CN110724333B - Linear low-density polyethylene additive master batch, preparation method and application thereof - Google Patents
Linear low-density polyethylene additive master batch, preparation method and application thereof Download PDFInfo
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- CN110724333B CN110724333B CN201810778663.4A CN201810778663A CN110724333B CN 110724333 B CN110724333 B CN 110724333B CN 201810778663 A CN201810778663 A CN 201810778663A CN 110724333 B CN110724333 B CN 110724333B
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- linear low
- density polyethylene
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- polyethylene additive
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- 229920000092 linear low density polyethylene Polymers 0.000 title claims abstract description 61
- 239000004707 linear low-density polyethylene Substances 0.000 title claims abstract description 61
- 239000004596 additive masterbatch Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000005469 granulation Methods 0.000 claims abstract description 14
- 230000003179 granulation Effects 0.000 claims abstract description 14
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000008262 pumice Substances 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 claims 1
- 239000004359 castor oil Substances 0.000 claims 1
- 235000019438 castor oil Nutrition 0.000 claims 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims 1
- -1 polyethylene Polymers 0.000 abstract description 20
- 239000004698 Polyethylene Substances 0.000 abstract description 14
- 229920000573 polyethylene Polymers 0.000 abstract description 14
- 230000003287 optical effect Effects 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 46
- 239000004594 Masterbatch (MB) Substances 0.000 description 25
- 239000012752 auxiliary agent Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920001973 fluoroelastomer Polymers 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000009459 flexible packaging Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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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
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- 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
- C08K3/346—Clay
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K5/20—Carboxylic acid amides
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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Abstract
The invention belongs to the field of polyethylene processing, and particularly relates to a linear low-density polyethylene additive master batch, and a preparation method and application thereof. The linear low-density polyethylene additive master batch is prepared from the following raw materials in parts by mass: 100 parts of LLDPE resin; 0.25-1.5 parts of antioxidant; 0.25-2.0 parts of slipping agent; 0.25-1.0 part of zinc stearate; 0.3-5.0 parts of opening agent; 0.25-2.0 parts of borate. The invention improves the processability of polyethylene and reduces the processing energy consumption, and the prepared film product has good optical performance. The preparation method is scientific, reasonable, simple and feasible. The invention also provides the application of the composition, and when the composition for blown film is prepared, the linear low-density polyethylene additive master batch is added into the base resin, and extrusion granulation is carried out, so that the composition product for blown film is prepared.
Description
Technical Field
The invention belongs to the field of polyethylene processing, and particularly relates to a linear low-density polyethylene additive master batch, and a preparation method and application thereof.
Background
Linear Low Density Polyethylene (LLDPE) is an important polyethylene resin, has wide application fields, and can be used in the fields of films, injection molding, rotational molding, cables and the like. Wherein the film is the largest field of application of LLDPE resin and accounts for more than 70% of the whole LLDPE resin.
Increasing the output per unit time during the production process is very important for film processing enterprises, but too high an extrusion speed may cause melt fracture, resulting in the occurrence of sharkskin on the film surface, thereby affecting the film appearance. The resin for the film, which is easy to process and convenient to extrude at high speed, is developed, so that the problems existing at present can be solved, the production efficiency of film enterprises is improved, and the energy consumption is reduced.
At present, in order to improve the processability of polymers, a fluoroelastomer is generally added into the polymers, the fluoroelastomer is attached to a screw in the extrusion process, and the friction between materials and the screw is reduced to improve the processability of the polymers. However, when fluoroelastomers are used as processing aids, the optical properties of the film article are affected.
Disclosure of Invention
The invention aims to provide a linear low-density polyethylene additive master batch, which improves the processability of polyethylene and reduces the processing energy consumption, and simultaneously, the prepared film product has good optical performance; the invention also provides a preparation method and application thereof.
The linear low-density polyethylene additive master batch is prepared from the following raw materials in parts by weight:
preferably, the linear low-density polyethylene additive master batch is prepared from the following raw materials in parts by weight:
more preferably, the antioxidant is 0.4-0.8 part by weight.
Wherein,
the LLDPE resin is a copolymer of ethylene and butene-1 or a copolymer of ethylene and hexene-1.
The density of the LLDPE resin is 0.91-0.92g/cm3The melt Mass Flow Rate (MFR) is from 2 to 10g/10 min.
The antioxidant is one or more of hindered phenol antioxidant, phosphite antioxidant or thioester antioxidant.
Preferably, the antioxidant is a hindered phenol antioxidant and a phosphite antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 1.
the slipping agent is erucamide.
Zinc stearate is used as an acid absorbent and also plays a role in internal lubrication. When stearate is uniformly distributed in polyethylene, the polymer begins to soften when the processing is heated, molecules of stearate penetrate into molecular chains of the polymer, mutual attraction among the molecular chains is weakened, and the molecular chains are easier to slide and rotate when the polymer is deformed.
The opening agent is one or more of calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, aluminum oxide, zinc oxide, talc, clay, kaolin, silicon oxide, hydrotalcite, diatomite, bentonite, mica, zeolite, glass powder, sepiolite, fly ash, rectorite or pumice.
The borate is organic borate containing nitrogen.
Borate esters are commonly used as coupling agents or surfactants in plastics. The nitrogen-containing organic boric acid ester, such as amino, amido, imido, imidazolinyl, oxazolinyl and the like, has nitrogen with lone pair electrons occupying an empty P track of a boron atom, reacts under the action of heat and shear during screw extrusion to generate boron nitride, coats the boron nitride on the screw to play a role in external lubrication, and is favorable for improving the processability of polyethylene.
The zinc stearate has an internal lubricating effect, the nitrogen-containing organic boric acid ester has an external lubricating effect, and when the mass ratio of the zinc stearate to the nitrogen-containing organic boric acid ester is 1: 1-1: 2, the two components have synergistic effect, so that the processability of the polyethylene can be better improved.
The preparation method of the linear low-density polyethylene additive master batch comprises the following steps:
(1) adding an opening agent into an ethanol solution of borate, heating and refluxing for 10-15min, evaporating the solvent, drying solid particles, and grinding into powder for later use;
(2) adding an antioxidant, zinc stearate, a slipping agent and the powder obtained in the step (1) into LLDPE resin powder, uniformly mixing, adding the uniformly mixed material into a double-screw extruder, and carrying out melting, plasticizing, extruding and granulating to obtain the linear low-density polyethylene additive master batch.
In the step (2), the mixing time is 5-10 min.
When the composition for blown film is prepared, the linear low-density polyethylene additive master batch is added into the base resin, and extrusion granulation is carried out, so as to obtain the composition product for blown film.
The addition amount of the linear low-density polyethylene additive master batch is 10 wt.% of the base resin.
The base resin is one or more of LLDPE, LDPE or HDPE.
The composition can be used for polyethylene packaging films.
In recent years, china has a very large consumption in the field of flexible packaging, and is expected to grow at a high rate of 6.9% in the next 5 years, with polyethylene film representing a large share in the field of flexible packaging. The processability of the resin directly affects the productivity of the film, and the transparency of the film directly affects the appearance of the package, both of which properties have been attracting attention.
Therefore, the transparent polyethylene film which is easy to process has huge market prospect.
The invention has the following beneficial effects:
1. the invention provides the easily-processed linear low-density polyethylene additive master batch, and the prepared film product has good optical performance while improving the processability of polyethylene and reducing the processing energy consumption.
2. The master batch provided by the invention is used for preparing a film product, can improve the extrusion speed and reduce the energy consumption of an extruder, so that the production cost is reduced, and meanwhile, compared with the common processing aid, namely the fluoroelastomer, the optical performance of the film is improved, and the comprehensive performance is improved.
3. The film product prepared by the master batch has high critical shear rate, low shear viscosity and film haze, and good processability and optical performance.
4. The master batch for the polyethylene film with excellent optical performance and processability is prepared by utilizing the synergistic effect of zinc stearate and nitrogenous organic borate through a two-step addition method.
5. The linear low-density polyethylene additive master batch is applied to the preparation of polyethylene compositions in the field of films, has lower shear viscosity, screw torque and higher critical shear rate compared with the existing polyethylene compositions, and can be extruded at higher speed in the production of films, thereby improving the production efficiency, solving the film breaking phenomenon and the sharkskin phenomenon on the surfaces of the films when the films are extruded and processed by resin at high speed, and simultaneously improving the optical performance of the films.
6. The preparation method provided by the invention is scientific, reasonable, simple and feasible.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The linear low-density polyethylene additive master batch is prepared from the following raw materials in parts by mass:
the preparation method comprises the following steps:
(1) adding talcum powder into ethanol solution of boric acid ester, heating and refluxing, evaporating solvent, drying solid particles, and grinding into powder for later use.
(2) Adding an antioxidant, zinc stearate, erucamide and the dry powder obtained in the step (1) into LLDPE powder resin, mixing for 10min in a high-speed stirrer, adding the uniformly mixed materials into a double-screw extruder, and melting, plasticizing, extruding and granulating to obtain the linear low-density polyethylene additive master batch.
The application of the linear low-density polyethylene additive master batch, namely the preparation method of the composition, is as follows:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) To this mixture, 10 parts of an auxiliary master batch was added, followed by granulation to obtain the composition of example 1.
Example 2
The linear low-density polyethylene additive master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) To this mixture was added 10 parts of an auxiliary master batch, followed by granulation to obtain the composition of example 2.
Example 3
The linear low-density polyethylene additive master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) To this mixture was added 10 parts of an auxiliary master batch, followed by granulation to obtain the composition of example 3.
Example 4
The linear low-density polyethylene additive master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) To this mixture was added 10 parts of an auxiliary master batch, followed by granulation to obtain the composition of example 4.
Comparative example 1
The auxiliary agent master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) The composition of comparative example 1 was prepared by adding 10 parts of the auxiliary master batch to the mixture and granulating the mixture.
Comparative example 2
The auxiliary agent master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) And 10 parts of an auxiliary master batch was added thereto, followed by granulation to obtain the composition of comparative example 2.
Comparative example 3
The auxiliary agent master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) And 10 parts of an auxiliary master batch was added thereto, followed by granulation to obtain the composition of comparative example 3.
Comparative example 4
The auxiliary agent master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) And 10 parts of an auxiliary master batch was added thereto, followed by granulation to obtain the composition of comparative example 4.
Comparative example 5
The auxiliary agent master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) And 10 parts of an auxiliary master batch was added thereto, followed by granulation to obtain the composition of comparative example 5.
Comparative example 6
The auxiliary agent master batch is prepared from the following raw materials in parts by mass:
the preparation method comprises the following steps:
adding 0.4 part of antioxidant, 0.3 part of zinc stearate, 0.5 part of erucamide, 1.0 part of talcum powder and 0.3 part of boric acid ester into 100 parts of LLDPE powder resin, mixing for 10min in a high-speed stirrer, adding the uniformly mixed materials into a double-screw extruder, and carrying out melting, plasticizing, extruding and granulating to obtain the linear low-density polyethylene additive master batch.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) And 10 parts of an auxiliary master batch was added thereto, followed by granulation to obtain the composition of comparative example 6.
Comparative example 7
The auxiliary agent master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) And 10 parts of an auxiliary master batch was added thereto, followed by granulation to obtain the composition of comparative example 7.
Comparative example 8
The auxiliary agent master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) To this mixture was added 10 parts of the D8 auxiliary master batch, followed by granulation to obtain the composition of comparative example 8.
Comparative example 9
The auxiliary agent master batch is prepared from the following raw materials in parts by mass:
the preparation method is the same as example 1.
The following applies:
in LLDPE resin (MFR 2.0g/10min, density 0.920 g/cm)3) The composition of comparative example 9 was prepared by adding 10 parts of the auxiliary master batch to the mixture and granulating the mixture.
The processability of the compositions of examples and comparative examples was tested according to GB/T25278-: 1. the results are shown in tables 1-2.
The compositions were blown to 30 μm films and the optical properties were measured according to GB/T2410-2008A using a transmission hazemeter model AT4725 from BYK-Gardner, Germany, and the results are given in Table 3.
TABLE 1 Critical shear rates (units: 1/sec) at different temperatures
| Temperature, C | 170 | 180 | 190 |
| Example 1 | 400 | 450 | 500 |
| Example 2 | 500 | 550 | 650 |
| Example 3 | 450 | 550 | 550 |
| Example 4 | 400 | 500 | 550 |
| Comparative example 1 | 350 | 400 | 500 |
| Comparative example 2 | 200 | 300 | 300 |
| Comparative example 3 | 300 | 300 | 400 |
| Comparison ofExample 4 | 200 | 300 | 300 |
| Comparative example 5 | 350 | 450 | 450 |
| Comparative example 6 | 350 | 400 | 500 |
| Comparative example 7 | 350 | 450 | 500 |
| Comparative example 8 | 300 | 350 | 400 |
| Comparative example 9 | 350 | 400 | 450 |
TABLE 2190 ℃ shear viscosity (Pa. s)
| Shear rate, 1/sec | 100 | 200 | 300 |
| Example 1 | 1104 | 985 | 855 |
| Example 2 | 1000 | 922 | 750 |
| Example 3 | 1030 | 932 | 800 |
| Example 4 | 1032 | 920 | 832 |
| Comparative example 1 | 1225 | 1118 | 1020 |
| Comparative example 2 | 1430 | 1222 | 1146 |
| Comparative example 3 | 1270 | 1172 | 1166 |
| Comparative example 4 | 1406 | 1250 | 1152 |
| Comparative example 5 | 1143 | 1020 | 900 |
| Comparative example 6 | 1128 | 1052 | 1023 |
| Comparative example 7 | 1180 | 1155 | 1096 |
| Comparative example 8 | 1212 | 1074 | 1048 |
| Comparative example 9 | 1187 | 1143 | 1042 |
TABLE 3 preparation of film optical Properties
| Sample (I) | Haze% |
| Example 1 | 11.0 |
| Example 2 | 9.6 |
| Example 3 | 10.8 |
| Example 4 | 11.2 |
| Comparative example 1 | 20.0 |
| Comparative example 2 | 15.2 |
| Comparative example 3 | 15.9 |
| Comparative example 4 | 18.6 |
| Comparative example 5 | 14.8 |
| Comparative example 6 | 17.1 |
| Comparative example 7 | 16.0 |
| Comparative example 8 | 22.3 |
| Comparative example 9 | 17.8 |
From a comparison of the properties of the examples and comparative examples it can be seen that: the borate and the zinc stearate are beneficial to improving the processability of the composition, the borate and the zinc stearate are mixed in a proper proportion to synergistically improve the processability of the composition, and meanwhile, the film prepared by the method has good optical performance.
The additive master batch disclosed by the invention is not only limited to be applied to LLDPE, but also is effective in LDPE, HDPE and a mixture of LDPE, HDPE and LDPE or a mixture of LDPE, HDPE and HDPE.
Claims (8)
1. A linear low density polyethylene additive masterbatch is characterized in that: the feed is prepared from the following raw materials in parts by mass:
100 parts of LLDPE resin;
0.25-1.5 parts of antioxidant;
0.25-2.0 parts of slipping agent;
0.3 part of zinc stearate;
0.3-5.0 parts of opening agent;
0.3-1.0 part of borate;
wherein:
the borate is oleic acid diethanolamide borate or castor oil alkanolamide borate;
the preparation method of the linear low-density polyethylene additive master batch comprises the following steps:
(1) adding an opening agent into an ethanol solution of borate, heating and refluxing for 10-15min, evaporating the solvent, drying solid particles, and grinding into powder for later use;
(2) and (2) adding an antioxidant, zinc stearate, a slipping agent and the powder obtained in the step (1) into LLDPE resin powder, uniformly mixing, adding the uniformly mixed material into a double-screw extruder, and carrying out melting, plasticizing, extruding and granulating to obtain the linear low-density polyethylene additive master batch.
2. The linear low density polyethylene additive masterbatch according to claim 1, wherein: the LLDPE resin is a copolymer of ethylene and butene-1 or a copolymer of ethylene and hexene-1.
3. The linear low density polyethylene additive masterbatch according to claim 1, wherein: the density of the LLDPE resin is 0.91-0.92g/cm3The melt mass flow rate is 2-10g/10 min.
4. The linear low density polyethylene additive masterbatch according to claim 1, wherein: the antioxidant is one or more of hindered phenol antioxidant, phosphite antioxidant or thioester antioxidant.
5. The linear low density polyethylene additive masterbatch according to claim 1, wherein: the slipping agent is erucamide.
6. The linear low density polyethylene additive masterbatch according to claim 1, wherein: the opening agent is one or more of calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, silicon oxide, hydrotalcite, diatomite, bentonite, mica, zeolite, glass powder, sepiolite, fly ash, rectorite or pumice.
7. Use of the linear low density polyethylene additive masterbatch according to any one of claims 1 to 6, wherein: when the composition for blown film is prepared, the linear low-density polyethylene additive master batch is added into the base resin, and extrusion granulation is carried out, so as to obtain the composition product for blown film.
8. The use of the linear low density polyethylene additive masterbatch of claim 7, wherein: the addition amount of the linear low-density polyethylene additive master batch is 10 wt.% of the base resin.
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