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CN-121974804-A - Plant-based plasticizer, continuous flow process production method and application thereof

CN121974804ACN 121974804 ACN121974804 ACN 121974804ACN-121974804-A

Abstract

The invention discloses a plant-based plasticizer and a continuous flow process production method and application thereof. The plant-based plasticizer provided by the invention can be used as a plasticizer for rubber compositions, so that the Mooney viscosity of the rubber compositions can be obviously reduced, the processability can be improved, and the scorching time, the vulcanizing efficiency and the strength of the rubber compositions can be obviously improved. Meanwhile, the modified plant-based plasticizer is prepared by adopting a continuous flow process, so that the production safety can be obviously improved, the efficiency of the epoxidation reaction and the consistency of products are improved, and the method is suitable for large-scale production.

Inventors

  • YAO QIANYU
  • LI HAI
  • PENG HUALONG
  • YAO XIANG
  • WANG JIE

Assignees

  • 江苏麒祥高新材料有限公司

Dates

Publication Date
20260505
Application Date
20251224

Claims (10)

  1. 1. A plant-based plasticizer comprising at least one of the following structures: (1) Wherein R 2 is a phenolic hydroxyl protecting group and is any one of acyl, alkyl, aralkyl, tetrahydropyranyl, methoxymethyl, alkoxycarbonyl, silane and hydroxyalkyl.
  2. 2. A continuous flow process production method of a plant-based plasticizer according to claim 1, characterized in that either of the following two methods is used: the method one comprises the following steps: S1, mixing cardanol capped by phenolic hydroxyl and an oxygen carrier to obtain a cardanol phase, and then starting a cardanol phase feeding pump and a hydrogen peroxide phase feeding pump to enable two materials to stably enter a first continuous flow reactor; s2, directly separating liquid after discharging the materials in the step S1 from the first continuous flow reactor, treating water phase wastewater, pumping an oil phase into the second continuous flow reactor, continuously washing with water, separating water after discharging, and removing residual volatile solvent in vacuum to obtain the plant-based plasticizer; The second method comprises the following steps: s1, starting an oxygen carrier phase feeding pump and a hydrogen peroxide phase feeding pump to enable two materials to stably enter a first continuous flow reactor; s2, pumping the material obtained in the step S1 from the first continuous flow reactor into a second continuous flow reactor, and simultaneously starting a cardanol phase feeding pump capped by phenolic hydroxyl groups to pump the material into the second continuous flow reactor; s3, directly separating liquid after discharging the materials from the second continuous flow reactor, treating water phase wastewater, pumping an oil phase into a third continuous flow reactor for continuous water washing, separating water after discharging, and removing residual volatile solvent in vacuum to obtain the plant-based plasticizer; The preparation method of the phenolic hydroxyl terminated cardanol comprises the following steps: Adding cardanol into a reaction kettle, adding a catalyst, then adding a modifier, heating for reaction, and then obtaining the cardanol with the end capped by phenolic hydroxyl groups through distillation, extraction and water washing.
  3. 3. The continuous flow process production method according to claim 2, wherein the temperature of the first continuous flow reactor in the first method is controlled to be 40-100 ℃, and the temperature of the first continuous flow reactor in the second method is controlled to be 20-60 ℃.
  4. 4. The continuous flow process production method according to claim 2, wherein the molar ratio of cardanol, modifier and catalyst is 1 (1.05-2): 0.01-2.
  5. 5. The continuous flow process production method according to claim 2, wherein the molar ratio of the phenolic hydroxyl terminated cardanol to the oxygen carrier to the hydrogen peroxide is 1 (0.1-1.0): 1.5-4.
  6. 6. The continuous flow process production method according to claim 2, wherein the mass concentration of the hydrogen peroxide is 10% -75%.
  7. 7. The continuous flow process production method of claim 2, wherein the oxygen carrier is any one or more of formic acid, acetic acid, propionic acid, benzoic acid, chlorobenzoic acid, trichloroacetic acid or trifluoroacetic acid.
  8. 8. The continuous flow process production method according to claim 2, wherein the modifier is any one of acid anhydride compounds, carbonic ester compounds, acyl chloride compounds, halogenated hydrocarbon compounds, silane compounds, sulfuric ester compounds, sulfonic ester compounds, 3, 4-dihydropyran and methoxymethyl chloride.
  9. 9. The continuous flow process production method of claim 2, wherein the cardanol has the structural formula: (2) Wherein r=c 15 H 31-2n , n=0-3.
  10. 10. Use of the plant-based plasticizer according to claims 1 to 9 in rubber processing.

Description

Plant-based plasticizer, continuous flow process production method and application thereof Technical Field The invention relates to the technical field of rubber and plastic industry, in particular to a plant-based plasticizer, a continuous flow process production method and application thereof. Background Plasticizers play an important role in the rubber and plastic industry, mainly for improving the processability, ductility and flexibility of rubber and plastic materials. With the increasing strictness of environmental protection requirements, conventional petroleum-based plasticizers are increasingly facing dual challenges of safety and environmental protection. Thus, the growing market demand for green, sustainable plasticizers has prompted researchers to explore more plasticizers of natural origin and environmental protection. Compatibility, processability, ductility, flexibility and other special application properties of rubber and plastic products are often improved by chemical means, such as the addition of plasticizers, e.g., polyvinyl chloride materials having glass transition temperatures above room temperature, which are used to modify the glass-like brittleness characteristics at room temperature and improve processing and application properties. Cashew oil is a low-cost and widely-available natural vegetable oil, and has a main structure of Cardanol (Cardanol), and the structure of Cardanol (Cardanol) contains phenolic hydroxyl groups and saturated and unsaturated side chains, and is usually used as a plasticizer of rubber, but has limited improvement effect on various properties of the rubber. At present, the cardanol is subjected to epoxidation to improve the performance of the cardanol, the traditional epoxidation process is mostly carried out by adopting an intermittent process, but no matter what oxidant or catalyst is adopted, the cardanol is subjected to epoxidation through a kettle reaction, the problems of long reaction time, inaccurate temperature and pressure control and the like exist, the uniformity of products is poor, the industrial mass production is not suitable, and more importantly, the safety risk is high due to the large accumulation of peroxide in the intermittent process. Therefore, there is a need to develop a continuous flow production process capable of safely carrying out cardanol modification, and guaranteeing the stability and safety of production and the stability of plant-based plasticizers. Disclosure of Invention In order to overcome the defects in the prior art, the invention provides a plant-based plasticizer, a continuous flow process production method and application thereof, and the prepared plasticizer is of a bio-based source, is safe, environment-friendly and resistant to migration, has an ageing-delaying effect on halogen-containing polymer materials, and improves the efficiency of an epoxidation reaction and the consistency of products. The invention provides a plant-based plasticizer, which comprises at least one of the following structures: (1) Wherein R 2 is a phenolic hydroxyl protecting group, which is any one of acyl, alkyl, aralkyl, tetrahydropyranyl, methoxymethyl, alkoxycarbonyl, silane and hydroxyalkyl, and R 1 is fifteen carbon chains after partial or complete epoxidation of cardanol side chain double bonds. According to the invention, the cardanol hydroxyl is subjected to end capping treatment, and then the side chain double bonds of the cardanol hydroxyl are subjected to epoxidation to a certain degree to obtain an epoxidized plant-based plasticizer product, so that the prepared epoxidized plasticizer is safe and environment-friendly, has good extraction resistance and migration resistance, and contains epoxy groups which can absorb hydrogen chloride generated by degradation of polyvinyl chloride under the action of light, heat and the like, so that further degradation under the catalysis of the hydrogen chloride is prevented, and the service life of the epoxidized plant-based plasticizer is prolonged. When the rubber is used as a rubber plasticizer, the viscosity of the rubber can be reduced, the flowability of the rubber can be improved, the hardness and the wear resistance of the rubber can be improved to a certain extent, the vulcanization time of the rubber composite material is shortened, the vulcanization crosslinking density is increased, meanwhile, the Mooney viscosity is reduced, the processing of the rubber is facilitated, the tensile strength and the breaking elongation are obviously improved, the wear resistance and the rebound resilience are enhanced under a low load, and the rolling resistance of the tire can be improved. The synthetic route of the plant-based plasticizer in the invention is as follows; Wherein (A) is cardanol, R is a natural cardanol side chain containing fifteen saturated or unsaturated carbons, the molecular formula is C 15H31-2n,n=0, 1, 2, 3;R2 -X, R 2 is a phenolic hydroxyl protecting group, and is a