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CN-120775352-B - Environment-friendly dicyclopentadiene polymeric material and preparation method thereof

CN120775352BCN 120775352 BCN120775352 BCN 120775352BCN-120775352-B

Abstract

The invention relates to the technical field of dicyclopentadiene polymerization, in particular to an environment-friendly dicyclopentadiene polymerization material which is prepared from the following raw materials in parts by weight: according to the DCPD polymer provided by the invention, the modified lignin which is a raw material prepared based on natural biomass is added in the preparation process, so that the environmental protection performance of the DCPD polymer can be improved, lignin on the modified lignin and aluminum hydroxide are subjected to microwave treatment, and the lignin is partially carbonized, and aluminum hydroxide is partially decomposed to generate aluminum oxide, so that rich pore channels are generated on the surface of the modified lignin, and the pore channels can absorb free DCPD in the DCPD polymer, thereby reducing the release probability of the DCPD, further reducing the peculiar smell of the product and further improving the environmental protection performance of the product.

Inventors

  • ZHANG FULONG

Assignees

  • 旭景新材料科技(常州)有限责任公司

Dates

Publication Date
20260508
Application Date
20250707

Claims (8)

  1. 1. The environment-friendly dicyclopentadiene polymer material is characterized by being prepared from the following raw materials, by weight, 80-90 parts of dicyclopentadiene, 0.003-0.05 part of a catalyst, 1-3.5 parts of an activating agent, 20-30 parts of a regulator and 8-12 parts of modified lignin; The preparation method of the modified lignin comprises the following steps of a, dissolving lignin in a sodium hydroxide solution, slowly dropwise adding an aluminum salt solution into the lignin solution, stirring at a high speed, adjusting the pH value of the solution to 7-9 after the dropwise adding of the aluminum salt solution is completed, hydrolyzing aluminum ions to generate aluminum hydroxide, standing and aging for 2-4 hours after the reaction is completed, filtering, washing and drying to obtain lignin loaded with aluminum hydroxide, b, stirring the lignin loaded with aluminum hydroxide at a high speed by adopting a mixer, diluting a silane coupling agent with ethanol, spraying the diluted lignin into the lignin loaded with aluminum hydroxide which is stirred at a high speed, continuing stirring for 30-60 minutes, controlling the temperature to 50-80 ℃, standing and curing for 2-4 hours after the stirring is completed, and performing microwave treatment to obtain the modified lignin.
  2. 2. The environment-friendly dicyclopentadiene polymer material according to claim 1, wherein in the preparation process of the modified lignin, the mass ratio of lignin to aluminum in aluminum salt is 8-15:1, the mass ratio of lignin to silane coupling agent is 6-12:1, the concentration of sodium hydroxide solution is 0.5-2mol/L, and the mass ratio of silane coupling agent to ethanol is 1:0.3-1.5.
  3. 3. The environmentally friendly dicyclopentadiene polymer material according to claim 2, wherein the aluminum salt is one of aluminum nitrate and aluminum chloride, and the silane coupling agent is one of KH550 and KH 570.
  4. 4. The environment-friendly dicyclopentadiene polymer material according to claim 2, wherein in the step a, the rotation speed of high-speed stirring is 800-1000r/min, in the step b, the rotation speed of high-speed stirring is 1200-1500r/min, in the step b, the microwave reaction power is 50-1000W, and the microwave treatment time is 10-15 seconds.
  5. 5. The environment-friendly dicyclopentadiene polymer material according to claim 1, wherein the activator is a mixture of diethyl aluminum chloride and diethyl zinc, and the mass ratio of diethyl aluminum chloride to diethyl zinc is 1:1.5-3.
  6. 6. The environment-friendly dicyclopentadiene polymer material according to claim 1, wherein the regulator is a mixture of diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, and the mass ratio of the diethylene glycol dimethyl ether to the diethylene glycol dibutyl ether is 1:0.3-1.
  7. 7. The environment-friendly dicyclopentadiene polymerization material according to claim 1, wherein the catalyst comprises a main catalyst and a cocatalyst, the main catalyst is a ruthenium catalyst, the cocatalyst is triethylamine, and the mass ratio of the main catalyst to the cocatalyst is 1:20-30.
  8. 8. A method for preparing the environment-friendly dicyclopentadiene polymer material according to any one of claims 1 to 7, comprising the steps of: step 1, accurately weighing all raw materials, and uniformly mixing dicyclopentadiene, a regulator and modified lignin to obtain a mixture; step 2, dividing the mixture into two parts, adding a catalyst into the first part, uniformly mixing, and marking the mixture as a component A, adding an activating agent into the first part, uniformly mixing, and marking the mixture as a component B; And 3, impacting and mixing the component A and the component B in a RIM machine head, controlling the material temperature to be 20-40 ℃ and the pressure to be 3.0MPa, and injecting into a die preheated to 40-60 ℃ to finish polymerization and solidification.

Description

Environment-friendly dicyclopentadiene polymeric material and preparation method thereof Technical Field The invention relates to the technical field of dicyclopentadiene polymerization, in particular to an environment-friendly dicyclopentadiene polymerization material and a preparation method thereof. Background The DCPD polymer prepared by polymerization reaction of dicyclopentadiene (DCPD) is a novel engineering plastic, and the DCPD is polymerized under the action of a ring-opening metathesis catalyst, and has the characteristics of good heat resistance, creep resistance, dimensional stability, corrosion resistance, abrasion resistance and the like. At present, a catalyst system for preparing dicyclopentadiene polymerization comprises tungsten-molybdenum complexes or a carbene catalyst of molybdenum and ruthenium, and the adopted process is a Reaction Injection Molding (RIM) process, so that the catalyst system has the advantages of high molding speed, high efficiency, low energy consumption and the like, and can be used for manufacturing various large-sized thin-wall products with complex shapes. The DCPD polymer processed and formed by the RIM technology has excellent mechanical property, thermal stability, ageing resistance and the like, and can be widely applied to the aspects of automobile parts, industrial equipment, medical appliances and the like. The existing DCPD polymer can release a certain peculiar smell in the use process, and the main reason for the peculiar smell is that the DCPD is not completely reacted, the residual monomers volatilize and generate the peculiar smell, and the flame retardant effect of the existing DCPD polymer is not ideal. Therefore, we propose an environment-friendly dicyclopentadiene polymer material and a preparation method thereof for solving the problems. Disclosure of Invention The invention aims to solve the defects in the prior art, and provides an environment-friendly dicyclopentadiene polymer material and a preparation method thereof. An environment-friendly dicyclopentadiene polymer material is prepared from the following raw materials, by weight, 80-90 parts of dicyclopentadiene, 0.003-0.05 part of a catalyst, 1-3.5 parts of an activating agent, 20-30 parts of a regulator and 8-12 parts of modified lignin. The preparation method of the modified lignin comprises the following steps of a, dissolving lignin in a sodium hydroxide solution, slowly dropwise adding an aluminum salt solution into the lignin solution, stirring at a high speed, adjusting the pH value of the solution to 7-9 after the dropwise adding of the aluminum salt solution is completed, hydrolyzing aluminum ions to generate aluminum hydroxide, standing and aging for 2-4 hours after the reaction is completed, filtering, washing and drying to obtain the lignin loaded with aluminum hydroxide, b, stirring the lignin loaded with aluminum hydroxide at a high speed by adopting a mixer, diluting a silane coupling agent by ethanol, spraying the diluted lignin coupling agent into the lignin loaded with aluminum hydroxide stirred at a high speed, continuing stirring for 30-60 minutes, controlling the temperature to 50-80 ℃, standing and curing for 2-4 hours after the stirring is completed, and carrying out microwave treatment to obtain the modified lignin. Preferably, in the preparation process of the modified lignin, the mass ratio of lignin to aluminum in aluminum salt is 8-15:1, the mass ratio of lignin to silane coupling agent is 6-12:1, the concentration of sodium hydroxide solution is 0.5-2mol/L, and the mass ratio of silane coupling agent to ethanol is 1:0.3-1.5. Preferably, the aluminum salt is one of aluminum nitrate or aluminum chloride, and the silane coupling agent is one of KH550 or KH 570. Preferably, in the step a, the rotating speed of high-speed stirring is 800-1000r/min, in the step b, the rotating speed of high-speed stirring is 1200-1500r/min, in the step b, the microwave reaction power is 50-1000W, and the microwave treatment time is 10-15 seconds. Preferably, the activator is a mixture of diethyl aluminum chloride and diethyl zinc, and the mass ratio of the diethyl aluminum chloride to the diethyl zinc is 1:1.5-3. Preferably, the regulator is a mixture of diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, and the mass ratio of the diethylene glycol dimethyl ether to the diethylene glycol dibutyl ether is 1:0.3-1. Preferably, the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is a ruthenium catalyst, the cocatalyst is triethylamine, and the mass ratio of the main catalyst to the cocatalyst is 1:20-30. Preferably, the preparation method of the environment-friendly dicyclopentadiene polymer material comprises the following steps: step 1, accurately weighing all raw materials, and uniformly mixing dicyclopentadiene, a regulator and modified lignin to obtain a mixture; step 2, dividing the mixture into two parts, adding a catalyst into t