CN108929477A - Resistance to discoloration high strength polyethylene tubing of one kind and preparation method thereof - Google Patents
Resistance to discoloration high strength polyethylene tubing of one kind and preparation method thereof Download PDFInfo
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- CN108929477A CN108929477A CN201810961582.8A CN201810961582A CN108929477A CN 108929477 A CN108929477 A CN 108929477A CN 201810961582 A CN201810961582 A CN 201810961582A CN 108929477 A CN108929477 A CN 108929477A
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- density polyethylene
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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
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- 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
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- 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
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2312/00—Crosslinking
Abstract
The present invention provides a kind of resistance to discoloration high strength polyethylene tubing and preparation method thereof, comprising: high density polyethylene, metallocene linear-low density polyethylene mLLDPE, polyoctenamer rubber TOR, azodiisobutyronitrile, aryl sulfonation diazonium salt, nanometer calcium carbonate, light stabilizer and dispersing agent；The mass ratio of the azodiisobutyronitrile, aryl sulfonation diazonium salt is 1:1-5:1；The high density polyethylene, metallocene linear-low density polyethylene mLLDPE, polyoctenamer rubber TOR mass ratio be 10:2-5:1-2；The aryl sulfonation diazonium salt, which reacts under conditions of concentrated hydrochloric acid for p-aminobenzene sulfonic acid with sodium nitrite, to be prepared.Polyvinyl piping materials of the invention improve the discoloration-resistant of polyvinyl piping materials and promote intensity, while process is simple compared with prior art for preparation method of the invention, at low cost, are suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of resistance to discoloration high strength polyethylene tubing and preparation method thereof.
Background technique
In recent years, with the development of plastics industry, polyvinyl piping materials are light-weight with its, corrosion-resistant, thermal coefficient is low, insulation
Performance is good, construction and installation and it is easy to maintenance the features such as be increasingly valued by people, and have become after PVC, the world
The maximum plastic conduit kind of consumption figure, application field is throughout water supply, agricultural irrigation, fuel gas transmission, blowdown, the conveying of mine mortar
Etc. the fields such as engineerings and oil field, chemical industry and post and telecommunications.
In polyvinyl piping materials, high density polyethylene (HDPE) (HDPE) pipe has light, excellent in mechanical performance, crimpiness and flexibility
The features such as excellent is the tubing kind for most having competitiveness.But due to the structure of HDPE resin itself, form, easily lead to tubing
It will appear fracture phenomena under certain time, certain load effect, i.e. environmental stress cracking resistance (ESCR) is poor, thus shadow
HDPE tubing has been rung in the application in the fields such as outdoor water supply pipe, fuel gas conduit, irrigation pipe.Therefore, ESCR is evaluation and influences
One important indicator in HDPE tubing service life.
Some researches show that, the ESCR of HDPE resin is not only influenced by extraneous factors such as temperature, external force, and with resin sheet
Molecular weight, molecular weight distribution, the degree of branching and the branch lengths of body, the relationship for crystallizing the internal factors such as situation are bigger.Therefore, existing
In technology, there is the angle from polymerization, by reactor series connection, long-chain branch monomer, control reaction condition, change catalyst system is added
Etc. modes can produce the polyvinyl resin of high ESCR, such as CN1903896, CN1513002 report.It but is more after resin
Processing modified angle improves the ESCR of material by modulation resinous molecular structure, and there are two types of main paths: first is that mixing in resin
Enter second component such as polyolefin, elastomer to be modified, the second component played in polyethylene refinement spherocrystal, reduce crystallinity and
The effect for preventing crackle from stretching.This method is most common method, and relevant report is more, as CN1556835,
CN1247204 etc..Second is that forming the structure of crosslinking by chemical crosslinking modified, increase the connection of molecule interchain, improves polyethylene
The environmental stress cracking resistance of material.As CN2492729 uses organosilane crosslinked polyethylene layer；ZL 0215154804 uses one
Kind novel silane crosslinked polyethylene is produced for tubing.CN102993535B discloses a kind of polyethylene resin for tubular material group
It closes object and passes through metallocene linear-low density polyethylene (mLLDPE) weatherable master batch and organic peroxy using HDPE resin as base-material
Object is micro- cross-linking modified to be realized.The resin combination has excellent ESCR performance (> 2500 hours).It is not mentioned in the technology
The weatherability of high high molecular weight polyethylene board material improves its effectively method for being easy the shortcomings that fading and the product
Intensity there are also the rising spaces, while the preparation flow of the technology is excessively complicated, is not suitable for industrialized production.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of resistance to discoloration high strength polyethylene tubing and preparation method thereof, it should
Product is strong so as to improve the discoloration-resistant and promotion of polyvinyl piping materials by composite crosslinking auxiliary agent and sulfonation modifying macromolecular chain
Degree, while process is simple compared with prior art for preparation method of the invention, it is at low cost, it is suitble to industrialized production.
The present invention provides a kind of resistance to discoloration high strength polyethylene tubing comprising: 100 matter of high density polyethylene
Measure part, metallocene linear-low density polyethylene mLLDPE20-50 mass parts, polyoctenamer rubber TOR10-20 mass parts, azo two
Isobutyronitrile 0.05-0.2 mass parts, aryl sulfonation diazonium salt 0.01-0.2 mass parts, nanometer calcium carbonate 1-5 mass parts, light are stablized
Agent .02-0.25 mass parts and dispersing agent 0.1-1 mass parts；The mass ratio of the azodiisobutyronitrile, aryl sulfonation diazonium salt
For 1:1-5:1；The high density polyethylene, metallocene linear-low density polyethylene mLLDPE, polyoctenamer rubber TOR
Mass ratio is 10:2-5:1-2；The aryl sulfonation diazonium salt is p-aminobenzene sulfonic acid and sodium nitrite under conditions of concentrated hydrochloric acid
Reaction is prepared.
Further, the high density polyethylene (HDPE) (HDPE) is PE100 resin.
Further, light stabilizer is hindered amine light stabilizer, and based on the weight percent of mLLDPE, dosage is
0.1%~0.5%.
Further, the polyoctenamer rubber TOR is import hypocrystalline polyoctenamer rubber.
Further, the diameter of the nanometer calcium carbonate is 10-20nm.
Further, the dispersing agent is one of petroleum ether, paraffin, atoleine, naphthenic oil, polyethylene wax
Or it is a variety of.
Further, the preparation condition of the aryl sulfonation diazonium salt are as follows: p-aminobenzene sulfonic acid, sodium nitrite, 15 DEG C-
It is dissolved in 25 DEG C of tepidarium；Then sodium nitrite is added in the above solution under the conditions of 25 DEG C of -45 DEG C of temperature, by this solution
It is poured into concentrated hydrochloric acid ice water under agitation, and keeps the temperature at 30min-60min in ice-water bath, form aryldiazonium
Salt.
The present invention also provides a kind of manufacturing methods of above-mentioned polyvinyl piping materials, it is characterised in that by high density polyethylene (HDPE)
HDPE, metallocene linear-low density polyethylene mLLDPE, polyoctenamer rubber TOR, azodiisobutyronitrile, aryl sulfonation diazonium salt,
High-speed mixer stirring is added together after nanometer calcium carbonate, light stabilizer and dispersing agent ratio weighing according to claim 1
10-15 minutes, extruder is added and is granulated, fully automatic integral extruder extrusion Vacuum shaping then is added in pellet, coding, is cut
It cuts, examine, pack, be put in storage.
Further, extrusion temperature is: feed zone is 150-180 DEG C, and compression section is 200-220 DEG C, fluxing zone 220-
230 DEG C, homogenizing zone is 200-210 DEG C, and mold temperature is 190-210 DEG C, 15-20 DEG C of cooling water temperature；Cooling and shaping vacuum is
0.4MPa。
Polyoctenamer rubber is added and HDPE, mLLDPE are mixed in a certain ratio, the mechanical strength of enhancing can be obtained
Can, here because polyoctenamer includes linear and cyclic macromolecular, there is high resiliency, it can the effectively enhancing polymerization when squeezing out
The collapse resistance and anisotropy of object.Simultaneously polyoctenamer rubber have unsaturated group, it is easier to azodiisobutyronitrile with
Aryl sulfonation diazonium salt action issues raw cross-linking reaction, so that a degree of promotion improves discoloration-resistant performance and mechanical property.
Azodiisobutyronitrile adds to have by a certain percentage with aryl sulfonation diazonium salt cooperates with composite crosslinking effect, with routine
Cross-linking reagent peroxide compare, the azo and diazonium compound that the present invention selects have better reactivity and free radical
Generation ability has the crosslinking more effectively promoted, to enhance intensity, while can also effectively improve the resistance to change of polymer
Color performance, this is because sulfonic acid based structures blocked polymer hydroxyl, can be improved the stability of polymer molecule, prevent in acidity
Or degrade under alkaline condition, while utilizing sulfonic electronic effect, the stability under intensity and ultraviolet light can be improved.But it crosses
The degree of danger that the aryl sulfonation diazonium salt addition of amount will lead to extrusion process increases, and excessive cross-linking reaction occurs, therefore
It is preferred that azodiisobutyronitrile adds by a certain percentage with aryl sulfonation diazonium salt.
Nanometer calcium carbonate can effectively improve the discoloration-resistant performance of polymer as brightening agent, but the addition of calcium carbonate
Amount needs to control in a certain proportion, and mechanical property will be greatly reduced in excessive calcium carbonate addition.Hindered amine light stabilizer
Agent is added by a certain percentage in polymer of the invention as a kind of conventional additive, can effectively promote fastness energy
The further promotion of power.
Product of the invention has further promotion in mechanical property and resistance to metachrosis compared with prior art, simultaneously
Sharpest edges of the invention are the simplification of production process, the reduction of cost of material.
The present invention provides a kind of resistance to discoloration high strength polyethylene tubing and preparation method thereof, which passes through compound friendship
Join auxiliary agent and sulfonation modifying macromolecular chain, so as to improve polyvinyl piping materials discoloration-resistant and promote intensity, while it is of the invention
Process is simple compared with prior art for preparation method, at low cost, is suitble to industrialized production.
Specific embodiment
The present invention is explained combined with specific embodiments below.
A kind of resistance to discoloration high strength polyethylene tubing, including in parts by mass: 100 mass parts of PE100 resin, metallocene
Linear low density polyethylene mLLDPE20-50 mass parts, import hypocrystalline polyoctenamer rubber 10-20 mass parts, two isobutyl of azo
Nitrile 0.05-0.2 mass parts, aryl sulfonation diazonium salt 0.01-0.2 mass parts, diameter 10-20nm nanometer calcium carbonate 1-5 mass parts,
Hindered amine light stabilizer 0.02-0.25 mass parts and atoleine 0.1-1 mass parts；The azodiisobutyronitrile, aryl sulphur
The mass ratio for changing diazonium salt is 1:1-5:1；The PE100 resin, metallocene linear-low density polyethylene mLLDPE, import half
The mass ratio for crystallizing polyoctenamer rubber is 10:2-5:1-2；The aryl sulfonation diazonium salt is p-aminobenzene sulfonic acid and sodium nitrite
It reacts and is prepared under conditions of concentrated hydrochloric acid.
The manufacturing method of embodiment 1-5 and comparative example 1-8:
It is prepared as follows according to the formula of table 1:
The preparation condition of aryl sulfonation diazonium salt are as follows: the amount of p-aminobenzene sulfonic acid (SA) is 1.3g-4.5g, sodium nitrite
(NaNO2) amount is 0.1g-1.5g, is dissolved in 15 DEG C -25 DEG C of tepidarium；Then under the conditions of 25 DEG C of -45 DEG C of temperature
NaNO2 is added in above-mentioned solution, after NaNO2 is dissolved in mixed solution, this solution is poured under agitation containing 1mL
In the 20mL ice water of concentrated hydrochloric acid (HCl), and 30min-60min in ice-water bath is kept the temperature at, forms aryl diazonium salts.
The manufacturing method of polyvinyl piping materials: by high density polyethylene, metallocene linear-low density polyethylene mLLDPE,
Polyoctenamer rubber TOR, azodiisobutyronitrile, aryl sulfonation diazonium salt, nanometer calcium carbonate, light stabilizer and dispersing agent according to the form below 1
Ratio weighing after high-speed mixer be added together stir 10-15 minute, extruder is added and is granulated, then by pellet be added it is complete certainly
Movement and motor-driven integrative extruder squeezes out Vacuum shaping, coding, cutting, inspection, packaging, storage.Feed zone is 150-180 DEG C, compression section
It is 200-220 DEG C, fluxing zone is 220-230 DEG C, and homogenizing zone is 200-210 DEG C, and mold temperature is 190-210 DEG C, coolant water temperature
15-20 DEG C of degree；Cooling and shaping vacuum is 0.4MPa.
The formula of table 1 embodiment and comparative example
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| HDPE | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| mLLDPE | 35 | 35 | 35 | 20 | 50 | 35 | 35 | 35 | 35 | 35 | 35 | 35 | 35 |
| Polyoctenamer rubber TOR | 15 | 15 | 15 | 20 | 10 | 0 | 0 | 15 | 15 | 15 | 15 | 15 | 15 |
| Azodiisobutyronitrile | 0.1 | 0.1 | 0.1 | 0.05 | 0.2 | 0 | 0.1 | 0 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Aryl sulfonation diazonium salt | 0.05 | 0.1 | 0.02 | 0.05 | 0.04 | 0 | 0.05 | 0.05 | 0 | 0.05 | 0.05 | 0.2 | 0.05 |
| Nanometer calcium carbonate | 3 | 3 | 3 | 5 | 1 | 0 | 3 | 3 | 3 | 0 | 3 | 3 | 10 |
| Hindered amine light stabilizer | 0.1 | 0.1 | 0.1 | 0.02 | 0.25 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0 | 0.1 | 0.1 |
| Atoleine | 0.5 | 0.5 | 0.5 | 1 | 0.1 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
The tubing that comparative example 9 is prepared according to the embodiment 1 of CN102993535B.
Performance test:
Under the conditions of 80 DEG C of temperature, after above-described embodiment and comparative example are carried out aging 168 hours in UV baking oven, surface is observed
Whether jaundice discoloration is graded, and 0 is completely non-discolouring, and 5 be obvious discoloration.
Standard sample is made with injecting method in the product of the embodiment and comparative example, and performance is shown in Table 1 after tested
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | |
| Discoloration | 0 | 0 | 0 | 0 | 0 | 4 | 2 | 3 | 3 | 2 | 3 | 1 | 1 | 1 |
| Tensile break strength MPa | 57.3 | 51.6 | 47.5 | 53.4 | 48.9 | 15.8 | 23.1 | 31.0 | 35.6 | 50.5 | 56.8 | 48.2 | 30.6 | 39.1 |
| Elongation at break | 867 | 815 | 796 | 824 | 763 | 364 | 543 | 601 | 673 | 806 | 852 | 745 | 612 | 792 |
Comparative example and comparative example 2, it is known that polyoctenamer rubber is added and HDPE, mLLDPE are mixed in a certain ratio, can obtain
The mechanical strength performance that must enhance has high resiliency here because polyoctenamer includes linear and cyclic macromolecular, can be effective
Squeeze out when enhance polymer collapse resistance and anisotropy.Polyoctenamer rubber has unsaturated group simultaneously, more holds
Raw cross-linking reaction easily is issued in azodiisobutyronitrile and aryl sulfonation diazonium salt action, so that a degree of promotion improves resistance to change
Color performance and mechanical property.Comparative example and comparative example 3,4,7, it is known that azodiisobutyronitrile and aryl sulfonation diazonium salt press one
Certainty ratio addition has collaboration composite crosslinking effect, compared with the cross-linking reagent peroxide of routine, azo that the present invention selects
With diazonium compound there is better reactivity and free radical to generate ability, there is the crosslinking more effectively promoted, thus
Enhance intensity, while can also effectively improve the discoloration-resistant performance of polymer, this is because sulfonic acid based structures blocked polymer hydroxyl
The stability of polymer molecule can be improved in base, prevents from degrading under acid or alkaline conditions, while utilizing sulfonic electronics
The stability under intensity and ultraviolet light can be improved in effect.But excessive aryl sulfonation diazonium salt addition will lead to extrusion process
Degree of danger increase, and excessive cross-linking reaction occurs, therefore preferably azodiisobutyronitrile and aryl sulfonation diazonium salt presses one
Certainty ratio addition.Comparative example and comparative example 5,8, it is known that nanometer calcium carbonate can effectively improve polymer as brightening agent
Discoloration-resistant performance, but the additive amount of calcium carbonate needs to control in a certain proportion, and the addition of excessive calcium carbonate will
Mechanical property is greatly reduced.Comparative example and comparative example 6, it is known that hindered amine light stabilizer as a kind of conventional additive,
It is added by a certain percentage in polymer of the invention, the further promotion of anti-tarnishing ability can be effectively promoted.Comparison is implemented
Example and comparative example 9, it is known that product of the invention has further promotion, while the present invention in mechanical property and resistance to metachrosis
Sharpest edges be the simplification of production process, the reduction of cost of material.
Claims (9)
1. a kind of resistance to discoloration high strength polyethylene tubing characterized by comprising 100 mass parts of high density polyethylene,
Metallocene linear-low density polyethylene mLLDPE20-50 mass parts, polyoctenamer rubber TOR10-20 mass parts, azodiisobutyronitrile
0.05-0.2 mass parts, aryl sulfonation diazonium salt 0.01-0.2 mass parts, nanometer calcium carbonate 1-5 mass parts, light stabilizer .02-
0.25 mass parts and dispersing agent 0.1-1 mass parts；The mass ratio of the azodiisobutyronitrile, aryl sulfonation diazonium salt is 1:1-
5:1；The mass ratio of the high density polyethylene, metallocene linear-low density polyethylene mLLDPE, polyoctenamer rubber TOR
For 10:2-5:1-2；The aryl sulfonation diazonium salt be p-aminobenzene sulfonic acid with sodium nitrite the system of reacting under conditions of concentrated hydrochloric acid
It is standby to obtain.
2. polyvinyl piping materials according to claim 1, which is characterized in that the high density polyethylene is PE100 tree
Rouge.
3. polyvinyl piping materials according to claim 1, which is characterized in that light stabilizer is hindered amine light stabilizer, is pressed
The weight percent meter of mLLDPE, dosage are 0.1%~0.5%.
4. polyvinyl piping materials according to claim 1, which is characterized in that the polyoctenamer rubber TOR is import hypocrystalline
Polyoctenamer rubber.
5. polyvinyl piping materials according to claim 1, which is characterized in that the diameter of the nanometer calcium carbonate is 10-20nm.
6. polyvinyl piping materials according to claim 1, which is characterized in that the dispersing agent is petroleum ether, paraffin, liquid stone
One of wax, naphthenic oil, polyethylene wax are a variety of.
7. polyvinyl piping materials according to claim 1, which is characterized in that the preparation condition of the aryl sulfonation diazonium salt are as follows:
P-aminobenzene sulfonic acid, sodium nitrite dissolve in 15 DEG C -25 DEG C of tepidarium；Then upper under the conditions of 25 DEG C of -45 DEG C of temperature
It states and sodium nitrite is added in solution, this solution is poured under agitation in concentrated hydrochloric acid ice water, and keep the temperature at ice
30min-60min in water-bath forms aryl diazonium salts.
8. a kind of manufacturing method of polyvinyl piping materials described in claim 1, which is characterized in that by high density polyethylene,
Metallocene linear-low density polyethylene mLLDPE, polyoctenamer rubber TOR, azodiisobutyronitrile, aryl sulfonation diazonium salt, nano-sized carbon
10-15 points of high-speed mixer stirring is added together after sour calcium, light stabilizer and dispersing agent ratio weighing according to claim 1
Clock is added extruder and is granulated, and fully automatic integral extruder then is added in pellet and squeezes out Vacuum shaping, coding, cutting, inspection
It tests, pack, be put in storage.
9. the manufacturing method of polyvinyl piping materials according to claim 8, which is characterized in that extrusion temperature is: feed zone is
150-180 DEG C, compression section is 200-220 DEG C, and fluxing zone is 220-230 DEG C, and homogenizing zone is 200-210 DEG C, and mold temperature is
190-210 DEG C, 15-20 DEG C of cooling water temperature；Cooling and shaping vacuum is 0.4MPa.
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| CN111793266A (en) * | 2020-08-17 | 2020-10-20 | 埃维勒（北京）化工科技有限公司 | Color masterbatch, preparation method and application thereof, and PE-RT (polyethylene-reverse transcription) pipe |
| CN115519863A (en) * | 2022-10-25 | 2022-12-27 | 广东瑞远新材料有限公司 | Easily-regenerated environment-friendly polyethylene composite pipe and preparation method thereof |
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| CN111793266A (en) * | 2020-08-17 | 2020-10-20 | 埃维勒（北京）化工科技有限公司 | Color masterbatch, preparation method and application thereof, and PE-RT (polyethylene-reverse transcription) pipe |
| CN115519863A (en) * | 2022-10-25 | 2022-12-27 | 广东瑞远新材料有限公司 | Easily-regenerated environment-friendly polyethylene composite pipe and preparation method thereof |
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| CN108929477B (en) | 2020-09-22 |
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