CN110698797B - Preparation method of carboxylated carbon nanotube modified pentaerythritol acrolein resin - Google Patents
Preparation method of carboxylated carbon nanotube modified pentaerythritol acrolein resin Download PDFInfo
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- CN110698797B CN110698797B CN201911057177.4A CN201911057177A CN110698797B CN 110698797 B CN110698797 B CN 110698797B CN 201911057177 A CN201911057177 A CN 201911057177A CN 110698797 B CN110698797 B CN 110698797B
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- pentaerythritol
- carboxylated carbon
- carbon nanotubes
- acrolein resin
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- 239000011347 resin Substances 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 63
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 carbon nanotube modified pentaerythritol acrolein Chemical class 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 15
- LDSINNHLPFCWNV-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enal Chemical compound C=CC=O.OCC(CO)(CO)CO LDSINNHLPFCWNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940008406 diethyl sulfate Drugs 0.000 claims abstract description 11
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 abstract description 10
- 239000002360 explosive Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of pentaerythritol acrolein resin modified by carboxylated carbon nanotubes, belonging to the technical field of energetic materials. The method comprises the following steps: step 1: crushing and grinding the carboxylated carbon nanotubes by using an agate grinding rod; step 2: mixing the ground carboxylated carbon nanotubes in the step 1 with pentaerythritol acrolein resin, and primarily stirring uniformly; and step 3: then, carrying out ultrasonic dispersion treatment on the mixture obtained in the step 2 by using an ultrasonic instrument; and 4, step 4: stirring the mixture subjected to the dispersion treatment in the step 3 by adopting a mechanical stirring method again; and 5: next, adding diethyl sulfate into the mixture obtained in the step 4, uniformly stirring, and then pouring into a mold; step 6: and (5) placing the mixture obtained in the step (5) in an oven, and curing to obtain the carboxylated carbon nanotube modified pentaerythritol acrolein resin.
Description
Technical Field
The invention belongs to the field of preparation of energetic materials, and particularly relates to a preparation method of pentaerythritol acrolein resin modified by carboxylated carbon nanotubes.
Background
Many thermosetting explosive components with high requirements on dimensional stability adopt pentaerythritol acrolein resin (also called 123 resin) as a bonding agent. The 123 resin is a prepolymer of an adhesive formed by chemical crosslinking of pentaerythritol and acrolein in the presence of an acid catalyst, is a transparent viscous liquid resin, and is cured by self-polymerization or polymerization reaction with a polyhydroxy compound under the action of the acid catalyst. The catalyst is diethyl sulfate in proper acid value range (acid value less than 1%), and the cured 123 resin is one kind of hard plastic with high transparency, no pore, excellent mechanical performance, high heat resistance and high chemical corrosion resistance. The high polymer bonded explosive (PBX) using the high polymer bonded explosive as the matrix has good mechanical properties, and the high polymer bonded explosive is widely applied due to high quality stability, excellent size and shape stability and flexible forming process.
However, the high brittleness of the 123 resin makes the explosive member prone to crack during temperature shock, which causes quality risk of the explosive member during the curing process, and the internal damage of the brittle material also brings safety risk to the application of the explosive. At present, the military pays more and more attention to the quality and the safety performance of the explosive, and an explosive part with lower sensitivity and reliable quality needs to be obtained urgently. Toughening the adhesive material 123 resin to improve the mechanical properties of the PBX is a very effective approach. The carbon nanotube is a nanofiber material with excellent performance, but the carbon nanotube is difficult to modify the 123 resin directly, firstly, the carbon nanotube is a nanomaterial and is easy to agglomerate, so that the dispersibility in the 123 resin is poor, and secondly, the surface of the carbon nanotube lacks of active groups and lacks of strong interface interaction with a matrix, which is not beneficial to improving the mechanical property of the matrix material.
Disclosure of Invention
The invention aims to provide a preparation method of pentaerythritol acrolein resin modified by carboxylated carbon nanotubes, which is characterized in that 123 resin is modified by the carboxylated carbon nanotubes innovatively, and meanwhile, the properties of the carbon nanotubes such as 123 resin section elongation and the like are improved based on a certain dispersion technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a carboxylated carbon nanotube modified pentaerythritol acrolein resin comprises the following steps:
step 1: crushing and grinding the carboxylated carbon nanotubes by adopting an agate grinding rod;
step 2: mixing the ground carboxylated carbon nanotubes in the step 1 with pentaerythritol acrolein resin, and primarily stirring uniformly;
and step 3: then, carrying out ultrasonic dispersion treatment on the mixture obtained in the step 2 by using an ultrasonic instrument;
and 4, step 4: stirring the mixture subjected to the dispersion treatment in the step 3 by adopting a mechanical stirring method again;
and 5: next, adding diethyl sulfate into the mixture obtained in the step 4, uniformly stirring, and then pouring into a mold;
step 6: and (5) placing the mixture obtained in the step (5) in an oven, and curing to obtain the carboxylated carbon nanotube modified pentaerythritol acrolein resin.
The further technical scheme is that in the step 2, the proportion of the carboxylated carbon nanotubes in the pentaerythritol acrolein resin is 0.04-0.08 wt%.
The further technical scheme is that in the step 3, the time of ultrasonic dispersion treatment is 30 min.
The further technical scheme is that in the step 4, the mechanical stirring time is 15 min.
The further technical scheme is that in the step 5, the mass volume ratio of the pentaerythritol acrolein resin to the diethyl sulfate is as follows: 50-100 g: 0.9-1.8 mL.
The further technical scheme is that in the step 6, the curing temperature is 60 ℃, and the curing time is 8 hours.
The invention specifically adopts a carboxylated Carbon Nano Tube (CNTs) to realize doping modification of 123 resin, adopts a certain dispersion technology to uniformly disperse the CNTs in the 123 resin, and prepares the 123 resin composite material after being cured by diethyl sulfate (DES), thereby realizing improvement of mechanical properties of the 123 resin and showing that the method can effectively improve the toughness of the 123 resin.
Compared with the prior art, the invention has the beneficial effects that:
1. the adopted carboxylated CNTs and 123 resin have stronger interfacial interaction, which is beneficial to improving the toughening effect of the fiber.
2. Because the surface of the carboxylated CNTs has more active groups, the CNTs can be uniformly dispersed in the 123 resin by the dispersion method.
3. The method uses low fiber mass ratio, but obviously improves the section elongation of the resin, and can improve the section elongation of 123 resin by 7.9 percent by adopting 0.04 weight percent mass ratio.
Drawings
FIG. 1 is a photograph of samples after a tensile test of a prepared modified 123 resin sample and a non-modified 123 resin sample;
FIG. 2 is an SEM photograph of a sample cross section of a CNTs modified 123 resin.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, other embodiments used by those skilled in the art without any creative effort belong to the protection scope of the present invention.
FIG. 1 is a photograph of a sample after a tensile test of the prepared carboxylated carbon nanotube modified 123 resin sample. The sample No. 1 is a sample after 123 resin is cured, the sample No. 2 is 123 resin modified by doping 0.04 wt% of CNTs, and the sample No. 3 is 123 resin modified by doping 0.04 wt% of carboxylated CNTs.
Table 1 shows the results of the unmodified 123 resin samples and the modified 123 resin samples test pieces. It can be seen that the addition of the two CNTs is beneficial to improving the strength and the section elongation of the material, and compared with the CNTs which are not subjected to carboxylation treatment, the carboxylated CNTs can obviously improve the section elongation of the material, namely the toughness of the material is enhanced.
TABLE 1 test results for unmodified 123 resin samples and modified 123 resin samples test pieces
FIG. 2 is an SEM photograph of a sample cross section of a CNTs modified 123 resin. Panel (a) corresponds to a 123 resin blank, panel (b) is 0.04 wt% CNTs modified 123 resin, and panels (c, d) are 0.04 wt% carboxylated CNTs modified 123 resin. From the aspect of dispersibility of CNTs, it can be seen that the CNTs in the sample 3 have better dispersibility than that in the sample 2, which indicates that the carboxylation of CNTs is helpful to improve the dispersibility of CNTs in 123 resin. The cross section structure of the sample has obvious difference, the cross section of the 2# sample mainly presents a dimple shape, the 3# sample (on the basis of the dimple shape, a drawn line with the dimension of a few micrometers appears, careful observation can find that most drawn ends can observe slender fibers, the slender fibers of the ends are deduced to be carboxylated CNTs, two points can be deduced from the appearance, and 1) compared with the CNTs, the interface compatibility between the carboxylated CNTs and 123 resin is better; 2) the carboxylated CNTs can greatly improve the section elongation of the material, just because the resistance of crack propagation in the direction perpendicular to the direction of the force is increased after the fibers are added, so that the toughness of the 123 resin is increased,
example 1:
firstly weighing 0.02g of carboxylated CNTs, and crushing and grinding the CNTs by adopting an agate grinding rod; weighing 50g of 123 resin, then mixing the ground CNTs with the 123 resin, and primarily stirring uniformly; then, carrying out ultrasonic dispersion treatment on the mixture for 30min by adopting an ultrasonic instrument; processing for 15min by mechanical stirring; then adding 0.9mL of DES into the mixture, stirring uniformly, and pouring into a mold; and finally, placing the sample in a 60 ℃ oven, and curing for 8h to prepare a 123 resin sample modified by the carboxylated CNTs.
Example 2:
weighing 0.04g of carboxylated CNTs, and crushing and grinding the CNTs by adopting an agate grinding rod; weighing 100g of 123 resin, then mixing the ground CNTs with the 123 resin, and primarily stirring uniformly; then, carrying out ultrasonic dispersion treatment on the mixture for 30min by adopting an ultrasonic instrument; processing for 15min by mechanical stirring; then adding 1.8mL of DES into the mixture, stirring uniformly, and pouring into a mold; and finally, placing the sample in a 60 ℃ oven, and curing for 8h to prepare a 123 resin sample modified by the carboxylated CNTs.
Example 3:
weighing 0.03g of carboxylated CNTs, and crushing and grinding the CNTs by adopting an agate grinding rod; weighing 100g of 123 resin, then mixing the ground CNTs with the 123 resin, and primarily stirring uniformly; then, carrying out ultrasonic dispersion treatment on the mixture for 30min by adopting an ultrasonic instrument; treating for 15min by mechanical stirring; then adding 1.8mL of DES into the mixture, stirring uniformly, and pouring into a mold; finally, the mixture is placed in a 60 ℃ oven and cured for 8 hours, so that a 0.03 wt% carboxylated CNTs modified 123 resin sample is prepared.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. A preparation method of a carboxylated carbon nanotube modified pentaerythritol acrolein resin is characterized by comprising the following steps:
step 1: crushing and grinding the carboxylated carbon nanotubes by adopting an agate grinding rod;
step 2: mixing the ground carboxylated carbon nanotubes in the step 1 with pentaerythritol acrolein resin, and primarily stirring uniformly; the proportion of the carboxylated carbon nanotubes in the pentaerythritol acrolein resin is 0.04-0.08 wt%;
and step 3: then, carrying out ultrasonic dispersion treatment on the mixture obtained in the step 2 by using an ultrasonic instrument;
and 4, step 4: stirring the mixture subjected to the dispersion treatment in the step 3 by adopting a mechanical stirring method again;
and 5: next, adding diethyl sulfate into the mixture obtained in the step 4, uniformly stirring, and then pouring into a mold; the mass volume ratio of the pentaerythritol acrolein resin to the diethyl sulfate is as follows: 50-100 g: 0.9-1.8 mL;
step 6: and (5) placing the mixture obtained in the step (5) in an oven, and curing to obtain the carboxylated carbon nanotube modified pentaerythritol acrolein resin.
2. The method for preparing pentaerythritol acrolein resin modified by carboxylated carbon nanotubes as claimed in claim 1, wherein the time of the ultrasonic dispersion treatment in step 3 is 30 min.
3. The method for preparing pentaerythritol acrolein resin modified by carboxylated carbon nanotubes as claimed in claim 1, wherein the mechanical stirring time in step 4 is 15 min.
4. The method for preparing pentaerythritol acrolein resin modified by carboxylated carbon nanotubes as claimed in claim 1, wherein in the step 6, the curing temperature is 60 ℃ and the curing time is 8 h.
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| CN201911057177.4A CN110698797B (en) | 2019-10-30 | 2019-10-30 | Preparation method of carboxylated carbon nanotube modified pentaerythritol acrolein resin |
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| CN201911057177.4A CN110698797B (en) | 2019-10-30 | 2019-10-30 | Preparation method of carboxylated carbon nanotube modified pentaerythritol acrolein resin |
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| CN110698797B true CN110698797B (en) | 2022-05-03 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532243A (en) * | 2009-04-20 | 2009-09-16 | 沈阳航空工业学院 | Shaping agent for nano composite reinforced fabric and application thereof |
| CN103073847A (en) * | 2013-01-23 | 2013-05-01 | 苏州大学 | Modified carbon nano tube/thermosetting resin composite material and preparation method thereof |
| CN106977875A (en) * | 2017-04-13 | 2017-07-25 | 中国工程物理研究院化工材料研究所 | A kind of low-temperature catalyzed solidification aldol resin system and preparation method thereof |
| CN107415420A (en) * | 2017-08-02 | 2017-12-01 | 河南工程学院 | It is electromagnetically shielded the preparation method of TPU film |
| CN107722551A (en) * | 2017-10-31 | 2018-02-23 | 中国工程物理研究院化工材料研究所 | A kind of toughening type pentaerythrite acrolein resin and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532243A (en) * | 2009-04-20 | 2009-09-16 | 沈阳航空工业学院 | Shaping agent for nano composite reinforced fabric and application thereof |
| CN103073847A (en) * | 2013-01-23 | 2013-05-01 | 苏州大学 | Modified carbon nano tube/thermosetting resin composite material and preparation method thereof |
| CN106977875A (en) * | 2017-04-13 | 2017-07-25 | 中国工程物理研究院化工材料研究所 | A kind of low-temperature catalyzed solidification aldol resin system and preparation method thereof |
| CN107415420A (en) * | 2017-08-02 | 2017-12-01 | 河南工程学院 | It is electromagnetically shielded the preparation method of TPU film |
| CN107722551A (en) * | 2017-10-31 | 2018-02-23 | 中国工程物理研究院化工材料研究所 | A kind of toughening type pentaerythrite acrolein resin and preparation method thereof |
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