CN102093498B - Material special for polyethylene and preparation method thereof - Google Patents
Material special for polyethylene and preparation method thereof Download PDFInfo
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- CN102093498B CN102093498B CN2009102424479A CN200910242447A CN102093498B CN 102093498 B CN102093498 B CN 102093498B CN 2009102424479 A CN2009102424479 A CN 2009102424479A CN 200910242447 A CN200910242447 A CN 200910242447A CN 102093498 B CN102093498 B CN 102093498B
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Abstract
The invention relates to a material special for polyethylene and a preparation method thereof. The material special for the polyethylene has a uniform short branched chain structure, wherein melt index (MI21.6) is 1 to 3 grams per 10 minutes; average granularity is 200 to 300 mu m; bulk density is 0.35 to 0.40 g/cm<3>; and density is 0.947 to 0.950 g/cm<3>. Polyethylene powder for crosslinking to form a pipe is not required to be subsequently processed and crushed and can be directly distributed relatively reasonably; and in the crosslinking process, the same and even higher crosslinking degree is achieved under the condition of using a small amount of peroxide.
Description
Technical field:
The present invention relates to produce extrusion molding with polyethylene special-purpose material of peroxide crosslinked polyethylene tubing and preparation method thereof.
Background technology:
Vilaterm mixes with superoxide, and under molten state, peroxide breakdown produces radical, makes between the Vilaterm molecule and forms carbon-carbon bond, and a large amount of intermolecular carbon-carbon bonds makes Vilaterm become crosslinking structure.In order to form tridimensional network, need polyvinyl resin be heated to produce crosslinked action.Must fully infiltrate superoxide and oxidation inhibitor before the processing, through the plunger tpe extruding machine peroxide crosslinked polyethylene (PEX-a) powder processing become tubing then.With new LDPE (film grade) and linear low density polyethylene composition is that the tubing that raw material is processed exists many defectives such as heat-resisting creep properties is poor, shock resistance is poor, swelling behavior difference.The crosslinked course of processing requires the size-grade distribution of polyethylene powders to be in specified range, mixes with superoxide and oxidation inhibitor to help this powder, reaches the effect that identical degree of crosslinking is only used less superoxide.
Patent CN1523052A discloses a kind of rotation molding and has used cross-linked polyethylene special material, is linea low density and low-density polyethylene composition.New LDPE (film grade) powder discharging operation easier is big, and the granularity of said composition is bigger, needs follow-up crushing processing process, and irrational size distribution possibly cause and superoxide, oxidation inhibitor undercompounding, and cross-linking effect is undesirable.
Patent CN200410026533.3 discloses a kind of radiant crosslinked polyethylene tubing, is used for squeezing the polyvinyl resin of managing and is made up of 70%～100% high density polyethylene(HDPE) and 0～30% linear low density polyethylene.Tube extruding machine obtains through the electron rays radiation after being squeezed into pipe, and degree of crosslinking is on the low side, a little less than the tubing degree of deflection resistance.
Summary of the invention:
The objective of the invention is to produce a kind of polyethylene special-purpose material of suitable production peroxide crosslinked polyethylene tubing; Being used in the polyethylene powders granularity that is cross-linked into pipe does not need following process broken; Directly reach relatively reasonable distribution, cross-linking process is issued to identical even higher degree of crosslinking in the situation of using less superoxide.Satisfy the problem of domestic these type of cross-linked polyethylene special material production domesticization needs, provide a kind of slurry process to prepare poly method.
The present invention provides a kind of Vilaterm raw material method that is used to prepare peroxide crosslinking tubing.Under whipped state, in polymeric kettle, add Ziegler-Natta catalyst, a certain amount of straight chain saturated alkane or straight chain saturated alkane mixture (C
nH
2n+2) (wherein n is 6-8), add aluminum alkyls (AlR then successively
3) (wherein R is that carbon number is the saturated alkyl of 1-4) and catalyzer, when the polymeric kettle temperature rises to 50 ℃, feed ethene and hydrogen, control reaction temperature and reaction pressure.After reaction is accomplished, cooling discharge, polymer paste obtains polyethylene powders through separating and drying treatment.
Polyethylene powders is characterized as, melting index (MI
21.6) be 1～3g/10min, average particle size distribution is 200 μ m～300 μ m, tap density is 0.35～0.40g/cm
3Density is 0.947g/cm
3-0.950g/cm
3, particularly this Vilaterm is resin dedicated has a uniform short-chain branch structure
Ethene polymerization process condition and step are following:
1) under nitrogen protection, with 0.2～0.5L aluminum alkyls (AlR
3) (wherein R is that carbon number is the saturated alkyl of 1-4) join 1800L straight chain saturated alkane or straight chain saturated alkane mixture (C
nH
2n+2) in (wherein n is 6-8).
2) add the 100-200g Ziegler-Natta catalyst to reaction system.
3) polymeric kettle is warming up to 50 ℃ and stirred 20 minutes.
4) in above-mentioned reaction system, add 45～90mol hydrogen, feed the mixture of ethene and propylene then, ethylene pressure is controlled at≤0.9MPa.
4) control reaction temperature is 80～85 ℃, and reaction pressure is controlled at 0.6MPa-1.0MPa.
5) reaction product is filtered and dry, obtain polyethylene powders.
The polyethylene powders granularity that is used to be cross-linked into pipe does not need following process broken, directly reaches relatively reasonable distribution, and cross-linking process is issued to identical even higher degree of crosslinking in the situation of using less superoxide.
Embodiment
Embodiment 1
1. under nitrogen protection, 0.2L triethyl aluminum aluminum alkyls is joined in the 1800L hexane, add the 100g Ziegler-Natta catalyst then.Polymeric kettle is warming up to 50 ℃ and stirred 20 minutes.In reaction system, add 48mol hydrogen, feed the mixture of ethene and propylene then, ethylene pressure is controlled at≤0.9MPa, 80 ℃ of control reaction temperature, and when the ethene add-on reaches 520Kg, stopped reaction.Reactant is filtered and drying, obtain polyethylene product 500Kg.Measuring the polyethylene powders mean particle size is 220 μ m, and bulk density is 0.38g/cm
3
Embodiment 2
2. under nitrogen protection, 0.2L triethyl aluminum aluminum alkyls is joined in the 1800L straight chain saturated alkane mixture, add the 120g Ziegler-Natta catalyst then.Polymeric kettle is warming up to 50 ℃ and stirred 20 minutes.In reaction system, add 55mol hydrogen, feed the mixture of ethene and propylene then, ethylene pressure is controlled at≤0.9MPa.83 ℃ of control reaction temperature, when the ethene add-on reaches 520Kg, stopped reaction.Reactant is filtered and drying, obtain polyethylene product 500Kg.Measuring the polyethylene powders mean particle size is 300 μ m, and bulk density is 0.40g/cm
3
Embodiment 3
3. under nitrogen protection, 0.2L triethyl aluminum aluminum alkyls is joined in the 1800L straight chain saturated alkane mixture, add the 120g Ziegler-Natta catalyst then.Polymeric kettle is warming up to 50 ℃ and stirred 20 minutes.In reaction system, add 64mol hydrogen, feed the mixture of ethene and propylene then, ethylene pressure is controlled at≤0.9MPa, 84 ℃ of control reaction temperature, and when the ethene add-on reaches 620Kg, stopped reaction.Reactant is filtered and drying, obtain polyethylene product 600Kg.Measuring the polyethylene powders mean particle size is 260 μ m, and bulk density is 0.38g/cm
3
Embodiment 4
Under nitrogen protection, 0.5L triethyl aluminum aluminum alkyls is joined in the 1800L hexane, add the 200g Ziegler-Natta catalyst then.Polymeric kettle is warming up to 50 ℃ and stirred 20 minutes.In reaction system, add 80mol hydrogen, feed the mixture of ethene and propylene then, ethylene pressure is controlled at≤0.9MPa, 83 ℃ of control reaction temperature, and when the ethene add-on reaches 620Kg, stopped reaction.Reactant is filtered and drying, obtain polyethylene product 600Kg.Measuring the polyethylene powders mean particle size is 240 μ m, and bulk density is 0.35g/cm
3
Claims (2)
1. the preparation method of a polyethylene special-purpose material, it is characterized in that: ethene polymerization process condition and step are following:
1) under nitrogen protection, be that the saturated alkyl aluminium of 1-4 joins in the straight chain saturated alkane or straight chain saturated alkane mixture that the 1800L carbon number is 6-8 with 0.2～0.5L carbon number;
2) add the 100-200g Ziegler-Natta catalyst to reaction system;
3) polymeric kettle is warming up to 50 ℃ and stirred 20 minutes;
4) in above-mentioned reaction system, add 45～90mol hydrogen, feed ethene and propylene mixtures then, ethylene pressure is controlled at≤0.9MPa;
5) control reaction temperature is 80～85 ℃, and reaction pressure is controlled at 0.6MPa-1.0MPa;
6) reaction product is filtered and dry, obtain polyethylene powders.
2. the polyethylene special-purpose material of the preparation method of a polyethylene special-purpose material according to claim 1 preparation, it is characterized in that: it has uniform short-chain branch structure, melting index MI
21.6Be 1～3g/10min, average particle size distribution is 200 μ m～300 μ m, and tap density is 0.35～0.40g/cm
3, density is 0.947g/cm
3-0.950g/cm
3
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102424479A CN102093498B (en) | 2009-12-11 | 2009-12-11 | Material special for polyethylene and preparation method thereof |
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|---|---|---|---|
| CN2009102424479A CN102093498B (en) | 2009-12-11 | 2009-12-11 | Material special for polyethylene and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102093498A CN102093498A (en) | 2011-06-15 |
| CN102093498B true CN102093498B (en) | 2012-07-18 |
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| CN104045756B (en) * | 2013-03-13 | 2016-08-10 | 中国石油天然气股份有限公司 | A kind of high-density polyethylene alkene copolymer and preparation thereof and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001016191A1 (en) * | 1999-08-31 | 2001-03-08 | Eastman Chemical Company | Process for producing polyolefins |
| CN1869079A (en) * | 2005-05-27 | 2006-11-29 | 中国石油天然气股份有限公司 | Preparation method of linea low density polyethylene |
| CN1939937A (en) * | 2005-09-28 | 2007-04-04 | 北京金鼎科化工科技有限公司 | Catalyst active component, its preparation and catalyst containing it |
| CN101096390A (en) * | 2007-06-22 | 2008-01-02 | 中国石油化工股份有限公司 | Catalyzer for polyethylene with high stacking density and preparation method thereof |
| CN101550210A (en) * | 2009-03-10 | 2009-10-07 | 中国石化扬子石油化工有限公司 | High-density polyethylene resin and preparation method thereof |
-
2009
- 2009-12-11 CN CN2009102424479A patent/CN102093498B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001016191A1 (en) * | 1999-08-31 | 2001-03-08 | Eastman Chemical Company | Process for producing polyolefins |
| CN1869079A (en) * | 2005-05-27 | 2006-11-29 | 中国石油天然气股份有限公司 | Preparation method of linea low density polyethylene |
| CN1939937A (en) * | 2005-09-28 | 2007-04-04 | 北京金鼎科化工科技有限公司 | Catalyst active component, its preparation and catalyst containing it |
| CN101096390A (en) * | 2007-06-22 | 2008-01-02 | 中国石油化工股份有限公司 | Catalyzer for polyethylene with high stacking density and preparation method thereof |
| CN101550210A (en) * | 2009-03-10 | 2009-10-07 | 中国石化扬子石油化工有限公司 | High-density polyethylene resin and preparation method thereof |
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| CN102093498A (en) | 2011-06-15 |
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