CN101250302A - Anti-static polyolefin ventilated membrane composition and method for preparing the same - Google Patents
Anti-static polyolefin ventilated membrane composition and method for preparing the same Download PDFInfo
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- CN101250302A CN101250302A CNA200810027192XA CN200810027192A CN101250302A CN 101250302 A CN101250302 A CN 101250302A CN A200810027192X A CNA200810027192X A CN A200810027192XA CN 200810027192 A CN200810027192 A CN 200810027192A CN 101250302 A CN101250302 A CN 101250302A
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- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- 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
- B29C48/92—Measuring, controlling or regulating
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
Abstract
The invention discloses an antistatic polyolefin permeable film compound and a process for preparing the antistatic polyolefin permeable film. The compound comprises 30-60 parts by weight of linear low density polyethylene, 10-40 parts by weight of high-pressure polyethylene, 30-60 parts by weight of antistatic resin, 100-180 parts by weight of calcium carbonate and 0.4-1.0 parts by weight of anti-oxidant. The invention overcomes the weakness of traditional antistatic agent and antistatic filling, not only ensures the antistatic property of permeable film through adding antistatic resin, but also not affects the processing property, permeable property and the appearance of film. The processing flow-ability, the dispersing evenness of organic filling and processing stability of antistatic polyolefin permeable film compound in the invention can meet the production requirements of extrusion filmmaking. The water vapor permeable rate of the antistatic polyolefin permeable film which is prepared by the invention is not lower 2000g/m2 24h, and the surface electrical resistivity is no higher 10 9 omega/m2.
Description
Technical field
The invention belongs to the modifying plastics technical field, be meant a kind of anti-static polyolefin air-permeable envelope composition especially and prepare the method for anti-static polyolefin air-permeable envelope.
Background technology
The method of polymeric film waterproof and breathable is comprised: (for example 30～70wt%) inorganic particles packing (for example lime carbonate) mixes, and by this blend extrusion molding film with polyolefin resin (for example polypropylene or polyethylene, various olefin copolymer and/or polyolefin blends) and some amount; Then, heat and this film that stretches, cause in the filler particles peripheral region and form the space, it allows vapour transmission but does not allow liquid to see through, and prepares the polyolefine waterproof breathable membrane.
This film can be used on outdoor fabrics, waterproof cloth, product next to the shin, infection control goods, electronic packaging goods, protective clothes goods, sanitary product and numerous other goods.For following particular application, polyolefin permeable membrane need possess static resistance: 1) have the explosion potential place, for example as mine, processing solvent or superfine powder place; 2) the work workshop or the place of tool physiology susceptibility, for example Operation theatre, precision engineering workshop; 3) handle the electronic component place of susceptibility, these elements need be protected in transportation, processing and use, in case discharge spark and it is wrecked; 4) need the place of anti-electron radiation.Tradition is improved the method for the static resistance of air permeable polyolefin film, usually have three kinds: first kind is, outer static inhibitor is dissolved in earlier in the appropriate solvent carrier, and the method with spraying or dipping is coated on film surface with static inhibitor then, and solvent carrier then evaporates to be removed.The characteristics of this method are that the static inhibitor consumption is few, and effect is direct, but static resistance lose easily, and be difficult to coat and evenly cause printing and compound difficulty, the while evaporation of solvent causes environmental pollution easily.Second kind is, by in the blend extrusion, adding the small molecules static inhibitor, static inhibitor is moved to film surface and is improved the static resistance of film then, and the small molecules static inhibitor generally includes non-ionic antistatic agent (for example fatty acid ester, ethoxyquin alkanamine, diethanolamine, ethoxylated alcohol etc.), anionic antistatic agent (for example alkylsulfonate, alkylphosphonic), cationic static inhibitor (for example quaternary ammonium salt), both sexes static inhibitor (for example alkyl betaine).The characteristics of this method are that the film static resistance is even; antistatic effect is good; but antistatic persistence is relatively poor; and polyolefin permeable membrane makes static inhibitor addition big (because the adsorption of filler causes) owing to containing a large amount of mineral fillers, causes mouthful mould buildup problem easily simultaneously in the course of processing and influences product appearance and reduce the permeability of air-permeable envelope.The third is to add conductive filler material, normally some conductive carbon blacks and electrically conductive graphite etc.The characteristics of this method are that the antistatic effect of film is good, but film can only make black or dark color, simultaneously the conductive filler material addition is big, adds high-load mineral filler and makes thin film mechanical performance very poor.Above method all can not active balance polyolefin permeable membrane antistatic property and mechanical property, permeability, product appearance and processibility between contradiction.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide a kind of permeability and mechanical property that can guarantee polyolefin permeable membrane, simultaneously do not influence the processing characteristics of product again, and improved the anti-static polyolefin air-permeable envelope composition of the static resistance of film again.The present invention makes the processing characteristics of this resin combination, dispersing uniformity, permeability, static resistance and the mechanical property of lime carbonate all can satisfy the service requirements of product in conjunction with polymerization technique, dispersion treatment technology, compatible technique and twin screw expressing technique.
Another object of the present invention is to provide the method for above-mentioned anti-static polyolefin air-permeable envelope preparation of compositions anti-static polyolefin air-permeable envelope.
The antistatic resin that characteristics of the present invention are to adopt pearl filler, linear low density polyethylene, the high-pressure polyethylene through coating processing and have a permanent anti-static is a main raw material, in conjunction with polymerization technique, dispersion treatment technology, compatible technique and twin screw expressing technique, make the same processing characteristics of antistatic property of anti-static polyolefin air-permeable envelope composition of the present invention, dispersing uniformity, mechanical property and the permeability of lime carbonate reach perfect adaptation.
Purpose of the present invention is achieved through the following technical solutions: a kind of anti-static polyolefin air-permeable envelope composition comprises following component:
The linear low density polyethylene of (1) 30～60 weight part, its melting index are 1.0～4.0g/10min, and density is 0.890～0.940g/cm
3, range of molecular weight distributions is 3～15;
The high-pressure polyethylene of (2) 10～40 weight parts, its melting index are 2.0～20.0g/10min, and density is 0.900～0.920g/cm
3
The antistatic resin of (3) 30～60 weight parts, its melting index are 2.0～4.0g/10min, and density is 0.885～0.930g/cm
3, surface resistivity is 10
7～10
9Ω/m
2
The lime carbonate of (4) 100～180 weight parts, its particle diameter are 0.5～5.0 μ m;
The oxidation inhibitor of (5) 0.4～1.0 weight parts.
Described linear low density polyethylene is the multipolymer of the 'alpha '-olefin monomers of ethene and at least a C4～C8, and its melting index is 1.0～4.0g/10min, and density is 0.890～0.940g/cm
3, range of molecular weight distributions is 3～15.If range of molecular weight distributions is less than 3, back pressure is excessive when extruding, and causes when high-speed production simultaneously and extrudes wave phenomenon, makes the film became uneven, on the other hand, when molecular weight distribution greater than 15 the time, mechanical properties in films descends.
To extrude the stability of processing and the ventilation property of film when making film in order further improving, to add the high-pressure polyethylene of 10～40 weight parts, melting index is 2.0～20.0g/10min, and density is 0.900～0.920g/cm
3When high-pressure polyethylene is lower than 10 weight parts, do not have the effect that improves processing characteristics, when addition during greater than 40 weight parts, mechanical properties in films descends.
In order to improve the static resistance of air-permeable envelope, in anti-static polyolefin air-permeable envelope composition, add 30～60 parts of antistatic resins, its melting index is 2.0～4.0g/10min, density is 0.885～0.930g/cm
3, surface resistivity is 10
7～10
9Ω/m
2When the antistatic resin addition was lower than 30 weight parts, film was difficult to reach antistatic requirement, when addition is higher than 60 weight parts, too much caused the permeability decline of film owing to static inhibitor on the antistatic resin and extraneous water molecules.On the other hand, because static inhibitor is grafted on the polyolefine macromolecular chain with the form of chemical bond, thereby the disadvantage of traditional static inhibitor, for example mouthful mould buildup, product appearance difference etc. have been avoided simultaneously at the antistatic property that has guaranteed composition.
In order to obtain having the film of highly air-permeable energy, add the lime carbonate of 100～180 weight parts, its particle diameter is 0.5～5.0 μ m.When the lime carbonate addition was lower than 100 weight parts, the permeability of film was poor; On the other hand, when the lime carbonate consumption is higher than 180 weight parts, can reduce mechanical properties in films and processing characteristics.
Described antistatic resin be with static inhibitor (AS), the unsaturated monomer that contains carboxyl and vinylbenzene under the initiator effect, in polyolefine, get by the twin screw melting graft reaction.Wherein, the addition of static inhibitor AS is 10～30% of a polyolefine weight, the addition that contains the unsaturated monomer of carboxyl is 5～30% of a polyolefine weight, the 3rd monomer styrene is 20～40% of an AS weight, initiator is 0.2～0.5% of a polyolefine weight, temperature of reaction is 150～200 ℃, screw speed 50～100rpm.Described polyolefine is a kind of in polypropylene (PP), polyethylene (PE), ethylene propylene copolymer (EPR) or the thermoplastic elastomer (POE).
Described static inhibitor (AS) makes by the following method: vulcabond and Fatty Alcohol(C12-C14 and C12-C18) are reacted 2～4h get the pre-reaction thing under 60～80 ℃ of conditions of temperature, then pre-reaction thing and end amine based polymer are reacted 5～10min down at 120～180 ℃, make static inhibitor AS.Wherein (NCO) the hydroxyl mole ratio in mole number and the Fatty Alcohol(C12-C14 and C12-C18) is 2 to the isocyanate group in the vulcabond, and the mol ratio of end amino polymer and pre-reaction thing is not less than 1.Described vulcabond comprises '-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, 2,4-tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), cyclohexyl diisocyanate (HDI), dicyclohexyl methane diisocyanate (H12MDI), Methylcyclohexyl diisocyanate (HTDI), xylylene diisocyanate (XDI) or naphthalene-1,5-vulcabond (NDI).The carbon atom number range of described Fatty Alcohol(C12-C14 and C12-C18) is 10～20; Described end amino polymer comprises Amino Terminated polyether(ATPE), the amino polyoxyethylene glycol of end or end aminophenyl polypropylene glycol, its weight-average molecular weight (M
w) be 1000～4000.
The described unsaturated monomer that contains carboxyl comprises methacrylic acid, vinylformic acid, maleic anhydride, fumaric acid, methylene-succinic acid or glycidyl methacrylate.
Described initiator comprises ditertiary butyl peroxide (DTBP), two (3,5, the 5-trimethyl acetyl) superoxide, dilauroyl peroxide (LPO), dibenzoyl peroxide (BPO), peroxidation neodecanoic acid isopropyl benzene ester (CPND), new peroxide tert-butyl caprate (TBPD), the special pentyl ester (TAPV) of peroxidation trimethylacetic acid, the peroxidation trimethylacetic acid tert-butyl ester (TBPV), the special pentyl ester (TAPEH) of peroxidation-2 ethyl hexanoic acid, peroxide-2-ethyl hexanoic acid tert-butyl (TBPEH), tert-butyl hydroperoxide isobutyrate (TBPI), tert-butyl hydroperoxide-3,5,5-tri-methyl hexanoic acid ester (TBPMH), peroxide acetic acid butyl ester (TBPA), peroxidized t-butyl perbenzoate (TBPB), 1,1-di-tert-butyl peroxide-3,3,5-trimethyl-cyclohexane (CH335), 1,1-cyclohexane di-tert-butyl peroxide (CH-B50), 2,2-two (tert-butyl hydroperoxide) butane (DBPB), two (4-tert-butylcyclohexyl) peroxy dicarbonates (BCHPC), two (2-ethylhexyl) peroxy dicarbonates (EHPC), peroxy dicarbonate two hexadecyl esters (CEPC) peroxy dicarbonate 24 esters (MYPC), two tertiary amyl superoxide (DTAP), dicumyl peroxide (DCP), two (tert-butyl hydroperoxide sec.-propyl) benzene (BPIB), 2,5-dimethyl-2,5-di-t-butyl hexane peroxide (BPDH), 2,5-dimethyl-2,5-di-tert-butyl peroxide hexin (DYBP), diisopropylbenzenehydroperoxide (DBHP), isopropyl benzene hydroperoxide (CHP), tertiary amyl hydrogen peroxide (TAHP), tertbutyl peroxide (TBHP), t-tutyl cumyl peroxide, diisopropylbenzenehydroperoxide, p-menthane hydroperoxide (PMHP), peroxidation carbonic acid-2 ethyl hexanoic acid the tert-butyl ester (TAEC), tert-butyl hydroperoxide carbonic acid-2-ethylhexyl (TBEC), two (2, the 4-dichloro-benzoyl) superoxide (DCBP), 4,4-two (tert-butyl hydroperoxide) n-butyl pentanoate, methylethyl ketone peroxide (MEKP) or peroxidation hexanaphthene.
In order to improve the dispersion of lime carbonate in composition, must carry out surface-coated earlier to lime carbonate and handle; Advantageously, the antistatic resin that uses among the present invention is owing to contain polar group and nonpolar macromolecular chain, can play the effect of macromolecular coupling agent, further improve the dispersion of lime carbonate in the polyvinyl resin system, reduce the influence of lime carbonate film performance.
It is as follows that described lime carbonate carries out the surface-coated treatment process: lime carbonate and surface-modifying agent are placed high-speed mixer, surface-modifying agent carries out surface-coated to lime carbonate to be handled, described surface-modifying agent weight is 0.5～2.0% (weight percent) of weight of calcium carbonate, described surface-coated treatment process condition is as follows: rotating speed is 1500～3000r/min, treatment temp is 90～130 ℃, and the treatment time is 10～45min.
Described surface-modifying agent comprises lipid acid, titanic acid ester or aluminic acid ester; Described lipid acid comprises stearic acid, lauric acid, palmitinic acid or the acid of nutmeg beans; Described titanic acid ester comprises sec.-propyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanic acid ester, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, sec.-propyl three oleic acid acyloxy titanic acid ester, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester, three hard ester acid isopropyl titanates, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate or tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester; Described aluminic acid ester comprises isopropoxy two (octadecane oxygen base) aluminium, isopropoxy two oily acyloxy two (diethylamine) aluminium, isopropoxy two (diisooctyl phosphoric acid acyloxy) aluminium, isopropoxy two (p-isopropyl phenoxy group) aluminium, isopropoxy two (dodecyl tosyloxy) aluminium, isopropoxy two (maleic acid list Virahol ester acyloxy) aluminium, two (glycerine two oleum lini acid esters list hydroxyl oxygen bases) aluminium or isopropoxy oil acyloxy octadecane oxygen base aluminium.
In the course of processing, in order to reduce the course of processing since heat, oxygen, shearing to the influence of resin property, the oxidation inhibitor of need 0.4～1.0 weight part.Described oxidation inhibitor is any in phenolic antioxidant, phosphite ester kind antioxidant or the phenolic antioxidant+phosphite ester kind antioxidant, and phenolic antioxidant in described phenolic antioxidant+phosphite ester kind antioxidant: the mass ratio of phosphite ester kind antioxidant is 1: 1～2: 1.Described phenolic antioxidant comprises 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) triketone, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester or four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Described phosphite ester kind antioxidant comprises three (2.4-di-tert-butyl-phenyl) phosphorous acid esters or two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
Method with above-mentioned anti-static polyolefin air-permeable envelope preparation of compositions anti-static polyolefin air-permeable envelope comprises the steps:
(1) with the linear low density polyethylene of 30～60 weight parts, its melting index is 1.0～4.0g/10min, and density is 0.890～0.940g/cm
3, range of molecular weight distributions is 3～15; The high-pressure polyethylene of 10～40 weight parts, its melting index are 2.0～20.0g/10min, and density is 0.900～0.920g/cm
3The antistatic resin of 30～60 weight parts, its melting index are 2.0～4.0g/10min, and density is 0.885～0.930g/cm
3, surface resistivity is 10
7～10
9Ω/m
2The lime carbonate of 100～180 weight parts, its particle diameter are 0.5～5.0 μ m; 0.4 the oxidation inhibitor of～1.0 weight parts mixes in high-speed mixer, and obtains the plastic cement particle by the parallel double-screw extruder extruding pelletization, described screw slenderness ratio is 40～50, and processing temperature is 160～220 ℃;
(2) the prepared plastic cement particle of step (1) is sent into the casting machine of single-bolt type or film that inflation film manufacturing machine makes through 1.0～3.5 times of uniaxial extensions, draft temperature is 80～90 ℃, makes the anti-static polyolefin air-permeable envelope.
Prepared its water vapour permeability of anti-static polyolefin air-permeable envelope is not less than 2000g/m
224h, the surface resistivity of air-permeable envelope is not higher than 10
9Ω/m
2
Prepared anti-static polyolefin air-permeable envelope is used for but is not limited to the protection of following special occasions and packs purposes: 1) have the explosion potential place, for example mine, processing solvent or superfine powder place; 2) the work workshop or the place of tool physiology susceptibility, for example Operation theatre, precision engineering workshop; 3) handle the electronic component place of susceptibility, these elements need be protected in transportation, processing and use, in case discharge spark and it is wrecked; 4) need the place of anti-electron radiation.
The present invention compared with prior art has following advantage and beneficial effect:
1) the present invention has overcome the disadvantage of traditional static inhibitor, antistatic filler, by adding the antistatic property that antistatic resin had both guaranteed air-permeating film, does not influence processing characteristics, permeability, the film appearance of film again.
2) the present invention is by polymerization technique, dispersion treatment technology, compatible technique and twin screw expressing technique, makes processing fluidity, the dispersing uniformity of mineral filler, the processing stability of anti-static polyolefin air-permeable envelope composition all can satisfy to extrude and makes the film production requirement.
3) the anti-static polyolefin air-permeable envelope preparation of compositions polyolefin permeable membrane that adopts the present invention to prepare, its permeability (water vapour permeability) is not less than 2000g/m
224h, the surface resistivity of air-permeable envelope is not higher than 10
9Ω/m
2
4) the antistatic waterproof breathable membrane that adopts the present invention to prepare is used for but is not limited to the protection of following special occasions and packs purposes: 1) have the explosion potential place, for example mine, processing solvent or superfine powder place; 2) the work workshop or the place of tool physiology susceptibility, for example Operation theatre, precision engineering workshop; 3) handle the electronic component place of susceptibility, these elements need be protected in transportation, processing and use, in case discharge spark and it is wrecked; 4) need the place of anti-electron radiation.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
The preparation of antistatic resin:
1, the preparation of antistatic resin 1
(1) 2,4 toluene diisocyanate (TDI) and stearyl alcohol react 2～3h and get the pre-reaction thing under 60～70 ℃ of conditions of temperature, and wherein (NCO) the hydroxyl mole ratio in mole number and the stearyl alcohol is 2 to the isocyanate group in the 2,4 toluene diisocyanate.Be that 2500 end amido polyoxyethylene glycol is 1 proportioning at 150～160 ℃ of reaction 5～10min down in molar ratio then with pre-reaction thing and molecular weight, make static inhibitor AS.
(2) with static inhibitor (AS), glycidyl methacrylate and the 3rd monomer styrene under the effect of dicumyl peroxide initiator, to ethylene propylene copolymer (EPR) macromolecular chain, make antistatic resin 1 by the twin screw fusion-grafting.Wherein the addition of static inhibitor AS is 30% of a polyolefine weight, the addition of glycidyl methacrylate is 30% of a polyolefine weight, the 3rd monomer styrene is 20% of an AS weight, initiator is 0.3% of a polyolefine weight, temperature of reaction is 170～200 ℃, screw speed 70～100rpm.
(3) prepared antistatic resin 1, its melting index is 2.5g/10min, density is 0.895g/cm
3, surface resistivity is 10
7Ω/m
2
2, the preparation of antistatic resin 2
(1) '-diphenylmethane diisocyanate (MDI) and tetradecyl alcohol react 2～3h and get the pre-reaction thing under 70～80 ℃ of conditions of temperature, and wherein (NCO) the hydroxyl mole ratio in mole number and the tetradecyl alcohol is 2 to the isocyanate group in the '-diphenylmethane diisocyanate (MDI).Be that 1000 end amido polyoxyethylene glycol is 1 at 120～150 ℃ of reaction 5～10min down in molar ratio then with pre-reaction thing and molecular weight, make static inhibitor AS.
(2) with static inhibitor (AS), maleic anhydride and the 3rd monomer styrene under the effect of dibenzoyl peroxide (BPO) initiator, in polypropylene (PP), make antistatic resin 2 by the twin screw melting graft reaction.Wherein, the addition of static inhibitor AS is 20% of a polyolefine weight, and the addition of maleic anhydride is 5% of a polyolefine weight, the 3rd monomer styrene is 20% of an AS weight, initiator is 0.5% of a polyolefine weight, and temperature of reaction is 150～190 ℃, screw speed 50～80rpm.
(3) prepared antistatic resin 2, its melting index is 4.0g/10min, density is 0.905g/cm
3, surface resistivity is 10
8Ω/m
2
3, the preparation of antistatic resin 3
(1) isophorone diisocyanate (IPDI) and eicosanol react 3～4h and get the pre-reaction thing under 65～75 ℃ of conditions of temperature, and wherein (NCO) the hydroxyl mole ratio in mole number and the eicosanol is 2 to the isocyanate group in the isophorone diisocyanate (IPDI).Be that 4000 ending amino polyether is 2.0 proportioning at 160～180 ℃ of reaction 5～8min down in molar ratio then with pre-reaction thing and molecular weight, make static inhibitor AS.
(2) with static inhibitor (AS), fumaric acid and the 3rd monomer styrene 2, under the effect of 2-two (tert-butyl hydroperoxide) butane (DBPB) initiator, in thermoplastic elastomer (POE), make antistatic resin 3 by the twin screw melting graft reaction.Wherein, the addition of static inhibitor AS is 10% of a polyolefine weight, and the addition of fumaric acid is 20% of a polyolefine weight, the 3rd monomer styrene is 40% of an AS weight, initiator is 0.15% of a polyolefine weight, and temperature of reaction is 170～200 ℃, screw speed 80～100rpm.
(3) prepared antistatic resin 3, its melting index is 2.0g/10min, density is 0.885g/cm
3, surface resistivity is 10
9Ω/m
2
4, the preparation of antistatic resin 4
(1) cyclohexyl diisocyanate (HDI) and decyl alcohol react 2～3h and get the pre-reaction thing under 70～80 ℃ of conditions of temperature, and wherein (NCO) the hydroxyl mole ratio in mole number and the decyl alcohol is 2 to the isocyanate group in the cyclohexyl diisocyanate (HDI).Be that 1000 end aminocarbonyl phenyl polypropylene glycol is 1.5 proportioning at 120～150 ℃ of reaction 5～10min down in molar ratio then with pre-reaction thing and molecular weight, make static inhibitor AS.
(2) with static inhibitor (AS), methacrylic acid and the 3rd monomer styrene under the effect of peroxide acetic acid butyl ester (TBPA) initiator, in polyethylene (PE), make antistatic resin 4 by the twin screw melting graft reaction.Wherein, the addition of static inhibitor AS is 25% of a polyolefine weight, the addition of methacrylic acid is 30% of a polyolefine weight, the 3rd monomer styrene is 30% of an AS weight, the initiator peroxide acetic acid butyl ester is 0.2% of a polyolefine weight, temperature of reaction is 150～180 ℃, screw speed 50～80rpm.
(3) prepared antistatic resin 4, its melting index is 4.0g/10min, density is 0.930g/cm
3, surface resistivity is 10
8Ω/m
2
The preparation of embodiment 1 anti-static polyolefin air-permeable envelope
(1) in high-speed mixer lime carbonate (particle diameter is 5.0 μ m) is carried out the surface-coated processing with the surface-modifying agent stearic acid and obtain coated calcium carbonate, the consumption of surface-modifying agent is 2.0% (weight percent) of lime carbonate total amount.Treatment process condition is: rotating speed is 3000r/min, and treatment temp is respectively 100 ℃, and the treatment time is 45min.
(2) according to the weight ratio shown in the table 1, with 50 weight part linear low density polyethylenes of ethene and hexene (C6) copolymerization, its melting index is 1.0g/10min, and density is 0.915g/cm
3, molecular weight distribution is 3; The high-pressure polyethylene of 20 weight parts, melting index are 2.0g/10min, and density is 0.920g/cm
3The antistatic resin 1 of 30 weight parts; 100 weight parts (wherein contain 0.3 weight part oxidation inhibitor four [β-(3 through the lime carbonate of coating processing and the oxidation inhibitor of 0.4 weight part, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] three (2.4-di-tert-butyl-phenyl) phosphorous acid esters (IGANOX168) of pentaerythritol ester (IGANOX 1010) and 0.1 weight part) mix in high-speed mixer, obtain the plastic cement particle by the parallel double-screw extruder extruding pelletization.Wherein, screw slenderness ratio is 40, and processing temperature is 170～190 ℃.
(3) the plastic cement particle that will make is sent into the inflation film manufacturing machine of single screw rod, blow film forming down in 190～230 ℃ extrusion temperatures, film is made the anti-static polyolefin air-permeable envelope through 2.0 times of uniaxial extensions, and wherein draft temperature is 80 ℃, carry out relevant performance test with made air-permeable envelope, the results are shown in Table 1.
Embodiment 2
(1) in high-speed mixer lime carbonate (particle diameter is 0.5 μ m) is carried out the surface-coated processing with surface-modifying agent sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester and obtain coated calcium carbonate, the consumption of surface-modifying agent is 1.5% (weight percent) of lime carbonate total amount.Treatment process condition is: rotating speed is 3000r/min, and treatment temp is respectively 90 ℃, and the treatment time is 30min.
(2) according to the weight ratio shown in the table 1, with 60 weight part linear low density polyethylenes of ethene and butylene (C4) copolymerization, its melting index is 4.0g/10min, and density is 0.940g/cm
3, molecular weight distribution is 15; The high-pressure polyethylene of 10 weight parts, melting index are 20.0g/10min, and density is 0.900g/cm
3The antistatic resin 2 of 50 weight parts; 100 weight parts (wherein contain 0.5 weight part oxidation inhibitor four [β-(3 through the lime carbonate of coating processing and the oxidation inhibitor of 0.8 weight part, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] three (2.4-di-tert-butyl-phenyl) phosphorous acid esters (IGANOX168) of pentaerythritol ester (IGANOX 1010) and 0.3 weight part) mix in high-speed mixer, obtain the plastic cement particle by the parallel double-screw extruder extruding pelletization.Wherein, screw slenderness ratio is 42, and processing temperature is 160～180 ℃.
(3) the plastic cement particle that will make is sent into the casting machine of single screw rod, casting film-forming under 190～230 ℃ extrusion temperature, film is made the anti-static polyolefin air-permeable envelope for 1.0 times through uniaxial extension, and wherein draft temperature is 80 ℃, carry out relevant performance test with made air-permeable envelope, the results are shown in Table 1.
Embodiment 3
(1) in high-speed mixer lime carbonate (particle diameter is 5.0 μ m) is carried out the surface-coated processing with surface-modifying agent sec.-propyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanic acid ester and obtain coated calcium carbonate, the consumption of surface-modifying agent is 0.5% (weight percent) of lime carbonate total amount.Treatment process condition is: rotating speed is 1500r/min, and treatment temp is respectively 130 ℃, and the treatment time is 10min.
(2) according to the weight ratio shown in the table 1, with 30 weight part linear low density polyethylenes of ethene and octene (C8) copolymerization, its melting index is 3.0g/10min, and density is 0.890g/cm
3, molecular weight distribution is 12; The high-pressure polyethylene of 40 weight parts, melting index are 2.0g/10min, and density is 0.915g/cm
3The antistatic resin 3 of 60 weight parts; 140 weight parts (wherein contain 0.4 weight part oxidation inhibitor four [β-(3 through the lime carbonate of coating processing and the oxidation inhibitor of 0.8 weight part, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] three (2.4-di-tert-butyl-phenyl) phosphorous acid ester (IGANOX 168) of pentaerythritol ester (IGANOX 1010) and 0.4 weight part) mix in high-speed mixer, obtain the plastic cement particle by the parallel double-screw extruder extruding pelletization.Wherein, screw slenderness ratio is 50, and processing temperature is 170～190 ℃.
(3) the plastic cement particle that will make is sent into the inflation film manufacturing machine of single screw rod, blow film forming down in 190～220 ℃ extrusion temperatures, film is made the anti-static polyolefin air-permeable envelope through 3.5 times of uniaxial extensions, and wherein draft temperature is 90 ℃, carry out relevant performance test with made air-permeable envelope, the results are shown in Table 1.
Embodiment 4
(1) at first use surface-modifying agent isopropoxy two (octadecane oxygen base) aluminium in high-speed mixer lime carbonate (particle diameter is 4.0 μ m) to be carried out the surface-coated processing and obtain coated calcium carbonate, the consumption of surface-modifying agent is 0.8% (weight percent) of lime carbonate total amount.Treatment process condition is: rotating speed is 2000r/min, and treatment temp is respectively 100 ℃, and the treatment time is 20min.
(2) according to the weight ratio shown in the table 1, with 50 weight part linear low density polyethylenes of ethene and octene (C8) copolymerization, its melting index is 3.0g/10min, and density is 0.905g/cm
3, molecular weight distribution is 8; The high-pressure polyethylene of 10 weight parts, melting index are 4.0g/10min, and density is 0.910g/cm
3The antistatic resin 4 of 40 weight parts; 180 weight parts (wherein contain 0.6 weight part oxidation inhibitor four [β-(3 through the lime carbonate of coating processing and the oxidation inhibitor of 1.0 weight parts, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] three (2.4-di-tert-butyl-phenyl) phosphorous acid ester (IGANOX 168) of pentaerythritol ester (IGANOX 1010) and 0.4 weight part) mix in high-speed mixer, obtain the plastic cement particle by the parallel double-screw extruder extruding pelletization.Wherein, screw slenderness ratio is 44, and processing temperature is 190～220 ℃.
(3) the plastic cement particle that will make is sent into the casting machine of single screw rod, blow film forming down in 200～230 ℃ extrusion temperatures, film is made the anti-static polyolefin air-permeable envelope through 1.5 times of uniaxial extensions, and wherein draft temperature is 90 ℃, carry out relevant performance test with made air-permeable envelope, the results are shown in Table 1.
Comparative example 1
(1) in high-speed mixer lime carbonate (particle diameter is 5.0 μ m) is carried out the surface-coated processing with the surface-modifying agent stearic acid and obtain coated calcium carbonate, the consumption of surface-modifying agent is 1.0% (weight percent) of lime carbonate total amount.Treatment process condition is: rotating speed is 3000r/min, and treatment temp is respectively 95 ℃, and the treatment time is 30min.
(2) according to the weight ratio shown in the table 1, with 80 weight part linear low density polyethylenes of ethene and hexene (C6) copolymerization, its melting index is 1.5g/10min, and density is 0.915g/cm
3, molecular weight distribution is 4; The high-pressure polyethylene of 20 weight parts, melting index are 2.0g/10min, and density is 0.910g/cm
3The nonionic organic antistatic agents compound of the lime carbonate through coating processing of 100 weight parts, 2.0 weight parts (glycerol monostearate GMS and ethoxyquin alkanamine mass ratio are 2: 1) (wherein contains 0.3 weight part oxidation inhibitor four [β-(3 with the oxidation inhibitor of 0.4 weight part, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] three (2.4-di-tert-butyl-phenyl) phosphorous acid esters (IGANOX168) of pentaerythritol ester (IGANOX 1010) and 0.1 weight part) mix in high-speed mixer, obtain the plastic cement particle by the parallel double-screw extruder extruding pelletization.Wherein, screw slenderness ratio is 40, and processing temperature is 170～190 ℃.
(3) the plastic cement particle that will make is sent into the inflation film manufacturing machine of single screw rod, blow film forming down in 190～230 ℃ extrusion temperatures, film is made the anti-static polyolefin air-permeable envelope through 2.0 times of uniaxial extensions, and wherein draft temperature is 80 ℃, carry out relevant performance test with made air-permeable envelope, the results are shown in Table 1.
Comparative example 2
(1) in high-speed mixer lime carbonate (particle diameter is 0.5 μ m) is carried out the surface-coated processing with surface-modifying agent sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester and obtain coated calcium carbonate, the consumption of surface-modifying agent is 1.0% (weight percent) of lime carbonate total amount.Treatment process condition is: rotating speed is 3000r/min, and treatment temp is respectively 105 ℃, and the treatment time is 30min.
(2) according to the weight ratio shown in the table 1, with 90 weight part linear low density polyethylenes of ethene and hexene (C6) copolymerization, its melting index is 3.5g/10min, and density is 0.915g/cm
3, molecular weight distribution is 8; The high-pressure polyethylene of 10 weight parts, melting index are 3.0g/10min, and density is 0.915g/cm
3The nonionic organic antistatic agents compound of the lime carbonate through coating processing of 100 weight parts, 1.5 weight parts (glycerol monostearate GMS and ethoxyquin alkanamine mass ratio are 2: 1) (wherein contains 0.5 weight part oxidation inhibitor four [β-(3 with the oxidation inhibitor of 0.8 weight part, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] three (2.4-di-tert-butyl-phenyl) phosphorous acid esters (IGANOX168) of pentaerythritol ester (IGANOX 1010) and 0.3 weight part) mix in high-speed mixer, obtain the plastic cement particle by the parallel double-screw extruder extruding pelletization.Wherein, screw slenderness ratio is 42, and processing temperature is 160～180 ℃.
(3) the plastic cement particle that will make is sent into the casting machine of single screw rod, casting film-forming under 190～230 ℃ extrusion temperature, film is made the anti-static polyolefin air-permeable envelope for 2.0 times through uniaxial extension, and wherein draft temperature is 80 ℃, carry out relevant performance test with made air-permeable envelope, the results are shown in Table 1.
Comparative example 3
(1) in high-speed mixer lime carbonate (particle diameter is 0.5 μ m) is carried out the surface-coated processing with surface-modifying agent sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester and obtain coated calcium carbonate, the consumption of surface-modifying agent is 1.0% (weight percent) of lime carbonate total amount.Treatment process condition is: rotating speed is 3000r/min, and treatment temp is respectively 105 ℃, and the treatment time is 30min.
(2) according to the weight ratio shown in the table 1, with 90 weight part linear low density polyethylenes of ethene and hexene (C6) copolymerization, its melting index is 3.5g/10min, and density is 0.915g/cm
3, molecular weight distribution is 8; The high-pressure polyethylene of 10 weight parts, melting index are 3.0g/10min, and density is 0.915g/cm
3The oxidation inhibitor of the lime carbonate through coating processing of 100 weight parts, the conductive carbon black of 50 weight parts and 0.8 weight part (wherein contains 0.5 weight part oxidation inhibitor four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] three (2.4-di-tert-butyl-phenyl) phosphorous acid esters (IGANOX168) of pentaerythritol ester (IGANOX 1010) and 0.3 weight part) mix in high-speed mixer, obtain the plastic cement particle by the parallel double-screw extruder extruding pelletization.Wherein, screw slenderness ratio is 42, and processing temperature is 160～180 ℃.
(3) the plastic cement particle that will make is sent into the casting machine of single screw rod, casting film-forming under 190～230 ℃ extrusion temperature, film is made the anti-static polyolefin air-permeable envelope for 2.0 times through uniaxial extension, and wherein draft temperature is 80 ℃, carry out relevant performance test with made air-permeable envelope, the results are shown in Table 1.
Table 1
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. anti-static polyolefin air-permeable envelope composition, it is characterized in that: described anti-static polyolefin air-permeable envelope composition comprises following component:
The linear low density polyethylene of (1) 30～60 weight part, its melting index are 1.0～4.0g/10min, and density is 0.890～0.940g/cm
3, range of molecular weight distributions is 3～15;
The high-pressure polyethylene of (2) 10～40 weight parts, its melting index are 2.0～20.0g/10min, and density is 0.900～0.920g/cm
3
The antistatic resin of (3) 30～60 weight parts, its melting index are 2.0～4.0g/10min, and density is 0.885～0.930g/cm
3, surface resistivity is 10
7～10
9Ω/m
2
The lime carbonate of (4) 100～180 weight parts, its particle diameter are 0.5～5.0 μ m;
The oxidation inhibitor of (5) 0.4～1.0 weight parts;
Described oxidation inhibitor is any in phenolic antioxidant, phosphite ester kind antioxidant or the phenolic antioxidant+phosphite ester kind antioxidant.
2. a kind of anti-static polyolefin air-permeable envelope composition according to claim 1, it is characterized in that: described linear low density polyethylene is the multipolymer of the 'alpha '-olefin monomers of ethene and at least a C4～C8.
3. a kind of anti-static polyolefin air-permeable envelope composition according to claim 1, it is characterized in that: described antistatic resin be with static inhibitor, the unsaturated monomer that contains carboxyl and vinylbenzene under the initiator effect, in polyolefine, get by the twin screw melting graft reaction; Wherein, the addition of static inhibitor is 10～30% of a polyolefine weight, the addition that contains the unsaturated monomer of carboxyl is 5～30% of a polyolefine weight, vinylbenzene is 20～40% of static inhibitor weight, initiator is 0.2～0.5% of a polyolefine weight, temperature of reaction is 150～200 ℃, screw speed 50～100rpm;
Described static inhibitor is to make by the following method: vulcabond and Fatty Alcohol(C12-C14 and C12-C18) are reacted 2～4h get the pre-reaction thing under 60～80 ℃ of conditions of temperature, then pre-reaction thing and end amine based polymer are reacted 5～10min down at 120～180 ℃, make static inhibitor; Wherein isocyanate group mole number in the vulcabond and the hydroxyl mole ratio in the Fatty Alcohol(C12-C14 and C12-C18) are 2, and the mol ratio of end amino polymer and pre-reaction thing is not less than 1;
The described unsaturated monomer that contains carboxyl comprises methacrylic acid, vinylformic acid, maleic anhydride, fumaric acid, methylene-succinic acid or glycidyl methacrylate;
Described initiator comprises ditertiary butyl peroxide, two (3,5, the 5-trimethyl acetyl) superoxide, dilauroyl peroxide, dibenzoyl peroxide, peroxidation neodecanoic acid isopropyl benzene ester, new peroxide tert-butyl caprate, the special pentyl ester of peroxidation trimethylacetic acid, the peroxidation trimethylacetic acid tert-butyl ester, the special pentyl ester of peroxidation-2 ethyl hexanoic acid, peroxide-2-ethyl hexanoic acid tert-butyl, the tert-butyl hydroperoxide isobutyrate, tert-butyl hydroperoxide-3,5,5-tri-methyl hexanoic acid ester, peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, 1,1-di-tert-butyl peroxide-3,3, the 5-trimethyl-cyclohexane, 1, the 1-cyclohexane di-tert-butyl peroxide, 2,2-two (tert-butyl hydroperoxide) butane, two (4-tert-butylcyclohexyl) peroxy dicarbonate, two (2-ethylhexyl) peroxy dicarbonate, peroxy dicarbonate two hexadecyl esters, peroxy dicarbonate 24 esters, two tertiary amyl superoxide, dicumyl peroxide, two (tert-butyl hydroperoxide sec.-propyl) benzene, 2,5-dimethyl-2, the 5-di-t-butyl hexane peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexin, diisopropylbenzenehydroperoxide, isopropyl benzene hydroperoxide, the tertiary amyl hydrogen peroxide, tertbutyl peroxide, t-tutyl cumyl peroxide, diisopropylbenzenehydroperoxide, p-menthane hydroperoxide, peroxidation carbonic acid-2 ethyl hexanoic acid the tert-butyl ester, tert-butyl hydroperoxide carbonic acid-2-ethylhexyl, two (2, the 4-dichloro-benzoyl) superoxide, 4,4-two (tert-butyl hydroperoxide) n-butyl pentanoate, methylethyl ketone peroxide or peroxidation hexanaphthene;
Described polyolefine is a kind of in polypropylene, polyethylene, ethylene propylene copolymer or the thermoplastic elastomer.
4. a kind of anti-static polyolefin air-permeable envelope composition according to claim 3, it is characterized in that: described vulcabond comprises '-diphenylmethane diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, dicyclohexyl methane diisocyanate, Methylcyclohexyl diisocyanate, xylylene diisocyanate or naphthalene-1, the 5-vulcabond; The carbon atom number range of described Fatty Alcohol(C12-C14 and C12-C18) is 10～20; Described end amino polymer comprises Amino Terminated polyether(ATPE), the amino polyoxyethylene glycol of end or end aminophenyl polypropylene glycol, and its weight-average molecular weight is 1000～4000.
5. a kind of anti-static polyolefin air-permeable envelope composition according to claim 1 is characterized in that:
Described lime carbonate carries out following surface-coated earlier to be handled: lime carbonate and surface-modifying agent are placed high-speed mixer, surface-modifying agent carries out surface-coated to lime carbonate to be handled, described surface-modifying agent weight is 0.5～2.0% of weight of calcium carbonate, described surface-coated treatment process condition is as follows: rotating speed is 1500～3000r/min, treatment temp is 90～130 ℃, and the treatment time is 10～45min;
Described surface-modifying agent comprises lipid acid, titanic acid ester or aluminic acid ester; Described lipid acid comprises stearic acid, lauric acid, palmitinic acid or the acid of nutmeg beans; Described titanic acid ester comprises sec.-propyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanic acid ester, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, sec.-propyl three oleic acid acyloxy titanic acid ester, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester, three hard ester acid isopropyl titanates, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate or tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester; Described aluminic acid ester comprises isopropoxy two (octadecane oxygen base) aluminium, isopropoxy two oily acyloxy two (diethylamine) aluminium, isopropoxy two (diisooctyl phosphoric acid acyloxy) aluminium, isopropoxy two (p-isopropyl phenoxy group) aluminium, isopropoxy two (dodecyl tosyloxy) aluminium, isopropoxy two (maleic acid list Virahol ester acyloxy) aluminium, two (glycerine two oleum lini acid esters list hydroxyl oxygen bases) aluminium or isopropoxy oil acyloxy octadecane oxygen base aluminium.
6. a kind of anti-static polyolefin air-permeable envelope composition according to claim 1, it is characterized in that: described phenolic antioxidant comprises 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) triketone, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester or four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Described phosphite ester kind antioxidant comprises three (2.4-di-tert-butyl-phenyl) phosphorous acid esters or two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
7. a kind of anti-static polyolefin air-permeable envelope composition according to claim 1, it is characterized in that: phenolic antioxidant in described phenolic antioxidant+phosphite ester kind antioxidant: the mass ratio of phosphite ester kind antioxidant is 1: 1～2: 1.
8. with the method for the described anti-static polyolefin air-permeable envelope of claim 1 preparation of compositions anti-static polyolefin air-permeable envelope, it is characterized in that comprising the steps:
(1) with the linear low density polyethylene of 30～60 weight parts, its melting index is 1.0～4.0g/10min, and density is 0.890～0.940g/cm
3, range of molecular weight distributions is 3～15; The high-pressure polyethylene of 10～40 weight parts, its melting index are 2.0～20.0g/10min, and density is 0.900～0.920g/cm
3The antistatic resin of 30～60 weight parts, its melting index are 2.0～4.0g/10min, and density is 0.885～0.930g/cm
3, surface resistivity is 10
7～10
9Ω/m
2The lime carbonate of 100～180 weight parts, its particle diameter are 0.5～5.0 μ m; 0.4 the oxidation inhibitor of～1.0 weight parts mixes in high-speed mixer, and obtains the plastic cement particle by the parallel double-screw extruder extruding pelletization, described screw slenderness ratio is 40～50, and processing temperature is 160～220 ℃;
(2) the prepared plastic cement particle of step (1) is sent into the casting machine of single-bolt type or film that inflation film manufacturing machine makes through 1.5～3.5 times of uniaxial extensions, draft temperature is 80～90 ℃, makes the anti-static polyolefin air-permeable envelope.
9. the method for preparing the anti-static polyolefin air-permeable envelope according to claim 8 is characterized in that: prepared its water vapour permeability of anti-static polyolefin air-permeable envelope is not less than 2000g/m
224h, the surface resistivity of air-permeable envelope is not higher than 10
9Ω/m
2
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