CN102146179A - Full density LLDPE/HDPE (Linear Low Density Polyethylene/High-Density Polyethylene) polyethylene premixing assistant and preparation method thereof - Google Patents
Full density LLDPE/HDPE (Linear Low Density Polyethylene/High-Density Polyethylene) polyethylene premixing assistant and preparation method thereof Download PDFInfo
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- CN102146179A CN102146179A CN 201110003951 CN201110003951A CN102146179A CN 102146179 A CN102146179 A CN 102146179A CN 201110003951 CN201110003951 CN 201110003951 CN 201110003951 A CN201110003951 A CN 201110003951A CN 102146179 A CN102146179 A CN 102146179A
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Abstract
The invention discloses a full density LLDPE/HDPE (Linear Low Density Polyethylene/High-Density Polyethylene) polyethylene premixing assistant and a preparation method thereof. The assistant comprises 10-20% of alpha crystal form nucleating agent, 6-10% of calcium stearate nucleating agent, 5-10% of full-vulcanized silicon rubber, 12-18% of antioxidant 1076, 8-13% of antioxidant 1010, 20-30% of silica gel, 5-11% of oleic acylamide, 2-5% of antistatic agent and 2-5% of o-hydroxyl benzophenone. The ingredients are orderly stirred, premixed, extensively dispersed, dispersed in a refining way, blended and extruded to form granules, and thus the granule dispersion problem of granule materials and the compatibility problem of raw materials can be solved well. Compared with a full density polyethylene material without addition of the assistant provided by the invention, in the full density polyethylene material with addition of the assistant provided by the invention, the passing rate of moisture is reduced by more than 40%, the haze is reduced by at least 40%, the degree of finish is improved by about 100%, and the tear resistance and the impact resistance are synchronously improved.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of theoretical density LLDPE/HDPE polyethylene premix auxiliary formula and preparation method thereof.
Background technology
Full density polythene is meant linear polyethylene and high density polyethylene(HDPE) (being called for short LLDPE/HDPE), wherein its density range of linear, low density PE (LLDPE) and hp-ldpe are basic identical, again because its molecular side chain is a short-chain branch, molecular structure is between the line style high-density and have between the hp-ldpe of long-chain branch, so its physical and mechanical properties is better than common new LDPE (film grade), be widely used in the outer laminated film field of the packing of food, medicine, cigarette and identity card, bank card etc.High density polyethylene(HDPE) (HDPE) claims low pressure polyethylene again, also is line style owing to molecular structure is similar to LLDPE, and its performance is better than common new LDPE (film grade), not only is widely used in special shoe film field, also is widely used in other mechanicals.
But theoretical density LLDPE/HDPE polyethylene special-purpose material remains in following defective at present: the one, and rigidity or toughness can not reach application requiring.The 2nd, the opening difficulty adhesion phenomenon appears easily, after making film; The 3rd, the transparency is not good enough, and mist degree is higher, and smooth finish is poor.
Polyethylene premix auxiliary agent commonly used if increase the polyethylene rigidity then toughness reduce, if improve then rigidity deficiency of its toughness, its thermotolerance in addition, the key technical indexes such as stretchiness are also difficult to be improved synchronously, adds a kind of premix auxiliary agent usually and is difficult to address the above problem.At present auxiliary agent often only at poly smooth, the easy opening of single classification, height is transparent and anti-oxidant, stretch-proof is antistatic, a binomial performance is carried out modification in the antiultraviolet, want many-sided auxiliary agent that poly performance just need be added several different trades mark simultaneously that changes, not only increase production cost, also reduced efficiency simultaneously.
Therefore, need the efficient premix auxiliary agent that theoretical density LLDPE/HDPE polyethylene is carried out multifunctional modification badly.
Summary of the invention
The objective of the invention is to solve the problems referred to above that existing theoretical density (LLDPE/HDPE) polyethylene premix auxiliary agent exists, a kind of theoretical density LLDPE/HDPE polyethylene premix auxiliary agent and preparation method thereof is provided.
The objective of the invention is to realize in the following manner:
A kind of theoretical density LLDPE/HDPE polyethylene premix auxiliary agent, this premix auxiliary agent comprises following each component:
Alpha-crystal form nucleator 10～20%
Calcium stearate nucleator 6～10%
Full sulphurated siliastic 5～10%
Antioxidant 1076 12～18%
Antioxidant 1010 8～13%
Silica gel 20～30%
Amine hydroxybenzene 5～11%
O-hydroxyl-diphenyl ketone 2～5%
Above-mentioned theoretical density LLDPE/HDPE polyethylene premix auxiliary agent preferably includes following each component:
Alpha-crystal form nucleator 15～20%
Calcium stearate nucleator 8～10%
Full sulphurated siliastic 8～10%
Antioxidant 1076 15～18%
Antioxidant 1010 10～13%
Silica gel 26～30%
Amine hydroxybenzene 7～9%
O-hydroxyl-diphenyl ketone 2～5%
Each constituent mass per-cent sum of above prescription is 100%.
Above-mentioned alpha-crystal form nucleator is preferably nucleator Hyperform HPN-20E, is to be produced by U.S. Milliken Co..
Above-mentioned full sulphurated siliastic is preferably methyl vinyl silicone rubber, and particle diameter is 300～500nm.Described silica gel particle diameter is the 1000-3000 order, is preferably silica gel 244.
The chemical name of above-mentioned antioxidant 1076 is β-(4-hydroxyl-3.5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid.
The chemical name of above-mentioned antioxidant 1010 is four [β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester.
Above-mentioned static inhibitor is preferably static inhibitor 1800, and its chemical name is alkyl imidazoline (in add type).
The present invention's prescription has used two class nucleators simultaneously: category-A is alpha-crystal form nucleator (particularly adopting the nucleator Hyperform HPN-20E of Milliken Co.'s exploitation), category-B is calcium stearate nucleator (nucleator BDS), this mixes after nucleator and other proportioning raw materials, gained theoretical density LLDPE/HDPE polyethylene products appearance transparence significantly increases, thereby the crystallization velocity that has also improved material is simultaneously enhanced productivity, particularly at adopting expressing technique to obtain polyethylene mechanicals such as hollow container, tubing, electric wire, physicalies such as cable improve more outstanding.We have used two kinds of oxidation inhibitor in this auxiliary agent goods: antioxidant 1076, antioxidant 1010.Being used in combination of two kinds of oxidation inhibitor makes poly performance more stable, and be more remarkable with the consistency of other raw materials.What slipping agent adopted is amine hydroxybenzene, usually in new LDPE (film grade) (LDPE) resin, add 0.05%～0.3% amine hydroxybenzene, can significantly reduce the quiet of resin, dynamic friction factor, be used for LLDPE/HDPE polyethylene products auxiliary agent hardly, but the contriver finds to add a certain amount of amine hydroxybenzene in LLDPE/HDPE polyethylene products auxiliary agent of the present invention, significantly improved consistency, frictional coefficient significantly reduces, simultaneously can also improve its dispersiveness, the printing of goods and binding property, increase the feel and the smooth finish of improving product surface of film or moulded products, therefore, the selection of slipping agent is very important, need reasonably to select kind and using dosage, just can reach ideal effect.In addition, mix a certain amount of 1000-3000 purpose silica gel in the auxiliary agent of the present invention, be used the performance that can further improve film product opening with above-mentioned amine hydroxybenzene and two kinds of nucleators, and can improve mechanical properties such as the tensile strength of polymer materials and elongation at break.
Auxiliary agent preparation method of the present invention comprises the steps:
1) each component is stirred the extensive dispersion of premix: the technological operation rotating speed is 110～130 rev/mins, and churning time is 25-35 minute;
2) each component after utilizing ball milling to extensive dispersion again refinement disperse: employed ball-milling technology control rotating speed is 60～90 rev/mins, and the time is 65～85 minutes; The ball milling temperature is 25～60 ℃, preferred 45～50 ℃.
3) blend extruding pelletization: the extruding pelletization temperature is controlled at 140～170 ℃ of scopes, per hour 0.5 ton of process flow rate output, and temperature is controlled in 20～25 ℃ of scopes during discharging.
During the discharging of blend extruding pelletization, because of the work in-process retractility is stronger, the too high and too fast meeting of flow velocity of temperature makes the pelletizing difficulty, so temperature will be controlled in 20～25 ℃ of scopes during discharging.During ball milling, the ball milling temperature is too high or mistake is low all can be dispersed with remarkable influence to refinement.In addition, because raw material and product water absorbability are stronger, starting material take out to throw in back five minutes at sealing bag and use; Finished product will keep than the exsiccant environment in the workshop directly packing after the oven dry on the production line.
Beneficial effect of the present invention compared with the prior art: the present invention is by three one-step physical dispersing technology methods, particularly use levigate dispersion of clipping the ball barreling and blend extruding and pelletizing process, plurality of raw materials is mixed, has solved the particle scattering problem of granular material and the compatibility problem of raw material well.Use premix auxiliary agent of the present invention, make that theoretical density LLDPE/HDPE polythene material intensity and toughness are improved simultaneously, and, compare with the theoretical density LLDPE/HDPE polyethylene film that does not add auxiliary agent of the present invention, the moisture percent of pass descends more than 40%, mist degree descends at least 40%, smooth finish improves more than 90%, anti tear and erosion-resisting characteristics improve more than 20% simultaneously, resin height crystallization simultaneously, reduce producing striped and inconsistent possibility, therefore, theoretical density LLDPE/HDPE polyethylene premix auxiliary agent of the present invention is the compound product of a kind of high-efficiency multi-function.
Description of drawings
Fig. 1 is the transparency contrast synoptic diagram that line style (LLDPE) polyethylene and high-density (HDPE) polyethylene add premix auxiliary agent of the present invention front and back.
Fig. 2 is the smooth finish contrast synoptic diagram that line style (LLDPE) polyethylene and high-density (HDPE) polyethylene add premix auxiliary agent of the present invention front and back.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Each embodiment according to the form below ratio is allocated:
Table 1
The preparation method of above-mentioned theoretical density LLDPE/HDPE polyethylene premix auxiliary agent:
1) each component is stirred the extensive dispersion of premix; Stirring technique operation rotating speed is 110～130 rev/mins, and churning time is 25-35 minute; Use the tapered stirrer of cantilever duplex to stir.
2) adopt horizontal ball mill to carry out ball milling, to the refinement dispersion again of the component after the extensive dispersion; Employed ball-milling technology control rotating speed is 60～90 rev/mins, and the time is 65～85 minutes; The ball milling temperature is 45～50 ℃.
3) adopting dual-screw pelletizer to carry out the blend extruding pelletization makes each component further strengthen dispersion: under 140～170 ℃, with 0.5 ton of flow velocity extruding pelletization per hour, temperature is controlled in 20～25 ℃ of scopes during discharging.
Table 2 is physical indexs of premix auxiliary agent of the present invention:
Table 2
| Project | Index |
| Outward appearance | White or canescence granular particle |
| Fugitive constituent, WT% | ≤1.0 |
| Total ash, WT% | 4.0-7.0 |
| Tap density, g/L | 480-550 |
| Benzene insoluble, WT% | ≤4.5 |
As shown in table 3, the present invention uses the twin screw granulating equipment and produces, and makes powder material through further being processed into particulate product, has reduced supplies consumption, has stablized quality product, has avoided pollution, has increased economic benefit.
Table 3
| Title | Waste |
| Powdery product | 1-2％ |
| Granular product | 0.1-0.5％ |
Product of the present invention is used for petroleum chemical enterprise LLDPE LLDPE (film-grade) is carried out modification, addition is 2.5 ‰, makes every performance index after the modification all above enterprise's top grade product standard, and table 4 is to detect data:
The contrast of table 4 performance index
The present invention is used for petroleum chemical enterprise high density polyethylene(HDPE) (HDPE) (film-grade) is carried out modification, addition is 2.5 ‰, makes every performance index after the modification all above enterprise's top grade product standard, and table 5 is to detect data:
The contrast of table 5 performance index
The film article of above-mentioned adding premix auxiliary agent of the present invention is placed the monthly phenomenons such as oily, bloom, flavescence of not finding half; The product of preserving after three months and producing seven days contrasts transparency, smooth finish and skin friction coefficient indifference.
In addition, record line style (LLDPE) polyethylene, high-density (HDPE) polyethylene transparency and smooth finish correlation data before and after the adding embodiment of the invention 2 premix auxiliary agents and see Fig. 1 and Fig. 2 respectively.
Claims (7)
1. theoretical density LLDPE/HDPE polyethylene premix auxiliary agent is characterized in that this premix auxiliary agent comprises following each component:
Alpha-crystal form nucleator 10～20%
Calcium stearate nucleator 6～10%
Full sulphurated siliastic 5～10%
Antioxidant 1076 12～18%
Antioxidant 1010 8～13%
Silica gel 20～30%
Amine hydroxybenzene 5～11%
O-hydroxyl-diphenyl ketone 2～5%
Static inhibitor 2～5%.
2. theoretical density LLDPE/HDPE polyethylene premix auxiliary agent according to claim 1 is characterized in that this premix auxiliary agent comprises following each component:
Alpha-crystal form nucleator 15～20%
Calcium stearate nucleator 8～10%
Full sulphurated siliastic 8～10%
Antioxidant 1076 15～18%
Antioxidant 1010 10～13%
Silica gel 26～30%
Amine hydroxybenzene 7～9%
O-hydroxyl-diphenyl ketone 2～5%
Static inhibitor 2～5%.
3. theoretical density LLDPE/HDPE polyethylene premix auxiliary agent according to claim 1 and 2 is characterized in that described alpha-crystal form nucleator is nucleator Hyperform HPN-20E.
4. theoretical density LLDPE/HDPE polyethylene premix auxiliary agent according to claim 1 and 2 is characterized in that described full sulphurated siliastic is a methyl vinyl silicone rubber, and particle diameter is 300～500nm.
5. theoretical density LLDPE/HDPE polyethylene premix auxiliary agent according to claim 1 and 2 is characterized in that described silica gel particle diameter is the 1000-3000 order.
6. theoretical density LLDPE/HDPE polyethylene premix auxiliary agent according to claim 1 and 2 is characterized in that described static inhibitor is a static inhibitor 1800.
7. the preparation method of claim 1 or 2 described theoretical density LLDPE/HDPE polyethylene premix auxiliary agents is characterized in that this method comprises the steps:
1) each component is stirred the extensive dispersion of premix: the stirring operation rotating speed is 110～130 rev/mins, and churning time is 25-35 minute;
2) component after utilizing ball milling to extensive dispersion again refinement disperse: the control rotational speed of ball-mill is 60～90 rev/mins, and the time is 65～85 minutes;
3) blend extruding pelletization: the extruding pelletization temperature is controlled at 140～170 ℃ of scopes, and temperature is controlled in 20～25 ℃ of scopes during discharging.
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| CN 201110003951 CN102146179B (en) | 2011-01-10 | 2011-01-10 | Full density LLDPE/HDPE (Linear Low Density Polyethylene/High-Density Polyethylene) polyethylene premixing assistant and preparation method thereof |
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| CN 201110003951 CN102146179B (en) | 2011-01-10 | 2011-01-10 | Full density LLDPE/HDPE (Linear Low Density Polyethylene/High-Density Polyethylene) polyethylene premixing assistant and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642129A (en) * | 2013-11-25 | 2014-03-19 | 常熟市蓝天新材料科技有限公司 | Preparation method of antistatic and fire-retardant polypropylene composite material |
| CN104031303A (en) * | 2014-04-02 | 2014-09-10 | 南京淳达科技发展有限公司 | Polyethylene master batch compound additive and preparation method thereof |
| CN110845780A (en) * | 2019-10-31 | 2020-02-28 | 浙江比例聚合科技股份有限公司 | PE colorful heat shrinkable film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056505A (en) * | 1990-05-14 | 1991-11-27 | 希蒙特公司 | The Nonextruded concentrates of additive, filler or pigment |
| CN101012322A (en) * | 2006-11-16 | 2007-08-08 | 扬子石油化工股份有限公司 | Antistatic adhesion-resistant slippery linear low density polyethylene composition and method of making the same |
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2011
- 2011-01-10 CN CN 201110003951 patent/CN102146179B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056505A (en) * | 1990-05-14 | 1991-11-27 | 希蒙特公司 | The Nonextruded concentrates of additive, filler or pigment |
| CN101012322A (en) * | 2006-11-16 | 2007-08-08 | 扬子石油化工股份有限公司 | Antistatic adhesion-resistant slippery linear low density polyethylene composition and method of making the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642129A (en) * | 2013-11-25 | 2014-03-19 | 常熟市蓝天新材料科技有限公司 | Preparation method of antistatic and fire-retardant polypropylene composite material |
| CN104031303A (en) * | 2014-04-02 | 2014-09-10 | 南京淳达科技发展有限公司 | Polyethylene master batch compound additive and preparation method thereof |
| CN104031303B (en) * | 2014-04-02 | 2017-01-11 | 南京淳达科技发展有限公司 | Polyethylene master batch compound additive and preparation method thereof |
| CN110845780A (en) * | 2019-10-31 | 2020-02-28 | 浙江比例聚合科技股份有限公司 | PE colorful heat shrinkable film and preparation method thereof |
| CN110845780B (en) * | 2019-10-31 | 2021-12-21 | 浙江比例聚合科技股份有限公司 | PE colorful heat shrinkable film and preparation method thereof |
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