CN106317555B - A kind of high-density polyethylene resin and preparation method thereof, application - Google Patents
A kind of high-density polyethylene resin and preparation method thereof, application Download PDFInfo
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Abstract
The present invention provides a kind of high-density polyethylene resins and preparation method thereof, application, are related to technical field of polymer materials.High-density polyethylene resin is mainly prepared from the following raw materials, percentage, fire retardant 6~28%, inorganic filler 10~15%, other auxiliary agents 1~2% and high density polyethylene (HDPE) surplus, inorganic filler is spherical inorganic filler, the partial size of inorganic filler is at 50 μm hereinafter, high density polyethylene (HDPE) is selected from one of the high density polyethylene (HDPE) that melt mass flow rate is 0.1~1g/10min, high density polyethylene (HDPE) that melt mass flow rate is 15~25g/10min or a variety of.The toughness and good fluidity of high-density polyethylene resin provided by the invention, weather-resistance flame-retardant might as well.
Description
Technical field
The present invention relates to technical field of polymer materials, in particular to a kind of high-density polyethylene resin and its system
Preparation Method, application.
Background technique
High density polyethylene (HDPE) is that a kind of crystallinity is high, nonpolar thermoplasticity general engineering plastic, it has heat resistance, resistance to
The advantages that cold good, chemical stability is good, high mechanical strength, dielectric properties and good environmental stress crack resistance.But high density is poly-
The loss of properties on aging of ethylene, especially thermal oxidation can make its degradation, and shrinking percentage is larger, and anti-flammability is also poor, no
It can be directly used as the fire-retardant material of lower shrinkage, high durable, also therefore and product application field is greatly limited outdoors.
And currently, there is outdoor electric system aspects great market therefore to develop the high-density polyethylene resin of a weather-resistance flame-retardant
The demand in terms of electric system is adapted to, there is good development prospect.
In the prior art, the high density polyethylene (HDPE) for preparing weather-resistance flame-retardant is mainly started with from many aspects.It is main at fire-retardant aspect
It is also exactly to use if being modified using halogen-free flame retardants, magnesium hydroxide, aluminium hydroxide, red phosphorus etc. to high density polyethylene (HDPE)
Decabrominated dipheny ethylene, antimony oxide are composite modified to be made；In terms of reducing shrinking percentage, mainly by filling talcum powder to height
Density polyethylene is modified；At weather-proof aspect, mainly it is modified by addition antioxidant and uvioresistant photo etching.Final
To the fire retardancy of high-density polyethylene material of weather-resistance flame-retardant can achieve V0 rank, but the high density of these weather-resistance flame-retardants
The shortcomings that specific gravity of the product of polythene material production is larger, and generally existing toughness is insufficient, poor fluidity.To guarantee to produce
The toughness and mobility of product only use red phosphorus as fire retardant, then its fire retardant that can only be used as dark colour or black product,
Using being restricted；If using decabromodiphenylethane, antimony oxide compounding as fire retardant, the fire-retardant aspect of material obtained is again
It is also easy to produce drippage when in the presence of burning, than the problems such as great, toughness is insufficient.
Summary of the invention
The purpose of the present invention is to provide a kind of high-density polyethylene resin, the toughness and stream of this high-density polyethylene resin
Dynamic property is good, and weather-resistance flame-retardant might as well.
Another object of the present invention is to provide the preparation method of above-specified high density polyvinyl resin, this method operation letters
Single, preparation is convenient.
Another object of the present invention is to provide the applications in terms of above-specified high density polyvinyl resin outdoors electric system.
The present invention solves its technical problem and adopts the following technical solutions to realize:
A kind of high-density polyethylene resin, is mainly prepared from the following raw materials, percentage, fire retardant 6~28%,
Inorganic filler 10~15%, other auxiliary agents 1~2% and high density polyethylene (HDPE) surplus,
Inorganic filler is spherical inorganic filler, and the partial size of inorganic filler is at 50 μm hereinafter, high density polyethylene (HDPE) is selected from molten
High density polyethylene (HDPE) that weight flow rate is 0.1~1g/10min, melt mass flow rate are 15~25g/10min's
One of high density polyethylene (HDPE) is a variety of.
Preferably, in a preferred embodiment of the present invention, above-mentioned fire retardant is in decabromodiphenylethane, new flame retardant
One or more, the bromine content of decabromodiphenylethane is 81~83%, and new flame retardant is that Shenzhen combines the prosperous limited public affairs of science and technology
Take charge of the LHX-999-IV new flame retardant of production.
Preferably, in a preferred embodiment of the present invention, above-mentioned fire retardant is the mixed of decabromodiphenylethane and new flame retardant
Close object, percentage, decabromodiphenylethane 15~20%, new flame retardant 6~8%.
Preferably, in a preferred embodiment of the present invention, the whiteness of above-mentioned new flame retardant is 95% or more, new flame retardant
Partial size be 1.5~2.0 μm.
Preferably, in a preferred embodiment of the present invention, above-mentioned other auxiliary agents are selected from antioxidant, lubricant, heat stabilizer, resistance to
Wait one of agent or a variety of, the preferably mixture of antioxidant, lubricant, heat stabilizer and weather resisting agent.
In addition, the preparation method of above-specified high density polyvinyl resin, be by raw material it is mixed and modified after, be granulated.
Preferably, in a preferred embodiment of the present invention, the above-mentioned mixed time is 5~8min.
Preferably, in a preferred embodiment of the present invention, above-mentioned modification includes: to add raw materials into dual-screw pelletizer,
2~3min is handled at 175~200 DEG C.
Preferably, in a preferred embodiment of the present invention, above-mentioned granulation specifically: be granulated at 0.06~0.1Pa.
In addition, the application in terms of electric system outdoors of above-specified high density polyvinyl resin.
Compared with the existing technology, the present invention include following the utility model has the advantages that the inorganic filler in the present invention shape and partial size
Selection can guarantee that it is in microballoon state, as raw material insert resin after, in the case where being subject to external force, particle and grain
Resistance is small between son, good fluidity.By selecting melt mass flow rate for 0.1~1g/10min and/or 15~25g/
The high density polyethylene (HDPE) of 10min prepares resin to be cooperated with other raw materials such as inorganic filler jointly.In specific melt
Within the scope of mass flow rate, high density polyethylene (HDPE) and other raw materials act synergistically, and the viscosity of resin obtained is smaller, mobility
It is good, it is easy to get shape, good toughness.
High-density polyethylene resin provided by the invention can use in rugged environment condition outdoors, mobility
Good, good stability of the dimension, anti-flammability can reach the V0 rank of UL94 standard, without dripping off, light specific gravity, good toughness,
It is not limited by color, can be used for making various colors product.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to high-density polyethylene resin of the embodiment of the present invention and preparation method thereof, using being specifically described.
High-density polyethylene resin is mainly prepared from the following raw materials, percentage, fire retardant 6~28%, inorganic
Filler 10~15%, other auxiliary agents 1~2% and high density polyethylene (HDPE) surplus, wherein inorganic filler is spherical inorganic filler,
The partial size of inorganic filler is at 50 μm hereinafter, high density polyethylene (HDPE) is selected from the height that melt mass flow rate is 0.1~1g/10min
One of density polyethylene, high density polyethylene (HDPE) that melt mass flow rate is 15~25g/10min are a variety of.
Wherein, inorganic filler is selected from silica, talcum, kaolinite, wollastonite, calcium carbonate, titanium oxide, aluminium oxide, sulphur
One of sour barium is a variety of.
Fire retardant is selected from one of decabromodiphenylethane, new flame retardant or a variety of, the bromine content of decabromodiphenylethane
It is 81~83%, new flame retardant is the LHX-999-IV new flame retardant of Shenzhen Lianhexin Technology Co., Ltd.'s production.Ten
Bromine diphenylethane can choose the product of well-established business's production, and still, such selection is not intended as limiting, and contains as long as it meets bromine
Amount is 81~83%.The main component of new flame retardant is silicon, magnesium, can be with equivalent substitution antimony oxide, and is made
The product properties come are better than the performance of antimony oxide.
Fire retardant is the mixture of decabromodiphenylethane and new flame retardant, percentage, decabromodiphenylethane
15~20%, new flame retardant 6~8%.Specific preparation, conduct after mixing are carried out using decabromodiphenylethane and new flame retardant
Fire retardant, flame retardant effect is very good, and the toughness of resin obtained might as well.
For the whiteness of new flame retardant 95% or more, the partial size of new flame retardant is 1.5~2.0 μm.Whiteness and partial size
Limitation, can guarantee that new flame retardant is added in resin, and obtained high-density polyethylene resin had both had preferable anti-flammability,
It has preferable mobility again.
Other auxiliary agents are selected from one of antioxidant, lubricant, heat stabilizer, weather resisting agent or a variety of, preferably antioxidant, profit
The mixture of lubrication prescription, heat stabilizer and weather resisting agent.In the presence of antioxidant is only a small amount of in polymeric system, it can delay or inhibit
The progress of polymer oxidation process, to prevent the aging of polymer and prolong its service life, antioxidant can select antioxygen
One of agent 168, antioxidant 1010, antioxidant 1076, anti-oxidant DLTP are a variety of.Lubricant can select paraffin, tristearin
One of sour magnesium, Lubricate EBS are a variety of.Heat stabilizer can select calcium stearate, maleic anhydride, one in zinc stearate
Kind is a variety of.Weather resisting agent can select ESCALOL 567.
Because the additive amount of other auxiliary agents is few, and need to play respective action, thus above other auxiliary agents preferably into
Mouthful, select quality preferable.As irgasfos 168 and antioxidant 1010 can select vapour bar, Lubricate EBS can be selected day
This flower king's.
The present invention also provides the preparation methods of above-specified high density polyvinyl resin: raw material is weighed according to the proportion, by raw material
After mixed and modified, it is granulated.
Wherein, the mixed time is 5~8min.Mixing time enough can guarantee that raw material is uniformly mixed, and be conducive to be modified.
Hybrid manipulation can use batch mixer progress.
Mixed modification includes: to add raw materials into dual-screw pelletizer, and 2~3min is handled at 175~200 DEG C.
Dual-screw pelletizer can be used for the modification of resin, and is modified using dual-screw pelletizer, can guarantee that material is good
Dispersibility, in this way, the toughness of resin obtained can be improved.The draw ratio of dual-screw pelletizer is 37~42:1, and draw ratio is excellent
It is selected as 40:1, the type of dual-screw pelletizer can be 65#.
Modified granulation specifically: be granulated at 0.06~0.1Pa.High density polyethylene (HDPE) is polymer substance,
And some other raw materials are lower-molecular substances, after modification, are granulated under the vacuum environment of 0.06~0.1Pa, it can
The precipitation of substance is avoided, guarantees the compactness of resin obtained.
The present invention also provides the applications in terms of above-specified high density polyvinyl resin outdoors electric system.
Feature and performance of the invention are described in further detail with reference to embodiments:
Embodiment one
High-density polyethylene resin provided in this embodiment, is mainly prepared from the following raw materials, and percentage, bromine contains
Measure the decabromodiphenylethane 15% for 81%, the spherical wollastonite 10% that partial size is 30 μm, antioxidant 1076 0.5%, 2- hydroxyl
The high density polyethylene (HDPE) 74% that base -4- methoxy benzophenone 0.5% and melt mass flow rate are 0.1g/10min.
The present embodiment additionally provides the preparation method of above-specified high density polyvinyl resin, comprising the following steps: mixes raw material
5min is closed, is then added in dual-screw pelletizer, 3min is handled at 175 DEG C, then be granulated at 0.06Pa.
Embodiment two
High-density polyethylene resin provided in this embodiment, is mainly prepared from the following raw materials, and percentage is novel
Fire retardant 8%, the spherical talcum 15% that partial size is 50 μm, antioxidant 1010 0.8%, magnesium stearate 0.8%, maleic anhydride
0.4% and melt mass flow rate be 25g/10min high density polyethylene (HDPE) 75%；Wherein, new flame retardant is Shenzhen
Combine the LHX-999-IV new flame retardant of prosperous Science and Technology Ltd.'s production, whiteness 98%, partial size is 2.0 μm.
The present embodiment additionally provides the preparation method of above-specified high density polyvinyl resin, comprising the following steps: mixes raw material
8min is closed, is then added in dual-screw pelletizer, 2min is handled at 200 DEG C, then be granulated at 0.1Pa.
Embodiment three
High-density polyethylene resin provided in this embodiment, is mainly prepared from the following raw materials, percentage, ten bromines
Diphenylethane 20%, new flame retardant 7%, the spherical talcum 5% that partial size is 40 μm, antioxidant 1010 0.3%, Lubricate EBS
0.6%, calcium stearate 0.6%, ESCALOL 567 0.5% and melt mass flow rate are 0.5g/
The high density polyethylene (HDPE) 66% of 10min；Wherein, the bromine content of decabromodiphenylethane is 82%, and new flame retardant is Shenzhen's connection
The LHX-999-IV new flame retardant of He Xin Science and Technology Ltd. production, whiteness 97%, partial size are 1.8 μm, antioxidant
1010 produce for vapour bar, and Lubricate EBS is Japanese Kao production.
The present embodiment additionally provides the preparation method of above-specified high density polyvinyl resin, comprising the following steps: mixes raw material
6min is closed, is then added in dual-screw pelletizer, 3min is handled at 185 DEG C, then be granulated at 0.08Pa.
Example IV
High-density polyethylene resin provided in this embodiment, is mainly prepared from the following raw materials, percentage, ten bromines
Diphenylethane 20%, new flame retardant 7%, the spherical silicon dioxide 10% that partial size is 40 μm, irgasfos 168 0.5%, tristearin
Sour magnesium 0.4%, calcium stearate 0.5%, ESCALOL 567 0.6% and melt mass flow rate are 0.7g/
The high density polyethylene (HDPE) 61% of 10min；Wherein, the bromine content of decabromodiphenylethane is 82%, and new flame retardant is Shenzhen's connection
The LHX-999-IV new flame retardant of He Xin Science and Technology Ltd. production, whiteness 95%, partial size are 1.8 μm, irgasfos 168
For vapour bar production.
The present embodiment additionally provides the preparation method of above-specified high density polyvinyl resin, wherein operating procedure, operating condition
It is identical as in embodiment three.
Embodiment five
High-density polyethylene resin provided in this embodiment, is mainly prepared from the following raw materials, percentage, ten bromines
Diphenylethane 20%, new flame retardant 7%, the spherical talcum 10% that partial size is 45 μm, antioxidant 1010 0.5%, lubricant
EBS 0.5%, zinc stearate 0.5%, ESCALOL 567 0.5%, melt mass flow rate 0.4g/
The high density polyethylene (HDPE) 30% and melt mass flow rate of 10min is the high density polyethylene (HDPE) 31% of 18g/10min；Wherein,
The bromine content of decabromodiphenylethane is 81%, and new flame retardant is the LHX-999- of Shenzhen Lianhexin Technology Co., Ltd.'s production
IV new flame retardant, whiteness 96%, partial size are 1.8 μm, and antioxidant 1010 is vapour bar production, and Lubricate EBS is Japan's flower
King's production.
The present embodiment additionally provides the preparation method of above-specified high density polyvinyl resin, wherein operating procedure, operating condition
It is identical as in embodiment three.
Embodiment six
High-density polyethylene resin provided in this embodiment, is mainly prepared from the following raw materials, percentage, ten bromines
Diphenylethane 20%, new flame retardant 7%, the spherical calcium carbonate 10% that partial size is 30 μm, irgasfos 168 0.4%, paraffin
0.5%, calcium stearate 0.4%, ESCALOL 567 0.7%, melt mass flow rate 0.6g/10min
High density polyethylene (HDPE) 40% and melt mass flow rate be 15g/10min high density polyethylene (HDPE) 21%；Wherein, ten bromine two
The bromine content of vinylbenzene is 83%, and new flame retardant is that the LHX-999-IV of Shenzhen Lianhexin Technology Co., Ltd.'s production is novel
Fire retardant, whiteness 98%, partial size are 1.6 μm, and irgasfos 168 is vapour bar production.
The present embodiment additionally provides the preparation method of above-specified high density polyvinyl resin, wherein operating procedure, operating condition
It is identical as in embodiment three.
High-density polyethylene resin made from three~embodiment of embodiment six is tested for the property: taking 1~2kg and is made
High-density polyethylene resin, be placed in pallet, be sent into baking oven, 2.5h is toasted at 90 DEG C, then using injection molding machine be molded
Molding, obtains test bars, then be tested for the property.
Test result is referring to table 1:
Table 1
| Test item | Embodiment three | Example IV | Embodiment five | Embodiment six |
| Tensile strength | 20.2 | 26.5 | 23.4 | 24.1 |
| Izod notch shock | 14.1 | 12.5 | 10.2 | 11.5 |
| MFR | 1.2 | 1.0 | 5.4 | 5.2 |
| Fire-retardant 3.2mm | V0 | V0 | V0 | V0 |
| Fire-retardant 1.6mm | V0 | V0 | V0 | V0 |
| Density | 1.18 | 1.21 | 1.19 | 1.2 |
As seen from the above table, high-density polyethylene resin provided by the invention has good anti-flammability, and 1.6mm can reach
The V0 rank of UL94 standard, without dripping off, dimension stability is good, toughness is good.
In addition, the high-density polyethylene resin of other embodiments provided is used to be tested for the property, the result of acquisition
It is consistent with the above results.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of high-density polyethylene resin, which is characterized in that be mainly prepared from the following raw materials, percentage is fire-retardant
Agent 6~28%, inorganic filler 10~15%, other auxiliary agents 1~2% and high density polyethylene (HDPE) surplus；
The inorganic filler is spherical inorganic filler, and the partial size of the inorganic filler is at 50 μm hereinafter, the high-density polyethylene
Alkene is selected from the high density polyethylene (HDPE) that melt mass flow rate is 0.1~1g/10min, blend melt mass flow rate is 15
One of the high density polyethylene (HDPE) of~25g/10min and 0.1~1g/10min；
The fire retardant is the mixture of decabromodiphenylethane and new flame retardant, percentage, the decabrominated dipheny
Ethane 15~20%, the new flame retardant 6~8%, the new flame retardant are raw for Shenzhen Lianhexin Technology Co., Ltd.
The LHX-999-IV new flame retardant of production.
2. high-density polyethylene resin according to claim 1, which is characterized in that the bromine content of the decabromodiphenylethane
It is 81~83%.
3. high-density polyethylene resin according to claim 1, which is characterized in that the whiteness of the new flame retardant exists
95% or more, the partial size of the new flame retardant is 1.5~2.0 μm.
4. high-density polyethylene resin according to claim 1, which is characterized in that other auxiliary agents be selected from antioxidant,
One of lubricant, heat stabilizer, weather resisting agent are a variety of.
5. high-density polyethylene resin according to claim 4, which is characterized in that other auxiliary agents be selected from antioxidant,
The mixture of lubricant, heat stabilizer and weather resisting agent.
6. a kind of preparation method of the described in any item high-density polyethylene resins of Claims 1 to 5, which is characterized in that by institute
State raw material it is mixed and modified after, be granulated.
7. the preparation method of high-density polyethylene resin according to claim 6, which is characterized in that the mixed time
For 5~8min.
8. the preparation method of high-density polyethylene resin according to claim 6, which is characterized in that the modification includes:
The raw material is added in dual-screw pelletizer, 2~3min is handled at 175~200 DEG C.
9. the preparation method of high-density polyethylene resin according to claim 6, which is characterized in that described to be granulated specifically
Are as follows: it is granulated at 0.06~0.1Pa.
10. the application in terms of electric system outdoors of the described in any item high-density polyethylene resins of Claims 1 to 5.
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| CN107266764A (en) * | 2017-06-07 | 2017-10-20 | 常州市绿意管道有限公司 | A kind of fire-retardant polyethylene material and preparation method thereof |
| CN109929169B (en) * | 2017-12-15 | 2022-03-29 | 中蓝晨光化工研究设计院有限公司 | Modified polyethylene material for electric power insulator and preparation method thereof |
| CN109929168B (en) * | 2017-12-15 | 2022-04-01 | 中蓝晨光化工研究设计院有限公司 | Modified polyethylene material suitable for electric power insulator and preparation method thereof |
| CN110591201B (en) * | 2019-09-23 | 2022-04-12 | 安徽滁州德威新材料有限公司 | Heat-resistant 150 ℃ irradiation crosslinked polyolefin material for automobile wire and preparation method thereof |
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| JP2012036345A (en) * | 2010-08-11 | 2012-02-23 | Prime Polymer Co Ltd | Polypropylene resin composition and airbag cover comprising the same |
| CN102690457A (en) * | 2011-03-25 | 2012-09-26 | 陈姜志 | Flame-retardant environment-friendly material and manufacturing process thereof |
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