein the magnolol derivative in step S2 is prepared by a process comprising: (1) Adding magnolol and benzoyl peroxide into n-octane, stirring uniformly, placing at-10 ℃ to-5 ℃, slowly introducing hydrogen bromide, and continuing stirring for reaction for 1.5-2 hours to obtain brominated magnolol; (2) Adding magnolol bromide and urea into N, N-dimethylformamide, stirring uniformly, placing at 70-80 ℃, slowly dropwise adding formaldehyde solution, and continuing stirring and reacting for 3-4h after dropwise adding to obtain magnolol derivatives.
  5. 5. The modified polyurea adhesive of claim 4, wherein the molar ratio of magnolol, hydrogen bromide, benzoyl peroxide in step (1) is 1:2.1-2.2:0.08-0.1.
  6. 6. The modified polyurea adhesive of claim 4, wherein the molar ratio of magnolol bromide, urea and formaldehyde in step (2) is 1:2.1-2.2:2.2-2.3 and the formaldehyde solution has a concentration of 37wt%.
  7. 7. The modified polyurea adhesive of claim 1, wherein the polyether diamine is any one or a mixture of more of polyoxypropylene diamine-1000, polyoxypropylene diamine-2000, polyoxyethylene diamine-1000, and polyoxyethylene diamine-2000.
  8. 8. The modified polyurea adhesive according to claim 1, wherein the isocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate, and the polyol is one or more of polytetrahydrofuran diol, polycaprolactone diol and polycarbonate diol.
  9. 9. The modified polyurea adhesive according to claim 1, wherein the chain extender is any one or a mixture of hexamethylenediamine, decamethylenediamine and ethylenediamine, the catalyst is stannous octoate, and the antioxidant is antioxidant 1010 or antioxidant 1076.
  10. 10. The preparation method of the modified polyurea adhesive according to any one of claims 1 to 9, which is characterized by comprising the steps of adding polyether diamine, functionalized nano calcium carbonate, a chain extender, a catalyst and an antioxidant into a reaction kettle according to the weight part ratio, uniformly mixing, dehydrating in vacuum, adding isocyanate, stirring and reacting for 1 to 1.5 hours at 70 to 80 ℃ to form a prepolymer, adding polyol, uniformly mixing, injecting into a double-screw reactor for reaction, extruding, granulating and drying to obtain the polyurea adhesive.

Description

Modified polyurea adhesive and preparation method thereof Technical Field The invention belongs to the technical field of adhesives, and particularly relates to a modified polyurea adhesive and a preparation method thereof. Background The polyurea adhesive is a high-performance elastomer adhesive material generated by reacting isocyanate components with amino compound components, has the characteristics of strong adhesion, chemical corrosion resistance, excellent weather resistance, wear resistance and the like, can firmly bond various materials such as metal, glass, ceramic, plastic and the like, provides firm connection and fixing effects, is widely applied to various fields such as constructional engineering, pipeline engineering, traffic fields, sports facilities, electronic appliances and the like, generally belongs to spraying reaction type materials, generally consists of A, B components, has high requirements on construction equipment and personnel, needs a special high-pressure airless sprayer when spraying, uniformly mixes the two components, ensures uniform coating thickness, prevents the problems of thick spraying, thin spraying, pinholes and the like, is difficult to repair in later period, has high construction threshold, has no oil pollution and floating dust on the surface of a substrate, is easy to foam and fall off after the coating is solidified, and especially in the south plum rain construction, the drying of the substrate needs extra renting equipment and time, increases the cost, the polyurea adhesive has low-temperature environment, the coating can slowly change the activity of molecular chains, has the elasticity lower than 20 ℃ and is easy to crack when the coating is low in temperature or is difficult to shrink in severe areas due to low temperature or low temperature. The Chinese patent with the application number of CN202410470157.4 discloses an in-situ durable adhesive polyurea adhesive in an ultralow temperature environment, a preparation method and application thereof, wherein the preparation method comprises the steps of 1, enabling polyurethane-terminated polydimethylsiloxane to undergo a ring-opening reaction with ethylene carbonate to obtain a product PDMS-EC, 2, carrying out pre-polycondensation after blending the product PDMS-EC with the polyurethane-terminated polydimethylsiloxane and a catalyst, vacuumizing to remove byproducts until reactants generate a Weissenberg effect to obtain a prepolymer, and 3, carrying out melt polycondensation on the obtained prepolymer in a vacuum state to obtain the polyurea adhesive. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a modified polyurea adhesive and a preparation method thereof, and in order to improve the comprehensive performance of the polyurea adhesive, the modified polyurea adhesive is modified by adding functional nano calcium carbonate, so that the peeling strength, mechanical property and antibacterial property of the polyurea adhesive are enhanced. The technical scheme adopted by the invention for achieving the purpose is as follows: The modified polyurea adhesive comprises, by weight, 40-45 parts of polyether diamine, 30-40 parts of isocyanate, 10-15 parts of polyol, 8-10 parts of functionalized nano calcium carbonate, 2-8 parts of chain extender, 0.01-0.02 part of catalyst and 0.1-0.5 part of antioxidant. Further, the polyether diamine is any one or a mixture of more than one of polypropylene oxide diamine-1000, polypropylene oxide diamine-2000, polyethylene oxide diamine-1000 and polyethylene oxide diamine-2000. Further, the isocyanate is any one or a mixture of more than one of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate. Further, the polyol is any one or a mixture of a plurality of polytetrahydrofuran glycol, polycaprolactone glycol and polycarbonate glycol. Further, the chain extender is any one or a mixture of a plurality of hexamethylenediamine, decaenediamine and ethylenediamine. Further, the catalyst is stannous octoate. Further, the antioxidant is antioxidant 1010 or antioxidant 1076. Further, the preparation method of the functionalized nano calcium carbonate comprises the following steps: S1, adding nano calcium carbonate into a reaction solvent, uniformly stirring, adding dopamine hydrochloride, adjusting the pH value to 8.5-8.6, and stirring and reacting for 20-22 hours at room temperature to obtain modified nano calcium carbonate; S2, adding modified nano calcium carbonate into 50-60wt% ethanol solution, uniformly stirring, adding magnolol derivative and triethylamine, placing at 70-80 ℃, and stirring and reacting for 5-6h to obtain the functional nano calcium carbonate. Further, in the step S1, the mass ratio of the nano calcium carbonate to the reaction solvent is 1:20-25, the concentration of dopamine hydrochloride in the reaction solvent is 3-4mg/mL, the reaction solvent is Tris-HCL buffer solution, and the conce