阅读说明：本技术 一种抗菌pe材料及其制备方法 (Antibacterial PE material and preparation method thereof ) 是由 连鑫森 于 2021-08-23 设计创作，主要内容包括：本发明提出了一种抗菌PE材料及其制备方法,属于塑料技术领域,由以下原料按重量份制备而成：抗菌PE树脂100-150份、阻燃剂5-10份、抗氧剂2-3份、增塑剂3-5份；所述抗菌PE树脂具有如式Ⅰ所示结构；其中,n=100-500。本发明制得的抗菌PE树脂,不仅具有良好的抗菌、抑菌性能,还具有极佳的阻燃性能,力学性能好,抗氧化、耐老化性能佳,具有广阔的应用前景。(The invention provides an antibacterial PE material and a preparation method thereof, belonging to the technical field of plastics and being prepared from the following raw materials in parts by weight: 100-150 parts of antibacterial PE resin, 5-10 parts of flame retardant, 2-3 parts of antioxidant and 3-5 parts of plasticizer; the antibacterial PE resin has the formula I)

1. The antibacterial PE material is characterized by being prepared from the following raw materials: antibacterial PE resin, a flame retardant, an antioxidant and a plasticizer; the antibacterial PE resin has a structure as shown in a formula I:

formula I;

wherein n = 100-500.

2. The antibacterial PE material according to claim 1, which is prepared from the following raw materials in parts by weight: 100-150 parts of antibacterial PE resin, 5-10 parts of flame retardant, 2-3 parts of antioxidant and 3-5 parts of plasticizer.

3. The antibacterial PE material according to claim 2, wherein the antibacterial PE resin is prepared by a method comprising:

s1, dissolving 4-aminobenzene-1, 3-diol in dichloromethane, adding benzoic acid and polyphosphoric acid, reacting for 5-10 hours under reflux, adding a saturated sodium carbonate solution, filtering, washing a solid with dichloromethane, and drying to obtain an intermediate A, wherein the structure of the intermediate A is shown in a formula II;

formula II;

s2, dissolving the intermediate A in dichloromethane, placing in an ice water bath, dropwise adding thionyl chloride, reacting at room temperature for 1-2h, adding a saturated sodium carbonate solution, filtering, washing the solid with dichloromethane, and drying to obtain an intermediate B, wherein the structure is shown in a formula III;

formula III;

s3, dissolving polyvinyl alcohol in DMF, placing in an ice water bath, adding NaH under the protection of nitrogen, stirring to react for 1-2h, then adding the intermediate B, stirring to react for 3-5h at 50-70 ℃, adding a saturated sodium carbonate solution, filtering, washing the solid with ethanol, and drying to obtain the antibacterial PE resin.

4. The antibacterial PE material according to claim 3, wherein the ratio of the amounts of the 4-aminobenzene-1, 3-diol, benzoic acid and polyphosphoric acid in step S1 is 1: (1.02-1.1): (0.5-1).

5. The antibacterial PE material of claim 3, wherein the ratio of the amounts of intermediate a and thionyl chloride in step S2 is 1: (1.05-1.2).

6. The PE material as claimed in claim 3, wherein the mass ratio of the PVA, NaH and intermediate B in step S3 is 4: (3-5): (25-30).

7. The antimicrobial PE material according to claim 1, wherein the flame retardant is selected from the group consisting of aluminum hydroxide, magnesium hydroxide, phosphorus-based flame retardants, nitrogen-based flame retardants, preferably phosphorus-based flame retardants selected from at least one of red phosphorus, ammonium polyphosphate, tricresyl phosphate, resorcinol bis (diphenyl) phosphate, melamine polyphosphate, and ammonium polyphosphate.

8. The antibacterial PE material according to claim 7, wherein the phosphorus flame retardant is a compound mixture of resorcinol bis (diphenyl) phosphate and ammonium polyphosphate, and the mass ratio is (3-7): 2.

9. the antimicrobial PE material according to claim 1, wherein the antioxidant is selected from at least one of diphenylamine, p-phenylenediamine, dihydroquinoline, 2, 6-t-butyl-4-methylphenol, bis (3, 5-t-butyl-4-hydroxyphenyl) sulfide, pentaerythrityl tetrakis [ β - (3, 5-t-butyl-4-hydroxyphenyl) propionate ] and dioctadecyl thiodipropionate; the plasticizer is at least one selected from di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, diisodecyl phthalate and dialkyl adipate.

10. A process for the preparation of an antimicrobial PE material according to any one of claims 1 to 9, characterized in that it comprises the following steps: and (3) carrying out melt extrusion on the antibacterial PE resin, the flame retardant, the antioxidant and the plasticizer at the temperature of 170-200 ℃ to obtain the antibacterial PE material.

Technical Field

The invention relates to the technical field of plastics, in particular to an antibacterial PE material and a preparation method thereof.

Background

The plastic is a synthetic polymer material with wide application, and the finished plastic products are all better in daily life. From school supplies, living goods to household appliances, plastics gradually replace many utensils and materials which have been used for decades or even hundreds of years with excellent performance, and become indispensable substances in people's life. With the rapid development of the polymer material industry, plastic processing has formed a department with complete types and various varieties and playing a great role in the development of national economy for several decades.

Polyethylene (PE) has excellent physical and mechanical properties, electrical insulation properties, and flexible and versatile processing properties, and its overall properties are incomparable with most other thermoplastic resins, and is one of the most widely used thermoplastics. Although polyethylene has been widely used in engineering, its inherent drawbacks and deficiencies limit its further applications. With the development of science and technology, engineering application puts higher requirements on the antibacterial property, the mechanical property and the flame retardant property of polyethylene materials.

Patent No. CN101081928A proposes a method for preparing a nano composite material, which adopts a water-assisted method to prepare a polyamide/nano montmorillonite master batch, and the preparation method comprises the steps of using deionized water as an intercalation agent, mixing purified montmorillonite and deionized water, fully dispersing to prepare montmorillonite slurry, gradually adding the montmorillonite slurry into polyamide with completely melted components, and then extruding and granulating to obtain the polyamide/nano montmorillonite master batch. The preparation method is simple and low in production cost, but the montmorillonite slurry is added after the polyamide is melted, so that the montmorillonite slurry is not ready to be completely mixed with the copolymer, water between layers is gasified at high temperature, and the montmorillonite cannot be well dispersed into the polyamide, so that the product performance is improved to a limited extent; in addition, the montmorillonite slurry can be injected into the double screws only by increasing a certain pressure in the charging mode, and meanwhile, because the processing section of the double screws is short, the feeding interval of the montmorillonite slurry is increased midway, the length of the double screws needs to be increased, so that the process is more complicated and the cost is higher.

Patent No. CN107216530B proposes a PE composite material and a preparation method thereof, wherein the PE composite material comprises the following components in parts by weight: 80-100 parts of PE; 10-20 parts of modified wollastonite; 0.1 to 0.5 portion of antioxidant; 0.1 to 0.3 portion of lubricant. In the application, alcoholic hydroxyl in the rare earth solution treating agent can be chemically combined with silicon hydroxyl on the surface of wollastonite, which is beneficial to improving the dispersion of mica powder in a polyolefin matrix; by preparing the modified wollastonite with the wollastonite as a core and the PE as a shell, the structure is formed so that the modified wollastonite has good compatibility with the PE at a contact interface. However, the rare earth solution has high cost, so that the application of the PE composite material is greatly limited.

Disclosure of Invention

The invention aims to provide an antibacterial PE material and a preparation method thereof, which not only have good antibacterial and bacteriostatic properties, but also have excellent flame retardant property, good mechanical property, good oxidation resistance and aging resistance, and have wide application prospect.

The technical scheme of the invention is realized as follows:

the invention provides an antibacterial PE material which is prepared from the following raw materials: antibacterial PE resin, a flame retardant, an antioxidant and a plasticizer; the antibacterial PE resin has a structure as shown in a formula I:

formula I;

wherein n = 100-500.

As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 100-150 parts of antibacterial PE resin, 5-10 parts of flame retardant, 2-3 parts of antioxidant and 3-5 parts of plasticizer.

As a further improvement of the invention, the antibacterial PE resin is prepared by the following method:

s1, dissolving 4-aminobenzene-1, 3-diol in dichloromethane, adding benzoic acid and polyphosphoric acid, reacting for 5-10 hours under reflux, adding a saturated sodium carbonate solution, filtering, washing a solid with dichloromethane, and drying to obtain an intermediate A, wherein the structure of the intermediate A is shown in a formula II;

formula II;

s2, dissolving the intermediate A in dichloromethane, placing in an ice water bath, dropwise adding thionyl chloride, reacting at room temperature for 1-2h, adding a saturated sodium carbonate solution, filtering, washing the solid with dichloromethane, and drying to obtain an intermediate B, wherein the structure is shown in a formula III;

formula III;

s3, dissolving polyvinyl alcohol in DMF, placing in an ice water bath, adding NaH under the protection of nitrogen, stirring to react for 1-2h, then adding the intermediate B, stirring to react for 3-5h at 50-70 ℃, adding a saturated sodium carbonate solution, filtering, washing the solid with ethanol, and drying to obtain the antibacterial PE resin.

As a further improvement of the present invention, the ratio of the amounts of the 4-aminobenzene-1, 3-diol, benzoic acid and polyphosphoric acid in step S1 is 1: (1.02-1.1): (0.5-1).

As a further improvement of the present invention, the ratio of the amounts of the intermediate a and thionyl chloride in step S2 is 1: (1.05-1.2).

As a further improvement of the present invention, in step S3, the mass ratio of the polyvinyl alcohol, NaH, and intermediate B is 4: (3-5): (25-30).

In a further improvement of the present invention, the flame retardant is selected from aluminum hydroxide, magnesium hydroxide, phosphorus flame retardants, nitrogen flame retardants, preferably phosphorus flame retardants, and at least one selected from red phosphorus, polyphosphoric acid amine, tricresyl phosphate, resorcinol bis (diphenyl) phosphate, melamine polyphosphate, and ammonium polyphosphate.

As a further improvement of the invention, the phosphorus flame retardant is a compound mixture of resorcinol bis (diphenyl) phosphate and ammonium polyphosphate, and the mass ratio is (3-7): 2.

in a further improvement of the present invention, the antioxidant is at least one selected from diphenylamine, p-phenylenediamine, dihydroquinoline, 2, 6-tert-butyl-4-methylphenol, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythrityl tetrakis [ beta- (3, 5-tert-butyl-4-hydroxyphenyl) propionate ] and dioctadecyl thiodipropionate; the plasticizer is at least one selected from di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, diisodecyl phthalate and dialkyl adipate.

The invention further provides a preparation method of the antibacterial PE material, which comprises the following steps: and (3) carrying out melt extrusion on the antibacterial PE resin, the flame retardant, the antioxidant and the plasticizer at the temperature of 170-200 ℃ to obtain the antibacterial PE material.

The invention has the following beneficial effects: according to the antibacterial PE resin, a structure with an oxazole ring is connected to a polyethylene molecular chain through the reaction of polyvinyl alcohol and an intermediate B, so that a resin molecular structure with the oxazole ring on each unit of the polyethylene molecular chain is obtained, and due to the special nitrogen-oxygen heterocyclic structure of the oxazole ring, various non-covalent interactions can occur, including the formation of hydrogen bonds, coordination with metal ions, hydrophobic interaction, pi-pi accumulation, electrostatic interaction and the like, so that the antibacterial PE resin can easily react with microorganisms such as bacteria, fungi, viruses and the like to damage the biological structure of germs, and thus, the antibacterial PE resin has strong antibacterial activity and broad-spectrum antibacterial performance; in addition, the nitrogen element in the oxazole ring structure on the unit makes the resin rich in nitrogen, so that the resin is heated to release CO₂、N₂、NH₃And H₂The concentration of combustible materials generated by oxygen in air and polymer decomposition under heating is diluted by incombustible gases such as O and the like, and meanwhile, a part of heat can be taken away in heat convection, so that a good flame-retardant heat-resistant effect is achieved;

the flame retardant is preferably a phosphorus flame retardant, the phosphorus flame retardant is decomposed to generate a phosphoric acid liquid film to protect a polymer matrix, phosphoric acid is further dehydrated to generate metaphosphoric acid, the metaphosphoric acid is further polymerized to generate polymetaphosphoric acid, the generation of the polymetaphosphoric acid is the key of dehydration and carbonization of a high polymer, and a carbon layer coated on the surface of the material is formed after the high polymer is dehydrated and carbonized, so that the phosphorus flame retardant can synergize with nitrogen in the antibacterial resin, and a good flame retardant effect is achieved;

the antibacterial PE resin prepared by the invention has good antibacterial and bacteriostatic properties, excellent flame retardant property, good mechanical property, good oxidation resistance and aging resistance, and wide application prospect.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Preparation example 1

The antibacterial PE resin is prepared by the following method:

s1, dissolving 1mol of 4-aminobenzene-1, 3-diol in 200mL of dichloromethane, adding 1.02mol of benzoic acid and 0.5mol of polyphosphoric acid, reacting for 5 hours under reflux, adding 200mL of saturated sodium carbonate solution, filtering, washing a solid with dichloromethane, and drying to obtain an intermediate A, wherein the structure of the intermediate A is shown as a formula II;

formula II;

the synthetic route is as follows:

s2, dissolving 1mol of the intermediate A in 200mL of dichloromethane, placing in an ice water bath, dropwise adding 1.05mol of thionyl chloride, reacting for 1h at room temperature, adding 200mL of saturated sodium carbonate solution, filtering, washing the solid with dichloromethane, and drying to obtain an intermediate B, wherein the structure is shown in a formula III;

formula III;

the synthetic route is as follows:

s3, dissolving 40g of polyvinyl alcohol in 200mL of DMF, placing in an ice water bath, adding 30g of NaH under the protection of nitrogen, stirring for reaction for 1h, then adding 250g of intermediate B, stirring for reaction for 3h at 50 ℃, adding 200mL of saturated sodium carbonate solution, filtering, washing the solid with ethanol, and drying to obtain the antibacterial PE resin.

The synthetic route is as follows:

preparation example 2

The antibacterial PE resin is prepared by the following method:

s1, dissolving 1mol of 4-aminobenzene-1, 3-diol in 200mL of dichloromethane, adding 1.1mol of benzoic acid and 1mol of polyphosphoric acid, reacting for 10 hours under reflux, adding 200mL of saturated sodium carbonate solution, filtering, washing a solid with dichloromethane, and drying to obtain an intermediate A;

s2, dissolving 1mol of the intermediate A in 200mL of dichloromethane, placing in an ice water bath, dropwise adding 1.2mol of thionyl chloride, reacting for 2 hours at room temperature, adding 200mL of saturated sodium carbonate solution, filtering, washing the solid with dichloromethane, and drying to obtain an intermediate B;

s3, dissolving 40g of polyvinyl alcohol in 200mL of DMF, placing in an ice water bath, adding 50g of NaH under the protection of nitrogen, stirring for reacting for 2h, then adding 300g of intermediate B, stirring for reacting for 5h at 70 ℃, adding 200mL of saturated sodium carbonate solution, filtering, washing the solid with ethanol, and drying to obtain the antibacterial PE resin.

Preparation example 3

The antibacterial PE resin is prepared by the following method:

s1, dissolving 1mol of 4-aminobenzene-1, 3-diol in 200mL of dichloromethane, adding 1.08mol of benzoic acid and 0.7mol of polyphosphoric acid, reacting for 7 hours under reflux, adding 200mL of saturated sodium carbonate solution, filtering, washing a solid with dichloromethane, and drying to obtain an intermediate A;

s2, dissolving 1mol of the intermediate A in 200mL of dichloromethane, placing in an ice water bath, dropwise adding 1.1mol of thionyl chloride, reacting at room temperature for 1.5h, adding 200mL of saturated sodium carbonate solution, filtering, washing the solid with dichloromethane, and drying to obtain an intermediate B;

s3, dissolving 40g of polyvinyl alcohol in 200mL of DMF, placing in an ice water bath, adding 40g of NaH under the protection of nitrogen, stirring for reacting for 1.5h, then adding 270g of intermediate B, stirring for reacting for 4h at 60 ℃, adding 200mL of saturated sodium carbonate solution, filtering, washing the solid with ethanol, and drying to obtain the antibacterial PE resin.

Example 1

The raw materials comprise the following components in parts by weight: 100 parts of the antibacterial PE resin obtained in preparation example 1, 5 parts of a flame retardant, 2 parts of tetra [ beta- (3, 5-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 3 parts of dialkyl adipate. The flame retardant is a phosphorus flame retardant which is a compound mixture of resorcinol bis (diphenyl) phosphate and ammonium polyphosphate, and the mass ratio is (3-7): 2.

the method comprises the following steps: carrying out melt extrusion on the antibacterial PE resin, the flame retardant, the tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and the adipic acid dialkyl ester at the temperature of 190 ℃ to obtain the antibacterial PE material.

Example 2

Compared with the example 1, the raw materials and the mixture ratio are different, and other conditions are not changed.

The raw materials comprise the following components in parts by weight: 150 parts of the antibacterial PE resin prepared in preparation example 2, 10 parts of a flame retardant, 3 parts of p-phenylenediamine and 5 parts of dicyclohexyl phthalate. The flame retardant is a phosphorus flame retardant, is a compound mixture of resorcinol bis (diphenyl) phosphate and ammonium polyphosphate, and has a mass ratio of 3: 2.

example 3

Compared with the example 1, the raw materials and the mixture ratio are different, and other conditions are not changed

The raw materials comprise the following components in parts by weight: 125 parts of the antibacterial PE resin prepared in preparation example 3, 7 parts of a flame retardant, 2.5 parts of dioctadecyl thiodipropionate and 4 parts of di (2-ethylhexyl) phthalate. The flame retardant is a phosphorus flame retardant, is a compound mixture of resorcinol bis (diphenyl) phosphate and ammonium polyphosphate, and has a mass ratio of 7: 2.

example 4

Compared with example 3, the flame retardant is resorcinol bis (diphenyl) phosphate, and other conditions are not changed.

Example 5

Compared with example 3, the flame retardant is ammonium polyphosphate, and other conditions are not changed.

Comparative example 1

In comparison with example 3, no flame retardant was added, and the other conditions were not changed.

The raw materials comprise the following components in parts by weight: 132 parts of the antibacterial PE resin prepared in preparation example 3, 2.5 parts of dioctadecyl thiodipropionate and 4 parts of di (2-ethylhexyl) phthalate.

Comparative example 2

Compared with example 3, the antibacterial PE resin prepared in preparation 3 was replaced with a general PE resin, and other conditions were not changed.

The raw materials comprise the following components in parts by weight: 125 parts of PE resin, 7 parts of flame retardant, 2.5 parts of dioctadecyl thiodipropionate and 4 parts of di (2-ethylhexyl) phthalate. The flame retardant is a phosphorus flame retardant, is a compound mixture of resorcinol bis (diphenyl) phosphate and ammonium polyphosphate, and has a mass ratio of 7: 2.

test example 1

Test objects: the antibacterial PE materials obtained in examples 1 to 5 and comparative examples 1 to 2.

The flame-retardant antibacterial PVC material is dried for 5 hours in a constant-temperature oven at 95 ℃, and then is heated and injected into a plastic sample with the diameter of 50mm multiplied by 50mm for an antibacterial test.

1. Antibacterial activity against Escherichia coli and Staphylococcus aureus

Testing is carried out according to a test method 1 pasting method of standard GB21551.2-2010, and bacteria for detection: escherichia coli; staphylococcus aureus bacteria; candida albicans; each example and comparative example was tested in parallel for 5 and averaged. The results are shown in Table 1.

TABLE 1

Group of	Antibacterial ratio of Escherichia coli (%)	Staphylococcus aureus antibacterial ratio (%)	Candida albicans (%)
				Example 1	>99.9	>99.9	>99.9
Example 2	>99.9	>99.9	>99.9
				Example 3	>99.9	>99.9	>99.9
Example 4	98.3	97.8	96.5
				Example 5	97.9	97.4	96.2
Comparative example 1	97.0	96.9	95.7
				Comparative example 2	45.2	40.1	34.5

2. Inhibition rate to mould

The test was carried out according to the test method of Standard QB/T2591 (2003) with the following bacteria: aspergillus niger, Aspergillus terreus, Aureobasidium pullulans, 5 per example and comparative example were tested in parallel and the average was taken. The results are shown in Table 2.

TABLE 2

Group of	Aspergillus niger mould growth grade	Aspergillus terreus growth grade	Aureobasidium pullulans grade of mold growth
				Example 1	Level 0	Level 0	Level 0
Example 2	Level 0	Level 0	Level 0
				Example 3	Level 0	Level 0	Level 0
Example 4	Level 0	Level 0	Level 0
				Example 5	Level 0	Level 0	Level 0
Comparative example 1	Level 1	Level 0	Level 0
				Comparative example 2	Level 0	Level 1	Level 0

As can be seen from the above table, the antibacterial PE material prepared by the invention has good antibacterial, bacteriostatic and mildewproof effects.

Test example 2

Test objects: the antibacterial PE materials obtained in examples 1 to 5 and comparative examples 1 to 2.

The products obtained in the above examples and comparative examples were subjected to a performance test after artificially accelerated aging under conditions of (90 ℃, 500 hours); the results are shown in Table 3.

TABLE 3

Group of	Mass change rate before and after aging (%)	Tensile Strength holding ratio (%)	Retention ratio of impact Strength (%)
				Example 1	0.34	95.6	96.2
Example 2	0.32	95.2	96.8
				Example 3	0.31	96.4	97.2
Example 4	0.54	92.1	91.5
				Example 5	0.57	91.0	91.0
Comparative example 1	0.67	87.5	86.8
				Comparative example 2	0.92	84.2	82.4

As can be seen from the above table, the antibacterial PE material prepared by the embodiment of the invention has good aging resistance.

Test example 4

Test objects the antibacterial PE materials prepared in examples 1 to 7 and comparative examples 1 to 3 were used.

The test method comprises the following steps:

the oxygen index is tested according to the GB/T2406-1993 standard; the vertical burning grade is tested according to GB/T2408 + 2008 standard, and the thickness of the test sample is 3.2 mm; the results are shown in Table 4.

TABLE 4

Group of	Oxygen index (%)	Vertical combustion rating
			Example 1	32.5	V-0
Example 2	32.7	V-0
			Example 3	33.0	V-0
Example 4	29.5	V-1
			Example 5	30.2	V-1
Comparative example 1	27.2	V-2
			Comparative example 2	22.5	HB

As can be seen from the table above, the antibacterial PE material prepared by the invention has good flame retardant and high temperature resistance.

Test example 4

Test objects the antibacterial PE materials prepared in examples 1 to 7 and comparative examples 1 to 3 were used.

The test method comprises the following steps: the tensile strength is tested according to the method GB/T8804.3-2003, the elongation at break is determined according to the method GB/T8804.3-2003, and the impact strength is determined according to the method GB/T1043.1-2008. The results are shown in Table 5.

TABLE 5

Group of	Tensile Strength (MPa)	Elongation at Break (%)	Impact Strength (KJ/m)2）
				Example 1	58.9	490	24
Example 2	59.2	510	25
				Example 3	59.5	515	27
Example 4	54.2	470	22
				Example 5	55.7	475	21
Comparative example 1	50.4	400	20
				Comparative example 2	42.5	310	19

As can be seen from the above table, the antibacterial PE material prepared by the invention has good mechanical properties.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.