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CN-122011597-A - Modified PPR pipe with remarkable antibacterial effect and preparation method thereof

CN122011597ACN 122011597 ACN122011597 ACN 122011597ACN-122011597-A

Abstract

The invention discloses a modified PPR pipe with remarkable antibacterial effect and a preparation method thereof, and belongs to the technical field of high polymer materials. The preparation method has the advantages that the antibacterial effect is remarkably improved through various antibacterial mechanisms, the broad-spectrum antibacterial property is shown, the prepared graphene oxide has proper epoxy functional groups, the compatibility and the dispersion stability of the graphene oxide in a matrix can be improved through the modification of isocyanate and ethylenediamine, more antibacterial active sites are given to the graphene oxide, the graphene oxide is effectively prevented from being stacked in the processing process, the remarkable antibacterial property is further exerted, in addition, the nano zinc oxide is loaded on a porous silicon dioxide carrier, the long-lasting release is realized, the synergistic effect of antibacterial components is realized, and the service life of the pipe is prolonged. In addition, when the modified graphene oxide is added into the resin base material, the surface groups can be covalently grafted with the resin base material, so that the mechanical property of the PPR pipe is improved.

Inventors

  • HAN YANWANG
  • Lv Ailong
  • YUAN NAN
  • LIN GUOZHAO
  • WU SHAOZHEN
  • Ruan Fangjie

Assignees

  • 日丰企业（佛山）有限公司
  • 日丰新材有限公司
  • 日丰科技有限公司

Dates

Publication Date
20260512
Application Date
20260305

Claims (10)

  1. 1. The modified PPR pipe with remarkable antibacterial effect is characterized by comprising the following preparation raw materials in parts by weight: 100 parts of PPR resin base stock, 0.5-5 parts of composite antibacterial material, 1-5 parts of compatilizer, 0.5-5 parts of plasticizer, 0.5-5 parts of coupling agent, 0.2-1 part of antioxidant and 0.3-1.5 parts of lubricant; the composite antibacterial material is prepared by mixing an antibacterial component A and an antibacterial component B in a mass ratio of (4-7) to (3-6); the antibacterial component A is modified graphene oxide, and the antibacterial component B comprises a carrier and nano zinc oxide loaded on the carrier.
  2. 2. The modified PPR tubing with significant antimicrobial properties of claim 1, wherein the modified graphene oxide is prepared by the process of: Adding graphite powder into a certain amount of concentrated sulfuric acid, uniformly mixing, carrying out electromagnetic stirring treatment for 10 min-15 min in an ice-water bath, slowly adding KMnO 4 , reacting for 1H-3H at 30-45 ℃, gradually adding deionized water, continuously stirring for 1H-3H at 90-95 ℃, cooling to room temperature, adding H 2 O 2 , uniformly stirring, standing for 3H-5H, washing with hydrochloric acid and deionized water, centrifuging, washing with deionized water again to neutrality, and obtaining graphene oxide; Dispersing the graphene oxide in N, N-dimethylamide, carrying out ultrasonic treatment to peel off the graphene oxide, then adding isocyanate and ethylenediamine, magnetically stirring for 20-30min, carrying out suction filtration, washing for multiple times with ethanol and deionized water, and drying to obtain the modified graphene oxide.
  3. 3. The modified PPR pipe with remarkable antibacterial effect according to claim 2, wherein the addition amount ratio of the graphite powder to the concentrated sulfuric acid is (1-5) g/100mL; the proportion of the graphite powder to the KMnO 4 to the H 2 O 2 is (1-5) g (15-20) mL; The ratio of graphene oxide to N, N-dimethylamide to isocyanate to ethylenediamine is (1-7) g (10-15) mL (1-2) g (5-10) mL.
  4. 4. The modified PPR tubing with significant antimicrobial properties of claim 2, wherein the graphene oxide has an oxygen containing functional group ratio of 10% -50% and a size of 1-20 μm.
  5. 5. The modified PPR tubing with significant antimicrobial properties according to claim 1, wherein the carrier is porous silica having an average particle size of 20-100 μm and a pore volume of 0.5cm 3 /g~10cm 3 /g.
  6. 6. The modified PPR tubing with significant antimicrobial properties of claim 5, wherein the nano zinc oxide loading is 5% -20% by weight.
  7. 7. The modified PPR tubing with substantial antimicrobial properties of claim 1, wherein the compatibilizer is at least one of maleic anhydride, maleic anhydride grafted polyethylene wax, polyvinyl butyral.
  8. 8. The modified PPR tubing with substantial antimicrobial properties of claim 1, wherein the plasticizer is at least one of glycerol and polyethylene glycol, and the molecular weight of the glycerol or polyethylene glycol is less than 600.
  9. 9. A preparation method of a modified PPR pipe with remarkable antibacterial effect, which is characterized in that the preparation method is used for preparing the PPR pipe with the composite antibacterial material as claimed in claims 1-8, and comprises the following steps: s1, premixing a PPR resin base material, a composite antibacterial material, a compatilizer, a plasticizer, a coupling agent, an antioxidant and a lubricant at a high speed, and then carrying out melt blending through a double-screw extruder, and carrying out extrusion molding to obtain a tube blank; S2, sizing, cooling, traction and cutting the tube blank to obtain the modified PPR tube with remarkable antibacterial property.
  10. 10. The preparation method according to claim 9, wherein the temperatures of the sections of the twin-screw extruder are set to 150-165 ℃ in the first zone, 170-190 ℃ in the second zone, 190-210 ℃ in the third zone, 200-220 ℃ in the head, and 210-230 ℃ in the die.

Description

Modified PPR pipe with remarkable antibacterial effect and preparation method thereof Technical Field The invention relates to the technical field of high polymer materials, in particular to a modified PPR pipe with remarkable antibacterial effect and a preparation method thereof. Background The random copolymer polypropylene (PPR) pipe has become one of the first choice pipes in the fields of cold and hot water delivery, drinking water systems and the like of buildings because of corrosion resistance, smooth inner wall, convenient installation and good long-term pressure resistance. However, PPR, which is an organic polymer material, does not have an antibacterial function by itself. In the long-term use process, especially when drinking water with proper temperature is conveyed, organic matters and microorganisms in the water are easily adsorbed on the inner wall of the pipeline to form a biological film, so that the biological film becomes a warm bed for bacteria breeding and reproduction, such as escherichia coli, staphylococcus aureus, legionella and the like. The method not only affects the water quality, but also causes scaling and flux reduction on the inner wall of the pipeline, and affects the service life of the material. In order to solve the problems, a blending modification method is generally adopted in the prior art, and an antibacterial agent is added into a PPR base material to prepare the antibacterial PPR pipe. The antibacterial agent commonly used in the prior art mainly comprises organic antibacterial agents such as quaternary ammonium salts, biguanides and the like. The antibacterial agent has the characteristics of high antibacterial speed and remarkable initial effect, but has the problems of poor heat resistance, poor chemical stability, easiness in migration and loss, short effective period and the like, and is difficult to meet the long-term use requirement. The single inorganic antibacterial agent also has the limitation that the ideal balance among high-efficiency broad-spectrum antibacterial, long-acting stability, processing adaptability, cost control and maintaining the original excellent physical properties of the PPR pipe is difficult to achieve. Therefore, the novel composite antibacterial material is developed, the defect of a single antibacterial agent is overcome through the synergistic effect of a plurality of antibacterial components, and the antibacterial agent is stably and uniformly dispersed in a PPR matrix, so that the antibacterial PPR pipe with excellent comprehensive performance is prepared, and the technical problem to be solved in the field is urgent. The invention aims to provide a PPR pipe based on a specific composite antibacterial material and a high-efficiency preparation method thereof, so as to realize the durable, broad-spectrum and safe antibacterial performance of the pipe, and simultaneously ensure that the mechanical performance and the processing performance of the pipe meet the national standard and the use requirement. Disclosure of Invention Based on the above, in order to solve one of the above technical problems, the invention provides a modified PPR pipe with remarkable antibacterial effect and a preparation method thereof, and the specific technical scheme is as follows: the modified PPR pipe with remarkable antibacterial effect comprises the following preparation raw materials in parts by weight: 100 parts of PPR resin base stock, 0.5-5 parts of composite antibacterial material, 1-5 parts of compatilizer, 0.5-5 parts of plasticizer, 0.5-5 parts of coupling agent, 0.2-1 part of antioxidant and 0.3-1.5 parts of lubricant; the composite antibacterial material is prepared by mixing an antibacterial component A and an antibacterial component B in a mass ratio of (4-7) to (3-6); the antibacterial component A is modified graphene oxide, and the antibacterial component B comprises a carrier and nano zinc oxide loaded on the carrier. Further, the preparation method of the modified graphene oxide comprises the following steps: Adding graphite powder into a certain amount of concentrated sulfuric acid, uniformly mixing, carrying out electromagnetic stirring treatment for 10 min-15 min in an ice-water bath, slowly adding KMnO 4, reacting for 1H-3H at 30-45 ℃, gradually adding deionized water, continuously stirring for 1H-3H at 90-95 ℃, cooling to room temperature, adding H 2O2, uniformly stirring, standing for 3H-5H, washing with hydrochloric acid and deionized water, centrifuging, washing with deionized water again to neutrality, and obtaining graphene oxide; Dispersing the graphene oxide in N, N-dimethylamide, carrying out ultrasonic treatment to peel off the graphene oxide, then adding isocyanate and ethylenediamine, magnetically stirring for 20-30min, carrying out suction filtration, washing for multiple times with ethanol and deionized water, and drying to obtain the modified graphene oxide. Further, the addition amount ratio of the graphite p