CN112480809A - Green polyhexahydrotriazine self-lubricating coating, preparation method and degradation method thereof - Google Patents
Green polyhexahydrotriazine self-lubricating coating, preparation method and degradation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
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- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
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Abstract
The invention provides a green polyhexamethylene triazine self-lubricating coating, a preparation method and a degradation method thereof2And O is used as a catalyst to depolymerize Paraformaldehyde (PFA), and then the depolymerized Paraformaldehyde (PFA) reacts with 1, 4-bis (4-aminophenoxy) -benzene (TPE-Q) to perform prepolymerization to generate an intermediate product, namely, a Hemiaminal Dynamic Covalent Network (HDCN) resin solution, so that the reaction speed is greatly improved. And spraying the HDCN resin liquid on the surface of the base material, and curing in a gradient heating mode to obtain the poly-hexahydrotriazine (PHT) resin coating. The poly hexahydrotriazine self-lubricating coating prepared by the invention has simple preparation conditions and easy operation; the friction performance is excellent; can realize complete degradation, is recovered in a micromolecule form, and has good environmental protection property.
Description
Technical Field
The invention belongs to the field of novel green high polymer materials, and particularly relates to a preparation method of a green polyhexamethylene triazine self-lubricating coating.
Background
The large-scale use of plastic products and the disposal of waste plastic products are urgent. Conventional thermosetting resins such as: phenolic resins, epoxy resins, polyimide resins, benzoxazine resins, and the like all have the characteristic of being difficult to dissolve and melt after curing. However, thermosetting resins have incomparable advantages in the fields of construction, machinery, and particularly aerospace science due to their excellent thermal, mechanical, and chemical stability. At present, the waste treatment method of thermosetting resin is divided into two methods, namely a physical method and a chemical method. Both the physical method high-temperature calcination and the chemical method high-temperature pyrolysis have the disadvantages of complex operation and huge energy consumption. Therefore, the thermosetting resin composition meets the requirements of industrial and scientific development, and becomes the mainstream direction of the current research on thermosetting resin in accordance with the modern concept of green and environmental protection.
On the basis of the research on triazine ring micromolecules by a Garci ia team in 2014, the first polyhexamethylene triazine (ODA-PHT) resin is successfully prepared by taking paraformaldehyde and 4, 4' -Oxydianiline (ODA) as raw materials for the first time. The reaction condition is mild, the preparation process is simple, and the prepared PHT resin can be degraded at PH < 2. Then, Sun replaces ODA with 4, 4' -diaminodiphenyl ether (BAPP), takes water as catalyst, and takes asymmetric monomer as raw material to prepare BAPP-PHT resin which is degraded under acidic condition. In addition, Sun also explored the catalytic effect of water on PHT synthesis and the adhesive properties of PHT. However, the degree of degradation of the starting material, paraformaldehyde, determines the success of PHT preparation.
Currently reported yield numbers for the preparation and use of polyhexahydrotriazines. The system in the method for preparing hemiaminal and polyhexahydrotriazine by Chinese patent CN105636998A illustrates part of monomers and solvents required by PHT preparation. The first step uses poly hemiacetal amine (HDCN) as intermediate product, the second step raises temperature again, HDCN removes H2O and solvent cure to Polyhexahydrotriazine (PHT). The prepared PHT is researched for mechanical properties, thermal properties and the like by changing the ratio of the diamine monomer to the paraformaldehyde.
However, researchers neglected the depolymerization problem of paraformaldehyde, the conversion of the PHT resin produced would be greatly affected. Moreover, the position and the number of benzene rings in the diamine monomer are also important factors influencing the strength of the PHT, and the single molding process also limits the industrial production and use of the PHT.
Disclosure of Invention
The invention aims to prepare a degradable green self-lubricating poly-hexahydrotriazine (PHT) coating to relieve the embarrassment situation that the prior waste resin is difficult to treat. Through the adjustment of the reaction process, the synthesis time of the poly-hexahydrotriazine (PHT) is shortened, the application field of the poly-hexahydrotriazine (PHT) resin is widened, and particularly the application in the aspect of tribology is realized.
A preparation method of a green polyhexahydrotriazine self-lubricating coating is characterized by comprising the following steps:
step 1: depolymerization of PFA: dissolving Paraformaldehyde (PFA) in N-methylpyrrolidone (NMP), placing into a glass screw bottle, heating in water bath, and adding H2O as a catalyst to depolymerize PFA;
step 2: synthesis of PHT: measuring N-methylpyrrolidone (NMP) to dissolve 1, 4-bis (4-aminophenoxy) -benzene (TPE-Q), injecting the solution into the completely depolymerized PFA solution after the temperature in a water bath is reduced to 50-40 ℃, spraying the formed light yellow transparent prepolymer on the surface of a base material after the reaction is finished, and putting the base material into a muffle furnace to be heated to 170-200 ℃ in a gradient manner for solidification to obtain the self-lubricating coating of the poly-hexahydrotriazine (PHT).
Further, the temperature of the water bath heating in the step 1 is 85 ℃.
Further, catalyst H in the step 12The volume ratio of O to NMP is 2-2.5: 9-10.
Further, the amount ratio of NMP to PFA in step 1 is 4ml-5ml:0.3-0.35 g.
Further, the molar ratio of PFA to TPE-Q in step 2 is 9.5-10: 2.4-2.5.
Further, the thickness of the self-lubricating coating of the poly-hexahydrotriazine (PHT) prepared in the step 2 is 60-80 μm.
Further, the time for preparing the yellow pre-polymerization solution in the step 2 is 20min-30 min.
Further, the gradient temperature raising method in the step 2 comprises the following steps: heating from room temperature 25 deg.c for 1 hr to 50-60 deg.c, maintaining for 1 hr, heating from 50-60 deg.c for 1 hr to 180-200 deg.c, maintaining for 1-3 hr, and final cooling in the furnace.
The preparation method is characterized in that the prepared poly-hexahydrotriazine self-lubricating coating has the decomposition temperature of 288 ℃ and the friction coefficient and wear rate of 0.0634 and 7.87 multiplied by 10 respectively- 5mm3/Nm。
The degradation method of the hexahydrotriazine self-lubricating coating is characterized in that the hexahydrotriazine self-lubricating coating can be degraded by soaking in a mixed solution of hydrochloric acid and tetrahydrofuran, wherein the volume ratio of the hydrochloric acid to the tetrahydrofuran is 1: 4.
The invention takes 1, 4-bis (4-aminophenoxy) -benzene (TPE-Q) and Paraformaldehyde (PFA) as raw materials, takes N-methylpyrrolidone (NMP) as a solvent, and firstly takes H as a solvent2And O is used as a catalyst to depolymerize Paraformaldehyde (PFA), and then the depolymerized Paraformaldehyde (PFA) reacts with 1, 4-bis (4-aminophenoxy) -benzene (TPE-Q) to perform prepolymerization to generate the half aminal dynamic covalent network HDCN resin solution, so that the reaction speed is greatly improved. And spraying the HDCN resin solution on the surface of the base material, and curing at high temperature to form the PHT resin coating. The PHT resin coating is used as a self-lubricating coating and has excellent thermal and outstanding tribological properties.
The preparation method of the invention is different from the synthesis reaction conditions of common thermosetting resin, can be synthesized under the mild condition of 50-40 ℃ by taking water as a catalyst, and realizes short reaction time and simple spray forming process. In addition, PHT resins have lower coefficients of friction and wear rates than the self-lubricating thermoset resins that are currently in widespread use. Finally, the complete degradation of the PHT resin achieves the aim of environmental protection and no pollution.
Because the efficiency of degrading paraformaldehyde in N-methyl pyrrolidone (NMP) to obtain a formaldehyde solution is greatly influenced by temperature, the optimal depolymerization temperature of the paraformaldehyde is determined to be 85 ℃, and a rigid monomer with rich benzene rings is selected to enhance the strength of a polymer, so that the prepared PHT coating has excellent thermal property, mechanical property and tribological property.
Drawings
FIG. 1 NMR spectra of TPE-Q used as a raw material in the present invention: (1HNMR) map.
FIG. 2 NMR spectra of HDCN coatings prepared according to the invention: (1HNMR) map.
FIG. 3 is a diagram of an example of a PHT coating prepared according to the present invention.
FIG. 4 is a graph of the infrared spectrum (FTIR) of HDCN coatings and PHT coatings prepared in accordance with the present invention.
FIG. 5 is a Thermogravimetric (TG) plot of HDCN coatings and PHT coatings prepared according to the present invention.
FIG. 6 friction coefficient curve plot of PHT prepared by the present invention and epoxy resin (EP), Polyimide (PI), GO/CNTs/PI within 30 min.
FIG. 7 is a graph of the average friction coefficient and wear rate of PHT prepared according to the present invention, as well as Epoxy (EP), Polyimide (PI), GO/CNTs/PI.
FIG. 8 is a graph of the average coefficient of friction and wear rate of PHT prepared according to the present invention in air, DI water, and seawater.
FIG. 9 is a diagram showing the degradation process of PHT prepared by the present invention.
Detailed Description
The present invention will be further illustrated with reference to specific examples, which are not intended to limit the scope of the invention.
Example 1
Weighing 4ml of NMP, dissolving 0.3g of PFA, putting into a glass screw bottle, and taking and putting magnetons. The screw bottle is placed in a reaction device, the temperature is raised to 85 ℃, and the magnetic stirring is started. 2ml of water was added until the white turbid liquid was completely depolymerized to a clear solution and PFA was completely depolymerized. Adjusting the temperature, measuring 3ml of NMP to dissolve 0.7015g of TPE-Q after the temperature is reduced to 50 ℃, adding the mixture into a screw bottle after uniformly stirring, and spraying the light yellow transparent prepolymer solution on the surface of the base material after reacting for 20 min. And drying in a vacuum oven at 50 ℃ for 24h to obtain the HDCN coating material. Or the curing is carried out by adopting gradient temperature rise. And a temperature rising step, namely, rising the temperature from room temperature to 60 ℃ within 1 hour, preserving the temperature for 1 hour, then rising the temperature from 60 ℃ to 190 ℃ within 1 hour, preserving the temperature for one hour, and finally cooling along with the furnace to obtain the PHT coating material.
Example 2
A volume of 8ml of NMP was weighed out, 0.6g of PFA was dissolved in the NMP solution, and the solution was put into a glass screw bottle, and magnetons were put into the bottle. The screw bottle is placed in a reaction device, the temperature is raised to 85 ℃, and the magnetic stirring is started. 2ml of water was added until the white turbid liquid was completely depolymerized to a clear solution and PFA was completely depolymerized. Adjusting the temperature of the device, measuring 3ml of NMP to dissolve 1.403g of TPE-Q after the temperature is reduced to 45 ℃, uniformly stirring, adding into a screw bottle, reacting for 20min, spraying the light yellow transparent prepolymer solution on the surface of the substrate, and drying in a vacuum oven at 50 ℃ for 24h to obtain the HDCN coating material. Or adopting gradient heating to cure, heating from room temperature to 55 ℃ for 1 hour, keeping the temperature for 1 hour, heating from 55 ℃ to 180 ℃ for 1 hour, keeping the temperature for one hour, and finally cooling along with a furnace to obtain the PHT coating material.
Example 3
6ml of NMP is weighed, 0.45g of PFA is dissolved in the NMP, and the solution is put into a glass screw bottle, and magnetons are taken and put into the glass screw bottle. The screw bottle is placed in a reaction device, the temperature is raised to 85 ℃, and the magnetic stirring is started. 2.5ml of water was added until the white turbid liquid was completely depolymerized to a clear solution and PFA was completely depolymerized. Adjusting the temperature of the device, measuring 3ml of NMP to dissolve 1.052g of TPE-Q after the temperature is reduced to 50 ℃, uniformly stirring, adding into a screw bottle, spraying a light yellow transparent prepolymer solution on the surface of a substrate after reacting for 20min, and drying in a vacuum oven at 50 ℃ for 24h to obtain the HDCN coating material. Or curing by adopting gradient heating, heating from room temperature to 50 ℃ within 1 hour, preserving heat for 1 hour, heating from 50 ℃ to 200 ℃ within 1 hour, preserving heat for one hour, and finally cooling along with a furnace to obtain the PHT coating material.
Example 4
A sample of 7ml of NMP was weighed, 0.40g of PFA was dissolved in the NMP solution, and the solution was put into a glass screw bottle, and magnetons were put into the bottle. The screw bottle is placed in a reaction device, the temperature is raised to 85 ℃, and the magnetic stirring is started. Adding 3ml of water until the white turbid liquid is finishedThe depolymerization to clear solution was complete and the PFA was completely depolymerized. Adjusting the temperature of the device, measuring 3ml of NMP to dissolve 1.052g of TPE-Q after the temperature is reduced to 50 ℃, uniformly stirring, adding into a screw bottle, spraying a light yellow transparent prepolymer solution on the surface of a substrate after reacting for 20min, and drying in a vacuum oven at 50 ℃ for 24h to obtain the HDCN coating material. Or curing by adopting gradient heating, wherein the temperature is increased from room temperature to 50 ℃ within 1 hour, the temperature is maintained for 1 hour, then the temperature is increased from 50 ℃ to 200 ℃ within 1 hour, the temperature is maintained for one hour, and finally the PHT coating material is obtained by furnace cooling as shown in figure 3. The prepared HDCN coating is used for carrying out1HNMR, FTIR, TG tests. The test results are shown in fig. 2, 4 and 5. Of HDCN in FIG. 21HNMR showed that the disappearance of the hydrogen peak on the amino group and the appearance of the hydrogen peak on the triazine ring marked the successful preparation of the intermediate HDCN. The prepared PHT coating is used for FTIR, TG test and other tests. The test results are shown in fig. 4 and 5. As can be taken from fig. 4, the absence of solvent and water peaks of PHT after curing at high temperatures of 200 ℃ achieves a radical transition from HDCN to PHT. In FIG. 5, compared with HDCN, PHT has higher decomposition temperature of 288.8 ℃, and the application of PHT resin in the high temperature field is expanded.
The model of a friction tester selected for analyzing the tribological performance of the PHT resin coating is MS-T3000. The hardness of the friction ball made of GCr15 bearing steel selected in the experiment is 62HRC, the diameter of the steel ball is 4mm, the material of the steel sheet is 45# steel, and the rotating radius is 3 mm. The test rotating speed, the load and the time of a single sample are respectively 200r/min, 5N and 30 min. After the PHT is sprayed on a steel sheet and cured, friction tests are respectively carried out in air, deionized water and seawater. The results of the tests on the friction performance, friction coefficient and wear rate of the PHT resin prepared according to the present invention are shown in FIGS. 6, 7 and 8 by using the methods described in the publications in Table 1, epoxy resin (EP), polyimide resin (PI) and GO/CNTs/PI resin as comparative examples and referring to the comparative examples.
TABLE 1
As shown in fig. 6 and 7, the PHT resin has a lower coefficient of friction and a lower wear rate than the friction wear of the current self-lubricating thermosetting resin, which is hotter than the friction wear of the current self-lubricating thermosetting resin, under the same test conditions. Fig. 8 shows that PHT resin exhibits good rub and abrasion resistance in both dry rub and deionized water.
Weighing 8ml of Tetrahydrofuran (THF) and 4ml of HCl, mixing (the ratio is 4:1), putting into a glass screw bottle (20ml), shearing small pieces of PHT resin, putting into the glass screw bottle, and completely immersing the PHT resin into the mixed solution. Standing at 25 ℃, 5min, 10min, 30min, 60min, 120min, 180min, 240min, 420min, 480min, 540min, 600min, observing and photographing after 800min, and completely degrading the PHT resin after 800 min. The degradation process of the resin is shown in FIG. 9.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A preparation method of a green polyhexahydrotriazine self-lubricating coating is characterized by comprising the following steps:
step 1: depolymerization of PFA: dissolving Paraformaldehyde (PFA) in N-methylpyrrolidone (NMP), placing into a glass screw bottle, heating in water bath, and adding H2O as a catalyst to depolymerize PFA;
step 2: synthesis of PHT: measuring N-methylpyrrolidone (NMP) to dissolve 1, 4-bis (4-aminophenoxy) -benzene (TPE-Q), injecting the solution into the completely depolymerized PFA solution after the temperature in a water bath is reduced to 50-40 ℃, spraying the formed light yellow transparent prepolymer on the surface of a base material after the reaction is finished, and putting the base material into a muffle furnace to be heated to 180-200 ℃ in a gradient manner for solidification to obtain the polyhexamethylene triazine (PHT) self-lubricating coating.
2. The method for preparing green polyhexahydrotriazine self-lubricating coating according to claim 1, wherein the temperature of the water bath heating in the step 1 is 85 ℃.
3. The method for preparing green polyhexahydrotriazine self-lubricating coating according to claim 1, wherein catalyst H in the step 1 is catalyst H2The volume ratio of O to NMP is 2-2.5: 9-10.
4. The method for preparing green polyhexahydrotriazine self-lubricating coating according to claim 1, wherein the dosage ratio of NMP to PFA in the step 1 is 4ml-5ml:0.3-0.35 g.
5. The method for preparing green polyhexahydrotriazine self-lubricating coating according to claim 1, wherein the molar ratio of PFA to TPE-Q in step 2 is 9.5-10: 2.4-2.5.
6. The method for preparing a green polyhexahydrotriazine self-lubricating coating according to claim 1, wherein the thickness of the Polyhexahydrotriazine (PHT) self-lubricating coating prepared in the step 2 is 60-80 μm.
7. The method for preparing a green polyhexahydrotriazine self-lubricating coating according to claim 1, wherein the time for preparing the yellow pre-polymerization solution in the step 2 is 20min to 30 min.
8. The preparation method of the green polyhexahydrotriazine self-lubricating coating as claimed in claim 1, wherein the gradient temperature rise method in the step 2 comprises the following steps: heating from room temperature 25 deg.c for 1 hr to 50-60 deg.c, maintaining for 1 hr, heating from 50-60 deg.c for 1 hr to 180-200 deg.c, maintaining for 1-3 hr, and final cooling in the furnace.
9. The self-lubricating coating of hexahydrotriazine prepared by the method of any one of claims 1 to 8, wherein the self-lubricating coating of hexahydrotriazine is prepared to have a decomposition temperature of 288 ℃ and a friction coefficient and wear rate of 0.0634 and 7.87 x 10 respectively-5mm3(iv)/Nm; and can also be degraded.
10. The degradation method of the hexahydrotriazine self-lubricating coating according to claim 9, wherein the coating is degraded by soaking in a mixed solution of hydrochloric acid and tetrahydrofuran, and the volume ratio of the hydrochloric acid to the tetrahydrofuran is 1: 4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429535A (en) * | 2021-06-09 | 2021-09-24 | 广西民族大学 | Degradable bio-based thermosetting resin containing isosorbide structure and preparation method thereof |
| CN113583276A (en) * | 2021-08-27 | 2021-11-02 | 中国民用航空飞行学院 | Benzoxazine toughening modification preparation method |
| CN115821637A (en) * | 2022-10-12 | 2023-03-21 | 天津科技大学 | Preparation method of degradable engine oil filter paper |
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| CN105636998A (en) * | 2013-10-10 | 2016-06-01 | 国际商业机器公司 | Methods of preparing polyhemiaminals and polyhexahydrotriazines |
| CN108456309A (en) * | 2018-01-17 | 2018-08-28 | 中国科学院兰州化学物理研究所 | A kind of high-performance thermosetting shape memory polyimides for being laminated and welding |
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| CN105636998A (en) * | 2013-10-10 | 2016-06-01 | 国际商业机器公司 | Methods of preparing polyhemiaminals and polyhexahydrotriazines |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429535A (en) * | 2021-06-09 | 2021-09-24 | 广西民族大学 | Degradable bio-based thermosetting resin containing isosorbide structure and preparation method thereof |
| CN113429535B (en) * | 2021-06-09 | 2023-12-08 | 广西民族大学 | Degradable bio-based thermosetting resin containing isosorbide structure and preparation method thereof |
| CN113583276A (en) * | 2021-08-27 | 2021-11-02 | 中国民用航空飞行学院 | Benzoxazine toughening modification preparation method |
| CN115821637A (en) * | 2022-10-12 | 2023-03-21 | 天津科技大学 | Preparation method of degradable engine oil filter paper |
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