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CN-121975045-A - High-strength heat-resistant adhesive based on polybrominated dichlorobutadiene and preparation method thereof

CN121975045ACN 121975045 ACN121975045 ACN 121975045ACN-121975045-A

Abstract

The invention discloses a high-strength heat-resistant adhesive based on polybrominated dichlorobutadiene and a preparation method thereof, wherein a polymerization unit of the adhesive consists of [ (CHBr-C (Cl) =C (Cl) -CHBr- ] n ], the preparation method of the polybrominated dichlorobutadiene polymer comprises the following steps of S1, reacting 2, 3-dichloro-1, 3-butadiene with bromine at a temperature of between 20 ℃ below zero and 10 ℃ below zero to generate 1, 4-dibromo-2, 3-dichloro-2-butene monomer, and S2, polymerizing the 1, 4-dibromo-2, 3-dichloro-2-butene monomer at a temperature of between 50 ℃ and 80 ℃ in the presence of a catalyst to obtain the polybrominated dichlorobutadiene polymer. The glass transition temperature (Tg) of the adhesive body resin-polybrominated dichlorobutadiene is higher than 115 ℃ and is far higher than that of the traditional neoprene adhesive (Tg is usually less than 0 ℃). The technical bottleneck that the environmental intensity of the traditional neoprene is suddenly reduced above 80 ℃ is fundamentally solved.

Inventors

  • LI DESHENG
  • LI TENG
  • XUE BOYONG
  • YANG ZHENLIN
  • MA DELONG
  • JIA CHUNLIN
  • GAO XINGBO
  • ZHAO ZHENWEI
  • WANG BOYU
  • MENG YUTING

Assignees

  • 山东阳谷华泰化工股份有限公司

Dates

Publication Date
20260505
Application Date
20260305

Claims (10)

  1. 1. A polybrominated dichlorobutadiene polymer is characterized in that a polymerization unit of the polybrominated dichlorobutadiene polymer is composed of [ (CHBr-C (Cl) =C (Cl) -CHBr- ] n , wherein the bromine content of the polymer is 24.6-49.7wt%, the chlorine content is 29.4-43.7wt%, the number average molecular weight M n is 15,000-50,000g/mol, the molecular weight distribution PDI is less than 1.8, and the glass transition temperature Tg is more than or equal to 115 ℃.
  2. 2. A process for preparing a polybrominated dichlorobutadiene polymer according to claim 1, characterized in that, S1, reacting 2, 3-dichloro-1, 3-butadiene with bromine at a temperature of between 20 ℃ below zero and 10 ℃ below zero to generate 1, 4-dibromo-2, 3-dichloro-2-butene monomer; S2, polymerizing the 1, 4-dibromo-2, 3-dichloro-2-butene monomer in the presence of a catalyst at a temperature of 50-80 ℃ to obtain the polybrominated dichlorobutadiene polymer.
  3. 3. A process for preparing a polybrominated dichlorobutadiene polymer according to claim 2, In the step S1, the molar ratio of the 2, 3-dichloro-1, 3-butadiene to the bromine is 1:1-1:1.1.
  4. 4. A process for preparing a polybrominated dichlorobutadiene polymer according to claim 2, The catalyst in the step S2 is one or a mixture of Ni (naph) 2 /AlEt 2 Cl and lauroyl peroxide.
  5. 5. A process for preparing a polybrominated dichlorobutadiene polymer according to claim 2, The reaction conditions in step S2 are 8 hours at 60 ℃,4 hours at 70 ℃ or 1 hour at 80 ℃.
  6. 6. The high-strength heat-resistant adhesive is characterized by comprising a component A and a component B, wherein: The component A comprises the following raw materials in parts by mass: 100 parts of the polybrominated dichlorobutadiene polymer of claim 1; 15-25 parts of zinc oxide; 0.5-2 parts of antioxidant; 100-300 parts of a solvent; the component B is phenolic resin.
  7. 7. The high-strength heat-resistant adhesive according to claim 6, wherein the mass of the phenolic resin of the B-component is 4 to 10% of the total mass of the A-component.
  8. 8. The high-strength heat-resistant adhesive according to claim 6, wherein the zinc oxide in the component A is nano zinc oxide with the particle size of 20-50nm, and the antioxidant is hindered phenol antioxidant 1010.
  9. 9. The high-strength heat-resistant adhesive according to claim 6, wherein the solvent is a mixed solvent of cyclohexane and ethyl acetate in a mass ratio of 1:1, and the viscosity of the adhesive is controlled to be 1500-3000 mPa s.
  10. 10. The use of a high strength heat resistant adhesive as claimed in any one of claims 6 to 9, wherein the adhesive is for rubber-metal bonding.

Description

High-strength heat-resistant adhesive based on polybrominated dichlorobutadiene and preparation method thereof Technical Field The invention belongs to the technical field of high polymer adhesives, and particularly relates to a polychloroprene derivative with a main chain containing bromine/chlorine double functional groups and application of the polychloroprene derivative as a high-temperature stable adhesive in the fields of rubber-metal adhesion, conveyor belt repair, aerospace composite materials and the like. Background The disclosure of this background section is only intended to increase some understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art. The traditional neoprene adhesive has low price and strong applicability, is one of the most widely used synthetic rubber adhesives at present, and can be also used in the industries of automobiles, furniture, buildings, machinery and the like. However, the traditional neoprene adhesive has 50 percent of peel strength attenuation under the environment of more than 80 ℃ and is easy to lose effectiveness under long-term heat load. Although the flame-retardant adhesive has good high temperature resistance, the flame-retardant adhesive depends on additives (such as decabromodiphenyl ether) to cause phase separation or mechanical property reduction. Disclosure of Invention In order to improve the temperature resistance of the neoprene adhesive, the invention provides a high-strength heat-resistant adhesive based on polybrominated dichlorobutadiene and a preparation method thereof. The molecular dual-halogen synergistic structure is designed, bromine (C-Br bond energy 238 kJ/mol) provides gas-phase flame retardance and free radical capture, chlorine (C-Cl bond energy 339 kJ/mol) enhances the carbon forming rate and high-temperature crosslinking activity of a carbon layer, and the self-flame-retardant adhesive replaces an external flame retardant with main resin to solve migration and compatibility problems. The technical scheme adopted by the invention is as follows: In a first aspect of the invention, there is provided a polybrominated dichlorobutadiene polymer having a polymerized unit consisting of [ (CHBr-C (Cl) =C (Cl) -CHBr- ] n ], a bromine content of 24.6 to 49.7wt%, a chlorine content of 29.4 to 43.7wt%, a number average molecular weight M n of 15,000 to 50,000g/mol, a molecular weight distribution PDI of less than 1.8, and a glass transition temperature Tg of not less than 115 ℃. The bromine content of the polymer is 24.6-49.7wt% and the chlorine content is 29.4-43.7wt%, the PDI is less than 1.8, the rheological property of the solution is optimized, the glass transition temperature Tg is more than or equal to 115 ℃, and the high-temperature dimensional stability is ensured. Preferably, the bromine content is 38-45wt% and the chlorine content is 32-38wt%. In a second aspect of the present invention, there is provided a process for preparing the polybrominated dichlorobutadiene polymer, the process comprising the steps of: S1, reacting 2, 3-dichloro-1, 3-butadiene with bromine at a temperature of between 20 ℃ below zero and 10 ℃ below zero to generate 1, 4-dibromo-2, 3-dichloro-2-butene monomer; S2, polymerizing the 1, 4-dibromo-2, 3-dichloro-2-butene monomer in the presence of a catalyst at a temperature of 50-80 ℃ to obtain the polybrominated dichlorobutadiene polymer. Preferably, the molar ratio of 2, 3-dichloro-1, 3-butadiene to bromine in step S1 is 1:1 to 1:1.1, more preferably 1:1.05. Preferably, the catalyst in step S2 is one or a mixture of several of Ni (naph) 2/AlEt2 Cl, lauroyl peroxide, etc. Preferably, the reaction conditions in step S2 are reaction at 60 ℃ for 8 hours, at 70 ℃ for 4 hours or at 80 ℃ for 1 hour. In a third aspect of the present invention, there is provided a high strength heat resistant adhesive consisting of a component a and a component B, wherein: The component A comprises the following raw materials in parts by mass: 100 parts of the polybrominated dichlorobutadiene polymer; 15-25 parts of zinc oxide; 0.5-2 parts of antioxidant; 100-300 parts of a solvent; the component B is phenolic resin. Preferably, the mass of the phenolic resin of the B component is 4-10% of the total mass of the A component. Preferably, the zinc oxide in the component A is nano zinc oxide, and the particle size of the nano zinc oxide is 20-50nm. The purpose of zinc oxide addition is to promote the catalysis of the crosslinking of the AB component. Preferably, the antioxidant is a hindered phenolic antioxidant 1010. Preferably, the solvent is a mixed solvent of cyclohexane and ethyl acetate according to a mass ratio of 1:1, and the viscosity of the adhesive is controlled to be 1500-3000 mPa s. The design principle is that the component B activates hydroxymethyl to react wit