CN104045756A - High-density polyethylene copolymer and its preparation method and use - Google Patents
High-density polyethylene copolymer and its preparation method and use Download PDFInfo
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Abstract
The invention relates to a high-density polyethylene copolymer and its preparation method and use. The preparation method comprises the following steps of adding magnesium dichloride, decane and fatty alcohol into a dissolving kettle, carrying out dissolution, adding the solution into a catalyst preparation kettle, dropwisely adding titanium tetrachloride into the catalyst preparation kettle at a temperature of -20 to 130 DEG C for a reaction, then carrying out filtration, washing and pre-activation, adding aluminum alkyl as a catalyst assistant, hexane and the above catalyst into a polymerization reaction vessel, feeding hydrogen and ethylene into the polymerization reaction vessel, carrying out a reaction process at a reaction temperature of 83-85 DEG C under reaction pressure of 0.8-1.0MPa, discharging unreactive hydrogen, adding a comonomer CnH2n (n >=4 and <=8), feeding ethylene, and carrying out a reaction process at a reaction temperature of 70-72 DEG C under reaction pressure of 0.3-0.5MPa to obtain the high-density polyethylene copolymer. The high-density polyethylene copolymer as a raw material, an antioxidant and an assistant are processed to form a large-scale hollow container having breakage elongation greater than or equal to 800% and tensile yield strength greater than or equal to 28MPa.
Description
Technical field
(density is 0.948-0.955g/cm to the present invention relates to a kind of high-density
3) polyethylene and ethylene copolymers and preparation method thereof, and the Large Hollow Container goods that made by it.
Background technology
What Chinese patent CN95195179.3 related to is to produce wide/double peak molecular weight distribution polyvinyl resin by specific catalyzer in single reactor, and described reactor is fluidized-bed reactor, and the present invention is single anchor formula stirring slurry-phase reactor; What China Patent No. CN200510078197.1 related to is to prepare double peak weight distributing polyethylene resin at single reactor by bimetallic catalyst, the polymkeric substance making is suitable for blow molding applications, and the present invention is efficient Z-N catalyzer, the polymkeric substance making is suitable for Large Hollow Container goods.What Chinese patent CN200610041102.3 related to is double-reactor tandem process, and the present invention is the preparation that realizes double-peak high-density polytene in single reactor.What Chinese patent CN201210108129.5 related to is to prepare double peak weight distributing polyethylene resin at single reactor by common Z-N catalyzer, the polymkeric substance making is suitable for tubing goods, and the present invention is efficient Z-N catalyzer, the polymkeric substance making is suitable for Large Hollow Container goods.
Summary of the invention
The object of the invention is to develop a kind of high-density polyethylene alkene copolymer and preparation method thereof, it has bimodal molecular weight distribution, has good mechanical property and processing characteristics.Taking this high-density polyethylene alkene copolymer as raw material, add oxidation inhibitor and auxiliary agent to be processed into Large Hollow Container, make it have good yield strength and elongation at break.
The invention provides a kind of preparation method of high-density polyethylene alkene copolymer.Comprise the steps:
(1) magnesium dichloride, decane, fatty alcohol are added to dissolution kettle, control temperature (50～180 DEG C), stir revolution 10-1000rpm, after fully dissolving, add catalyzer to prepare still.Control temperature, pressure and input speed, temperature of reaction within the scope of-20 DEG C～130 DEG C, low temperature drip titanium tetrachloride, magnesium dichloride and titanium tetrachloride composite by weight for 0.1-99.0%(sum of the two be a hundred per cent), after having reacted, filter, wash, activate in advance;
(2) adding aluminum alkyls is agent promotor, and its general formula is AlR
nx
3-nin formula, R is the alkyl of carbonatoms 1～10, and X is halogen, and X is chlorine and bromine particularly, the integer that n is 0<n≤3;
(3) catalyzer in hexane, (1) is added to polymerization reaction kettle;
(4) pass into hydrogen, hydrogen/volume of ethylene is than being a hundred per cent for 1%-4%(sum of the two);
(5) when polymeric kettle temperature rises to 50 DEG C, open ethylene feed valve, pass into ethene;
(6) temperature of reaction is controlled at 83 DEG C-85 DEG C, and reaction pressure is controlled at 0.8MPa-1.0MPa;
(7) emit unreacted hydrogen, add comonomer C
nh
2n(4≤n≤8);
(8) when polymeric kettle temperature rises to 50 DEG C, open ethylene feed valve, pass into ethene;
(9) temperature of reaction is controlled at 70 DEG C-72 DEG C, and reaction pressure is controlled at 0.3MPa-0.5MPa, after having reacted, obtains copolymerization product;
Invention effect
Prepare a kind of high-density polyethylene alkene copolymer, it presents bimodal molecular weight distribution, has good mechanical property and processing characteristics, and its density is 0.948-0.955g/cm
3, melting index MI
21.6for 7.0-10.0g/10min, molecular weight distribution 20-40MWD, elongation at break>=800%, tensile yield strength>=28MPa.Taking this high-density polyethylene alkene copolymer as raw material, add oxidation inhibitor and auxiliary agent to be processed into Large Hollow Container goods, make it have good yield strength and elongation at break.
Embodiment
Embodiment 1
Magnesium dichloride, decane, fatty alcohol are added in dissolution kettle, at 130 DEG C of temperature, stir revolution 100rpm, after fully dissolving, add catalyzer to prepare still.At-20 DEG C of temperature, drip titanium tetrachloride, the composite of magnesium dichloride and titanium tetrachloride is 0.5% by weight, after having reacted, filters, washs, activates in advance.Itself and promotor triethyl aluminum are added to polymerization reaction kettle; Pass into hydrogen, hydrogen/volume of ethylene ratio is 1.2%; When still temperature rises to 50 DEG C, open ethylene feed valve, pass into ethene; Temperature of reaction is controlled at 83 DEG C, and reaction pressure is controlled at 0.8MPa; Emit unreacted hydrogen, add comonomer hexene, pass into ethene, temperature of reaction is controlled at 70 DEG C, and reaction pressure is controlled at 0.3MPa, after having reacted, obtains copolymerization product.
Taking obtain high-density polyethylene alkene copolymer as raw material, add oxidation inhibitor and auxiliary agent to be processed into Large Hollow Container goods, its yield strength is 28MPa, elongation at break >=800%.
Embodiment 2
Magnesium dichloride, decane, fatty alcohol are added in dissolution kettle, at 125 DEG C of temperature, stir revolution 200rpm, after fully dissolving, add catalyzer to prepare still.At-18 DEG C of temperature, drip titanium tetrachloride, the composite of magnesium dichloride and titanium tetrachloride is 2% by weight, after having reacted, filters, washs, activates in advance.Itself and promotor triethyl aluminum are added to polymerization reaction kettle; Pass into hydrogen, hydrogen/volume of ethylene ratio is 1.7%; When still temperature rises to 50 DEG C, open ethylene feed valve, pass into ethene; Temperature of reaction is controlled at 83.5 DEG C, and reaction pressure is controlled at 0.9MPa; Emit unreacted hydrogen, add comonomer hexene, pass into ethene, temperature of reaction is controlled at 71 DEG C, and reaction pressure is controlled at 0.4MPa, after having reacted, obtains copolymerization product.
Taking obtain high-density polyethylene alkene copolymer as raw material, add oxidation inhibitor and auxiliary agent to be processed into Large Hollow Container goods, its yield strength is 29MPa, elongation at break >=800%.
Embodiment 3
Magnesium dichloride, decane, fatty alcohol are added in dissolution kettle, at 120 DEG C of temperature, stir revolution 300rpm, after fully dissolving, add catalyzer to prepare still.At-16 DEG C of temperature, drip titanium tetrachloride, the composite of magnesium dichloride and titanium tetrachloride is 5% by weight, after having reacted, filters, washs, activates in advance.Itself and promotor triethyl aluminum are added to polymerization reaction kettle; Pass into hydrogen, hydrogen/volume of ethylene ratio is 2%; When still temperature rises to 50 DEG C, open ethylene feed valve, pass into ethene; Temperature of reaction is controlled at 84 DEG C, and reaction pressure is controlled at 0.9MPa; Emit unreacted hydrogen, add comonomer hexene, pass into ethene, temperature of reaction is controlled at 72 DEG C, and reaction pressure is controlled at 0.3MPa, after having reacted, obtains copolymerization product.
Taking obtain high-density polyethylene alkene copolymer as raw material, add oxidation inhibitor and auxiliary agent to be processed into Large Hollow Container goods, its yield strength is 28MPa, elongation at break >=800%.
Embodiment 4
Magnesium dichloride, decane, fatty alcohol are added in dissolution kettle, at 110 DEG C of temperature, stir revolution 400rpm, after fully dissolving, add catalyzer to prepare still.At-15 DEG C of temperature, drip titanium tetrachloride, the composite of magnesium dichloride and titanium tetrachloride is 10% by weight, after having reacted, filters, washs, activates in advance.Itself and promotor triethyl aluminum are added to polymerization reaction kettle; Pass into hydrogen, hydrogen/volume of ethylene ratio is 2.5%; When still temperature rises to 50 DEG C, open ethylene feed valve, pass into ethene; Temperature of reaction is controlled at 84.5 DEG C, and reaction pressure is controlled at 0.9MPa; Emit unreacted hydrogen, add comonomer hexene, pass into ethene, temperature of reaction is controlled at 71 DEG C, and reaction pressure is controlled at 0.4MPa, after having reacted, obtains copolymerization product.
Taking obtain high-density polyethylene alkene copolymer as raw material, add oxidation inhibitor and auxiliary agent to be processed into Large Hollow Container goods, its yield strength is 29MPa, elongation at break >=800%.
Embodiment 5
Magnesium dichloride, decane, fatty alcohol are added in dissolution kettle, at 100 DEG C of temperature, stir revolution 400rpm, after fully dissolving, add catalyzer to prepare still.At-20 DEG C of temperature, drip titanium tetrachloride, the composite of magnesium dichloride and titanium tetrachloride is 15% by weight, after having reacted, filters, washs, activates in advance.Itself and promotor triethyl aluminum are added to polymerization reaction kettle; Pass into hydrogen, hydrogen/volume of ethylene ratio is 3.3%; When still temperature rises to 50 DEG C, open ethylene feed valve, pass into ethene; Temperature of reaction is controlled at 83 DEG C, and reaction pressure is controlled at 1.0MPa; Emit unreacted hydrogen, add comonomer hexene, pass into ethene, temperature of reaction is controlled at 72 DEG C, and reaction pressure is controlled at 0.5MPa, after having reacted, obtains copolymerization product.
Taking obtain high-density polyethylene alkene copolymer as raw material, add oxidation inhibitor and auxiliary agent to be processed into Large Hollow Container goods, its yield strength is 29MPa, elongation at break >=800%.
Claims (3)
1. a preparation method for high-density polyethylene alkene copolymer, is characterized in that: comprise the steps:
(1) magnesium dichloride, decane, fatty alcohol are added to dissolution kettle, controlling temperature is 50～180 DEG C, stir revolution 10-1000rpm, after fully dissolving, add catalyzer to prepare still, control temperature, pressure and input speed, temperature of reaction is within the scope of-20 DEG C～130 DEG C, low temperature drips titanium tetrachloride, and the composite of magnesium dichloride and titanium tetrachloride is 0.1-99.0% by weight, and sum of the two is absolutely, after having reacted, filter, wash, activate in advance;
(2) adding aluminum alkyls is agent promotor, and its general formula is AlR
nx
3-nin formula, R is the alkyl of carbonatoms 1～10, and X is halogen, and X is chlorine and bromine particularly, the integer that n is 0<n≤3;
(3) catalyzer in hexane, (1) is added to polymerization reaction kettle;
(4) pass into hydrogen, hydrogen/volume of ethylene is than being 1%-4%, and sum of the two is absolutely;
(5) when polymeric kettle temperature rises to 50 DEG C, open ethylene feed valve, pass into ethene;
(6) temperature of reaction is controlled at 83 DEG C-85 DEG C, and reaction pressure is controlled at 0.8MPa-1.0MPa;
(7) emit unreacted hydrogen, add comonomer C
nh
2n(4≤n≤8);
(8) when polymeric kettle temperature rises to 50 DEG C, open ethylene feed valve, pass into ethene;
(9) temperature of reaction is controlled at 70 DEG C-72 DEG C, and reaction pressure is controlled at 0.3MPa-0.5MPa, after having reacted, obtains copolymerization product.
2. a high-density polyethylene alkene copolymer, is characterized in that: it is prepared by method according to claim 1.
3. an application for high-density polyethylene alkene copolymer, is characterized in that: taking the high-density polyethylene alkene copolymer in claim 2 as raw material, add oxidation inhibitor and auxiliary agent to be processed into Large Hollow Container goods.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146712A (en) * | 2015-03-27 | 2016-11-23 | 中国石油天然气股份有限公司 | Polyethylene is resin dedicated, its preparation method, application and the preparation method of catalyst |
| CN108084311A (en) * | 2017-12-28 | 2018-05-29 | 宁波俐辰新能源有限公司 | A kind of ecologic planting nuisanceless light transmission film and its manufacturing method |
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| WO2007015927A1 (en) * | 2005-07-27 | 2007-02-08 | Univation Technologies, Llc | Blow molding polyethylene resins |
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| 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
- 2013-03-13 CN CN201310079096.0A patent/CN104045756B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158135A (en) * | 1994-09-22 | 1997-08-27 | 美孚石油公司 | Process for controlling the NWD of a broad/bimodal produced in a single reactor |
| WO2007015927A1 (en) * | 2005-07-27 | 2007-02-08 | Univation Technologies, Llc | Blow molding polyethylene resins |
| CN101880339A (en) * | 2009-05-05 | 2010-11-10 | 中国石油化工股份有限公司 | Ziegler-Natta polyethylene catalyst with wide molecular weight distribution, and preparation method thereof |
| 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 |
| CN102002124A (en) * | 2009-09-02 | 2011-04-06 | 中国石油天然气股份有限公司 | Method for preparing superfine polyethylene powder |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146712A (en) * | 2015-03-27 | 2016-11-23 | 中国石油天然气股份有限公司 | Polyethylene is resin dedicated, its preparation method, application and the preparation method of catalyst |
| CN108084311A (en) * | 2017-12-28 | 2018-05-29 | 宁波俐辰新能源有限公司 | A kind of ecologic planting nuisanceless light transmission film and its manufacturing method |
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| CN104045756B (en) | 2016-08-10 |
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