CN107556596A - A kind of linear low density polyethylene composition of high glaze puncture-resistant and preparation method thereof - Google Patents
A kind of linear low density polyethylene composition of high glaze puncture-resistant and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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Abstract
The invention discloses a kind of linear low density polyethylene composition with high glaze puncture-resistant, the raw material of following mass percent is included：Ethylene butene linear polyethylene copolymer 99.50~99.66%, nanometer EVA composite nucleating agents 0.25~0.35%, primary antioxidant 0.03~0.05%, auxiliary antioxidant 0.06~0.10%.The invention also discloses the preparation method of said composition.Said composition has the characteristics that excellent glossiness and higher paracentesis resistance energy.
Description
Technical field
The present invention relates to belong to linear low density polyethylene composition, and in particular to a kind of high glaze puncture-resistant it is linear low
Density polyethylene compositions.Meanwhile the invention further relates to the preparation method of the linear low density polyethylene composition.
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.
The content of the invention
It is an object of the present invention to provide a kind of linear low density polyethylene composition with high glaze puncture-resistant, said composition
There is excellent glossiness and higher paracentesis resistance energy.
Second technical problem to be solved by this invention is to provide the preparation of above-mentioned linear low density polyethylene composition
Method, this method technique simple and stable, cost is low, and supplies stabilization.
First purpose of the invention is to be achieved through the following technical solutions:It is a kind of linear low with high glaze puncture-resistant
Density polyethylene compositions, include the raw material of following mass percent：
Wherein the melt flow rate (MFR) of ethylene butene linear polyethylene resin powder is 0.8~1.2g/10min, and density is
0.916~0.920kg/m3。
In the nanometer EVA composite nucleating agents comprising nanometer EVA, odium stearate, neopelex, nucleator and
Silicate hydrate magnesium powder, wherein, hard resin acid sodium ﹕ neopelex=90 of the EVA ﹕~﹕ 1~5 of 98 ﹕ 1~5, into core agent ﹕ EVA ﹕
The ﹕ 3~5 of hydrated magnesium silicate=12~15 ﹕ 10~15, above ratio are mass ratio.
Specifically, the preparation method of the nanometer EVA composite nucleating agents is:By the nanometer that VA contents are 40%~60%
EVA emulsions are placed in container, and odium stearate, neopelex, EVA are added dropwise under agitation:Odium stearate:Dodecyl
Benzene sulfonic acid sodium salt=90~98:1~5:1~5, then emulsion and nucleator aqueous suspension and silicate hydrate magnesium powder aqueous suspension
Mixing, by respective dry weight than calculating, nucleator:EVA ﹕ hydrated magnesium silicate=12~15:10~15:3~5, stir, then adopt
It is spray-dried with spray dryer, the inlet temperature of spray dryer is 130~180 DEG C, and outlet temperature is 40~70 DEG C,
Collected in cyclone separator and obtain a nanometer EVA composite nucleating agents after drying, its particle diameter is 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 HPN-20E (Milliken).
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：LLDPE combination described above
The preparation method of thing, comprises the following steps：
(1) by VA contents be 40%~60% EVA emulsions 5kg be placed in container, under agitation be added dropwise odium stearate and
Neopelex, EVA:Odium stearate:Neopelex=90~98:1~5:1~5, then emulsion with into
Core agent aqueous suspension and the mixing of silicate hydrate magnesium powder aqueous suspension, by respective dry weight than calculating, nucleator:EVA ﹕ silicate hydrates
Magnesium=12~15:10~15:3~5, stir, be then spray-dried using spray dryer, spray dryer enters
Mouth temperature is 130~180 DEG C, and outlet temperature is 40~70 DEG C, and it is compound to obtain nanometer EVA after collection is dry in cyclone separator
Nucleator, its particle diameter are 50nm~300nm；
(2) ethylene butene linear polyethylene resin powder, nanometer EVA composite nucleating agents, primary antioxidant are weighed according to proportioning
And 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
The linear polyethylene resin of puncture.
The present invention has advantages below compared with prior art：
1. by the present invention in that with nanometer EVA, silicate hydrate magnesium powder convergent improvement nucleator, while adjust antioxidant, auxiliary
The formula of aid anti-oxidants, obtain the high glaze puncture-resistant linear polyethylene with excellent glossiness and higher paracentesis resistance energy
Material.The film of same transparency is obtained, material cost provided by the present invention is gathered compared with using the linear of pure anti-reflection nucleating agent
Vinyl cost about reduces by 20%.Good glossiness is had concurrently using the film of linear polyethylene material blowing simultaneously and opened
Mouth property, paracentesis resistance can significantly improve, and have wider application field.
2.HPN-20E 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.Nanometer EVA be a kind of mobility compared with
Good rubber phase packing material, the material scatter is good, and nucleator inorganic particulate is dispersed in rubber phase, and this mixture promotees
The peptizaitons of nucleator HPN-20E are in the plastic entered, have added micro silicate hydrate magnesium powder inorganic particulate and also promote out-phase
Nucleation, further increase 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 trees of pure nucleator
Fat, the draftability of the LLDPE material manufactured by the present invention, anti-puncture performance all increase, meanwhile, can be by the addition of nucleator
Amount is down to its 60% dosage and reaches same transparent effect, is effectively saved cost.
Embodiment
Embodiment 1
(1) nanometer EVA composite nucleating agents are prepared：(it is preferably Beijing Orient by the EVA emulsions that VA contents are 40%~60%
The trade mark of Organic Chemical Plant of petrochemical industry Co., Ltd production is BJ-707EVA elastomer emulsions) 5kg is placed in container, stirring
Lower dropwise addition odium stearate and neopelex are mixed, respective dry weight proportioning is EVA:Odium stearate:Detergent alkylate sulphur
Sour sodium=98:1:1, with HPN-20E nucleators (Milliken) aqueous suspension and silicate hydrate magnesium powder (Allihn reaches) water in suspension
Solution, mixed by certain proportioning of respective dry weight, respective dry weight proportioning is HPN-20E:EVA:Hydrated magnesium silicate=12:10:
3,2 hours are stirred, then use the inlet temperature of spray dryer progress Spray Drying Spray drier as 170~180 DEG C,
Outlet temperature is 60~70 DEG C, is collected in cyclone separator and obtains a nanometer EVA composite nucleating agents after drying, its particle diameter is 50nm
~300nm.
(2) ethylene butene linear polyethylene resin powder, nanometer EVA composite nucleating agents, main anti-is weighed according to following proportioning
Oxygen agent and auxiliary antioxidant, are placed in homogenizer and are sufficiently mixed 3~6min, obtain mixture.
99.66 parts of ethylene butene linear polyethylene resin powder
(its component is that HPN-20E is 0.12 part to 0.25 part of nanometer EVA composite nucleating agents, and nanometer EVA is 0.10 part, hydration
Silicic acid magnesium powder is 0.03 part)
0.03 part of primary antioxidant
0.06 part of auxiliary antioxidant
Wherein ethylene butene linear polyethylene resin powder is preferably the LLDPE MLPE- of sinopec Maoming branch company production
1810 powders, melt flow rate (MFR) are 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.
(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
The linear polyethylene resin of puncture.
Embodiment 2
(1) nanometer EVA composite nucleating agents are prepared：(it is preferably Beijing Orient by the EVA emulsions that VA contents are 40%~60%
The trade mark of Organic Chemical Plant of petrochemical industry Co., Ltd production is BJ-707EVA elastomer emulsions) 5kg is placed in container, stirring
Lower dropwise addition odium stearate and neopelex are mixed, respective dry weight proportioning is EVA:Odium stearate:Detergent alkylate sulphur
Sour sodium=96.5:2:1.5, suspended with HPN-20E nucleators (Milliken) aqueous suspension, silicate hydrate magnesium powder (Allihn reaches)
The aqueous solution, mixed by certain proportioning of respective dry weight, respective dry weight proportioning is HPN-20E:EVA ﹕ hydrated magnesium silicate=13:
12:4,2 hours are stirred, then use spray dryer to carry out the inlet temperature of Spray Drying Spray drier as 170~180
DEG C, outlet temperature is 60~70 DEG C, is collected in cyclone separator and obtains a nanometer EVA composite nucleating agents after drying, its particle diameter is
50nm~300nm.
(2) according to it is following proportioning weigh ethylene butene linear polyethylene resin powder, nanometer powder EVA composite nucleating agents,
Primary antioxidant and auxiliary antioxidant, are placed in homogenizer and are sufficiently mixed 3~6min, obtain mixture.
99.62 parts of ethylene butene linear polyethylene resin powder
(its component is that HPN-20E is 0.13 part to 0.29 part of nanometer EVA composite nucleating agents, and nanometer EVA is 0.12 part, hydration
Silicic acid magnesium powder is 0.04 part)
0.03 part of primary antioxidant
0.06 part of auxiliary antioxidant
Wherein ethylene butene linear polyethylene resin powder is preferably the LLDPE MLPE- of sinopec Maoming branch company production
1810 powders, melt flow rate (MFR) are 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.
(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
The linear polyethylene resin of puncture.
Embodiment 3
(1) nanometer EVA composite nucleating agents are prepared：(it is preferably Beijing Orient by the EVA emulsions that VA contents are 40%~60%
The trade mark of Organic Chemical Plant of petrochemical industry Co., Ltd production is BJ-707EVA elastomer emulsions) 5kg is placed in container, stirring
Lower dropwise addition odium stearate and neopelex are mixed, respective dry weight proportioning is EVA:Odium stearate:Detergent alkylate sulphur
Sour sodium=95:3:2, suspended with HPN-20E nucleators (Milliken) aqueous suspension, silicate hydrate magnesium powder (Allihn reaches) water-soluble
Liquid, mixed by certain proportioning of respective dry weight, respective dry weight proportioning is HPN-20E:EVA ﹕ hydrated magnesium silicate=14:14:3,
2 hours are stirred, then use the inlet temperature that spray dryer carries out Spray Drying Spray drier to go out for 170~180 DEG C
Mouthful temperature is 60~70 DEG C, is collected in cyclone separator and a nanometer EVA composite nucleating agents are obtained after drying, its particle diameter be 50nm~
300nm。
(2) according to it is following proportioning weigh ethylene butene linear polyethylene resin powder, nanometer powder EVA composite nucleating agents,
Primary antioxidant and auxiliary antioxidant, are placed in homogenizer and are sufficiently mixed 3~6min, obtain mixture.
99.57 parts of ethylene butene linear polyethylene resin powder
(its component is that HPN-20E is 0.14 part to 0.31 part of nanometer EVA composite nucleating agents, and nanometer EVA is 0.14 part, hydration
Silicic acid magnesium powder is 0.03 part)
0.04 part of primary antioxidant
0.08 part of auxiliary antioxidant
Wherein ethylene butene linear polyethylene resin powder is preferably the LLDPE MLPE- of sinopec Maoming branch company production
1810 powders, melt flow rate (MFR) are 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.
(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
The linear polyethylene resin of puncture.
Embodiment 4
(1) nanometer EVA composite nucleating agents are prepared：(it is preferably Beijing Orient by the EVA emulsions that VA contents are 40%~60%
The trade mark of Organic Chemical Plant of petrochemical industry Co., Ltd production is BJ-707EVA elastomer emulsions) 5kg is placed in container, stirring
Lower dropwise addition odium stearate and neopelex are mixed, respective dry weight proportioning is EVA:Odium stearate:Detergent alkylate sulphur
Sour sodium=95:3:2, suspended with HPN-20E nucleators (Milliken) aqueous suspension, silicate hydrate magnesium powder (Allihn reaches) water-soluble
Liquid, mixed by certain proportioning of respective dry weight, respective dry weight proportioning is HPN-20E:EVA ﹕ hydrated magnesium silicate=12:14:4,
2 hours are stirred, then use the inlet temperature that spray dryer carries out Spray Drying Spray drier to go out for 170~180 DEG C
Mouthful temperature is 60~70 DEG C, is collected in cyclone separator and a nanometer EVA composite nucleating agents are obtained after drying, its particle diameter be 50nm~
300nm。
(2) according to it is following proportioning weigh ethylene butene linear polyethylene resin powder, nanometer powder EVA composite nucleating agents,
Primary antioxidant and auxiliary antioxidant, are placed in homogenizer and are sufficiently mixed 3~6min, obtain mixture.
99.58 parts of ethylene butene linear polyethylene resin powder
(its component is that HPN-20E is 0.12 part to 0.30 part of nanometer EVA composite nucleating agents, and nanometer EVA is 0.14 part, hydration
Silicic acid magnesium powder is 0.04 part)
0.04 part of primary antioxidant
0.08 part of auxiliary antioxidant
Wherein ethylene butene linear polyethylene resin powder is preferably the LLDPE MLPE- of sinopec Maoming branch company production
1810 powders, melt flow rate (MFR) are 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.
(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
The linear polyethylene resin of puncture.
Embodiment 5
(1) nanometer EVA composite nucleating agents are prepared：(it is preferably Beijing Orient by the EVA emulsions that VA contents are 40%~60%
The trade mark of Organic Chemical Plant of petrochemical industry Co., Ltd production is BJ-707EVA elastomer emulsions) 5kg is placed in container, stirring
Lower dropwise addition odium stearate and neopelex are mixed, respective dry weight proportioning is EVA:Odium stearate:Detergent alkylate sulphur
Sour sodium=95:2.5:2.5, it is outstanding with HPN-20E nucleators (Milliken) aqueous suspension and silicate hydrate magnesium powder (Allihn reaches)
Swim solution, mixed by certain proportioning of respective dry weight, respective dry weight proportioning is HPN-20E:EVA ﹕ hydrated magnesium silicate=15:
15:5,2 hours are stirred, then use spray dryer to carry out the inlet temperature of Spray Drying Spray drier as 170~180
DEG C, outlet temperature is 60~70 DEG C, is collected in cyclone separator and obtains a nanometer EVA composite nucleating agents after drying, its particle diameter is
50nm~300nm.
(2) according to it is following proportioning weigh ethylene butene linear polyethylene resin powder, nanometer powder EVA composite nucleating agents,
Primary antioxidant and auxiliary antioxidant, are placed in homogenizer and are sufficiently mixed 3~6min, obtain mixture.
99.50 parts of ethylene butene linear polyethylene resin powder
(its component is that HPN-20E is 0.15 part to 0.35 part of nanometer EVA composite nucleating agents, and nanometer EVA is 0.15 part, hydration
Silicic acid magnesium powder is 0.05 part)
0.05 part of primary antioxidant
0.10 part of auxiliary antioxidant.
Wherein ethylene butene linear polyethylene resin powder is preferably the LLDPE MLPE- of sinopec Maoming branch company production
1810 powders, melt flow rate (MFR) are 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.
(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 to linear polyethylene resin.
Comparative example 1
(1) ethylene butene linear polyethylene resin powder, primary antioxidant and auxiliary antioxidant are weighed according to following proportioning, put
3~6min is sufficiently mixed in homogenizer, obtains mixture.
99.97 parts of ethylene butene linear polyethylene resin powder
0.01 part of primary antioxidant
0.02 part of auxiliary antioxidant
Wherein ethylene butene linear polyethylene resin powder is preferably the LLDPE MLPE- of sinopec Maoming branch company production
1810 powders, melt flow rate (MFR) are 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, it is resistance to obtain high glaze
The linear polyethylene resin of puncture.
Comparative example 2
(1) nanometer EVA composite nucleating agents are prepared：(it is preferably Beijing Orient by the EVA emulsions that VA contents are 40%~60%
The trade mark of Organic Chemical Plant of petrochemical industry Co., Ltd production is BJ-707 EVA elastomer emulsions) 5kg is placed in container, stirring
Lower dropwise addition odium stearate and neopelex are mixed, respective dry weight proportioning is EVA:Odium stearate:Detergent alkylate sulphur
Sour sodium=95:3:2, then mixed with HPN-20E nucleators (Milliken) aqueous suspension by certain proportioning of respective dry weight,
Respective proportioning is HPN-20E:EVA=13:10,2 hours are stirred, Spray Drying Spray is then carried out using spray dryer
The inlet temperature of drier is 170~180 DEG C, and outlet temperature is 60~70 DEG C, collects in cyclone separator and is obtained after drying
Nanometer EVA composite nucleating agents, its particle diameter is 50nm~300nm.
(2) linear polyethylene resin powder, nanometer powder EVA composite nucleating agents, primary antioxidant are weighed according to following proportioning
And auxiliary antioxidant, it is placed in homogenizer and is sufficiently mixed 3~6min, obtains mixture.
99.68 parts of ethylene butene linear polyethylene resin powder
(its component is that HPN-20E is 0.13 part to 0.23 part of nanometer powder EVA composite nucleating agents, and nanoscale EVA is 0.10
Part)
0.03 part of primary antioxidant
0.06 part of auxiliary antioxidant.
Wherein ethylene butene linear polyethylene resin powder is preferably the LLDPE MLPE- of sinopec Maoming branch company production
1810 powders, melt flow rate (MFR) are 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.
(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
The thorn linear polyethylene resin worn.
Comparative example 3
(1) nanometer EVA composite nucleating agents are prepared：(it is preferably Beijing Orient by the EVA emulsions that VA contents are 40%~60%
The trade mark of Organic Chemical Plant of petrochemical industry Co., Ltd production is BJ-707EVA elastomer emulsions) 5kg is placed in container, stirring
Lower dropwise addition odium stearate and neopelex are mixed, respective dry weight proportioning is EVA:Odium stearate:Detergent alkylate sulphur
Sour sodium=95:3:2, suspended with HPN-20E nucleators (Milliken) aqueous suspension and hydrated magnesium silicate (Allihn reaches) water-soluble
Liquid is mixed by certain proportioning of respective dry weight, and respective proportioning is HPN-20E:Hydrated magnesium silicate=14:4,2 hours are stirred,
Then use spray dryer to carry out the inlet temperature of Spray Drying Spray drier as 170~180 DEG C, outlet temperature for 60~
70 DEG C, collected in cyclone separator and obtain a nanometer EVA composite nucleating agents after drying, its particle diameter is 50nm~300nm.
(2) according to it is following proportioning weigh ethylene butene linear polyethylene resin powder, nanometer powder EVA composite nucleating agents,
Primary antioxidant and auxiliary antioxidant, are placed in homogenizer and are sufficiently mixed 3~6min, obtain mixture.
99.67 parts of ethylene butene linear polyethylene resin powder
0.18 part of nanometer EVA composite nucleating agents (its component is that HPN-20E is 0.14 part, and silicate hydrate magnesium powder is 0.04 part)
0.05 part of primary antioxidant
0.10 part of auxiliary antioxidant.
Wherein ethylene butene linear polyethylene resin powder is preferably the LLDPEMLPE- of sinopec Maoming branch company production
1810 powders, melt flow rate (MFR) are 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, it is resistance to obtain high glaze
The linear polyethylene resin of puncture.
Comparative example 4
(1) ethylene butene linear polyethylene resin powder, nucleator, primary antioxidant and auxiliary is weighed according to following proportioning to resist
Oxygen agent, is placed in homogenizer and is sufficiently mixed 3~6min, obtains mixture.
99.70 parts of ethylene butene linear polyethylene resin powder
0.15 part of HPN20E
0.05 part of primary antioxidant
0.10 part of auxiliary antioxidant.
Wherein ethylene butene linear polyethylene resin powder is preferably the LLDPE MLPE- of sinopec Maoming branch company production
1810 powders, melt flow rate (MFR) are 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, it is resistance to obtain high glaze
The linear polyethylene resin of puncture.
Comparative example 5
(1) ethylene butene linear polyethylene resin powder, nucleator, primary antioxidant and auxiliary is weighed according to following proportioning to resist
Oxygen agent, is placed in homogenizer and is sufficiently mixed 3~6min, obtains mixture.
99.60 parts of ethylene butene linear polyethylene resin powder
0.25 part of HPN-20E
0.05 part of primary antioxidant
0.10 part of auxiliary antioxidant
Wherein ethylene butene linear polyethylene resin powder is preferably the LLDPE MLPE- of sinopec Maoming branch company production
1810 powders, melt flow rate (MFR) are 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, it is resistance to obtain high glaze
The linear polyethylene resin of puncture.
Embodiment and comparative example formula table
The linear polyethylene product particle of obtained 1~embodiment of embodiment 5,1~comparative example of comparative example 5 will be granulated 60
6h is dried at 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 it is as follows
Shown in table:
It can be seen that from above-mentioned experimental result and integrated according to the LLDPE material of this method addition nanometer EVA composite nucleating agents
Performance is optimal, and the film blown has relatively low turbidity, higher gloss degree, while available higher anti-puncture.Contrast
Any auxiliary agent is not added with example 1 in addition to base resin and antioxidant, equivalent to currently common linear polyethylene product,
Embodiment 1 and the contrast of contrast 1, it is seen that turbidity, glossiness, which are obtained for, to be obviously improved, while the anti-property exposed increases.
Embodiment 5 and the turbidity and glossiness of the film of comparative example 5 are very close, but embodiment 5 has only been used equivalent to right
The nucleator of 60% content in ratio 5, while obtain higher, the more preferable thin-film material of Kekelé structure count of the anti-property exposed.Embodiment 5 with it is right
Ratio 4 contrasts, and when adding the nucleator of equivalent, the film of embodiment 5 has lower turbidity and preferably comprehensive
Energy.The contrast of embodiment 3 and comparative example 3, embodiment 2 and comparative example 2 indicates adding for powdered rubber and ultrafine hydrous magnesium silicate
Enter the improvement to the mechanical property of whole system.
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 (8)
1. a kind of linear low density polyethylene composition with high glaze puncture-resistant, it is characterized in that, include following quality percentage
The raw material of ratio：
Ethylene butene linear polyethylene copolymer 99.50~99.66%
Nanometer EVA composite nucleating agents 0.25~0.35%
Primary antioxidant 0.03~0.05%
Auxiliary antioxidant 0.06~0.10%.
2. the linear low density polyethylene composition according to claim 1 with high glaze puncture-resistant, it is characterized in that, institute
The melt flow rate (MFR) for stating ethylene butene linear polyethylene copolymer is 0.8~1.2g/10min, density is 0.916~
0.920kg/m3。
3. the linear low density polyethylene composition according to claim 1 with high glaze puncture-resistant, it is characterized in that, institute
State and nanometer EVA, odium stearate, neopelex, nucleator and hydrated magnesium silicate are included in nanometer EVA composite nucleating agents
Powder, wherein, EVA ﹕ Ying resin acid Na ﹕ neopelex=90~98 ﹕ 1~5 ﹕ 1~5, Cheng He Ji ﹕ EVA ﹕ hydrated magnesium silicates
The ﹕ 3~5 of=12~15 ﹕ 10~15, above ratio are mass ratio.
4. the linear low density polyethylene composition according to claim 3 with high glaze puncture-resistant, it is characterized in that, institute
Stating a nanometer preparation method for EVA composite nucleating agents is:The nanometer EVA emulsions that VA contents are 40%~60% are placed in container,
Odium stearate, neopelex, EVA are added dropwise under agitation:Odium stearate:Neopelex=90~98:1
~5:1~5, then emulsion mixed with nucleator aqueous suspension and silicate hydrate magnesium powder aqueous suspension, by respective dry weight ratio
Calculate, nucleator:EVA ﹕ hydrated magnesium silicate=12~15:10~15:3~5, stir, 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 a nanometer EVA composite nucleating agents after drying, and its particle diameter is 50nm~300nm.
5. the linear low density polyethylene composition with high glaze puncture-resistant according to claim 3 or 4, its feature
It is that the nucleator is HPN-20E.
6. the linear low density polyethylene composition according to claim 1 with high glaze puncture-resistant, it is characterized in that, institute
It is phenolic antioxidant to state primary antioxidant, and the auxiliary antioxidant is phosphate antioxidant, and the slipping agent is erucyl amide.
7. the linear low density polyethylene composition according to claim 6 with high glaze puncture-resistant, it is characterized in that, institute
It is octadecyl 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic ester to state phenolic antioxidant, the phosphate antioxidant be three (2,
4- di-tert-butyl-phenyls) phosphite ester.
8. the preparation side of the linear low density polyethylene composition with high glaze puncture-resistant described in claim any one of 1-7
Method, it is characterized in that, comprise the following steps：
(1) the EVA emulsions 5kg that VA contents are 40%~60% is placed in container, odium stearate and 12 is added dropwise under agitation
Sodium alkyl benzene sulfonate, EVA:Odium stearate:Neopelex=90~98:1~5:1~5, then emulsion and nucleator
Aqueous suspension and the mixing of silicate hydrate magnesium powder aqueous suspension, by respective dry weight than calculating, nucleator:EVA ﹕ hydrated magnesium silicates=
12~15:10~15:3~5, stir, be then spray-dried using spray dryer, the import temperature of spray dryer
Spend for 130~180 DEG C, outlet temperature is 40~70 DEG C, is collected in cyclone separator and obtains the compound nucleation of nanometer EVA after drying
Agent, its particle diameter are 50nm~300nm；
(2) ethylene butene linear polyethylene resin powder, nanometer EVA composite nucleating agents, primary antioxidant and auxiliary are weighed according to proportioning
Aid anti-oxidants, 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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| CN112852120B (en) * | 2020-12-28 | 2022-07-15 | 上海金发科技发展有限公司 | PBT composition with ultralow polyurethane adhesive bonding strength |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3704275A (en) * | 1969-08-07 | 1972-11-28 | Hoechst Ag | Thermoplastic molding compositions on the basis of polyoxymethylenes |
| EP0209085A2 (en) * | 1985-07-11 | 1987-01-21 | Union Carbide Corporation | Impact promoters for mineral-filled thermoplastics |
| CN101020775A (en) * | 2007-03-15 | 2007-08-22 | 复旦大学 | High strength and high toughness modified poly-propylene material |
| CN101360776A (en) * | 2005-11-29 | 2009-02-04 | 索罗蒂亚公司 | Polymer interlayers comprising ethylene-vinyl acetate copolymer |
| CN102746563A (en) * | 2011-04-22 | 2012-10-24 | 中国石油天然气股份有限公司 | Preparation method for special-purpose material of LLDPE transparent shed film |
| CN102952326A (en) * | 2012-10-16 | 2013-03-06 | 中国石油化工股份有限公司 | Modified linear polyethylene resin and preparation method thereof |
| CN103554632A (en) * | 2013-10-21 | 2014-02-05 | 中国石油化工股份有限公司 | High-strength linear low density polyethylene film resin and preparation method thereof |
| CN103627062A (en) * | 2012-08-23 | 2014-03-12 | 中国石油天然气股份有限公司 | High transparent polyolefin film master batch |
| CN105601994A (en) * | 2016-02-29 | 2016-05-25 | 广州呈和科技有限公司 | Rigidity-increasing nucleating agent composition containing vinyl distearamide |
| CN106317584A (en) * | 2015-06-29 | 2017-01-11 | 中国石油化工股份有限公司 | Polyethylene resin and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160081103A (en) * | 2014-12-30 | 2016-07-08 | 삼성전자주식회사 | Thermoplastic resin composition, molded articles made therefrom, and preparation method therof |
-
2017
- 2017-08-30 CN CN201810098655.5A patent/CN108410057B/en active Active
- 2017-08-30 CN CN201710762762.9A patent/CN107556596B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3704275A (en) * | 1969-08-07 | 1972-11-28 | Hoechst Ag | Thermoplastic molding compositions on the basis of polyoxymethylenes |
| EP0209085A2 (en) * | 1985-07-11 | 1987-01-21 | Union Carbide Corporation | Impact promoters for mineral-filled thermoplastics |
| CN101360776A (en) * | 2005-11-29 | 2009-02-04 | 索罗蒂亚公司 | Polymer interlayers comprising ethylene-vinyl acetate copolymer |
| CN101020775A (en) * | 2007-03-15 | 2007-08-22 | 复旦大学 | High strength and high toughness modified poly-propylene material |
| CN102746563A (en) * | 2011-04-22 | 2012-10-24 | 中国石油天然气股份有限公司 | Preparation method for special-purpose material of LLDPE transparent shed film |
| CN103627062A (en) * | 2012-08-23 | 2014-03-12 | 中国石油天然气股份有限公司 | High transparent polyolefin film master batch |
| CN102952326A (en) * | 2012-10-16 | 2013-03-06 | 中国石油化工股份有限公司 | Modified linear polyethylene resin and preparation method thereof |
| CN103554632A (en) * | 2013-10-21 | 2014-02-05 | 中国石油化工股份有限公司 | High-strength linear low density polyethylene film resin and preparation method thereof |
| CN106317584A (en) * | 2015-06-29 | 2017-01-11 | 中国石油化工股份有限公司 | Polyethylene resin and preparation method thereof |
| CN105601994A (en) * | 2016-02-29 | 2016-05-25 | 广州呈和科技有限公司 | Rigidity-increasing nucleating agent composition containing vinyl distearamide |
Non-Patent Citations (1)
| Title |
|---|
| 刘伯元: "多元复合理论在透明薄膜母料研制中的应用", 《中国粉体技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852120B (en) * | 2020-12-28 | 2022-07-15 | 上海金发科技发展有限公司 | PBT composition with ultralow polyurethane adhesive bonding strength |
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