CN115181364A - Modified core-shell master batch toughened PPR pipe - Google Patents
Modified core-shell master batch toughened PPR pipe Download PDFInfo
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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
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- 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
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- 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
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- C08K2003/0806—Silver
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
The invention discloses a modified core-shell master batch toughened PPR (polypropylene random) pipe which comprises a pipe body, wherein the pipe body sequentially consists of an outer layer, a middle layer and an inner layer from outside to inside, and the outer layer consists of 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 and 1-2 parts of dispersant; the middle layer is composed 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, 5-8 parts of graphene oxide-nano silver particles and 1-5 parts of antioxidant. The PPR pipe provided by the invention has the advantages of high impact strength, creep resistance, simple process and low production cost, the middle layer is an ultraviolet-resistant layer to reduce bacterial breeding generated by illumination, and the antibacterial layer arranged on the inner layer enables the PPR pipe to be directly contacted with water to generate self-cleaning, and the PPR pipe is strong in self-cleaning capability.
Description
Technical Field
The invention belongs to the technical field of plastic pipeline materials, and particularly relates to a modified core-shell master batch toughened PPR pipe.
Background
The PPR pipe is also called a polypropylene terpolymer pipe, is prepared from a nontoxic, light-weight 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, gas supply systems, heating systems and drinking water systems.
PPR tubular product easily leads to thermal expansion because of high temperature to be big, and the breach impact strength is low, and impact resistance is low in low temperature to because in water pressure environment for a long time, easily produce the creep, if there is little crackle in the manufacturing process tubular product is inside, can produce the creep under the environment is pressed to long-term the area and increase gradually, thereby lead to the tubular product fracture. In addition, because the PPR water supply pipe is arranged on a wall body or underground, the PPR water supply pipe cannot be easily replaced, a large amount of bacteria are easily bred on the inner pipe wall after long-time use, water body bacterial pollution is caused, the self-cleaning capability of the inner wall of the pipe body is poor, and a large amount of dirt, bacteria and algae plants are bred, so that the water body quality is influenced, and the conveying resistance is increased.
At present, the scheme of low-temperature impact resistance includes increasing beta nucleating agent (such as Chinese patent CN 106380698A), increasing alpha nucleating agent (CN 112852061A) and the like, but the beta nucleating agent has harsh nucleating conditions, extremely high cost, low crystallization rate of the alpha nucleating agent and long cooling time. The antibacterial self-cleaning scheme is to perform antibacterial self-cleaning through the strong expansion capacity of the pipe body (such as Chinese patent CN 109253321A), the method is to make the surface of the inner wall into a corrugated shape, but if the shrinkage and expansion degree of the inner layer is insufficient, dirt is deposited in the groove, and thus complete cleaning cannot be realized.
In view of the above, the invention provides a modified core-shell master batch toughened PPR pipe.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified core-shell master batch toughened PPR pipe. The technical scheme used for realizing the purpose of the invention is as follows:
the modified core-shell master batch toughened PPR pipe 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 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 and 1-2 parts of dispersant;
the middle layer is composed 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, 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 and 1.2-1.8 parts of dispersant;
the middle layer is composed 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, 6-8 parts of graphene oxide-nano silver particles and 2-4 parts of antioxidant.
Further, the outer layer comprises the following raw materials in mass: the quality of the raw materials of the middle layer is as follows: the raw material mass of the inner layer is 2.
Further, the preparation method of the modified nano calcium carbonate comprises the following steps: adding calcium carbonate into a high-speed mixer at a certain temperature, stirring for a period of time, slowly adding metered Acrylic Acid (AA) dissolved in acetone and an initiator, continuing stirring, adding polypropylene wax (PPW) into the high-speed mixer, stirring, increasing the temperature of the high-speed mixer, and discharging after stirring. The mass ratio of the added calcium carbonate, the added acrylic acid and the added initiator polypropylene wax (PPW) is 4: 2: (2-4).
Further, adding calcium carbonate into a high-speed mixer in a charging basket at 50-60 ℃, stirring for 20-80min, slowly adding metered Acrylic Acid (AA) dissolved in acetone and an initiator, continuing stirring, adding polypropylene wax into the high-speed mixer, stirring, raising the temperature of the high-speed mixer to 80-120 ℃, stirring at the rotating speed of 100-120r/min, and discharging.
The inorganic rigid particles for the outer layer pipe are modified nano calcium carbonate (CaCO) 3 ) The elastomer adopts Ethylene Propylene Diene Monomer (EPDM), the EPDM and PPR have good compatibility and are often used as a PPR toughening agent, but the calcium carbonate has high surface energy and poor interfacial bonding force with EPDM and PPR resin, and is difficult to uniformly disperse in a matrix, and the surface of the calcium carbonate is pretreated by Acrylic Acid (AA): the calcium carbonate is added to a high speed mixer at a barrel temperature and after stirring for a period of time, metered amounts of Acrylic Acid (AA) and initiator (preferably BPO) dissolved in acetone are added slowly and stirring is continued. Active double bond groups are introduced into the surface of the calcium carbonate. Solid phase graft polymer: continuously adding metered polypropylene wax (PPW) into a high-speed mixer, stirring and discharging, increasing the temperature of a charging basket of the high-speed mixer, pouring the materials into the charging basket, discharging after high-speed stirring to obtain solid-phase graft modified CaCO 3 -PPW。
Outer layer tube CaCO 3 Blending PPR, EPDM, PPR and dispersant to prepare PPR/EPDM/CaCO 3 -PPW mixed material, caCO 3 -PPW is coated with EPDM to form core-shell structure master batch, caCO 3 PPW as the "core" and EPDM as the "shell", with rigid CaCO 3 PPW is distributed in the resin matrix at the same time, so that the rigidity and the strength of the material are ensured, the PPW is uniformly dispersed in the PPR resin matrix through the dispersing agent, the PPR resin matrix has good compatibility, effective interface bonding is formed with the resin matrix, uniform stress transmission is promoted, stress concentration is slowed down, crack expansion and creep fracture are prevented, and the toughness and the 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) Reacting graphite, concentrated sulfuric acid, potassium permanganate and sodium nitrate for a certain time under the condition of water bath ultrasound;
(2) Adjusting the pH value, heating, adding hydrogen peroxide to react for a period of time, and cooling to room temperature;
(3) Centrifuging and washing to remove redundant hydrogen peroxide;
(4) Placing silver nitrate powder in the solution of the step (3);
(5) Heating the solution in the step (4), carrying out ultrasonic mixing for a period of time, adding sodium citrate, mixing and stirring, and standing for precipitation;
(6) And (5) washing, filtering and drying the precipitate to obtain the product.
Further, in the step (1), the quantity ratio of the graphite, the concentrated sulfuric acid, the potassium permanganate and the sodium nitrate is (1-2): (10-20): (10-20): (0.1-2); and reacting for 40-50min under the water bath ultrasonic condition of 30-35 ℃.
Further, in the step (2), the temperature is increased to 85-90 ℃, 20-30 omega t% hydrogen peroxide is added for reaction for 10-20min, and then 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) to (12-15); in the step (5), the solution is heated to 80-90 ℃ and is subjected to ultrasonic mixing 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 in 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 100-120 deg.C for 60-80min, stirring the inner layer material at 110-150 deg.C for 50-70min,
(3) The inner layer mixed material is put into an extruder to be extruded 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 molten material to 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 mixture to 175-185 ℃ to be in a molten state, attaching the outer layer mixture to the outer surface of the middle layer to form a pipe body with the thickness of 1-2mm, cooling and shaping the formed pipe body in a vacuum environment, cooling and drawing 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, due to the adoption of the technical scheme, the invention has the following technical effects:
(1) The outer layer pipe body of the invention firstly modifies calcium carbonate with polypropylene wax to obtain a solid phase graft structure, and CaCO is adopted 3 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 needed in the processing process. The toughness and the strength of the pipe prevent the creep deformation of the pipe in a hydraulic environment, and the service life of the pipe is prolonged.
(2) The carbon fibers have the effect of improving the low-temperature impact strength of the composite material, the carbon fibers are uniformly dispersed in the matrix, and the POE plastic and the ethylene-vinyl alcohol copolymer are blended, so that the composite material has the ultraviolet-proof effect, reduces more micro cracks and plastic deformation generated under the impact action, promotes energy absorption and further improves 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 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 the bacteria breeding is reduced, the bacteria in the water body are killed through the nano-silver, the nano-silver loaded on the graphene particles has a slow release effect, the bacteria can be continuously killed, and the effects of cleaning and keeping antibacterial are achieved.
(4) The PPR pipe has good hot melting performance, good compatibility, high strength, high toughness and a low linear expansion system by adding the modified sodium carbonate into the ethylene propylene diene monomer rubber and the PPR, an ultraviolet-proof layer is added to the middle layer through the POE plastic and the 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 below with reference to preferred embodiments. However, it should be noted that the numerous details set forth in the description are merely intended to provide a thorough understanding of one or more aspects of the present invention, even though such aspects of the invention may be practiced without these specific details.
Example 1:
the calcium carbonate modification method comprises the following steps: adding calcium carbonate into a high-speed mixer in a charging basket at 50-60 ℃, stirring for 20-80min, slowly adding metered acrylic acid and initiator dissolved in acetone, continuing to stir, continuously adding polypropylene wax into the high-speed mixer, stirring, increasing the temperature of the high-speed mixer to 160-200 ℃, and discharging after high-speed stirring.
The mass ratio of the added calcium carbonate, the added acrylic acid, the added initiator and the added polypropylene wax (PPW) is 4: 2: (1-2), the initiator is any one of benzoyl peroxide, tetra-tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and azobisisobutyronitrile. 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) Reacting graphite, concentrated sulfuric acid, potassium permanganate and sodium nitrate for a certain time under the condition of water bath ultrasound;
(2) Adjusting the pH value, heating, adding hydrogen peroxide to react for a period of time, and cooling to room temperature;
(3) Centrifuging and washing to remove redundant hydrogen peroxide;
(4) Placing a silver nitrate solution in the solution obtained in the step (3);
(5) Heating the solution in the step (4), carrying out ultrasonic mixing for a period of time, adding sodium citrate, mixing and stirring, and standing for precipitation;
(6) And (5) washing, filtering and drying the precipitate to obtain the catalyst.
In the step (1), the mass ratio of the graphite, the concentrated sulfuric acid, the potassium permanganate and the sodium nitrate is (1-2): (10-20): (1-10): (0.1-2); and reacting for 40-50min under the water bath ultrasonic condition of 30-35 ℃.
And (3) heating to 85-90 ℃, adding 20-30 omega t% 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;
in the step (5), the solution is heated to 80-90 ℃ and is subjected to ultrasonic mixing for 30-40min.
Example 3 example 10
Embodiment 3-embodiment 10 provide a series of modified core-shell masterbatch toughened PPR pipe preparation methods
The modified nano calcium carbonate is prepared by the method of example 1, the graphene oxide-nano silver particles are prepared by the method of example 2, the composition ratios of the raw materials in examples 3 to 10 are shown in 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 100-120 deg.C for 60-80min, and stirring the inner layer raw material at 110-150 deg.C for 50-70min;
(3) The inner layer mixed material is put into an extruder to be extruded 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 melted middle layer ingredients to the outer surface of the inner layer to form a thickness of 1-2mm, and cooling the formed middle layer tube body to 120-140 ℃ in a vacuum environment;
(5) Heating the outer layer materials to 175-185 deg.C to melt, attaching to the outer surface of the middle layer to form a thickness of 1-2mm, cooling the formed tube body in vacuum environment, cooling, and drawing out. The prepared PPR pipe has a pipe wall thickness of 2.8-3.5mm.
TABLE 1 composition of raw materials (parts by weight) of each example
Examples of applications
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 PPR 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 respectively tested at 0 ℃, 1kg of weight, 0.8m of height and 25 hammers for the prepared PPR pipes, wherein the PPR pipes do not break and pass, and the PPR pipes break and do not pass, and the low-temperature impact resistance of the PPR pipes is represented by the pass rate (%).
(3) Rigidity: according to GB/T6111-2003 standard, hydraulic experiments of 20 ℃,1h and 95 ℃ and 22h are respectively carried out by adopting an A-type end socket, 100 PPR pipes are tested, whether pipe explosion exists or not is observed, the pipe explosion is qualified, and the qualification rate (%) is evaluated.
(4) Heat resistance: PPR heat resistance was evaluated using the load deflection temperature and tested according to GB/T1643.2-2004.
Table 2 results of performance testing
The results in table 2 show that the modified core-shell masterbatch toughened pipes prepared in examples 3 and 4 have improved low-temperature toughness, rigidity, heat resistance and static pressure qualification rate, and the pipes have good compatibility and obvious toughening effect. Example 5 has no modified nano calcium carbonate, example 6 has no modified nano calcium carbonate and ethylene-vinyl alcohol copolymer, example 7 has no ethylene propylene diene monomer combination, example 8 has no ethylene propylene diene monomer combination and carbon fiber, and example 10 has only ethylene propylene diene monomer, dispersant and coupling agent, and the low temperature toughness, rigidity and heat resistance are reduced, and the material compatibility is poor. In example 9, the graphene oxide-nano silver particles have small influences on low-temperature toughness, rigidity, heat resistance and static pressure tests, 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 tests, and each test pipe was tested according to GB5749-2006, and the pipes were used at 20 to 30 ℃ for 7 days, respectively, and the effluent quality of the pipes was measured, and the results are shown in table 3.
TABLE 3 antibacterial results of the tubing after 7 days use
Experimental example 3
And (4) continuously using each water pipe, and detecting the effluent quality of the water supply pipe material on 365 days according to the GB5749-2006 standard. The results are shown in Table 4 below.
TABLE 4 antibacterial results of 365 days of pipe material
The results in tables 3 and 4 show that the pipes of examples 3, 4, 5 and 7 have no significant fouling on the inner wall of the pipes after 7 days and 1 year of use, the total coliform and the total number of colonies are all higher than the standard requirements, the produced PPR pipes have no off-flavor and no odor, the PPR pipes produced by the pipe methods of examples 6 and 8-10 have slightly off-flavor in water after one year of use, the turbidity is higher, the total number of colonies is also increased a lot, the PPR pipes produced by examples 3, 4 and 5 and 7 have no off-flavor, and the turbidity and the total number of colonies are not increased or are increased a little. The pipe added with the ethylene-vinyl alcohol copolymer, the carbon fiber and the graphene oxide-nano silver particles can reduce the growth of bacteria in the water body and kill the original bacteria in the water body. The antibacterial rate of the PPR pipes produced in the embodiments 3 and 4 is higher than the standard requirement, and the soluble solid in the pipe body is also higher than the standard requirement.
In conclusion, the pipes produced by the methods in examples 3-4 have high impact strength, good creep resistance, rigidity and heat resistance, antibacterial and antibacterial effects, no attachment on the inner wall after one year of use, small effluent turbidity and strong self-cleaning capability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The utility model provides a modified nucleocapsid master batch toughening PPR tubular product, includes the body, the body comprises skin, middle level and inlayer from outer to interior 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 and 1-2 parts of dispersant;
the middle layer is composed 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, 5-8 parts of graphene oxide-nano silver particles and 1-5 parts of antioxidant.
2. The modified core-shell masterbatch toughened PPR pipe material 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 and 1.2-1.8 parts of dispersant;
the middle layer is composed 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, 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: the outer layer comprises the following raw materials in mass: the quality of the raw materials of the middle layer is as follows: the raw material mass of the inner layer is 2.
4. The modified core-shell masterbatch toughened PPR pipe material of claim 1, wherein: the preparation method of the modified nano calcium carbonate comprises the following steps: adding calcium carbonate into a high-speed mixer at a certain temperature, stirring for a period of time, slowly adding metered acrylic acid and initiator dissolved in acetone, continuing stirring, adding polypropylene wax into the high-speed mixer, stirring, increasing the temperature of the high-speed mixer, and discharging after stirring.
5. The modified core-shell masterbatch toughened PPR pipe of claim 4, wherein: adding calcium carbonate into a high-speed mixer at 50-60 ℃, stirring for 20-80min, slowly adding metered acrylic acid and initiator dissolved in acetone, continuing stirring, adding polypropylene wax into the high-speed mixer, stirring, raising the temperature of the high-speed mixer to 80-120 ℃, stirring at the rotating speed of 100-120r/min, and discharging.
6. The modified core-shell masterbatch toughened PPR pipe of claim 1, wherein: the preparation method of the graphene oxide-nano silver particles comprises the following steps:
(1) Reacting graphite, concentrated sulfuric acid, potassium permanganate and sodium nitrate under the condition of water bath ultrasound for a certain time;
(2) Adjusting the pH value, heating, adding hydrogen peroxide to react for a period of time, and cooling to room temperature;
(3) Centrifuging and washing to remove redundant hydrogen peroxide;
(4) Placing silver nitrate powder in the solution of the step (3);
(5) Heating the solution obtained in the step (4), carrying out ultrasonic mixing for a period of time, adding sodium citrate, mixing and stirring, and standing for precipitation;
(6) And (5) washing, filtering and drying the precipitate to obtain the product.
7. The modified core-shell masterbatch toughened PPR pipe as claimed in claim 6, wherein: in the step (1), the quantity ratio of the 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 water bath ultrasonic condition of 30-35 ℃.
8. The modified core-shell masterbatch toughened PPR pipe as claimed in claim 6, wherein: in the step (2), the temperature is increased to 85-90 ℃, 20-30 omegat% hydrogen peroxide is added for reaction for 10-20min, and then the mixture is cooled to room temperature.
9. The modified core-shell masterbatch toughened PPR pipe of claim 6, wherein: in the step (4), adding silver nitrate powder and graphite in a mass ratio of (3-5) to (12-15); in the step (5), the solution is heated to 80-90 ℃ and is subjected to ultrasonic mixing for 30-40min.
10. 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 raw material at 100-120 deg.C for 60-80min, stirring the inner layer raw material at 110-150 deg.C for 50-70min,
(3) The inner layer mixed material is put into an extruder to be extruded 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 molten material to 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 mixture to 175-185 deg.C to melt, attaching to the outer surface of the middle layer to form a thickness of 1-2mm, cooling and shaping the formed tube body in vacuum environment, cooling, and drawing out.
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| 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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Patent Citations (5)
| 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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