CN109096946B - Graphene oxide aqueous adhesive and preparation method thereof - Google Patents
Graphene oxide aqueous adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN109096946B CN109096946B CN201810557188.8A CN201810557188A CN109096946B CN 109096946 B CN109096946 B CN 109096946B CN 201810557188 A CN201810557188 A CN 201810557188A CN 109096946 B CN109096946 B CN 109096946B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- oxide aqueous
- stirring
- agent
- aqueous adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Abstract
The invention discloses a novel graphene oxide aqueous adhesive and a preparation method thereof. The preparation method of the adhesive mainly comprises two steps: (1) preparing a graphene oxide solution by adopting a plant resource corn starch through a hydrothermal synthesis method; (2) and adding an aqueous tackifying emulsion, a thickening agent, a defoaming agent, a film-forming agent, a pH regulator, a mildew preventive and other auxiliaries into the prepared graphene oxide solution, and uniformly stirring to obtain the aqueous adhesive. The novel graphene oxide aqueous adhesive prepared by the invention has the advantages of fast curing, strong initial adhesion, environmental protection and the like.
Description
Technical Field
The invention relates to an aqueous adhesive and a preparation method thereof, and particularly relates to a novel graphene oxide aqueous adhesive and a preparation method thereof.
Background
In 2004, England scientists prepared sp from carbon atoms for the first time2Graphene, a novel two-dimensional atomic crystal composed of hybridized and connected monoatomic layers, is only 0.3354nm thick and is the thinnest material found in the world at present. The graphene has a special monoatomic layer structure and novel physical properties, namely the thermal conductivity is about 5000J/(m.K.s), the forbidden band width is almost zero, the transparency is high (about 97.7 percent), particularly the strength is as high as 130GPa, and the Young modulus (1100GPa) and the fracture strength (125GPa) of the graphene are equivalent to those of a carbon nano tube. At present, the traditional method for preparing graphene is mainly an oxidation cutting method, and strong oxidants such as sulfuric acid or nitric acid are required to be used for oxidation cutting of various carbon materials (graphite, carbon fibers and carbon nanotubes), so that certain influence is brought to the environment. Moreover, the subsequent treatment of the product after the oxidation reaction is complicated. On the other hand, with the general improvement of the environmental awareness of people, the trend of the adhesive industry is to gradually replace the existing solvent-based adhesives with more environmental-friendly water-based adhesives. However, the existing aqueous adhesive has insufficient initial adhesion and is firmThe chemical conversion speed is slow, and the use requirement can not be well met.
Disclosure of Invention
The invention aims to solve the defects of the existing aqueous adhesive, prepare a novel graphene oxide aqueous adhesive and provide a preparation method thereof.
The novel graphene oxide aqueous adhesive is prepared by adopting corn starch which is a natural plant resource as a raw material, preparing a nano material graphene oxide through a hydrothermal synthesis method, further using a graphene oxide aqueous solution as a main component, and adding auxiliary agents such as an aqueous tackifying emulsion, a thickening agent, a defoaming agent, a film-forming agent, a pH regulator, a mildew preventive and the like in a proper proportion into the solution. The aqueous adhesive prepared by the method is green and environment-friendly, and has strong initial adhesion, high curing speed and good application prospect. The technical scheme is as follows:
(1) adding deionized water with a certain mass into a container with a stirring device, adding soluble starch with a certain mass according to a ratio, and stirring for 10-30min to completely dissolve the starch; (2) adding the obtained solution into a hydrothermal kettle reactor, gradually heating to 250 ℃ at 120 ℃, keeping the pressure within 8Mpa, carrying out hydrothermal reaction, and discharging after reacting for 1-15 h; (3) and (3) carrying out centrifugal separation on the black brown material obtained in the step (2) in a centrifugal machine at the speed of 3000-15000r/min to obtain light yellow transparent liquid, namely the aqueous solution of the graphene oxide.
(2) Firstly, weighing 50-80 parts of graphene oxide aqueous solution, 10-30 parts of aqueous tackifying emulsion and 0.1-0.5 part of defoaming agent in a metering manner, adding the graphene oxide aqueous solution, the aqueous tackifying emulsion and the defoaming agent into a high-speed stirrer, uniformly dispersing the graphene oxide aqueous solution, wherein the rotating speed of the high-speed stirrer is 200-300r/min, and the stirring time is 5-10 min; (2) then keeping the rotating speed unchanged, sequentially adding 0.1-0.5 part of film forming agent and 0.1-0.5 part of mildew preventive, and continuously stirring for 5-10 min; (3) then the rotating speed is reduced to 100-200r/min, 0.2-0.8 part of thickening agent is added, the mixture is continuously stirred for 5-10min, finally 0.1-0.6 part of PH regulator is added, and the mixture is discharged after being uniformly dispersed by stirring for 5-10 min.
Wherein the proportion of the deionized water to the corn starch is 50-200: 5-30, preferably 80-100: 15 to 25.
The aqueous tackifying emulsion is acrylic acid modified rosin tackifying emulsion.
The thickening agent is corn starch.
The defoaming agent is an organic silicon defoaming agent.
The film forming agent is propylene glycol butyl ether.
The pH regulator is sodium bicarbonate.
The mildew preventive is p-chloro-m-dimethylphenol.
Compared with the prior art, the invention has the advantages that: the graphene oxide aqueous solution is prepared by adopting natural plant resource starch as a main raw material, strong oxidants such as sulfuric acid and nitric acid which are necessary in the traditional preparation are not needed, and the problems of complex post-treatment and the like are solved; the solution is added with auxiliary agents such as aqueous tackifying emulsion, thickening agent, defoaming agent, film forming agent, pH regulator, mildew preventive and the like in a proper proportion to prepare the novel graphene oxide aqueous adhesive. The acrylic acid modified rosin tackifying emulsion is compounded with other additives for use, so that a good tackifying effect can be achieved, and the adhesive property of the adhesive can be effectively improved; the product has simple preparation process and no pollution in the preparation process, thereby being more suitable for industrialization; meanwhile, the prepared novel graphene oxide aqueous adhesive is green and environment-friendly, strong in initial adhesion, high in curing speed and good in application prospect.
Drawings
Fig. 1 is an XRD pattern of graphene oxide.
Fig. 2 is an SEM image of graphene oxide.
Fig. 3 is the graphene oxide aqueous adhesive prepared in example 1.
Detailed Description
Example 1
Adding 50kg of deionized water into a container with a stirring device, adding 5kg of corn starch according to the proportion, and stirring for 15min to completely dissolve the corn starch; adding the obtained solution into a hydrothermal kettle reactor, gradually heating to 180 ℃, keeping the pressure within 8Mpa, carrying out hydrothermal reaction, and discharging after 5h of reaction; and centrifuging the obtained black brown material in a centrifuge at the speed of 5000r/min to obtain a light yellow transparent liquid, namely the aqueous solution of the graphene oxide. Weighing 50 parts of graphene oxide aqueous solution, 10 parts of aqueous tackifying emulsion and 0.1 part of defoaming agent, adding into a high-speed stirrer, uniformly dispersing, wherein the rotating speed of the high-speed stirrer is 200r/min, and the stirring time is 5 min; then keeping the rotating speed unchanged, sequentially adding 0.1 part of film forming agent and 0.2 part of mildew preventive, and continuously stirring for 5 min; then the rotating speed is reduced to 100r/min, 0.3 part of thickening agent is added, stirring is continued for 5min, finally 0.2 part of pH regulator is added, stirring is carried out for 5min, and discharging is carried out after the pH regulator is dispersed uniformly.
Example 2
Adding 60kg of deionized water into a container with a stirring device, adding 8kg of corn starch according to the proportion, and stirring for 20min to completely dissolve the corn starch; adding the obtained solution into a hydrothermal kettle reactor, gradually heating to 170 ℃, keeping the pressure within 8Mpa, carrying out hydrothermal reaction, and discharging after 6h of reaction; and centrifuging the obtained black brown material in a centrifuge at 6000r/min to obtain a light yellow transparent liquid, namely the aqueous solution of the graphene oxide. Weighing 60 parts of graphene oxide aqueous solution, 13 parts of aqueous tackifying emulsion and 0.2 part of defoaming agent, adding the graphene oxide aqueous solution, the aqueous tackifying emulsion and the defoaming agent into a high-speed stirrer, and uniformly dispersing the graphene oxide aqueous solution and the aqueous tackifying emulsion at a rotating speed of 200r/min for 7 min; then keeping the rotating speed unchanged, sequentially adding 0.2 part of film forming agent and 0.2 part of mildew preventive, and continuously stirring for 7 min; then the rotating speed is reduced to 100r/min, 0.3 part of thickening agent is added, stirring is continued for 6min, finally 0.1 part of pH regulator is added, stirring is carried out for 6min, and discharging is carried out after the pH regulator is dispersed uniformly.
Example 3
Adding 30kg of deionized water into a container with a stirring device, adding 5kg of corn starch according to the proportion, and stirring for 10min to completely dissolve the corn starch; adding the obtained solution into a hydrothermal kettle reactor, gradually heating to 160 ℃, keeping the pressure within 8Mpa, carrying out hydrothermal reaction, and discharging after 7h of reaction; and centrifuging the obtained black brown material in a centrifuge at the speed of 7000r/min to obtain light yellow transparent liquid, namely the aqueous solution of the graphene oxide. Weighing 70 parts of graphene oxide aqueous solution, 20 parts of aqueous tackifying emulsion and 0.3 part of defoaming agent, adding into a high-speed stirrer, uniformly dispersing, wherein the rotating speed of the high-speed stirrer is 200r/min, and the stirring time is 9 min; then keeping the rotating speed unchanged, sequentially adding 0.3 part of film forming agent and 0.3 part of mildew preventive, and continuously stirring for 9 min; then the rotating speed is reduced to 100r/min, 0.5 part of thickening agent is added, the stirring is continued for 9min, finally 0.3 part of pH regulator is added, the stirring is carried out for 9min, and the mixture is discharged after being dispersed uniformly. TABLE I shows the properties of the graphene oxide aqueous adhesives prepared in the above examples 1 to 3
Claims (5)
1. The graphene oxide aqueous adhesive is characterized by comprising the following components:
50-80 parts of a graphene oxide aqueous solution;
10-30 parts of water-based tackifying emulsion;
0.2-0.8 part of thickening agent;
0.1-0.5 part of defoaming agent;
0.1-0.5 part of film forming agent;
0.1-0.6 part of pH regulator;
0.1-0.5 part of mildew preventive;
the specific preparation method of the graphene oxide comprises the following steps:
(1) adding deionized water into a container with a stirring device, adding starch, and stirring for 10-30min to completely dissolve;
(2) adding the obtained solution into a hydrothermal kettle reactor, gradually heating to 250 ℃ at 120 ℃, keeping the pressure within 8Mpa, carrying out hydrothermal reaction, and discharging after reacting for 1-15 h;
(3) and (3) carrying out centrifugal separation on the black brown material obtained in the step (2) in a centrifugal machine at the speed of 3000-15000r/min to obtain light yellow transparent liquid, namely the aqueous solution of the graphene oxide.
2. The graphene oxide aqueous adhesive according to claim 1, wherein the aqueous tackifying emulsion is an acrylic acid modified rosin tackifying emulsion; the thickening agent is starch; the defoaming agent is an organic silicon defoaming agent; the film forming agent is propylene glycol butyl ether; the pH regulator is sodium bicarbonate; the mildew preventive is p-chloro-m-dimethylphenol.
3. The method for preparing graphene oxide aqueous adhesive according to claim 1 or 2,
(1) weighing the graphene oxide aqueous solution, the aqueous tackifying emulsion and the defoaming agent, adding the graphene oxide aqueous solution, the aqueous tackifying emulsion and the defoaming agent into a high-speed stirrer, uniformly dispersing the graphene oxide aqueous solution, the water-based tackifying emulsion and the defoaming agent, wherein the rotating speed of the high-speed stirrer is 200-300r/min, and the stirring time is 5-10 min;
(2) then keeping the rotating speed unchanged, sequentially adding the film forming agent and the mildew preventive, and continuously stirring for 5-10 min;
(3) then the rotating speed is reduced to 100-150 r/min, the thickening agent is added, the stirring is continued for 5-10min, finally the pH regulator is added to adjust to be neutral, the stirring is carried out for 5-10min to ensure that the pH regulator is dispersed evenly, and then the material is discharged.
4. The preparation method of the graphene oxide aqueous adhesive as claimed in claim 1, wherein the mass ratio of the deionized water to the corn starch is 50-200: 5 to 30.
5. The preparation method of the graphene oxide aqueous adhesive as claimed in claim 4, wherein the mass ratio of the deionized water to the corn starch is 80-100: 15 to 25.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810557188.8A CN109096946B (en) | 2018-06-01 | 2018-06-01 | Graphene oxide aqueous adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810557188.8A CN109096946B (en) | 2018-06-01 | 2018-06-01 | Graphene oxide aqueous adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109096946A CN109096946A (en) | 2018-12-28 |
| CN109096946B true CN109096946B (en) | 2020-06-30 |
Family
ID=64796644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810557188.8A Active CN109096946B (en) | 2018-06-01 | 2018-06-01 | Graphene oxide aqueous adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109096946B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112376318B (en) * | 2020-11-18 | 2022-10-21 | 无锡海博源包装科技有限公司 | Anti-counterfeiting coating, anti-counterfeiting label printing process and anti-counterfeiting label |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633249A (en) * | 2012-03-23 | 2012-08-15 | 太原理工大学 | Method for rapidly preparing carbon microspheres by using cotton cellulose |
| CN106206032A (en) * | 2016-06-24 | 2016-12-07 | 中国海洋大学 | Graphene quantum dot prepared by a kind of natural macromolecular and the application in preparing quantum dot sensitization solar battery thereof |
| CN107022312A (en) * | 2017-05-27 | 2017-08-08 | 杭州高烯科技有限公司 | A kind of graphene oxide bonding agent and adhering method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2456716A2 (en) * | 2009-07-22 | 2012-05-30 | Wisys Technology Foundation, Inc. | Carbon microbeads with hierarchical structure |
-
2018
- 2018-06-01 CN CN201810557188.8A patent/CN109096946B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633249A (en) * | 2012-03-23 | 2012-08-15 | 太原理工大学 | Method for rapidly preparing carbon microspheres by using cotton cellulose |
| CN106206032A (en) * | 2016-06-24 | 2016-12-07 | 中国海洋大学 | Graphene quantum dot prepared by a kind of natural macromolecular and the application in preparing quantum dot sensitization solar battery thereof |
| CN107022312A (en) * | 2017-05-27 | 2017-08-08 | 杭州高烯科技有限公司 | A kind of graphene oxide bonding agent and adhering method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109096946A (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107556721A (en) | A kind of SMC polyester molding compounds and preparation method thereof | |
| CN107556492A (en) | A kind of aqueous epoxy resin emulsion of graphene-containing and preparation method thereof | |
| CN104291330B (en) | Preparation method of modified functionalized graphene nanometer material | |
| CN109698040B (en) | Water-based electronic paste and preparation method thereof | |
| CN107331437A (en) | Graphene low-temperature solidified silver paste compound and preparation method thereof | |
| CN109369886B (en) | Method for applying eutectic solvent modified lignin to epoxy resin curing agent | |
| CN109096946B (en) | Graphene oxide aqueous adhesive and preparation method thereof | |
| CN103321099A (en) | Surface sizing agent for papermaking and preparation method thereof | |
| CN110422869A (en) | A kind of method and super strong gypsum of coproducing alpha-super strong gypsum and sodium chloride | |
| CN110282901A (en) | A kind of cement grinding aid and preparation method thereof | |
| CN107805442A (en) | Graphene modified water-soluble anticorrosive paint and preparation method thereof | |
| CN106433317A (en) | Water-based ink-jet nano-silver conductive ink and preparation method thereof | |
| CN106564881A (en) | Preparation of reduced graphene oxide by one-step method | |
| CN103236291A (en) | Conductive carbon paste and preparation method thereof | |
| CN105062211A (en) | Halogen-free mirror ink and preparation method thereof | |
| CN111100505A (en) | Ternary vinyl chloride-vinyl acetate epoxy conductive ink | |
| CN103360984B (en) | Hemp degumming waste liquid is utilized to prepare corn starch gluing agent | |
| CN106749709A (en) | A kind of water-preserving agent for cement crosslinked carboxymethyl fecula and preparation method thereof | |
| CN102936052B (en) | Method for recycling carboxymethylcellulose production wastewater | |
| CN109401635A (en) | Graphene Aqueous Adhesives and preparation method thereof | |
| CN107446384A (en) | A kind of preparation method of composite calcium carbonate | |
| CN103756260B (en) | A kind of biomass modified thermosetting resin and preparation method thereof | |
| CN112625501B (en) | Environment-friendly ink and processing treatment process thereof | |
| CN114316689B (en) | Water-based waterproof paint with high temperature resistance and preparation method thereof | |
| CN114196213B (en) | Multifunctional modified silicone rubber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |