CN118388926B - Barium sulfate polymer composite material and preparation method thereof - Google Patents
Barium sulfate polymer composite material and preparation method thereof Download PDFInfo
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 216
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003365 glass fiber Substances 0.000 claims abstract description 19
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 21
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 17
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 17
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 17
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000005642 Oleic acid Substances 0.000 claims description 17
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 8
- 229910001626 barium chloride Inorganic materials 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000012360 testing method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
- 238000005406 washing Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010125 resin casting Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000007676 flexural strength test Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a barium sulfate polymer composite material and a preparation method thereof in the technical field of material preparation, wherein the barium sulfate polymer composite material comprises the following components in parts by weight: 80-100 parts of epoxy resin, 10-20 parts of modified nano barium sulfate, 6-8 parts of multi-wall carbon nano tubes, 7-9 parts of glass fibers, 20-30 parts of acetone and 10-15 parts of 4, 4-diamino diphenyl methane curing agent. According to the invention, the surface of nano barium sulfate is coated by methyl methacrylate, then the nano barium sulfate is modified by ethylenediamine, finally polyethyleneimine is grafted on the surface to obtain modified nano barium sulfate, and the modified nano barium sulfate is matched with a 4, 4-diaminodiphenylmethane curing agent to prepare an epoxy resin composite material with higher curing density, and simultaneously, the multi-wall carbon nano tube and glass fiber are added to further improve the mechanical property of the epoxy resin.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a barium sulfate polymer composite material and a preparation method thereof.
Background
Epoxy resin is one of the most widely applied thermosetting materials, and compared with other thermosetting resins, the epoxy resin has special characteristics, such as low shrinkage rate, short curing time, excellent adhesive force, high mechanical strength, chemical corrosion resistance and the like during curing, and is widely applied to the fields of aerospace, ocean engineering, chemical corrosion resistance, environment-friendly paint, civil use and the like, but the curing system of the epoxy resin has the defects of large brittleness, poor toughness, impact resistance and the like, so that the epoxy resin is limited to the application in the field of key materials with high requirements on mechanical properties; the barium sulfate has the advantages of easy development, low cost, no toxicity, no harm, strong stability and the like, and is widely applied to the industries of coating, paper making, rubber, plastics and textile, while the application value of the nano barium sulfate is higher, the nano barium sulfate not only has the advantages of common barium sulfate, but also has great application prospect in the fields of polymer materials, nonlinear optics, medical treatment, catalysis and the like, the application value and the specific application field of the nano barium sulfate are closely related to the self dispersibility of the nano barium sulfate, and the nano barium sulfate prepared by the traditional method has the defects of poor dispersibility and serious particle aggregation, so that the application of the nano barium sulfate is greatly limited.
The prior art mainly has the following problems: the epoxy resin has poor properties and the barium sulfate has poor dispersibility.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides a barium sulfate polymer composite material and a preparation method thereof, the invention provides a method for coating the surface of nano barium sulfate by methyl methacrylate, then modifying the nano barium sulfate by ethylenediamine, finally, grafting the polyethyleneimine on the surface to obtain modified nano barium sulfate, preparing an epoxy resin composite material with higher curing density by matching with a4, 4-diaminodiphenyl methane curing agent, and simultaneously adding the multi-wall carbon nano tube and glass fiber to further improve the mechanical property of the epoxy resin.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a barium sulfate polymer composite material and a preparation method thereof, wherein the barium sulfate polymer composite material comprises the following components in parts by weight: 80-100 parts of epoxy resin, 10-20 parts of modified nano barium sulfate, 6-8 parts of multi-wall carbon nano tubes, 7-9 parts of glass fibers, 20-30 parts of acetone and 10-15 parts of 4, 4-diamino diphenyl methane curing agent.
Further, the preparation method of the modified nano barium sulfate comprises the following steps:
(1) Adding barium chloride and sodium sulfate into 100mL of deionized water, stirring to fully dissolve, transferring to a flask, adding oleic acid, heating to 80-90 ℃, stirring at 600rpm for reaction for 30-40min, filtering after finishing, washing with deionized water for 3 times, and vacuum drying at 50 ℃ to obtain oleic acid modified nano barium sulfate;
(2) Adding the oleic acid modified nano barium sulfate obtained in the step (1) into a flask, adding methyl methacrylate, adding divinylbenzene, performing ultrasonic treatment for 10-20min, enabling the power to be 400W, then adding an initiator azo-diisobutyronitrile, reacting for 40-60min under the condition that the rotating speed of 60 ℃ is 400rpm, washing the precipitate with deionized water for 3 times, adding into 100mL of methanol, adding ethylenediamine, and reacting for 20-24h at 60 ℃ to obtain ethylenediamine modified nano barium sulfate;
(3) Adding polyethylenimine into methanol to obtain polyethylenimine solution, adding ethylenediamine modified nano barium sulfate obtained in the step (1) into polyethylenimine solution, magnetically stirring for 20-24h at room temperature at the stirring speed of 300-400rpm, adding 1wt% glutaraldehyde water solution, continuously stirring for 30-40min, and washing with deionized water for 3 times to obtain modified nano barium sulfate.
Further, in the step (1), the mass ratio of the barium chloride to the sodium sulfate is 1:2-3.
Further, in the step (1), the volume ratio of the oleic acid to the deionized water is 1-2:100.
Further, in the step (2), the volume ratio of the divinylbenzene to the methyl methacrylate is 1:15-20.
Further, in the step (2), the mass ratio of the oleic acid modified nano barium sulfate to the azodiisobutyronitrile is 1:1-2.
Further, in the step (2), the mass ratio of the oleic acid modified nano barium sulfate to the ethylenediamine is 1:2-4.
Further, in the step (3), the mass fraction of the polyethyleneimine in methanol is 2% -3%.
Further, in the step (3), the mass concentration of the ethylenediamine modified nano barium sulfate in the polyethyleneimine solution is 20-30g/L.
Further, in the step (3), the volume ratio of the glutaraldehyde aqueous solution to the polyethyleneimine solution is 3-4:1.
The invention provides a preparation method of a barium sulfate polymer composite material, which specifically comprises the following steps:
Adding the multi-wall carbon nano tube and glass fiber into acetone, stirring for 2-3h, then adding epoxy resin, continuously stirring for 3-4h, adding modified nano barium sulfate and 4, 4-diaminodiphenylmethane curing agent, stirring for 1-2h, and curing at room temperature for 10-20h to obtain the barium sulfate polymer composite material.
The beneficial effects obtained by the invention are as follows:
According to the invention, methyl methacrylate is used as a medium to cover the surface of nano barium sulfate, then ethylenediamine is used for modifying the nano barium sulfate, finally polyethyleneimine is grafted on the surface to obtain modified nano barium sulfate, and the modified nano barium sulfate is matched with a 4, 4-diaminodiphenylmethane curing agent to prepare an epoxy resin composite material with higher curing density, and simultaneously, multiwall carbon nanotubes and glass fibers are added to further improve the mechanical properties of epoxy resin; the nano barium sulfate is modified, so that the surface chemical structure of the nano barium sulfate is changed, functional groups such as ester groups, amide groups, amino groups and the like are formed, the functional groups can react with epoxy groups to form covalent bonds, the interface interaction between the nano barium sulfate and epoxy resin is enhanced, the compatibility of the nano barium sulfate and the epoxy resin is improved, meanwhile, the abundant amino groups on the modified nano barium sulfate can effectively cure the epoxy resin, and the epoxy resin composite material with high curing density is prepared by matching with a 4, 4-diaminodiphenylmethane curing agent; the glass fiber reinforced epoxy resin has the advantages of light weight and high strength, but has poor toughness, and the introduced multi-wall carbon nano tube has the characteristics of small volume, high length-diameter ratio and excellent mechanical property, can be effectively fused with a resin matrix, obviously influences the generation and expansion of microcracks in the matrix, and compensates the toughness of the composite material.
Drawings
FIG. 1 is a graph showing the tensile strength test results of examples 1-3 and comparative examples 1-2 according to the present invention;
FIG. 2 is a graph showing the results of compressive strength testing for examples 1-3 and comparative examples 1-2 of the present invention;
FIG. 3 is a graph showing the results of the flexural strength test of examples 1-3 and comparative examples 1-2 of the present invention;
FIG. 4 is a scanning electron microscope image of the barium sulfate polymer composite material prepared in example 1 of the present invention.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
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. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials used in the examples described below, unless otherwise specified, were purchased from commercial sources.
Example 1
The barium sulfate polymer composite material comprises the following components in parts by weight: 80 parts of epoxy resin, 10 parts of modified nano barium sulfate, 6 parts of multi-wall carbon nano tube, 7 parts of glass fiber, 20 parts of acetone and 10 parts of 4, 4-diaminodiphenyl methane curing agent.
The preparation method of the modified nano barium sulfate comprises the following steps:
(1) Adding 1g of barium chloride and 2g of sodium sulfate into 100mL of deionized water, stirring to fully dissolve, transferring to a flask, adding 1mL of oleic acid, heating to 80 ℃, stirring at 600rpm for reaction for 30min, filtering after finishing, washing with deionized water for 3 times, and vacuum drying at 50 ℃ to obtain oleic acid modified nano barium sulfate;
(2) Adding 500mg of oleic acid modified nano barium sulfate obtained in the step (1) into a flask, adding 3mL of methyl methacrylate, adding 200 mu L of divinylbenzene, performing ultrasonic treatment for 10min with the power of 400W, then adding 500mg of azobisisobutyronitrile, performing reaction for 40min under the condition of the rotating speed of 400rpm at 60 ℃, taking the precipitate, washing 3 times with deionized water, then adding into 100mL of methanol, adding 1g of ethylenediamine, and performing reaction for 20h at 60 ℃ to obtain ethylenediamine modified nano barium sulfate;
(3) Adding polyethylenimine into methanol to prepare polyethylenimine solution with mass fraction of 2%, adding 1g of ethylenediamine modified nano barium sulfate obtained in the step (2) into 50mL of polyethylenimine solution, magnetically stirring at room temperature for 20h at a stirring speed of 300rpm, adding 150mL of 1wt% glutaraldehyde aqueous solution, continuously stirring for 30min, and washing with deionized water for 3 times to obtain modified nano barium sulfate.
The embodiment provides a preparation method of a barium sulfate polymer composite material, which specifically comprises the following steps:
Adding the multiwall carbon nanotube and the glass fiber into acetone, stirring for 2 hours, then adding the epoxy resin, continuing stirring for 3 hours, adding the modified nano barium sulfate and the 4, 4-diaminodiphenyl methane curing agent, stirring for 1 hour, and curing for 10 hours at room temperature to obtain the barium sulfate polymer composite material.
Example 2
The barium sulfate polymer composite material comprises the following components in parts by weight: 100 parts of epoxy resin, 20 parts of modified nano barium sulfate, 8 parts of multi-wall carbon nano tube, 9 parts of glass fiber, 30 parts of acetone and 15 parts of 4, 4-diaminodiphenyl methane curing agent.
The preparation method of the modified nano barium sulfate comprises the following steps:
(1) Adding 1g of barium chloride and 3g of sodium sulfate into 100mL of deionized water, stirring to fully dissolve, transferring to a flask, adding 2mL of oleic acid, heating to 90 ℃, stirring at 600rpm for reaction for 40min, filtering after finishing, washing with deionized water for 3 times, and vacuum drying at 50 ℃ to obtain oleic acid modified nano barium sulfate;
(2) Adding 500mg of oleic acid modified nano barium sulfate obtained in the step (1) into a flask, adding 4mL of methyl methacrylate, adding 200 mu L of divinylbenzene, performing ultrasonic treatment for 20min with the power of 400W, then adding 1000mg of azobisisobutyronitrile, performing reaction for 60min under the condition of the rotating speed of 400rpm at 60 ℃, taking the precipitate, washing 3 times with deionized water, then adding into 100mL of methanol, adding 2g of ethylenediamine, and performing reaction for 24h at 60 ℃ to obtain ethylenediamine modified nano barium sulfate;
(3) Adding polyethylenimine into methanol to prepare polyethylenimine solution with mass fraction of 3%, adding 2g of ethylenediamine modified nano barium sulfate obtained in the step (2) into 50mL of polyethylenimine solution, magnetically stirring at room temperature for 24h at a stirring speed of 400rpm, adding 200mL of 1wt% glutaraldehyde aqueous solution, continuously stirring for 40min, and washing with deionized water for 3 times to obtain modified nano barium sulfate.
The embodiment provides a preparation method of a barium sulfate polymer composite material, which specifically comprises the following steps:
adding the multiwall carbon nanotube and the glass fiber into acetone, stirring for 3 hours, then adding the epoxy resin, continuing stirring for 4 hours, adding the modified nano barium sulfate and the 4, 4-diaminodiphenyl methane curing agent, stirring for 2 hours, and curing at room temperature for 20 hours to obtain the barium sulfate polymer composite material.
Example 3
The barium sulfate polymer composite material comprises the following components in parts by weight: 90 parts of epoxy resin, 15 parts of modified nano barium sulfate, 7 parts of multi-wall carbon nano tube, 8 parts of glass fiber, 25 parts of acetone and 13 parts of 4, 4-diaminodiphenyl methane curing agent.
The preparation method of the modified nano barium sulfate comprises the following steps:
(1) Adding 1g of barium chloride and 2.5g of sodium sulfate into 100mL of deionized water, stirring to fully dissolve the barium chloride and the sodium sulfate, transferring the mixture into a flask, adding 1.5mL of oleic acid, heating to 85 ℃, stirring at 600rpm for reaction for 35min, filtering after the reaction is finished, washing the mixture with deionized water for 3 times, and drying the mixture in vacuum at 50 ℃ to obtain oleic acid modified nano barium sulfate;
(2) Adding 500mg of oleic acid modified nano barium sulfate obtained in the step (1) into a flask, adding 3.5mL of methyl methacrylate, adding 200 mu L of divinylbenzene, performing ultrasonic treatment for 15min with the power of 400W, then adding 750mg of azodiisobutyronitrile, reacting for 50min at the rotating speed of 400rpm at 60 ℃, taking the precipitate, washing 3 times with deionized water, then adding into 100mL of methanol, adding 1.5g of ethylenediamine, and reacting for 22h at 60 ℃ to obtain ethylenediamine modified nano barium sulfate;
(3) Adding polyethylenimine into methanol to prepare polyethylenimine solution with mass fraction of 2.5%, adding 1.5g of ethylenediamine modified nano barium sulfate obtained in the step (2) into 50mL of polyethylenimine solution, magnetically stirring for 22h at room temperature, wherein the stirring speed is 350rpm, adding 180mL of 1wt% glutaraldehyde aqueous solution, continuously stirring for 35min, and washing with deionized water for 3 times to obtain modified nano barium sulfate.
The embodiment provides a preparation method of a barium sulfate polymer composite material, which specifically comprises the following steps:
Adding the multi-wall carbon nano tube and glass fiber into acetone, stirring for 2.5 hours, then adding epoxy resin, continuously stirring for 3.5 hours, adding modified nano barium sulfate and 4, 4-diaminodiphenylmethane curing agent, stirring for 1.5 hours, and curing for 15 hours at room temperature to obtain the barium sulfate polymer composite material.
Comparative example 1
This comparative example provides a barium sulfate polymer composite material and a method for preparing the same, which is different from example 1 in that the modified nano barium sulfate is replaced by nano barium sulfate without modifying nano barium sulfate, and the rest components and the content of the components are the same as example 1.
Comparative example 2
This comparative example provides a barium sulfate polymer composite material and a method for preparing the same, which is different from example 1 in that multi-walled carbon nanotubes and glass fibers are not added, and the remaining components and the content of the components are the same as example 1.
Experimental example 1
The tensile strength test was conducted on examples 1 to 3 and comparative examples 1 and 2 according to the method of testing the performance of the resin casting body of GB/T2567-2008 by using a universal material testing machine, and a static tensile load was applied at a constant speed along the axial direction of the test specimen until the test specimen broke or reached a predetermined elongation, and in the whole process, the load applied to the test specimen and the elongation of the test specimen were measured to determine the tensile stress at a test speed of 10mm/min, and the tensile strength was calculated according to the following formula:
σt=P/(b×h)
Wherein: σ t is tensile strength (Mpa), P is breaking load (N), b is specimen width (mm), and h is specimen thickness (mm).
Experimental example 2
The compressive strength test was conducted on examples 1 to 3 and comparative examples 1 and 2 of the present invention, and the test method was conducted with reference to GB/T2567-2008 resin casting body performance test, using a universal material tester, compressing the test specimen at a constant rate in the axial direction of the test specimen to reduce the destruction or height of the test specimen to a predetermined value, and in the whole process, measuring the load applied to the test specimen and the height or strain of the test specimen, measuring the compressive stress at a test speed of 5mm/min, and calculating the tensile strength according to the following formula:
σc=P/(b×h)
Wherein: σ t is the compressive strength (Mpa), P is the breaking load (N), b is the specimen width (mm), and h is the specimen thickness (mm).
Experimental example 3
The flexural strength test was conducted on examples 1 to 3 and comparative examples 1 and 2 of the present invention, and the test method was conducted with reference to the performance test method of the GB/T2567-2008 resin casting body, using a universal material tester, using an unconstrained support, breaking or reaching a predetermined deflection value of the test specimen at a constant loading rate by three-point bending, and in the whole process, measuring the load applied to the test specimen and the deflection of the test specimen, measuring the flexural strength, and calculating the flexural strength according to the following formula:
σe=3P×L/(2b×h2)
Wherein: σ e is the flexural strength (Mpa), P is the breaking load (N), L is the span (mm), b is the specimen width (mm), and h is the specimen thickness (mm).
4. The barium sulfate polymer composite material prepared in example 1 was observed by a scanning electron microscope.
Analysis of results
FIG. 1 is a graph showing the tensile strength test results of examples 1 to 3 and comparative examples 1 to 2 according to the present invention, wherein the tensile strengths of examples 1 to 3 are 71MPa, 72MPa, 70MPa, 52MPa, and 59MPa, respectively, as shown in the graph; examples 1-3 have significantly greater tensile strength than comparative example 1, demonstrating that modifying nano barium sulfate enhances the tensile strength of the material, and examples 1-3 have significantly greater tensile strength than comparative example 2, demonstrating that the addition of multi-walled carbon nanotubes and glass fibers enhances the tensile strength of the material.
FIG. 2 is a graph showing the results of the compressive strength test of examples 1 to 3 and comparative examples 1 to 2 of the present invention, wherein the compressive strengths of examples 1 to 3 are 89MPa, 90MPa, 91MPa, 61MPa and 67MPa, respectively, as shown in the graph; the compressive strength of examples 1-3 is significantly greater than that of comparative example 1, demonstrating that modification of nano barium sulfate enhances the compressive strength of the material, and examples 1-3 are significantly greater than comparative example 2, demonstrating that the addition of multi-walled carbon nanotubes and glass fibers enhances the compressive strength of the material.
FIG. 3 is a graph showing the results of the bending strength test of examples 1 to 3 and comparative examples 1 to 2 according to the present invention, wherein the bending strengths of examples 1 to 3 are 92MPa, 93MPa, 92MPa, 66MPa, and 71MPa, respectively, as shown in the drawings; the flexural strength of examples 1-3 was significantly greater than that of comparative example 1, demonstrating that modification of nano barium sulfate enhanced the flexural strength of the material, and that of examples 1-3 were significantly greater than comparative example 2, demonstrating that the addition of multi-walled carbon nanotubes and glass fibers enhanced the flexural strength of the material.
FIG. 4 is a scanning electron microscope image of the barium sulfate polymer composite material prepared in example 1 of the present invention.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made hereto without departing from the spirit and principles of the present invention.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (9)
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| CN112299467B (en) * | 2019-07-31 | 2022-10-28 | 北京化工大学 | Preparation method of monodisperse oil-phase nano barium sulfate dispersoid |
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