CN115181364B - Modified core-shell master batch toughened PPR pipe - Google Patents

Modified core-shell master batch toughened PPR pipe Download PDF

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CN115181364B
CN115181364B CN202210910654.2A CN202210910654A CN115181364B CN 115181364 B CN115181364 B CN 115181364B CN 202210910654 A CN202210910654 A CN 202210910654A CN 115181364 B CN115181364 B CN 115181364B
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ppr
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pipe
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CN115181364A (en
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蓝俊
梁玉梓
施凯隆
李鸿林
李源辉
卢展
莫衍超
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Guangxi Xiongsu Technology Development Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • F16L9/121—Rigid pipes of plastics with or without reinforcement with three layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment

Abstract

The invention discloses a modified core-shell master batch toughened PPR pipe, which comprises a pipe body, wherein the pipe body sequentially comprises an outer layer, a middle layer and an inner layer from outside to inside, and the outer layer comprises the following raw materials in parts by weight: 90-120 parts of PPR resin, 1-3 parts of modified nano calcium carbonate, 3-5 parts of polypropylene wax, 4-6 parts of ethylene propylene diene monomer rubber and 1-2 parts of dispersing agent; the middle layer consists of the following raw materials in parts by weight: 95-130 parts of PPR resin, 0.1-0.9 part of POE plastic, 3-5 parts of ethylene-vinyl alcohol copolymer, 15-25 parts of carbon fiber and 1-3 parts of coupling agent; the inner layer is composed of the following raw materials in parts by weight: 90-120 parts of PPR resin, 3-5 parts of ethylene propylene diene monomer rubber, 5-8 parts of graphene oxide-nano silver particles and 1-5 parts of antioxidant. The PPR pipe has high impact strength, creep resistance, simple process, low production cost, the middle layer is an ultraviolet resistant layer, bacterial breeding generated by illumination is reduced, and the antibacterial layer arranged on the inner layer enables self-cleaning to be directly generated by contact with water, so that the self-cleaning capability is strong.

Description

Modified core-shell master batch toughened PPR pipe
Technical Field
The invention belongs to the technical field of plastic pipeline materials, and particularly relates to a modified core-shell masterbatch toughened PPR (polypropylene random) pipe.
Background
The PPR pipe is also called as a three-type propylene copolymer pipe, is prepared from a non-toxic, light and pressure-resistant random copolymer polypropylene material, has the advantages of corrosion resistance, aging resistance, environmental protection, safety and the like, has the characteristics of smooth inner wall, small water flow loss, long service life, convenient construction and the like, and plays an extremely important role in industrial production and civil building cold and hot water pipe systems, air supply systems, heating systems and drinking water systems.
PPR pipe is easy to cause thermal expansion to be large because of high temperature, notch impact resistance is low, impact resistance is low in low temperature, creep deformation is easy to generate in a hydraulic environment for a long time, if micro cracks exist in the pipe in the manufacturing process, the creep deformation is gradually increased in a long-time pressure environment, and therefore pipe fracture is caused. In addition, because PPR water supply pipe is installed in wall body or subaerial, generally can not change easily, breeds a large amount of bacteria on the inner pipe wall very easily after long-time use, causes water bacterial pollution, and the self-cleaning ability of body inner wall is poor, breeds a large amount of dirt, bacteria, algae plant, influences the water quality on the one hand, on the other hand increases the conveying resistance.
At present, the low-temperature impact resistance performance schemes comprise adding a beta nucleating agent (such as Chinese patent CN 106380698A), adding an alpha nucleating agent (CN 112852061A) and the like, but the beta nucleating agent has harsh nucleating conditions, extremely high cost, lower crystallization rate of the alpha nucleating agent and longer cooling time. The antibacterial self-cleaning scheme has the antibacterial self-cleaning function through the strong expansion capability of the pipe body (such as Chinese patent CN 109253321A), and the method is that the inner wall surface is made into a corrugated shape, but if the contraction and expansion degree of the inner layer is insufficient, dirt is deposited in the groove, so that the cleaning cannot be completely realized.
In view of the above, the invention provides a modified core-shell masterbatch toughened PPR pipe.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified core-shell masterbatch toughened PPR pipe. The technical scheme used for realizing the purpose of the invention is as follows:
the modified core-shell masterbatch toughened PPR pipe comprises a pipe body, wherein the pipe body is composed of an outer layer, a middle layer and an inner layer from outside to inside in sequence, and the outer layer is composed of the following raw materials in parts by weight: 90-120 parts of PPR resin, 1-3 parts of modified nano calcium carbonate, 4-6 parts of ethylene propylene diene monomer rubber and 1-2 parts of dispersing agent;
the middle layer consists of the following raw materials in parts by weight: 95-130 parts of PPR resin, 0.1-0.9 part of POE plastic, 3-5 parts of ethylene-vinyl alcohol copolymer, 15-25 parts of carbon fiber and 1-3 parts of coupling agent;
the inner layer is composed of the following raw materials in parts by weight: 90-120 parts of PPR resin, 3-5 parts of ethylene propylene diene monomer rubber, 5-8 parts of graphene oxide-nano silver particles and 1-5 parts of antioxidant.
Further, the outer layer is composed of the following raw materials in parts by weight: 95-110 parts of PPR resin, 2-3 parts of modified nano calcium carbonate, 4.5-5.5 parts of ethylene propylene diene monomer rubber and 1.2-1.8 parts of dispersing agent;
the middle layer consists of the following raw materials in parts by weight: 100-125 parts of PPR resin, 0.5-0.8 part of POE plastic, 3.5-4.5 parts of ethylene-vinyl alcohol copolymer, 18-23 parts of carbon fiber and 1.5-2.5 parts of coupling agent;
the inner layer is composed of the following raw materials in parts by weight: 95-115 parts of PPR resin, 3.5-4.5 parts of ethylene propylene diene monomer rubber, 6-8 parts of graphene oxide-nano silver particles and 2-4 parts of antioxidant.
Further, the raw material mass of the outer layer: the mass of the raw materials of the middle layer: the mass of the raw materials of the inner layer is 2:1:1.
Further, the preparation method of the modified nano calcium carbonate comprises the following steps: adding calcium carbonate into a high-speed mixer with a certain temperature, stirring for a period of time, slowly adding the Acrylic Acid (AA) dissolved in the acetone and the initiator, continuously stirring, adding polypropylene wax (PPW) into the high-speed mixer, stirring, increasing the temperature of the high-speed mixer, stirring, and discharging. The mass ratio of the added calcium carbonate to the acrylic acid to the initiator polypropylene wax (PPW) is 4:1:2: (2-4).
Further, adding calcium carbonate into a high-speed mixer of a charging basket at 50-60 ℃, stirring for 20-80min, slowly adding the Acrylic Acid (AA) dissolved in the acetone and the initiator, continuously stirring, adding polypropylene wax into the high-speed mixer, stirring, raising the temperature of the high-speed mixer to 80-120 ℃, stirring at a rotating speed of 100-120r/min, and discharging.
Inorganic rigid particles for outer-layer pipes are modified nano calcium carbonate (CaCO) 3 ) The elastomer adopts Ethylene Propylene Diene Monomer (EPDM), the EPDM has good compatibility with PPR, and is often used as a PPR toughening agent, but the calcium carbonate has high surface energy, poor interfacial bonding force with EPDM and PPR resin, and is difficult to uniformly disperse in a matrix, and firstly, acrylic Acid (AA) is used for preprocessing the surface of the calcium carbonate: calcium carbonate is added into a high-speed mixer with a certain charging basket temperature, after stirring for a period of time, the Acrylic Acid (AA) and an initiator (preferably BPO) which are metered and dissolved in acetone are slowly added, and stirring is continued. At this time, an active double bond group is introduced to the surface of the calcium carbonate. Solid phase graft polymer: continuously adding metered polypropylene wax (PPW) into a high-speed mixer, stirring and discharging, raising the temperature of a charging basket of the high-speed mixer, pouring the materials into the charging basket, stirring at high speed, discharging to obtain solid-phase grafting modified CaCO 3 -PPW。
CaCO (CaCO) for outer layer pipe 3 Blending PPW, EPDM, PPR and dispersant to prepare PPR/EPDM/CaCO 3 -PPW mix, caCO 3 PPW is coated by EPDM to form core-shell structure master batch, caCO 3 PPW as "core" and EPDM as "shell" with rigid CaCO 3 The PPW is distributed in the resin matrix at the same time, so that the rigidity and strength of the material are ensured, the PPW is uniformly dispersed in the PPR resin matrix through the dispersing agent, so that the PPW has good compatibility, and forms effective interfacial adhesion with the resin matrix, so that the uniform stress transmission is promoted, the stress concentration is slowed down, the crack growth and creep rupture are prevented, and the toughness and strength of the outer layer composite material are improved.
Further, the preparation method of the graphene oxide-nano silver particles comprises the following steps:
(1) Graphite, concentrated sulfuric acid, potassium permanganate and sodium nitrate react for a certain time under the water bath ultrasonic condition;
(2) After the pH is regulated, the temperature is raised, hydrogen peroxide is added for reaction for a period of time, and then the mixture is cooled to room temperature;
(3) Centrifuging and washing off superfluous hydrogen peroxide;
(4) Placing silver nitrate powder into the solution in the step (3);
(5) Heating the solution in the step (4), performing ultrasonic mixing for a period of time, adding sodium citrate, mixing and stirring, and standing for precipitation;
(6) Washing, suction filtering and drying the precipitate obtained in the step (5) to obtain the nano-porous material.
Further, in the step (1), the mass ratio of graphite, concentrated sulfuric acid, potassium permanganate and sodium nitrate is (1-2): (10-20): (10-20): (0.1-2); and reacting for 40-50min under the condition of water bath ultrasonic at 30-35 ℃.
Further, in the step (2), the temperature is raised to 85-90 ℃, and after adding 20-30 ωt% hydrogen peroxide for reaction for 10-20min, the mixture is cooled to room temperature.
Further, in the step (4), adding silver nitrate powder and graphite in a mass ratio of (3-5) (12-15); in the step (5), the temperature of the solution is raised to 80-90 ℃ and ultrasonic mixing is carried out for 30-40min.
Further, the preparation method of the modified core-shell master batch toughened PPR pipe comprises the following steps:
(1) Weighing the raw materials according to the outer layer, the middle layer and the inner layer in sequence for proportioning;
(2) Stirring the outer layer raw material at 80-90 ℃ for 2-3h; stirring the middle layer material at 100-120deg.C for 60-80min, stirring the inner layer material at 110-150deg.C for 50-70min,
(3) Putting the inner layer mixed material into an extruder for extrusion to obtain an inner layer pipe body, wherein the temperature of a charging barrel of the extruder is controlled to be 170-180 ℃, and the temperature of a die is controlled to be 180-200 ℃; cooling the formed inner layer pipe body to 100-150 ℃ in a vacuum environment;
(4) Heating the middle layer mixed material to 185-195 ℃ to be in a molten state, attaching the mixed material on the outer surface of the inner layer to form a thickness of 1-2mm, and cooling the formed middle layer pipe body to 120-140 ℃ in a vacuum environment;
(5) Heating the outer layer mixed material to 175-185 ℃ to be in a molten state, adhering the outer layer mixed material to the outer surface of the middle layer to form a thickness of 1-2mm, cooling and shaping the formed pipe body in a vacuum environment, and pulling out the pipe body after cooling.
The modified core-shell master batch toughened PPR pipe is particularly suitable for cold and hot water conveying pipes.
In summary, the invention adopts the technical scheme, and has the following technical effects:
(1) The invention firstly modifies calcium carbonate with polypropylene wax to obtain a solid phase grafting structure, adopts CaCO 3 The PPW is used as a nucleating agent, the process is simple and convenient, the cost is low, the crystallization rate is high, and cooling is not required in the processing process. The toughness and strength of the pipe can prevent the creep of the pipe in the hydraulic environment and prolong the service life of the pipe.
(2) The carbon fiber has an effect of improving the low-temperature impact strength of the composite material, the carbon fiber is uniformly dispersed in a matrix, and the carbon fiber is combined with POE plastic and ethylene-vinyl alcohol copolymer for blending, so that the carbon fiber has an ultraviolet-proof effect, reduces more microcracks and plastic deformation generated when the carbon fiber is impacted, and promotes energy absorption, thereby improving the low-temperature impact strength of the material; the carbon fiber and the coupling agent are co-melted, so that the compatibility with PPR is good, the occurrence of agglomeration phenomenon is reduced, and the low-temperature impact strength of the composite material is improved.
(3) According to the invention, the nano silver particles are loaded on the graphene oxide particles and are arranged on the inner layer and the middle ultraviolet-proof layer of the tube body, so that bacterial breeding is reduced, bacteria in water are killed through the nano silver, the nano silver loaded on the graphene particles has a slow release effect, and bacteria can be continuously killed, so that cleaning and antibacterial effects are realized.
(4) The PPR pipe provided by the invention has good hot melting performance, is added into ethylene propylene rubber and PPR through modified sodium carbonate, has good compatibility, and has a high-strength, high-toughness and low linear expansion system, wherein an ultraviolet-proof layer is added to the middle layer through POE plastic and ethylene-vinyl alcohol copolymer, and graphene oxide-nano silver particles are added to the inner layer, so that the PPR pipe has good antibacterial and antibacterial effects.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail by referring to preferred embodiments. It should be noted, however, that many of the details set forth in the description are merely provided to provide a thorough understanding of one or more aspects of the invention, and that these aspects of the invention may be practiced without these specific details.
Example 1:
the method for modifying the calcium carbonate comprises the following steps: adding calcium carbonate into a high-speed mixer of a charging basket at 50-60 ℃, stirring for 20-80min, slowly adding metered acrylic acid and an initiator dissolved in acetone, continuously stirring, continuously adding polypropylene wax into the high-speed mixer, stirring, increasing the temperature of the high-speed mixer to 160-200 ℃, stirring at a high speed, and discharging.
The mass ratio of the added calcium carbonate, acrylic acid, initiator and polypropylene wax (PPW) is 4:1:2: (1-2) the initiator is any one of benzoyl peroxide, tetra-tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and azodiisobutyronitrile. The concentration of the acrylic acid is 2-6mol/L, and the concentration of the initiator is 0.1-0.3mol/L.
Example 2
The preparation method of the graphene oxide-nano silver particles comprises the following steps:
(1) Graphite, concentrated sulfuric acid, potassium permanganate and sodium nitrate react for a certain time under the water bath ultrasonic condition;
(2) After the pH is regulated, the temperature is raised, hydrogen peroxide is added for reaction for a period of time, and then the mixture is cooled to room temperature;
(3) Centrifuging and washing off superfluous hydrogen peroxide;
(4) Placing a silver nitrate solution into the solution in the step (3);
(5) Heating the solution in the step (4), performing ultrasonic mixing for a period of time, adding sodium citrate, mixing and stirring, and standing for precipitation;
(6) Washing, suction filtering and drying the precipitate obtained in the step (5) to obtain the nano-porous material.
In the step (1), the mass ratio of graphite, concentrated sulfuric acid, potassium permanganate and sodium nitrate is (1-2): (10-20): (1-10): (0.1-2); and reacting for 40-50min under the condition of water bath ultrasonic at 30-35 ℃.
And (2) heating to 85-90 ℃, adding 20-30 ωt% hydrogen peroxide to react for 10-20min, and cooling to room temperature.
In the step (4), adding silver nitrate powder and graphite in a mass ratio of 3-5:12-15;
in the step (5), the temperature of the solution is raised to 80-90 ℃ and ultrasonic mixing is carried out for 30-40min.
Example 3-example 10
Example 3-example 10 provides a series of modified core-shell masterbatch toughened PPR pipe preparation methods
Wherein, the modified nano calcium carbonate is prepared by using the method of the example 1, the graphene oxide-nano silver particles are prepared by using the method of the example 2, the composition ratios of the raw materials in the examples 3-10 are shown in the table 1, and the specific preparation method of the PPR pipe comprises the following steps:
(1) Weighing the raw materials according to the outer layer, the middle layer and the inner layer in sequence for proportioning;
(2) Stirring the outer layer raw material at 80-90 ℃ for 2-3h; stirring the middle layer raw material at 100-120deg.C for 60-80min, and stirring the inner layer raw material at 110-150deg.C for 50-70min;
(3) Putting the inner layer mixed material into an extruder for extrusion to obtain an inner layer pipe body, wherein the temperature of a charging barrel of the extruder is controlled to be 170-180 ℃, and the temperature of a die is controlled to be 180-200 ℃; cooling the formed inner layer pipe body to 100-150 ℃ in a vacuum environment;
(4) Heating the middle layer ingredients to 185-195 ℃ to be in a molten state, attaching the ingredients on the outer surface of the inner layer to form a thickness of 1-2mm, and cooling the formed middle layer pipe body to 120-140 ℃ in a vacuum environment;
(5) Heating the outer layer ingredients to 175-185 ℃ to be in a molten state, adhering the ingredients to the outer surface of the middle layer to form a thickness of 1-2mm, cooling and shaping the formed pipe body in a vacuum environment, and pulling out the pipe body after cooling. The pipe wall thickness of the prepared PPR pipe is 2.8-3.5mm.
Table 1 raw material composition (parts by weight) of each example
Application instance
Experimental example 1
The PPR pipes prepared in examples 3-10 were subjected to performance testing, as shown in Table 2, with the following test items and test methods:
(1) Low temperature impact resistance: the low-temperature impact resistance of the PPR pipe is evaluated by measuring a simple beam impact test of the PPR pipe, and the notch impact strength of the pipe at-20 ℃ and 20 ℃ is detected according to GB/T1043.2-2018.
(2) Low temperature drop hammer impact strength: according to the standard of GB/T14152-2001, 100 PPR pipes are tested at 0 ℃ with a hammer weight of 1kg and a height of 0.8m and a hammer head of 25, wherein the PPR pipes are not broken to pass, the PPR pipes are broken to not pass, and the low-temperature impact resistance of the PPR pipes is represented by the passing rate (%).
(3) Rigidity: according to GB/T6111-2003 standard, A-type sealing heads are adopted, hydraulic experiments are respectively carried out at 20 ℃,1h and 95 ℃ for 22h, 100 PPR pipes are tested, whether pipe explosion exists or not is observed, no pipe explosion is qualified, and the qualification rate (%) is evaluated.
(4) Heat resistance: PPR heat resistance was evaluated by using load deformation temperature, and tested according to GB/T1643.2-2004.
TABLE 2 Performance test results
The results in table 2 show that the modified core-shell masterbatch toughened pipe prepared in examples 3 and 4 has improved low-temperature toughness, rigidity, heat resistance and static pressure qualification rate, good compatibility among materials and obvious toughening effect. The modified nano calcium carbonate is not used in the example 5, the modified nano calcium carbonate and ethylene-vinyl alcohol copolymer are not used in the example 6, the ethylene propylene diene monomer rubber combination is not used in the example 7, the ethylene propylene diene monomer rubber combination and carbon fiber are not used in the example 8, the ethylene propylene diene monomer rubber, the dispersing agent and the coupling agent are only used in the example 10, the low-temperature toughness, the rigidity and the heat resistance are reduced, and the material compatibility is poor. Example 9 graphene oxide-nano silver particles have small influence on low-temperature toughness, rigidity, heat resistance and hydrostatic test, so that the mechanical properties of the graphene oxide-nano silver particles are similar to those of examples 3 and 4.
Experimental example 2
The PPR pipes prepared in examples 3 to 10 were subjected to antibacterial property, antibacterial durability and cleaning test, each test pipe was tested according to GB5749-2006, the pipes were respectively placed at 20-30℃for 7 days, and the water quality of the pipes was measured, and the results are shown in Table 3.
Table 3 antimicrobial results of pipes for 7 days
Experimental example 3
And (5) continuously using each water pipe, and detecting the water quality of the water outlet of the water supply pipe on the 365 th day according to the GB5749-2006 standard. The test results are shown in Table 4 below.
Table 4 antibacterial results of pipes for 365 days
The results in tables 3 and 4 show that the pipes of examples 3, 4 and 5 and 7 have no obvious dirt on the inner wall of the pipe after 7 days and 1 year of use, the total escherichia coli and the total colony count are higher than the standard requirements, the produced PPR pipes have no peculiar smell and stink, the pipe methods of examples 6 and 8-10 produce PPR pipes which have slightly peculiar smell and high turbidity after one year of use, the total colony count is increased greatly, and the PPR pipes produced in examples 3, 4 and 5 and 7 have no peculiar smell and have no or little increase in turbidity and colony count. The pipe material added with the ethylene-vinyl alcohol copolymer, the carbon fiber and the graphene oxide-nano silver particles can reduce bacteria breeding in water and kill original bacteria in water. The antibacterial rate of the PPR pipe produced in the embodiment 3 and the embodiment 4 is higher than the standard requirement, and the dissolubility solid in the pipe is also higher than the standard requirement.
In summary, the pipe produced by the method of the embodiment 3-4 has high impact strength, better creep resistance, rigidity and heat resistance, and the produced pipe has antibacterial and antibacterial effects, has no attachments on the inner wall after one year of use, has small turbidity of effluent, and has strong self-cleaning capability.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (4)

1. The utility model provides a modified core-shell masterbatch toughens PPR tubular product, includes the body, the body comprises skin, middle level and inlayer from outside to inside in proper order, its characterized in that: the outer layer is composed of the following raw materials in parts by weight: 90-120 parts of PPR resin, 1-3 parts of modified nano calcium carbonate, 4-6 parts of ethylene propylene diene monomer rubber and 1-2 parts of dispersing agent;
the middle layer consists of the following raw materials in parts by weight: 95-130 parts of PPR resin, 0.1-0.9 part of POE plastic, 3-5 parts of ethylene-vinyl alcohol copolymer, 15-25 parts of carbon fiber and 1-3 parts of coupling agent;
the inner layer is composed of the following raw materials in parts by weight: 90-120 parts of PPR resin, 3-5 parts of ethylene propylene diene monomer rubber, 5-8 parts of graphene oxide-nano silver particles and 1-5 parts of antioxidant;
the mass of the raw materials of the outer layer is as follows: the mass of the raw materials of the middle layer: the mass of the raw materials of the inner layer is 2:1:1;
the preparation method of the modified nano calcium carbonate comprises the following steps: adding calcium carbonate into a high-speed mixer at 50-60 ℃, stirring for 20-80min, slowly adding metered acrylic acid and an initiator dissolved in acetone, continuously stirring, adding polypropylene wax into the high-speed mixer, stirring, raising the temperature of the high-speed mixer to 80-120 ℃, stirring at a rotating speed of 100-120r/min, and discharging;
the preparation method of the graphene oxide-nano silver particles comprises the following steps:
(1) Graphite, concentrated sulfuric acid, potassium permanganate and sodium nitrate react for a certain time under the water bath ultrasonic condition;
(2) After the pH is regulated, the temperature is raised, hydrogen peroxide is added for reaction for a period of time, and then the mixture is cooled to room temperature;
(3) Centrifuging and washing off superfluous hydrogen peroxide;
(4) Placing silver nitrate powder into the solution in the step (3);
(5) Heating the solution in the step (4), performing ultrasonic mixing for a period of time, adding sodium citrate, mixing and stirring, and standing for precipitation;
(6) Washing, suction filtering and drying the precipitate obtained in the step (5) to obtain the catalyst;
in the step (1), the mass ratio of graphite, concentrated sulfuric acid, potassium permanganate and sodium nitrate is (1-2): (10-20): (10-20): (0.1-2); and reacting for 40-50min under the condition of water bath ultrasonic at 30-35 ℃;
in the step (2), the temperature is raised to 85-90 ℃, and after 20-30wt% of hydrogen peroxide is added for reaction for 10-20min, the mixture is cooled to room temperature.
2. The modified core-shell masterbatch toughened PPR pipe of claim 1, wherein: the outer layer is composed of the following raw materials in parts by weight: 95-110 parts of PPR resin, 2-3 parts of modified nano calcium carbonate, 4.5-5.5 parts of ethylene propylene diene monomer rubber and 1.2-1.8 parts of dispersing agent;
the middle layer consists of the following raw materials in parts by weight: 100-125 parts of PPR resin, 0.5-0.8 part of POE plastic, 3.5-4.5 parts of ethylene-vinyl alcohol copolymer, 18-23 parts of carbon fiber and 1.5-2.5 parts of coupling agent;
the inner layer is composed of the following raw materials in parts by weight: 95-115 parts of PPR resin, 3.5-4.5 parts of ethylene propylene diene monomer rubber, 6-8 parts of graphene oxide-nano silver particles and 2-4 parts of antioxidant.
3. The modified core-shell masterbatch toughened PPR pipe of claim 1, wherein: in the step (4), adding silver nitrate powder and graphite in a mass ratio of (3-5) (12-15); in the step (5), the temperature of the solution is raised to 80-90 ℃ and ultrasonic mixing is carried out for 30-40min.
4. The modified core-shell masterbatch toughened PPR pipe of claim 1, wherein: the preparation method of the modified core-shell master batch toughened PPR pipe comprises the following steps:
(1) Weighing the raw materials according to the outer layer, the middle layer and the inner layer in sequence for proportioning;
(2) Stirring the outer layer raw material at 80-90 ℃ for 2-3h; stirring the middle layer material at 100-120deg.C for 60-80min, stirring the inner layer material at 110-150deg.C for 50-70min,
(3) Putting the inner layer mixed material into an extruder for extrusion to obtain an inner layer pipe body, wherein the temperature of a charging barrel of the extruder is controlled to be 170-180 ℃, and the temperature of a die is controlled to be 180-200 ℃; cooling the formed inner layer pipe body to 100-150 ℃ in a vacuum environment;
(4) Heating the middle layer mixed material to 185-195 ℃ to be in a molten state, attaching the mixed material on the outer surface of the inner layer to form a thickness of 1-2mm, and cooling the formed middle layer pipe body to 120-140 ℃ in a vacuum environment;
(5) Heating the outer layer mixed material to 175-185 ℃ to be in a molten state, attaching the outer layer mixed material on the outer surface of the middle layer to form a thickness of 1-2mm, cooling and shaping the formed pipe body in a vacuum environment, and pulling out the pipe body after cooling.
CN202210910654.2A 2022-07-29 2022-07-29 Modified core-shell master batch toughened PPR pipe Active CN115181364B (en)

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Publication number Priority date Publication date Assignee Title
US4997880A (en) * 1987-03-13 1991-03-05 Groep Lambertus A V D Polymer composition, a process for producing a polymer composition, and the use of such a polymer composition
JP2012149246A (en) * 2010-12-27 2012-08-09 Unitika Ltd Polypropylene resin composition, method of manufacturing the same, and molded article produced by molding the same
CN102898729A (en) * 2012-11-09 2013-01-30 华东理工大学 Nano core-shell structure and method for beta-form synergistic toughening of polypropylene
CN106380694A (en) * 2016-09-30 2017-02-08 无锡市长安曙光手套厂 Carbon fiber reinforced polypropylene composite material and preparation method thereof
CN112143093A (en) * 2020-09-27 2020-12-29 新奥石墨烯技术有限公司 Graphene reinforced polypropylene composite material and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4997880A (en) * 1987-03-13 1991-03-05 Groep Lambertus A V D Polymer composition, a process for producing a polymer composition, and the use of such a polymer composition
JP2012149246A (en) * 2010-12-27 2012-08-09 Unitika Ltd Polypropylene resin composition, method of manufacturing the same, and molded article produced by molding the same
CN102898729A (en) * 2012-11-09 2013-01-30 华东理工大学 Nano core-shell structure and method for beta-form synergistic toughening of polypropylene
CN106380694A (en) * 2016-09-30 2017-02-08 无锡市长安曙光手套厂 Carbon fiber reinforced polypropylene composite material and preparation method thereof
CN112143093A (en) * 2020-09-27 2020-12-29 新奥石墨烯技术有限公司 Graphene reinforced polypropylene composite material and preparation method and application thereof

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