CN-122011350-A - Flame-retardant-plasticizing environment-friendly plasticizer for polyvinyl chloride and preparation method thereof

Abstract

The invention provides a preparation method and application of a flame-retardant-plasticizing-self-repairing type polyester plasticizer for polyvinyl chloride, and belongs to the technical field of high-molecular functional materials and polyvinyl chloride modification. The method uses dibasic acid and dihydric alcohol as basic raw materials, and the main chain of polyester is constructed through esterification and polycondensation reaction under the action of a catalyst, and a phosphorus-nitrogen flame-retardant structural unit and a reversible disulfide bond structure are cooperatively constructed in polyester molecules by introducing a dibasic acid monomer containing DOPO-hydrazide structure and 4,4' -diaminodiphenyl disulfide. The molecular structure of the obtained polyester plasticizer simultaneously has a flexible aliphatic chain segment, an internal flame retardant group and a dynamic reversible covalent bond, and has good plasticizing performance, flame retardant performance and structural reconstruction capability. When the plasticizer is used in a blending way with the polyvinyl chloride resin, the flame-retardant safety of the plasticizer can be improved while the flexibility and the processing performance of the material are maintained, and the rearrangement and the self-repairing of the microstructure are realized under the heating condition, so that the plasticizer is suitable for the field of polyvinyl chloride materials with comprehensive requirements on flame retardance, flexibility and service stability.

Inventors

• GAO CHUANHUI
• XU NANNAN
• ZHANG NA
• WANG CHUANXING
• LIU YUETAO

Assignees

• 青岛科技大学
• 山东万图高分子材料股份有限公司

Dates

Publication Date

20260512

Application Date

20260106

Claims (10)

1. 1. A method for preparing a flame retardant-plasticizing-self-healing polyester plasticizer for polyvinyl chloride, comprising: In the presence of an esterification catalyst and a blocking agent, at least one dibasic acid and dihydric alcohol are subjected to esterification reaction, and after the reaction is finished, the dibasic acid containing DOPO-hydrazide structure and 4,4' -diaminodiphenyl disulfide are added, and the temperature is raised for decompression polycondensation reaction, so that the polymer is obtained.
2. 2. The method for preparing the flame retardant-plasticizing-self-repairing type polyester plasticizer for polyvinyl chloride according to claim 1, wherein the molar ratio of the dibasic acid to the dihydric alcohol is 1:0.5-1.3.
3. 3. The method of preparing a flame retardant-plasticizing-self healing polyester plasticizer for polyvinyl chloride according to claim 1, wherein the dibasic acid is selected from one or more of adipic acid, azelaic acid, sebacic acid, and mixtures thereof; Or, the dihydric alcohol is selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol and 2, 4-trimethyl-1, 3-pentanediol.
4. 4. The method for preparing a flame retardant-plasticizing-self-repairing type polyester plasticizer for polyvinyl chloride according to claim 1, wherein the esterification catalyst is phosphoric acid, p-toluenesulfonic acid or tetrabutyl titanate; Or the addition amount of the esterification catalyst is 0.05-0.3wt% of the total mass of the dibasic acid and the dihydric alcohol; Or, the end-capping agent is 2-ethylhexanol; or the mole ratio of the end capping agent to the dibasic acid is 0.05-0.4:1.
5. 5. The method for preparing a flame retardant-plasticizing-self-repairing type polyester plasticizer for polyvinyl chloride according to claim 1, wherein the amount of the dibasic acid containing DOPO-hydrazide structure is 8 to 20mol% based on the total acid equivalent.
6. 6. The method for preparing a flame retardant-plasticizing-self-repairing type polyester plasticizer for polyvinyl chloride according to claim 1, wherein the amount of 4,4' -diaminodiphenyl disulfide is 2 to 8mol% based on the equivalent of carboxyl group.
7. 7. The method for preparing the flame-retardant, plasticizing and self-repairing type polyester plasticizer for polyvinyl chloride according to claim 1 is characterized in that the method for preparing the dibasic acid containing DOPO-hydrazide structure comprises the steps of adding DOPO and itaconic acid, maleic acid or fumaric acid to obtain phosphorus-containing dibasic acid, and then carrying out condensation reaction with diamine compound ethylenediamine to obtain the flame-retardant, plasticizing and self-repairing type polyester plasticizer.
8. 8. The method for preparing a flame retardant-plasticizing-self-repairing type polyester plasticizer for polyvinyl chloride according to claim 1, wherein the esterification reaction condition is 150-160 ℃ for 3-4 hours; or the condition of the decompression polycondensation reaction is that the decompression polycondensation is carried out for 1.5-2h at 180-190 ℃.
9. 9. A flame retardant-plasticizing-self-healing polyester plasticizer prepared by the process of any of claims 1-8.
10. 10. Use of the flame retardant-plasticising-self-repairing polyester plasticiser according to claim 9 for the preparation of PVC material.

Description

Flame-retardant-plasticizing environment-friendly plasticizer for polyvinyl chloride and preparation method thereof Technical Field The invention belongs to the technical field of polymer material additives and polyvinyl chloride (PVC) modification, and relates to a flame-retardant-plasticizing environment-friendly plasticizer for polyvinyl chloride and a preparation method thereof. Background The disclosure of this background section is only intended to increase the 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. Polyvinyl chloride (PVC) is widely applied to the fields of wires and cables, architectural decorations, traffic decorations, films, hoses and the like because of the advantages of low cost, good chemical corrosion resistance, good processability and the like. To meet the performance requirements of flexible articles during molding and use, it is often necessary to incorporate plasticizers into the PVC system to lower the glass transition temperature and increase the flexibility and processability of the material. At present, most of commonly used plasticizers are phthalate esters or citrate esters small molecular compounds, the plasticizers are easy to be separated out or migrate in the use process, and the plasticizers can cause the decrease of flexibility, the decay of mechanical properties and the low use stability of materials under the actions of heat aging, long-term load or external media. Meanwhile, a part of small molecular plasticizers have a certain environmental and health safety disputes in practical application, and the application of the small molecular plasticizers in the field of high safety requirements is limited. On the other hand, the flexible PVC has higher requirements on flame retardant property in application scenes such as cable protection, aviation interior decoration and the like. Although PVC itself has certain flame retardant properties, plasticizers and adjuvants introduced during plasticization can adversely affect the flame retardant properties of the system. At present, flame retardant modification is usually carried out on PVC by an additive type flame retardant, but the method has the problems of large addition amount, limited compatibility with a matrix, easy migration, influence on the mechanical property and processing stability of the material and the like, so that the improvement of the comprehensive performance of the material is restricted to a certain extent. Based on the above problems, a research idea of reactive plasticizer in which a flame retardant unit and a plasticizing structure are integrally designed has been developed in recent years in order to improve flame retardant properties while maintaining flexibility of materials. However, there are still common disadvantages in that the synthetic route is complicated, the cost is high, or the plasticization efficiency is reduced due to the introduction of the rigid flame retardant structure. In addition, even if the flame retardant and plasticizing performance are combined, microcracks and structural damage of the flexible PVC caused by repeated bending, plugging or assembly stress in the actual service process are still difficult to effectively relieve. Under the conditions of thermal aging and continuous loading, the microscopic defects are prone to gradually expanding and evolving into macroscopic failures, which are manifested by reduced material strength, reduced elongation and even early failure. The existing method for improving the crosslinking degree or introducing the repairing component often has adverse effects on the processing performance and the system stability of the material, and is difficult to consider the flexibility, the flame retardance and the long-term service reliability. Therefore, there is a need to develop a functionalized plasticizer capable of simultaneously achieving plasticization, flame retardance and self-repairing functions in a PVC system, so as to improve flame retardance safety and long-term service stability of the material while maintaining processability and flexibility of the material. Disclosure of Invention The invention aims to solve the problems that the existing plasticizer system for polyvinyl chloride has single function, flame retardant property and flexibility are difficult to be compatible, damage generated in the service process of the material is difficult to recover, and the like, and provides a preparation method and application of a polyester plasticizer with flame retardant, plasticizing and self-repairing functions. In order to achieve the above purpose, the present invention adopts the following technical scheme: in a first aspect of the present invention, there is provided a method for preparing a flame retardant-plasticizing-self-repairing type polyester p