CN114805990A - Oxidation-resistant, corrosion-resistant and ageing-resistant polyolefin material and application thereof - Google Patents
Oxidation-resistant, corrosion-resistant and ageing-resistant polyolefin material and application thereof Download PDFInfo
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention relates to the technical field of plastic pipes, in particular to an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material and application thereof. The raw materials comprise the following components in parts by weight: 10-30 parts of polyolefin master batch, 40-75 parts of powder, 2-10 parts of lubricant and 0.1-5 parts of coupling agent. The invention has the following advantages: (1) the material has strong chemical stability, excellent oxidation resistance and ageing resistance, prolonged oxidation induction period of the product and strong bearing capacity on changes of light radiation and temperature (particularly high temperature); (2) the material has excellent mechanical property and stronger corrosion resistance, has small reduction of the mechanical property of the material after being soaked in acid and alkaline reagents, and can improve the carrying range of polyolefin pipes; (3) the material of the invention is mixed with a large proportion of inorganic powder, thus improving the comprehensive performance of the material and simultaneously obviously reducing the cost of the raw material, and the process is simple and convenient, thus being suitable for being widely popularized in building engineering materials and commodity packaging materials.
Description
Technical Field
The invention relates to the technical field of plastic pipes, in particular to an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material and application thereof.
Background
With the development of industry and national economy, the material demand in the fields of building water supply and drainage, gas pipes and the like is increased rapidly, plastic pipes become the first choice of industrial pipes due to strong safety, environmental protection and harmlessness, and the plastic pipe replaces steel to become the revolutionary development of the pipeline field in the century. The current various types of plastic pipes have some problems in the practical use process, such as: (1) although the PVC pipe has the advantages of high modulus, strong chemical stability, small water flow resistance and the like, the PVC pipe is sensitive to temperature change, is easy to embrittle at low temperature, is easy to soften at high temperature, is not suitable for being used as a hot water pipe, and is also not suitable for being used in cold regions; (2) the PPR pipe is light in weight and resistant to chemical corrosion, but the pressure resistance is poor, a thicker inner wall needs to be arranged, the space utilization rate is small, and the PPR pipe cannot be applied to occasions with higher requirements on size; (3) the temperature resistance of PB tubular product is strong, and it is effectual to keep warm, but the thermal diffusivity is poor, the crackle appears easily, and is required highly to the construction, is unsuitable to use in pipelines such as ground heating.
Polyolefins are a generic term of polymers formed by olefin monomers, and have extremely high cost performance due to the advantages of low cost, easy processing and forming and the like. Polyolefins are widely used in the fields of film products, pipes, hollow products, engineering plastics and the like according to the difference of performances. Polyethylene and polypropylene are two of the most widely used types, and the production of the two can account for 35% of the market share of synthetic resins. High Density Polyethylene (HDPE) is favored in the drainage field due to excellent performance and low cost, and products such as an HDPE solid-wall drainage pipe, an HDPE winding structure wall pipe, an HDPE double-wall corrugated pipe, an HDPE steel rib composite spiral pipe and the like are developed at present, so that the requirements of sealing property and leakage resistance can be met; however, the comprehensive properties of the existing polyethylene pipe are not balanced enough, and only certain properties such as chemical corrosion resistance, high temperature resistance and mechanical properties can be met, but the comprehensive properties still have a larger space for improvement, and the application of the polyolefin pipe is limited. With the rapid development of polymer science and technology, the deepening and improving processes of the development and utilization of plastic pipes are also continuously promoted; based on the above, the preparation of a polyolefin material with stable performance, corrosion resistance, aging resistance and high mechanical strength is an urgent problem to be solved in the field.
Disclosure of Invention
The polyolefin material with the advantages of oxidation resistance, corrosion resistance and aging resistance provided by the invention overcomes the defects of poor weather resistance, easy corrosion, poor timeliness and the like of plastic pipes in the prior art, and realizes the polyolefin material with stable performance, corrosion resistance, aging resistance and high mechanical strength.
The invention provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, which comprises the following raw materials in parts by weight: 10-30 parts of polyolefin master batch, 40-75 parts of powder, 2-10 parts of lubricant and 0.1-5 parts of coupling agent.
In a preferred embodiment, the polyolefin material further comprises 0.1-2 parts of a composite antioxidant; the composite antioxidant is at least 2 selected from phenolic antioxidants, amine antioxidants and ester antioxidants.
The polymerization monomer of the polyolefin master batch is alpha-olefin and/or cycloolefin.
The alpha-olefin comprises at least 1 of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene.
The melt flow rate of the polyolefin master batch is 0.5-20g/10 min.
The powder comprises at least 1 of silicate minerals, carbonate minerals, metal oxides and carbon black.
The particle size of the powder is 10-420 μm.
The polyolefin master batch, the powder and the lubricant are mixed according to the weight ratio of (2-5): (6-14): 1.
the invention provides an application of an oxidation-resistant, corrosion-resistant and ageing-resistant polyolefin material, wherein the polyolefin material is applied to building engineering materials and commodity packaging materials.
Has the advantages that:
the polyolefin material obtained by the invention has the following advantages:
(1) the material has strong chemical stability, excellent oxidation resistance and ageing resistance, prolonged oxidation induction period of the product and strong bearing capacity on changes of light radiation and temperature (especially high temperature);
(2) the material has excellent mechanical property and stronger corrosion resistance, has small reduction of the mechanical property of the material after being soaked in acid and alkaline reagents, and can improve the carrying range of polyolefin pipes;
(3) the material of the invention is mixed with a large proportion of inorganic powder, thus improving the comprehensive performance of the material and simultaneously obviously reducing the cost of the raw material, and the process is simple and convenient, thus being suitable for being widely popularized in building engineering materials and commodity packaging materials.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein in the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes equivalent parts that are acceptable for use in a generic sense without departing from the spirit and scope of the invention. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer". "interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to polymers prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to polymers prepared from three different monomers). It also includes polymers made by polymerizing more monomers. "blend" means a polymer formed by two or more polymers being mixed together by physical or chemical means.
In order to solve the problems, the invention provides an oxidation-resistant, corrosion-resistant and ageing-resistant polyolefin material, which comprises the following raw materials in parts by weight: 10-30 parts of polyolefin master batch, 40-75 parts of powder, 2-10 parts of lubricant and 0.1-5 parts of coupling agent.
In some preferred embodiments, the polyolefin material further comprises 0.1-2 parts of a composite antioxidant; the composite antioxidant is at least 2 selected from phenolic antioxidants, amine antioxidants and ester antioxidants.
More preferably, the compound antioxidant is a phenol antioxidant and an ester antioxidant; the weight ratio of the phenolic antioxidant to the ester antioxidant is 1: (0.5-3).
Examples of the phenolic antioxidant include, but are not limited to, octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2, 6-di-t-butyl-p-cresol, 1, 2-bis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl ] hydrazine, pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ].
Examples of the ester antioxidant include, but are not limited to, phenyl tris (2, 4-di-t-butyl) phosphite, triphenyl phosphite, diphenyl monoisooctyl phosphite, and trilauryl phosphite.
Still more preferably, the complex antioxidant is octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-p-cresol and tris (2, 4-di-tert-butyl) phenyl phosphite; octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-p-cresol and tris (2, 4-di-tert-butyl) phenyl phosphite in a weight ratio of (1.3-4): (0.5-2): (1.6-5.2).
The Time of the sample initially generating catalytic Oxidation reaction under the conditions of high temperature and oxygen atmosphere is tested in an Oxidation Induction period (OIT), and an exothermic reaction signal when the molecular chain of the sample is broken is detected by setting an accelerated aging program, so that the test sample is a common index for representing the heat resistance and the degradation resistance of the material. The polyolefin can not completely eliminate oxygen in the processing process, the oxygen exists in the base material, the polyolefin degradation process is catalyzed to a great extent, the degradation of the polyolefin directly influences the quality and the service life of the pipe, and various safety problems are derived. According to the invention, through the exploration, the composite antioxidant is adopted, particularly, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-p-cresol and tris (2, 4-di-tert-butyl) phenyl phosphite are used together, so that the stability of polyolefin can be obviously improved, the degradation trend of polyolefin is reduced, and the oxidation induction period is prolonged. The reason may be that on the one hand the antioxidant traps reactive free radicals in the material, forcing termination of the chain-lock reaction; on the other hand, the antioxidant blocks the decomposition of intermediate products in the oxidation reaction process, thereby improving the thermal stability of the polyolefin material.
In some preferred embodiments, the polymerized monomer of the polyolefin masterbatch is an alpha-olefin and/or a cyclic olefin.
In some preferred embodiments, the α -olefin comprises at least 1 of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene.
In some preferred embodiments, the polyolefin masterbatch has a melt flow rate of 0.5 to 20g/10 min.
The polyolefin master batch is an ethylene copolymer and a propylene copolymer; the weight ratio of the ethylene copolymer to the propylene copolymer is (4-7): 1.
the water and steam pipelines not only need to have good mechanical strength, but also more importantly have chemical stability, and can maintain corrosion resistance, oxidation resistance and aging resistance when transmitting liquid and gas media. The invention has found through a great deal of research that the ethylene copolymer and the propylene copolymer are adopted, and the weight ratio is (4-7): 1, the anti-aging performance of the polyolefin material can be remarkably improved; the weight ratio under the condition is guessed to be (1.3-4): (0.5-2): octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate of (1.6-5.2), 2, 6-di-tert-butyl-p-cresol and tris (2, 4-di-tert-butyl) phenyl phosphite can play a synergistic role in a polyolefin matrix, excited-state molecules formed by polyolefin under the action of light and heat are stabilized in sprouts, polymer macromolecules are stably crosslinked, and the light stability and the heat stability of the formed polyolefin material are obviously improved.
In some preferred embodiments, the powder comprises at least 1 of silicate minerals, carbonate minerals, metal oxides, and carbon black.
In some preferred embodiments, the powder has a particle size of 10 to 420 μm.
The powder is silicate minerals, carbonate minerals and metal oxides; the weight ratio of the silicate mineral to the carbonate mineral to the metal oxide is (1-4): 1: (0.2-0.6).
The invention further discovers that the addition of the powder into a polyolefin system can reduce the manufacturing cost of the material, improve the mechanical property of the polyolefin, improve the external stress resistance of the prepared polyolefin material, and prevent the polyolefin material from being embrittled, cracked, pulverized and the like. It is further found that when the powder selects silicate minerals, carbonate minerals and metal oxides to act together, the mechanical property of the polyolefin is improved, the chemical stability of the polyolefin material is also improved, after the polyolefin contacts chemicals, the internal nano powder inhibits the permeation and erosion of the chemicals in the molecular structure of the polyolefin polymer, the corrosion resistance of the polyolefin material is greatly improved, and the carrying medium range of the formed pipe is enlarged. However, the amount of the powder added should not be too high because the powder and the polyolefin have interfacial incompatibility characteristics, and when the amount of the powder added is too large, the properties of the polyolefin deteriorate rather.
In some preferred embodiments, the weight ratio of the polyolefin master batch, the powder and the lubricant is (2-5): (6-14): 1.
in some preferred embodiments, the lubricant comprises at least 1 of a mineral wax, a synthetic wax, a C10-C20 alkanoic acid, a fatty acid ester, a silicone oil, a mineral oil.
Further preferably, the lubricant is mineral wax, synthetic wax, C10-C20 alkanoic acid and mineral oil; the weight ratio of the mineral wax, the synthetic wax, the C10-C20 alkanoic acid and the mineral oil is (1.4-3): (1-2.6): 1: (2-5).
As examples of mineral waxes, including but not limited to paraffin; as examples of synthetic waxes, including, but not limited to, polyethylene wax; as examples of C10-C20 alkanoic acids, but are not limited to octadecanoic acid.
More preferably, the mineral oil has a viscosity of 7 to 46mm 2 /s(40℃)
According to the invention, a large number of researches show that the compatibility of inorganic and organic phases can be greatly improved and the agglomeration and precipitation tendency of inorganic powder in a polyolefin molecular chain is inhibited by adopting the mineral wax, the synthetic wax, the C10-C20 alkanoic acid and the mineral oil to jointly act on a polyolefin system. It has further been found that when paraffin wax, polyethylene wax, octadecanoic acid and mineral oil are used for lubricating inorganic powder, the combination ability of the inorganic powder with ethylene copolymer and propylene copolymer can be promoted, on the basis, the addition of the powder can reach more than 50 percent of the polyolefin raw material, thereby greatly reducing the production cost of the polyolefin, the obtained polyolefin has excellent mechanical property and chemical stability, can play a role in light and heat for a long time, endows the polyolefin with excellent workability, has excellent corrosion resistance, corrosion resistance and aging resistance, further prolongs the oxidation induction period, can play a role in bearing and transporting for a long time, is particularly suitable for blow-off pipes (particularly double-wall corrugated pipes, winding pipes, clarias pipes and the like), meanwhile, the material can be used as a main auxiliary material of packaging products such as plastic-uptake lunch boxes and the like, and the safety of the material is improved.
The preparation method of the polyolefin material is not particularly limited, and is a method commonly used in the art, for example: the raw materials are put into a high-speed mixer according to the formula amount for mixing, cooled, conveyed into a double-screw granulator for extrusion, granulated and discharged to obtain a finished product.
The invention provides an application of an oxidation-resistant, corrosion-resistant and ageing-resistant polyolefin material, wherein the polyolefin material is applied to building engineering materials and commodity packaging materials.
Examples
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the raw materials are commercially available and the extraction methods of the extract are all conventional extraction methods, if not otherwise specified.
Example 1.
The embodiment provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, which comprises the following raw materials in parts by weight: 22 parts of polyolefin master batch, 70 parts of powder, 8 parts of lubricant, 2 parts of coupling agent and 0.5 part of composite antioxidant.
The polyolefin master batch is an ethylene copolymer and a propylene copolymer; the weight ratio of ethylene copolymer to propylene copolymer is 5: 1. the melt flow rate of the ethylene copolymer is 8.75g/10min, and the ethylene copolymer is purchased from Liaoning Huajin chemical industry and has the model number of K44-08-122; the melt flow rate of the propylene copolymer is 9g/10min, and the propylene copolymer is purchased from the chemical industry of Qilu and has the type of the Qilu petrochemical industry; the test conditions were 190 ℃ and 2.16 kg.
The powder is silicate minerals, carbonate minerals and metal oxides; the weight ratio of the silicate mineral to the carbonate mineral to the metal oxide is 2: 1: 0.4. the silicate mineral is talcum powder with the particle size of 19 mu m, and is purchased from Changsha Jianghong chemical technology Co., Ltd; the carbonate mineral is heavy calcium carbonate with the grain diameter of 38 mu m, and is purchased from Guangzhou Hongmu mining science and technology company Limited; the metal oxide was titanium dioxide, 23 μm in particle size, purchased from a manufacturer of Tianlong mineral products, Lingshou county.
The lubricant is mineral wax, synthetic wax, C10-C20 alkanoic acid and mineral oil; the weight ratio of the mineral wax, the synthetic wax, the C10-C20 alkanoic acid and the mineral oil is 2.2: 1.7: 1: 3. the mineral wax is No. 56 fully refined paraffin wax, and is purchased from Jinan Jiachen Longji chemical Co., Ltd; the synthetic wax is polyethylene wax, the melting point is 115 ℃, and the synthetic wax is purchased from Jinchuan commercial and trade Co., Ltd, Jinan; the C10-C20 alkanoic acid is octadecanoic acid, purchased from Jining Sanshi Biotech, Inc.; the mineral oil is white oil with viscosity of 15mm 2 At 40 ℃ from Schlumbergera oil (Chongqing) Ltd.
The composite antioxidant is octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS number: 2082-79-3), 2, 6-di-tert-butyl-p-cresol (CAS number: 128-37-0) and tris (2, 4-di-tert-butyl) phenyl phosphite (CAS number: 31570-04-4); the weight ratio of octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-p-cresol and tris (2, 4-di-tert-butyl) phenyl phosphite is 3: 1: 4.
the coupling agent is KR-TTS (Kenrich oil Co., U.S.A.) with CAS number 61417-49-0.
The preparation method of the polyolefin material comprises the steps of putting the raw materials into a high-speed mixer according to the formula amount, mixing, cooling, conveying to a double-screw granulator, extruding, granulating, and discharging to obtain a finished product.
Example 2.
The embodiment provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, which comprises the following raw materials in parts by weight: 27 parts of polyolefin master batch, 65 parts of powder, 6 parts of lubricant, 1.7 parts of coupling agent and 0.5 part of composite antioxidant.
The polyolefin master batch is an ethylene copolymer and a propylene copolymer; the weight ratio of ethylene copolymer to propylene copolymer is 5: 1. the melt flow rate of the ethylene copolymer is 8.75g/10min, and the ethylene copolymer is purchased from Liaoning Huajin chemical industry and has the model number of K44-08-122; the melt flow rate of the propylene copolymer is 9g/10min, and the propylene copolymer is purchased from the chemical industry of Qilu and has the type of the Qilu petrochemical industry; the test conditions were 190 ℃ and 2.16 kg.
The powder is silicate minerals, carbonate minerals and metal oxides; the weight ratio of silicate minerals to carbonate minerals to metal oxides is 2: 1: 0.4. the silicate mineral is talcum powder with the particle size of 19 mu m, and is purchased from Changshanjianlong chemical science and technology limited company; the carbonate mineral is heavy calcium carbonate with the grain diameter of 38 mu m, and is purchased from Guangzhou Hongmu mining science and technology company Limited; the metal oxide was titanium dioxide, 23 μm in particle size, purchased from a manufacturer of Tianlong mineral products, Lingshou county.
The lubricant is mineral wax, synthetic wax, C10-C20 alkanoic acid and mineral oil; the weight ratio of the mineral wax, the synthetic wax, the C10-C20 alkanoic acid and the mineral oil is 2.2: 1.7: 1: 3. the mineral wax is No. 56 fully refined paraffin wax, and is purchased from Jinan Jiachen Longji chemical Co., Ltd; the synthetic wax is polyethylene wax, the melting point is 115 ℃, and the synthetic wax is purchased from Jinchuan commercial and trade Co., Ltd, Jinan; the C10-C20 alkanoic acid is octadecanoic acid, purchased from Jining Sanshi Biotech, Inc.; the mineral oil is white oil with viscosity of 15mm 2 At 40 ℃ from Schlumbergera oil (Chongqing) Ltd.
The composite antioxidant is octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS number: 2082-79-3), 2, 6-di-tert-butyl-p-cresol (CAS number: 128-37-0) and tris (2, 4-di-tert-butyl) phenyl phosphite (CAS number: 31570-04-4); the weight ratio of octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-p-cresol and tris (2, 4-di-tert-butyl) phenyl phosphite is 3: 1: 4.
the coupling agent is KR-TTS (Kenrich oil Co., U.S.A.) with CAS number 61417-49-0.
The preparation method of the polyolefin material comprises the steps of putting the raw materials into a high-speed mixer according to the formula amount, mixing, cooling, conveying to a double-screw granulator, extruding, granulating, and discharging to obtain a finished product.
Example 3.
The embodiment provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, which comprises the following raw materials in parts by weight: 22 parts of polyolefin master batch, 70 parts of powder, 8 parts of lubricant, 2 parts of coupling agent and 0.5 part of composite antioxidant.
The polyolefin master batch is an ethylene copolymer and a propylene copolymer; the weight ratio of ethylene copolymer to propylene copolymer is 5: 1. the melt flow rate of the ethylene copolymer is 8.75g/10min, and the ethylene copolymer is purchased from Liaoning Huajin chemical industry and has the model number of K44-08-122; the melt flow rate of the propylene copolymer is 9g/10min, and the propylene copolymer is purchased from Qilu chemical industry and has the type of Qilu petrochemical industry; the test conditions were 190 ℃ and 2.16 kg.
The powder is silicate minerals, carbonate minerals and metal oxides; the weight ratio of the silicate mineral, the carbonate mineral and the metal oxide is 2. 5: 1: 0.5. the silicate mineral is talcum powder with the particle size of 19 mu m, and is purchased from Changsha Jianghong chemical technology Co., Ltd; the carbonate mineral is heavy calcium carbonate with the grain diameter of 38 mu m, and is purchased from Guangzhou Hongmu mining science and technology company Limited; the metal oxide was titanium dioxide, 23 μm in particle size, purchased from a manufacturer of Tianlong mineral products, Lingshou county.
The lubricant is mineral wax, synthetic wax, C10-C20 alkanoic acid and mineral oil; the weight ratio of the mineral wax, the synthetic wax, the C10-C20 alkanoic acid and the mineral oil is 2.2: 1.7: 1: 3. the mineral wax is No. 56 fully refined paraffin wax, and is purchased from Jinan Jiachen Longji chemical Co., Ltd; the synthetic wax is polyethylene wax, the melting point is 115 ℃, and the synthetic wax is purchased from Jinchuan commercial and trade Co., Ltd, Jinan; the C10-C20 alkanoic acid is octadecanoic acid, purchased from Jining Sanshi Biotech, Inc.; the mineral oil is white oil with viscosity of 15mm 2 At 40 ℃ from Schlumbergera oil (Chongqing) Ltd.
The composite antioxidant is octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS number: 2082-79-3), 2, 6-di-tert-butyl-p-cresol (CAS number: 128-37-0) and tris (2, 4-di-tert-butyl) phenyl phosphite (CAS number: 31570-04-4); the weight ratio of octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-p-cresol and tris (2, 4-di-tert-butyl) phenyl phosphite is 3: 1: 4.
the coupling agent is KR-TTS (Kenrich oil Co., U.S.A.) with CAS number 61417-49-0.
The preparation method of the polyolefin material comprises the steps of putting the raw materials into a high-speed mixer according to the formula amount, mixing, cooling, conveying to a double-screw granulator, extruding, granulating, and discharging to obtain a finished product.
Example 4.
The embodiment provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, and the specific implementation manner is the same as that of embodiment 1; the difference is that the weight ratio of silicate mineral, carbonate mineral and metal oxide is 1: 1: 2. .
Example 5.
The embodiment provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, and the specific implementation manner is the same as that of embodiment 1; the difference is that the silicate mineral is talcum powder, the particle size is 5 mu m, and the silicate mineral is purchased from a processing plant of Waitai mineral products in Lingshou county.
Example 6.
The embodiment provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, and the specific implementation manner is the same as that of embodiment 1; the difference is that the ethylene copolymer has a melt flow rate of 36g/10min, purchased from the metallocene petrochemical, model 2410T.
Example 7.
The embodiment provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, and the specific implementation manner is the same as that of embodiment 1; the difference is that the weight ratio of the ethylene copolymer to the propylene copolymer is 2: 1.
example 8.
The embodiment provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, and the specific implementation manner is the same as that of embodiment 1; except that octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate was replaced with 1, 2-bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine (CAS No. 32687-78-8).
Example 9.
The embodiment provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, and the specific implementation manner is the same as that of embodiment 1; the difference is that the composite antioxidant is octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS number: 2082-79-3) and 2, 6-di-tert-butyl-p-cresol (CAS number: 128-37-0); the weight ratio of octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate to 2, 6-di-tert-butyl-p-cresol is 3: 1.
example 10.
The embodiment provides an oxidation-resistant, corrosion-resistant and anti-aging polyolefin material, and the specific implementation manner is the same as that of embodiment 1; the difference lies in that the weight ratio of the mineral wax, the synthetic wax, the C10-C20 alkanoic acid and the mineral oil is 1: 3: 1: 1.
performance test method
Oxidation induction period:
the polyolefin materials obtained in examples 1-10 were tested for oxidation induction period with reference to SN/T4372-2015; the test temperature was 220 ℃.
Aging resistance:
the polyolefin materials obtained in examples 1 to 10 were placed under a xenon lamp for accelerated aging simulation experiments; the experimental time is 6800h, each group of samples is set to be 10 parallel samples in the experiment, and the number k of parallel samples damaged (cracked or pulverized) in the parallel samples is observed after the accelerated aging simulation experiment is finished. Defining k less than or equal to 1 as A grade, k less than or equal to 2 and less than or equal to 5 as B grade, and n more than or equal to 6 as C grade.
Corrosion resistance:
the polyolefin materials obtained in examples 1 to 10 were immersed in chemical reagents (reagent A: 15 wt% HCl aqueous solution; reagent B: 15 wt% NaOH aqueous solution) for 7 days, and the tensile strength K of the polyolefin materials was tested with reference to GB/T8804.3-2003; calculating the tensile strength reduction rate delta of the soaked polyolefin material; Δ ═ K (K) Before soaking -K After soaking )/K Before soaking *100％。
Performance test data
TABLE 1 Performance test results
Finally, it is pointed out that the foregoing examples are illustrative only, serving to explain some of the characteristics of the process according to the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. An oxidation-resistant, corrosion-resistant and anti-aging polyolefin material is characterized by comprising the following raw materials in parts by weight: 10-30 parts of polyolefin master batch, 40-75 parts of powder, 2-10 parts of lubricant and 0.1-5 parts of coupling agent.
2. The oxidation-resistant, corrosion-resistant and aging-resistant polyolefin material according to claim 1, further comprising 0.1-2 parts of a composite antioxidant; the composite antioxidant is at least 2 selected from phenolic antioxidants, amine antioxidants and ester antioxidants.
3. The oxidation-resistant, corrosion-resistant and aging-resistant polyolefin material according to claim 1 or 2, wherein the polymerized monomer of the polyolefin masterbatch is α -olefin and/or cyclic olefin.
4. An oxidation, corrosion and aging resistant polyolefin material according to claim 3, wherein the α -olefin comprises at least 1 of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene.
5. The oxidation-resistant, corrosion-resistant and aging-resistant polyolefin material according to any one of claims 1 to 4, wherein the melt flow rate of the polyolefin masterbatch is 0.5 to 20g/10 min.
6. The oxidation-resistant, corrosion-resistant and aging-resistant polyolefin material according to any one of claims 1 to 5, wherein the powder comprises at least 1 of silicate minerals, carbonate minerals, metal oxides and carbon black.
7. An oxidation-resistant, corrosion-resistant and aging-resistant polyolefin material according to any one of claims 1 to 6, wherein the powder has a particle size of 10 to 420 μm.
8. The oxidation-resistant, corrosion-resistant and aging-resistant polyolefin material according to any one of claims 1 to 7, wherein the lubricant comprises at least 1 of mineral wax, synthetic wax, C10-C20 alkanoic acid, fatty acid ester, silicone oil and mineral oil.
9. The oxidation-resistant, corrosion-resistant and aging-resistant polyolefin material according to claim 8, wherein the weight ratio of the polyolefin master batch, the powder and the lubricant is (2-5): (6-14): 1.
10. use of an oxidation-resistant, corrosion-resistant, ageing-resistant polyolefin material according to any one of claims 1 to 9 in construction engineering materials and commodity packaging materials.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333395A (en) * | 2013-07-15 | 2013-10-02 | 合肥工业大学 | High fill polyolefin composite film masterbatch and preparation method thereof |
| CN105153531A (en) * | 2015-09-17 | 2015-12-16 | 安徽玉发塑业有限公司 | High-temperature-resistant PE (polyethylene) corrugated pipe filling master batch and preparation method thereof |
| CN110066447A (en) * | 2019-05-10 | 2019-07-30 | 江阴市江泰高分子新材料有限公司 | A kind of high wet and heat ageing resistant and the PE film of anti-corrosive properties and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333395A (en) * | 2013-07-15 | 2013-10-02 | 合肥工业大学 | High fill polyolefin composite film masterbatch and preparation method thereof |
| CN105153531A (en) * | 2015-09-17 | 2015-12-16 | 安徽玉发塑业有限公司 | High-temperature-resistant PE (polyethylene) corrugated pipe filling master batch and preparation method thereof |
| CN110066447A (en) * | 2019-05-10 | 2019-07-30 | 江阴市江泰高分子新材料有限公司 | A kind of high wet and heat ageing resistant and the PE film of anti-corrosive properties and preparation method thereof |
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