CN114479263A - Polypropylene composite material with memory function and preparation method thereof - Google Patents
Polypropylene composite material with memory function and preparation method thereof Download PDFInfo
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- CN114479263A CN114479263A CN202011165077.6A CN202011165077A CN114479263A CN 114479263 A CN114479263 A CN 114479263A CN 202011165077 A CN202011165077 A CN 202011165077A CN 114479263 A CN114479263 A CN 114479263A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 53
- -1 Polypropylene Polymers 0.000 title claims abstract description 52
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 230000006386 memory function Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 23
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 14
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000001125 extrusion Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 9
- 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 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000006870 function Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012781 shape memory material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 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 group 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 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Landscapes
- 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)
Abstract
The invention discloses a polypropylene composite material with a memory function, which is prepared from the following raw material components in parts by mass: 100 parts of polypropylene, 10-35 parts of filler, 3-5 parts of low-density polyethylene, 5-12 parts of ethylene butyl acrylate, 1-2 parts of lubricant and 0.5-1 part of antioxidant. The invention also discloses a preparation method of the polypropylene composite material. The polypropylene composite material provided by the invention has good compatibility with a polypropylene matrix through the synergistic effect of the low-density polyethylene and the ethylene butyl acrylate, and can be restored to be close to an original shape through proper heating after the polypropylene material is damaged by external force and has the functions of microstructure stability and shape memory.
Description
Technical Field
The invention belongs to the field of modified high polymer materials, and particularly relates to a polypropylene composite material with a memory function and a preparation method thereof.
Background
Polypropylene (abbreviated as PP) material has advantages of low cost, light weight, good chemical resistance, excellent processing property, easy recovery, etc., and is widely used in automobile and household appliance industry in recent years, especially applied to automobile interior and exterior parts, such as: door trim, instrument panel, pillar, seat guard, bumper, side surround, deflector, fender, and the like. The problems of the bumper, the side wall, the fender, the door panel, and the like of the vehicle often occur in a dent, a crack, and the like due to a collision, and the problems are more and more prominent with the recent rapid increase in the amount of automobiles kept in a home.
The shape memory plastic is a novel heat-sensitive functional material. It is a high molecular material which can be deformed at room temp. -constant temp., can be fixedly deformed at room temp. and can be stored for a long period, and when the temp. is raised to a certain specific temp., it can quickly recover to the form before deformation.
The shape memory plastic is technically characterized in that the deformation temperature of a molecular chain segment with a memory function in a shape memory material is controlled within a certain range, and the deformation temperature of a final product is adjusted within a certain temperature range by adjusting a non-memory function molecular chain segment of the shape memory material, so that deformation and deformation recovery can be generated under the temperature condition slightly higher than room temperature. Such plastics can be used for a longer period of time before degradation and can even reduce losses due to material scrap.
At present, shape memory material research mainly focuses on the following two aspects, namely, the structural design of shape memory macromolecules, such as the improvement of material performance by changing material components, adjusting the structural composition, content and molecular weight of soft and hard segments of a molecular chain, and the formation of different network structures through crosslinking, physical winding and non-covalent bond (such as hydrogen bond and Van der Waals force) effects; and secondly, the mechanical property of the high polymer material is improved through composite reinforcement, such as the strength of the material is enhanced by adding nano filler or fiber blend, but the shape memory property of the material is lost. Generally the structure of the polymer determines its properties. Therefore, many researchers have focused on the structure-activity relationship between the structure and the shape memory performance of the shape memory material, and by designing and synthesizing the shape memory material with a novel molecular structure, the problems existing in the field at present are expected to be solved, so that the shape memory material can be widely applied.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a polypropylene composite material with a memory function.
The purpose of the invention is realized by the following technical scheme:
the polypropylene composite material with the memory function is prepared from the following raw material components in parts by mass:
in a further scheme, the melt index of the polypropylene under the conditions of 230 ℃ and 2.16kg of load is 50-100g/10 min.
In a further scheme, the filler is at least one of talcum powder and calcium carbonate. The average particle size of the filler is 1000-5000 meshes.
In a further scheme, the low-density polyethylene has a melt index of 40-80g/10min at 190 ℃ under the condition of a load of 2.16 kg.
Further, the lubricant is white oil.
In a further scheme, the antioxidant is an antioxidant 1010 and an antioxidant 168 in a weight ratio of 1: 1, in a mixture of the components.
The invention also aims to provide a preparation method of the polypropylene composite material, which comprises the following steps: uniformly mixing 100 parts of polypropylene, 10-35 parts of filler, 5-12 parts of ethylene butyl acrylate, 3-5 parts of low-density polyethylene, 1-2 parts of lubricant and 0.5-1 part of antioxidant, adding the obtained mixed material into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the final product, namely the polypropylene composite material with the memory function. Preferably, the extrusion temperature of each extrusion zone in the twin-screw extruder is 150-.
Compared with the prior art, the invention has the following advantages:
1. according to the polypropylene composite material with the memory function, the low-density polyethylene and the ethylene butyl acrylate have synergistic effect, so that on one hand, the polypropylene composite material has good compatibility with a polypropylene matrix, and on the other hand, after the polypropylene material is damaged by external force and generates pits and bulges, the polypropylene material can be restored to be close to the original shape through proper heating.
2. The polypropylene composite material prepared by the invention has the functions of microstructure stability and shape memory.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The types and suppliers of reagents used in this example were as follows:
the polypropylene is BX3900 of Korean SK company, and the melt index is 60g/10 min;
the filler is preferably selected from pulvis Talci and calcium carbonate, and has an average particle size of 3000 meshes.
The low-density polyethylene is LG chemical LB7500, and the melt index is 50g/10min under the conditions of 190 ℃ and 2.16kg of load;
the white oil producer is Yongzhen industrial oil products Co.
The antioxidant is an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1, in a mixture of the components. The antioxidant 1010, antioxidant 168 manufacturers were both american cyanite chemistry.
The reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.
Example 1
Adding 100 parts of polypropylene, 10 parts of talcum powder, 5 parts of ethylene butyl acrylate, 3 parts of low-density polyethylene, 1 part of white oil and 0.5 part of antioxidant into a high-speed mixer, and uniformly mixing at normal temperature; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the polypropylene composite material with the memory function; wherein the extrusion temperature of each extrusion interval in the double-screw extruder is 150 ℃, 160 ℃, 175 ℃, 185 ℃, 195 ℃, 205 ℃ and 210 ℃ respectively;
example 2
Adding 100 parts of polypropylene, 20 parts of calcium carbonate, 8 parts of ethylene butyl acrylate, 4 parts of low-density polyethylene, 2 parts of white oil and 1 part of antioxidant into a high-speed mixer, and uniformly mixing at normal temperature; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the polypropylene composite material with the memory function; wherein the extrusion temperature of each extrusion interval in the double-screw extruder is 160 ℃, 175 ℃, 185 ℃, 195 ℃, 205 ℃, 215 ℃ and 220 ℃ respectively;
example 3
Adding 100 parts of polypropylene, 30 parts of talcum powder, 12 parts of ethylene butyl acrylate, 5 parts of low-density polyethylene, 2 parts of white oil and 1 part of antioxidant into a high-speed mixer, and uniformly mixing at normal temperature; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the polypropylene composite material with the memory function; wherein the extrusion temperature of each extrusion interval in the double-screw extruder is 155 ℃, 165 ℃, 185 ℃, 195 ℃, 205 ℃, 215 ℃ and 220 ℃ respectively;
example 4
Adding 100 parts of polypropylene, 35 parts of talcum powder, 10 parts of ethylene butyl acrylate, 5 parts of low-density polyethylene, 2 parts of white oil and 1 part of antioxidant into a high-speed mixer, and uniformly mixing at normal temperature; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the polypropylene composite material with the memory function; wherein the extrusion temperature of each extrusion interval in the double-screw extruder is 155 ℃, 165 ℃, 185 ℃, 195 ℃, 205 ℃, 215 ℃ and 220 ℃ respectively;
comparative example 1
Adding 100 parts of polypropylene, 30 parts of talcum powder, 15 parts of low-density polyethylene, 2 parts of white oil and 1 part of antioxidant into a high-speed mixer, and uniformly mixing at normal temperature; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the polypropylene composite material with the memory function; wherein the extrusion temperature of each extrusion interval in the double-screw extruder is 155 ℃, 165 ℃, 185 ℃, 195 ℃, 205 ℃, 215 ℃ and 220 ℃ respectively;
comparative example 2
Adding 100 parts of polypropylene, 30 parts of talcum powder, 15 parts of ethylene butyl acrylate, 2 parts of white oil and 1 part of antioxidant into a high-speed mixer, and uniformly mixing at normal temperature; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the polypropylene composite material with the memory function; wherein the extrusion temperature of each extrusion interval in the double-screw extruder is 155 ℃, 165 ℃, 185 ℃, 195 ℃, 205 ℃, 215 ℃ and 220 ℃ respectively;
comparative example 3
Adding 100 parts of polypropylene, 30 parts of talcum powder, 2 parts of white oil and 1 part of antioxidant into a high-speed mixer, and uniformly mixing at normal temperature; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the polypropylene composite material with the memory function; wherein the extrusion temperature of each extrusion interval in the double-screw extruder is 155 ℃, 165 ℃, 185 ℃, 195 ℃, 205 ℃, 215 ℃ and 220 ℃ respectively;
the performance test methods of the products prepared in the above examples and comparative examples are respectively as follows:
tensile strength tests of the products obtained in the examples and comparative examples were carried out using tensile bars of type (170.0. + -. 5.0) mm (13.0. + -. 0.5) mm (3.2. + -. 0.2) mm, at a tensile rate of 50mm/min, test Standard GB/T1040. The model of a cantilever beam notch impact strength spline used for testing the cantilever beam notch impact strength is as follows: (125.0 ± 5.0) mm (13.0 ± 0.5) mm (3.2 ± 0.2) mm, machining of the notch, depth of notch (2.6 ± 0.2) mm, test standard GB/T1843.
Stretch recovery ratio at 100 ℃/%: the test is that the test is stopped when the sample is stretched to 100 percent elongation according to the tensile test method of GB 1040, and the sample is quickly placed in an oven at 100 ℃ for heat treatment for 180S, and the shape recovery degree of the sample in the stretching direction is measured;
the results of the performance test of the manufactured products of the respective examples and comparative examples are shown in the following table 1:
TABLE 1 Performance test results
From the above table, it can be seen that the polypropylene material with a memory function provided by the invention has good compatibility with a polypropylene matrix through the synergistic effect of the low-density polyethylene and the ethylene butyl acrylate, and after the polypropylene material is damaged by an external force, the polypropylene material can be restored to an original shape through appropriate heating.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should understand that they can make improvements and modifications without departing from the scope of the present invention.
Claims (9)
1. A polypropylene composite material with a memory function is characterized in that: the feed is prepared from the following raw materials in parts by mass:
2. the polypropylene composite according to claim 1, wherein: the melt index of the polypropylene under the conditions of 230 ℃ and 2.16kg of load is 50-100g/10 min.
3. The polypropylene composite according to claim 1, wherein: the filler is at least one of talcum powder and calcium carbonate.
4. The polypropylene composite according to claim 3, wherein: the average particle size of the filler is 1000-5000 meshes.
5. The polypropylene composite according to claim 1, wherein: the low-density polyethylene has a melt index of 40-80g/10min at 190 ℃ under a load of 2.16 kg.
6. The polypropylene composite according to claim 1, wherein: the lubricant is white oil.
7. The polypropylene composite according to claim 1, wherein: the antioxidant is prepared from the following components in parts by weight of 1: 1, in a mixture of the components.
8. A process for the preparation of a polypropylene composite according to any one of claims 1 to 7, wherein: the method comprises the following steps: uniformly mixing 100 parts of polypropylene, 10-35 parts of filler, 5-12 parts of ethylene butyl acrylate, 3-5 parts of low-density polyethylene, 1-2 parts of lubricant and 0.5-1 part of antioxidant, adding the obtained mixed material into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the final product, namely the polypropylene composite material with the memory function.
9. The method of claim 8, wherein: the extrusion temperature of each extrusion zone in the double-screw extruder is respectively 150-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202011165077.6A CN114479263A (en) | 2020-10-27 | 2020-10-27 | Polypropylene composite material with memory function and preparation method thereof |
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| CN202011165077.6A CN114479263A (en) | 2020-10-27 | 2020-10-27 | Polypropylene composite material with memory function and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401689A (en) * | 2001-08-07 | 2003-03-12 | 阿托菲纳公司 | Composition based on polypropylene and ethylene/alkyl acrylate copolymer |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401689A (en) * | 2001-08-07 | 2003-03-12 | 阿托菲纳公司 | Composition based on polypropylene and ethylene/alkyl acrylate copolymer |
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