CN105692589B - A kind of glass-like carbon material preparation method based on phenol-formaldehyde resin modified presoma - Google Patents
A kind of glass-like carbon material preparation method based on phenol-formaldehyde resin modified presoma Download PDFInfo
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- CN105692589B CN105692589B CN201610142651.3A CN201610142651A CN105692589B CN 105692589 B CN105692589 B CN 105692589B CN 201610142651 A CN201610142651 A CN 201610142651A CN 105692589 B CN105692589 B CN 105692589B
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- formaldehyde resin
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
Abstract
The invention discloses a kind of glass-like carbon material preparation method based on phenol-formaldehyde resin modified presoma.The present invention is used as the macromolecule prepolymer presoma for preparing glass-like carbon using the phenol-formaldehyde resin modified of anti-oxidant modification, the doped chemical for improving inoxidizability by introducing boron, silicon, titanium etc. in phenolic resin, on the premise of it need not significantly change the existing glass-like carbon preparation technology based on macromolecule prepolymer presoma, mechanical property, wearability and the inoxidizability of obtained glass-like carbon can be significantly improved.The present invention while further lifting material property, effectively reduces manufacturing cycle, reduces energy resource consumption further by optimizing improvement to process conditions such as low-temperature setting, charing process.
Description
Technical field
The present invention relates to a kind of glass-like carbon material preparation method, more particularly to it is a kind of based on phenol-formaldehyde resin modified presoma
Glass-like carbon material preparation method.
Background technology
Glass-like carbon is as a kind of new carbon material, because its fracture apperance and architectural feature are referred to as glass similar to glass
Charcoal.Glass-like carbon is with excellent properties are needed, such as：It is low-density, high intensity, high rigidity, highly conductive and high-termal conductivity, corrosion-resistant, resistance to
Abrasion, almost airtight and isotropism etc., are widely used in electronics industry, semi-conductor industry, metallurgical industry, chemical work
Industry, nuclear industry and medical domain etc..The macromolecule prepolymer presoma for preparing glass Carbon Materials at present mainly has phenolic resin, chaff
Alcohol resin, poly furfuryl alcohol, polyvinyl chloride, polyimides etc..According to the physical property of macromolecule prepolymer presoma, by accurately controlling life
Each step process parameter of production process (such as solidification heating rate, carbonization heating rate), you can obtain the glass-like carbon system being molded only
Product.
Using conventional polymer prepolymer presoma as raw material, the glass-like carbon prepared can not increasingly meet industrial circle
To with complex shape and high performance material active demand, such as high temperature mechanical sealing, graphite or C/C surface-sealings coating, table
The anti-oxidant painting in face, coating material etc., more and more harsher to glass-like carbon performance requirement, its antioxygenic property, anti-wear performance need to enter one
Step improves.
Chinese patent " CN 102618841B, a kind of boron doped-glass Carbon Materials and preparation method thereof " uses chemical gaseous phase
Deposition process, using graphite as depositing base, using hydrocarbon as carbon source, using halogenation boron or borine as boron source, in 1100-
1400 DEG C, the glass-like carbon that boron doping amount is 2-15at% is prepared.The material structure even compact prepared and with good
Antioxygenic property.But coating sample can only be prepared using the method for chemical vapor deposition in substrate material surface by using,
The thickness of glass-like carbon is restricted.In addition, using chemical vapour deposition technique can not one-shot forming various shapes and specification block
Material.
The content of the invention
The technical problems to be solved by the invention are to overcome prior art insufficient, there is provided one kind is based on phenol-formaldehyde resin modified
The glass-like carbon material preparation method of presoma, it can quickly prepare the block of the excellent performances such as density, bending strength, oxidation resistance
Shape glass Carbon Materials.
It is of the invention specifically to solve above-mentioned technical problem using following technical scheme：
A kind of glass-like carbon material preparation method based on phenol-formaldehyde resin modified presoma, to macromolecule prepolymer presoma with
The mixed solution of organic solvent carries out low-temperature setting and charing process successively, obtains glass Carbon Materials；The macromolecule prepolymer
Presoma is the phenol-formaldehyde resin modified of anti-oxidant modification.
Preferably, the phenol-formaldehyde resin modified of the anti-oxidant modification is one or two kinds of in following phenol-formaldehyde resin modified
And two or more mixture：Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium Si modification
Phenolic resin.
Preferably, the organic solvent is methanol, ethanol or acetone.
Preferably, the content of macromolecule prepolymer presoma is 10~60wt% in the mixed solution.
Preferably, the process conditions of the low-temperature setting are specific as follows：60 are warming up to 0.5~2 DEG C/h heating rate
~80 DEG C, it is incubated 10~20h；100 DEG C are continuously heating to 0.5~2 DEG C/h heating rate, is incubated 10~20h；With 0.5~2
DEG C/h heating rate is continuously heating to 120 DEG C, it is incubated 10~20h；150 are continuously heating to 0.5~2 DEG C/h heating rate
DEG C, it is incubated 10~20h；Cooling.
Preferably, the process conditions of the charing process are specific as follows：250 are warming up to 10~30 DEG C/h heating rate
~300 DEG C, it is incubated 2h；550~700 DEG C are continuously heating to 10~20 DEG C/h heating rate, is incubated 2h；Again with 10~20
DEG C/h heating rate is warming up to 1000~1100 DEG C, it is incubated 2h；Cooling.
Further, the glass-like carbon material preparation method is additionally included in the graphitization processing step carried out after charing process
Suddenly, the treatment temperature of the graphitization processing is 2500 DEG C, processing time 2h.
A kind of glass Carbon Materials, it is prepared by as above preparation method described in any technical scheme.
Compared with prior art, technical solution of the present invention has the advantages that:
The performances such as density, bending strength, oxidation resistance using the glass Carbon Materials of the inventive method preparation are compared to existing
There is technology to be greatly improved, be applicable to high temperature mechanical sealing, graphite or C/C surface-sealings coating, surface oxidation-resistant applies, applies
Layer material etc., to the more stringent field of glass-like carbon performance requirement；
The inventive method can prepare the both bulk glasses Carbon Materials of any thickness, shape；
The present invention has carried out further optimization to the process conditions of low-temperature setting and charing process, and preparation time is shorter, disappears
It is less to consume the energy, it is significant for improving production efficiency and energy-saving and emission-reduction.
Embodiment
In order to quickly prepare the both bulk glasses Carbon Materials of the excellent performances such as density, bending strength, oxidation resistance,
The invention thinking of the present invention is to be improved in conventional polymer prepolymer presoma for the preparation method of raw material, is changed with organosilicon
The modification phenol of the anti-oxidant modifications such as property phenolic resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium Si modification phenolic resin
Urea formaldehyde prepares glass Carbon Materials as macromolecule prepolymer presoma.
Derivative of the phenol-formaldehyde resin modified as phenolic resin, it is its modified impact flexibility, caking property, mechanical strength, resistance to
The characteristics such as hot, dimensional stability, curing rate, moulded manufacturability can respectively obtain raising.According to performance improvement direction not
Together, the species of phenol-formaldehyde resin modified mainly has at present：Pioloform, polyvinyl acetal phenol-formaldehyde resin modified, polyimide modified phenolic aldehyde tree
Fat, epoxy modified phenolic resin, Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium are modified phenol
Urea formaldehyde, titanium Si modification phenolic resin etc..
Study and find through inventor, in many different types of phenol-formaldehyde resin modifieds, using organic silicon modified phenolic tree
The phenol-formaldehyde resin modified of the anti-oxidant modifications such as fat, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium Si modification phenolic resin is made
For macromolecule prepolymer presoma, the glass Carbon Materials being substantially improved compared with conventional method performance can be obtained, while overcome and adopt again
The many restrictions of existing material thickness, shape, specification etc. during with chemical vapour deposition technique.On this basis, this hair
It is bright that improvement further is optimized to other process conditions, while further lifting material property, effectively reduce preparation
In the cycle, reduce energy resource consumption.
For the ease of public understanding, come below with several specific embodiments further detailed to technical solution of the present invention progress
Explanation.
Embodiment 1
The phenol-formaldehyde resin modified of anti-oxidant modification is dissolved in ethanol by 40wt% mass ratio.
Then solution prepared by above-mentioned steps is poured into mould and is put into baking oven and carry out low-temperature setting.During solidification, with 2
DEG C/h heating rate is warming up to 60-80 DEG C, it is incubated 10h；100 DEG C are warming up to from 80 DEG C with 2 DEG C/h heating rate, insulation
10h；120 DEG C are warming up to 2 DEG C/h heating rate, is incubated 10h；150 DEG C are warming up to 2 DEG C/h heating rate again, insulation
20h；Glass-like carbon green compact are made after cooling.
Obtained glass-like carbon green compact are placed in retort and carry out charing process.During charing, with 30 DEG C/h heating rate
250 DEG C are warming up to, is incubated 2h；550 DEG C are warming up to from 250 DEG C with 20 DEG C/h heating rate, is incubated 2h；Again with 20 DEG C/h liter
Warm speed is warming up to 1000 DEG C, is incubated 2h；It is cooled to room temperature and obtains glass-like carbon.
In order to further improve material property, the glass-like carbon for preparing above-mentioned steps in the present embodiment is put into pyrographite
Change in treatment furnace and carry out graphitization processing.Treatment temperature is 2500 DEG C, processing time 2h, that is, obtains final glass raw material of wood-charcoal
Material.
In the present embodiment, changed with Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium silicon
Property phenolic resin be the density of glass-like carbon made from macromolecule prepolymer presoma, the porosity, bending strength and 600 DEG C of oxidations 24
The weight-loss ratio of hour is shown in Table 1.
The performance of the glass-like carbon prepared in the embodiment 1 of table 1
Embodiment 2：
The phenol-formaldehyde resin modified of anti-oxidant modification is dissolved in ethanol by 50wt% mass ratio.
Then solution prepared by above-mentioned steps is poured into mould and is put into baking oven and carry out low-temperature setting.During solidification, with 1
DEG C/h heating rate is warming up to 60-80 DEG C, it is incubated 10h；100 DEG C are warming up to from 80 DEG C with 1 DEG C/h heating rate, insulation
10h；120 DEG C are warming up to 1 DEG C/h heating rate, is incubated 10h；150 DEG C are warming up to 1 DEG C/h heating rate again, insulation
20h；Cooling, glass-like carbon green compact are made.
Obtained glass-like carbon green compact are placed in retort and carry out charing process.During charing, with 20 DEG C/h heating rate
270 DEG C are warming up to, is incubated 2h；650 DEG C are warming up to from 270 DEG C with 15 DEG C/h heating rate, is incubated 2h；Again with 15 DEG C/h liter
Warm speed is warming up to 1050 DEG C, is incubated 2h；It is cooled to room temperature and obtains glass-like carbon.
The glass-like carbon that above-mentioned steps are prepared, which is put into high temperature graphitization treatment furnace, carries out graphitization processing.Treatment temperature
For 2500 DEG C, processing time 2h, that is, obtain final glass Carbon Materials.
In the present embodiment, changed with Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium silicon
Property phenolic resin be the density of glass-like carbon made from macromolecule prepolymer presoma, the porosity, bending strength and 600 DEG C of oxidations 24
The weight-loss ratio of hour refers to table 2.
The performance of the glass-like carbon prepared in the embodiment 2 of table 2
Embodiment 3：
The phenol-formaldehyde resin modified of anti-oxidant modification is dissolved in ethanol by 60wt% mass ratio.
Then solution prepared by above-mentioned steps is poured into mould and is put into baking oven and carry out low-temperature setting.During solidification, with
0.5 DEG C/h heating rate is warming up to 60-80 DEG C, is incubated 10h；100 DEG C are warming up to from 80 DEG C with 0.5 DEG C/h heating rate,
It is incubated 10h；120 DEG C are warming up to 0.5 DEG C/h heating rate, is incubated 10h；Again 150 are warming up to 0.5 DEG C/h heating rate
DEG C, it is incubated 20h；Glass-like carbon green compact are made in cooling.
Obtained glass-like carbon green compact are placed in retort and carry out charing process.During charing, with 10 DEG C/h heating rate
300 DEG C are warming up to, is incubated 2h；700 DEG C are warming up to from 300 DEG C with 10 DEG C/h heating rate, is incubated 2h；Again with 10 DEG C/h liter
Warm speed is warming up to 1100 DEG C, is incubated 2h；It is cooled to room temperature and obtains glass-like carbon.
The glass-like carbon that above-mentioned steps are prepared, which is put into high temperature graphitization treatment furnace, carries out graphitization processing.Treatment temperature
For 2500 DEG C, processing time 2h, that is, obtain final glass Carbon Materials.
In the present embodiment, changed with Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium silicon
Property phenolic resin be the density of glass-like carbon made from macromolecule prepolymer presoma, the porosity, bending strength and 600 DEG C of oxidations 24
The weight-loss ratio of hour refers to table 3.
The performance of the glass-like carbon prepared in the embodiment 3 of table 3
It is can be seen that according to three above embodiment compared to glass of the tradition using phenolic resin as macromolecule prepolymer presoma
Glass charcoal, use the phenol-formaldehyde resin modified of anti-oxidant modification for glass-like carbon made from macromolecule prepolymer presoma density of material,
Significantly exceed in terms of many characteristics such as the porosity, intensity, anti-oxidant.
In addition, according to the research of inventor, when the content of the phenol-formaldehyde resin modified is more than 30wt%, during charing process
The porosity of glass carbon product is low, bending strength is higher, and oxidation resistance strengthens.In above three embodiment, particularly
When the content of phenol-formaldehyde resin modified is 60wt%, density, bending strength, the oxidation resistance of glass carbon product are best.
Above-described, only presently preferred embodiments of the present invention is not limited to the scope of the present invention, of the invention is upper
Stating embodiment can also make a variety of changes.What i.e. every claims and description according to the present patent application were made
Simply, equivalent changes and modifications, the claims of patent of the present invention are fallen within.The not detailed description of the present invention is
Routine techniques content.
Claims (8)
- A kind of 1. glass-like carbon material preparation method based on phenol-formaldehyde resin modified presoma, to macromolecule prepolymer presoma with having The mixed solution of solvent carries out low-temperature setting and charing process successively, obtains glass Carbon Materials；Characterized in that, the high score Sub- prepolymer presoma is the phenol-formaldehyde resin modified of anti-oxidant modification；This method is additionally included in the graphite carried out after charing process Change processing step, the treatment temperature of the graphitization processing is 2500oC, processing time 2h；The modification of the anti-oxidant modification Phenolic resin is one or more kinds of mixtures in following phenol-formaldehyde resin modified：Effect of Organosilicon-modified Phenol-formaldehyde Resin, molybdenum Phenol-formaldehyde resin modified, titanium Si modification phenolic resin.
- 2. glass-like carbon material preparation method as claimed in claim 1, it is characterised in that the organic solvent be methanol, ethanol or Acetone.
- 3. glass-like carbon material preparation method as claimed in claim 1, it is characterised in that macromolecule prepolymer in the mixed solution The content of presoma is 10 ~ 60wt%.
- 4. glass-like carbon material preparation method as claimed in claim 3, it is characterised in that macromolecule prepolymer in the mixed solution The content of presoma is 30 ~ 60wt%.
- 5. glass-like carbon material preparation method as claimed in claim 4, it is characterised in that macromolecule prepolymer in the mixed solution The content of presoma is 60wt%.
- 6. glass-like carbon material preparation method as claimed in claim 1, it is characterised in that the process conditions of the low-temperature setting are specific It is as follows：60~80 are warming up to 0.5~2 DEG C/h heating rate o C, it is incubated 10~20h；With 0.5~2o C/h heating speed Rate is continuously heating to 100o C, it is incubated 10~20h；With 0.5~2 o C/h heating rate is continuously heating to 120 o C, insulation 10~20h；With 0.5~2 o C/h heating rate is continuously heating to 150 o C, it is incubated 10~20h；Cooling.
- 7. glass-like carbon material preparation method as claimed in claim 1, it is characterised in that the process conditions of the charing process are specific It is as follows：With 10~30oC/h heating rate is warming up to 250~300oC, it is incubated 2h；With 10~20oC/h heating rate continues It is warming up to 550~700oC, it is incubated 2h；Again with 10~20oC/h heating rate is warming up to 1000~1100oC, it is incubated 2h；Drop Temperature.
- 8. a kind of glass Carbon Materials, it is characterised in that be prepared by the preparation method as described in any one of claim 1~7.
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| CN106496851A (en) * | 2016-10-26 | 2017-03-15 | 安徽飞达电气科技有限公司 | A kind of metallized film of anti-surge capacity device and preparation method thereof |
| CN106747668A (en) * | 2017-02-17 | 2017-05-31 | 南通市苏中纺织有限公司 | The modifies high heat conduction C/C composites of ZrC organosilane precursors |
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