CN104098818B - High-density polyethylene composition, preparation and application thereof - Google Patents
High-density polyethylene composition, preparation and application thereof Download PDFInfo
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- CN104098818B CN104098818B CN201310114343.6A CN201310114343A CN104098818B CN 104098818 B CN104098818 B CN 104098818B CN 201310114343 A CN201310114343 A CN 201310114343A CN 104098818 B CN104098818 B CN 104098818B
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- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 229920001903 high density polyethylene Polymers 0.000 title claims abstract description 18
- 239000004700 high-density polyethylene Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000005977 Ethylene Substances 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000003960 organic solvent Substances 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000011777 magnesium Substances 0.000 claims abstract 2
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 2
- 229910052719 titanium Inorganic materials 0.000 claims abstract 2
- 239000010936 titanium Substances 0.000 claims abstract 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 19
- 238000013019 agitation Methods 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 11
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 13
- 230000002902 bimodal effect Effects 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a high-density polyethylene composition, its preparation and application; under the protection of nitrogen, adding organic solvent as dispersant, uniformly dispersing magnesium ethoxide in the organic solvent, stirring at 60-150 deg.C for 40-1000rpm, adding TiCl4The molar ratio of titanium to magnesium is 0.5-5.0; after the complex reaction, washing, filtering and drying to obtain a catalyst; adding alkyl aluminum as a cocatalyst, and introducing hydrogen/ethylene with the volume ratio of 4.5-7.5; the reaction temperature is 80-83 ℃, and the reaction pressure is 0.8-1.0 MPa; addition of comonomer CnH2nIntroducing ethylene; the reaction temperature is 70-72 ℃, and the reaction pressure is 0.2-0.5 MPa; the composition is used as a raw material, and an auxiliary agent is added to prepare a film product, wherein the tensile yield strength is more than or equal to 28MPa, and the elongation at break is more than or equal to 1000%.
Description
Technical field
The present invention relates to a kind of film dual-peak distributed high density density is (0.951-0.955g/cm3) polyethylene composition and preparation thereof and application.
Background technology
Chinese patent CN95195179.3 refers to produce wide/double peak molecular weight distribution polyvinyl resin by specific catalyst in single reactor, and described reactor is fluidized-bed reactor, and the present invention is stirring for autoclave slurry phase reactor；China Patent No. CN200510078197.1 refers to prepare double peak weight distributing polyethylene resin at single reactor by bimetallic catalyst, the polymer prepared is suitable for blow molding applications, and the present invention is the catalyst of independent development, prepared polymer is suitable for thin film.Chinese patent CN200610041102.3 refers to double-reactor tandem process, and the present invention realizes the preparation of double-peak high-density polytene in single reactor.
Summary of the invention
It is an object of the present invention to provide a kind of thin film dual-peak distributed high density polyethylene compositions and preparation thereof and application, method is to adopt catalyst to prepare the double-peak high-density polytene compositions of film article with single still tandem process.Single tank reactor adds catalyst and promoter, by certain hydrogen/ethylene ratio under certain temperature and pressure, add hydrogen and ethylene gas and comonomer carries out polyreaction, prepare the high-density polyethylene composition that a kind of molecular weight distribution is bimodal distribution, with said composition for raw material, add auxiliary agent and make film article, its tensile yield strength >=28MPa, elongation at break >=1000%.
A kind of thin film dual-peak distributed high density polyethylene compositions of the present invention, the High molecular weight polyethylene component containing 45%-55% weight, the low molecular weight polyethylene component of 45%-55% weight, composition density is 0.951-0.955g/cm3, high molecular melt index MI5For 0.01-1.0g/10min, low-molecular-weight MI5For 300-1000g/10min.
Of the present invention a kind of adopt single still tandem process to prepare the method that molecular weight distribution is the high-density polyethylene composition of bimodal distribution, comprise the steps:
(1) stir in catalyst preparing still at band, under nitrogen protection, add organic solvent as dispersant, magnesium ethylate is dispersed in organic solvent, at 60-150 DEG C of temperature, agitation revolution 40-1000rpm, add TiCl4, magnesium ethylate/TiCl4Weight ratio be 0.1-99.0%；After complex reaction, wash, filter, dry, obtain catalyst；
(2) adding organic solvent in vinyl polymerization still as dispersant, organic solvent is C4-C6Linear paraffin；Addition alkyl aluminum is promoter, and its formula is AlRnX3-nIn formula, R is the alkyl of carbon number 1～10, and X is halogen, X particularly chlorine and bromine, and n is the integer of 0 < n≤3；
(3) catalyst in (1) is added polymerization reaction kettle；
(4) passing into hydrogen, hydrogen/volume of ethylene is than for 4.5-7.5；
(5), when polymeric kettle temperature rises to 40-60 DEG C, open ethylene feed valve, pass into ethylene；
(6) reaction temperature controls at 80 DEG C-83 DEG C, and reaction pressure controls at 0.8MPa-1.0MPa；
(7) ethylene reaction is to 0.675Kg～0.825Kg, and reaction system is lowered the temperature, pressure release, adds comonomer CnH2n(2 < n≤8)；(8) it is warming up to 40-60 DEG C, opens ethylene feed valve, pass into ethylene；
(9) reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls at 0.2MPa-0.5MPa；
With said composition for raw material, add auxiliary agent and make film article, its tensile yield strength >=28MPa, elongation at break >=1000%.
Invention effect
Preparing molecular weight by independent development catalyst with single still tandem process is dual-peak distributed high density polyethylene, and this polymer has the tensile mechanical properties of excellence, and its processing characteristics is excellent.The film article performance that this bimodal polyethylene is made is very excellent, and its tensile yield strength and extension at break degree all exceed like product performance.
Detailed description of the invention
Embodiment 1
Stir in catalyst preparing still at band, under nitrogen protection, add organic solvent (C6-C13Linear paraffin) as dispersant, magnesium ethylate is dispersed in organic solvent, at 150 DEG C of temperature, agitation revolution 40rpm, add TiCl4, magnesium ethylate/TiCl4Weight ratio be 0.1%；After complex reaction, wash, filter, dry, obtain catalyst；
Triethyl aluminum and prepared catalyst are joined in reactor with organic solvent, passes into hydrogen；Still temperature rise, to 50 DEG C, opens ethylene feed valve；Hydrogen/volume of ethylene ratio is 4.5；Reaction temperature controls at 80 DEG C-83 DEG C, and reaction pressure controls at 0.8MPa；Ethylene reaction is to 0.675Kg, and reaction system is lowered the temperature, pressure release, adds comonomer hexene；It is warming up to 50 DEG C, opens ethylene feed valve, pass into ethylene；Reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls at 0.3MPa；
The high-density polyethylene composition of bimodal distribution is raw material, adds auxiliary agent and makes film article, its tensile yield strength >=28MPa, elongation at break >=1000%.
Embodiment 2
Stir in catalyst preparing still at band, under nitrogen protection, add organic solvent (C6-C13Linear paraffin) as dispersant, magnesium ethylate is dispersed in organic solvent, at 130 DEG C of temperature, agitation revolution 100rpm, add TiCl4, magnesium ethylate/TiCl4Weight ratio be 5.0%；After complex reaction, wash, filter, dry, obtain catalyst；
Triethyl aluminum and prepared catalyst are joined in reactor with organic solvent, passes into hydrogen；Still temperature rise, to 50 DEG C, opens ethylene feed valve；Hydrogen/volume of ethylene ratio is 5.0；Reaction temperature controls at 80 DEG C-83 DEG C, and reaction pressure controls at 0.9MPa；Ethylene reaction is to 0.705Kg, and reaction system is lowered the temperature, pressure release, adds comonomer butene-1；It is warming up to 50 DEG C, opens ethylene feed valve, pass into ethylene；Reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls at 0.4MPa；
The high-density polyethylene composition of bimodal distribution is raw material, adds auxiliary agent and makes film article, its tensile yield strength >=28.5MPa, elongation at break >=1000%.
Embodiment 3
Stir in catalyst preparing still at band, under nitrogen protection, add organic solvent (C6-C13Linear paraffin) as dispersant, magnesium ethylate is dispersed in organic solvent, at 110 DEG C of temperature, agitation revolution 160rpm, add TiCl4, magnesium ethylate/TiCl4Weight ratio be 16.0%；After complex reaction, wash, filter, dry, obtain catalyst；
Triethyl aluminum and prepared catalyst are joined in reactor with organic solvent, passes into hydrogen；Still temperature rise, to 50 DEG C, opens ethylene feed valve；Hydrogen/volume of ethylene ratio is 6.0；Reaction temperature controls at 80 DEG C-83 DEG C, and reaction pressure controls at 1.0MPa；Ethylene reaction is to 0.75Kg, and reaction system is lowered the temperature, pressure release, adds comonomer hexene；It is warming up to 50 DEG C, opens ethylene feed valve, pass into ethylene；Reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls at 0.5MPa；
The high-density polyethylene composition of bimodal distribution is raw material, adds auxiliary agent and makes film article, its tensile yield strength >=29MPa, elongation at break >=1000%.
Embodiment 4
Stir in catalyst preparing still at band, under nitrogen protection, add organic solvent (C6-C13Linear paraffin) as dispersant, magnesium ethylate is dispersed in organic solvent, at 90 DEG C of temperature, agitation revolution 300rpm, add TiCl4, magnesium ethylate/TiCl4Weight ratio be 21.0%；After complex reaction, wash, filter, dry, obtain catalyst；
Triethyl aluminum and prepared catalyst are joined in reactor with organic solvent, passes into hydrogen；Still temperature rise, to 55 DEG C, opens ethylene feed valve；Hydrogen/volume of ethylene ratio is 7.0；Reaction temperature controls at 80 DEG C-83 DEG C, and reaction pressure controls at 1.0MPa；Ethylene reaction is to 0.78Kg, and reaction system is lowered the temperature, pressure release, adds comonomer butene-1；It is warming up to 50 DEG C, opens ethylene feed valve, pass into ethylene；Reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls at 0.5MPa；
The high-density polyethylene composition of bimodal distribution is raw material, adds auxiliary agent and makes film article, its tensile yield strength >=29MPa, elongation at break >=1000%.
Embodiment 5
Stir in catalyst preparing still at band, under nitrogen protection, add organic solvent (C6-C13Linear paraffin) as dispersant, magnesium ethylate is dispersed in organic solvent, at 90 DEG C of temperature, agitation revolution 450rpm, add TiCl4, magnesium ethylate/TiCl4Weight ratio be 21.0%；After complex reaction, wash, filter, dry, obtain catalyst；
Triethyl aluminum and prepared catalyst are joined in reactor with organic solvent, passes into hydrogen；Still temperature rise, to 55 DEG C, opens ethylene feed valve；Hydrogen/volume of ethylene ratio is 7.0；Reaction temperature controls at 80 DEG C-83 DEG C, and reaction pressure controls at 1.0MPa；Ethylene reaction is to 0.825Kg, and reaction system is lowered the temperature, pressure release, adds comonomer hexene；It is warming up to 50 DEG C, opens ethylene feed valve, pass into ethylene；Reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls at 0.3MPa；
The high-density polyethylene composition of bimodal distribution is raw material, adds auxiliary agent and makes film article, its tensile yield strength >=28MPa, elongation at break >=1000%.
Embodiment 6
Stir in catalyst preparing still at band, under nitrogen protection, add organic solvent (C6-C13Linear paraffin) as dispersant, magnesium ethylate is dispersed in organic solvent, at 60 DEG C of temperature, agitation revolution 750rpm, add TiCl4, magnesium ethylate/TiCl4Weight ratio be 61.0%；After complex reaction, wash, filter, dry, obtain catalyst；
Triethyl aluminum and prepared catalyst are joined in reactor with organic solvent, passes into hydrogen；Still temperature rise, to 50 DEG C, opens ethylene feed valve；Hydrogen/volume of ethylene ratio is 7.5；Reaction temperature controls at 80 DEG C-83 DEG C, and reaction pressure controls at 1.0MPa；Ethylene reaction is to 0.825Kg, and reaction system is lowered the temperature, pressure release, adds comonomer butene-1；It is warming up to 50 DEG C, opens ethylene feed valve, pass into ethylene；Reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls at 0.5MPa；
The high-density polyethylene composition of bimodal distribution is raw material, adds auxiliary agent and makes film article, its tensile yield strength >=28.5MPa, elongation at break >=1000%.
Embodiment 7
Stir in catalyst preparing still at band, under nitrogen protection, add organic solvent (C6-C13Linear paraffin) as dispersant, magnesium ethylate is dispersed in organic solvent, at 130 DEG C of temperature, agitation revolution 1000rpm, add TiCl4, magnesium ethylate/TiCl4Weight ratio be 52.0%；After complex reaction, wash, filter, dry, obtain catalyst；
Triethyl aluminum and prepared catalyst are joined in reactor with organic solvent, passes into hydrogen；Still temperature rise, to 55 DEG C, opens ethylene feed valve；Hydrogen/volume of ethylene ratio is 7.0；Reaction temperature controls at 80 DEG C-83 DEG C, and reaction pressure controls at 1.0MPa；Ethylene reaction is to 0.78Kg, and reaction system is lowered the temperature, pressure release, adds comonomer hexene；It is warming up to 50 DEG C, opens ethylene feed valve, pass into ethylene；Reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls at 0.4MPa；
The high-density polyethylene composition of bimodal distribution is raw material, adds auxiliary agent and makes film article, its tensile yield strength >=29MPa, elongation at break >=1000%.
Embodiment 8
Stir in catalyst preparing still at band, under nitrogen protection, add organic solvent (C6-C13Linear paraffin) as dispersant, magnesium ethylate is dispersed in organic solvent, at 135 DEG C of temperature, agitation revolution 280rpm, add TiCl4, magnesium ethylate/TiCl4Weight ratio be 99.0%；After complex reaction, wash, filter, dry, obtain catalyst；
Triethyl aluminum and prepared catalyst are joined in reactor with organic solvent, passes into hydrogen；Still temperature rise, to 50 DEG C, opens ethylene feed valve；Hydrogen/volume of ethylene ratio is 7.0；Reaction temperature controls at 80 DEG C-83 DEG C, and reaction pressure controls at 1.0MPa；Ethylene reaction is to 0.75Kg, and reaction system is lowered the temperature, pressure release, adds comonomer butene-1；It is warming up to 50 DEG C, opens ethylene feed valve, pass into ethylene；Reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls at 0.5MPa；
The high-density polyethylene composition of bimodal distribution is raw material, adds auxiliary agent and makes film article, its tensile yield strength >=28MPa, elongation at break >=1000%.
Claims (1)
1. the preparation method of high-density polyethylene composition one kind described, it is characterized in that, described high-density polyethylene composition contains the High molecular weight polyethylene component of 45%-55% weight, the low molecular weight polyethylene component of 45%-55% weight, and composition density is 0.951-0.955g/cm3, high molecular melt index MI5For 0.01-1.0g/10min, low-molecular-weight MI5For 300-1000g/10min；
Described preparation method comprises the steps:
(1) stir in catalyst preparing still at band, under nitrogen protection, add organic solvent as dispersant, magnesium ethylate is dispersed in organic solvent, at 60-150 DEG C of temperature, agitation revolution 40-1000rpm, add TiCl4, the mol ratio of titanium/magnesium is 0.5-5.0；After complex reaction, wash, filter, dry, obtain catalyst；
(2) adding dispersant in vinyl polymerization still, described dispersant is C4-C6The organic solvent of linear paraffin；And in vinyl polymerization still addition agent promoter, described dose of promoter is alkyl aluminum, add alkyl aluminum be agent promoter, its formula is AlRnX3-nIn formula, R is the alkyl of carbon number 1～10, and X is chlorine and bromine, and n is the integer of 0 < n≤3；
(3) catalyst in (1) is added polymerization reaction kettle；
(4) passing into hydrogen, hydrogen/volume of ethylene is than for 4.5-7.5；
(5), when polymeric kettle temperature rises to 40-60 DEG C, open ethylene feed valve, pass into ethylene；
(6) reaction temperature controls at 80 DEG C-83 DEG C, and reaction pressure controls at 0.8MPa-1.0MPa；
(7) ethylene reaction is to 0.675Kg～0.825Kg, and reaction system is lowered the temperature, pressure release, adds comonomer CnH2n, 2 < n≤8；
(8) it is warming up to 40-60 DEG C, opens ethylene feed valve, pass into ethylene；
(9) reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls at 0.2MPa-0.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310114343.6A CN104098818B (en) | 2013-04-03 | 2013-04-03 | High-density polyethylene composition, preparation and application thereof |
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| CN201310114343.6A CN104098818B (en) | 2013-04-03 | 2013-04-03 | High-density polyethylene composition, preparation and application thereof |
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| CN104098818B true CN104098818B (en) | 2016-07-06 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1993417A (en) * | 2004-06-09 | 2007-07-04 | 英尼奥斯制造业比利时有限公司 | Polyethylene pipe fitting resins |
| JP2010270300A (en) * | 2009-05-22 | 2010-12-02 | Samsung Total Petrochemicals Co Ltd | Method for producing dialkoxy magnesium carrier for olefin polymerization catalyst, method for producing olefin polymerization catalyst by utilizing the same and method for polymerizing olefin by utilizing the same |
| CN102731879A (en) * | 2011-04-07 | 2012-10-17 | 中国石油化工股份有限公司 | Material specially used for high density polyethylene hollow container and preparation method thereof |
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2013
- 2013-04-03 CN CN201310114343.6A patent/CN104098818B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1993417A (en) * | 2004-06-09 | 2007-07-04 | 英尼奥斯制造业比利时有限公司 | Polyethylene pipe fitting resins |
| JP2010270300A (en) * | 2009-05-22 | 2010-12-02 | Samsung Total Petrochemicals Co Ltd | Method for producing dialkoxy magnesium carrier for olefin polymerization catalyst, method for producing olefin polymerization catalyst by utilizing the same and method for polymerizing olefin by utilizing the same |
| CN102731879A (en) * | 2011-04-07 | 2012-10-17 | 中国石油化工股份有限公司 | Material specially used for high density polyethylene hollow container and preparation method thereof |
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