CN117445487A - High-strength anti-scale PE-RT pipe and preparation method and application thereof - Google Patents

High-strength anti-scale PE-RT pipe and preparation method and application thereof Download PDF

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Publication number
CN117445487A
CN117445487A CN202311319085.5A CN202311319085A CN117445487A CN 117445487 A CN117445487 A CN 117445487A CN 202311319085 A CN202311319085 A CN 202311319085A CN 117445487 A CN117445487 A CN 117445487A
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strength
parts
master batch
scaling
resin
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CN117445487B (en
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李艳芳
郑先伟
何梦华
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Guangdong Liansu Technology Industrial Co Ltd
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Guangdong Liansu Technology Industrial 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • 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
    • F16L55/00—Devices or appurtenances for use in, or in connection with, pipes or pipe systems
    • F16L55/24—Preventing accumulation of dirt or other matter in the pipes, e.g. by traps, by strainers
    • 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
    • F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
    • 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
    • F16L9/133—Rigid pipes of plastics with or without reinforcement the walls consisting of two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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 belongs to the technical field of PE-RT pipes, and particularly relates to a high-strength anti-scaling PE-RT pipe and a preparation method and application thereof. The outer layer of the high-strength anti-scale PE-RT pipe is used for enhancing the integral mechanical property of the PE-RT matrix through the high-strength filling master batch, and enhancing the capability of the pipeline for resisting external impact or internal pressure; the inner layer is designed with a modified long-acting antibacterial formula, so that the PE-RT surface is converted into a hydrophobic layer, the inner wall of the pipeline can be kept clean for a long time, microorganisms are efficiently destroyed, and the formula system has a certain enhancement effect, so that the strength of the inner layer and the outer layer of the pipeline is improved at the same time, and the safety of the long-term operation of a heating system is further improved.

Description

High-strength anti-scale PE-RT pipe and preparation method and application thereof
Technical Field
The invention belongs to the technical field of PE-RT pipes. More particularly, relates to a high-strength anti-scale PE-RT pipe, and a preparation method and application thereof.
Background
The low-temperature ground radiation heating is a novel heating technology which is gradually popularized in the urban advancing process in recent years, and the comfort of living environment is improved by reasonably laying heating pipelines to form micro-temperature convection. As a heat radiation terminal in a heating system, the heating pipe needs to have good heat radiation performance and enough mechanical properties to ensure the efficient and safe operation of the heating system. The heating pipes on the market at present mainly comprise five types of crosslinked polyethylene (PE-X) pipes, random copolymer polypropylene (PP-R) pipes, polybutylene (PB) pipes, crosslinked aluminum-plastic composite (XPAP) pipes and uncrosslinked heat-resistant polyethylene (PE-RT) pipes, and the five types of heating pipes generally have the advantages of simple construction, good heat resistance and corrosion resistance and the like.
The heat conduction efficiency of the non-crosslinked heat-resistant polyethylene (PE-RT) pipe is relatively high, the heat conduction efficiency is high, the heat conduction pipe has strong flexibility, can be made into a coil pipe, is convenient to transport, can be recycled, is environment-friendly, and improves the market share in the heating field year by year. As disclosed in chinese patent application CN111349281a, an oxygen-blocking PE-RT heating pipe is disclosed, by blending modified PE-RT material, the performance of the PE-RT heating pipe for blocking oxygen permeation is improved, and a PE-RT heating pipe with high oxygen-blocking rate is obtained, and the oxygen-blocking rate is improved by 80-97% compared with that of a conventional PE-RT pipe. Meanwhile, PE-RT materials have obvious defects of insufficient mechanical properties, and during the operation of a heating system, the oxygen content of circulating water in a pipeline is accumulated, bacteria are easy to grow in the system, microorganism mud and dirt are accumulated, and the microorganism mud and dirt are adhered to the inner wall of a pipeline together, so that the heat exchange efficiency of the heating system is reduced, the pressure bearing of the pipeline is increased, and the risk of water leakage in the operation of the heating system is greatly increased. Therefore, the anti-scaling capability and mechanical property of the inner wall of the heating plastic pipe are greatly improved.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of poor mechanical property and insufficient anti-scaling capability of the conventional PE-RT, and provides a PE-RT pipe with good mechanical property and high-strength anti-scaling capability.
The invention aims to provide a preparation method of the PE-RT pipe.
The invention further aims to provide an application of the PE-RT pipe in the technical field of heat-resistant water pipes.
The above object of the present invention is achieved by the following technical scheme:
the research and development of the heating pipeline system at the present stage is focused on improving the heat conduction performance of the material, and the common method is to add metal powder, inorganic or organic heat conduction filler into the material formula system, so that the heat conduction coefficient of the material is improved, and the heat exchange efficiency is enhanced. However, most of the heat conducting filler in the system is a small molecular material, so that the dispersibility in the material system is poor, and the mechanical property of the pipeline system is easy to reduce; meanwhile, after the pipeline system runs for a long time, the inner wall is scaled, so that the pressure bearing of the pipeline system is increased, and the leakage condition is more likely to occur.
In order to solve the problems, the invention provides a high-strength anti-scaling PE-RT pipe which is of a double-layer structure, wherein the outer layer is mainly made of PE-RT resin and high-strength filling master batch, and the inner layer is mainly made of PE-RT resin and modified long-acting antibacterial master batch;
wherein the high-strength filling master batch is prepared from PE-RT resin, polyamide, glycidyl methacrylate compatibilizer and antioxidant;
the modified long-acting antibacterial master batch is prepared from PE-RT resin, an antioxidant and modified zinc oxide whiskers.
The polyamide is a good toughening and reinforcing material, has good impact resistance and has polar groups in a molecular structure. Blending non-crosslinked heat-resistant polyethylene (PE-RT) with polyamide, wherein the polyamide can be used as a reinforcing agent to improve the impact strength of the PE-RT; however, the PE-RT has a large difference between the structure and the polarity of the polyamide, so that the PE-RT has poor direct blending compatibility, and even in a high-speed shearing state, the PE-RT can only maintain the dynamic balance of a large disperse phase, the molecular chains between the PE-RT and the polyamide have little mutual penetration, and the interface is clear, so that the PE-RT is easier to damage when impacted. According to the invention, the PE-RT surface is grafted with the glycidyl methacrylate, the molecular structure of the glycidyl methacrylate is provided with the polar epoxy functional group, and the polar epoxy functional group can react with the polar group part on the molecular structure of the polyamide in the high-temperature melt extrusion process to form the heat-resistant polyethylene-glycidyl methacrylate-polyamide copolymer. The copolymer plays a role in permeation between the heat-resistant polyethylene and polyamide two-phase interfaces, enhances the bonding strength of the interfaces, obscures the two-phase interfaces, reduces the particle size of the polyamide phase, and is uniformly dispersed in the PE-RT phase, so that the compatibility between the two phases is improved, larger external or internal impact force can be born, and the overall strength of the material is greatly improved.
Further, the high-strength filling master batch comprises, by weight, 40-60 parts of PE-RT resin, 25-35 parts of polyamide, 15-25 parts of glycidyl methacrylate compatibilizer and 1-3 parts of antioxidant.
Preferably, the preparation method of the high-strength filling master batch comprises the following steps: mixing PE-RT resin, polyamide, glycidyl methacrylate compatibilizer and antioxidant for 10-15 min, and carrying out melt extrusion, cooling, granulating and drying at 160-200 ℃ to obtain the high-strength filling master batch.
Further, the modified long-acting antibacterial master batch comprises, by weight, 70-90 parts of PE-RT resin, 0.5-2 parts of antioxidant and 15-25 parts of modified zinc oxide whisker.
Further, the modified zinc oxide whisker is obtained by modifying zinc oxide whisker with a silane coupling agent. Preferably, the mass of the silane coupling agent is 2% -5% of that of the zinc oxide whisker.
Preferably, the root diameter of the zinc oxide whisker is 1-2 mu m, and the length is 15-20 mu m.
More preferably, the preparation method of the modified zinc oxide whisker comprises the following steps: hydrolyzing the silane coupling agent in water-ethanol solution with pH value of 3-5 (wherein the volume fraction of ethanol is 20% -30%) for 15-45 min, adding zinc oxide whisker, stirring in water bath at 35-45 ℃ for 25-50 min, decompressing, filtering, washing the product with deionized water, and drying at 80-100 ℃ to obtain the product.
The zinc oxide whisker has a regular three-dimensional space structure, the diameter of the root is 0.1-10 mu m, the length is 10-300 mu m, the size of the tip part of the whisker is in a nanoscale, a special tip nanometer effect is shown, bacteria can be effectively killed, and the zinc oxide whisker has the functional characteristics of good high temperature resistance, wear resistance, high strength and the like. The zinc oxide whisker is used as a functional inorganic filler, has high surface energy, and the PE-RT resin matrix is low in surface energy, so that the compatibility of the zinc oxide whisker and the PE-RT resin matrix is poor. If zinc oxide whisker is directly added into a PE-RT resin matrix for compounding, the compatibility with the resin matrix is poor, the interface binding force is affected, and the molding and mechanical properties of the composite material are further affected. It is therefore necessary to surface modify the zinc oxide whiskers prior to compounding. The surface modification method of inorganic material includes physical, chemical and mechanical methods, and the present invention adopts coupling agent to chemically modify the surface of zinc oxide whisker. The zinc oxide whisker surface is rich in hydroxyl groups, can react with functional groups in the silane coupling agent, changes the polarity of the whisker surface into non-polarity, can be uniformly dispersed in the PE-RT resin matrix, and has increased binding force with the resin matrix to form firm interface adhesion. Meanwhile, the whiskers are overlapped to a certain extent and intertwined, so that the overall strength of the resin matrix can be greatly improved. When the pipeline is impacted or the internal pressure is increased, the unique structure of the zinc oxide whisker can not only absorb energy, but also transfer the received stress to the adjacent whisker from the whisker through the resin matrix, disperse the stress to the periphery, prevent the pipeline from being impacted by local stress concentration, avoid the early damage of materials and further improve the strength of a pipeline system. In addition, the special structure of the zinc oxide whisker can enable the zinc oxide whisker to be in contact with the resin matrix in different directions, and the same reinforcing effect of other filling materials can be achieved by using a small addition amount.
In addition, after the zinc oxide whisker is modified by the coupling agent, the surface of the zinc oxide whisker is changed from polarity to non-polarity, and the zinc oxide whisker presents stronger hydrophobicity, so that the friction resistance of the inner wall of a pipeline can be effectively reduced, the adhesion of microorganisms and mud is reduced, the pipeline system is in lower operating pressure for a long time, and the operating life of the pipeline is prolonged. Specifically, the size of the tip end part of the zinc oxide whisker is in the nanometer level, so that the whisker has the nanometer size effect of a nanometer material, the biological activity of bacteria in a PE-RT pipeline can be efficiently destroyed, and microbial sludge generated by microbial accumulation is reduced. The three-dimensional space structure of the zinc oxide whisker can be combined with the resin matrix in four directions, the whiskers are overlapped and intertwined to a certain extent, and the zinc oxide whisker can stably exist in a long-term hot water environment, so that a pipeline system can keep a high-efficiency antibacterial effect for a long time, an organic antiscaling agent with a polluted water body is not required to be additionally added, and the environment-friendly and sanitary effect is realized.
Further, the preparation of the glycidyl methacrylate compatibilizer (PERT-g-GMA) specifically comprises the following steps:
fully and uniformly mixing glycidyl methacrylate, styrene and dicumyl peroxide, adding PE-RT resin, uniformly mixing, melting and blending at 160-200 ℃ for 5-10 min, crushing the blend, dissolving in dimethylbenzene, and heating and refluxing for 3-4 h at 137-145 ℃; and after the reaction is finished, adding acetone, precipitating a product, filtering, washing, collecting a precipitate, and drying in vacuum for 20-24 hours to obtain the catalyst.
Preferably, the mass ratio of the glycidyl methacrylate, the styrene, the dicumyl peroxide and the PE-RT resin is (2.3-2.7): (2.3-2.7): (0.1-0.15): (50-60).
Further, the weight parts of the outer layer raw materials are 100 parts of PE-RT resin and 2-8 parts of high-strength filling master batch.
Further, the weight portion of the inner layer raw material is 100 portions of PE-RT resin and 3 to 10 portions of modified long-acting antibacterial master batch.
Further, the antioxidant is a hindered phenol antioxidant and/or a phosphite antioxidant. Preferably, the antioxidant is selected from one or more of hindered phenolic antioxidants 1010, 1076, phosphite antioxidants 168.
In addition, the invention also provides a preparation method of the high-strength anti-scaling PE-RT pipe, which specifically comprises the following steps:
the components of each layer are respectively and evenly mixed, fully melted and dispersed, and then are co-extruded and molded at 160-220 ℃ to obtain the composite material.
The invention also claims the application of the high-strength anti-scale PE-RT pipe in a heat-resistant water pipe.
The invention has the following beneficial effects:
in order to improve the long-term scale prevention capability of the heating pipeline system, the operating pressure of the pipeline system is increased due to the fact that microorganisms or mud and dirt are accumulated in the pipeline is reduced, the integral bearing capability of the pipeline system is further improved, the service life of the pipeline is prolonged, and the maintenance cost of a user is reduced. The invention provides a high-strength anti-scale double-layer PE-RT pipe, wherein the outer layer enhances the integral mechanical property of a PE-RT matrix through high-strength filling master batch, and enhances the capability of the pipe for resisting external impact or internal pressure; the inner layer is designed with a modified long-acting antibacterial formula, so that the PE-RT surface is converted into a hydrophobic layer, the inner wall of the pipeline can be kept clean for a long time, microorganisms are efficiently destroyed, and the formula system has a certain enhancement effect, so that the strength of the inner layer and the outer layer of the pipeline is improved at the same time, and the safety of the long-term operation of a heating system is further improved.
Compared with the prior art, the pipeline with the double-layer structure is designed, the inner layer of the pipeline is modified into the hydrophobic layer, dirt adhesion is reduced, heating efficiency of the system is not reduced due to scaling of the inner wall of the pipeline, the inner layer and the outer layer of the pipeline are toughened and reinforced at the same time, mechanical properties are greatly improved, long-term efficient and safe operation of the pipeline system is ensured, and market competitiveness of the pipeline is improved.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Non-crosslinked heat-resistant polyethylene resin: SP980, LG chemistry.
Polyamide: PA6, commercially available, medium petrochemical.
Glycidyl methacrylate: GMA, industrial purity, nanjing Rong Anhua chemical industry Co., ltd.
Styrene: st, chemical purity, national drug group chemical reagent.
Dicumyl peroxide: DCP, national drug group chemical reagent.
Xylene: chemical pure, national medicine group chemical reagent
Acetone: chemical purity, national drug group chemical reagent.
Zinc oxide whisker: commercially available from Hangzhou Jikang New Material Co., ltd.
Silane coupling agent: KH570, longsand billion chemical industry limited.
An antioxidant: 1010, guangzhou and wall chemical materials Co., ltd.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of a high Strength filling masterbatch
The preparation of the high-strength filling master batch specifically comprises the following steps:
s1, preparation of glycidyl methacrylate compatibilizer
Preparing glycidyl methacrylate and styrene (weight ratio of 5:5) into a mixed solution, adding 0.2 part of dicumyl peroxide, and fully mixing; adding the obtained solution and 100 parts of PE-RT resin into a mixer for continuous mixing for 5min, adding into an internal mixer for melt blending, setting the temperature of the internal mixer to 190 ℃ and the reaction time to 8min, and shearing and bagging the melt blend for later use;
5 parts of the melt blend are dissolved in 150 parts of xylene solution, heated, condensed and refluxed for 4 hours at 140 ℃, the reacted solution is poured into acetone while the solution is still hot to generate precipitate, the precipitate is filtered, fully washed by the acetone, and the precipitate is dried in vacuum for 24 hours to obtain the glycidyl methacrylate compatibilizer (PERT-g-GMA).
S2, preparation of PE-RT/Polyamide/glycidyl methacrylate compatibilizer blend (high-strength filling masterbatch)
Adding non-crosslinked heat-resistant polyethylene (PE-RT), polyamide, glycidyl methacrylate compatibilizer and antioxidant 1010 (the proportion is 50:30:20:2 by weight parts) into a high-speed mixer for mixing for 10min, adding the mixed materials into a single-screw extruder, and carrying out melt extrusion at 160-200 ℃, cooling, granulating and drying to obtain the high-strength filling master batch.
Example 2 preparation of modified Long-acting antibacterial masterbatch
The preparation of the modified long-acting antibacterial master batch specifically comprises the following steps:
s1, modification of zinc oxide whisker surface
Hydrolyzing a silane coupling agent in a water-ethanol solution (volume ratio is 3:1) with a pH value of 3-5 for 15-45 minutes, and adding zinc oxide whisker, wherein the weight part ratio of the silane coupling agent to the zinc oxide whisker is 4:100, continuing to mechanically stir for 25-50 minutes in a water bath at 35-45 ℃, filtering under reduced pressure, washing a product by deionized water, and drying in an oven at 80 ℃ to obtain the modified zinc oxide whisker material.
S2, PE-RT/modified zinc oxide whisker material composite (modified long-acting antibacterial master batch)
The PE-RT resin, the antioxidant 1010 and the modified zinc oxide whisker material obtained in the step S1 are prepared according to the following weight portions: 1:20 are added into a high-speed mixer for stirring for 10-15 min, and are added into a single screw extruder after being fully mixed, and are cut into particles after being melted and extruded at 160-200 ℃ to obtain the modified long-acting antibacterial master batch.
Example 3 preparation of a high-Strength anti-fouling PE-RT tube
The preparation of the high-strength anti-scaling PE-RT pipe specifically comprises the following steps:
an outer layer of the pipeline: the high-strength filling master batch is prepared from non-crosslinked heat-resistant polyethylene and the high-strength filling master batch prepared in the example 1, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the high-strength filling master batch is 100:2;
an inner layer of the pipeline: the modified long-acting antibacterial masterbatch is prepared from non-crosslinked heat-resistant polyethylene and the modified long-acting antibacterial masterbatch prepared in the example 2, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the modified long-acting antibacterial masterbatch is 100:3, a step of;
the raw materials of the inner layer and the outer layer of the pipeline are respectively put into different hoppers, and after being fully melted and dispersed by a screw area, the extrusion temperature is set to 160-220 ℃ and the extrusion molding is carried out.
Example 4 preparation of a high-Strength anti-fouling PE-RT tube
The preparation of the high-strength anti-scaling PE-RT pipe specifically comprises the following steps:
an outer layer of the pipeline: the high-strength filling master batch is prepared from non-crosslinked heat-resistant polyethylene and the high-strength filling master batch prepared in the example 1, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the high-strength filling master batch is 100:8, 8;
an inner layer of the pipeline: the modified long-acting antibacterial masterbatch is prepared from non-crosslinked heat-resistant polyethylene and the modified long-acting antibacterial masterbatch prepared in the example 2, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the modified long-acting antibacterial masterbatch is 100:10;
the raw materials of the inner layer and the outer layer of the pipeline are respectively put into different hoppers, and after being fully melted and dispersed by a screw area, the extrusion temperature is set to 160-220 ℃ and the extrusion molding is carried out.
Example 5 preparation of a high-strength anti-fouling PE-RT tube
The preparation of the high-strength anti-scaling PE-RT pipe specifically comprises the following steps:
an outer layer of the pipeline: the high-strength filling master batch is prepared from non-crosslinked heat-resistant polyethylene and the high-strength filling master batch prepared in the example 1, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the high-strength filling master batch is 100:6, preparing a base material;
an inner layer of the pipeline: the modified long-acting antibacterial masterbatch is prepared from non-crosslinked heat-resistant polyethylene and the modified long-acting antibacterial masterbatch prepared in the example 2, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the modified long-acting antibacterial masterbatch is 100:5, a step of;
the raw materials of the inner layer and the outer layer of the pipeline are respectively put into different hoppers, and after being fully melted and dispersed by a screw area, the extrusion temperature is set to 160-220 ℃ and the extrusion molding is carried out.
Example 6 preparation of a high-Strength anti-fouling PE-RT tube
The preparation of the high-strength anti-scaling PE-RT pipe specifically comprises the following steps:
an outer layer of the pipeline: the high-strength filling master batch is prepared from non-crosslinked heat-resistant polyethylene and the high-strength filling master batch prepared in the example 1, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the high-strength filling master batch is 100:4, a step of;
an inner layer of the pipeline: the modified long-acting antibacterial masterbatch is prepared from non-crosslinked heat-resistant polyethylene and the modified long-acting antibacterial masterbatch prepared in the example 2, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the modified long-acting antibacterial masterbatch is 100:9, a step of performing the process;
the raw materials of the inner layer and the outer layer of the pipeline are respectively put into different hoppers, and after being fully melted and dispersed by a screw area, the extrusion temperature is set to 160-220 ℃ and the extrusion molding is carried out.
Example 7 preparation of a high-strength anti-fouling PE-RT tube
The preparation of the high-strength anti-scaling PE-RT pipe specifically comprises the following steps:
an outer layer of the pipeline: the high-strength filling master batch is prepared from non-crosslinked heat-resistant polyethylene and the high-strength filling master batch prepared in the example 1, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the high-strength filling master batch is 100:7, preparing a base material;
an inner layer of the pipeline: the modified long-acting antibacterial masterbatch is prepared from non-crosslinked heat-resistant polyethylene and the modified long-acting antibacterial masterbatch prepared in the example 2, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the modified long-acting antibacterial masterbatch is 100:7, preparing a base material;
the raw materials of the inner layer and the outer layer of the pipeline are respectively put into different hoppers, and after being fully melted and dispersed by a screw area, the extrusion temperature is set to 160-220 ℃ and the extrusion molding is carried out.
Comparative example 1 preparation of PE-RT tube
The PE-RT pipe is prepared specifically as follows:
an outer layer of the pipeline: is prepared from non-crosslinked heat-resistant polyethylene, polyamide and glycidyl methacrylate compatibilizer, wherein the weight portion ratio of the non-crosslinked heat-resistant polyethylene to the polyamide to the glycidyl methacrylate compatibilizer is 100:4.8:3.2;
an inner layer of the pipeline: the modified long-acting antibacterial masterbatch is prepared from non-crosslinked heat-resistant polyethylene and the modified long-acting antibacterial masterbatch prepared in the example 2, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the modified long-acting antibacterial masterbatch is 100:10;
the raw materials of the inner layer and the outer layer of the pipeline are respectively put into different hoppers, and after being fully melted and dispersed by a screw area, the extrusion temperature is set to 160-220 ℃ and the extrusion molding is carried out.
Comparative example 2 preparation of PE-RT tube
The PE-RT pipe is prepared specifically as follows:
an outer layer of the pipeline: the high-strength filling master batch is prepared from non-crosslinked heat-resistant polyethylene and the high-strength filling master batch prepared in the example 1, wherein the weight part ratio of the non-crosslinked heat-resistant polyethylene to the high-strength filling master batch is 100:8, 8;
an inner layer of the pipeline: is prepared from non-crosslinked heat-resistant polyethylene, zinc oxide whisker and a silane coupling agent in a weight ratio of 100:8:2;
the raw materials of the inner layer and the outer layer of the pipeline are respectively put into different hoppers, and after being fully melted and dispersed by a screw area, the extrusion temperature is set to 160-220 ℃ and the extrusion molding is carried out.
Performance testing
The PE-RT pipes prepared in examples and comparative examples were tested for tensile strength, antibacterial rate, contact angle and hydrostatic properties. The hydrostatic properties were measured according to GB/T28799.2-2020 "heat-resistant polyethylene for Cold and Hot Water ((PE-RT) tubing part 2: tubing", tensile properties were measured according to the method specified in GB/T1040.2-2006, contact angles were measured according to the method specified in GB/T30693-2014, and antibacterial properties were measured according to the method specified in QB/T2591. The results are shown in Table 1.
Table 1 examples and comparative PE-RT pipeline performance testing
Group of Tensile Strength/MPa Antibacterial rate/% Contact angle/° Hydrostatic performance
Example 3 22.3 84 121.7 No rupture/no permeation
Example 4 25.1 99 146.7 No rupture/no permeation
Example 5 24.7 98 144.7 No rupture/no permeation
Example 6 23.9 97 145.9 No rupture/no permeation
Example 7 24.5 99 145.5 No rupture/no permeation
Comparative example 1 17.4 95 144.9 No rupture/no permeation
Comparative example 2 19.9 71 87.3 No rupture/no permeation
The table shows that the high-strength filling master batch and the modified long-acting antibacterial master batch are added into the PE-RT pipeline material system, the tensile property, the antibacterial rate and the contact angle test data of the pipeline are obviously improved, and the modified filling material can be uniformly dispersed in the PE-RT resin matrix, so that the chemical property, the hydrophobic property and the antibacterial property of the pipeline are effectively improved. As can be seen from comparison of comparative examples 1 and 2 with example 4, the mechanical properties of the pipes are obviously reduced by adding non-modified polyamide into the PE-RT pipe material system; the zinc oxide whisker and the coupling agent do not react in advance, and the antibacterial rate and the hydrophobicity of the inner layer of the pipeline are also greatly reduced.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (10)

1. The high-strength anti-scaling PE-RT pipe is characterized in that the high-strength anti-scaling PE-RT pipe is of a double-layer structure, the outer layer is mainly made of PE-RT resin and high-strength filling master batch, and the inner layer is mainly made of PE-RT resin and modified long-acting antibacterial master batch;
wherein the high-strength filling master batch is prepared from PE-RT resin, polyamide, glycidyl methacrylate compatibilizer and antioxidant;
the modified long-acting antibacterial master batch is prepared from PE-RT resin, an antioxidant and modified zinc oxide whiskers.
2. The high-strength anti-scaling PE-RT pipe according to claim 1, wherein the high-strength filling master batch comprises, by weight, 40-60 parts of PE-RT resin, 25-35 parts of polyamide, 15-25 parts of glycidyl methacrylate compatibilizer and 1-3 parts of antioxidant.
3. The high-strength anti-scaling PE-RT pipe according to claim 1, wherein the modified long-acting antibacterial master batch comprises, by weight, 70-90 parts of PE-RT resin, 0.5-2 parts of antioxidant and 15-25 parts of modified zinc oxide whisker.
4. The high-strength anti-scaling PE-RT pipe according to claim 1, wherein the modified zinc oxide whisker is obtained by modifying zinc oxide whisker with a silane coupling agent.
5. The high strength anti-fouling PE-RT pipe according to claim 1, wherein the preparation of the glycidyl methacrylate compatibilizer comprises the following steps:
and (3) fully and uniformly mixing glycidyl methacrylate, styrene and dicumyl peroxide, adding PE-RT resin, uniformly mixing, melting and blending at 160-200 ℃, crushing the blend, dissolving in dimethylbenzene, heating, condensing and refluxing at 137-145 ℃ for complete reaction, adding acetone for precipitation, filtering, washing, collecting precipitate, and drying to obtain the product.
6. The high-strength anti-scaling PE-RT pipe according to claim 1, wherein the weight parts of the outer layer raw materials are 100 parts of PE-RT resin and 2-8 parts of high-strength filling master batch.
7. The high-strength anti-scaling PE-RT pipe according to claim 1, wherein the weight parts of the inner layer raw materials are 100 parts of PE-RT resin and 3-10 parts of modified long-acting antibacterial master batch.
8. The high strength anti-fouling PE-RT pipe of claim 1, wherein the antioxidant is a hindered phenolic antioxidant and/or a phosphite antioxidant.
9. The method for preparing the high-strength anti-scaling PE-RT pipe according to any one of claims 1 to 8, which is characterized by comprising the following steps:
the components of each layer are respectively and evenly mixed, fully melted and dispersed, and then are co-extruded and molded at 160-220 ℃ to obtain the composite material.
10. Use of the high-strength anti-scaling PE-RT pipe according to any of claims 1-8 in heat-resistant water pipes.
CN202311319085.5A 2023-10-12 High-strength anti-scale PE-RT pipe and preparation method and application thereof Active CN117445487B (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4039382A1 (en) * 1989-12-11 1991-06-13 G C Dental Ind Corp Modelling liq. for building up dental porcelain - contg. photopolymerisable cpd., photopolymerisation inhibitor, reducing agent and polymerisation inhibitor
CN1922010A (en) * 2004-01-20 2007-02-28 危邦诺创新Ab Plastic pipe
CN107187114A (en) * 2017-05-31 2017-09-22 爱康企业集团(上海)有限公司 A kind of good antiscale property type floor heating pipe and preparation method thereof
CN110256758A (en) * 2019-05-16 2019-09-20 广州大学 A kind of antibiotic plastic and preparation method thereof based on microwave synthesis quaternary ammonium salt
CN111349281A (en) * 2020-04-22 2020-06-30 广东联塑科技实业有限公司 Oxygen-barrier PE-RT heating pipe and preparation method thereof
CN112212083A (en) * 2020-10-12 2021-01-12 浙江爱康实业有限公司 Shading type anti-scale PE-RT composite pipe structure
CN113292793A (en) * 2021-02-05 2021-08-24 武汉市九牧管业科技有限公司 Anti-fouling and antibacterial PP-R double-layer pipe and preparation method thereof
CN114953680A (en) * 2022-06-17 2022-08-30 贵州恒通源管业有限公司 High-strength antibacterial PE water supply pipe and production process thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4039382A1 (en) * 1989-12-11 1991-06-13 G C Dental Ind Corp Modelling liq. for building up dental porcelain - contg. photopolymerisable cpd., photopolymerisation inhibitor, reducing agent and polymerisation inhibitor
CN1922010A (en) * 2004-01-20 2007-02-28 危邦诺创新Ab Plastic pipe
CN107187114A (en) * 2017-05-31 2017-09-22 爱康企业集团(上海)有限公司 A kind of good antiscale property type floor heating pipe and preparation method thereof
CN110256758A (en) * 2019-05-16 2019-09-20 广州大学 A kind of antibiotic plastic and preparation method thereof based on microwave synthesis quaternary ammonium salt
CN111349281A (en) * 2020-04-22 2020-06-30 广东联塑科技实业有限公司 Oxygen-barrier PE-RT heating pipe and preparation method thereof
CN112212083A (en) * 2020-10-12 2021-01-12 浙江爱康实业有限公司 Shading type anti-scale PE-RT composite pipe structure
CN113292793A (en) * 2021-02-05 2021-08-24 武汉市九牧管业科技有限公司 Anti-fouling and antibacterial PP-R double-layer pipe and preparation method thereof
CN114953680A (en) * 2022-06-17 2022-08-30 贵州恒通源管业有限公司 High-strength antibacterial PE water supply pipe and production process thereof

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