CN114773699A - Composite auxiliary agent for improving weather resistance and tensile property of linear polyethylene film material and preparation method thereof - Google Patents
Composite auxiliary agent for improving weather resistance and tensile property of linear polyethylene film material and preparation method thereof Download PDFInfo
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- CN114773699A CN114773699A CN202210597288.XA CN202210597288A CN114773699A CN 114773699 A CN114773699 A CN 114773699A CN 202210597288 A CN202210597288 A CN 202210597288A CN 114773699 A CN114773699 A CN 114773699A
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- 239000004698 Polyethylene Substances 0.000 title claims abstract description 78
- -1 polyethylene Polymers 0.000 title claims abstract description 59
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 title description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 71
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 52
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 22
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 22
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 22
- 239000002667 nucleating agent Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims abstract description 9
- 239000000428 dust Substances 0.000 claims abstract description 6
- 238000005469 granulation Methods 0.000 claims abstract description 5
- 230000003179 granulation Effects 0.000 claims abstract description 5
- 238000007791 dehumidification Methods 0.000 claims abstract description 4
- 238000001125 extrusion Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 4
- 238000013329 compounding Methods 0.000 claims description 14
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group 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 10
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 8
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000006698 induction Effects 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 229920000092 linear low density polyethylene Polymers 0.000 description 6
- 239000004707 linear low-density polyethylene Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ZMRUPTIKESYGQW-UHFFFAOYSA-N propranolol hydrochloride Chemical compound [H+].[Cl-].C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 ZMRUPTIKESYGQW-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000003971 tillage Methods 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a composite additive of a linear polyethylene film material, which comprises the following raw materials in percentage by weight: 5-25 parts of nano butadiene styrene rubber nucleating agent, 5-20 parts of phenol antioxidant, 5-30 parts of phosphite antioxidant, 2-60 parts of anti-ultraviolet stabilizer and 10-40 parts of hydrated magnesium silicate, and the preparation method comprises the following steps: s1, performing pre-dispersion in a high-speed disperser, adding a powdery nano styrene-butadiene rubber nucleating agent, a phenolic antioxidant and hydrated magnesium silicate into the high-speed disperser respectively according to the proportion for pre-dispersion, wherein the dispersion time is 1-10 hours, S2, adding the pre-dispersion obtained in the step S1 into a slow disperser, then mixing and dispersing the mixture with a granular phosphite antioxidant and an anti-ultraviolet stabilizer for 1-10 hours, and performing extrusion granulation, dust removal and dehumidification, screening and packaging after uniform dispersion to obtain the linear polyethylene film material composite additive.
Description
Technical Field
The invention relates to the field of linear polyethylene composite additives, in particular to a composite additive for improving the weather resistance and tensile property of a linear polyethylene film material and a preparation method thereof.
Background
The polyethylene PE is the simplest resin molecular structure, has rich raw material sources, low price, excellent electrical insulation and chemical stability, is easy to form and process, has more varieties and can meet the requirements of different performances, so that the polyethylene PE has the largest yield in synthetic resin, is fastest in development and is most actively developed in variety. Because PE has excellent low temperature resistance, chemical stability, resistance to most of acid and alkali corrosion, electrical insulation and the like, and because of its characteristics of light weight, easy processing and the like, the production of PE has been rapidly developed, wherein there are many types of PE industrially synthesized, and PE is generally classified into low density polyethylene, high density polyethylene, medium density polyethylene, metallocene polyethylene, linear low density polyethylene, high relative molecular weight polyethylene, ultrahigh molecular weight polyethylene, low molecular weight polyethylene and the like according to the difference of molecular structure and relative molecular weight.
The aging problem of the high polymer material PE is also a key point of constant attention, the high polymer material can cause the change of the internal chemical structure of the material due to various external factors in the processing and using processes, so that the performance is deteriorated, the practical value is lost, and the aging occurs, wherein the aging of the material is represented as convenient appearance and performance, darkening and discoloration of the surface of the appearance, cracks, embrittlement, mildewing and the like; performance aspects include impact strength, modulus, hardness, heat resistance, cold resistance, surface resistance, dielectric constant, breakdown voltage variation, and the like. In order to prevent the aging problem of the high polymer material, in particular the linear polyethylene film material. In order to prevent decomposition in the processing process, a heat stabilizer needs to be added, in order to prevent the aging problem, a light stabilizer and an antioxidant need to be added, in order to meet the requirement of safe production, a flame retardant and an antistatic agent need to be added, and in order to ensure the safety and environmental protection of a packaging material, an anti-mildew agent needs to be added. As is well known, the molding process of plastic products is basically completed by the steps of compounding, plasticating, molding, etc. In this process, resins, auxiliaries, processing equipment (including molds) are indispensable essential elements. In contrast, the auxiliaries are used in minor amounts in the formulation of plastics, but their effect on improving and enhancing the processing and application properties of the articles is of great importance. It can be said that after the structure of the polymer resin is determined, the selection and application of the auxiliary agent is the key to determine the success or failure of the product; the openness, the oxygen resistance and the slip of the product are important external indexes of a polyethylene product, and fisheyes, stripes, density, haze, breaking stress, tensile breaking nominal strain and the like in the product are the key for analyzing the quality of the polyethylene product.
Four common antioxidants, 1010, BHT,1076 and 1096, were added to the polyethylene material, respectively, and the compatibility of the antioxidants with the material was studied by infrared spectroscopy and mass-gain method. As a result, it was found that the compatibility of the antioxidant with polyethylene materials was less stable at high temperatures, and the concentration had less influence on the compatibility of 4 antioxidants with polyethylene materials. The 4 antioxidants have good compatibility with polyethylene material resin within the addition range, and the optimum is BHT, then the antioxidants 1098 and 1076, and finally the antioxidant 1010. The antioxidant can inhibit or delay the polymerization to generate an auxiliary agent for an autoxidation reaction, and is divided into phenols, amines, phosphites, thioesters and the like according to chemical compositions. While the phenolic antioxidant functions as a primary antioxidant to act as a chain termination, which provides hydrogen protons to terminate the radical chain reaction. The antioxidants are phosphites and thioesters (auxiliary antioxidants), which react with hydroperoxide to prevent the generation of free radicals, and from the action mechanism, the combination of the main antioxidant and the auxiliary antioxidant can generate a certain synergistic effect. The traditional polyethylene mulching film has poor weather resistance, is easy to break after being irradiated by sunlight for a period of time, has no tensile property, cannot be mechanically recovered when being used in a large area, and has white plastic pollution caused by burying a large amount of mulching film fragments in a field during secondary re-tillage.
Disclosure of Invention
In order to solve the technical problems and overcome the defects of poor aging resistance of the polymer PE caused by easy breakage, no tensile property, easy agglomeration, poor volatility resistance and poor migration resistance of the polymer additive in the prior art, the invention aims to solve the problems in the prior art and provides the composite additive of the linear polyethylene film material and the preparation method thereof. The composite auxiliary agent adopts the nano styrene-butadiene rubber nucleating agent, the phenol antioxidant, the phosphite antioxidant, the ultraviolet-resistant stabilizer and the hydrated magnesium silicate, has the advantages of simple preparation method, low preparation process cost, no dust pollution in the preparation process, safety, environmental protection and the like, and simultaneously solves the problems of easy migration and easy volatilization of the antioxidant. Meanwhile, the application also inspects the influence of the oxidation of the two antioxidants on the oxidation induction period and the mechanical property of the polyethylene.
The invention relates to a first technical scheme, in particular to a composite auxiliary agent for a linear polyethylene film material, which comprises the following raw materials in percentage by weight: 5-25 parts of nano butadiene styrene rubber nucleating agent, 5-20 parts of phenol antioxidant, 5-30 parts of phosphite antioxidant, 2-60 parts of anti-ultraviolet stabilizer and 10-40 parts of hydrated magnesium silicate.
The composite auxiliary agent comprises the following raw materials in percentage by weight: 10-20 parts of nano butadiene styrene rubber nucleating agent, 5-15 parts of phenol antioxidant, 10-20 parts of phosphite antioxidant, 10-50 parts of ultraviolet-resistant stabilizer and 20-30 parts of hydrated magnesium silicate.
The composite auxiliary agent comprises the following raw materials in percentage by weight: 10-20 parts of nano butadiene styrene rubber nucleating agent, 5-15 parts of phenol antioxidant, 10-20 parts of phosphite antioxidant, 30-50 parts of anti-ultraviolet stabilizer and 20-30 parts of hydrated magnesium silicate.
In the composite auxiliary agent, the phenolic antioxidant is one or more of octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, antioxidant 264(BHT), antioxidant 1076, antioxidant 736 and antioxidant 1010, and the phosphite ester antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite ester.
In the compound auxiliary agent, the phenolic antioxidant is selected from one or more of antioxidant 264(BHT), antioxidant 1076, antioxidant 736 and antioxidant 1010.
The invention relates to a second technical scheme, and relates to a preparation method of the linear polyethylene film material composite additive, which comprises the following preparation steps:
s1, pre-dispersing in a high-speed disperser, respectively adding powdery nano styrene-butadiene rubber nucleating agent, phenolic antioxidant and hydrated magnesium silicate in the high-speed disperser according to the proportion for pre-dispersing for 1-10 hours, and controlling the temperature of the mixture to be not higher than 80 ℃; preferably, the temperature of the mixture is not higher than 50 ℃;
s2, adding the pre-dispersion obtained in the step S1 into a slow disperser, mixing and dispersing the pre-dispersion with the granular phosphite ester antioxidant and the ultraviolet-resistant stabilizer for 1-10 hours, and controlling the temperature of the mixture to be not higher than 85 ℃; preferably, the temperature of the mixture is not higher than 60 ℃; after being dispersed evenly, the composite additive is obtained after extrusion granulation, dust removal and dehumidification, screening and packaging.
Wherein the temperature of the mixture is not higher than 50 ℃ in the step S1; the invention relates to a third technical scheme that the temperature of a mixed material in step S2 is not higher than 60 ℃, in particular to a linear polyethylene film material, which is characterized by containing the composite additive in claim 1, wherein the content of the composite additive is 2-4 per mill.
The invention achieves the following beneficial technical effects:
1. the invention provides a composite auxiliary agent of a linear polyethylene film material and a preparation method thereof. The composite auxiliary agent adopts a nano styrene-butadiene rubber nucleating agent, a phenol antioxidant, a phosphite antioxidant, an ultraviolet-resistant stabilizer and hydrous magnesium silicate, and has the advantages of simple preparation method, low preparation process cost, no dust pollution in the preparation process, safety, environmental protection and the like.
2. Meanwhile, the invention solves the problems of easy migration and easy volatilization of the antioxidant, and compared with the traditional auxiliary agent, the composite auxiliary agent prepared by the invention has excellent tensile load and fracture nominal strain, so that the composite auxiliary agent has oxidation resistance and light stability, and the aging resistance of the polymer can be improved.
3. The invention also investigates the influence of the oxidation action of the two antioxidants on the oxidation induction period and the mechanical property of the polyethylene. The maximum oxidation induction period can reach 97.6 minutes, and according to tests, the combined use of the antioxidant can improve the oxidation induction period time of the LDPE, so that the antioxidant property of the polyethylene film material can be improved; wherein, the combination of the antioxidant can improve the tensile strength and the breaking strength, thereby improving the mechanical property of the polyethylene material, wherein the tensile strength reaches 29.32Mpa, and the breaking strength reaches 28.58 Mpa.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for the purpose of further illustration, and are not to be construed as limiting the scope of the present invention, and that the skilled person can make some insubstantial modifications and adaptations in light of the above disclosure.
Test materials and instruments
The linear low-density polyethylene LLDPE with the sequence number of LD200GHD is selected as a main test material in the embodiment, and the selected antioxidants are respectively antioxidant 1010 with the chemical name of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester; antioxidant 264(BHT), chemical name 2, 6-di-tert-butyl-p-methylphenol; antioxidant 1076, chemical name: n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the antioxidant 736 has a chemical name of 4, 4-thiobis (6-tert-butyl-o-cresol), and the above reagents and chemical materials are purchased from Beijing Yan Union chemical Co., Ltd, Kemi European chemical reagent Co., Tianjin and Yongda chemical reagent Co., Ltd.
Example one
The composite auxiliary agent for the linear polyethylene film material comprises the following raw materials in parts by weight: 10g of nano styrene-butadiene rubber nucleating agent, 10105 g of phenolic antioxidant, 5g of tris (2, 4-di-tert-butylphenyl) phosphite antioxidant, 15g of ultraviolet-resistant stabilizer and 15g of hydrated magnesium silicate.
The preparation method comprises the following steps: s1, performing pre-dispersion in a high-speed disperser, and adding a powdery nano styrene-butadiene rubber nucleating agent, a phenolic antioxidant and hydrous magnesium silicate into the high-speed disperser respectively according to the proportion for pre-dispersion, wherein the dispersion time is 4 hours, and the temperature of a mixed material is 45 ℃; and S2, adding the pre-dispersion obtained in the step S1 into a slow disperser, mixing and dispersing the pre-dispersion with the granular phosphite antioxidant and the anti-ultraviolet stabilizer for 2 hours at the mixed material temperature of 45 ℃, uniformly dispersing, and then performing extrusion granulation, dust removal and dehumidification, screening and packaging to obtain the polyethylene composite additive of the numbered example 1.
Example two
The linear polyethylene composite additive is composed of the following raw materials by weight: 10g of nano butadiene styrene rubber nucleating agent, 2645 g of phenolic antioxidant, 5g of tris (2, 4-di-tert-butylphenyl) phosphite antioxidant, 15g of ultraviolet-resistant stabilizer and 15g of hydrated magnesium silicate. The polyethylene compounding aid of reference example 2 was prepared according to the preparation method of example one.
EXAMPLE III
The linear polyethylene composite additive is composed of the following raw materials by weight: 10g of nano styrene-butadiene rubber nucleating agent, 10765 g of phenolic antioxidant, 5g of tris (2, 4-di-tert-butylphenyl) phosphite antioxidant, 15g of ultraviolet-resistant stabilizer and 15g of hydrated magnesium silicate. The polyethylene compounding aid of reference example 3 was prepared according to the preparation method of example one.
Example four
The linear polyethylene composite additive is composed of the following raw materials by weight: 10g of nano butadiene styrene rubber nucleating agent, 10765 g of phenolic antioxidant, 15g of ultraviolet-resistant stabilizer and 15g of hydrated magnesium silicate. In this example, the polyethylene compounding aid of reference example 4 was prepared according to the preparation method of example one without adding tris (2, 4-di-t-butylphenyl) phosphite antioxidant.
EXAMPLE five
The linear polyethylene composite additive is composed of the following raw materials by weight: 10g of nano styrene-butadiene rubber nucleating agent, 5g of tris (2, 4-di-tert-butylphenyl) phosphite antioxidant, 15g of anti-ultraviolet stabilizer and 15g of hydrated magnesium silicate. In this example, the polyethylene compounding aid of the reference example 5 was prepared according to the preparation method of example one without adding any phenolic antioxidant.
Example six
The linear polyethylene composite additive is prepared from the following raw materials in parts by weight: 10g of nano styrene-butadiene rubber nucleating agent, 15g of ultraviolet-resistant stabilizer and 15g of hydrated magnesium silicate. In this example, the polyethylene compounding aid of reference example 6 was prepared according to the preparation method of example one without adding any phenol antioxidant and phosphite antioxidant.
EXAMPLE seven
The linear polyethylene composite additive is prepared from the following raw materials in parts by weight: 12g of nano styrene-butadiene rubber nucleating agent, 2647 g of phenolic antioxidant, 8g of tris (2, 4-di-tert-butylphenyl) phosphite antioxidant, 15g of ultraviolet-resistant stabilizer and 15g of hydrated magnesium silicate. The polyethylene compounding aid of reference example 7 was prepared according to the preparation method of example one.
Example eight
The linear polyethylene composite additive is composed of the following raw materials by weight: 12g of nano styrene-butadiene rubber nucleating agent, 2647 g of phenolic antioxidant, 8g of tris (2, 4-di-tert-butylphenyl) phosphite antioxidant, 10g of ultraviolet-resistant stabilizer and 15g of hydrated magnesium silicate. The polyethylene compounding aid of reference example 8 was prepared according to the preparation method of example one.
Example nine
The linear polyethylene composite additive is composed of the following raw materials by weight: 12g of nano butadiene styrene rubber nucleating agent, 2649 g of phenolic antioxidant, 10g of tris (2, 4-di-tert-butylphenyl) phosphite antioxidant, 10g of anti-ultraviolet stabilizer and 12g of hydrated magnesium silicate. The polyethylene compounding aid of reference example 9 was prepared according to the preparation method of example one.
Experimental effect example 1:
the oxidative induction period (OIT) is the time during which the polymeric material begins to undergo autocatalytic oxidation under high temperature aerobic conditions. The oxidation induction period can intuitively and accurately reflect the thermal oxygen stability of the high polymer material, and the longer the oxidation induction period is, the better the oxidation resistance of the high polymer material is. The oxidation induction periods of the special polyethylene pipe material added with different antioxidants are different.
According to the compound assistant of the first embodiment to the ninth embodiment, 5000g of LLDPE and one of the first embodiment to the ninth embodiment are added into a high-speed mixer and mixed for 4-15 minutes at 25 ℃ to obtain a mixture, the mixture is added into a screw extruder, the temperature of the screw extruder and a die head is controlled at 165-220 ℃ and the screw rotating speed is controlled at 160-280rmp, the mixture is plasticized and melt blended, and the mixture is melt blended and extruded by the extruder for granulation.
The PE sample of example 1, the PE sample of example 2, the PE sample of example 3, the PE sample of example 4, the PE sample of example 5, the PE sample of example 6, the PE sample of example 7, the PE sample of example 8 and the PR sample of example 9 were obtained and tested for mechanical properties according to GB/T1040-2006, respectively. The PE pellets were shaped into 5A dumbbell test specimens by compression molding and left at a temperature of 23. + -. 2 ℃ and a relative humidity of 50. + -. 5% for 24 hours. The pull rate was 50 mm/min.
TABLE 1 Oxidation Induction period data of polyethylene materials OIT (in minutes)
As can be seen from table 1, the oxidative induction period data OIT values in the example samples were lower without the addition of an oxidizing agent; the OIT values for the oxidative induction period data in the example samples were increased by adding the antioxidant alone, e.g., only the phosphite antioxidant or only the phenolic antioxidant; the oxidative induction period data OIT values in the example samples were further increased when both antioxidants were added, indicating that the addition of both antioxidants is more favorable for increasing the oxidative induction period OIT. The invention evaluates the antioxidant effect of the polyethylene after compounding the antioxidants jointly used among different types by applying the method of the oxidation induction period, and the combined use of the antioxidants can improve the oxidation induction period time of the LDPE according to the test, so that the antioxidant performance of the polyethylene film material can be improved.
Experimental effect example 2:
according to the compound auxiliary agents of the first embodiment to the ninth embodiment, 5000g of linear low density polyethylene LLDPE and the first embodiment to the ninth embodiment are added into a high-speed mixer and mixed for 4-15 minutes at 25 ℃ to obtain a mixture, the mixture is added into a screw extruder, the temperature of the screw extruder and a die head is controlled at 165-220 ℃ and the screw rotating speed is controlled at 160-280rmp, the mixture is plasticized and melt blended, and the mixture is melt blended and extruded by the extruder to be pelletized. PE samples of examples 1-9 were obtained, respectively, and were subjected to mechanical property testing in accordance with GB/T1040-2006. The PE pellets were shaped into 5A dumbbell test specimens by compression molding and left at a temperature of 23. + -. 2 ℃ and a relative humidity of 50. + -. 5% for 24 hours. The pulling rate is 50 mm/min; the mechanical property indexes of the alloy are respectively as follows.
TABLE 2 mechanical Properties of polyethylene PE materials with different antioxidants added
As can be seen from table 2, the tensile strength and breaking strength values in the example samples were lower without the addition of the oxidizing agent; the tensile strength and breaking strength in the example samples are improved by adding the antioxidant alone, for example, only the phosphite antioxidant or only the phenol antioxidant; the tensile strength and breaking strength in the example samples are further enhanced when two antioxidants are added, indicating that adding two antioxidants is more beneficial in increasing the tensile strength and breaking strength of the material. The invention evaluates the mechanical property of the polyethylene material after the compounding of the antioxidants jointly used among different types by applying the tensile strength and the breaking strength, and according to the test, the combination of the antioxidants can improve the tensile strength and the breaking strength, so that the mechanical property of the polyethylene material can be improved.
Experimental effect example 3:
the composite additives prepared by the methods described in examples 1 to 9 were added to a linear polyethylene film material in an amount of 1 to 4% per thousand, and then tested for mechanical properties according to relevant standards, and weatherable films (0.010mm and 0.014mm thick) were subjected to manual accelerated aging tests for a weathering time of 180 days and 360 days, and then tested according to the national GB standard, and tested for tensile load and nominal strain at break as follows: the tensile load (N, longitudinal direction and transverse direction) is more than or equal to 29.7/30.7, and the fracture nominal strain (%, longitudinal direction and transverse direction) is more than or equal to 745/732.
TABLE 3 tensile load/N, nominal strain% at break performance index of polyethylene PE materials with different antioxidants added
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The composite additive for the linear polyethylene film material comprises the following raw materials in percentage by weight: 5-25 parts of nano butadiene styrene rubber nucleating agent, 5-20 parts of phenol antioxidant, 5-30 parts of phosphite antioxidant, 2-60 parts of anti-ultraviolet stabilizer and 10-40 parts of hydrated magnesium silicate.
2. The composite additive according to claim 1, which is characterized by comprising the following raw materials in percentage by weight: 10-20 parts of nano butadiene styrene rubber nucleating agent, 5-15 parts of phenol antioxidant, 10-20 parts of phosphite antioxidant, 10-50 parts of ultraviolet-resistant stabilizer and 20-30 parts of hydrated magnesium silicate.
3. The composite additive according to claim 1, which is characterized by comprising the following raw materials in percentage by weight: 10-20 parts of nano butadiene styrene rubber nucleating agent, 5-15 parts of phenol antioxidant, 10-20 parts of phosphite antioxidant, 30-50 parts of anti-ultraviolet stabilizer and 20-30 parts of hydrated magnesium silicate.
4. The compounding aid according to any one of claims 1-3, wherein the phenolic antioxidant is one or more of octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, antioxidant 264(BHT), antioxidant 1076, antioxidant 736, and antioxidant 1010, and the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
5. The compounding aid according to any one of claims 1 to 3, wherein the phenolic antioxidant is selected from one or more of antioxidant 264(BHT), antioxidant 1076, antioxidant 736 and antioxidant 1010.
6. A method for preparing the linear polyethylene film material compounding aid according to any one of claims 1 to 3, wherein the method comprises the following steps: the preparation method comprises the following preparation steps:
s1, pre-dispersing in a high-speed disperser, adding powdery nano styrene-butadiene rubber nucleating agent, phenolic antioxidant and hydrated magnesium silicate into the high-speed disperser according to the proportion for pre-dispersing for 1-10 hours, and controlling the temperature of the mixture to be not higher than 80 ℃;
s2, adding the pre-dispersion obtained in the step S1 into a slow disperser, mixing and dispersing the pre-dispersion with the granular phosphite antioxidant and the ultraviolet-resistant stabilizer for 1-10 hours, and controlling the temperature of the mixture to be not higher than 85 ℃; after being dispersed uniformly, the composite additive is obtained after extrusion granulation, dust removal and dehumidification, screening and packaging.
7. The method according to claim 6, wherein the temperature of the mixture is not higher than 50 ℃ in step S1; the temperature of the mixture in step S2 is not higher than 60 ℃.
8. A linear polyethylene film material is characterized by comprising the compound additive disclosed in claim 1, wherein the content of the compound additive accounts for 2-4 per mill.
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| US20200239669A1 (en) * | 2017-10-12 | 2020-07-30 | Si Group Usa (Usaa), Llc | Antidegradant blend |
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| WO1997049758A1 (en) * | 1996-06-27 | 1997-12-31 | Clariant International Limited | Stabilizer compositions |
| JP2001123021A (en) * | 1999-10-26 | 2001-05-08 | Asahi Denka Kogyo Kk | Composite additive for granular polyolefin and its preparation process |
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