阅读说明：本技术 一种防霉塑料及其制备方法 (Mildew-proof plastic and preparation method thereof ) 是由 魏刚印 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种防霉塑料的制备方法,其特征在于,包括如下步骤：步骤S1、双羧基硫羰基二咪唑中间产物的制备；步骤S2、苯砜基硫羰基二咪唑盐类聚酰胺的制备；步骤S3、注塑成型。本发明还提供了一种根据所述一种防霉塑料的制备方法制备得到的防霉塑料。本发明公开的防霉塑料抗菌防霉效果显著,综合性能和性能稳定性佳,耐老化性能和机械力学性能好,使用寿命长。(The invention discloses a preparation method of a mildew-proof plastic, which is characterized by comprising the following steps: step S1, preparing a dicarboxyl thiocarbonyl diimidazole intermediate product; step S2, preparing phenyl sulfone group thiocarbonyl diimidazole salt polyamide; and step S3, injection molding. The invention also provides the mildewproof plastic prepared by the preparation method of the mildewproof plastic. The mildew-proof plastic disclosed by the invention has the advantages of obvious antibacterial and mildew-proof effects, good comprehensive performance and performance stability, good aging resistance and mechanical properties and long service life.)

1. The preparation method of the mildew-proof plastic is characterized by comprising the following steps:

step S1, preparation of a dicarboxylthiocarbonyldiimidazole intermediate: adding N, N' -thiocarbonyl diimidazole and 3-chloropropionic acid into an organic solvent, refluxing and stirring at 40-60 ℃ for reaction for 4-6 hours, then performing rotary evaporation to remove the solvent, washing the product with diethyl ether for 3-6 times, and then performing rotary evaporation to remove residual diethyl ether to obtain a dicarboxyl thiocarbonyl diimidazole intermediate product;

step S2, preparing the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide: adding the dicarboxyl thiocarbonyl diimidazole intermediate product prepared in the step S1, 4' -diaminodiphenyl sulfone, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a high boiling point solvent to obtain a reaction liquid, then transferring the reaction liquid into a reaction kettle, replacing the air in the kettle with inert gas, and reacting at 160-180 ℃ for 1-3 hours at normal pressure; heating to 230 ℃ for primary polycondensation reaction for 6-8 hours; vacuumizing to 500Pa, heating to 240-260 ℃, performing polycondensation reaction for 8-12 hours, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 3-7 times, and performing rotary evaporation to remove the ethanol to obtain the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide;

step S3, injection molding: and (4) uniformly mixing the phenylsulfonyl dicarbonyl diimidazole salt polyamide prepared in the step (S2), ABS resin, garlicin, an initiator, tea polyphenol, a plasticizer and 2, 3-dimercaptosuccinic acid to obtain a mixed material, and then putting the mixed material into an injection molding machine for injection molding to obtain a finished product of the mildewproof plastic.

2. The method for preparing the mildewproof plastic of claim 1, wherein the molar ratio of the N, N' -thiocarbonyldiimidazole, the 3-chloropropionic acid and the organic solvent in the step S1 is 1:2 (9-15).

3. The method for preparing the mildewproof plastic according to claim 1, wherein the organic solvent is any one of tetrahydrofuran, dichloromethane and toluene.

4. The method for preparing mildewproof plastic according to claim 1, wherein the molar ratio of the biscarboxylthiocarbonyldiimidazole intermediate, the 4,4' -diaminodiphenyl sulfone, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the 4-dimethylaminopyridine and the high boiling point solvent in the step S2 is 1:1 (0.8-1.2) to 0.5 (6-10).

5. The method for preparing a mildewproof plastic according to claim 1, wherein the high boiling point solvent is at least one of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.

6. The method for preparing a mold-proof plastic according to claim 1, wherein the mass ratio of the phenylsulfonyl dicarbonyl diimidazole salt polyamide, the ABS resin, the allicin, the initiator, the tea polyphenol, the plasticizer and the 2, 3-dimercaptosuccinic acid in step S3 is (15-25): 55-65): 3-6): 1-2): 3-5): 4-8): 3.

7. The method for preparing a mildewproof plastic according to claim 1, wherein the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, lauroyl peroxide and tert-butyl peroxybenzoate.

8. The method for preparing the mildewproof plastic according to claim 1, wherein the plasticizer is at least one of epoxidized soybean oil and tributyl citrate.

9. The method for preparing the mildewproof plastic according to claim 1, wherein the injection molding is carried out by a screw injection molding machine, and during the injection molding, the heating temperature of the first section of the screw is 175-185 ℃, the heating temperature of the second section of the screw is 190-205 ℃, the heating temperature of the third section of the screw is 210-220 ℃, and the heating temperature of the die head is 225-235 ℃.

10. A mildewproof plastic prepared by the method for preparing the mildewproof plastic according to any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of plastics, in particular to a mildew-proof plastic and a preparation method thereof.

Background

In recent years, with the progress of society and the development of polymer material synthesis technology, polymer materials represented by plastics play more and more important roles in daily life of people, and products made of the polymer materials bring convenience to the life of people and become one of important marks of the development degree of modern civilization. The plastic products become a part of people's life, so that the application of the plastic cannot be separated from the life of modern people.

Plastics are one kind of synthetic high molecular compound, which is a material obtained by using monomer raw materials through synthesis or condensation reaction polymerization, and consists of synthetic resin, fillers, plasticizers, stabilizers, lubricants, pigments and other additives. Plastics are inherently very stable and do not deteriorate with microorganisms. However, it is actually attacked by microorganisms, and it is easy to become a hotbed for the microorganisms to reproduce as long as it has three elements of temperature, humidity and nutrition, which limits its wide application. How to effectively improve the antibacterial and mildew resistance of plastics is a difficult problem to be solved urgently in the industry.

The existing method for improving the antibacterial and mildew-proof performance of plastics is mainly to add an antibacterial and mildew-proof agent into the plastics. The method has the defects of poor performance stability and further improvement of the antibacterial and mildewproof effects. In addition, the antibacterial and mildewproof plastic on the market has the defects of poor comprehensive performance, short service life and poor aging resistance.

For example, the Chinese patent application No. 201310246603.5 discloses a mildew-proof plastic, which comprises a plastic body, a plasticizer and a mildew-proof material, wherein the plasticizer is tributyl citrate, the plastic body accounts for 32-48% of the mildew-proof plastic by mass, the plasticizer accounts for 45-60% of the mildew-proof plastic by mass, and the mildew-proof material accounts for 7-8% of the mildew-proof plastic by mass. The invention provides the mildew-proof plastic which has the advantages of no toxicity, no harm, antibiosis and mildew resistance. However, the mildew-proof materials of the plastics can seep out of the plastics in the long-term use process, the performance stability is influenced, and the service life of the plastics is shortened.

Therefore, the development of the mildew-proof plastic with remarkable antibacterial and mildew-proof effects, good comprehensive performance and performance stability, good aging resistance and mechanical property and long service life meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of functional plastics.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a preparation method of a mildew-proof plastic, which is characterized by comprising the following steps:

step S1, preparation of a dicarboxylthiocarbonyldiimidazole intermediate: adding N, N' -thiocarbonyl diimidazole and 3-chloropropionic acid into an organic solvent, refluxing and stirring at 40-60 ℃ for reaction for 4-6 hours, then performing rotary evaporation to remove the solvent, washing the product with diethyl ether for 3-6 times, and then performing rotary evaporation to remove residual diethyl ether to obtain a dicarboxyl thiocarbonyl diimidazole intermediate product;

step S2, preparing the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide: adding the dicarboxyl thiocarbonyl diimidazole intermediate product prepared in the step S1, 4' -diaminodiphenyl sulfone, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a high boiling point solvent to obtain a reaction liquid, then transferring the reaction liquid into a reaction kettle, replacing the air in the kettle with inert gas, and reacting at 160-180 ℃ for 1-3 hours at normal pressure; heating to 230 ℃ for primary polycondensation reaction for 6-8 hours; vacuumizing to 500Pa, heating to 240-260 ℃, performing polycondensation reaction for 8-12 hours, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 3-7 times, and performing rotary evaporation to remove the ethanol to obtain the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide;

step S3, injection molding: and (4) uniformly mixing the phenylsulfonyl dicarbonyl diimidazole salt polyamide prepared in the step (S2), ABS resin, garlicin, an initiator, tea polyphenol, a plasticizer and 2, 3-dimercaptosuccinic acid to obtain a mixed material, and then putting the mixed material into an injection molding machine for injection molding to obtain a finished product of the mildewproof plastic.

Preferably, the molar ratio of the N, N' -thiocarbonyldiimidazole, the 3-chloropropionic acid and the organic solvent in the step S1 is 1:2 (9-15).

Preferably, the organic solvent is any one of tetrahydrofuran, dichloromethane and toluene.

Preferably, the molar ratio of the biscarboxylthiocarbonyldiimidazole intermediate, 4' -diaminodiphenyl sulfone, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine and high-boiling solvent in step S2 is 1:1 (0.8-1.2) 0.5 (6-10).

Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.

Preferably, in step S3, the mass ratio of the phenylsulfonyl dicarbonyl diimidazole salt polyamide, the ABS resin, the garlicin, the initiator, the tea polyphenol, the plasticizer and the 2, 3-dimercaptosuccinic acid is (15-25): 55-65): 3-6: (1-2): 3-5): 4-8): 3.

Preferably, the ABS resin is an ABS resin having a model number of AP-163 of LG chemical company, Korea.

Preferably, the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, lauroyl peroxide and tert-butyl peroxybenzoate.

Preferably, the plasticizer is at least one of epoxidized soybean oil and tributyl citrate.

Preferably, the injection molding is carried out by adopting a screw injection molding machine, and during injection molding, the heating temperature of the first section of the screw is 175-185 ℃, the heating temperature of the second section of the screw is 190-205 ℃, the heating temperature of the third section of the screw is 210-220 ℃, and the heating temperature of the die head is 225-235 ℃.

The invention also aims to provide the mildewproof plastic prepared by the preparation method of the mildewproof plastic.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

(1) the preparation method of the mildew-proof plastic provided by the invention has the advantages of simple process, low equipment investment, low energy consumption, high preparation efficiency and high finished product qualification rate, is suitable for continuous large-scale production, and has higher economic value and social value.

(2) The mildew-proof plastic provided by the invention overcomes the defects that the existing mildew-proof plastic has poor performance stability, the antibacterial and mildew-proof effects need to be further improved, the comprehensive performance is poor, the service life is short, and the aging resistance is poor; through the synergistic effect of the components, the prepared plastic has the advantages of remarkable antibacterial and mildewproof effects, good comprehensive performance and performance stability, good aging resistance and mechanical property and long service life.

(3) According to the mildew-proof plastic provided by the invention, the synergistic effect of the thiocarbonyl imidazolium salt structure, the allicin structure and the tea polyphenol structure introduced into the molecular chain of the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide enables the plastic to have excellent antibacterial and mildew-proof properties; the active functional components are connected together by chemical bonds and do not contain inorganic components, so that the processing fluidity is good, and the defects that the performance stability and the service life of plastic products are influenced by phase separation and exosmosis caused by the compatibility problem of the inorganic and organic components are effectively avoided.

(4) The components of the mildew-proof plastic provided by the invention interact and influence each other, so that the prepared plastic has better comprehensive performance and performance stability, wherein the imidazolium salt cation on the phenylsulfonyl-dicarbonyl diimidazole salt polyamide can be connected with the phenolic hydroxyl on the tea polyphenol and the carboxyl on the 2, 3-dimercaptosuccinic acid through ionic bonds; under the action of an initiator, the mercapto group on the 2, 3-dimercaptosuccinic acid can respectively perform click reaction with unsaturated alkene on the molecular chain of the ABS resin and vinyl bonds on the allicin; the vinyl on the allicin can also perform melt grafting reaction with ABS resin under the action of an initiator, so that all components are connected by chemical bonds to form a three-dimensional network structure, the comprehensive performance of the material is effectively improved, and the allicin and the ABS resin have better performance stability, better durability and longer service life.

(5) According to the mildew-proof plastic provided by the invention, through the synergistic effect of the components, the prepared plastic molecular chain not only contains a phenylsulfonyl group, but also contains a thiocarbonyl group, an imidazolyl group, a polyamide group and a cyano group, and the prepared plastic has better aging resistance and mechanical property under the multiple actions of an electronic effect, a steric effect and a conjugate effect.

Detailed Description

In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.

The ABS resin in the examples of the present invention was an ABS resin manufactured by LG chemical company, Korea, model No. AP-163.

Example 1

The preparation method of the mildew-proof plastic is characterized by comprising the following steps:

step S1, preparation of a dicarboxylthiocarbonyldiimidazole intermediate: adding N, N' -thiocarbonyl diimidazole and 3-chloropropionic acid into an organic solvent, refluxing and stirring at 40 ℃ for reaction for 4 hours, then performing rotary evaporation to remove the solvent, washing the product with diethyl ether for 3 times, and then performing rotary evaporation to remove residual diethyl ether to obtain a dicarboxyl thiocarbonyl diimidazole intermediate product;

step S2, preparing the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide: adding the dicarboxyl thiocarbonyl diimidazole intermediate product prepared in the step S1, 4' -diamino diphenyl sulfone, 1-ethyl- (3-dimethyl amino propyl) carbodiimide hydrochloride and 4-dimethylamino pyridine into a high boiling point solvent to obtain a reaction solution, transferring the reaction solution into a reaction kettle, replacing the air in the kettle with inert gas, and reacting for 1 hour at 160 ℃ under normal pressure; heating to 210 ℃, and carrying out primary polycondensation for 6 hours; vacuumizing to 500Pa, heating to 240 ℃, performing polycondensation reaction for 8 hours, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 3 times, and performing rotary evaporation to remove the ethanol to obtain the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide;

step S3, injection molding: and (4) uniformly mixing the phenylsulfonyl dicarbonyl diimidazole salt polyamide prepared in the step (S2), ABS resin, garlicin, an initiator, tea polyphenol, a plasticizer and 2, 3-dimercaptosuccinic acid to obtain a mixed material, and then putting the mixed material into an injection molding machine for injection molding to obtain a finished product of the mildewproof plastic.

In the step S1, the molar ratio of the N, N' -thiocarbonyl diimidazole to the 3-chloropropionic acid to the organic solvent is 1:2: 9; the organic solvent is tetrahydrofuran.

The molar ratio of the dicarboxyl thiocarbonyl diimidazole intermediate, 4' -diaminodiphenyl sulfone, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine and high boiling point solvent in step S2 is 1:1:0.8:0.5: 6; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen.

In the step S3, the mass ratio of the phenylsulfonyl-dicarbonyl diimidazole salt polyamide to the ABS resin to the allicin to the initiator to the tea polyphenol to the plasticizer to the 2, 3-dimercaptosuccinic acid is 15:55:3:1:3:4: 3; the initiator is azobisisobutyronitrile; the plasticizer is epoxidized soybean oil.

The injection molding is carried out by adopting a screw injection molding machine, and during injection molding, the heating temperature of the first section of the screw is 175 ℃, the heating temperature of the second section of the screw is 190 ℃, the heating temperature of the third section of the screw is 210 ℃, and the heating temperature of the die head is 225 ℃.

The mildew-proof plastic prepared according to the preparation method of the mildew-proof plastic.

Example 2

The preparation method of the mildew-proof plastic is characterized by comprising the following steps:

step S1, preparation of a dicarboxylthiocarbonyldiimidazole intermediate: adding N, N' -thiocarbonyl diimidazole and 3-chloropropionic acid into an organic solvent, refluxing and stirring at 45 ℃ for reaction for 4.5 hours, then performing rotary evaporation to remove the solvent, washing the product with diethyl ether for 4 times, and then performing rotary evaporation to remove residual diethyl ether to obtain a dicarboxyl thiocarbonyl diimidazole intermediate product;

step S2, preparing the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide: adding the dicarboxyl thiocarbonyl diimidazole intermediate product prepared in the step S1, 4' -diamino diphenyl sulfone, 1-ethyl- (3-dimethyl amino propyl) carbodiimide hydrochloride and 4-dimethylamino pyridine into a high boiling point solvent to obtain a reaction liquid, then transferring the reaction liquid into a reaction kettle, replacing the air in the kettle with inert gas, and reacting for 1.5 hours at 165 ℃ under normal pressure; heating to 215 ℃, and carrying out primary polycondensation for 6.5 hours; vacuumizing to 500Pa, heating to 245 ℃, performing polycondensation reaction for 9 hours, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 4 times, and performing rotary evaporation to remove the ethanol to obtain the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide;

step S3, injection molding: and (4) uniformly mixing the phenylsulfonyl dicarbonyl diimidazole salt polyamide prepared in the step (S2), ABS resin, garlicin, an initiator, tea polyphenol, a plasticizer and 2, 3-dimercaptosuccinic acid to obtain a mixed material, and then putting the mixed material into an injection molding machine for injection molding to obtain a finished product of the mildewproof plastic.

In the step S1, the molar ratio of the N, N' -thiocarbonyl diimidazole to the 3-chloropropionic acid to the organic solvent is 1:2: 10; the organic solvent is dichloromethane.

The molar ratio of the dicarboxyl thiocarbonyl diimidazole intermediate, 4' -diaminodiphenyl sulfone, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine and high boiling point solvent in step S2 is 1:1:0.9:0.5: 7; the high boiling point solvent is N, N-dimethylformamide; the inert gas is helium.

In the step S3, the mass ratio of the phenylsulfonyl-dicarbonyl diimidazole salt polyamide to the ABS resin to the allicin to the initiator to the tea polyphenol to the plasticizer to the 2, 3-dimercaptosuccinic acid is 18:58:4:1.3:3.5:5: 3; the initiator is azobisisoheptonitrile; the plasticizer is tributyl citrate.

The injection molding is carried out by adopting a screw injection molding machine, and during injection molding, the heating temperature of the first section of the screw is 178 ℃, the heating temperature of the second section of the screw is 195 ℃, the heating temperature of the third section of the screw is 213 ℃, and the heating temperature of the die head is 228 ℃.

The mildew-proof plastic prepared according to the preparation method of the mildew-proof plastic.

Example 3

The preparation method of the mildew-proof plastic is characterized by comprising the following steps:

step S1, preparation of a dicarboxylthiocarbonyldiimidazole intermediate: adding N, N' -thiocarbonyl diimidazole and 3-chloropropionic acid into an organic solvent, refluxing and stirring at 50 ℃ for 5 hours to react, then performing rotary evaporation to remove the solvent, washing the product with diethyl ether for 5 times, and then performing rotary evaporation to remove residual diethyl ether to obtain a dicarboxyl thiocarbonyl diimidazole intermediate product;

step S2, preparing the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide: adding the dicarboxyl thiocarbonyl diimidazole intermediate product prepared in the step S1, 4' -diaminodiphenyl sulfone, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a high boiling point solvent to obtain a reaction liquid, transferring the reaction liquid into a reaction kettle, replacing the air in the kettle with inert gas, and reacting for 2 hours at 170 ℃ under normal pressure; heating to 220 ℃, and carrying out primary polycondensation for 7 hours; vacuumizing to 500Pa, heating to 250 ℃, performing polycondensation reaction for 10 hours, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 5 times, and performing rotary evaporation to remove the ethanol to obtain the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide;

step S3, injection molding: and (4) uniformly mixing the phenylsulfonyl dicarbonyl diimidazole salt polyamide prepared in the step (S2), ABS resin, garlicin, an initiator, tea polyphenol, a plasticizer and 2, 3-dimercaptosuccinic acid to obtain a mixed material, and then putting the mixed material into an injection molding machine for injection molding to obtain a finished product of the mildewproof plastic.

In the step S1, the molar ratio of the N, N' -thiocarbonyl diimidazole to the 3-chloropropionic acid to the organic solvent is 1:2: 12; the organic solvent is toluene.

In step S2, the molar ratio of the dicarboxyl thiocarbonyl diimidazole intermediate product, 4' -diaminodiphenyl sulfone, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine and the high boiling point solvent is 1:1:1:0.5: 8; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is neon.

In the step S3, the mass ratio of the phenylsulfonyl-dicarbonyl diimidazole salt polyamide to the ABS resin to the allicin to the initiator to the tea polyphenol to the plasticizer to the 2, 3-dimercaptosuccinic acid is 20:60:4.5:1.5:4:6: 3; the initiator is lauroyl peroxide; the plasticizer is epoxidized soybean oil.

The injection molding is carried out by adopting a screw injection molding machine, and during injection molding, the heating temperature of the first section of the screw is 180 ℃, the heating temperature of the second section of the screw is 198 ℃, the heating temperature of the third section of the screw is 215 ℃, and the heating temperature of the die head is 230 ℃.

The mildew-proof plastic prepared according to the preparation method of the mildew-proof plastic.

Example 4

The preparation method of the mildew-proof plastic is characterized by comprising the following steps:

step S1, preparation of a dicarboxylthiocarbonyldiimidazole intermediate: adding N, N' -thiocarbonyl diimidazole and 3-chloropropionic acid into an organic solvent, refluxing and stirring at 55 ℃ for reaction for 5.7 hours, then performing rotary evaporation to remove the solvent, washing the product with diethyl ether for 6 times, and then performing rotary evaporation to remove residual diethyl ether to obtain a dicarboxyl thiocarbonyl diimidazole intermediate product;

step S2, preparing the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide: adding the dicarboxyl thiocarbonyl diimidazole intermediate product prepared in the step S1, 4' -diamino diphenyl sulfone, 1-ethyl- (3-dimethyl amino propyl) carbodiimide hydrochloride and 4-dimethylamino pyridine into a high boiling point solvent to obtain a reaction liquid, then transferring the reaction liquid into a reaction kettle, replacing the air in the kettle with inert gas, and reacting for 2.5 hours at 175 ℃ under normal pressure; heating to 227 ℃, and carrying out primary polycondensation for 7.8 hours; vacuumizing to 500Pa, heating to 257 ℃, performing polycondensation reaction for 11 hours, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 6 times, and performing rotary evaporation to remove the ethanol to obtain the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide;

step S3, injection molding: and (4) uniformly mixing the phenylsulfonyl dicarbonyl diimidazole salt polyamide prepared in the step (S2), ABS resin, garlicin, an initiator, tea polyphenol, a plasticizer and 2, 3-dimercaptosuccinic acid to obtain a mixed material, and then putting the mixed material into an injection molding machine for injection molding to obtain a finished product of the mildewproof plastic.

In the step S1, the molar ratio of the N, N' -thiocarbonyl diimidazole to the 3-chloropropionic acid to the organic solvent is 1:2: 14; the organic solvent is tetrahydrofuran.

The molar ratio of the dicarboxyl thiocarbonyl diimidazole intermediate, 4' -diaminodiphenyl sulfone, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine and high boiling point solvent in step S2 is 1:1:1.1:0.5: 9.5; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:2:2: 3; the inert gas is argon.

In the step S3, the mass ratio of the phenylsulfonyl-dicarbonyl diimidazole salt polyamide to the ABS resin to the allicin to the initiator to the tea polyphenol to the plasticizer to the 2, 3-dimercaptosuccinic acid is 23:63:5.5:1.8:4.5:7.5: 3; the initiator is prepared by mixing azodiisobutyronitrile, azodiisoheptonitrile, lauroyl peroxide and tert-butyl peroxybenzoate according to the mass ratio of 1:3:2: 1; the plasticizer is prepared by mixing epoxidized soybean oil and tributyl citrate according to the mass ratio of 3:5.

The injection molding is carried out by adopting a screw injection molding machine, and during injection molding, the heating temperature of the first section of the screw is 183 ℃, the heating temperature of the second section of the screw is 203 ℃, the heating temperature of the third section of the screw is 218 ℃, and the heating temperature of the die head is 233 ℃.

The mildew-proof plastic prepared according to the preparation method of the mildew-proof plastic.

Example 5

The preparation method of the mildew-proof plastic is characterized by comprising the following steps:

step S1, preparation of a dicarboxylthiocarbonyldiimidazole intermediate: adding N, N' -thiocarbonyl diimidazole and 3-chloropropionic acid into an organic solvent, refluxing and stirring at 60 ℃ for reaction for 6 hours, then performing rotary evaporation to remove the solvent, washing the product with diethyl ether for 6 times, and then performing rotary evaporation to remove residual diethyl ether to obtain a dicarboxyl thiocarbonyl diimidazole intermediate product;

step S2, preparing the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide: adding the dicarboxyl thiocarbonyl diimidazole intermediate product prepared in the step S1, 4' -diamino diphenyl sulfone, 1-ethyl- (3-dimethyl amino propyl) carbodiimide hydrochloride and 4-dimethylamino pyridine into a high boiling point solvent to obtain a reaction liquid, then transferring the reaction liquid into a reaction kettle, replacing the air in the kettle with inert gas, and reacting for 3 hours at 180 ℃ under normal pressure; heating to 230 ℃, and carrying out primary polycondensation for 8 hours; vacuumizing to 500Pa, heating to 260 ℃, performing polycondensation reaction for 12 hours, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol for 7 times, and performing rotary evaporation to remove the ethanol to obtain the phenylsulfonyl-thiocarbonyl diimidazole salt polyamide;

step S3, injection molding: and (4) uniformly mixing the phenylsulfonyl dicarbonyl diimidazole salt polyamide prepared in the step (S2), ABS resin, garlicin, an initiator, tea polyphenol, a plasticizer and 2, 3-dimercaptosuccinic acid to obtain a mixed material, and then putting the mixed material into an injection molding machine for injection molding to obtain a finished product of the mildewproof plastic.

In the step S1, the molar ratio of the N, N' -thiocarbonyl diimidazole to the 3-chloropropionic acid to the organic solvent is 1:2: 15; the organic solvent is dichloromethane.

In step S2, the molar ratio of the dicarboxyl thiocarbonyl diimidazole intermediate product, 4' -diaminodiphenyl sulfone, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine and high boiling point solvent is 1:1:1.2:0.5: 10; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is nitrogen.

In the step S3, the mass ratio of the phenylsulfonyl-dicarbonyl diimidazole salt polyamide to the ABS resin to the allicin to the initiator to the tea polyphenol to the plasticizer to the 2, 3-dimercaptosuccinic acid is 25:65:6:2:5:8: 3; the initiator is tert-butyl peroxybenzoate; the plasticizer is epoxidized soybean oil.

The injection molding is carried out by adopting a screw injection molding machine, and during injection molding, the heating temperature of the first section of the screw is 185 ℃, the heating temperature of the second section of the screw is 205 ℃, the heating temperature of the third section of the screw is 220 ℃, and the heating temperature of the die head is 235 ℃.

The mildew-proof plastic prepared according to the preparation method of the mildew-proof plastic.

Comparative example 1

This example provides a mold-proof plastic, the formulation and preparation method of which are substantially the same as those of example 1, except that no phenylsulfonyl-dicarbonyl diimidazole salt polyamide is added in the injection molding process of step S3.

Comparative example 2

This example provides a mold resistant plastic having substantially the same formulation and preparation method as example 1, except that no allicin is added during the injection molding process in step S3.

Comparative example 3

This example provides a mold resistant plastic having substantially the same formulation and preparation method as example 1, except that no tea polyphenol is added during the injection molding process of step S3.

Comparative example 4

This example provides a mold-resistant plastic, which has a formulation and a preparation method substantially the same as those of example 1, except that 2, 3-dimercaptosuccinic acid is not added in the injection molding process at step S3.

Taking the same mass of the mildewproof plastic prepared in each example to perform inactivation experiments, mildew growth experiments and tensile property test experiments on the gram-negative escherichia coli and the gram-positive staphylococcus aureus, and obtaining test results shown in table 1; and gram-negative escherichia coli is a strain 1, and gram-positive staphylococcus aureus is a strain 2; the aging resistance is measured by the retention rate of the tensile strength of each sample after the sample is subjected to artificial heat aging for 100 hours at 90 ℃, and the larger the value of the value is, the better the aging resistance is; the specific test method is referred to the corresponding national standard of each performance in China.

As can be seen from table 1, the mildew-proof plastic material disclosed in the embodiment of the present invention has better mechanical properties, mildew-proof antibacterial properties and thermal aging resistance than the comparative product, which are the result of synergistic effect of the raw materials.

TABLE 1

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.