CN113754949A - Barrier master batch for preparing polyethylene film and preparation method thereof - Google Patents
Barrier master batch for preparing polyethylene film and preparation method thereof Download PDFInfo
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- CN113754949A CN113754949A CN202111211879.0A CN202111211879A CN113754949A CN 113754949 A CN113754949 A CN 113754949A CN 202111211879 A CN202111211879 A CN 202111211879A CN 113754949 A CN113754949 A CN 113754949A
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- 230000004888 barrier function Effects 0.000 title claims abstract description 53
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 31
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 31
- -1 polyethylene Polymers 0.000 title claims abstract description 31
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 72
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 44
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 44
- 241001330002 Bambuseae Species 0.000 claims abstract description 44
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 44
- 239000011425 bamboo Substances 0.000 claims abstract description 44
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003610 charcoal Substances 0.000 claims abstract description 37
- 239000000835 fiber Substances 0.000 claims abstract description 37
- 229910052582 BN Inorganic materials 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 33
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 33
- 239000002135 nanosheet Substances 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 239000003208 petroleum Substances 0.000 claims description 16
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 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 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J2323/06—Polyethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08J2457/00—Characterised by the use of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08J2457/02—Copolymers of mineral oil hydrocarbons
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
- C08K2201/011—Nanostructured additives
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a barrier master batch for preparing a polyethylene film, which is prepared from the following raw materials in parts by weight: 100 parts of carrier resin, 3-15 parts of compatilizer, 10-20 parts of blocking filler, 0.5-3 parts of lubricant and 0.1-0.5 part of antioxidant, wherein the blocking filler is formed by compounding boron nitride modified bamboo charcoal fiber, nano titanium nitride and nano silicon dioxide according to the mass ratio of 10:1-2: 1. Compared with the prior art, the barrier master batch disclosed by the invention is simple in preparation process, is used in the processing of the polyethylene-based film material, is beneficial to improving the stability of the film material in molding and processing, can effectively improve the barrier property of the film material to water vapor and oxygen, endows the polyethylene film product with high economic added value, prolongs the service life of the product, saves raw materials and has good economic benefit.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a barrier master batch for preparing a polyethylene film and a preparation method thereof.
Background
People have higher and higher requirements on food packaging, and ordinary packaging materials are difficult to meet the requirements. With the continuous development of science and technology, the research on food preservation methods is also deepened, wherein the film material becomes a product widely used by people due to low cost and convenient use.
Among many film materials, polyethylene films made from polyethylene as a main raw material by casting using an extruder are increasingly popular among consumers because of their excellent overall properties. In general, a polyethylene film has characteristics of no odor, no toxicity, high safety, good heat sealability, etc., and has good printing properties and a relatively low price, and thus is widely used in fields such as packaging, decoration, packaging, etc. However, the barrier property of the polyethylene film to water vapor and oxygen is not ideal enough, and in the actual use process, along with the prolonging of the use time, the barrier property to water vapor and oxygen can be obviously reduced, which also greatly restricts the popularization and application of the polyethylene film.
Therefore, the development of the barrier master batch which is beneficial to obviously improving the water vapor and oxygen barrier property of the polyethylene film is particularly important for the modification processing of the existing polyethylene film, and the barrier master batch can endow the polyethylene film product with high economic added value, prolong the service life of the product and save raw materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a barrier master batch which has good compatibility with polyethylene, has excellent barrier property to water vapor and oxygen and is suitable for industrial mass production.
The invention also aims to provide a preparation method of the barrier master batch.
The purpose of the invention can be realized by the following technical scheme:
according to one aspect of the invention, the barrier master batch for preparing the polyethylene film is prepared from the following raw materials in parts by weight: 100 parts of carrier resin, 3-15 parts of compatilizer, 10-20 parts of barrier filler, 0.5-3 parts of lubricant and 0.1-0.5 part of antioxidant.
In one embodiment, the carrier resin is a blend of a linear low density polyethylene resin and a hydrogenated petroleum resin in a mass ratio of 2 to 5:8 to 5.
As an embodiment, the linear low density polyethylene resin may be selected from ULTZEX 1520L of premann, japan.
In one embodiment, the hydrogenated petroleum resin is a C5 hydrogenated petroleum resin, selected from the group consisting of the blue hydrogenated C5 petroleum resin LH 100-1.
In one embodiment, the compatibilizer is a linear low density polyethylene resin grafted glycidyl methacrylate with a grafting ratio of 1.10 to 1.35%.
As an embodiment, the linear low density polyethylene resin grafted glycidyl methacrylate (i.e. LLDPE-g-GMA) is prepared by the following method: the linear low-density polyethylene resin, glycidyl methacrylate, styrene and dibenzoyl peroxide are uniformly mixed according to the mass ratio of 100:1.5-4:0.5-2:0.01-0.04, then the mixture is led into a double-screw extruder to react for 10-15min at the temperature of 140 ℃ and 180 ℃, and then the mixture is extruded and granulated to obtain LLDPE-g-GMA.
As an implementation scheme, the blocking filler is formed by compounding boron nitride modified bamboo charcoal fibers, nano titanium nitride and nano silicon dioxide according to the mass ratio of 10:1-3: 1.
As an embodiment, the preparation method of the boron nitride modified bamboo charcoal fiber comprises the following steps:
step 1: adding boron nitride nanosheets and urea into 4-hydroxybutylamine, performing ultrasonic dispersion for 30min, then reacting for 12h at the temperature of 145-160 ℃, filtering after the reaction is finished, washing the solution to be neutral by absolute ethyl alcohol, and performing vacuum drying to obtain activated boron nitride nanosheets;
step 2: crushing the bamboo charcoal fiber, sieving with a 500-mesh sieve to obtain bamboo charcoal fiber powder, adding the activated boron nitride nanosheet and the silane coupling agent into absolute ethyl alcohol, adjusting the pH of the solution to 5.5, adding the bamboo charcoal fiber powder while stirring, performing ultrasonic treatment at 70 ℃ for 2-5h, cooling, filtering, washing, and drying to constant weight to obtain the boron nitride modified bamboo charcoal fiber.
As an embodiment, the mass ratio of the boron nitride nanosheets, urea and 4-hydroxybutylamine in step 1 is 1:1.5-3: 5-8.
As an embodiment, in the step 2, 1-4g of activated boron nitride nanosheet, 0.01-0.1g of silane coupling agent and 10-30g of bamboo charcoal fiber powder are added to every 100mL of anhydrous ethanol.
In one embodiment, the silane coupling agent may be selected from at least one of 3- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltris (. beta. -methoxyethoxy) silane, vinyltrimethoxysilane, or vinyltriethoxysilane.
As an embodiment, the lubricant is formed by mixing calcium stearate and zinc stearate according to the mass ratio of 2-4: 1.
As an embodiment, the antioxidant is prepared by mixing a commercially available antioxidant 168 and an antioxidant 1010 according to a mass ratio of 1: 1-4.
According to another aspect of the invention, the preparation method of the barrier master batch for preparing the polyethylene film is provided, namely, the carrier resin, the compatilizer, the barrier filler, the lubricant and the antioxidant are uniformly mixed according to the parts by weight, banburying is carried out for 10-20min at the temperature of 130-140 ℃, tabletting and granulating are carried out, and then extrusion granulation is carried out by a double-screw extruder, so that the barrier master batch is prepared.
As an embodiment, the heating temperature of each section of the twin-screw extruder is 110 ℃ in the first section, 125 ℃ in the second section, 135 ℃ in the third section, 140 ℃ in the fourth section and 130 ℃ in the fifth section.
As an embodiment, the length-diameter ratio of the double-screw extruder is 30-40, and the screw rotating speed is 30-40 r/min.
Compared with the prior art, the invention has the following characteristics:
1) the barrier master batch of the invention uses the linear low density polyethylene resin and the hydrogenated petroleum resin to be compounded as the carrier resin, wherein the linear low density polyethylene resin has good mechanical property and outstanding film forming processability, the hydrogenated petroleum resin has excellent tackifying property and better compatibility with the linear low density polyethylene resin, the compounding of the linear low density polyethylene resin and the hydrogenated petroleum resin is favorable for improving the forming stability, flexibility and transparency of a material system, in addition, in order to further enhance the compatibility between the linear low density polyethylene resin and the hydrogenated petroleum resin, the LLDPE-g-GMA is used as a compatilizer, the styrene is introduced in the synthesis process and is favorable for improving the reaction activity of the LLDPE, in the reaction, the styrene is preferentially jointed to the LLDPE to form a styrene macromolecular free radical which then further generates a grafting reaction with the GMA, and the styrene macromolecular free radical is more stable than a pure LLDPE macromolecular free radical, the styrene-grafted polyethylene-GMA-modified low-density polyethylene resin has high reactivity with GMA, can effectively inhibit the crosslinking of LLDPE, can effectively improve the grafting rate of the final LLDPE-g-GMA by adding styrene, and can further enhance the compatibility between the linear low-density polyethylene resin and the hydrogenated petroleum resin in the carrier resin, so that the linear low-density polyethylene resin and the hydrogenated petroleum resin can be fused together in a better form, and the stability of molding processing is ensured;
2) in order to improve the barrier property of a material system, the invention adopts the barrier filler compounded by boron nitride modified bamboo carbon fiber, nano titanium nitride and nano silicon dioxide, wherein the boron nitride modified bamboo carbon fiber is prepared by combining aminated boron nitride nanosheets to the surface of bamboo carbon fiber powder through a silane coupling agent, the boron nitride nanosheets have good layered structures and are combined with the bamboo carbon fiber to form intricate and complex tortuous paths in matrix resin, so that the permeation path of permeation molecules can be effectively prolonged, the diffusion of the permeation molecules in the matrix resin is prevented, and good water vapor and oxygen barrier properties are realized, in addition, the compatibility between the bamboo carbon fiber and carrier resin is obviously improved after the surface of the bamboo carbon fiber is activated by the silane coupling agent, and the nano titanium nitride and the nano silicon dioxide compounded with the bamboo carbon fiber can be filled in the layered structure formed by the boron nitride nanosheets, the filler chromatography phenomenon in the processing process can be prevented, and the filler chromatography phenomenon and the bamboo charcoal fiber can play a synergistic effect together to enhance the mechanical strength of the matrix resin, absorb and disperse the stress in the matrix resin in time and endow the matrix resin with good crack resistance;
3) the barrier master batch disclosed by the invention is simple in preparation process, is used in processing of a polyethylene-based film material, is beneficial to improving the stability of the film material in molding and processing, can effectively improve the barrier property of the film material to water vapor and oxygen, endows the polyethylene film product with high economic added value, prolongs the service life of the product, saves raw materials, is suitable for industrial mass production, and has good economic benefit.
Detailed Description
The barrier master batch uses the linear low-density polyethylene resin and the hydrogenated petroleum resin to be compounded as the carrier resin, wherein the linear low-density polyethylene resin has good mechanical property and outstanding film forming processability, the hydrogenated petroleum resin has excellent tackifying property and good compatibility with the linear low-density polyethylene resin, the compounding of the linear low-density polyethylene resin and the hydrogenated petroleum resin is favorable for improving the forming stability, flexibility and transparency of a material system, and LLDPE-g-GMA is used as a compatilizer to enhance the compatibility between the linear low-density polyethylene resin and the hydrogenated petroleum resin in the carrier resin, so that the linear low-density polyethylene resin and the hydrogenated petroleum resin can be fused together in a better form, and the stability of forming processing is ensured; in addition, in order to improve the barrier property of the material system, the barrier filler compounded by boron nitride modified bamboo charcoal fiber, nano titanium nitride and nano silicon dioxide is adopted, wherein the boron nitride modified bamboo charcoal fiber can form an intricate and complex tortuous path in the matrix resin, thereby effectively prolonging the permeation path of permeation molecules and preventing the diffusion of the permeation molecules in the matrix resin, thereby realizing good water vapor and oxygen barrier property, the nano titanium nitride and the nano silicon dioxide compounded with the nano titanium nitride and the nano silicon dioxide can be filled in a lamellar structure formed by the boron nitride nanosheets, not only is beneficial to preventing the occurrence of the chromatography phenomenon of the filler in the processing process, but also can play a role of synergy together with the bamboo charcoal fiber, so as to enhance the mechanical strength of the matrix resin, absorb and disperse the stress in the matrix resin in time and endow the matrix resin with good crack resistance.
Based on this, the present invention has been completed.
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed embodiment and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention.
As used herein, the term "about" when used to modify a numerical value means within + -5% of the error margin measured for that value.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism. The present invention will be described in detail with reference to specific examples.
Specific examples 1 to 5 are given below, wherein the components contained and their contents in parts by weight are shown in table 1 below.
Table 1 raw material components and their parts by weight
Item | Carrier resin | Compatilizer | Barrier filler | Lubricant agent | Antioxidant agent |
EXAMPLE 1 | 100 | 3 | 10 | 0.5 | 0.1 |
Example 2 | 100 | 6 | 12 | 1.0 | 0.3 |
Example 3 | 100 | 10 | 12 | 1.8 | 0.4 |
Example 4 | 100 | 12 | 16 | 2.5 | 0.5 |
Example 5 | 100 | 15 | 20 | 3.0 | 0.5 |
The carrier resins used in examples 1-5 above are shown in Table 2 below.
TABLE 2 Components in Carrier resin and parts by weight thereof
The compatibilizer used in examples 1 to 5 above was a linear low density polyethylene resin grafted glycidyl methacrylate prepared as follows:
the linear low-density polyethylene resin, glycidyl methacrylate, styrene and dibenzoyl peroxide are uniformly mixed according to the mass ratio of 100:1.5-4:0.5-2:0.01-0.04, then the mixture is introduced into a double-screw extruder to react for 10-15min at the temperature of 140 ℃ and 180 ℃, and then the mixture is extruded and granulated to obtain LLDPE-g-GMA.
In the preparation process of the LLDPE-g-GMA used in the embodiment 1, the linear low density polyethylene resin, the glycidyl methacrylate, the styrene and the dibenzoyl peroxide are reacted for 15min at 140 ℃ in a double screw extruder according to the mass ratio of 100: 1.5: 0.5: 0.01, and then the mixture is extruded and granulated; the resultant LLDPE-g-GMA had a grafting yield of about 1.10%.
In the preparation process of the LLDPE-g-GMA used in the embodiment 2, the linear low-density polyethylene resin, the glycidyl methacrylate, the styrene and the dibenzoyl peroxide are reacted for 15min at a mass ratio of 100:2:0.8:0.02 in a double-screw extruder at a temperature of about 156 ℃, and then the mixture is extruded and granulated to obtain the LLDPE-g-GMA; the resultant LLDPE-g-GMA had a grafting yield of about 1.18%.
For example 3, in the preparation process of the LLDPE-g-GMA used in the method, the linear low density polyethylene resin, the glycidyl methacrylate, the styrene and the dibenzoyl peroxide are reacted in a mass ratio of 100:2.6:1:0.02 in a twin-screw extruder at a temperature of about 162 ℃ for 10min, and then the mixture is extruded and granulated; the resultant LLDPE-g-GMA had a grafting yield of about 1.23%.
For example 4, in the preparation process of the LLDPE-g-GMA used in the method, the linear low density polyethylene resin, the glycidyl methacrylate, the styrene and the dibenzoyl peroxide are reacted in a mass ratio of 100:3.2:1.6:0.03 in a twin-screw extruder at about 170 ℃ for 15min, and then the mixture is extruded and granulated; the resultant LLDPE-g-GMA had a grafting yield of about 1.29%.
In the preparation process of the LLDPE-g-GMA used in the embodiment 5, the linear low-density polyethylene resin, the glycidyl methacrylate, the styrene and the dibenzoyl peroxide are reacted for 15min at the temperature of about 180 ℃ in a double-screw extruder according to the mass ratio of 100:4:2:0.04, and then the mixture is extruded and granulated; the resultant LLDPE-g-GMA had a grafting yield of about 1.35%.
The specific components and mass ratios of the barrier filler, lubricant and antioxidant used in examples 1-5 above are shown in Table 3 below.
TABLE 3 Components contained in functional auxiliary, lubricant, antioxidant and their mass ratios
The boron nitride modified bamboo charcoal fiber used in the above examples 1 to 5 was prepared by the following steps:
step 1: adding boron nitride nanosheets and urea into 4-hydroxybutylamine, performing ultrasonic dispersion for 30min, then reacting for 12h at the temperature of 145-160 ℃, filtering after the reaction is finished, washing the solution to be neutral by absolute ethyl alcohol, and performing vacuum drying to obtain activated boron nitride nanosheets;
step 2: crushing the bamboo charcoal fiber, sieving with a 500-mesh sieve to obtain bamboo charcoal fiber powder, adding the activated boron nitride nanosheet and the silane coupling agent into absolute ethyl alcohol, adjusting the pH of the solution to 5.5, adding the bamboo charcoal fiber powder while stirring, performing ultrasonic treatment at 70 ℃ for 2-5h, cooling, filtering, washing, and drying to constant weight to obtain the boron nitride modified bamboo charcoal fiber.
In the process of preparing the boron nitride modified bamboo charcoal fiber:
aiming at example 1, the mass ratio of the boron nitride nanosheet, the urea and the 4-hydroxybutylamine in step 1 is 1: 1.5: 5, the reaction temperature is about 145 ℃, and the reaction time is about 12 h; the silane coupling agent used in the step 2 is vinyl trimethoxy silane, 1g of activated boron nitride nanosheet, 0.01g of silane coupling agent and 10 g of bamboo charcoal fiber powder are added into every 100mL of absolute ethyl alcohol in terms of raw material dosage, and after the bamboo charcoal fiber powder is added, ultrasonic treatment is carried out for 5 hours at 70 ℃.
For example 2, the mass ratio of the boron nitride nanosheet, urea and 4-hydroxybutylamine in step 1 is 1:2:6, the reaction temperature is about 152 ℃, and the reaction time is about 12 hours; the silane coupling agent used in the step 2 is vinyl trimethoxy silane, 2g of activated boron nitride nanosheet, 0.03g of silane coupling agent and 15g of bamboo charcoal fiber powder are added into every 100mL of absolute ethyl alcohol in terms of raw material dosage, and after the bamboo charcoal fiber powder is added, ultrasonic treatment is carried out for 5 hours at 70 ℃.
For example 3, the mass ratio of the boron nitride nanosheet, urea and 4-hydroxybutylamine in step 1 is 1:2:5, the reaction temperature is about 155 ℃, and the reaction time is about 12 h; the silane coupling agent used in the step 2 is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 2.5g of activated boron nitride nanosheet, 0.05g of silane coupling agent and 20g of bamboo charcoal fiber powder are added into every 100mL of absolute ethyl alcohol in terms of raw material dosage, and after the bamboo charcoal fiber powder is added, ultrasonic treatment is carried out for 2 hours at 70 ℃.
For example 4, the mass ratio of the boron nitride nanosheet, urea and 4-hydroxybutylamine in step 1 is 1:2.5:6.5, the reaction temperature is about 158 ℃, and the reaction time is about 12 hours; the silane coupling agent used in the step 2 is vinyl tri (beta-methoxyethoxy) silane, 3.2g of activated boron nitride nanosheet, 0.08g of silane coupling agent and 24g of bamboo charcoal fiber powder are added into every 100mL of absolute ethyl alcohol in terms of the amount of raw materials, and after the bamboo charcoal fiber powder is added, ultrasonic treatment is carried out for 4 hours at 70 ℃.
For example 5, the mass ratio of the boron nitride nanosheet, urea and 4-hydroxybutylamine in step 1 is 1:3:8, the reaction temperature is about 160 ℃, and the reaction time is about 12 hours; the silane coupling agent used in the step 2 is vinyl triethoxysilane, and in terms of raw material usage, 4g of activated boron nitride nanosheet, 0.1g of silane coupling agent and 30g of bamboo charcoal fiber powder are added into each 100mL of absolute ethyl alcohol, and after the bamboo charcoal fiber powder is added, ultrasonic treatment is carried out for 4 hours at 70 ℃.
Based on the above examples 1-5, the following method can be used to prepare the barrier masterbatch: uniformly mixing the carrier resin, the compatilizer, the barrier filler, the lubricant and the antioxidant in parts by weight, banburying at the temperature of 130-140 ℃ for 10-20min, tabletting and granulating, and then extruding and granulating by a double-screw extruder to obtain the barrier master batch.
The process conditions used in examples 1-5 in the preparation of the barrier masterbatch described above are shown in table 4 below.
TABLE 4 Process conditions
Note: the twin-screw extruders used in examples 1 to 5 had a length to diameter ratio of 30 and a screw speed of 35r/min.
Comparative examples 1-3 are provided below with the following specific information:
comparative example 1:
this comparative example is the same as example 4 except that there is no compatibilizer.
Comparative example 2:
in this comparative example, the same procedure as in example 4 was repeated except that commercially available ordinary bamboo charcoal fiber powder was used instead of the boron nitride-modified bamboo charcoal fiber.
Comparative example 3:
the remainder of this comparative example was the same as example 4, with nano titanium nitride and nano silica being used as barrier fillers.
The barrier master batch prepared in the above examples 1-5 and comparative examples 1-3 was mixed with LDPE uniformly in an amount of 20% and added into a plastic extruder for casting to obtain a film. The temperature of each zone is 165, 175, 175, 180, 180, 180 and 180 ℃, the screw rotation speed is set to be 40r/min, and the winding speed is 3.3 r/min.
The prepared film was subjected to mechanical strength, oxygen transmission coefficient, and water vapor transmission rate tests, and the test results are shown in table 5 below.
TABLE 5 test results
The test results in table 5 show that the barrier master batch prepared by the invention is used in the forming processing of the polyethylene film, is beneficial to improving the mechanical strength of the film material, can effectively improve the barrier property of the film material to water vapor and oxygen, endows the polyethylene film with high economic added value, prolongs the service life of the product, saves raw materials, is suitable for industrial mass production, and has good economic benefit.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The barrier master batch for preparing the polyethylene film is characterized by being prepared from the following raw materials in parts by weight: 100 parts of carrier resin, 3-15 parts of compatilizer, 10-20 parts of barrier filler, 0.5-3 parts of lubricant and 0.1-0.5 part of antioxidant.
2. The barrier master batch for preparing the polyethylene film according to claim 1, wherein the carrier resin is prepared by mixing linear low-density polyethylene resin and hydrogenated petroleum resin according to the mass ratio of 2-5: 8-5.
3. The barrier masterbatch for polyethylene film according to claim 1, wherein the compatibilizer is linear low density polyethylene resin grafted glycidyl methacrylate, and the grafting ratio is 1.10-1.35%.
4. The barrier master batch for preparing the polyethylene film according to claim 3, wherein the preparation method of the linear low-density polyethylene resin grafted glycidyl methacrylate comprises the following steps: the linear low-density polyethylene resin, glycidyl methacrylate, styrene and dibenzoyl peroxide are uniformly mixed according to the mass ratio of 100:1.5-4:0.5-2:0.01-0.04, then the mixture is led into a double-screw extruder to react for 10-15min at the temperature of 140 ℃ and 180 ℃, and then the mixture is extruded and granulated to obtain LLDPE-g-GMA.
5. The barrier master batch for preparing the polyethylene film according to claim 1, wherein the barrier filler is prepared by compounding boron nitride modified bamboo charcoal fiber, nano titanium nitride and nano silicon dioxide according to the mass ratio of 10:1-3: 1.
6. The barrier master batch for preparing the polyethylene film according to claim 5, wherein the preparation method of the boron nitride modified bamboo charcoal fiber comprises the following steps:
step 1: adding boron nitride nanosheets and urea into 4-hydroxybutylamine, performing ultrasonic dispersion for 30min, then reacting for 12h at the temperature of 145-160 ℃, filtering after the reaction is finished, washing the solution to be neutral by absolute ethyl alcohol, and performing vacuum drying to obtain activated boron nitride nanosheets;
step 2: crushing the bamboo charcoal fiber, sieving with a 500-mesh sieve to obtain bamboo charcoal fiber powder, adding the activated boron nitride nanosheet and the silane coupling agent into absolute ethyl alcohol, adjusting the pH of the solution to 5.5, adding the bamboo charcoal fiber powder while stirring, performing ultrasonic treatment at 70 ℃ for 2-5h, cooling, filtering, washing, and drying to constant weight to obtain the boron nitride modified bamboo charcoal fiber.
7. The barrier master batch for preparing the polyethylene film according to claim 6, wherein the mass ratio of the boron nitride nanosheet, the urea and the 4-hydroxybutylamine in the step 1 is 1:1.5-3: 5-8.
8. The barrier master batch for preparing the polyethylene film according to claim 6, wherein 1-4g of the activated boron nitride nanosheet, 0.01-0.1g of the silane coupling agent and 10-30g of the bamboo charcoal fiber powder are added to every 100mL of anhydrous ethanol in the step 2.
9. The barrier master batch for preparing the polyethylene film according to claim 1, wherein the lubricant is prepared by mixing calcium stearate and zinc stearate according to a mass ratio of 2-4:1, and the antioxidant is prepared by mixing commercially available antioxidant 168 and antioxidant 1010 according to a mass ratio of 1: 1-4.
10. The method for preparing the barrier master batch for preparing the polyethylene film as claimed in any one of claims 1 to 9, wherein the barrier master batch is prepared by uniformly mixing the carrier resin, the compatilizer, the barrier filler, the lubricant and the antioxidant in parts by weight, banburying at 130-140 ℃ for 10-20min, tabletting and granulating, and extruding and granulating by a double-screw extruder.
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