CN113683938A - Epoxy graphene intermediate and preparation method and application thereof - Google Patents
Epoxy graphene intermediate and preparation method and application thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
The invention relates to an epoxy graphene intermediate and a preparation method and application thereof, wherein the epoxy graphene intermediate comprises the following raw materials in parts by weight: 1-5 parts of graphene, 80-150 parts of epoxy resin, 3-26 parts of cosolvent and 0-6 parts of catalyst, wherein the weight is not 0 part. The acrylic emulsion formed by the epoxy graphene intermediate has good storage stability, and a formed paint film has low water absorption, high toughness and excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to an epoxy graphene intermediate, and a preparation method and application thereof.
Background
The dilution solvent of the water-based paint is water or a hydrophilic organic solvent, can reduce the discharge of VOC, and plays a great role in protecting the environment, so the development of the water-based paint is very important.
CN109021160A discloses a preparation method of a high epoxy content waterborne epoxy/acrylate composite emulsion, which belongs to the field of high polymer materials, wherein the disclosed composite emulsion takes 61-90% of epoxy resin as a main body, a small amount of 10-39% of acrylate monomers are added, and the main body and the auxiliary emulsifier are subjected to the action of a high-shear homogenizer and a high-pressure homogenizer and then are initiated to polymerize a fine emulsion by using an oil-soluble reducing agent in the presence of the emulsifier and the auxiliary emulsifier to obtain the high epoxy content waterborne epoxy/acrylate composite emulsion. The emulsion can be stored at room temperature for more than one year. The emulsion is used as a film forming substance, various additives and pigments and fillers are added to prepare varnish and colored paint, the water-based epoxy resin curing agent is used for curing to obtain the water-based paint with high epoxy content, and when the base material is a steel plate, the salt spray resistance time can reach more than three months.
CN106675336A discloses a graphene anticorrosive paint, which is composed of the following components in parts by mass: 0.01-5 parts of graphene, 25-70 parts of epoxy resin, 5-15 parts of reactive diluent, 5-30 parts of titanium dioxide, 5-30 parts of barium sulfate, 5-30 parts of zinc phosphate, 3-10 parts of auxiliary agent and 5-30 parts of curing agent. The graphene anticorrosive paint is prepared by the method.
The traditional water-based paint is an acrylic emulsion type, and compared with a solvent type paint, the traditional water-based paint has many insufficient performances, such as poor adhesion, low paint film gloss, poor impact resistance, poor water resistance and the like.
In conclusion, it is important to develop an aqueous emulsion which is environmentally friendly and has excellent comprehensive properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an epoxy graphene intermediate and a preparation method and application thereof, wherein an acrylic emulsion formed by the epoxy graphene intermediate has good storage stability, and a formed paint film has low water absorption, high toughness and excellent comprehensive performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an epoxy graphene intermediate, wherein the epoxy graphene intermediate comprises the following raw materials in parts by weight:
according to the invention, the intermediate is synthesized from graphene and epoxy resin with high content, so that the stability of graphene in the emulsion can be enhanced when the intermediate is used for forming acrylic emulsion, and the comprehensive properties such as toughness and corrosion resistance of the emulsion are improved.
The graphene is 1-5 parts by weight, such as 2 parts, 3 parts, 4 parts and the like.
The epoxy resin is 80-150 parts by weight, such as 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts and the like.
The cosolvent is 3-26 parts by weight, such as 5 parts, 10 parts, 15 parts, 20 parts, 25 parts and the like.
The weight portion of the catalyst is 0-6 parts, and is not 0 part, such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts and the like.
Preferably, the graphene comprises carboxylated graphene.
According to the invention, the intermediate is formed through the ring-opening reaction of the carboxylated graphene and the epoxy resin, and the formed acrylic emulsion has excellent stability, corrosion resistance and comprehensive performance.
Preferably, the co-solvent comprises any one of N-methyl pyrrolidone, N-dimethylformamide, or specialty mineral spirits, or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of N-methylpyrrolidone and N, N-dimethylformamide, a combination of N, N-dimethylformamide and a specific mineral spirit, a combination of N-methylpyrrolidone, N-dimethylformamide and a specific mineral spirit, and the like.
Preferably, the specialty solvent oil comprises SMD 145/275.
Preferably, the weight parts of the N-methylpyrrolidone are 3-6 parts, such as 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, and the like.
Preferably, the weight portion of the N, N-dimethylformamide is 5 to 10 parts, such as 6 parts, 7 parts, 8 parts, 9 parts, and the like.
Preferably, the weight portion of the special solvent oil is 5-10 parts, such as 6 parts, 7 parts, 8 parts, 9 parts and the like.
Preferably, the catalyst comprises any one or a combination of at least two of tetramethylammonium chloride, triethylamine or dibutyltin dilaurate, which are not 0 parts at the same time, wherein a typical but non-limiting combination comprises: combinations of tetramethylammonium chloride and triethylamine, combinations of triethylamine and dibutyltin dilaurate, combinations of tetramethylammonium chloride, triethylamine and dibutyltin dilaurate, and the like.
Preferably, the tetramethylammonium chloride is present in an amount of 0 to 2 parts by weight, such as 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, and the like.
Preferably, the triethylamine is present in an amount of 0 to 2 parts by weight, such as 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, and the like.
Preferably, the weight portion of dibutyltin dilaurate is 0-2 parts, such as 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, and the like.
In a second aspect, the present invention provides a preparation method of the epoxy graphene intermediate according to the first aspect, including the following steps: mixing graphene, epoxy resin, a cosolvent and a catalyst according to parts by weight to obtain the epoxy graphene intermediate.
Preferably, the preparation method specifically comprises: mixing graphene in N-methyl pyrrolidone and N, N-dimethylformamide for the first time to obtain a first mixed solution;
mixing the epoxy resin, the special solvent oil and the catalyst for the second time, and heating in inert gas for the first time to obtain a second mixed solution;
and finally, mixing the first mixed solution and the second mixed solution for the third time, and heating for the second time to obtain the intermediate.
Preferably, the first mixing comprises homogenization.
According to the invention, the raw materials are uniformly mixed through homogenization, and the particle size is controlled within a certain range, so that the stability of the intermediate is improved.
Preferably, the pressure for homogenization is 700-1000MPa, such as 750MPa, 800MPa, 850MPa, 900MPa, 950MPa, and the like.
Preferably, the homogenization time is 5-20min, such as 8min, 10min, 15min, 18min, and the like.
Preferably, the temperature of the first heating is 80-120 deg.C, such as 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, etc.
Preferably, the time for the third mixing is 0.5-1.5h, e.g., 0.6h, 0.8h, 1h, 1.2h, 1.4h, etc.
Preferably, the second heating temperature is 100-.
Preferably, the time of the second heating is 1-3h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h, and the like.
In a third aspect, the invention provides an acrylic emulsion, which comprises the following components in parts by weight:
the intermediate is the epoxy graphene intermediate described in the first aspect, or the intermediate is prepared by the preparation method described in the second aspect.
According to the acrylic emulsion disclosed by the invention, graphene and epoxy resin with higher content are synthesized into an intermediate, so that the stability of the graphene in the emulsion is enhanced, and the comprehensive properties such as toughness, corrosion resistance and the like of the emulsion are improved; in addition, the invention adopts an oxidation-reduction initiation system consisting of an oxidant and a reducer to effectively promote the formation of the acrylic emulsion.
In the present invention, the actual weight of each of the intermediate components and the acrylic emulsion is not necessarily equal.
The acrylic emulsion is prepared from the following raw materials in parts by weight:
the acrylic monomer is present in an amount of 155-195 parts by weight, for example 160 parts, 165 parts, 170 parts, 175 parts, 180 parts, 185 parts, 190 parts, etc.
The emulsifier is 2-10 parts by weight, such as 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts and the like.
The reducing agent is 0.2-1 part by weight, such as 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part and the like.
The oxidant is 0.3-1 part by weight, such as 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part and the like.
The weight portion of the water is 220-340 portions, such as 240 portions, 260 portions, 280 portions, 300 portions, 320 portions and the like.
The weight portion of the intermediate is 50-100 portions, such as 55 portions, 60 portions, 65 portions, 70 portions, 75 portions, 80 portions, 85 portions, 90 portions, 95 portions and the like.
Preferably, the acrylic monomer comprises a combination of methyl methacrylate, butyl acrylate and acrylic acid.
Preferably, the weight portion of the methyl methacrylate is 100-120 parts, such as 105 parts, 110 parts, 115 parts and the like.
Preferably, the butyl acrylate is present in an amount of 50 to 65 parts by weight, such as 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 64 parts, and the like.
Preferably, the acrylic acid is present in an amount of 5 to 10 parts by weight, such as 6 parts, 7 parts, 8 parts, 9 parts, etc.
Preferably, the emulsifier comprises an anionic emulsifier and/or a nonionic emulsifier.
Preferably, the anionic emulsifier is present in an amount of 2 to 5 parts by weight, such as 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, etc.
Preferably, the non-ionic emulsifier is present in an amount of 2 to 5 parts by weight, such as 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, etc.
Preferably, the reducing agent comprises any one of, or a combination of at least two of, erythorbic acid, sodium formaldehyde sulfoxylate, or aqueous ammonia, wherein typical but non-limiting combinations include: combinations of erythorbic acid and sodium formaldehyde sulfoxylate, combinations of sodium formaldehyde sulfoxylate and ammonia, combinations of erythorbic acid, sodium formaldehyde sulfoxylate, and ammonia, and the like.
Preferably, the oxidizing agent comprises any one of, or a combination of at least two of, tert-butyl hydroperoxide, hydrogen peroxide, ammonium persulfate, or cumene hydroperoxide, wherein typical but non-limiting combinations include: a combination of t-butyl hydroperoxide and hydrogen peroxide, a combination of hydrogen peroxide, ammonium persulfate, and cumene hydroperoxide, a combination of t-butyl hydroperoxide, hydrogen peroxide, ammonium persulfate, and cumene hydroperoxide, and the like.
As a preferred technical scheme, the preparation raw material of the acrylic emulsion comprises the following components in parts by weight:
the preparation raw materials of the intermediate comprise the following components in parts by weight:
the tetramethylammonium chloride, the triethylamine and the dibutyltin dilaurate are not 0 part at the same time.
In a fourth aspect, the present invention provides a method for producing the acrylic emulsion according to the third aspect, the method comprising the steps of:
mixing an acrylic monomer, an emulsifier, an oxidant, a reducing agent, water and an intermediate according to parts by weight to obtain the acrylic emulsion.
Preferably, the preparation of the acrylic emulsion specifically comprises: mixing an acrylic monomer, an emulsifier, an intermediate and the first part of water for the fourth time to obtain a third mixed solution;
then, mixing the oxidant and the reducing agent with the second part of water and the third part of water for the fifth time respectively to obtain an oxidant solution and a reducing agent solution;
and finally, adding the oxidant solution and the reducing agent solution into the third mixed solution to obtain the acrylic emulsion.
According to the invention, the oxidant and the reducing agent are firstly formed into a solution and then mixed with other raw materials, so that the intersolubility of a system is favorably improved, and the stability of the acrylic emulsion is further improved.
Preferably, the fourth mixing comprises stirring and homogenizing in sequence.
Preferably, the stirring rate is 800-1500r/min, such as 900r/min, 1000r/min, 1100r/min, 1200r/min, 1300r/min, 1400r/min, etc.
Preferably, the stirring time is 5-15min, such as 6min, 7min, 8min, 10min, 12min, 14min, and the like.
Preferably, the number of homogenisations is 3-6, such as 4, 5, 6 etc.
Preferably, the pressure for homogenization is 500-800MPa, such as 550MPa, 600MPa, 650MPa, 700MPa, 750MPa, and the like.
Preferably, the fourth mixing further comprises a heating operation.
Preferably, the heating temperature is 50-65 deg.C, such as 52 deg.C, 54 deg.C, 56 deg.C, 58 deg.C, 60 deg.C, 62 deg.C, 64 deg.C, etc.
Preferably, the addition manner of the reducing agent solution includes dropwise addition.
Preferably, the number of times of dropping is 3 to 5 times, for example, 3 times, 4 times, 5 times, etc.
Preferably, the dropping times are 3 times, and the weight ratio of the dropping amount of the 3 times is 1 (1-1.5) to 1-1.5.
Preferably, the time of the dropping is each independently 15 to 45min, such as 20min, 25min, 30min, 35min, 40min, and the like.
Preferably, when the dripping is performed, the time interval between adjacent dripping is 5-15min, such as 6min, 8min, 10min, 12min, 14min and the like.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) preparation of an intermediate: mixing graphene and a first part of cosolvent for the first time to obtain a first mixed solution;
mixing the epoxy resin, a second part of cosolvent and the catalyst for the second time, and heating in inert gas for the first time to obtain a second mixed solution;
finally, mixing the first mixed solution and the second mixed solution for the third time, and heating for the second time to obtain the intermediate;
(2) preparation of acrylic emulsion: mixing an acrylic monomer, an emulsifier, an intermediate and the first part of water for the fourth time to obtain a third mixed solution;
then, mixing the oxidant and the reducing agent with the second part of water and the third part of water for the fifth time respectively to obtain an oxidant solution and a reducing agent solution;
and finally, adding the oxidant solution and the reducing agent solution into the third mixed solution to obtain the acrylic emulsion.
In a fifth aspect, the present invention provides a use of the acrylic emulsion according to the third aspect or the acrylic emulsion obtained by the preparation method according to the fourth aspect in a coating material.
Compared with the prior art, the invention has the following beneficial effects:
the acrylic emulsion formed by the epoxy graphene intermediate has good storage stability, and a paint film formed by the acrylic emulsion has low water absorption, high toughness and excellent comprehensive performance. Taking the case of selecting carboxylated graphene as the graphene, the acrylic emulsion of the invention has the storage stability of more than 180 days, the water absorption rate after film forming of less than 0.5 percent and the flexibility of at most 1 mm.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Examples 1 to 3 and comparative examples 1 to 2
The acrylic emulsion comprises the following raw materials in parts by weight as shown in tables 1-2:
TABLE 1 acrylic emulsion formulation
Table 2 epoxy graphene intermediate formulation
The epoxy resin is purchased from the Dow company and is named DER 667.
The carboxylated graphene is purchased from Xfnano and is under the trade name XF 048.
The method for preparing the acrylic emulsion described in example 1 and comparative example 1 comprises the following steps:
(1) preparation of an intermediate: homogenizing graphene and a first part of cosolvent (50 wt.% of cosolvent) at 800MPa for 15min to obtain a first mixed solution;
then, mixing the epoxy resin, a second part of cosolvent (50 wt.% of cosolvent) and the catalyst for the second time, and heating the mixture in nitrogen at 100 ℃ to obtain a second mixed solution;
finally, mixing the first mixed solution and the second mixed solution for 1 hour, and heating for 2 hours at 120 ℃ to obtain the intermediate;
(2) preparation of acrylic emulsion: stirring and mixing an acrylic monomer, an emulsifier, an intermediate and first part of water at 1000r/min for 10min, homogenizing at 500MPa for 3 times, pressurizing to 800MPa, homogenizing for 3 times, and heating to 60 ℃ to obtain a third mixed solution;
then, mixing the oxidant and the reducing agent with the second part of water and the third part of water for the fifth time respectively to obtain an oxidant solution and a reducing agent solution;
and finally, sequentially adding an oxidant solution into the third mixed solution, dropwise adding a reducing agent solution into the third mixed solution for three times, wherein the mass percentages of the dropwise adding amounts in the reducing agent solution are respectively 30%, 30% and 40%, the dropwise adding time is 30min each time, the time interval is 10min, and the heat preservation operation is carried out at intervals, so as to obtain the acrylic emulsion.
The method of making the acrylic emulsion described in example 2 includes the steps of:
(1) preparation of an intermediate: homogenizing graphene and a first part of cosolvent (N-methyl pyrrolidone and N, N-dimethylformamide) for 20min under 700MPa to obtain a first mixed solution;
secondly, mixing the epoxy resin, a second part of cosolvent (SMD145/275) and the catalyst for the second time, and heating the mixture at 80 ℃ in nitrogen to obtain a second mixed solution;
finally, mixing the first mixed solution and the second mixed solution for 1.5 hours, and heating for 3 hours at 100 ℃ to obtain the intermediate;
(2) preparation of acrylic emulsion: stirring and mixing an acrylic monomer, an emulsifier, an intermediate and first part of water at 800r/min for 15min, homogenizing at 600MPa for 3 times, pressurizing to-700 MPa, homogenizing for 3 times, and heating to 50 ℃ to obtain a third mixed solution;
then, mixing the oxidant and the reducing agent with the second part of water and the third part of water for the fifth time respectively to obtain an oxidant solution and a reducing agent solution;
and finally, sequentially adding an oxidant solution into the third mixed solution, dropwise adding a reducing agent solution into the third mixed solution for three times, wherein the mass percentages of the dropwise adding amounts in the reducing agent solution are respectively 30%, 30% and 40%, the dropwise adding time is 15min each time, the time interval is 15min, and the heat preservation operation is carried out at intervals to obtain the acrylic emulsion.
The method of making the acrylic emulsion described in example 3 includes the steps of:
(1) preparation of an intermediate: homogenizing graphene and a first part of cosolvent (N-methyl pyrrolidone and N, N-dimethylformamide) for 5min under 1000MPa to obtain a first mixed solution;
secondly, mixing the epoxy resin, a second part of cosolvent (SMD145/275) and the catalyst for the second time, and heating the mixture at 120 ℃ in nitrogen to obtain a second mixed solution;
finally, mixing the first mixed solution and the second mixed solution for 0.5h, and heating for 1h at 140 ℃ to obtain the intermediate;
(2) preparation of acrylic emulsion: stirring and mixing an acrylic monomer, an emulsifier, an intermediate and first part of water at 1500r/min for 5min, homogenizing at 500MPa for 3 times, pressurizing to 800MPa, homogenizing for 3 times, and heating to 65 ℃ to obtain a third mixed solution;
then, mixing the oxidant and the reducing agent with the second part of water and the third part of water for the fifth time respectively to obtain an oxidant solution and a reducing agent solution;
and finally, sequentially adding an oxidant solution into the third mixed solution, dropwise adding a reducing agent solution into the third mixed solution for three times, wherein the mass percentages of the dropwise adding amounts in the reducing agent solution are respectively 30%, 30% and 40%, the dropwise adding time is 45min each time, the time interval is 5min, and the heat preservation operation is carried out at intervals, so as to obtain the acrylic emulsion.
Comparative example 2 the acrylic emulsion was prepared according to the same method as in example 1 except that no graphene was added.
Example 4
The present embodiment is different from embodiment 1 in that the carboxylated graphene is replaced by equal mass of graphene (purchased from Xfnano, under the designation XFSG03), and the rest is the same as embodiment 1.
Comparative example 3
This comparative example differs from example 1 in that the intermediate was not prepared in advance and the components of the intermediate were mixed directly with the components of the acrylic emulsion.
The preparation method of the acrylic emulsion comprises the following steps:
(1) stirring and mixing an acrylic monomer, an emulsifier, graphene, epoxy resin, a cosolvent, a catalyst and water at 1000r/min for 10min, homogenizing at 500MPa for 3 times, pressurizing to 800MPa for 3 times, and heating to 60 ℃ to obtain a mixed solution;
(2) then, mixing the oxidant and the reducing agent with the second part of water and the third part of water for the fifth time respectively to obtain an oxidant solution and a reducing agent solution;
(3) and (2) finally, sequentially adding an oxidant solution into the mixed solution obtained in the step (1), dropwise adding a reducing agent solution into the mixed solution for three times, wherein the mass percentages of the dropwise adding amount in the reducing agent solution are respectively 30%, 30% and 40%, the dropwise adding time is 30min each time, the time interval is 10min, and the heat preservation operation is carried out at intervals to obtain the acrylic emulsion.
Performance testing
Examples 1-4 and comparative examples 1-3 were tested as follows:
(1) storage stability: according to the specification of GB/T20623-2006, the method has no hard block, no flocculation, no obvious layering and no skinning phenomenon.
(2) Water absorption of the paint film: according to the specifications of HG/T3344-.
(3) Flexibility: the procedure was carried out as specified in GB/T1731-1993.
The test results are summarized in table 3.
TABLE 3 storage stability of the emulsion, water absorption and flexibility of the film after film formation and curing
| Storage stability/day | Water absorption/% of paint film | Flexibility/mm | |
| Example 1 | ≥180 | 0.5 | 1 |
| Example 2 | ≥180 | 0.3 | 1 |
| Example 3 | ≥180 | 0.3 | 1 |
| Example 4 | ≤5 | 0.8 | 3 |
| Comparative example 1 | ≤5 | 0.7 | 5 |
| Comparative example 2 | ≥180 | 1.5 | 12 |
| Comparative example 3 | ≤5 | 0.7 | 9 |
Analysis of the data in Table 3 shows that when carboxylated graphene is selected as the graphene, the storage stability of the acrylic emulsion is more than 180 days, the water absorption after film formation is less than 0.5%, the flexibility is at most 1mm, the storage stability of the acrylic emulsion is good, the water absorption of a paint film is low, the toughness is high, and the comprehensive performance is excellent.
As can be seen from the analysis of comparative example 1 and example 1, comparative example 1 is inferior to example 1 in performance, and the acrylic emulsion formed without the addition of catalyst and N-methyl pyrrolidone is inferior in performance, and the acrylic emulsion formed according to the formulation of the present invention has better overall performance.
As can be seen from the analysis of comparative example 2 and example 1, the performance of comparative example 2 is inferior to that of example 1, and the acrylic emulsion formed by adding graphene is proved to have better performance.
As can be seen from the analysis of comparative example 3 and example 1, comparative example 3 is inferior to example 1 in performance, and the acrylic emulsion obtained by forming an intermediate between graphene and epoxy resin first is proved to have better performance.
Analysis of example 4 and example 1 shows that example 4 is inferior to example 1 in performance, and the acrylic emulsion formed by using the carboxylated graphene is better in performance.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The epoxy graphene intermediate is characterized by comprising the following raw materials in parts by weight:
2. the epoxy graphene intermediate of claim 1, wherein the graphene comprises carboxylated graphene;
preferably, the cosolvent comprises any one or a combination of at least two of N-methyl pyrrolidone, N-dimethylformamide or special solvent oil;
preferably, the specialty solvent oil comprises SMD 145/275;
preferably, the weight part of the N-methyl pyrrolidone is 3-6 parts;
preferably, the weight portion of the N, N-dimethylformamide is 5-10 portions;
preferably, the weight part of the special solvent oil is 5-10 parts;
preferably, the catalyst comprises any one or a combination of at least two of tetramethylammonium chloride, triethylamine or dibutyltin dilaurate, wherein the tetramethylammonium chloride, triethylamine and dibutyltin dilaurate are not 0 parts at the same time;
preferably, the weight portion of the tetramethylammonium chloride is 0 to 2 portions;
preferably, the triethylamine is 0-2 parts by weight;
preferably, the weight part of the dibutyltin dilaurate is 0-2 parts.
3. A method for preparing the epoxy graphene intermediate according to claim 1 or 2, wherein the method comprises the following steps: mixing graphene, epoxy resin, a cosolvent and a catalyst according to parts by weight to obtain the epoxy graphene intermediate.
4. The preparation method according to claim 3, characterized in that the preparation method specifically comprises: mixing graphene in N-methyl pyrrolidone and N, N-dimethylformamide for the first time to obtain a first mixed solution;
mixing the epoxy resin, the special solvent oil and the catalyst for the second time, and heating in inert gas for the first time to obtain a second mixed solution;
finally, mixing the first mixed solution and the second mixed solution for the third time, and heating for the second time to obtain the intermediate;
preferably, the first mixing comprises homogenization;
preferably, the pressure for homogenizing is 700-1000 MPa;
preferably, the homogenization time is 5-20 min;
preferably, the temperature of the first heating is 80-120 ℃;
preferably, the time for the third mixing is 0.5-1.5 h;
preferably, the temperature of the second heating is 100-140 ℃;
preferably, the time of the second heating is 1-3 h.
5. The acrylic emulsion is characterized by comprising the following raw materials in parts by weight:
the intermediate is the epoxy graphene intermediate of claim 1 or 2, or the intermediate is prepared by the preparation method of claim 3 or 4.
6. The acrylic emulsion of claim 5 wherein said acrylic monomer comprises a combination of methyl methacrylate, butyl acrylate, and acrylic acid;
preferably, the weight portion of the methyl methacrylate is 100-120 portions;
preferably, the butyl acrylate accounts for 50-65 parts by weight;
preferably, the acrylic acid accounts for 5-10 parts by weight;
preferably, the emulsifier comprises an anionic emulsifier and/or a nonionic emulsifier;
preferably, the weight portion of the anionic emulsifier is 2-5;
preferably, the weight portion of the nonionic emulsifier is 2-5;
preferably, the reducing agent comprises any one of or a combination of at least two of isoascorbic acid, sodium formaldehyde sulfoxylate or ammonia water;
preferably, the oxidizing agent comprises any one of tert-butyl hydroperoxide, hydrogen peroxide, ammonium persulfate or cumene hydroperoxide or a combination of at least two thereof.
7. A method for preparing the acrylic emulsion of claim 5 or 6, comprising the steps of:
mixing an acrylic monomer, an emulsifier, an oxidant, a reducing agent, water and an intermediate according to parts by weight to obtain the acrylic emulsion.
8. The method according to claim 7, wherein the acrylic emulsion is prepared by: mixing an acrylic monomer, an emulsifier, an intermediate and the first part of water for the fourth time to obtain a third mixed solution;
then, mixing the oxidant and the reducing agent with the second part of water and the third part of water for the fifth time respectively to obtain an oxidant solution and a reducing agent solution;
finally, adding an oxidant solution and a reducing agent solution into the third mixed solution to obtain the acrylic emulsion;
preferably, the fourth mixing comprises stirring and homogenizing in sequence;
preferably, the stirring speed is 800-;
preferably, the stirring time is 5-15 min;
preferably, the number of homogenisations is from 3 to 6;
preferably, the pressure for homogenizing is 500-800 MPa;
preferably, the fourth mixing further comprises heating;
preferably, the heating temperature is 50-65 ℃;
preferably, the addition mode of the reducing agent solution comprises dripping;
preferably, the dropping times are 3-5 times;
preferably, the dropping times are 3 times, and the weight ratio of the dropping amount of the 3 times is 1 (1-1.5) to 1-1.5;
preferably, the dropping time is 15-45min respectively and independently;
preferably, when the dripping is carried out, the time interval between adjacent dripping is 5-15 min.
9. The method according to claim 7 or 8, characterized in that it comprises the steps of:
(1) preparation of an intermediate: mixing graphene and a first part of cosolvent for the first time to obtain a first mixed solution;
mixing the epoxy resin, a second part of cosolvent and the catalyst for the second time, and heating in inert gas for the first time to obtain a second mixed solution;
finally, mixing the first mixed solution and the second mixed solution for the third time, and heating for the second time to obtain the intermediate;
(2) preparation of acrylic emulsion: mixing an acrylic monomer, an emulsifier, an intermediate and the first part of water for the fourth time to obtain a third mixed solution;
then, mixing the oxidant and the reducing agent with the second part of water and the third part of water for the fifth time respectively to obtain an oxidant solution and a reducing agent solution;
and finally, adding the oxidant solution and the reducing agent solution into the third mixed solution to obtain the acrylic emulsion.
10. Use of an acrylic emulsion according to claim 5 or 6 or obtained by the preparation process according to any one of claims 7 to 9 in coatings.
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