CN108976539A - A kind of double-wall corrugated pipe as special material of large size HDPE and preparation method - Google Patents
A kind of double-wall corrugated pipe as special material of large size HDPE and preparation method Download PDFInfo
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- CN108976539A CN108976539A CN201710401240.6A CN201710401240A CN108976539A CN 108976539 A CN108976539 A CN 108976539A CN 201710401240 A CN201710401240 A CN 201710401240A CN 108976539 A CN108976539 A CN 108976539A
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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
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
Abstract
A kind of double-wall corrugated pipe as special material of large size HDPE and preparation method, belong to the field of processing and application of high molecular material.It is characterized by: the temperature of control mixer is 255 DEG C ~ 265 DEG C, UHMWPE is given up in 70 ~ 80 parts of addition mixers of pipe broken material after temperature of charge is raised to 255 DEG C ~ 265 DEG C, 10 ~ 15 parts of HDPE16A, 10 ~ 15 parts of HDPE8008,2.0 ~ 4.0 parts and 0.4 ~ 0.8 part of 2,6-di-tert-butyl p-cresol of calcium stearate is added；Continue mixing, after being then granulated to obtain the final product.Selection high rigidity of the invention, fluidity of molten good injection molding material HDPE 8008 and HDPE 16A is used in compounding, instrumentality is played during UHMWPE gives up pipe broken material high-temperature fusion, the heat of effective dispersion and transmitting UHMWPE degradation release, the high temperature rapid cleavage of UHMWPE is reacted, slow controllable degradation reaction is become.
Description
Technical field
A kind of double-wall corrugated pipe as special material of large size HDPE and preparation method, the processing and application for belonging to high molecular material are led
Domain.
Background technique
In oilfield equipment assets, oil well pipe accounts for 60%, is that dosage is maximum, spends most material oils, its matter
Amount quality and performance superiority and inferiority, directly affect the exploration and development benefit of oil company, it is with oily, gas well security reliability and makes
It is closely related with the service life, it is great to the development relationship of petroleum industry.In oil field prospecting and development and production, metal pipe material and other
Metal component failure is a generally existing problem, such as the corrosion, wear of drilling tool and casing failure in drilling well production, is recovered the oil
The wear-out failure of sucker rod and oil well pipe in journey, the corrosion failure etc. of oil field ground pipe network.Reduce rod collar and oil well pipe
Coefficient of friction, crude oil and contained sewage can not only slow down its abrasion, but also can save ground energy to the corrosivity of metallic conduit
Consumption.
Ultra-high molecular weight polyethylene (UHMWPE) material reaches 200 × 10 using relative molecular mass4Above
UHMWPE resin, is manufactured by special process.The material is urged by American Association chemical company using Ziegler in nineteen fifty-seven
Agent is succeeded in developing first, belongs to linear polymer, relative molecular mass is usually in (100~500) × 104Between, crystallinity
65%~85%, 0.92~0.96g/cm of density3.Compared with numerous polymer materials, UHMWPE material has coefficient of friction low,
Wear-resisting, the corrosion-resistant, characteristics such as machine-shaping difficulty is big.UHMWPE pipe is used to utilize the excellent of the material as the bushing pipe of steel oil pipe
Good characteristic realizes wax control, eccentric abrasion prevention, etch-proof purpose.Country's Daqing oil field, Jilin Oil Field, Shengli Oil Field and carat at present
Ma starts the application for being widely popularized high abrasion, the compound oil well pipe of anticorrosive polyethylene according to oil field, and according to incompletely statistics, China is existing
About 130,000 mouthfuls of oil well, also to increase 6,000 mouthfuls of oil wells newly every year, there are also the waste oil tubes of up to a million mouthfuls of oil wells to scrap.High abrasion resists
The popularization and application of corrosion UHMWPE oil well internal lining pipe played an important role in the stable and high yields in oil field.
However, the useless pipe in the oil field UHMWPE scrapped is processed into one with the extensive application of UHMWPE oil well internal lining pipe
Technical problem, since this kind of useless pipe has adsorbed a large amount of organic greasy dirt in use process, not only tubing color becomes brown, but also
Kerosene smell excitatory can not blend with general UHMWPE and squeeze pipe or extrusion board use.In this kind of UHMWPE oil well
Since its molecular weight is huge, melt viscosity is high, the pellet through being crushed crusher machine cannot be carried out bushing pipe with common extruder again
Processing removing volatile matter.Therefore it is badly in need of the processing method for finding a kind of recycling, becomes the emphasis of this field research.
Summary of the invention
It is managed back the technical problem to be solved by the present invention is overcoming the deficiencies of the prior art and provide a kind of give up using UHMWPE
Expect, meet the double-wall corrugated pipe as special material of large-scale HDPE and preparation method that common twin-screw squeezes processing request.
The technical solution adopted by the present invention to solve the technical problems is: the double-wall corrugated pipe as special material of large size HDPE,
It is characterized in that, parts by weight of raw materials composition are as follows: UHMWPE gives up 70 ~ 80 parts of pipe broken material, 10 ~ 15 parts of HDPE16A, HDPE8008 10
~ 15 parts, 2.0 ~ 4.0 parts and 0.4 ~ 0.8 part of 2,6-di-tert-butyl p-cresol of calcium stearate.
The preparation method of the double-wall corrugated pipe as special material of above-mentioned large size HDPE, which is characterized in that processing step are as follows:
1) after the mixing chamber temperature for controlling mixer is 255 DEG C ~ 265 DEG C, UHMWPE is given up 70 ~ 80 parts of pipe broken material by weight
It is added in mixer and is stirred 12 ~ 15 minutes with 40 ~ 45 revs/min of internally mixes, after temperature of charge is raised to 255 DEG C ~ 265 DEG C, by weight
It measures part and 10 ~ 15 parts of HDPE16A, 10 ~ 15 parts of HDPE8008,2.0 ~ 4.0 parts of calcium stearate and 2 is added, 6- di-t-butyl is to first
0.4 ~ 0.8 part of phenol (antioxidant 264)；
2) continue constant temperature mixing 20 ~ 25 minutes, be drying to obtain after then carrying out single screw rod granulation.
The present invention provides a kind of UHMWPE and gives up that produce high density polyethylene (HDPE) (HDPE) large-sized double-walled bellows dedicated for pipe feed back
The method of material, especially for degradation treatment formula, special installation and the process route of the useless pipe of UHMWPE oil well liner.Pass through this
After the method processing of invention, so that the molecular weight of UHMWPE is declined to a great extent to meeting common compounding type double screw extruder and process
Requirement, there are also sufficiently rigid, intensity, toughness and elongation percentage for material；And the irritation kerosene smell that material has is by original
6 grades drop to 2 grades of levels, the material after this UHMWPE degradation can be used for manufacturing the large-sized double-walled corrugated drain pipe road HDPE.
The mixer is equipped with tetragonous rotor, and the ratio between the short rib of mixer and long rib are 0.25:1；The spiral shell of long rib and short rib
Swing angle is 30 degree ~ 35 degree；Long rib face advance is 85 ~ 90 degree, and short rib face advance is 15 ~ 20 degree.Rib rotor structure of the present invention is special
Point can make the Sheared axial flow of sizing material is dynamic to be greatly improved with dispersibility.
Preferably, the additional amount of the useless pipe broken material of the UHMWPE is 74 ~ 76 parts.
Preferably, the additional amount of the HDPE16A is 12 ~ 12.8 parts, and the additional amount of HDPE8008 is 12 ~ 12.8 parts,
The additional amount of calcium stearate is 2.7 ~ 3.4 parts, and the additional amount of 2,6-di-tert-butyl p-cresol is 0.5 ~ 0.7 part.
The best double-wall corrugated pipe as special material of large-scale HDPE of performance can be obtained after preferred material proportion reprocessing.
The draw ratio that the single screw rod is granulated single screw extrusion machine used is 13:1.
The extrusion temperature of single screw rod granulation single screw extrusion machine used is from 1st area to 6th area until head is respectively 180
DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 195 DEG C；It is 25 ~ 30 revs/min that single screw rod, which is granulated revolving speed,.
The single screw rod is granulated the strainer that 3 layer of 120 mesh is set before the die head of single screw extrusion machine used.
The particle that the single screw rod granulation is cut out is diameter and length is 2.6 ~ 3.4 cylindrical particles.
The drying temperature of the drying is 100 DEG C, drying time 2h.
The time of constant temperature mixing described in the step 2 is 22 ~ 23 minutes.
The revolving speed of mixer described in the step 1) is 42 ~ 43 revs/min.
Compared with prior art, possessed by the double-wall corrugated pipe as special material of a kind of large size HDPE of the invention and preparation method
Beneficial effect is: the present invention is drained using the large-sized double-walled ripple of above-mentioned formula for raw stock, mixing unit and process conditions manufacture
The performance of pipe as special material is as follows: tensile strength >=26.0MPa, stretching yield stress >=22.0MPa, and fracture norminal strain >=
450%, bending modulus >=1080MPa melt flow rate (MFR) (21.6 kilograms of loads) 2.8 ~ 3.5 grams/10min, 220 DEG C of oxidation inductions
Time 15 ~ 24 minutes.And the irritation kerosene smell having before material processing, the VS-01.00-T- provided according to SGS
The detection of 14004-A1-2004 method, drops to 2 grades of levels by original 6 grades.The HDPE ripple pipe as special material is through SBBW1200PE
The large-sized double-walled bellows unit extrusion molding of type, it is cooling after to get arriving high performance 1200 type HDPE large size corrugated conduit of Φ.
It is detected after being placed 48 hours at 23 DEG C of corrugated conduit of the 1200 type HDPE large size of Φ of manufacture, it is long-term in tubing
On hydrostatic pressure-resistant tester, test temperature: 80 DEG C, 3.9 MPa of circumference stress, bellows is not destroyed through 165 h test periods.When
80 DEG C of test temperature, when circumference stress is 2.8 MPa, 1 000 h test period of bellows is not destroyed, and is fully met large size and is buried wave
The Industry code requirements of line pipe.
Key problem in technology of the invention is the processing conditions for cooperating the tetragonous mixer of high shear, selects high rigidity, melt flows
Property the good lesser HDPE 16A of injection molding material HDPE 8008 and same high rigidity, melt flow rate (MFR), made with same ratio compounding
With playing instrumentality during UHMWPE gives up pipe broken material high-temperature fusion, effective dispersion and transmitting UHMWPE degradation being released
The heat put reacts the high temperature rapid cleavage of UHMWPE, becomes slow controllable degradation reaction.It prepares and meets Φ 1200
The HDPE PP Pipe Compound that large-sized double-walled bellows manufacture requires.Detected through DSC, the fusing point of the HDPE PP Pipe Compound prepared after degradation by
136 DEG C of UHMWPE drop to 133 DEG C.
Specific embodiment
The present invention will be further described combined with specific embodiments below.Illustrate formula and material by embodiment and comparative example
Expect the relationship between performance, further embodies science of the invention, innovation and practicality.The material of embodiment and comparative example
Accessory is shown in Table 1, table 2, and wherein embodiment 1 is most preferred embodiment.
The material proportion of 1 embodiment of table, part
。
The material proportion of 2 comparative example of table, part
。
Embodiment and comparative example 1 ~ 5 is using electric heating controllable temperature to 300 DEG C of 110L mixer, the tetragonous rotor of mixer
Feature: the ratio between short rib and long rib are 0.25；Long rib and short rib helical angle are 30 degree of -35 degree；(rib spiral is in circumference for its face advance
Shared angle of circumference on face) 85 ~ 90 degree of rib long, 15 ~ 20 degree of short rib；It is equipped with electric material behind mixer and promotes vehicle, promotes vehicle
Below with double 180 single screw extrusion machines of Φ for drawing feeding, promotes vehicle and squeeze the good material lifting of internal mixing and plasticizing to single screw rod
The double of machine draw in feeding hopper out, and the draw ratio of single screw extrusion machine is 13:1, and single screw extrusion machine uses electric-heating water cooling side
Formula；Mouth mold recycles die face cooling and dicing using water, before die head band from moving filter screen device, such mixer, promoted vehicle,
Single screw rod is used in combination, form one dedicated for UHMWPE give up pipe broken material processing mixing be granulated unit.
The process route that embodiment and comparative example 1 ~ 5 is implemented is as follows: by the mixing chamber temperature perseverance of mixer to 260 ± 5 DEG C
Afterwards, the UHMWPE pipe broken material that gives up is added in mixer and is stirred 12-15 minute with 40-45 revs/min of internally mix, shown to temperature of charge
Show after being also raised to 260 ± 5 DEG C, is added and is formulated load weighted HDPE16A, HDPE8008 calcium stearate and antioxidant 264.Continue permanent
Warm mixing 20-25 minutes, find that material under the shear action of closed-smelting machine rotor, is melted and is plasticized by appropriateness degradation at this time
Uniformly.Then material is discharged to and is promoted in vehicle hopper, started promotion handlebar material lifting and be granulated to double draw in hopper.Single screw rod
Prilling temperature from 1st area to 6th area until head is respectively 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 195
℃；It is 25-30 revs/min that single screw rod, which is granulated revolving speed, and head strainer uses 3 layers of 120 mesh.The particle size Φ 3 that water ring is cut out ±
0.4, long 3 ± 0.4, through dehydration, air-cooled, 100 DEG C × 2h is dry into feed bin weighing packaging.Obtain the large-sized double-walled corrugation rows of HDPE
Water pipe PP Pipe Compound.
The Preparation equipment of comparative example 6 and technique with above-described embodiment 1, unlike, the ratio between short rib and long rib of mixer
For 0.4:1；Long rib and short rib helical angle are 25 degree.
Table 3: embodiment sample the performance test results comparison
。
Table 4: comparative example the performance test results comparison
。
The test result being respectively formulated from table of the embodiment of the present invention 1 is listed in table 3, as seen from Table 3, when the useless pipe of UHMWPE is broken
Material presses mass fraction 80-70；Each dosage 10-15 parts of HDPE 16A and HDPE 8008；2.0-4.0 parts of calcium stearate；Antioxidant
264 be 0.4-0.80 parts.The PE material bending modulus with higher and stretching yield stress that mixing is granulated out, it is suitable molten
Body flow rate, the performance for being suitable for heavy caliber bellows are wanted.This is because the calcium stearate selected in formula has well
Thermal stability is not easy vaporization volatilization, melt state and HDPE 16A and HDPE 8008 is kept to cooperate with fusion plastification at 260 DEG C
Afterwards.When part UHMWPE solid at high temperature by shearing rapid cleavage after, a large amount of cracking thermal energy released is by HDPE
16A and the rapid transfer spreading of 8008 melt of HDPE make the UHMWPE to degrade slow down degradation speed because temperature reduces
Rate, while the calcium stearate being dissolved in 8008 melt of HDPE 16A and HDPE can neutralize rapidly UHMWPE degradation again and release
A large amount of H free radicals, avoid H free radical catalysis ethylene segment rapid cleavage.It is dissolved in 8008 melt of HDPE 16A and HDPE
In antioxidant 264, Quick stop UHMWPE degradation generate polyolefin free radical, avoid these macromolecular radicals occur coupling
It closes and terminates reaction.In this way, UHMWPE solid under high shear, high temperature rapid cleavage reaction, become controlled temperature, rate by
Control, sluggish degradation reaction, when average molecular weight is degraded to 500,000-80 ten thousand, the UHMWPE moderately to degrade is at 260 DEG C
It just will become melt, be provided with the high rigidity energy of the invention patent desired fusion plastification function and material.
Testing result in comparative example table 4 of the present invention finds out that it is disconnected that comparative example 1 finds that the plastic material squeezed out after mixing stretches
It is extremely low to split strain, it may be possible to which the melt flow rate (MFR) that HDPE 8008 is used alone is too high, the high temperature compatibility with UHMWPE waste material
Caused by bad.Discovery material mixing in 65 minutes is not plasticized the discovery of comparative example 2 formula in an experiment, is caught fire suddenly after plasticizing
Phenomenon illustrates that exclusive use HDPE 16A melting means is too small, it is not easy to be plasticized the high temperature of UHMWPE waste material, not play melting medium
Effect.HDPE 8008 contents of 16A and HDPE are too high in the formula of comparative example 3, and material plasticizing is granulated successfully, but the stretching of material
Yield stress is too low, and bending modulus is also low.It is not able to satisfy the rigid requirements of large plastic bellows；It is stearic in the formula of comparative example 4
Sour calcium content is too many, and the too high stretching yield stress that will also result in material of small molecule content is too low, and bending modulus is very low, can not
Meet the rigid requirements of large-scale bellows.5 antioxidant 264 content of comparative example is too low, and 200 DEG C of oxidation induction times of material are too
It is short, it is not able to satisfy bellows process requirements.The experimental result and Analysis on Mechanism designed by above-mentioned formula, has absolutely proved this hair
Novelty, creativeness and the practicability of bright formula, equipment combination structure and production process route.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection scope of technical solution of the present invention.
Claims (12)
1. a kind of double-wall corrugated pipe as special material of large size HDPE, which is characterized in that parts by weight of raw materials composition are as follows: UHMWPE is useless, and pipe is broken
70 ~ 80 parts of material, 10 ~ 15 parts of HDPE16A, 10 ~ 15 parts of HDPE8008,2.0 ~ 4.0 parts of calcium stearate and 2,6- di-t-butyl pair
0.4 ~ 0.8 part of cresols.
2. the preparation method of one kind double-wall corrugated pipe as special material of large size HDPE described in claim 1, which is characterized in that technique step
Suddenly are as follows:
1) after the mixing chamber temperature for controlling mixer is 255 DEG C ~ 265 DEG C, UHMWPE is given up 70 ~ 80 parts of pipe broken material by weight
It is added in mixer and is stirred 12 ~ 15 minutes with 40 ~ 45 revs/min of internally mixes, after temperature of charge is raised to 255 DEG C ~ 265 DEG C, by weight
It measures part and 10 ~ 15 parts of HDPE16A, 10 ~ 15 parts of HDPE8008,2.0 ~ 4.0 parts of calcium stearate and 2 is added, 6- di-t-butyl is to first
0.4 ~ 0.8 part of phenol；
2) continue constant temperature mixing 20 ~ 25 minutes, be drying to obtain after then carrying out single screw rod granulation.
3. a kind of preparation method of the double-wall corrugated pipe as special material of large size HDPE according to claim 2, it is characterised in that: institute
The mixer stated is equipped with tetragonous rotor, and the ratio between the short rib of mixer and long rib are 0.25:1；The helical angle of long rib and short rib is 30
~ 35 degree of degree；Long rib face advance is 85 ~ 90 degree, and short rib face advance is 15 ~ 20 degree.
4. a kind of preparation method of the double-wall corrugated pipe as special material of large size HDPE according to claim 2, it is characterised in that: institute
The additional amount of the useless pipe broken material of the UHMWPE stated is 74 ~ 76 parts.
5. a kind of preparation method of the double-wall corrugated pipe as special material of large size HDPE according to claim 2, it is characterised in that: institute
The additional amount of the HDPE16A stated is 12 ~ 12.8 parts, and the additional amount of HDPE8008 is 12 ~ 12.8 parts, and the additional amount of calcium stearate is
2.7 ~ 3.4 parts, the additional amount of 2,6-di-tert-butyl p-cresol is 0.5 ~ 0.7 part.
6. a kind of preparation method of the double-wall corrugated pipe as special material of large size HDPE according to claim 2, it is characterised in that: institute
Stating single screw rod and being granulated the draw ratio of single screw extrusion machine used is 13:1.
7. a kind of preparation method of the double-wall corrugated pipe as special material of large size HDPE according to claim 2, it is characterised in that: institute
It states single screw rod and is granulated the extrusion temperature of single screw extrusion machine used from 1st area to 6th area until head is respectively 180 DEG C, 190 DEG C,
200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 195 DEG C；It is 25 ~ 30 revs/min that single screw rod, which is granulated revolving speed,.
8. a kind of preparation method of the double-wall corrugated pipe as special material of large size HDPE according to claim 2, it is characterised in that: institute
State the strainer that 3 layer of 120 mesh is set before the die head of single screw rod granulation single screw extrusion machine used.
9. a kind of preparation method of the double-wall corrugated pipe as special material of large size HDPE according to claim 2, it is characterised in that: institute
It states single screw rod and is granulated that the particle that cuts out is diameter and length is 2.6 ~ 3.4 cylindrical particles.
10. a kind of preparation method of the double-wall corrugated pipe as special material of large size HDPE according to claim 2, it is characterised in that:
The drying temperature of the drying is 100 DEG C, drying time 2h.
11. a kind of preparation method of the double-wall corrugated pipe as special material of large size HDPE according to claim 2, it is characterised in that:
The time of constant temperature mixing described in the step 2 is 22 ~ 23 minutes.
12. a kind of preparation method of the double-wall corrugated pipe as special material of large size HDPE according to claim 2, it is characterised in that:
The revolving speed of mixer described in the step 1) is 42 ~ 43 revs/min.
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| CN111621078A (en) * | 2020-06-17 | 2020-09-04 | 湖北合聚高分子材料有限公司 | Super-tough environmental stress cracking resistant high-density polyethylene and preparation method thereof |
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