CN106554553B - Easy processing metallocene PE composition and preparation method thereof - Google Patents
Easy processing metallocene PE composition and preparation method thereof Download PDFInfo
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- CN106554553B CN106554553B CN201510634327.9A CN201510634327A CN106554553B CN 106554553 B CN106554553 B CN 106554553B CN 201510634327 A CN201510634327 A CN 201510634327A CN 106554553 B CN106554553 B CN 106554553B
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- 238000012545 processing Methods 0.000 title claims abstract description 62
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 16
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 14
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000008116 calcium stearate Substances 0.000 claims abstract description 12
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000155 melt Substances 0.000 claims abstract description 8
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000314 lubricant Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000004605 External Lubricant Substances 0.000 description 4
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 4
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010096 film blowing Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- NVKDFGCILHNHRS-UHFFFAOYSA-N C1(C=CC=C1)[Au] Chemical compound C1(C=CC=C1)[Au] NVKDFGCILHNHRS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical class C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
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Abstract
The present invention relates to a kind of easy processing metallocene PE compositions and preparation method thereof, belong to polymeric material field, are made of following raw materials, the parts by weight of each component are as follows: 100 parts of mLLDPE resin；0.15~1.0 part of polyethylene glycol；0.08~1.0 part of calcium stearate；0.02~0.8 part of zinc stearate；0.02~0.08 part of antioxidant 1076；0.06~0.24 part of irgasfos 168.Preparation method of the present invention is simple, low in cost, material environmental protection；Processing performance improves, hence it is evident that the melt viscosity for reducing mLLDPE facilitates resin processing and forming at low temperature, reduces energy consumption and Shear heating in process.In the case that the film strength of preparation does not reduce, optical property is significantly improved.Improve the processing efficiency of metallocene PE.
Description
Technical field
The present invention relates to a kind of easy processing metallocene PE compositions and preparation method thereof, belong to high molecular material neck
Domain.
Background technique
Metallocene linear polyethylene film has wide answer due to excellent mechanical property, hot property and optical property
Use prospect.But its processing is set to compare common polythene since relative molecular mass distribution is narrow, composition is distributed uniform design feature
Want difficult, melt viscosity is high, and shear-sensitive degree is low, and melt strength is low, and machine operating load is high, is also easy to produce melt fracture.Mesh
Before there are the various methods of processing performances for improving metallocene polymers such as to introduce long-chain branch, bimodal MWD molecular weight distribution
The abbreviation of Molecular Weight Distribution), width MWD, terpolymer and improve process equipment etc., these sides
Method high production cost implements difficult.
Processing aid PPA (fluoropolymer: being made of low surface energy fluorine carbon composition) is to improve polymer and add
A kind of common additive of work performance.This auxiliary agent is a kind of external lubricant, scattered to ensure, is needed in most cases with masterbatch
Form be added, and the viscosity of masterbatch will with processing resin viscosity match.When the resin formula of addition PPA is squeezed in extruder plasticizing
During out, under the effect of gesture potential difference, fluoropolymer is mobile to melt outer layer and has the tendency that adhering on the metal surface,
One layer of lubricant layer is formed between cavity, die surface inside extruder and polymer melt (when the lubricant layer forms one section of needs
Between, determined depending on machine size).In Continuous Extrusion Process, this coat is in dynamic equilibrium, when dynamic equilibrium is stablized
Afterwards, extrusion process and product quality can just reach stable.That is to see that a good dynamic equilibrium effect at least needs
15 minutes or more are wanted, production efficiency is influenced, increases production cost.
Chinese patent CN1465478A " method and apparatus for improving metallocene catalyzed polythene working property ", discloses one
The method and apparatus for improving processing capability of metallocene polyethylene is planted, its main feature is that metallocene catalysed polyethylene material is by ultrasound
The processing of wave infrastructure device squeezes out, and material heating plasticizing in equipment melts, and material melt is after ultrasonic irradiation from head mouth
The outflow of mould capillary.By ultrasound wave irradiation, the movement of metallocene catalysed polyethylene molecular melt segment is exacerbated, extrusion is caused
Molding pressure and apparent melt viscosity reduce to improve its processing performance.The invention is to improve cyclopentadienyl gold by a kind of ultrasonic equipment
Belong to the processing performance of polyethylene, it is significantly different by the way of with the invention patent.
Chinese patent CN1927897A " a method of improve processing capability of metallocene polyethylene ", disclose a kind of improvement
The method of processing capability of metallocene polyethylene, its main feature is that by 100 parts by weight of metallocene PE and 0.1~3 weight of antioxidant
Part is added in pan type physico chemical reactor after evenly mixing, in 15~35 degree of progress force-chemical reaction processing of temperature.Material exists
Under powerful shear stress field inducing action, optimize molecular chain structure and aggregated structure, acquisition can it is general it is general squeeze out,
The metallocene PE of smooth processing and forming on the process equipments such as injection.The invention is completed by a kind of Mechanico-chemical reactor
, it is different from the technical method and component that the present invention uses.
Summary of the invention
The object of the present invention is to provide a kind of easy processing metallocene PE composition and preparation method thereof, preparation method works
Skill is simple, low in cost, material environmental protection；With excellent machinability, the optical property of metallocene film article is further increased,
Improve the processing efficiency of metallocene PE.
A kind of easy processing metallocene PE composition of the present invention, is made of, the weight of each component following raw materials
Number are as follows:
MLLDPE resin melt mass flow rate MFR is 0.5~2.5g/l0min.
MLLDPE resin is obtained by ethylene and 1- hexene or 1- butene poly- in the presence of metalloscene catalyst
Close object, Breadth parameter of molecular weight distribution 2-4, density 0.916-0.920g/cm3。
0.03-0.05 parts of the parts by weight of antioxidant 1076.
The parts by weight of irgasfos 168 are 0.09-0.15 parts.
Calcium constituent relative mass content > 8.5% in calcium stearate, weight consumption are 0.1-0.6 parts；Zinc member in zinc stearate
Plain relative mass content > 19.2%, weight consumption are 0.03-0.5 parts.
Polyethylene glycol dosage is 0.2-0.8, and molecular weight is between 3500-7000, between the preferred 4000-6000 of molecular weight.
Calcium stearate and zinc stearate of the present invention are in-lubricant, and the two is used cooperatively, in granulation and process
In play lubricating action, can simultaneously serve as chloride ion absorbent, eliminate residual catalyst to color of resin and stability not
Good influence.Lubricant addition is less, and the improvement of resin processing performance is unobvious, and more will affect is added and prepares film surface, optics
Performance etc., while the two relative scale is improper is difficult to play good synergy.In-lubricant can reduce molecular resin chain
Between cohesive force, reduce melting viscosity, weaken macromolecule between interior friction, improve the mobility of resin.
The external lubricant is polyethylene glycol, it is a kind of nonionic surfactant, and molecule is the length of a sawtooth pattern
The flexibility of chain, chain structure arranged regular, segment is good, can weaken and interact between mLLDPE molecular resin, and it is molten to cause mLLDPE
Interface sliding of the body on polyethylene glycol particle face.In extrusion molding, certain wall slippage was both generated, while inducing stronger
Interior slip.The addition of external lubricant has certain saturation degree, and adding can have the opposite effect too much, and in addition there are also cost considerations.
Compatibility between external lubricant and resin is small compared with in-lubricant, it is attached to molten resin surface, processing equipment table
Face forms lubrication molecule layer, to reduce the friction between resin and process equipment, the lubricant of molecular carbon chain length can make two
A friction distance between the surface is farther, has bigger lubricant effect.
The synergistic effect of inside and outside lubricant agent keeps greasy property more preferable when the ratio of the two is 1:1-5, in extrusion process,
Initial stage lubricant effect, mid-term lubricant effect and later period lubricant effect mutually more balance.Three kinds of relationships follow following formula:
0.75x+y<z<4x+9.8y (1)
1.5<x/y<5.3 (2)
Wherein x represents calcium stearate levels；Y represents zinc stearate content；Z represents polyethyleneglycol content.
Resin needs the process by high-temperature fusion, polyethylene is in high-temperature fusion by heat, oxygen etc. when being processed into product
Effect, it may occur that degradation or crosslinking, for example gel can occur for film, the gel visually seen claims " flake ".In addition product
In use by extraneous heat, oxygen effect also can recurring structure variation, influence using to avoid resin from processing and product
The unfavorable factors bring such as heat, oxygen influences in use process, needs to be added antioxidant in polymeric system, keeps resin pair
Heat, the stability of oxygen.
The antioxidant is long-acting heat-staple Hinered phenols antioxidant 1076 and phosphite ester antioxidant 168, antioxygen
The capture free radical efficiency of agent 1076 is excellent, not volatile migration, and dosage is 0.02-0.8 parts, preferably 0.03-0.05 parts.Phosphorous acid
Esters irgasfos 168 dosage is 0.06-0.24 parts, preferably 0.09-0.15 parts.
The preparation method of easy processing metallocene PE composition:
In 100 parts of mLLDPE resins, 0.15~1.0 part of polyethylene glycol of addition, 0.08~1.0 part of calcium stearate, stearic acid
It 0.02~0.8 part of zinc, 0.02~0.08 part of antioxidant 1076,0.06~0.24 part of irgasfos 168, is mixed in high-speed mixer
It closes, 1200~1700 revs/min of speed of agitator, 10~14min of mixing time, 35~40 DEG C of whipping temp；By uniformly mixed object
Material, which is added in double screw extruder, to be melted, is plasticized, squeezing out, being granulated.
Screw slenderness ratio is 34~38,6~9 sections of cutouts in the screw combinations of use, wherein 2~4 sections of flip Trim blocks；
150~210 DEG C of processing temperature, distribution gradient；It is vacuumized in granulation process, granulation vacuumizes the vacuum degree -0.2 reached
~-0.4MPa.
The present invention is to obtain a kind of metallocene film article that processability is good by the synergistic effect of inside and outside lubricant agent.
Metallocene PE melt of the invention improves temperature, the sensibility of shear rate, cuts in processing temperature, processing
The apparent viscosity cut in speed range reduces, and processing fluidity is markedly improved, can be in common polythene process equipment
On, the excellent metallocene polyethylene film product of processability.
Compared with prior art, the invention has the following advantages:
(1) preparation method simple process and low cost, material environmental protection；
(2) there is good synergistic effect when polyethylene glycol and calcium stearate, zinc stearate are used in combination, in Compound Machining
Just improve processing performance rapidly in the case that lubricant usage amount is seldom, hence it is evident that the melt viscosity of mLLDPE is reduced,
Facilitate resin processing and forming at low temperature, reduces energy consumption and Shear heating in process.
(3) in the case that the film strength prepared does not reduce, optical property is significantly improved.
(4) processing efficiency of metallocene PE is improved.
Specific embodiment
The present invention will be further explained with reference to the examples below.
Embodiment 1
Prepare raw material and its parts by weight used in easy processing metallocene PE composition are as follows:
The preparation step of easy processing metallocene PE composition: in mLLDPE powder resin, being added polyethylene glycol, stearic
Sour calcium, zinc stearate, antioxidant mix in high-speed mixer, and 1200 revs/min of speed of agitator, mixing time 14min, stirring
40 DEG C of temperature；Uniformly mixed material is added in double screw extruder and melts, be plasticized, squeezing out, being granulated.
Screw slenderness ratio is 34,6 sections of cutouts in the screw combinations of use, wherein 3 sections of flip Trim blocks；Processing temperature
It 190 DEG C, is vacuumized in granulation process, granulation vacuumizes the vacuum degree -0.3Mpa reached.
Embodiment 2
Prepare raw material and its parts by weight used in easy processing metallocene PE composition are as follows:
The preparation step of easy processing metallocene PE composition: in mLLDPE powder resin, being added polyethylene glycol, stearic
Sour calcium, zinc stearate, antioxidant mix in high-speed mixer, and 1700 revs/min of speed of agitator, mixing time 12min, stirring
37 DEG C of temperature；Uniformly mixed material is added in double screw extruder and melts, be plasticized, squeezing out, being granulated.
Screw slenderness ratio is 38,8 sections of cutouts in the screw combinations of use, wherein 4 sections of flip Trim blocks；Processing temperature
It 210 DEG C, is vacuumized in granulation process, granulation vacuumizes the vacuum degree -0.2Mpa reached.
Embodiment 3
Prepare raw material and its parts by weight used in easy processing metallocene PE composition are as follows:
The preparation method of the present embodiment is same as Example 1.
Embodiment 4
Prepare raw material and its parts by weight used in easy processing metallocene PE composition are as follows:
The preparation step of easy processing metallocene PE composition: in mLLDPE powder resin, being added polyethylene glycol, stearic
Sour calcium, zinc stearate, antioxidant mix in high-speed mixer, and 1500 revs/min of speed of agitator, mixing time 12min, stirring
38 DEG C of temperature；Uniformly mixed material is added in double screw extruder and melts, be plasticized, squeezing out, being granulated.
Screw slenderness ratio is 36,6 sections of cutouts in the screw combinations of use, wherein 3 sections of flip Trim blocks；Processing temperature
It 190 DEG C, is vacuumized in granulation process, granulation vacuumizes the vacuum degree -0.3Mpa reached.
Embodiment 1-4 processing performance effect, which is shown in Table 1 and embodiment 1-4 and prepares film performance test, the results are shown in Table 2.
The preparation method of above embodiments is only explanation, and the scope of protection of the present invention is not limited, the technology people in the field
Member the content can make some nonessential modifications and adaptations to the present invention according to the present invention.
Comparative example 1
Prepare raw material and its parts by weight used in easy processing metallocene PE composition are as follows:
100 parts of mLLDPE resin (MFR=1.0g/10min)
0.05 part of antioxidant 1076
0.1 part of irgasfos 168.
Comparative example 2
Prepare raw material and its parts by weight used in easy processing metallocene PE composition are as follows:
Comparative example 3
Prepare raw material and its parts by weight used in easy processing metallocene PE composition are as follows:
Comparative example 4
Prepare raw material and its parts by weight used in easy processing metallocene PE composition are as follows:
The preparation method of comparative example: in 100 parts of mLLDPE powder resins, various auxiliary agents are added.It is mixed in high-speed mixer
It closes, 1500 revs/min of speed of agitator, mixing time 12min, 38 DEG C of whipping temp；Uniformly mixed material is added to twin-screw
It melts, be plasticized, squeeze out, be granulated in extruder.Screw slenderness ratio is 36,6 sections of cutouts in the screw combinations of use, wherein 3 sections
Flip Trim block；It 190 DEG C of processing temperature, is vacuumized in granulation process, granulation vacuumizes the vacuum degree -0.3MPa reached.
Comparative example 1-4 processing performance effect is shown in Table 1, and comparative example 1-4 prepares film performance test result such as table 2.
Performance test experiment
It is double at 210 DEG C by above-described embodiment 1~4 and the resin combination of comparative example 1~4 after high-speed mixer is blended
Screw rod is granulated, and is placed in dryer and is dried after granulation, and drying temperature controls within the scope of 50 DEG C.Then it is blown in inflation film manufacturing machine
Film does film performance test.
Film blowing method and reference standard are as follows:
1) blown film, inflation film manufacturing machine extruder screw diameter are carried out using Germany's OCS inflation film manufacturing machineL/D=25:l, mouth
Mode diameterFilm control thickness: 30 ± 3 μm.
2) film-blowing process condition are as follows: processing temperature (DEG C): 160,170,180,200,200,210,210,210,210,
205。
3) extruder engine speed: 40~50r/min, breadth 190mm, cooling air quantity 46%, blow-up ratio 2.0, condensation
Line height 75mm.
Test method:
Melt mass flow rate (MFR): being tested according to GB/T 3682~2000, load as 2.16Kg and
21.6Kg。
Film stretchability energy: being tested according to GB/T 1040.3~2006, II pattern item, tensile speed 200mm/
min。
Capillary rheology: it is tested by GB/T 25278-2010.Capillary diameter lmm, draw ratio 30:1；Before test
Piston preheats 5-10min；Precompression is less than 1KN；Shear rate is from 50s1、100s1... start value, under each shear rate,
Shear stress takes a little after reaching balance.
Film Optics performance mist degree: it is carried out by GB/T 2410-2008.
1 embodiment 1-4 of table and comparative example 1-4 processing performance effect
Embodiment and comparative example, which can be seen that the present invention, in table 1 just obtains processing performance rapidly using a small amount of auxiliary agent
Improve, improve the critical shear rate of material, thus can realize raising processing speed.
Critical shear rate is the shear rate critical value that polymer generates flow instabilities in extrusion molding, with Γ c
Phenomena such as expression, flow instabilities will lead to extrudate rough surface, uneven, helically twisted or even melt fracture, Γ c is got over
Height illustrates that processing is more stable.
Table 2 embodiment 1-4 and comparative example 1-4 prepares film performance test result
Embodiment and comparative example can be seen that the film prepared with the method for the invention in table 2, due to polyethylene glycol and
Calcium stearate, zinc stearate act synergistically well, and the intensity of film article is suitable；When preparing film, the decline of blown film torque
20% or more；The optical property mist degree of film has preferable improvement, and effect is optimal.Polyethylene glycol and calcium stearate in comparative example 4,
The ratio of zinc stearate is 0.7:l, does not play synergistic effect, the performance of composition does not improve, the processability of other comparative examples
It is not so good as embodiment with optical property.
Claims (7)
1. a kind of easy processing metallocene PE composition, which is characterized in that be made of following raw materials, the parts by weight of each component
Are as follows:
MLLDPE resin melt mass flow rate MFR is 0.5~2.5g/10min；
MLLDPE resin is in the presence of metalloscene catalyst, by ethylene and 1- polymerizeing of obtaining of alkene or 1- butene
Object, Breadth parameter of molecular weight distribution 2-4, density 0.916-0.920g/cm3；
The content of calcium stearate, zinc stearate and polyethylene glycol follows following formula:
0.75x+y<z<4x+9.8y (1)
1.5<x/y<5.3 (2)
Wherein x represents calcium stearate levels；Y represents zinc stearate content；Z represents polyethyleneglycol content.
2. easy processing metallocene PE composition according to claim 1, which is characterized in that the weight of antioxidant 1076
Number is 0.03-0.05 parts.
3. easy processing metallocene PE composition according to claim 1, which is characterized in that the weight of irgasfos 168
Number is 0.09-0.15 parts.
4. easy processing metallocene PE composition according to claim 1, which is characterized in that calcium constituent in calcium stearate
Relative mass content > 8.5%, weight consumption are 0.1-0.6 parts；Zn-ef ficiency relative mass content > 19.2% in zinc stearate, weight
Measuring dosage is 0.03-0.5 parts.
5. easy processing metallocene PE composition according to claim 1, which is characterized in that polyethylene glycol dosage is
0.2-0.8 parts；Molecular weight is between 3500-7000.
6. a kind of preparation method of easy processing metallocene PE composition described in claim 1, which is characterized in that 100 parts
In mLLDPE resin, 0.15~1.0 part of polyethylene glycol of addition, 0.08~1.0 part of calcium stearate, 0.02~0.8 part of zinc stearate,
It 0.02~0.08 part of antioxidant 1076,0.06~0.24 part of irgasfos 168, is mixed in high-speed mixer, speed of agitator
1200~1700 revs/min, 10~14min of mixing time, 35~40 DEG C of whipping temp；Uniformly mixed material is added to double spiral shells
It melts, be plasticized, squeeze out, be granulated in bar extruder.
7. the preparation method of easy processing metallocene PE composition according to claim 6, which is characterized in that screw rod is long
Diameter ratio is 34~38,6~9 sections of cutouts in the screw combinations of use, wherein 2~4 sections of flip Trim blocks；Processing temperature 150~
210 DEG C, distribution gradient；It is vacuumized in granulation process, granulation vacuumizes vacuum degree -0.2~-0.4MPa reached.
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| CN115803291A (en) | 2020-05-01 | 2023-03-14 | 国际人造丝公司 | Films having reduced shutdown temperatures and polymer compositions for making the same |
| CN112812404B (en) * | 2021-01-06 | 2022-12-02 | 中国石油天然气股份有限公司 | Special low-density polyethylene resin composition for transparent film material and preparation method of transparent film |
| CN115449146B (en) * | 2021-06-09 | 2023-10-20 | 中国石油化工股份有限公司 | Metallocene polyethylene film composition |
| CN115636994B (en) * | 2021-07-19 | 2024-03-01 | 中国石油天然气股份有限公司 | Low-density polyethylene resin composition for film |
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| JPS6015445A (en) * | 1983-07-08 | 1985-01-26 | Asahi Chem Ind Co Ltd | Novel polyethylene composition |
| CN1482167A (en) * | 2003-07-28 | 2004-03-17 | 四川大学 | Composite processing aid for polyolefin and its preparation method and application |
| CN102453274A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Viscosity-reducing master batch for polyolefin and preparation method and application thereof |
| CN104558789A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Easily-processed polyethylene composition |
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| JPS6015445A (en) * | 1983-07-08 | 1985-01-26 | Asahi Chem Ind Co Ltd | Novel polyethylene composition |
| CN1482167A (en) * | 2003-07-28 | 2004-03-17 | 四川大学 | Composite processing aid for polyolefin and its preparation method and application |
| CN102453274A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Viscosity-reducing master batch for polyolefin and preparation method and application thereof |
| CN104558789A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Easily-processed polyethylene composition |
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