CN109824920A - One-step method prepares polyvinyl alcohol copolymer melamine resin nanosphere - Google Patents
One-step method prepares polyvinyl alcohol copolymer melamine resin nanosphere Download PDFInfo
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- CN109824920A CN109824920A CN201910056681.6A CN201910056681A CN109824920A CN 109824920 A CN109824920 A CN 109824920A CN 201910056681 A CN201910056681 A CN 201910056681A CN 109824920 A CN109824920 A CN 109824920A
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- melamine resin
- necked flask
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- polyvinyl alcohol
- alcohol copolymer
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Abstract
The present invention relates to one-step method to prepare polyvinyl alcohol copolymer melamine resin nanosphere, which formed by melamine and formaldehyde condensation polymer, and synthesis process is added water soluble polymer PVAC polyvinylalcohol and participates in polymerization reaction, and regulates and controls the sphere diameter size of product.Preparation process is mainly that 0.2 g PVA is added in the three-necked flask for having appropriate amount of deionized water, 90o0.5 h of stirred in water bath of C is to being completely dissolved.5.1 g melamines are added in three-necked flask, move into formalin (37%wt) about 10.0 ml, the process is 60oIt is carried out in the water-bath of C.When three-necked flask solution fades to transparent, measures the appropriate glacial acetic acid of 1.8 ml and be added in three-necked flask, the system is made to keep pH value about 3.1.30 min are reacted up to final solution.Above-mentioned solution is centrifuged, dehydrated alcohol and deionized water alternately wash it is each three times, and after being freeze-dried, obtain that sphere diameter is controllable, prepares simple, evenly dispersed polyvinyl alcohol copolymer melamine resin nanosphere.
Description
Technical field
The invention belongs to new energy technical field of electronic materials, it is related to one-step method and prepares polyvinyl alcohol copolymer melamine resin receiving
Rice ball.
Background technique
Melamine resin, abbreviation MF, commonly referred to as melamine resin are one of relatively early industrialized chemical products.
In addition, melamine resin is a kind of cheap and commercially valuable aerotex, nitrogen content is abundant, and amino activity is high,
Excellent combination property, and be widely used in plastics, medicine, organic coating, paper industry, binder, adsorbent, fire retardant,
The various fields such as modifying agent, leather industry, paper industry.Simultaneously because melamine resin has, high N doping is horizontal, Ke Yiming
The aobvious performance for improving carbon material, is widely used in energy storage field.
Li M, Xue J etc. has studied using melamine resin as nitrogen source, using the conjunction of the hydro-thermal method synthesis doped meso-porous charcoal of N-
At technique.The melamine resin ball being prepared is spherical, and sphere diameter and uneven.Prepared N doping mesoporous carbon
(NC) and nitrogen-doped graphene (NG) electrode material surface product is big, and pore-size distribution is suitable, and evenly dispersed, doping is adjustable.These
Unique performance becomes the high-performance super capacitor electrode of great development prospect.For example, on the basis of three-electrode system
On, high nitrogen doped carbon (NCH) electrode and nitrogen-doped graphene (NG) electrode can mention respectively when current density is 0.2 A/g
For the specific capacitance of 238 F/g and 289 F/g.Under 0.5 A/g current density, NCH is relative to the pure mesoporous carbon undoped with nitrogen
Capacitor improves 91.6%.This illustrates that the either independent polycondensation of MF is still used as nitrogen source to introduce, and all shows excellent performance
(The Journal of Physical Chemistry C, 2014,118 (5): 2507-2517.).Chinese patent literature
CN108117663A discloses a kind of production technology of melamine resin hollow microsphere, includes the following steps: (1) according to molar ratio computing
Calculating is melamine: formaldehyde: distilled water is the ratio of 1:2.0 ~ 2.7:4 ~ 5, and melamine, formaldehyde and distilled water are added to appearance
75 ~ 80 are heated in device and after being uniformly mixedoControlled after C speed of agitator be 500 r/min be stirred to react 0.3 ~
0.4 h, obtains reaction solution；(2) it is 8 ~ 9 with the pH value that triethanolamine solution adjusts above-mentioned resulting reaction solution, continues to control
Temperature is 750oC, 500 r/min of revolving speed obtains melamine resin performed polymer until transparent；(3) melamine tree obtained above is adjusted
The solid content of rouge performed polymer is 10 ~ 20% wt, adds foaming agent and/or surfactant, is thoroughly mixed to form uniform slurry
The melamine resin hollow microsphere is made by the slurries through high temperature spray-drying in liquid.
Summary of the invention
In view of the deficiencies of the prior art, the present invention uses one-step method, is prepared for that sphere diameter is controllable, and the nanometer of favorable dispersibility is close
Polyimide resin ball.
Technical scheme is as follows:
A kind of resin base carbon material, the material are copolymerized by adding appropriate PVA in the preparation process of melamine resin.
According to the present invention, one-step method prepares nanometer melamine resin ball, comprises the following steps that
(1) g of 0.1 g ~ 0.5 PVA is added in the three-necked flask for having appropriate amount of deionized water, 90oThe stirred in water bath 0.5 of C
H is to being completely dissolved；
(2) the g melamine of 3.9 g ~ 5.9 is added in three-necked flask, moves into formalin (37% wt, similarly hereinafter) 7.5 ~ 12.0
Ml, the process is 60oIt is carried out in the water-bath of C；
(3) it when three-necked flask solution fades to transparent in (1), measures appropriate glacial acetic acid and is added in three-necked flask, protect the system
Holding pH value is 1 ~ 6.The min of 10 min ~ 120 is reacted up to final solution；Above-mentioned solution is centrifuged, dehydrated alcohol and go from
Sub- water alternately washs respectively three times, and is freeze-dried；
, according to the invention it is preferred to, best PVA dosage described in step (1) is 0.2 g.
, according to the invention it is preferred to, melamine dosage described in step (2) is 5.1 g.
, according to the invention it is preferred to, formaldehyde dosage is 10.0 ml in step (2).
, according to the invention it is preferred to, step (3) optimal pH is 3.1.
, according to the invention it is preferred to, step (3) optimum reacting time is 30 min.
Technical advantage of the invention is as follows:
(1) preparation process of the present invention is easy, and time-consuming is short, yield is high.
(2) melamine resin ball made from the preparation method that uses of the present invention, compared to non-uniform simple melamine resin ball,
It is nanosphere of uniform size.
(3) present invention in PVA addition, the sphere diameter of melamine resin ball, about 400 ~ 500 nm can be regulated and controled.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph that the melamine resin ball of 0.2 g PVA is added in the embodiment of the present invention 2.
Fig. 2 is the transmission electron microscope picture that the melamine resin ball of 0.2 g PVA is added in the embodiment of the present invention 2.
Fig. 3 is the scanning electron microscope (SEM) photograph of simple melamine resin ball in comparative example 1 of the present invention.
Specific embodiment
The present invention is described further with attached drawing combined with specific embodiments below, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously；The reagent and material
Material, unless otherwise specified, commercially obtains.
Embodiment 1:
0.1 g PVA is added in the three-necked flask for having appropriate amount of deionized water, 90o0.5 h of stirred in water bath of C is to complete
Dissolution.5.1 g melamines are added in three-necked flask, move into 10.0 ml of formalin, the process is 60oIn the water-bath of C
It carries out；When three-necked flask solution fades to transparent, measures appropriate glacial acetic acid and be added in three-necked flask, the system is made to keep pH value about
2.0.30 min are reacted up to final solution；Above-mentioned liquid is centrifuged, alternately washs each three with dehydrated alcohol and deionized water
It is secondary, and be freeze-dried.
Embodiment 2:
0.2 g PVA is added in the three-necked flask for having appropriate amount of deionized water, 90o0.5 h of stirred in water bath of C is to complete
Dissolution.5.1 g melamines are added in three-necked flask, move into 10.0 ml of formalin, the process is 60oIn the water-bath of C
It carries out.When three-necked flask solution fades to transparent, measures appropriate glacial acetic acid and be added in three-necked flask, the system is made to keep pH value about
3.1.100 min are reacted up to final solution；Above-mentioned liquid is centrifuged, alternately washs each three with dehydrated alcohol and deionized water
It is secondary, and be freeze-dried.
Embodiment 3:
0.3 g PVA is added in the three-necked flask for having appropriate amount of deionized water, 90o0.5 h of stirred in water bath of C is to complete
Dissolution.5.1 g melamines are added in three-necked flask, move into 10.0 ml of formalin, the process is 60oIn the water-bath of C
It carries out.When three-necked flask solution fades to transparent, measures appropriate glacial acetic acid and be added in three-necked flask, the system is made to keep pH value about
6.5.50 min are reacted up to final solution；Above-mentioned liquid is centrifuged, alternately washs each three with dehydrated alcohol and deionized water
It is secondary, and be freeze-dried.
Comparative example 1:
5.1 g melamines are added in three-necked flask, move into 10.0 ml of formalin, the process is 60oIn the water-bath of C into
Row.When three-necked flask solution fades to transparent, measures appropriate glacial acetic acid and be added in three-necked flask, the system is made to keep pH value about
3.1.100 min are reacted up to final solution；Above-mentioned liquid is centrifuged, alternately washs each three with dehydrated alcohol and deionized water
It is secondary, and be freeze-dried.
Claims (7)
1. one kind is described in claim 1, one-step method prepares polyvinyl alcohol copolymer melamine resin nanosphere according to the present invention, including
Steps are as follows:
(1) g of 0.1 g ~ 0.5 PVA is added in the three-necked flask for having appropriate amount of deionized water, 90oThe stirred in water bath 0.5 of C
H is to being completely dissolved.
(2) the g melamine of 3.9 g ~ 5.9 is added in three-necked flask, moves into formalin (37% wt) about 7.5 ~ 12.0 ml,
The process is 60oIt is carried out during the water-bath of C.
(3) it when three-necked flask solution fades to transparent in (1), measures appropriate glacial acetic acid and is added in three-necked flask, protect the system
Hold pH value about 1.0 ~ 6.0.The min of 10 min ~ 120 is reacted up to final solution；Above-mentioned liquid is centrifuged, with dehydrated alcohol and
Deionized water is alternately washed respectively three times, and is freeze-dried.
2. according to claim 1 prepare polyvinyl alcohol copolymer melamine resin nanosphere, which is characterized in that in step (1)
The best PVA dosage is 0.2 g.
3. according to claim 1 prepare melamine resin nanosphere, which is characterized in that melamine described in step (2)
Dosage is 5.1 g.
4. according to claim 1 prepare melamine resin nanosphere, which is characterized in that formaldehyde dosage is in step (2)
10.0 ml。
5. according to claim 1 prepare melamine resin nanosphere, which is characterized in that pH value is most preferably in step (3)
3.1。
6. according to claim 1 prepare melamine resin nanosphere, which is characterized in that step (3) optimum reacting time is
30 min。
7. one-step method prepares polyvinyl alcohol copolymer melamine resin nanosphere.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303363A (en) * | 2020-04-08 | 2020-06-19 | 安徽壹石通材料科技股份有限公司 | Preparation method of large-particle-size melamine formaldehyde resin microspheres |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS525859A (en) * | 1975-07-04 | 1977-01-17 | Japan Synthetic Rubber Co Ltd | Process for preparing water-containing spherical gel of polyvinyl alco hol |
| CN101380560A (en) * | 2008-10-16 | 2009-03-11 | 上海大学 | Preparation method of low cross-linking level melamine formaldehyde module for layer upon layer self-assembly |
| CN105153386A (en) * | 2015-10-19 | 2015-12-16 | 南京工程学院 | Preparation method and application of hollow melamine formaldehyde resin microspheres |
| CN105170092A (en) * | 2015-10-23 | 2015-12-23 | 蓝星（成都）新材料有限公司 | Resin-based activated carbon ball and preparation method thereof |
| CN105561901A (en) * | 2016-01-12 | 2016-05-11 | 南京工程学院 | Preparation method of mono-dispersed melamine resin microsphere |
| CN108102119A (en) * | 2017-12-21 | 2018-06-01 | 贺州宝兴新材料有限公司 | A kind of preparation method of melamine resin hollow microsphere |
| CN108511206A (en) * | 2018-03-28 | 2018-09-07 | 齐鲁工业大学 | A kind of preparation method and application of melamine resin base carbon material electrode material for super capacitor |
-
2019
- 2019-01-22 CN CN201910056681.6A patent/CN109824920B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS525859A (en) * | 1975-07-04 | 1977-01-17 | Japan Synthetic Rubber Co Ltd | Process for preparing water-containing spherical gel of polyvinyl alco hol |
| CN101380560A (en) * | 2008-10-16 | 2009-03-11 | 上海大学 | Preparation method of low cross-linking level melamine formaldehyde module for layer upon layer self-assembly |
| CN105153386A (en) * | 2015-10-19 | 2015-12-16 | 南京工程学院 | Preparation method and application of hollow melamine formaldehyde resin microspheres |
| CN105170092A (en) * | 2015-10-23 | 2015-12-23 | 蓝星（成都）新材料有限公司 | Resin-based activated carbon ball and preparation method thereof |
| CN105561901A (en) * | 2016-01-12 | 2016-05-11 | 南京工程学院 | Preparation method of mono-dispersed melamine resin microsphere |
| CN108102119A (en) * | 2017-12-21 | 2018-06-01 | 贺州宝兴新材料有限公司 | A kind of preparation method of melamine resin hollow microsphere |
| CN108511206A (en) * | 2018-03-28 | 2018-09-07 | 齐鲁工业大学 | A kind of preparation method and application of melamine resin base carbon material electrode material for super capacitor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303363A (en) * | 2020-04-08 | 2020-06-19 | 安徽壹石通材料科技股份有限公司 | Preparation method of large-particle-size melamine formaldehyde resin microspheres |
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