CN104558786B - A kind of heat-resistant stability polyethylene composition - Google Patents
A kind of heat-resistant stability polyethylene composition Download PDFInfo
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2286—Oxides; Hydroxides of metals of silver
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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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
A kind of heat-resistant stability polyethylene composition, belong to polymeric material field, it is characterized in that, it is made up of the component of following weight portion: polyvinyl resin 100 parts, 0.3 ~ 0.7 part of antioxidant, chloride ion nertralizer 0.05 ~ 0.15 part, N, N ' double [β (3,5 di-t-butyl 4 hydroxy phenyl) propionyl] hydrazine is as copper resistant agent 0.04 ~ 0.18 part；Described polyvinyl resin is ethylene and 1 butylene and/or the copolymer of 1 hexene, and density is 0.932 ~ 0.948g/cm3；Melt mass flow rate is 0.35 ~ 1.0g/10min；In compositions, end group double bond content is 0.0065 ~ 0.019, carbonyl content 0.32 ~ 0.71.The present invention more reasonably arranges in pairs or groups adjuvant system and resin structure makes polyethylene composition of the present invention, has more preferable high-temperature oxidation resistance, long-term Heat-resistant stable performance and higher physical mechanical strength.
Description
Technical field
A kind of heat-resistant stability polyethylene composition, belongs to polymeric material field, is specifically related to a kind of for meeting
Polyethylene resin composition under the conditions of long-term higher temperature use.
Background technology
Heat-proof polythene (Polyethylene of raised temperature resistance is called for short PE-RT) pipe
Material is latest generation heat-resistant tube and geothermal tube special plastic, is in recent years in the tubing industry resistance to hot pressing of the most adopted one
The polyethylene without crosslinking that performance is remarkable.The high temperature resistant hydrostatic strength grade of PE-RT tube material be by
The principle of grading that ISO24033:2009 specifies determines, is divided into PE-RT I type from low to high by high temperature resistant hydrostatic strength grade
With PE-RT II type, need to by under the conditions of multiple temperature (the highest 110 DEG C), the long-term hydrostatic experiment of tubing of more than 8760 hours
Determine.PE-RT tube material is currently mainly applied to have the hot and cold water conveyance conduit of heat resistant requirements and produces, such as floor heating,
Heat exchanger, solar pipe and oil transportation tubing etc..
The standard of PE-RT tubing has the most both at home and abroad: " cold and hot water supply system is with moulding for international standard ISO22391-2009
Pipe material system: heat-proof polythene ", national sector standard CJ/T175-2002 " hot and cold water heat-proof polythene pipeline system ",
GB/T 28799-2012 " hot and cold water heat-proof polythene pipeline system ".Three standards all long-term to PE-RT tubing and pipe fitting
Heat stability has done strict regulations, it is desirable to tubing time to rupture under the conditions of 110 DEG C (1.9MPa or 2.3MPa) is little more than 8760
Time.
Polyvinyl piping materials destroys and is divided into three kinds of forms, i.e. ductile failure, brittle break and Oxidative demage.Wherein ductile failure
The generation in stage relatively early, this is because first polyethylene occurs in that the broken of Van der Waals force between layers under the conditions of higher stress
Bad；Brittle break is the chief destructive stage that pressure tubing occurs when reality is applied, and the time of generation is longer, it is generally desirable to high
Under the conditions of temperature after 5000h even more for a long time, the stress that this destruction occurs is relatively low；The chemical depletion stage is due to long-acting
The losing efficacy or consumed and the Oxidative demage that occurs of antioxidant, this destruction should in use be avoided occurring, with material this
Structure and the adjuvant system of body have much relations, affect tube material Long Service Life.
Chinese patent 201110255221.x " a kind of heat-proof polythene compositions and application thereof ", discloses a kind of resistance to hot polymerization
Vinyl composition and application thereof, belongs to polyethylene pipe field, it is characterised in that include the component of following weight portion: resistance to hot polymerization second
100 parts of alkene (PE-RT) and antioxidant 0.1～1.5 parts, wherein heat-proof polythene is polyethylene-hexene-1 copolymer, density 0.926
～0.950g/cm3, melt flow rate (MFR) (190 DEG C, 2.16Kg counterweight) 0.1～2g/10min, molecular weight is Unimodal Distribution, phase
To the degree of branching 0.08～0.50；Antioxidant includes Hinered phenols antioxidant and phosphite ester kind antioxidant.The present invention uses heat-resisting
The components such as hervene copolymer polyethylene, antioxidant are prepared has excellent mechanical property, high temperature resistant croop property, heat-resistant aging
The heat-proof polythene compositions of processing characteristics and can be extruded, improve the Practical Performance of PE-RT tubing further, can be used for preparation heat
Water piping system tubing and pipe fitting.But inventive composition is not reasonable due to adjuvant system and resin structure, for a long time
Deficiency is still had on heat aging performance.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, it is provided that a kind of heat-resistant stability polyethylene
Compositions, meets the polyethylene resin composition under the conditions of long term high temperature uses, has the heat aging performance of longer-term.
The technical solution adopted for the present invention to solve the technical problems is: this heat-resistant stability polyethylene composition, and it is special
Levy and be, be made up of the component of following weight portion: polyvinyl resin 100 parts, 0.3 ~ 0.7 part of antioxidant, chloride ion nertralizer
0.05 ~ 0.15 part, copper resistant agent N, N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine 0.04 ~ 0.18 part；Institute
The polyvinyl resin stated is ethylene and 1-butylene and/or the arbitrary proportion copolymer of 1-hexene, and density is 0.932 ~ 0.948g/
cm3, melt mass flow rate (MFR) is 0.35 ~ 1.0g/10min.
In compositions, end group double bond content is 0.0065 ~ 0.019, carbonyl content 0.32 ~ 0.71；Through 4800h at 95 DEG C
After hot water is aging, end group double bond content is 0.0064 ~ 0.018, and carbonyl content is 0.30 ~ 0.65.
Preferably, in compositions, end group double bond content is 0.0075 ~ 0.015；Carbonyl content is 0.42 ~ 0.64.
Preferably, described polyethylene, resin density is 0.934 ~ 0.942g/cm3；Melt mass flow rate is 0.5 ~
0.8 g/10min.The high density of polyvinyl resin determines the high intensity of resin, such as hydrostatic strength, hot strength, bending modulus
Deng, but the performance such as the too high resistance to slow crack growth that can reduce material of density and pliability.By to polyethylene tree in the present invention
The control of lipid density reaches the optimal intensity of hot-water line and resistance to slow crack growth and pliability.
Preferably, the addition of described chloride ion nertralizer is 0.06 ~ 0.12 part, and chloride ion nertralizer is zinc oxide
And/or silver oxide.
Preferably, described N, N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine addition is
0.08 ~ 0.13 part.
Grade that described polyvinyl resin is pressure reaches ISO 24033:2009 to PE-RT resin requirement.
Polyethylene macromolecular chain easily issues heat oxidation reaction in the effect being heated and aoxidize and generates macromole alcoxyl freely
Base, himself occurs β-cleavage to form aldehyde, ketone, and this will form carbonyl at PE molecule.Infrared analysis spectroscopic assay carbonyl is used to contain
Amount, can symbolize the various oxidation reaction products that material formed because of thermal oxide generation degradation reaction number, thus checking group
The quality of compound oxidation resistance and the amount of precipitation change of adjuvant system.A carbonyl content part for examination of infrared spectrum comes from
The carbonyl that resin oxidative degradation is formed, another part derives from the antioxidant in resin containing carbonyl, and therefore carbonyl content is one
The result that antioxidant amount of precipitation is comprehensive with material degradation amount, is related to the ageing resistace of material, particularly long term heat ageing
Can, its pressure performance of material aging also can decline.The carbonyl content of the present composition is 0.32 ~ 0.71, preferably 0.42 ~
0.64；At 95 DEG C, after 4800h hot water is aging, carbonyl content is 0.30 ~ 0.65.
Tube material can occur thermal degradation and two kinds of Heat Ageings of crosslinking, end group during using under the conditions of long term high temperature
Double bond content change can be with the crosslinking degree of illustrative material, and crosslinking degree size also affects the ageing resistace of material, particularly
Long term heat ageing performance, its pressure performance of material aging also can decline.Present composition end group double bond content is 0.0065 ~
0.019, preferably 0.0075 ~ 0.015.
Through Cl2Containing a large amount of chloride ion in the water of sterilization, owing to the oxyacid of halogen is all with certain oxidisability, example
Such as hypochlorous acid, when tubing carries water for a long time, plastic pipe is affected by chloracid oxidation susceptibility, and tubing long-term behaviour declines,
Tubing may be caused just to destroy at not up to life expectancy.The chloride ion nertralizer that the present invention adds is zinc oxide or oxidation
One in silver or both mixture, chloride ion nertralizer 0.05 ~ 0.15 part, preferably 0.06 ~ 0.12 part.
When tube material and air contact, can and the oxygen in air carry out chemical reaction and oxidized, be a kind of typical
Radical reaction.Antioxidant adds in tube material, can with plastic material in because of oxidation produce oxyradical R.、ROO.Instead
Should, interrupt the growth of living chain, thus effectively suppress or reduce the degraded of plastic material, ageing process, extend plastic
Service life.
Preferably, described added quantity of antioxidant is 0.4 ~ 0.6 part, and antioxidant is Hinered phenols antioxidant and phosphite
The compound of kind antioxidant, Hinered phenols antioxidant is 1:(0.7 ~ 1 with the mass ratio of phosphite kind antioxidant).This kind of ratio
The antioxidant of proportioning can preferably be combined with polyethylene macromole, it is not easy to separates out.
Preferably, described Hinered phenols antioxidant is 1:(0.9 ~ 1 with the mass ratio of phosphite kind antioxidant)；It is obstructed
Phenolic antioxidant is four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, β-(3,5-bis-uncles
Butyl-4-hydroxy phenyl) propanoic acid positive octadecanol ester, 1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl
Base) benzene or 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone；Described
Phosphite ester kind antioxidant is three ［ 2.4-di-tert-butyl-phenyl ］ phosphite ester, double (2,4-DI-tert-butylphenol compounds) tetramethylolmethane two
Phosphite ester or diphosphorous acid tetramethylolmethane distearyl alcohol ester.
Tube material can contact with the metal parts such as copper, steel in actual application, and the existence of copper ion can accelerate tubing
Destruction, shorten the service life of tubing, it is therefore desirable to add that copper resistant agent is anti-to be endangered here.The copper resistant agent that the present invention uses is N
, N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, addition is 0.04 ~ 0.18 part.
Compared with prior art, a kind of heat-resistant stability polyethylene composition of the present invention is had the beneficial effect that
The present invention provides a kind of for meeting the polyethylene resin composition under the conditions of long term high temperature uses, and can improve tube material at height
The performance such as heat stability after life-time service, hydrostatic strength, hot strength under the conditions of temperature, thus ensure or extension tube material 50
The design service life in year.The polyethylene composition of the present invention, has good high-temperature oxidation resistance, long-term heat-resistant stability
Energy and higher physical mechanical strength.95 DEG C, 4800h hot water aging after, material oxidation induction time OIT (210 DEG C) >=
40min, tension failure norminal strain >=600%；It is prepared as ф 20*2.0mm Pipe samples, 110 DEG C, under the conditions of 2.4MPa, hydrostatic
Compressive Strength >=8860h；110 DEG C, tubing oxidation induction time (210 DEG C) >=20min after 2.4MPa, 8760h.
Detailed description of the invention
Below by specific embodiment, a kind of heat-resistant stability polyethylene composition of the present invention is described further, its
Middle embodiment 1 is most preferred embodiment.
This be used for hot water pipeline polyethylene resin composition proportioning component as shown in Table 1 and Table 2.
Density is carried out according to GB/T 1033.2-2010, uses D method, tests after boiling 30 minutes；Melt mass flow speed
Rate (MFR) is tested by GB/T 3682-2000, loads as 2.16kg；Compositions end group double bond amount and carbonyl content test side
Method is: use hot pressing masking mechanism sample, sample thick 250 m, pelletizing temperature 170 DEG C, pressure 2MPa, preheats 30s, dwell time
0.5min, is directly cooled to less than 50 DEG C after release；Infrared spectrum acquisition condition is scanning 32 times, resolution 4；Carbonyl contains relatively
1778 ~ 1685cm in amount sample-1Between carbonyl absorption peak area and sum of fundamental frequencies peak 2019 cm-1Area ratio obtains；Double bond
920 ~ 874cm in relative amount sample-1Between C=C double bond absorption peak and sum of fundamental frequencies peak 2019 cm-1Area ratio obtains.
The polyethylene resin composition (in parts by weight) of table 1 embodiment 1 ~ 5 hot water pipeline
。
Preparation method: a) by heat-proof polythene resin, antioxidant, chloride ion nertralizer, copper resistant agent puts into high-speed mixer
Stirring mixing, speed of agitator 1300 revs/min, mixing time 12min, whipping temp 38 DEG C；B) material of mix homogeneously is added
Melt in double screw extruder, plastify, extrude, pelletize.Screw slenderness ratio is 33, processing temperature 220 DEG C.
The polyethylene resin composition (in parts by weight) of table 2 embodiment 6 ~ 8 hot water pipeline
。
Preparation method: a) by heat-proof polythene resin, antioxidant, chloride ion nertralizer, copper resistant agent puts into high-speed mixer
Stirring mixing, speed of agitator 1300 revs/min, mixing time 12min, whipping temp 38 DEG C；B) material of mix homogeneously is added
Melt in double screw extruder, plastify, extrude, pelletize.Screw slenderness ratio is 33, processing temperature 220 DEG C.
Comparative example 1 ~ 3 is the contrast pipe composition of the properties design comparing the present composition.Composition component
Proportioning is as shown in table 3:
The polyethylene resin composition (in parts by weight) of table 3 comparative example 1 ~ 3 hot water pipeline
。
Preparation method: a) by heat-proof polythene resin, antioxidant, chloride ion nertralizer, copper resistant agent puts into high-speed mixer
Stirring mixing, speed of agitator 1300 revs/min, mixing time 12min, whipping temp 38 DEG C；B) material of mix homogeneously is added
Melt in double screw extruder, plastify, extrude, pelletize.Screw slenderness ratio is 33, processing temperature 220 DEG C.
Performance test is tested
By the resin combination of the various embodiments described above 1 ~ 10 and comparative example 1 ~ 4 after high-speed mixer is blended, 190 ~ 230 DEG C
Lower twin screw pelletize, makes standard batten after mold pressing procedure.According to GB/T1040.2-2006 test fracture norminal strain；According to
GB/T 19466.6-2009 test oxidation induction time (OIT)；After compositions is prepared as the tubing of ф 20*2.0mm specification,
Hydrostatic strength according to GB/T 18252-2000 test tubing.The performance test results is shown in Table 4 ~ 6.
Table 4 embodiment 1 ~ 5 the performance test results
Note: tubular object extruding temperature: the molten temperature of 170 ~ 215 DEG C of heads of machine barrel 225 ~ 195 DEG C 210 DEG C.
Table 5 embodiment 6 ~ 8 the performance test results
Note: tubular object extruding temperature: the molten temperature of 170 ~ 215 DEG C of heads of machine barrel 225 ~ 195 DEG C 210 DEG C.
Table 6 comparative example 1 ~ 3 the performance test results
Note: tubular object extruding temperature: the molten temperature of 170 ~ 215 DEG C of heads of machine barrel 225 ~ 195 DEG C 210 DEG C.
Contrast from the performance test results of table 4 ~ 6 it can be seen that embodiment 1 ~ 8 material 95 DEG C, 4800h hot water aging
After, material oxidation induction time OIT (210 DEG C) >=40min, 110 DEG C, under the conditions of 2.4MPa, hydrostatic strength >=8860h；110
DEG C, tubing oxidation induction time (210 DEG C) >=20min after 2.4MPa, 8760h.Illustrate that compositions high-temperature oxidation resistance obtains
Significantly improve, and there is the tubing hydrostatic strength of excellence under the high temperature conditions；After material 95 DEG C, 4800h hot water are aging, draw
Stretch fracture norminal strain >=600%, illustrate that it has good heat stability and mechanical property.Comparative example 1 ~ 3 is under the high temperature conditions
After life-time service, mechanical property, oxidation induction time, pressure performance are all decreased obviously.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention makees other form, appoints
What those skilled in the art changed possibly also with the technology contents of the disclosure above or be modified as equivalent variations etc.
Effect embodiment.But every without departing from technical solution of the present invention content, the technical spirit of the foundation present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still falls within the protection domain of technical solution of the present invention.
Claims (1)
1. a heat-resistant stability polyethylene composition, it is characterised in that: consisting of of weight portion: PE-RT resin 100 parts, four
[methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester 0.22 part, double (2,4-DTBPs)
Pentaerythritol diphosphites 0.20 part, zinc oxide 0.04 part, silver oxide 0.01 part, N, N '-bis-[β-(3,5-di-t-butyls-
4-hydroxy phenyl) propionyl] hydrazine 0.09 part；The density of MFR 0.35g/10min, the PE-RT resin of PE-RT resin is 0.941
g/cm3, the carbonyl content 0.48 of compositions, end group double bond content 0.0094.
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| US11479624B2 (en) * | 2017-11-17 | 2022-10-25 | Exxonmobil Chemical Patents Inc. | PE-RT pipes and processes for making the same |
| CN112745410A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of in-situ crosslinked polyethylene with high thermal stability |
| CN116462898B (en) * | 2023-04-26 | 2024-08-09 | 金发科技股份有限公司 | Thermal-oxidative aging-resistant polyethylene material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011235486A (en) * | 2010-05-07 | 2011-11-24 | Prime Polymer Co Ltd | Method of manufacturing molded body made of silane-modified ethylene-based polymer, and resin composition |
| CN103160014A (en) * | 2011-12-15 | 2013-06-19 | 中国石油化工股份有限公司 | Polyethylene resin composition for hot-water pipeline and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011235486A (en) * | 2010-05-07 | 2011-11-24 | Prime Polymer Co Ltd | Method of manufacturing molded body made of silane-modified ethylene-based polymer, and resin composition |
| CN103160014A (en) * | 2011-12-15 | 2013-06-19 | 中国石油化工股份有限公司 | Polyethylene resin composition for hot-water pipeline and preparation method thereof |
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