A kind of high-density polyethylene alkene copolymer and preparation thereof and applicationTechnical field
(density is 0.948-0.955g/cm to the present invention relates to a kind of high density3) polyethylene and ethylene copolymers and preparation method thereof,And by its prepared Large Hollow Container goods.
Background technology
Chinese patent CN95195179.3 refer in single reactor by specific catalyst produce width/Double peak weight distributing polyethylene resin, described reactor is fluidized-bed reactor, and the present invention is the stirring of single anchor formulaSlurry phase reactor；China Patent No. CN200510078197.1 refers to pass through bimetallic catalyst at single reactorPreparing double peak weight distributing polyethylene resin, prepared polymer is suitable for blow molding applications, and the present invention is efficientZ-N catalyst, prepared polymer is suitable for Large Hollow Container goods.Chinese patent CN200610041102.3Refer to double-reactor tandem process, and the present invention is the system realizing double-peak high-density polytene in single reactorStandby.Chinese patent CN201210108129.5 refers at single reactor double by common Z-N catalyst preparationPeak molecular weight distribution polyvinyl resin, prepared polymer is suitable for tubing article, and the present invention is efficient Z-NCatalyst, prepared polymer is suitable for Large Hollow Container goods.
Summary of the invention
It is an object of the invention to develop a kind of high-density polyethylene alkene copolymer and preparation method thereof, it presents bimodal distributionAmount distribution, has good mechanical performance and processing characteristics.With this high-density polyethylene alkene copolymer as raw material, add anti-Large Hollow Container is processed into by oxygen agent and auxiliary agent so that it is have good yield strength and elongation at break.
The present invention provides the preparation method of a kind of high-density polyethylene alkene copolymer.Comprise the steps:
(1) magnesium dichloride, decane, fatty alcohol are added dissolution kettle, control temperature (50～180 DEG C), agitation revolution10-1000rpm, adds catalyst and prepares still after fully dissolving.Control temperature, pressure and charging rate, reaction temperatureIn the range of-20 DEG C～130 DEG C, low temperature dropping titanium tetrachloride, magnesium dichloride with the compounding of titanium tetrachloride is by weight0.1-99.0%(sum of the two is absolutely), after having reacted, filter, wash, pre-activate；
(2) adding alkyl aluminum is agent promoter, and its formula is AlRnX3-nIn formula, R is the alkyl of carbon number 1～10,X is halogen, X particularly chlorine and bromine, and n is the integer of 0 < n≤3；
(3) catalyst in hexane, (1) is added polymerization reaction kettle；
(4) being passed through hydrogen, hydrogen/volume of ethylene is absolutely than for 1%-4%(sum of the two)；
(5), when polymeric kettle temperature rises to 50 DEG C, open ethylene feed valve, be passed through ethylene；
(6) reaction temperature controls at 83 DEG C-85 DEG C, and reaction pressure controls at 0.8MPa-1.0MPa；
(7) release unreacted hydrogen, add comonomer CnH2n(4≤n≤8)；
(8), when polymeric kettle temperature rises to 50 DEG C, open ethylene feed valve, be passed through ethylene；
(9) reaction temperature controls at 70 DEG C-72 DEG C, and reaction pressure controls, at 0.3MPa-0.5MPa, to obtain after having reactedCopolymerization product；
Invention effect
Preparing a kind of high-density polyethylene alkene copolymer, it presents bimodal molecular weight distribution, has good mechanical performanceAnd processing characteristics, its density is 0.948-0.955g/cm3, melt index MI21.6For 7.0-10.0g/10min, moleculeAmount distribution 20-40MWD, elongation at break >=800%, tensile yield strength >=28MPa.With this high density polyethylene (HDPE)Copolymer is raw material, adds antioxidant and auxiliary agent is processed into Large Hollow Container goods so that it is have good surrender strongDegree and elongation at break.
Detailed description of the invention
Embodiment 1
Magnesium dichloride, decane, fatty alcohol are added in dissolution kettle, at a temperature of 130 DEG C, agitation revolution 100rpm,Add catalyst after fully dissolving and prepare still.At a temperature of-20 DEG C, drip titanium tetrachloride, magnesium dichloride and four chlorinationsThe compounding of titanium is 0.5% by weight, after having reacted, filters, washs, pre-activate.By itself and promoter threeAluminium ethide adds polymerization reaction kettle；Being passed through hydrogen, hydrogen/volume of ethylene ratio is 1.2%；When still temperature rises to 50 DEG C,Open ethylene feed valve, be passed through ethylene；Reaction temperature controls at 83 DEG C, and reaction pressure controls at 0.8MPa；ReleaseUnreacted hydrogen, adds comonomer hexene, is passed through ethylene, and reaction temperature controls at 70 DEG C, reaction pressure controlSystem, at 0.3MPa, obtains copolymerization product after having reacted.
With obtain high-density polyethylene alkene copolymer as raw material, add antioxidant and auxiliary agent and be processed into Large Hollow ContainerGoods, its yield strength is 28MPa, elongation at break >=800%.
Embodiment 2
Magnesium dichloride, decane, fatty alcohol are added in dissolution kettle, at a temperature of 125 DEG C, agitation revolution 200rpm,Add catalyst after fully dissolving and prepare still.At a temperature of-18 DEG C, drip titanium tetrachloride, magnesium dichloride and four chlorinationsThe compounding of titanium is 2% by weight, after having reacted, filters, washs, pre-activate.By itself and promoter three secondBase aluminum adds polymerization reaction kettle；Being passed through hydrogen, hydrogen/volume of ethylene ratio is 1.7%；When still temperature rises to 50 DEG C, beatDrive ethylene feed valve, be passed through ethylene；Reaction temperature controls at 83.5 DEG C, and reaction pressure controls at 0.9MPa；ReleaseUnreacted hydrogen, adds comonomer hexene, is passed through ethylene, and reaction temperature controls at 71 DEG C, reaction pressure controlSystem, at 0.4MPa, obtains copolymerization product after having reacted.
With obtain high-density polyethylene alkene copolymer as raw material, add antioxidant and auxiliary agent and be processed into Large Hollow ContainerGoods, its yield strength is 29MPa, elongation at break >=800%.
Embodiment 3
Magnesium dichloride, decane, fatty alcohol are added in dissolution kettle, at a temperature of 120 DEG C, agitation revolution 300rpm,Add catalyst after fully dissolving and prepare still.At a temperature of-16 DEG C, drip titanium tetrachloride, magnesium dichloride and four chlorinationsThe compounding of titanium is 5% by weight, after having reacted, filters, washs, pre-activate.By itself and promoter three secondBase aluminum adds polymerization reaction kettle；Being passed through hydrogen, hydrogen/volume of ethylene ratio is 2%；When still temperature rises to 50 DEG C, openEthylene feed valve, is passed through ethylene；Reaction temperature controls at 84 DEG C, and reaction pressure controls at 0.9MPa；Release the most anti-The hydrogen answered, adds comonomer hexene, is passed through ethylene, and reaction temperature controls at 72 DEG C, and reaction pressure controls0.3MPa, obtains copolymerization product after having reacted.
With obtain high-density polyethylene alkene copolymer as raw material, add antioxidant and auxiliary agent and be processed into Large Hollow ContainerGoods, its yield strength is 28MPa, elongation at break >=800%.
Embodiment 4
Magnesium dichloride, decane, fatty alcohol are added in dissolution kettle, at a temperature of 110 DEG C, agitation revolution 400rpm,Add catalyst after fully dissolving and prepare still.At a temperature of-15 DEG C, drip titanium tetrachloride, magnesium dichloride and four chlorinationsThe compounding of titanium is 10% by weight, after having reacted, filters, washs, pre-activate.By itself and promoter three secondBase aluminum adds polymerization reaction kettle；Being passed through hydrogen, hydrogen/volume of ethylene ratio is 2.5%；When still temperature rises to 50 DEG C, beatDrive ethylene feed valve, be passed through ethylene；Reaction temperature controls at 84.5 DEG C, and reaction pressure controls at 0.9MPa；ReleaseUnreacted hydrogen, adds comonomer hexene, is passed through ethylene, and reaction temperature controls at 71 DEG C, reaction pressure controlSystem, at 0.4MPa, obtains copolymerization product after having reacted.
With obtain high-density polyethylene alkene copolymer as raw material, add antioxidant and auxiliary agent and be processed into Large Hollow ContainerGoods, its yield strength is 29MPa, elongation at break >=800%.
Embodiment 5
Magnesium dichloride, decane, fatty alcohol are added in dissolution kettle, at a temperature of 100 DEG C, agitation revolution 400rpm,Add catalyst after fully dissolving and prepare still.At a temperature of-20 DEG C, drip titanium tetrachloride, magnesium dichloride and four chlorinationsThe compounding of titanium is 15% by weight, after having reacted, filters, washs, pre-activate.By itself and promoter three secondBase aluminum adds polymerization reaction kettle；Being passed through hydrogen, hydrogen/volume of ethylene ratio is 3.3%；When still temperature rises to 50 DEG C, beatDrive ethylene feed valve, be passed through ethylene；Reaction temperature controls at 83 DEG C, and reaction pressure controls at 1.0MPa；Release notThe hydrogen of reaction, adds comonomer hexene, is passed through ethylene, and reaction temperature controls at 72 DEG C, and reaction pressure controlsAt 0.5MPa, after having reacted, obtain copolymerization product.
With obtain high-density polyethylene alkene copolymer as raw material, add antioxidant and auxiliary agent and be processed into Large Hollow ContainerGoods, its yield strength is 29MPa, elongation at break >=800%.