CN113321914A - Preparation method of graphene oxide-unsaturated polyester resin composite slurry - Google Patents
Preparation method of graphene oxide-unsaturated polyester resin composite slurry Download PDFInfo
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- CN113321914A CN113321914A CN202110760511.3A CN202110760511A CN113321914A CN 113321914 A CN113321914 A CN 113321914A CN 202110760511 A CN202110760511 A CN 202110760511A CN 113321914 A CN113321914 A CN 113321914A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000002002 slurry Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 167
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000004821 distillation Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000011268 mixed slurry Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000004593 Epoxy Chemical group 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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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
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
The invention relates to a preparation method of graphene oxide-unsaturated polyester resin composite slurry, which belongs to the field of graphene materials, wherein graphene oxide paste and UPR resin are used as raw materials, methanol is used as an intermediate solvent, water in the graphene oxide paste is replaced, the mixed solution is subjected to ultrasonic treatment to obtain GO-methanol dispersion liquid, then the GO-methanol-UPR dispersion liquid is added into a proper amount of UPR resin, the GO-methanol-UPR mixed slurry is obtained after stirring, and finally the GO-UPR composite slurry is obtained through reduced pressure distillation; the GO in the composite slurry prepared by the invention is uniformly dispersed, has higher storage stability and can effectively improve the mechanical property of the UPR matrix.
Description
Technical Field
The invention relates to the technical field of graphene materials, and particularly relates to a preparation method of graphene oxide-unsaturated polyester resin composite slurry.
Background
Graphene is a compound represented by sp2The two-dimensional honeycomb-shaped monoatomic layer structure formed by hybridized carbon atoms has many excellent properties such as large specific surface area, high carrier mobility, high strength, high thermal conductivity and the like, but on one hand, the graphene has a stable six-membered ring structure, the surface is inert, and larger van der Waals force exists between layers, so that the graphene is extremely easy to agglomerate and is difficult to dissolve in other media. Even if graphene is dispersed in a solvent, aggregation and sedimentation easily occur, which limits further applications of graphene.
Graphene Oxide (GO) is an important derivative generated in the preparation of graphene by a redox method, and the preparation process is simpler and lower in price than graphene. Meanwhile, except that the performances such as electric conduction and heat conduction are inferior to those of graphene, most other performances of graphene oxide are equivalent to those of graphene. The graphene oxide has a large number of functional groups such as hydroxyl, carboxyl, epoxy and the like, and can be easily combined with resin to form a stable composite material. Therefore, the GO is uniformly dispersed in a resin system by a proper method, and the prepared GO/resin composite material has a very wide application prospect.
Unsaturated Polyester Resin (UPR) composites find use in many applications because of their ease of molding, stable part dimensions, good insulation and other advantages. In the field of automobile accessories, in order to achieve energy conservation, emission reduction, greenness and no pollution, the automobile industry requires the automobile body to be light, and light materials are important supports for realizing the light weight of automobiles. In the field of electric appliances, alternating current contactors and air switches of low-voltage electric appliances, insulating devices in the field of high-voltage electric appliances and the like can be made of unsaturated polyester composite materials. However, problems have been found in the use of these electrical devices, such as excessive variation in ambient temperature and the tendency of the devices to wear when subjected to stress, resulting in reduced accuracy of operation. In response to these problems, researchers have tried solutions to improve the mechanical strength and wear resistance of UPR composites by adding graphene oxide to the UPR matrix. In the preparation process of the graphene oxide/UPR composite material, effective dispersion of GO in resin is crucial. At present, methods such as composite mixing dispersion, surface treatment, compatilizer addition, in-situ treatment and the like are generally adopted, but the methods generally have the phenomena of low efficiency and high cost.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of graphene oxide-unsaturated polyester resin composite slurry with high efficiency and low cost aiming at the defects of the prior art, wherein GO in the prepared composite slurry is uniformly dispersed, and the prepared composite slurry has high storage stability and can effectively improve the mechanical property of a UPR matrix.
The technical scheme for solving the technical problems is as follows: the preparation method of the graphene oxide-unsaturated polyester resin composite slurry is characterized in that a graphene oxide paste body and UPR resin are used as raw materials, methanol is used as an intermediate solvent, the graphene oxide paste body is a graphene oxide paste body which is produced by Shandong Jinlite New Material, Limited company and has the model of LN-GOB, the solid content of the graphene oxide paste body is 45%, and the preparation method comprises the following steps:
(1) treating graphene oxide paste: cutting the graphene oxide paste into particles, adding the particles into a proper amount of methanol solvent, stirring and filtering the graphene-methanol mixed solution until water in the graphene oxide paste is replaced by methanol, and carrying out ultrasonic treatment on the mixed solution to obtain a GO-methanol dispersion solution;
the purpose of this step is: the water in the graphene oxide paste is replaced by methanol, and the graphene oxide is crushed by ultrasound to form stable dispersion liquid, so that the subsequent uniform dispersion in resin is facilitated;
(2) dispersing GO-methanol dispersion liquid and UPR: adding the GO-methanol dispersion liquid prepared in the step (1) into a proper amount of UPR resin, wherein the UPR is a viscous liquid in the state of unsaturated polyester resin, and stirring to obtain GO-methanol-UPR mixed slurry;
the purpose of this step is: uniformly dispersing GO into UPR;
(3) and (3) reduced pressure distillation: placing the GO-methanol-UPR mixed slurry in a pressure reduction device, and carrying out reduced pressure distillation treatment while stirring; and cooling the sample subjected to reduced pressure distillation to room temperature to obtain the GO-UPR composite slurry.
The purpose of this step is: removing methanol in the mixed slurry so as to avoid influencing the subsequent curing and forming of the UPR resin;
further, in the step (1), in the process of replacing the moisture in the graphene oxide paste with methanol, the blending and filtering of the graphene oxide paste and methanol are performed at least twice, that is, the graphene oxide paste is firstly divided into particles and added into a proper amount of methanol solvent, then the graphene-methanol mixed solution is stirred and filtered, and then the filtered graphene oxide is added into methanol again and stirred and filtered.
Furthermore, in the two blending processes, the mass ratio of the first graphene oxide paste to the methanol is 1:50, and the mass ratio of the second graphene oxide to the methanol is 1: 20. the purpose is to reduce the moisture in the original graphene oxide paste to one thousandth of the original moisture by two times of methanol replacement.
Further, the raw material components comprise the following components in parts by weight: the graphene oxide paste comprises 1-10 parts of solid content and 1500-2000 parts of UPR resin.
Further, the UPR resin adopts industrial UPR.
Furthermore, the UPR resin contains 30-40% of styrene.
The invention has the beneficial effects that:
1. according to the invention, the graphene oxide paste with low cost is creatively used as a raw material, the water in the graphene oxide paste is replaced by methanol to prepare a graphene oxide-methanol dispersion liquid, and the graphene oxide-methanol dispersion liquid is mixed and dispersed with the UPR resin, so that GO in the prepared graphene oxide-unsaturated polyester resin is uniformly dispersed, the composite slurry has good stability, and is convenient for long-time storage; the mechanical property of the UPR matrix can be obviously improved after curing and forming, and the UPR matrix has a good reinforcing effect and a wide application prospect;
2. because the corresponding slurry is prepared by taking the graphene oxide powder or the graphene oxide water dispersion as the raw material in the prior art, the method breaks through the traditional thinking, selects the graphene oxide paste with low quality, and has the advantages of lower cost and higher utilization rate compared with the powdery GO. In addition, special surface treatment is not needed in the preparation process of the composite slurry, the preparation process is simplified, and the whole process is simple and feasible;
3. in the prior art, methanol is not a conventional organic solvent of graphene oxide (DMF is selected as the conventional organic solvent), and methanol is generally not selected as the solvent in a dispersion system of the conventional graphene oxide, because the graphene oxide-methanol dispersion liquid has very low concentration and cannot be stably stored for a long time; the method breaks through the traditional thinking, the graphene oxide paste is used as a raw material, methanol is used as an intermediate solvent, water in the graphene oxide paste is replaced, then the graphene oxide paste is subjected to ultrasonic treatment to form a methanol-graphene oxide dispersion liquid with a lamellar structure, then a uniform and stable GO-methanol-resin mixed system is formed by adding the graphene oxide dispersion liquid into resin, and finally the methanol is removed through distillation without influencing the later-stage curing molding of the resin.
Drawings
FIG. 1 is an SEM image of GO-methanol dispersion made in example 1 of the invention.
Detailed Description
The invention is described in further detail below to facilitate the public's understanding of the manner in which the invention is practiced, and the examples are given by way of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) Preparing the following components in parts by weight:
(2) treating graphene oxide paste: cutting the graphene oxide paste into small particles, and adding the small particles into a proper amount of methanol solvent, wherein the mass ratio of the graphene oxide paste to the methanol is 1: 50; then stirring the graphene-methanol mixed solution for 1h at the rotating speed of 1000r/min, filtering, adding the filtered GO into methanol again, and stirring for 1h, wherein the mass ratio of the graphene oxide to the methanol is 1: 20; then carrying out ultrasonic treatment on the mixed solution for 2 hours to obtain a graphene oxide-methanol dispersion solution; the SEM image of the resulting GO-methanol dispersion is shown in figure 1;
(3) dispersing GO-methanol dispersion liquid and UPR: 1 part (solid content of GO) of GO-methanol dispersion prepared in the previous step, and 1500 parts of UPR resin. Pouring all the dispersion liquid and the resin into a stirring tank, and stirring at the rotating speed of 1000r/min for 1h to obtain GO-methanol-UPR mixed slurry;
(4) and (3) reduced pressure distillation: placing the GO-methanol-UPR mixed slurry in a pressure reduction device, and carrying out reduced pressure distillation treatment for 1h while stirring; and cooling the sample subjected to reduced pressure distillation to room temperature to obtain the final GO-UPR composite slurry.
Example 2
(1) Preparing the following components in parts by weight:
(2) treating graphene oxide paste: cutting the graphene oxide paste into small particles, and adding the small particles into a proper amount of methanol solvent, wherein the mass ratio of the graphene oxide paste to the methanol is 1: 50; then stirring the graphene-methanol mixed solution for 1h at the rotating speed of 1000r/min, filtering, adding the filtered GO into methanol again, and stirring for 1h, wherein the mass ratio of the graphene oxide to the methanol is 1: 20; then carrying out ultrasonic treatment on the mixed solution for 2 hours to obtain a graphene oxide-methanol dispersion solution;
(3) dispersing GO-methanol dispersion liquid and UPR: taking 5 parts (solid content of GO) of GO-methanol dispersion prepared in the previous step, and taking 1750 parts of UPR resin; pouring all the dispersion liquid and the resin into a stirring tank, and stirring at the rotating speed of 1000r/min for 1h to obtain GO-methanol-UPR mixed slurry;
(4) and (3) reduced pressure distillation: placing the GO-methanol-UPR mixed slurry in a pressure reduction device, and carrying out reduced pressure distillation treatment for 1h while stirring; and cooling the sample subjected to reduced pressure distillation to room temperature to obtain the final GO-UPR composite slurry.
Example 3
(1) Preparing the following components in parts by weight:
(2) treating graphene oxide paste: cutting the graphene oxide paste into small particles, and adding the small particles into a proper amount of methanol solvent, wherein the mass ratio of the graphene oxide paste to the methanol is 1: 50; then stirring the graphene-methanol mixed solution for 1h at the rotating speed of 1000r/min, filtering, adding the filtered GO into methanol again, and stirring for 1h, wherein the mass ratio of the graphene oxide to the methanol is 1: 20; then carrying out ultrasonic treatment on the mixed solution for 2 hours to obtain a graphene oxide-methanol dispersion solution;
(3) dispersing GO-methanol dispersion liquid and UPR: taking 10 parts (solid content of GO) of GO-methanol dispersion prepared in the previous step, and taking 2000 parts of UPR resin; pouring all the dispersion liquid and the resin into a stirring tank, and stirring at the rotating speed of 1000r/min for 1h to obtain GO-methanol-UPR mixed slurry;
(4) and (3) reduced pressure distillation: placing the GO-methanol-UPR mixed slurry in a pressure reduction device, and carrying out reduced pressure distillation treatment for 1h while stirring; and cooling the sample subjected to reduced pressure distillation to room temperature to obtain the final GO-UPR composite slurry.
In the embodiment, the graphene oxide paste is a graphene oxide paste which is produced by Shandong Jinlite New Material, Limited liability company and has a model number of LN-GOB, and the solid content of the graphene oxide paste is 45%.
The GO-UPR composite slurry obtained in example 1 is subjected to curing molding, and the mechanical properties of the composite slurry are tested, and the test results are shown in Table 1.
TABLE 1 mechanical Properties data
As can be seen from the data in Table 1, compared with the UPR of the blank test, the UPR of the composite material obtained by curing and molding the slurry compounded by the graphene oxide and the UPR has obviously improved bending strength and bending modulus.
Comparative example 1
(1) Preparing the following components in parts by weight:
(2) treating graphene oxide paste: the graphene oxide paste is divided into small particles and added into a proper amount of methanol solvent, and the mass ratio of the graphene oxide paste to the methanol is 1: 50. Then stirring the graphene-methanol mixed solution for 1h at the rotating speed of 1000r/min, filtering, adding the filtered GO into methanol again, and stirring for 1h, wherein the mass ratio of the graphene oxide to the methanol is 1: 20. and then carrying out ultrasonic treatment on the mixed solution for 2 hours to obtain a graphene oxide-methanol dispersion solution.
(3) Dispersing GO-methanol dispersion liquid and UPR: 10 parts (GO solid content) of the GO-methanol dispersion prepared in the previous step were taken, and 2000 parts of UPR resin were taken. And (3) pouring all the dispersion liquid and the resin into a stirring tank, and stirring at the rotating speed of 1000r/min for 1h to obtain GO-methanol-UPR mixed slurry.
This comparative example eliminates the vacuum distillation process compared to the above examples, but the resulting GO-methanol-UPR mixed slurry does not cure and form normally in the subsequent process. It follows that the presence of methanol solvent directly affects the formation of the slurry.
Comparative example 2
The process of this comparative example is the same as example 1 except that the solvent methanol was replaced by ethanol, but a white cloudy precipitate was formed upon mixing together in step (3). Therefore, the effect of the intermediate solvent methanol adopted by the invention is not the effect which can be achieved by simple replacement of the conventional solvent.
In conclusion, the preparation method of the invention has the following advantages:
1. the graphene oxide paste adopted by the invention has low price and can be produced in a large scale;
2. the prepared graphene oxide-resin composite slurry is uniform and stable and can be stored for a long time;
3. obviously improves the mechanical property of the resin matrix.
Claims (6)
1. A preparation method of graphene oxide-unsaturated polyester resin composite slurry is characterized in that graphene oxide paste and UPR resin are used as raw materials, and comprises the following steps:
(1) treating graphene oxide paste: cutting the graphene oxide paste into particles, adding the particles into a proper amount of methanol solvent, stirring and filtering the graphene-methanol mixed solution until water in the graphene oxide paste is replaced by methanol, and carrying out ultrasonic treatment on the mixed solution to obtain a GO-methanol dispersion solution;
(2) dispersing GO-methanol dispersion liquid and UPR: adding the GO-methanol dispersion liquid prepared in the step (1) into a proper amount of UPR resin, and stirring to obtain GO-methanol-UPR mixed slurry;
(3) and (3) reduced pressure distillation: placing the GO-methanol-UPR mixed slurry in a pressure reduction device, and carrying out reduced pressure distillation treatment while stirring; and cooling the sample subjected to reduced pressure distillation to room temperature to obtain the GO-UPR composite slurry.
2. The preparation method of graphene oxide-unsaturated polyester resin composite slurry according to claim 1, wherein in the step (1), in the process of replacing water in the graphene oxide paste with methanol, the blending and filtering of the graphene oxide paste and methanol are performed at least twice, that is, the graphene oxide paste is firstly divided into particles and added into a proper amount of methanol solvent, then the graphene-methanol mixed solution is stirred and filtered, and the filtered graphene oxide is then added into methanol again and stirred and filtered.
3. The preparation method of the graphene oxide-unsaturated polyester resin composite slurry according to claim 2, wherein in the two blending processes, the mass ratio of the first graphene oxide paste to methanol is 1:50, and the mass ratio of the second graphene oxide to methanol is 1: 20.
4. The preparation method of the graphene oxide-unsaturated polyester resin composite slurry according to claim 1, wherein the raw material components comprise the following components in parts by weight: the graphene oxide paste comprises 1-10 parts of solid content and 1500-2000 parts of UPR resin.
5. The method for preparing graphene oxide-unsaturated polyester resin composite slurry according to claim 1 or 4, wherein the UPR resin is industrial UPR.
6. The method for preparing graphene oxide-unsaturated polyester resin composite slurry according to claim 5, wherein the UPR resin contains 30-40% of styrene.
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|---|---|---|---|---|
| CN102391632A (en) * | 2011-09-14 | 2012-03-28 | 中国林业科学研究院林产化学工业研究所 | Graphene oxide/unsaturated polyester composite material and preparation method thereof |
| CN103589197A (en) * | 2013-11-25 | 2014-02-19 | 桂林理工大学 | Method for preparing flexibilizer by adopting oxidized graphene and application thereof |
| KR20150026092A (en) * | 2013-08-30 | 2015-03-11 | 한국기계연구원 | Carbon fiber composites comprising partially reduced graphene oxide and the manufacturing method thereof |
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| CN111978771A (en) * | 2019-05-21 | 2020-11-24 | 中车唐山机车车辆有限公司 | Modified graphene oxide, preparation method thereof, anticorrosive paint containing modified graphene oxide and preparation method |
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2021
- 2021-07-06 CN CN202110760511.3A patent/CN113321914B/en active Active
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