CN103319639B - A kind of manufacture method of injection grade high density polyethylene (HDPE) - Google Patents
A kind of manufacture method of injection grade high density polyethylene (HDPE) Download PDFInfo
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Abstract
The invention discloses the manufacture method of a kind of injection grade high density polyethylene (HDPE), belong to the manufacture method of high density polyethylene (HDPE) PP Pipe Compound.On Mitsui Chemicals high density polyethylene (HDPE) process unit, use titanous chloride. and aluminum alkyl catalyst, ethylene is raw material, propylene is comonomer, and hexane is diluent, when operating temperature 78～86 DEG C, pressure 0.20～0.80MPa, ethylene flow is 2～5t/h, hydrogen/mole percent ethylene is 1.0～3.0, and propylene flow is 20～120kg/h, reacts in polymeric kettle is polymerized.Melt flow rate (MFR) of the present invention is high a lot, it is easy to machine-shaping, and injection pressure is little, and injection molding is abundant, and Knit-lines intensity is high, and percent defective is low, good rigidly, and product surface glossiness is high, is unlikely to deform, and oxidation induction period is long.
Description
Technical field:
The present invention relates to the manufacture method of a kind of high density polyethylene (HDPE) PP Pipe Compound, particularly relate to the manufacture method of a kind of high flow injection moulding level high-density polyethylene PP Pipe Compound.
Background technology:
Injection moulded products, in all molded plastic article, is that shape is the most complicated, the one of most species.Large injecting products has Turnover Box, plastic pallet, industry bucket, refuse bin, toy etc., generally requires that resin has good mobility, good environmental stress crack resistance and resistance to low temperature.HDPE injection-molded item market comsupton is powerful, but competition is also fierce, low cost is the target that producer is pursued forever, and proportion that plastic raw materials cost generally accounts for goods cost is bigger, account for 50～80%, thin-walled helps this proportion of reduction, therefore the designing requirement of the former parts of plastics develops to thin-walled injection moulding day by day, the mobility of resin is required more and more higher, injection molding material requires have good processability and mouldability, such as higher mobility, injection molding is abundant, Knit-lines intensity is high, product surface is smooth, glossiness, yield rate is high, at injection temperature, when pressure is constant, consume raw material to reduce as far as possible.Although HDPE injection-molded item has competition at Turnover Box and hopper, Storage container and thin-walled food containers field with polypropylene, it is contemplated that will develop by the average growth rate per annum of more than 3% in a few years from now on.
The producer of current domestic production injection grade high density polyethylene (HDPE) PP Pipe Compound is more, but melt flow rate (MFR) is mostly at below 10g/10min, as raised the HDPE5306J of son, the HDPE2100J of the Yanshan Mountain and grand celebration, three well process units once produced HDPE1300J, its melt flow rate (MFR) only has 14g/10min, and the said goods is held concurrently because material melt flow rate is on the low side, it is impossible to meet the long runner of large-scale injection molding and the injection flow requirement of thin-walled injection moulding part thin-walled.The melt flow rate (MFR) high flow injection moulding level high-density polyethylene PP Pipe Compound between 18～22g/10min is in the majority with import material, such as Malaysia great Teng company 1100J, India 5018, Saudi Arabia sabicM200056 and U.S. Phillips9018, domestic at present also develop high flow injection moulding level HDPE PP Pipe Compound, its melt flow rate (MFR) is 18～20g/10min, production for large-scale injection molding and thin-walled injection moulding part, this product is Development and Production on DuPont solwution method PE device, different from equipment therefor of the present invention, Technology and method are also just different.
In order to shorten and the external major company gap at PP Pipe Compound Technical Development Area, inventor utilizes three well technique high density polyethylene device of existing introduction, develop high flow injection moulding level HDPE PP Pipe Compound, fill up the domestic blank developing high flow injection moulding level high-density polyethylene PP Pipe Compound manufacturing process in three well technique high density polyethylene device.
Summary of the invention
The technical problem to be solved is: provide a kind of on three well devices, the manufacture method of high flow injection moulding level high-density polyethylene, it can improve material melt flow rate, meets the long runner of large-scale injection molding and the injection flow requirement of thin-walled injection moulding part thin-walled.
The technical solution used in the present invention is:
A kind of manufacture method of injection grade high density polyethylene (HDPE), on Mitsui Chemicals high density polyethylene (HDPE) process unit, using titanous chloride. and aluminum alkyl catalyst, ethylene is raw material, and propylene is comonomer, hexane is diluent, when operating temperature 78～86 DEG C, pressure 0.20～0.80MPa, ethylene flow is 2～5t/h, and hydrogen/mole percent ethylene is 1.0～3.0, propylene flow is 20～120kg/h, reacts in polymeric kettle is polymerized.First, second serosity still is respectively enterd after reacting 2～4 hours, then flash tank is respectively enterd, flash distillation enters whizzer after terminating, and is eventually adding high flow injection moulding level high-density polyethylene PP Pipe Compound special assistant formula and carries out pelletize, prepares high flow injection moulding level high-density polyethylene PP Pipe Compound.
The polyethylene slurry of polymerization output separated dry, add auxiliary agent after pelletize and be packaged to be polyethylene finished product.Regulate the hydrogen amount added, control the molecular weight of product, regulate the comonomer propylene added, control the density of product, thus obtaining the product of the various different trade mark.
Described employing polymeric kettle is that two polymeric kettles are in parallel.
The process conditions such as order and flow, reaction temperature and the reaction pressure that the responded component of the first polymeric kettle, each component add are identical with the second polymeric kettle, each reaction component under certain temperature, pressure so that certain flow addition reactor to react.Regulate the addition of hydrogen, make the molecular weight of the polymer of two polymeric kettle reaction generations, make the melt flow rate (MFR) of end product regulate in higher set point.Regulating the addition of comonomer propylene, the density making the polymer of two polymeric kettles generations is higher, makes the Auto-regulating System of Density of Heavy Medium of end product in higher set point.The separated dried pelletize of polyethylene slurry of polymerization output.In order to obtain high flow injection moulding level high-density polyethylene PP Pipe Compound, polyethylene powders after the drying is usually added into high flow injection moulding level high-density polyethylene PP Pipe Compound special assistant formula and carries out pelletize.The present invention adopts double; two stills parallel operation flow process of Mitsui Chemicals high density polyethylene (HDPE) technique, the performance making the polymer of two polymeric kettle reaction generations is completely the same, by regulating the addition of hydrogen, make the molecular weight of the polymer of two polymeric kettle reaction generations, make the melt flow rate (MFR) of end product regulate in higher set point.Regulate the addition of comonomer propylene, the density making the polymer of two polymeric kettles generations is higher, make the Auto-regulating System of Density of Heavy Medium of end product in higher set point, it is achieved the purpose of polymer high rigidity and high fluidity of molten, obtained product has good processability and processing characteristics.
Hydrogen/mole percent ethylene is 1.5～2.5, and propylene flow is 40～60kg/h.
Exceed the ethylene flow that the present invention limits, device will be exceeded and produce load；Less than the ethylene flow that the present invention limits, will be lower than device load, cause production efficiency low, so generally setting full production, namely ethylene is set as fully loaded addition.Exceed i.e. ethylene constant, raise higher by the addition of hydrogen, the product of higher melt flow rate (MFR) can be obtained in theory, but the problems such as postorder pelletizing can be brought simultaneously.Less than hydrogen/ethylene ratio, reduce by the addition of hydrogen, then the solution flow rate of product is just low, it is impossible to meet the solution flow rate index request of target product.Above or below propylene flow, namely propylene addition improves or reduces, then the density of product is just low or high, it is impossible to meet the density index requirement of target product.Solution flow rate and density, be product most basic be also topmost performance, which determine other performance indications a lot of of product.
Regulating the hydrogen/ethylene ratio of the first reactor and the second reactor, i.e. the molecular weight of the polymer that two polymeric kettle reactions of scalable produce, hydrogen/ethylene ratio is big, and polymer molecular weight is then low, otherwise, hydrogen/ethylene ratio is little, and polymer molecular weight is then high.The present invention strengthens the hydrogen/ethylene ratio of the first reactor and the second reactor, make the molecular weight control of polymer in two polymeric kettles in less state, its melt flow rate (MFR) is made to regulate in higher scope, it is achieved the purpose of polymer high fluidity and easy-formation.Under normal circumstances, the hydrogen/ethylene ratio (mol%) of first, second reactor is controlled in 1.0～3.0 scopes by the present invention.Hydrogen/the ethylene ratio (mol%) of the one the second reactors preferably range from 1.5～2.5.
According to the present invention program, first, second reactor adds comonomer propylene, control the addition of comonomer propylene, regulate the density of the polymer that two polymeric kettle reactions produce, make the Auto-regulating System of Density of Heavy Medium of polymer in two polymeric kettles in specific scope, it is achieved the purpose of polymer high rigidity.For preparing high flow injection moulding level high-density polyethylene PP Pipe Compound, the present invention is on the device of 2～5t/h at first, second reactor ethylene flow, and the propylene flow of addition is 20～120kg/h, and it preferably ranges from 40～60kg/h.
It is known that, Mitsui Chemicals high density polyethylene (HDPE) technique, it is with high-purity ethylene (99.9%, volume fraction) it is comonomer for primary raw material, propylene or butene-1, hexane is diluent, use effective catalyst Ziegler Natta catalyst (titanous chloride. and alkyl aluminum), when operating temperature 78～86 DEG C, pressure 0.20～0.80MPa, carry out double; two still low-pressure polymerization, about 2～4 hours General reactions time.The polyethylene slurry of polymerization output separated dry, add auxiliary agent after pelletize and be packaged to be polyethylene finished product.Adopt the arrangement mode of polymeric kettle serial or parallel connection, or regulate polymerization technique parameter, HDPE and the MDPE product of width or Narrow Molecular Weight Distribution can be produced.
On Mitsui Chemicals high density polyethylene (HDPE) process unit, use efficient Ziegler Natta catalyst, in operation temperature 78～86 DEG C, when pressure 0.20～0.80MPa, adopt double, two slurry polymerization still parallel connection B polyreaction flow process, with certain flow by catalyst, ethylene, propylene, hydrogen and diluent hexane etc. join and react in reactor, concrete technology operating parameter is in Table 1, the polyethylene slurry of polymerization output is separated after drying, add required auxiliary formula and carry out pelletize, obtain the middle flow injection moulding level HDPE that melt flow rate (MFR) is about 5.6g/10min.
Flow injection moulding level HDPE processing parameter in table 1
From table 1 in terms of hydrogen/ethylene ratio data, when hydrogen/ethylene ratio is 1.0mol%, melt flow rate (MFR) can be made to reach 14～18g/10min, when propylene addition is 130kg/h, density can be made to reach 0.951～0.954g/cm3。
The manufacture method of injection grade high density polyethylene (HDPE) PP Pipe Compound involved in the present invention, on existing Mitsui Chemicals high density polyethylene (HDPE) process unit, adopt double; two slurry polymerization still parallel connection A reaction process, each reaction component to add in reactor with specific flow under certain temperature, pressure to react.The separated dried addition of the polyethylene slurry high flow injection moulding level high-density polyethylene PP Pipe Compound special assistant of polymerization output carries out pelletize.This manufacturing process achieves the purpose of polymer high rigidity and high fluidity of molten, makes product have good processability and processing characteristics.
Beneficial effect:
The performance of product height flow injection moulding level high-density polyethylene PP Pipe Compound of the present invention Yu the injection grade high density polyethylene (HDPE) PP Pipe Compound of general mobile performance is tested, is listed in table 2.
The measured performance of the high flow injection moulding level high-density polyethylene PP Pipe Compound of table 2
Find out from table 2 data, the melt flow rate (MFR) of high flow injection moulding level high-density polyethylene PP Pipe Compound is 18g/10min, higher much than the melt flow rate (MFR) of the injection grade high density polyethylene (HDPE) PP Pipe Compound of general mobile performance, illustrate that its mobile performance is fine, it is easy to machine-shaping, particularly when processing large-scale injection molding and thin-walled injection moulding part, injection pressure is little, injection molding is abundant, and Knit-lines intensity is high, and percent defective is low.Density is 0.960g/cm3, bending modulus is 1167MPa, also high than the density of the injection grade high density polyethylene (HDPE) PP Pipe Compound of general mobile performance and bending modulus, illustrates that its rigidity is fine, and product surface glossiness is high, is unlikely to deform.Oxidation induction period is long, illustrates that its antioxygen property is excellent.Due to its mobility excellent characteristics, high flow injection moulding level high-density polyethylene PP Pipe Compound is also used for the production of blending and modifying material, it is therefore an objective to improve the mobile performance of blending and modifying material.
Figure of description
The typical process flow figure of Fig. 1 present invention
Detailed description of the invention
Describe the present invention below in conjunction with detailed description of the invention.The scope of the present invention is not limited with detailed description of the invention, but is limited by scope of the claims.
Embodiment 1
According to high flow injection moulding level high-density polyethylene PP Pipe Compound involved in the present invention and manufacture method thereof, on Mitsui Chemicals high density polyethylene (HDPE) process unit, adopt double; two slurry polymerization still parallel connection A polyreaction flow process, use efficient Ziegler Natta catalyst (titanous chloride. and alkyl aluminum), when operating temperature 78～86 DEG C, pressure 0.20～0.80MPa, it is simultaneously introduced ethylene, hydrogen, propylene and solvent hexane at first, second reactor and carries out copolyreaction, reacting 4 hours, the polymer of generation is high density low molecular weight polyethylene copolymer.The polyethylene slurry of polymerization output is separated after drying, adds high flow injection moulding level high-density polyethylene PP Pipe Compound special assistant formula and carries out pelletize.The concrete controlling of production process parameter of two reactors is in Table 3.
The processing parameter of table 3 embodiment one
The high density polyethylene (HDPE) produced under above-mentioned controlling of production process parameter, separated dried addition high flow injection moulding level high-density polyethylene PP Pipe Compound special assistant formula extruding pelletization, can be prepared by high flow injection moulding level high-density polyethylene PP Pipe Compound.The measured value of specific product (experiment lot number: 090702BC) performance is in Table 4.
The measured performance of the high flow injection moulding level high-density polyethylene PP Pipe Compound of table 4
Embodiment 2
According to the present invention, the addition of ethylene, hydrogen amount and propylene is specifically designed, to reach the performance needed for product.Control the hydrogen amount added well, make the molecular weight of the polymer that the reaction of two polymeric kettles produces, make in the melt flow rate (MFR) of the end product scope needed for higher, it is provided that the good machine-shaping property of polymer.Controlling the addition of comonomer propylene well, the density making the polymer that two polymeric kettles produce is higher, makes in the density of the end product scope needed for higher, it is achieved the purpose of polymer high rigidity.
In embodiment two, by changing the process control parameter in embodiment one, in particular improve hydrogen/ethylene ratio (mol%), it is possible to obtain the high density polyethylene (HDPE) PP Pipe Compound of higher melt flow speed.The concrete controlling of production process parameter of two reactors is in Table 5.
The processing parameter of table 5 embodiment two
The obtained high density polyethylene (HDPE) of the present embodiment is compared with embodiment one, due in the control of hydrogen/ethylene ratio (mol%), embodiment two improves the hydrogen/ethylene ratio (mol%) of two stills, it is 3.0, and the hydrogen/ethylene ratio (mol%) of two stills is 1.0 in embodiment one, therefore the melt flow rate (MFR) of the present embodiment products obtained therefrom is higher, and the melt flow rate (MFR) of embodiment one products obtained therefrom is relatively low.
Embodiment 3
According to the present invention, the addition of ethylene, hydrogen amount and propylene is specifically designed, to reach the performance needed for product.Control the hydrogen amount added well, make the molecular weight of the polymer that the reaction of two polymeric kettles produces, make in the melt flow rate (MFR) of the end product scope needed for higher, it is provided that the good machine-shaping property of polymer.Controlling the addition of comonomer propylene well, the density making the polymer that two polymeric kettles produce is higher, makes in the density of the end product scope needed for higher, it is achieved the purpose of polymer high rigidity.
In embodiment three, by changing the process control parameter in embodiment one, particularly decrease the addition of propylene, it is possible to obtain the polyethylene special-purpose material of higher density.The concrete controlling of production process parameter of two reactors is in Table 6.
The processing parameter of table 6 embodiment three
The obtained high density polyethylene (HDPE) of the present embodiment is compared with embodiment one, due in the control of propylene addition, embodiment three decreases the propylene addition of two stills, for 20kg/h, and the propylene addition of two stills is 120kg/h in embodiment one, therefore the density of the present embodiment products obtained therefrom is higher, and the density of embodiment one products obtained therefrom is relatively low.
Embodiment 4
According to the present invention, the addition of ethylene, hydrogen amount and propylene is specifically designed, to reach the performance needed for product.Control the hydrogen amount added well, make the molecular weight of the polymer that the reaction of two polymeric kettles produces, make in the melt flow rate (MFR) of the end product scope needed for higher, it is provided that the good machine-shaping property of polymer.Controlling the addition of comonomer propylene well, the density making the polymer that two polymeric kettles produce is higher, makes in the density of the end product scope needed for higher, it is achieved the purpose of polymer high rigidity.
In embodiment four, by changing the process control parameter in embodiment one, decrease again the addition of propylene while in particular improving hydrogen/ethylene ratio (mol%), it is possible to obtain significantly high melt flow rate (MFR) and obtain very highdensity polyethylene special-purpose material simultaneously.The concrete controlling of production process parameter of two reactors is in Table 7.
The processing parameter of table 7 embodiment four
The obtained polyethylene of the present embodiment is compared with embodiment one, due in the control of hydrogen/ethylene ratio (mol%) and propylene addition, hydrogen/the ethylene ratio (mol%) that improve two stills in embodiment four is 3.0, and in embodiment one, the hydrogen/ethylene ratio (mol%) of two stills is 1.0.Decreasing the propylene addition of two stills in embodiment four, for 20kg/h, and in embodiment one, the propylene addition of two stills is 120kg/h, and the while that therefore the melt flow rate (MFR) of the present embodiment products obtained therefrom being significantly high, density is also significantly high simultaneously.
Embodiment 5
According to the present invention, the addition of ethylene, hydrogen amount and propylene is specifically designed, to reach the performance needed for product.Control the hydrogen amount added well, make the molecular weight of the polymer that the reaction of two polymeric kettles produces, make in the melt flow rate (MFR) of the end product scope needed for higher, it is provided that the good machine-shaping property of polymer.Controlling the addition of comonomer propylene well, the density making the polymer that two polymeric kettles produce is higher, makes in the density of the end product scope needed for higher, it is achieved the purpose of polymer high rigidity.
In embodiment five, by changing the process control parameter in embodiment one, in particular improve hydrogen/ethylene ratio (mol%) to decreasing again the addition of propylene while preferred value to preferred value, it is possible to while obtaining significantly high melt flow rate (MFR), obtain the polyethylene special-purpose material of higher density.The concrete controlling of production process parameter of two reactors is in Table 8.
The processing parameter of table 8 embodiment five
The obtained polyethylene of the present embodiment is compared with embodiment one, due in the control of hydrogen/ethylene ratio (mol%) and propylene addition, embodiment five improves the hydrogen/ethylene ratio (mol%) of two stills to preferred value 2.5, and in embodiment one, the hydrogen/ethylene ratio (mol%) of two stills is 1.0.Embodiment five decreases the propylene addition of two stills simultaneously to preferred value 45kg/h, and the propylene addition of two stills is 120kg/h in embodiment one, therefore the while that the melt flow rate (MFR) of the present embodiment products obtained therefrom being higher, density is also higher, so higher melt flowability just meets the long runner of large-scale injection molding and the injection flow requirement of thin-walled injection moulding part thin-walled, goods have again higher rigidity simultaneously, it is unlikely to deform, ganoid characteristic.And the melt flow rate (MFR) of embodiment one products obtained therefrom is relatively low, density is relatively low.
Visible, the present invention is in application, and the adjustment of processing parameter can change the performance of product；Otherwise, adjusting process parameter can be needed according to properties of product.
Claims (3)
1. the manufacture method of an injection grade high density polyethylene (HDPE), on Mitsui Chemicals high density polyethylene (HDPE) process unit, using titanous chloride. and aluminum alkyl catalyst, ethylene is raw material, and propylene is comonomer, hexane is diluent, it is characterized in that: when operating temperature 78～86 DEG C, pressure 0.20～0.80MPa, ethylene flow is 2～5t/h, hydrogen and mole percent ethylene are 1.0～3.0, propylene flow is 20～120kg/h, reacts in polymeric kettle is polymerized.
2. the manufacture method of injection grade high density polyethylene (HDPE) according to claim 1, it is characterised in that: described polymeric kettle is that two polymeric kettles are in parallel.
3. the manufacture method of injection grade high density polyethylene (HDPE) according to claim 1 and 2, it is characterised in that: hydrogen/mole percent ethylene is 1.5～2.5, and propylene flow is 40～60kg/h.
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| CN1721451A (en) * | 2004-07-13 | 2006-01-18 | 中国石化北京燕化石油化工股份有限公司 | Process for preparing olefin copolymer with low content oligomer |
| CN1903901A (en) * | 2006-08-03 | 2007-01-31 | 扬子石油化工股份有限公司 | Preparation method of high density polyethylene communication cable insulating material |
| CN102796218A (en) * | 2012-05-09 | 2012-11-28 | 上海化工研究院 | Metallocene catalyst for producing low gel polyethylene, and preparation method and application thereof |
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| CN1721451A (en) * | 2004-07-13 | 2006-01-18 | 中国石化北京燕化石油化工股份有限公司 | Process for preparing olefin copolymer with low content oligomer |
| CN1903901A (en) * | 2006-08-03 | 2007-01-31 | 扬子石油化工股份有限公司 | Preparation method of high density polyethylene communication cable insulating material |
| CN102796218A (en) * | 2012-05-09 | 2012-11-28 | 上海化工研究院 | Metallocene catalyst for producing low gel polyethylene, and preparation method and application thereof |
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