CN107629301A - A kind of low density polyethylene (LDPE) master batch of high glaze puncture-resistant - Google Patents
A kind of low density polyethylene (LDPE) master batch of high glaze puncture-resistant Download PDFInfo
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Abstract
The invention discloses a kind of low density polyethylene (LDPE) master batch with high glaze puncture-resistant, the raw material of following mass parts is mainly included：100 parts of LLDPE, 10~40 parts of low density polyethylene (LDPE), 8~46 parts of nanometer EVA compound anti-reflections agent, 0.1~0.5 part of primary antioxidant, 0.2~1.0 part of auxiliary antioxidant.The master batch has the characteristics that excellent glossiness and higher paracentesis resistance energy.
Description
Technical field
The present invention relates to belong to low-density polyethylene composition, and in particular to a kind of low-density with high glaze puncture-resistant
Polyethylene master batch.
Background technology
LLDPE (referred to as LLDPE) is nontoxic, tasteless, odorless milky white granules, density 0.918
~0.935g/cm3.Compared with LDPE, LLDPE has higher softening temperature and melting temperature, there is intensity big, good toughness, just
The advantages that property is big, heat-resisting, cold resistance is good, also with good environmental stress crack resistance, impact strength, tear-resistant intensity etc.
Performance, it is widely used in and makes agricultural film, packing film, laminated film etc..
Because LLDPE strands are based on short-chain branch structure, there is higher crystallinity, its transparency is always relatively not
It is high.During the downstream application of reality, some electronic product pad pastings, protection film for automobile, the production enterprise of metal surface protection film
Industry proposes higher and higher requirement for the transparent performance of linear polyethylene, and the thin-film material with high glaze performance can be more
It is applied in wide field.Simultaneously as the particularity of diaphragm class product, can have for the paracentesis resistance of thin-film material
Higher requirement, common linear polyethylene product are difficult to have high-luster and paracentesis resistance concurrently.And in general, pass through
Addition nucleator come improve polyethylene film glossiness and it is transparent while, the crystallinity of polyethylene film can be increased, necessarily
The paracentesis resistance of material is influenceed in degree.
The content of the invention
It is an object of the present invention to provide a kind of low density polyethylene (LDPE) master batch with high glaze puncture-resistant, the master batch has excellent
Glossiness and the features such as higher paracentesis resistance energy.
The present invention seeks to be achieved through the following technical solutions：A kind of low density polyethylene (LDPE) with high glaze puncture-resistant
Master batch, mainly include the raw material of following mass parts：
The present invention high glaze puncture-resistant low density polyethylene (LDPE) master batch described in linear low density polyethylene resin can be
All kinds linear low density polyethylene resin disclosed in prior art, melt flow rate (MFR) are 0.5~30.0g/10min,
Density is 0.916~0.930kg/m3, DNDA- that preferably China Petroleum ＆ Chemical Co., Ltd. Maoming Branch is produced
7042, melt flow rate (MFR) is 1.6~2.4g/10min, and density is 0.918~0.922kg/m3.The a small amount of high melting means of addition is low close
Degree polyvinyl resin is advantageous to improve its processing fluidity and glossiness.
The Ldpe Melt flow rate is 1.0~60.0g/10min, and density is 0.916~0.925kg/
m3, 868-000 that preferably sinopec Maoming branch company is produced, melt flow rate (MFR) is 43~57g/10min, and density is
0.919~0.922kg/m3。
Further, the nanometer EVA compound anti-reflection agent is preferably 20~46 parts, wherein containing 2~20 parts of nucleator.
EVA, odium stearate, neopelex, nucleator and hydrated magnesium silicate are included in the nanometer EVA compound anti-reflection agent
Powder, wherein, EVA ﹕ Ying resin acid Na ﹕ neopelex=90~98 ﹕ 1~5 ﹕ 1~5, Cheng He Ji ﹕ EVA ﹕ hydrated magnesium silicates
The ﹕ 3~6 of=2~20 ﹕ 2~20, above ratio are mass ratio.
Specifically, the preparation method of the nanometer EVA compound anti-reflection agent is：By the EVA breasts that VA contents are 40%~60%
Liquid 5kg is placed in container, and odium stearate, neopelex are added dropwise under agitation, wherein, EVA ﹕ Ying resin acid Na ﹕ 12
The ﹕ 1~5 of sodium alkyl benzene sulfonate=90~98 ﹕ 1~5, then emulsion and nucleator (Milliken) aqueous suspension, silicate hydrate
Magnesium powder (Allihn reaches) aqueous suspension, mixed by certain proportioning of respective dry weight, the ﹕ of Cheng He Ji ﹕ EVA ﹕ hydrated magnesium silicate=2~20
2~20 ﹕ 3~6, are stirred, are then spray-dried using spray dryer, and the inlet temperature of spray dryer is 130
~180 DEG C, outlet temperature is 40~70 DEG C, is collected in cyclone separator and obtains the ultra-fine EVA powder containing nucleator after drying
Rubber, its particle diameter are 50nm~300nm.
The EVA emulsions are preferably Beijing DongFang petroleum chemical engineering Co., Ltd. Organic Chemical Plant, the trade mark：BJ-707EVA bullets
Property precursor emulsion.
The nucleator is Milliken HPN-20E.
Primary antioxidant of the present invention is phenolic antioxidant, preferably octadecyl 3- (3,5- di-t-butyl -4- oxybenzenes
Base) propionic ester.Auxiliary antioxidant is phosphate antioxidant, preferably three (2,4- di-tert-butyl-phenyl) phosphite esters.It is described refreshing
Lubrication prescription is erucyl amide, preferably the big erucyl amide of Britain's standing grain.
Second object of the present invention is achieved through the following technical solutions：It is described above to have the low close of high glaze puncture-resistant
The preparation method of polyethylene master batch is spent, is comprised the following steps：
(1) the EVA emulsions 5kg that VA contents are 40%~60% is placed in container, odium stearate, ten is added dropwise under agitation
Dialkyl benzene sulfonic acids sodium, the EVA ﹕ Ying resin acid Na ﹕ neopelex=90~﹕ 1~5 of 98 ﹕ 1~5, then emulsion is with being nucleated
Agent aqueous suspension, silicate hydrate magnesium powder aqueous suspension, mix by certain proportioning of respective dry weight, be hydrated into core agent ﹕ EVA ﹕
The ﹕ 3~6 of magnesium silicate=2~20 ﹕ 2~20, are stirred, are then spray-dried using spray dryer, spray dryer
Inlet temperature is 130~180 DEG C, and outlet temperature is 40~70 DEG C, is collected in cyclone separator and obtains containing nucleator after drying
Ultra-fine EVA powdered rubbers, its particle diameter is 50nm~300nm；
(2) according to proportioning weigh ethylene butene linear polyethylene resin powder, the agent of nanometer EVA compound anti-reflections, primary antioxidant,
Auxiliary antioxidant, it is placed in homogenizer and is sufficiently mixed 3~6min, obtains mixture；
(3) mixture for obtaining step (2) is added in screw extruder, controls screw extruder and die head temperature to exist
175~210 DEG C, 160~280rpm of screw speed, plastifying fusion blending is carried out to mixture, extruding pelletization, it is resistance to obtain high glaze
Puncture linear polyethylene resin.
The present invention has advantages below compared with prior art：
1. by the present invention in that with nanometer powder EVA, silicate hydrate magnesium powder convergent improvement transparent agent, while adjust antioxygen
Agent, the formula of auxiliary antioxidant, develop the high glaze puncture-resistant line with excellent glossiness and higher paracentesis resistance energy
Property polyethylene film construct blow-molded.The film of same transparency is obtained, material cost provided by the present invention relatively uses pure increasing
The linear polyethylene resin cost of saturating nucleator about reduces by 20%.Had concurrently simultaneously using the film of linear polyethylene material blowing
Good glossiness and Kekelé structure count, paracentesis resistance can significantly improve, and have wider application field.
2.HPN20E is a kind of crystallization rate for accelerating polyolefin, with stable with preferable contraction to PP plastics
Property, have to LLDPE material certain antireflective effect commercial applications nucleator, but the nucleator is expensive,
Reach the higher addition of obvious antireflective effect needs, bring higher cost pressure.Powder EVA be a kind of mobility compared with
Good rubber phase packing material, the material scatter is good, and transparent agent inorganic particulate is dispersed in rubber phase, and this mixture promotees
Entered the peptizaitons of transparent agent HPN20E in the plastic, add micro silicate hydrate magnesium powder inorganic particulate also promote out-phase into
Core acts on, and further increases the crystalline rate and effect of nucleator.Simultaneously as the addition of rubber phase, is effectively improved
The toughness of material, contribute to the nucleator particle of stable inorganic.Experiment shows that contrast only adds the LLDPE resins of pure transparent agent,
The draftability of LLDPE material manufactured by this method, anti-puncture performance all increase.
Embodiment
It is prepared by the agent of nanometer EVA compound anti-reflections：
Prepare nanometer EVA compound anti-reflection agent：(it is preferably Beijing Orient stone by the EVA emulsions that VA contents are 40%~60%
The trade mark of oily Organic Chemical Plant of Chemical Co., Ltd. production is BJ-707EVA elastomer emulsions) 5kg is placed in container, stirring
Lower dropwise addition odium stearate, neopelex (respective proportioning is shown in Table 1), it is outstanding with HPN-20E nucleators (Milliken)
Swim solution, silicate hydrate magnesium powder (Allihn reaches) aqueous suspension, mix (being shown in Table 1) by certain proportioning of respective dry weight, stirring 2
Individual hour, the inlet temperature that spray dryer carries out Spray Drying Spray drier is then used to export temperature for 170~180 DEG C
Spend for 60~70 DEG C, collected in cyclone separator and obtain the ultra-fine EVA powdered rubbers containing nucleator after drying, its particle diameter is
50nm~300nm.
It is prepared by high glaze puncture-resistant master batch：
(1) linear polyethylene resin, ldpe resin, nanometer powder EVA compound anti-reflections are weighed according to the proportioning of table 1
Agent, primary antioxidant and auxiliary antioxidant, are placed in homogenizer and are sufficiently mixed 3~6min, obtain mixture.
Wherein linear polyethylene resin be preferably sinopec Maoming branch company production DNDA-7042, melt flow rate (MFR)
For 1.6~2.4g/10min, density is 0.918~0.922kg/m3, ldpe resin is preferably sinopec Maoming point
The 868-000 of company's production, melt flow rate (MFR) is 43~57g/10min, and density is 0.919~0.922kg/m3。
Primary antioxidant is octadecyl 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic ester, and auxiliary antioxidant is three (2,4-
Di-tert-butyl-phenyl) phosphite ester.
(2) mixture for obtaining step (1) is added in screw extruder, controls screw extruder and die head temperature to exist
175~210 DEG C, 160~280rpm of screw speed, plastifying fusion blending is carried out to mixture, extruding pelletization, it is resistance to obtain high glaze
Puncture polyethylene master batch A~F..Its specific formula is shown in Table 1, and wherein each component content is in terms of parts by weight.
It is prepared by high glaze puncture-resistant linear polyethylene composition：
1~embodiment of embodiment 10：
By linear polyethylene resin (MLPE-1810, sinopec Maoming branch company, melt flow rate (MFR) 0.8-1.2g/
10min, density are 0.916~0.920kg/m3), above high glaze puncture-resistant polyethylene master batch and antioxidant add mixed at high speed
Device, 3~6min is sufficiently mixed with 300 revs/min of speed, each component is sufficiently mixed uniformly.Then said mixture is added
Enter in screw extruder, screw extruder and die head temperature are controlled at 175~210 DEG C, 160~280rpm of screw speed, to mixed
Compound carries out plastifying fusion blending, extruding pelletization, obtains high glaze puncture-resistant linear polyethylene resin.
Comparative example 1：
(1) LLDPE powder is weighed according to following proportioning (MLPE-1810, sinopec Maoming branch company, to melt
Body flow rate is 0.8-1.2g/10min, and density is 0.916~0.920kg/m3), primary antioxidant and auxiliary antioxidant, be placed in
3~6min is sufficiently mixed in homogenizer, each component is sufficiently mixed uniformly, obtains mixture.Specific formula component is shown in Table
2, wherein each component content is in terms of weight fraction.
100 parts of LLDPE
0.2 part of primary antioxidant
0.2 part of auxiliary antioxidant
Wherein linear polyethylene resin be preferably sinopec Maoming branch company production LLDPE MLPE1810, melt flows
Speed is 0.8-1.2g/10min, and density is 0.916~0.920kg/m3。
Primary antioxidant is octadecyl 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic ester, and auxiliary antioxidant is three (2,4-
Di-tert-butyl-phenyl) phosphite ester.
(2) mixture for obtaining step (1) is added in screw extruder, controls screw extruder and die head temperature to exist
175~210 DEG C, 160~280rpm of screw speed, plastifying fusion blending is carried out to mixture, extruding pelletization, obtains linear poly- second
Olefine resin.
Comparative example 2：
(1) linear polyethylene powder (MLPE-1810, sinopec Maoming branch company, melt flows are weighed according to following proportioning
Speed is 0.8-1.2g/10min, and density is 0.916~0.920kg/m3), transparent agent HPN-20E, primary antioxidant and auxiliary it is anti-
Oxygen agent, is placed in homogenizer and is sufficiently mixed 3~6min, obtains mixture.
Wherein linear polyethylene resin be preferably sinopec Maoming branch company production LLDPE DNDA-7042, melt flow
Dynamic speed is 1.6~2.4g/10min, and density is 0.918~0.922kg/m3。
Primary antioxidant is octadecyl 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic ester, and auxiliary antioxidant is three (2,4-
Di-tert-butyl-phenyl) phosphite ester.
(2) mixture for obtaining step (1) is added in screw extruder, controls screw extruder and die head temperature to exist
175~210 DEG C, 160~280rpm of screw speed, plastifying fusion blending is carried out to mixture, extruding pelletization, obtains linear poly- second
Alkene is anti-reflection master batch G.
(3) by linear polyethylene resin, (MLPE-1810, sinopec Maoming branch company, body flow rate are 0.8-1.2g/
10min, density are 0.916~0.920kg/m3), the anti-reflection master batch G of polyethylene obtained by step (2), (comparative example 2 is antioxidant
Primary antioxidant 1010 presses 1 with auxiliary antioxidant：2 proportion by weight) super mixer is put into, stirred under 300 revs/min of rotating speed
Blending 3 minutes, makes each component be sufficiently mixed uniformly.Said mixture material is then added into screw extruder, controls Screw Extrusion
Machine and temperature of getting to know carry out plastifying fusion blending at 170~210 DEG C, 160~280rpm of screw speed, to mixture, and extrusion is made
Grain, obtains linear polyethylene resin.
The component proportion of the master batch of table 1
Obtained 1~embodiment of embodiment 10 will be granulated, the linear polyethylene product particle of 1~comparative example of comparative example 2 exists
6h is dried at 60 DEG C, is blow molded at 190 DEG C 30 μm of film respectively using single screw rod inflation film manufacturing machine, carries out performance test.As a result such as
Shown in following table：
The component proportion and the performance test results of the embodiment 1~10 of table 2 and comparative example 1~2
As can be seen from the above table, the method for low density linear polyethylene addition powder EVA compound anti-reflection agent, can obviously improve
The turbidity of LLDPE films, glossiness, which are obtained for, to be obviously improved, while the anti-property exposed increases.Compared to only with the addition of increasing
Saturating agent HPN-20E LLDPE master batches, compound anti-reflection agent low density polyethylene (LDPE) master batch have higher anti-puncture, had more preferably
Combination property.
The present invention can be summarized with others without prejudice to the concrete form of the spirit or essential characteristics of the present invention, of the invention
Above-described embodiment can only all be considered the description of the invention rather than limitation, and every substantial technological according to the present invention is to the above
Any subtle modifications, equivalent variations and modifications that embodiment is made, are belonged in the range of technical solution of the present invention.
Claims (10)
1. a kind of low density polyethylene (LDPE) master batch with high glaze puncture-resistant, it is characterized in that, mainly include the originals of following mass parts
Material：
2. the low density polyethylene (LDPE) master batch according to claim 1 with high glaze puncture-resistant, it is characterized in that, described line
The melt flow rate (MFR) of property ldpe resin is 0.5~30.0g/10min, and density is 0.916~0.930kg/m3。
3. the low density polyethylene (LDPE) master batch according to claim 1 with high glaze puncture-resistant, it is characterized in that, it is described low close
Degree Melt Flow Rate of Polyethylene is 1.0~60.0g/10min, and density is 0.916~0.925kg/m3。
4. the low density polyethylene (LDPE) master batch according to claim 1 with high glaze puncture-resistant, it is characterized in that, the nanometer
The agent of EVA compound anti-reflections is 20~46 parts, wherein containing 2~20 parts of nucleator.
5. the low density polyethylene (LDPE) master batch according to claim 4 with high glaze puncture-resistant, it is characterized in that, the nanometer
EVA, odium stearate, neopelex, nucleator and silicate hydrate magnesium powder are included in EVA compound anti-reflection agent, wherein,
The ﹕ of EVA ﹕ Ying resin acid Na ﹕ neopelex=90~98 ﹕ 1~5 ﹕ 1~5, Cheng He Ji ﹕ EVA ﹕ hydrated magnesium silicate=2~20
2~20 ﹕ 3~6, above ratio are mass ratio.
6. the low density polyethylene (LDPE) master batch according to claim 1 with high glaze puncture-resistant, it is characterized in that, the nanometer
The preparation method of EVA compound anti-reflection agent is：The EVA emulsions 5kg that VA contents are 40%~60% is placed in container, under agitation
Odium stearate, neopelex is added dropwise, wherein, the ﹕ of EVA ﹕ Ying resin acid Na ﹕ neopelex=90~98 1~
5 ﹕ 1~5, then emulsion and nucleator aqueous suspension, silicate hydrate magnesium powder aqueous suspension, by certain proportioning of respective dry weight
Mixing, the Cheng He Ji ﹕ EVA ﹕ hydrated magnesium silicate=2~﹕ 3~6 of 20 ﹕ 2~20, is stirred, is then carried out using spray dryer
Spray drying, the inlet temperature of spray dryer is 130~180 DEG C, and outlet temperature is 40~70 DEG C, is received in cyclone separator
Collection obtains the ultra-fine EVA powdered rubbers containing nucleator after drying, and its particle diameter is 50nm~300nm.
7. the low density polyethylene (LDPE) master batch with high glaze puncture-resistant according to claim any one of 4-6, it is characterized in that,
The nucleator is Milliken HPN-20E.
8. the low density polyethylene (LDPE) master batch according to claim 1 with high glaze puncture-resistant, it is characterized in that, the master resists
Oxygen agent is phenolic antioxidant, and auxiliary antioxidant is phosphate antioxidant, and the slipping agent is erucyl amide.
9. the low density polyethylene (LDPE) master batch according to claim 8 with high glaze puncture-resistant, it is characterized in that, the phenols
Antioxidant is octadecyl 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic ester, and the phosphate antioxidant is three (2,4- bis- uncles
Butyl phenyl) phosphite ester.
10. the preparation method of the low density polyethylene (LDPE) master batch with high glaze puncture-resistant described in claim any one of 1-9, its
It is characterized in, comprises the following steps：
(1) the EVA emulsions 5kg that VA contents are 40%~60% is placed in container, odium stearate, dodecane is added dropwise under agitation
Base benzene sulfonic acid sodium salt, the EVA ﹕ Ying resin acid Na ﹕ neopelex=90~﹕ 1~5 of 98 ﹕ 1~5, then emulsion hanged with nucleator
Swim solution, silicate hydrate magnesium powder aqueous suspension, mixed by certain proportioning of respective dry weight, into core agent ﹕ EVA ﹕ silicate hydrates
The ﹕ 3~6 of magnesium=2~20 ﹕ 2~20, are stirred, are then spray-dried using spray dryer, the import of spray dryer
Temperature is 130~180 DEG C, and outlet temperature is 40~70 DEG C, is collected in cyclone separator and surpassing containing nucleator is obtained after drying
Thin EVA powdered rubbers, its particle diameter is 50nm~300nm；
(2) ethylene butene linear polyethylene resin powder, the agent of nanometer EVA compound anti-reflections, primary antioxidant, auxiliary are weighed according to proportioning
Antioxidant, it is placed in homogenizer and is sufficiently mixed 3~6min, obtains mixture；
(3) mixture obtained step (2) is added in screw extruder, control screw extruder and die head temperature 175~
210 DEG C, 160~280rpm of screw speed, plastifying fusion blending is carried out to mixture, extruding pelletization, obtains high glaze puncture-resistant
Linear polyethylene resin.
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| CN113896977A (en) * | 2021-10-26 | 2022-01-07 | 中国石油化工股份有限公司 | Polyethylene composition for bottle cap and preparation method thereof |
| CN114561054A (en) * | 2022-02-24 | 2022-05-31 | 金发科技股份有限公司 | Oil-resistant non-crosslinked polyethylene material and preparation and application thereof |
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| CN113896977A (en) * | 2021-10-26 | 2022-01-07 | 中国石油化工股份有限公司 | Polyethylene composition for bottle cap and preparation method thereof |
| CN113896977B (en) * | 2021-10-26 | 2023-10-20 | 中国石油化工股份有限公司 | Polyethylene composition for bottle cap and preparation method thereof |
| CN114561054A (en) * | 2022-02-24 | 2022-05-31 | 金发科技股份有限公司 | Oil-resistant non-crosslinked polyethylene material and preparation and application thereof |
| CN114561054B (en) * | 2022-02-24 | 2023-10-31 | 金发科技股份有限公司 | Oil-resistant non-crosslinked polyethylene material, and preparation and application thereof |
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