CN112063165A - MCPA6@ AgTAZ composite material and preparation method and application thereof - Google Patents

Abstract

The invention discloses an MCPA6@ AgTAZ composite material and a preparation method and application thereof, wherein the MCPA6@ AgTAZ composite material comprises, by weight, 100 parts of caprolactam monomer, 0.5-20 parts of AgTAZ, 0.6-2 parts of an initiator and 0.1-0.8 part of a catalyst. The invention utilizes the regular lattice structure of the metal organic framework compound of AgTAZ to prepare the framework structure composite material with holes. The prepared MCPA6@ AgTAZ composite material is high in thermal stability, and the MCPA6@ AgTAZ composite material can continuously release trace silver ions, so that the growth of various bacteria can be effectively inhibited. The MCPA6@ AgTAZ composite material disclosed by the invention is simple in preparation process, excellent in comprehensive performance and strong in product stability.

Description

MCPA6@ AgTAZ composite material and preparation method and application thereof

Technical Field

The invention relates to the technical field of casting nylon composite materials, and particularly relates to an MCPA6@ AgTAZ composite material and a preparation method and application thereof.

Background

MCPA6 has light weight, good mechanical property,Low noise, wear resistance, self-lubrication and the like, and also has the defects of poor low-temperature impact property, poor thermal stability, poor creep resistance, large water absorption and the like, thereby influencing the application in practical production. In order to meet the use requirements of different occasions, the modified nano particles are mainly subjected to copolymerization modification and nano particle in-situ filling modification. In the prior art, mostly, nano-ion in-situ filling modification is adopted, and SiO is mainly utilized₂、TiO₂The MCPA6 is modified by ZnO, carbon fiber, graphene, whisker, montmorillonite and the like, so that the thermal stability, the heat resistance, the creep resistance and the like of the MCPA6 are improved. However, the nano particles do not influence the crystallization of the whole system, even have local strengthening effect on the crystallization of the polymer, improve the shrinkage rate of the MC nylon and influence the molding size of the product.

The Metal Organic Frameworks (MOFs) are crystalline materials with three-dimensional pore structures, which are formed by connecting metal atoms serving as centers by organic molecules. Patent CN201710290282.7 discloses a blue MOFs/cast nylon nanocomposite, which adopts an organic metal frame with copper as a core, and nylon molecular chains penetrate through MOFs holes to form a special structure in which MOFs are sleeved on the nylon molecular chains, so that the crystallinity of the cast nylon is reduced and the shrinkage is reduced while the hardness of the cast nylon is ensured. However, as the content of the blue MOFs/is increased, the crystallinity of nylon is reduced, and the heat resistance of nylon is continuously reduced. Moreover, blue MOFs completely change the color of nylon, making it difficult to readjust the color of the product. Therefore, how to effectively improve the thermal stability and the dimensional stability of the cast nylon at the same time is a problem to be solved at present.

Disclosure of Invention

The invention aims to solve the technical problem of providing an MCPA6@ AgTAZ composite material aiming at the defect that the thermal stability and the dimensional stability of the existing composite casting nylon material are difficult to simultaneously and effectively improve.

The invention aims to solve another technical problem of providing the MCPA6@ AgTAZ composite material as well as a preparation method and application thereof.

The purpose of the invention is realized by the following technical scheme:

the MCPA6@ AgTAZ composite material comprises, by weight, 100 parts of caprolactam monomer, 0.5-20 parts of AgTAZ, 0.6-2 parts of an initiator and 0.1-0.8 part of a catalyst, wherein the AgTAZ is one or more of a metal organic framework material with a topological structure and a functional group derivative thereof. The invention utilizes the lattice structure of AgTAZ with regular two-dimensional holes, and molecular chains of caprolactam monomers can orderly penetrate through the AgTAZ holes to form a special structure in which a metal organic framework material is sleeved on a nylon molecular chain. The ultra-stability of AgTAZ improves the stability of MCPA6, and AgTAZ is white in color and does not affect the color of MCPA 6.

Further, the raw material of the MCPA6@ AgTAZ composite material also comprises an aprotic polar solvent, and the weight of the components of the aprotic polar solvent is not more than 20 times of the weight of the AgTAZ components.

Further, the MCPA6@ AgTAZ composite material comprises 100 parts of caprolactam monomer, 10 parts of AgTAZ, 2 parts of initiator, 0.1 part of catalyst and 50 parts of aprotic polar solvent.

Furthermore, the AgTAZ is a metal organic framework material synthesized by silver ions and 1,2, 4-triazole, and can continuously release trace silver ions, so that the growth of various bacteria can be effectively inhibited, and the MCPA6@ AgTAZ composite material has excellent antibacterial performance.

Furthermore, the structure size of the metal organic framework material is 10-100 nm.

Further, the initiator is isocyanate, and the isocyanate is one or more of MDI, TDI, HDI, NDI, PAPI, HTDI, HMDI, TMXDI and IPDI.

Further, the catalyst is one or more of sodium caprolactam, magnesium caprolactam bromide, NaOH, KOH, Na2CO3, NaH and LiH.

Further, the aprotic polar solvent is one or more of dimethylformamide, dimethylacetamide, pyridine, acetone, tetrahydrofuran, pyrrolidone, toluene, and cyclohexane.

The preparation method of the MCPA6@ AgTAZ composite material comprises the following steps:

s1, adding AgTAZ and an aprotic polar solvent into a kettle A filled with a caprolactam monomer I according to the proportion, adjusting the temperature of the kettle A to 70-85 ℃, and carrying out stirring reaction for 0.5-2 h;

s2, heating the kettle A in the step S1 to 130-140 ℃, and vacuumizing for 15-60 min under a certain vacuum degree, wherein the vacuum degree of vacuumizing is 99000-99997 Pa; then adding an initiator, and carrying out vacuum pumping reaction for 15-30 min;

s3, filling a caprolactam monomer II into a kettle B, heating until the caprolactam monomer II is dissolved, vacuumizing, completely melting the caprolactam monomer II, adding a catalyst, heating to 130-140 ℃, and continuously vacuumizing for 10-15 min;

and S4, mixing the substances obtained from the kettle A and the kettle B, pouring the mixture into a mold at the temperature of 150-170 ℃ for polymerization molding, reacting for 10-60 min, and naturally cooling to obtain the MCPA6@ AgTAZ composite material.

Further, the MCPA6@ AgTAZ composite material is applied to worm wheels, worms, bearings, gears, bearing bushes, sliding blocks and rollers.

Compared with the prior art, the beneficial effects are:

the AgTAZ is creatively used in the preparation of MCPA6 material, the molecular chain of caprolactam monomer can orderly penetrate through the AgTAZ holes in the synthesis process of caprolactam monomer by utilizing the lattice structure of the AgTAZ with regular two-dimensional holes, and then catalyst and initiator are added for casting reaction and molding. The MCPA6@ AgTAZ composite material forms a special structure in which a metal organic framework material is sleeved on a nylon molecular chain, the dimensional stability of a product is improved, the thermal deformation temperature of the material can be greatly improved, and the AgTAZ is white, so that the color matching of MCPA6 cannot be influenced.

On the premise of ensuring the strength, hardness and toughness of the MCPA6 material, the MCPA6@ AgTAZ composite material greatly improves the thermal deformation temperature of MCPA6, the maximum thermal deformation temperature can reach 140 ℃, and the thermal deformation temperature is improved by 73.5% compared with the thermal deformation temperature of the existing MCPA 6; the crystallinity of the material is reduced to 15.7 percent, and the maximum reduction rate of the material is 38 percent compared with the prior MCPA 6. The MCPA6@ AgTAZ composite material prepared by the method has good comprehensive performance and strong product stability, can inhibit the growth of various bacteria such as escherichia coli, staphylococcus and the like, and is widely used.

Drawings

FIG. 1 is an XRD pattern and a simulated pattern of AgTAZ (the upper part is an AgTAZXRD pattern, and the lower part is a simulated pattern);

FIG. 2 is a scanning electron micrograph of AgTAZ.

Detailed Description

The following examples are further explained and illustrated, but the present invention is not limited in any way by the specific examples. Unless otherwise indicated, the methods and equipment used in the examples are conventional in the art and all materials used are conventional commercially available materials.

The AgTAZ synthesis method used by the invention comprises the following steps: 1.70g of silver nitrate, 0.69g of 1,2, 4-triazole and 10mL of ammonia water (25%) are added into an autoclave with a polytetrafluoroethylene lining, and after sealing, the mixture is reacted at 100 ℃ for 60 hours. The resulting white solid was then washed three times with ethanol to give AgTAZ of the formula: c₂H₂AgN₃。

Example 1

This example provides a method for preparing MCPA6@ AgTAZ composite, comprising the steps of:

s1, adding AgTAZ and an aprotic polar solvent into a kettle A filled with a caprolactam monomer I according to the proportion, adjusting the temperature of the kettle A to 70-85 ℃, and carrying out stirring reaction for 0.5-2 h;

s2, heating the kettle A in the step S1 to 130-140 ℃, and vacuumizing for 15-60 min under a certain vacuum degree, wherein the vacuum degree of vacuumizing is 99000-99997 Pa; then adding an initiator, and carrying out vacuum pumping reaction for 15-30 min;

s3, filling a caprolactam monomer II into a kettle B, heating until the caprolactam monomer II is dissolved, vacuumizing, completely melting the caprolactam monomer II, adding a catalyst, heating to 130-140 ℃, and continuously vacuumizing for 10-15 min;

and S4, mixing the substances obtained from the kettle A and the kettle B, pouring the mixture into a mold at the temperature of 150-170 ℃ for polymerization molding, reacting for 10-60 min, and naturally cooling to obtain the MCPA6@ AgTAZ composite material.

The AgTAZ is a metal organic framework material synthesized by silver ions and 1,2, 4-triazole.

The structure size of the metal organic framework material is 10-100 nm.

The initiator is isocyanate, and the isocyanate is one or more of MDI, TDI, HDI, NDI, PAPI, HTDI, HMDI, TMXDI and IPDI.

The catalyst is one or more of caprolactam sodium, caprolactam magnesium bromide, NaOH, KOH, Na2CO3, NaH and LiH.

The aprotic polar solvent is one or more of dimethylformamide, dimethylacetamide, pyridine, acetone, tetrahydrofuran, pyrrolidone, toluene and cyclohexane.

Examples 2 to 5

This example provides the method shown in example 1, and prepares MCPA6@ AgTAZ composite from the raw materials in table 1.

TABLE 1

Comparative example 1

This comparative example prepares a nylon composite according to the method and raw materials shown in the examples in the patent with application number CN201710290282.7, a blue MOFs/cast nylon nanocomposite, a preparation method and applications thereof.

Comparative example 2

The comparative example discloses a preparation method of an organic montmorillonite/cast nylon nanocomposite material according to the application No. CN201310016483.X, wherein 10g of montmorillonite, 100g of water, 10g of ethanol, 1g of dodecyl trimethyl ammonium bromide and 1g of gamma-aminopropyltriethoxysilane are added into 500g of caprolactam in an A kettle, stirred at 70-85 ℃ for 30-120 min, vacuumized at 99340Pa vacuum degree for 15-60 min, then 10g of MDI is added, heated to 130-140 ℃ and continuously vacuumized; in addition, simultaneously heating 500g of caprolactam monomer in a B kettle until the monomer is dissolved, vacuumizing for 15-30 min at the vacuum degree of 99970Pa, adding 30g of NaOH, heating to 130-140 ℃, and continuously vacuumizing for 10-15 min; and finally, mixing the kettle A and the kettle B, pouring the mixture into a mold at the temperature of 150-170 ℃ for polymerization molding, reacting for 10-30 min, and naturally cooling to obtain the organic montmorillonite/cast nylon nanocomposite.

Comparative examples 3 to 5

This comparative example MCPA6@ AgTAZ composite was prepared as the raw material in table 2, in the manner shown in example 1.

TABLE 2

The heat distortion temperature, crystallinity and hardness bacteriostasis rate of the cast nylon composite materials prepared in the examples 2-5 and the comparative examples 1-5 are detected under 1.82MPa, and the performances obtained by detection are shown in the table 3 by taking pure cast nylon as a control group.

TABLE 3

As can be seen from tables 1 to 3, as the amount of AgTAZ added increases, the crystallinity of the cast nylon composite decreases and the heat distortion temperature increases, whereas when AgTAZ exceeds a certain content, the heat distortion temperature of MCPA6@ AgTAZ composite decreases sharply, and as the crystallinity decreases, the heat resistance thereof decreases. Meanwhile, compared with a cast nylon composite material prepared by adding an organic metal framework material taking copper atoms as a core and a nano montmorillonite lamellar structure, the invention has the advantages that the crystallinity and the shrinkage rate are reduced, the thermal deformation temperature is greatly improved on the premise of ensuring the strength, the hardness and the toughness of the material, and the nylon composite material is endowed with excellent antibacterial performance.

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The MCPA6@ AgTAZ composite material is characterized in that the MCPA6@ AgTAZ composite material comprises, by weight, 100 parts of caprolactam monomer, 0.5-20 parts of AgTAZ, 0.6-2 parts of initiator and 0.1-0.8 part of catalyst, wherein the AgTAZ is one or more of a metal organic framework material with a topological structure and a functional group derivative thereof.

2. The MCPA6@ AgTAZ composite material of claim 1, wherein the MCPA6@ AgTAZ composite material feedstock further comprises an aprotic polar solvent, the aprotic polar solvent having a component weight not exceeding 20 times the weight of the AgTAZ component.

3. The MCPA6@ AgTAZ composite material as claimed in claim 2, wherein the MCPA6@ AgTAZ composite material comprises 100 parts of caprolactam monomer, 10 parts of AgTAZ, 2 parts of initiator, 0.1 part of catalyst and 50 parts of aprotic polar solvent.

4. The MCPA6@ AgTAZ composite material as claimed in claim 1 or 3, wherein AgTAZ is a metal-organic framework material synthesized from silver ions and 1,2, 4-triazole.

5. The MCPA6@ AgTAZ composite material as claimed in claim 1 or 3, wherein the metal-organic framework material has a structural dimension of 10-100 nm.

6. The MCPA6@ AgTAZ composite material according to claim 1 or 3, wherein the initiator is an isocyanate, and the isocyanate is one or more of MDI, TDI, HDI, NDI, PAPI, HTDI, HMDI, TMXDI and IPDI.

7. The MCPA6@ AgTAZ composite according to claim 1 or 3, wherein the catalyst is one or more of sodium caprolactam, magnesium caprolactam bromide, NaOH, KOH, Na2CO3, NaH, LiH.

8. The MCPA6@ AgTAZ composite material according to claim 2 or 3, wherein the aprotic polar solvent is one or more of dimethylformamide, dimethylacetamide, pyridine, acetone, tetrahydrofuran, pyrrolidone, toluene and cyclohexane.

9. The MCPA6@ AgTAZ composite material as claimed in any one of claims 1 to 7, wherein the preparation step comprises:

s1, adding AgTAZ and an aprotic polar solvent into a kettle A filled with a caprolactam monomer I according to the proportion, adjusting the temperature of the kettle A to 70-85 ℃, and carrying out stirring reaction for 0.5-2 h;

s2, heating the kettle A in the step S1 to 130-140 ℃, and vacuumizing for 15-60 min under a certain vacuum degree, wherein the vacuum degree of vacuumizing is 99000-99997 Pa; then adding an initiator, and carrying out vacuum pumping reaction for 15-30 min;

s3, filling a caprolactam monomer II into a kettle B, heating until the caprolactam monomer II is dissolved, vacuumizing, completely melting the caprolactam monomer II, adding a catalyst, heating to 130-140 ℃, and continuously vacuumizing for 10-15 min;

and S4, mixing the substances obtained from the kettle A and the kettle B, pouring the mixture into a mold at the temperature of 150-170 ℃ for polymerization molding, reacting for 10-60 min, and naturally cooling to obtain the MCPA6@ AgTAZ composite material.

10. The MCPA6@ AgTAZ composite material as claimed in any one of claims 1 to 8, wherein the MCPA6@ AgTAZ composite material is applied to worm gears, worms, bearings, gears, bearing bushes, sliders and rollers.

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