CN110055625A - A method of using galapectite as catalyst preparation carbon nano-fiber - Google Patents
A method of using galapectite as catalyst preparation carbon nano-fiber Download PDFInfo
- Publication number
- CN110055625A CN110055625A CN201910244980.2A CN201910244980A CN110055625A CN 110055625 A CN110055625 A CN 110055625A CN 201910244980 A CN201910244980 A CN 201910244980A CN 110055625 A CN110055625 A CN 110055625A
- Authority
- CN
- China
- Prior art keywords
- galapectite
- fiber
- carbon nano
- catalyst
- polyester
- 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.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/26—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds from polyesters
Abstract
The invention discloses a kind of using galapectite as the method for catalyst preparation carbon nano-fiber, using polyester as carbon source material, using galapectite as catalyst, mixes through melting or solution, above-mentioned compound is prepared carbon nano-fiber through cracking.The carbon source used in the present invention is polyester or Pillar recovery, and catalyst used is galapectite, and abundance is cheap, environmentally protective.The mixing apparatus and cracking apparatus used is common apparatus, simple process.
Description
Technical field
The invention belongs to synthesize carbon nano-fiber materials field, and in particular to one kind is received by catalyst preparation carbon of galapectite
The method of rice fiber.
Background technique
Carbon nano-fiber refers to the hollow or solid carbon fiber with nanoscale.Its diameter is usually several angstroms to tens
Nanometer, draw ratio are tens to thousands of.Because it is with characteristics such as high-strength, light, excellent thermally conductive, electric conductivity, nano combined
The domain requirements amount such as material is big, has broad application prospects.But the preparation cost of current carbon nano-fiber is high, complex process limit
Its application development is made.
In general, carbon nano-fiber is using the side such as chemical vapour deposition technique, catalysis synthesis process, arc discharge method, electrostatic spinning
Method preparation, such as the carbon nanometer of CN200510037474.4, CN200510100053.1, CN200510100771.9 patent disclosure
The preparation method of material.Above-mentioned preparation method is first often using small organic molecule as carbon source, e.g., acetylene, ethylene, methane etc.；Two
Use metal or metal oxide as catalyst, synthesis temperature is high, expensive.Three carry out synthesis technology complexity, to equipment
There is particular/special requirement.Patent CN201110205487.3 is disclosed mutually to be tied using template with hydro-thermal method using natural galapectite as template
The method of conjunction is come the method for preparing carbon nanomaterial, acid that this method is related to hydro-thermal reaction autoclave, activates galapectite
Deng.Therefore, need to be explored and prepare carbon Nanowire using new raw material and inexpensive, environmentally protective, simple process new method
The new way of dimension.
Summary of the invention
In view of the above-mentioned problems, the present invention is intended to provide with new raw material, low cost, environmentally protective, simple process new side
Method prepares the new way of carbon nano-fiber.It is intended to provide a kind of using galapectite as the method for catalyst preparation carbon nano-fiber, packet
Include following steps:
1) galapectite is calcined into 60-240min at 600-900 DEG C, cooling obtains thermal activation galapectite；
Under agitation, organosilan is added into galapectite suspension or thermal activation galapectite suspension, then exists
10-48h is reacted at 80-150 DEG C, is separated solid, is dried to obtain modified galapectite；
Thermal activation galapectite or modified galapectite are galapectite catalyst；
2) in a solvent by polyester dissolution, 10- then is stirred to addition step 1) the galapectite catalyst in solvent
90min obtains polyester/galapectite compound after removing solvent；The polyester, solvent and galapectite catalyst amount, by weight
Meter, respectively 1 part of polyester, 10 parts of solvent, 0.001-0.2 parts of galapectite catalyst；
The polyester/galapectite compound, can also be by mixing the galapectite catalyst that mass ratio is 1:4-999 with polyester
It closes uniformly, is obtained by melt blending；
3) by the step 2) polyester/galapectite compound, under conditions of nitrogen atmosphere and 500-900 DEG C, 30- is heated
150min, cooling obtain carbon nano-fiber.
Preferably, the step 1) galapectite is powder state.
Preferably, step 1) the galapectite suspension or thermal activation galapectite suspension are by by galapectite powder
Or thermal activation galapectite powder is scattered in ethyl alcohol, forms suspension.
Preferably, the modified galapectite partial size is 0.01-20 μm, draw ratio 5-50, and modified galapectite partial size is preferred
It is 0.1-1.2 μm.
Preferably, the step 2) polyester is poly terephthalic acid/adipic acid butanediol copolyester, poly terephthalic acid second
One of diol ester, polybutylene terephthalate (PBT) and poly butylene succinate are a variety of.
Preferably, the step 2) solvent is at least one of chloroform, methylene chloride, tetrachloroethanes and phenol.
Preferably, the step 2) melt blending is to carry out in extruder or mixer, and melting temperature is 90-
300℃。
Preferably, step 3) the carbon nano-fiber length is 0.1-10 μm, diameter 5-100nm.
It is expensive for synthetic catalyst in the prior art with metal or metal oxide；Synthesis material is expensive；Synthesis
The problems such as complex process, equipment is special is synthesis it is an object of the present invention to disclosing a kind of using polyester or waste and old polyester
Raw material, the cheap inorganic non-metallic galapectite of green are catalyst, and the method for carbon nano-fiber is synthesized in common high-temperature service.
The present invention mixes polyester or waste and old polyester with galapectite catalyst, is prepared using above-mentioned composite material by high temperature cracking method
Carbon nano-fiber.
Beneficial effects of the present invention:
1) carbon source used in the present invention is cheap for polyester or Pillar recovery, from a wealth of sources；
2) catalyst used by is thermal activation galapectite or modified galapectite, and material is environmentally protective, abundance, inexpensively
It is easy to get；
3) mixing apparatus and cracking apparatus used in are common process equipment；
4) there is cost advantage using the carbon nano-fiber of the method for the present invention preparation, while technics of reclaim of plastic waste benefit can be solved
With problem, there is sustainability and applicating superiority.
Detailed description of the invention
Fig. 1 is the resulting carbon nano-fiber scanning electron microscope (SEM) photograph of embodiment 1；
Fig. 2 is the resulting carbon nano-fiber scanning electron microscope (SEM) photograph of embodiment 3.
Specific embodiment
Technical effect in order to further illustrate the present invention is specifically described the present invention below by embodiment.
Embodiment 1
100g galapectite powder is placed in Muffle furnace, calcines 60min at 700 DEG C, after natural cooling, obtains hot work
Change galapectite catalyst.
5g poly terephthalic acid/tetramethylene adipate (PBAT) is dissolved in 50ml methylene chloride；It is added above-mentioned angstrom
Lip river stone catalyst 0.5% is stirred by ultrasonic 30min, pours in a mold, PBAT compound is obtained after solvent flashing.
PBAT compound is placed in ceramic crucible, is placed in tube furnace, in a nitrogen atmosphere, 550 DEG C is warming up to, adds
Hot 45min, is cooled to room temperature to get carbon nano-fiber.
Embodiment 2
100g galapectite powder is placed in Muffle furnace, calcines 45min at 800 DEG C, after natural cooling, by sample point
It dissipates in ethyl alcohol, forms 0.5g/ml suspension, organosilan is added under stirring condition, 12h, centrifugation point are reacted at 100 DEG C
From after 120 DEG C of dryings, smashing and grinding obtains modified galapectite catalyst.
In mass ratio, the polyethylene terephthalate (PET) of 2% above-mentioned galapectite catalyst, 98% is uniformly mixed
It is added to after conjunction in extruder and carries out melting mixing, obtain PET compound.Extrusion temperature: 115,160,200,220,150 DEG C,
Revolving speed: 150 revs/min.
PET compound is placed in ceramic crucible, is placed in high temperature furnace, in a nitrogen atmosphere, 700 DEG C is warming up to, adds
Hot 45min, is cooled to room temperature to get carbon nano-fiber.
Embodiment 3
100g galapectite powder is placed in Muffle furnace, calcines 45min at 650 DEG C, after natural cooling, by sample point
It dissipates in ethyl alcohol, forms 1g/ml suspension, organosilan is added under stirring condition, 10h is reacted at 110 DEG C, be centrifugated,
After 120 DEG C of dryings, smashing and grinding obtains modified galapectite catalyst.
In mass ratio, the PBAT of 5% above-mentioned galapectite catalyst, 95% is added to after evenly mixing in extruder and is carried out
Melting mixing obtains PBAT compound.Extrusion temperature: 100,110,150,170,120 DEG C, revolving speed: 200 revs/min.
PBAT compound is placed in ceramic crucible, is placed in high temperature furnace, in a nitrogen atmosphere, 550 DEG C is warming up to, adds
Hot 90min, is cooled to room temperature to get carbon nano-fiber.
Embodiment 4
100g galapectite powder is placed in Muffle furnace, calcines 60min at 850 DEG C, after natural cooling, obtains hot work
Change galapectite catalyst.
In mass ratio, the polybutylene terephthalate (PBT) (PBT) of 8% above-mentioned galapectite catalyst, 92% is uniformly mixed
It is added to after conjunction in extruder and carries out melting mixing, obtain PBT compound.Extrusion temperature: 130,180,210,230,150 DEG C,
Revolving speed: 180 revs/min.
PBT compound is placed in ceramic crucible, is placed in tube furnace, in a nitrogen atmosphere, 800 DEG C is warming up to, adds
Hot 30min, is cooled to room temperature to get carbon nano-fiber.
Embodiment 5
100g galapectite powder is placed in Muffle furnace, calcines 50min at 700 DEG C, after natural cooling, obtains hot work
Change galapectite catalyst.
In mass ratio, PBT, 50%PET of 10% above-mentioned galapectite catalyst, 40% are added to extrusion after evenly mixing
Melting mixing is carried out in machine, obtains PET/PBT compound.Extrusion temperature: 140,190,220,240,150 DEG C, revolving speed: 240 turns/
Point.
Above-mentioned compound is placed in ceramic crucible, is placed in high temperature furnace, in a nitrogen atmosphere, 900 DEG C is warming up to, adds
Hot 60min, is cooled to room temperature to get carbon nano-fiber.
Embodiment 6
100g galapectite powder is placed in Muffle furnace, calcines 45min at 650 DEG C, after natural cooling, by sample point
It dissipates in ethyl alcohol, forms 2g/ml suspension, organosilan is added under stirring condition, 10h is reacted at 110 DEG C, be centrifugated,
After 120 DEG C of dryings, smashing and grinding obtains modified galapectite catalyst.
PET is dissolved in tetrachloroethanes/phenol 1:1 solvent；By weight, galapectite: PET=15:85, in addition
Galapectite catalyst is stated, 90min is stirred by ultrasonic, pours in a mold, PET compound is obtained after solvent flashing.
PET compound is placed in ceramic crucible, is placed in tube furnace, in a nitrogen atmosphere, 650 DEG C is warming up to, adds
Hot 120min, is cooled to room temperature to get carbon nano-fiber.
Embodiment 7
100g galapectite powder is placed in Muffle furnace, calcines 40min at 750 DEG C, after natural cooling, by sample point
It dissipates in ethyl alcohol, forms 1g/ml suspension, organosilan is added under stirring condition, 48h is reacted at 90 DEG C, be centrifugated,
After 120 DEG C of dryings, smashing and grinding obtains modified galapectite catalyst.
In mass ratio, by 20% above-mentioned galapectite catalyst, 70% PBAT, 10% poly butylene succinate (PBS)
It is added in extruder after evenly mixing and carries out melting mixing, obtain PBAT/PBS compound.Extrusion temperature: 90,120,170,
190,135 DEG C, revolving speed: 180 revs/min.
Above-mentioned compound is placed in ceramic crucible, is placed in tube furnace, in a nitrogen atmosphere, 600 DEG C is warming up to, adds
Hot 150min, is cooled to room temperature to get carbon nano-fiber.
Finally, it should be noted that the above examples are only used to illustrate the technical scheme of the present invention rather than limits, although ginseng
Technical solution of the present invention is described in detail according to preferred embodiment, it will be appreciated by those skilled in the art that can be to this
The technical solution of invention is modified or replaced equivalently, and without departing from the purpose and scope of the invention, should all be covered at this
In the protection scope of invention.
Claims (9)
1. a kind of using galapectite as the method for catalyst preparation carbon nano-fiber, which comprises the steps of:
1) galapectite is calcined into 60-240min at 600-900 DEG C, cooling obtains thermal activation galapectite；
Under agitation, organosilan is added into galapectite suspension or thermal activation galapectite suspension, then in 80-
10-48h is reacted at 150 DEG C, is separated solid, is dried to obtain modified galapectite；
Thermal activation galapectite or modified galapectite are galapectite catalyst；
2) 10-90min then in a solvent by polyester dissolution, is stirred to addition step 1) the galapectite catalyst in solvent,
Polyester/galapectite compound is obtained after removing solvent；The polyester, solvent and galapectite catalyst amount, by weight, respectively
It is 1 part of polyester, 10 parts of solvent, 0.001-0.2 parts of galapectite catalyst；
The polyester/galapectite compound, can also be by mixing the galapectite catalyst that mass ratio is 1:4-999 with polyester
It is even, it is obtained by melt blending；
3) by the step 2) polyester/galapectite compound, under conditions of nitrogen atmosphere and 500-900 DEG C, 30- is heated
150min, cooling obtain carbon nano-fiber.
2. according to claim 1 using galapectite as the method for catalyst preparation carbon nano-fiber, which is characterized in that step
1) galapectite is powder state.
3. according to claim 1 using galapectite as the method for catalyst preparation carbon nano-fiber, which is characterized in that step
1) the galapectite suspension or thermal activation galapectite suspension are by dividing galapectite powder or thermal activation galapectite powder
It dissipates in ethyl alcohol, forms suspension.
4. according to claim 1 using galapectite as the method for catalyst preparation carbon nano-fiber, which is characterized in that described
Modified galapectite partial size is 0.01-20 μm, draw ratio 5-50, and modified galapectite partial size is preferably 0.1-1.2 μm.
5. according to claim 1 using galapectite as the method for catalyst preparation carbon nano-fiber, which is characterized in that step
2) polyester is poly terephthalic acid/adipic acid butanediol copolyester, polyethylene terephthalate, poly terephthalic acid
One of butanediol ester and poly butylene succinate are a variety of.
6. according to claim 1 using galapectite as the method for catalyst preparation carbon nano-fiber, which is characterized in that step
2) solvent is at least one of chloroform, methylene chloride, tetrachloroethanes and phenol.
7. according to claim 1 using galapectite as the method for catalyst preparation carbon nano-fiber, which is characterized in that step
2) melt blending is to carry out in extruder or mixer, and melting temperature is 90-300 DEG C.
8. according to claim 1 using galapectite as the method for catalyst preparation carbon nano-fiber, which is characterized in that step
3) heating is carried out in high temperature furnace and tube furnace.
9. according to claim 1 using galapectite as the method for catalyst preparation carbon nano-fiber, which is characterized in that step
3) the carbon nano-fiber length is 0.1-10 μm, diameter 5-100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910244980.2A CN110055625B (en) | 2019-03-28 | 2019-03-28 | Method for preparing carbon nano-fiber by using halloysite as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910244980.2A CN110055625B (en) | 2019-03-28 | 2019-03-28 | Method for preparing carbon nano-fiber by using halloysite as catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110055625A true CN110055625A (en) | 2019-07-26 |
| CN110055625B CN110055625B (en) | 2022-03-22 |
Family
ID=67317795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910244980.2A Active CN110055625B (en) | 2019-03-28 | 2019-03-28 | Method for preparing carbon nano-fiber by using halloysite as catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110055625B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333906A (en) * | 2020-03-26 | 2020-06-26 | 中国科学院化学研究所 | Preparation method of solid acid catalyst and carbon nanofiber |
| CN111501133A (en) * | 2020-05-28 | 2020-08-07 | 中国科学院化学研究所 | Carbon nanofiber based on inorganic structure template and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935637A (en) * | 2005-09-23 | 2007-03-28 | 清华大学 | Method for preparing carbon nano tube |
| CN1939838A (en) * | 2005-09-29 | 2007-04-04 | 鸿富锦精密工业（深圳）有限公司 | Production of carbon nano-tubes |
| CN1955112A (en) * | 2005-10-27 | 2007-05-02 | 鸿富锦精密工业（深圳）有限公司 | Preparation method of carbon nano-tube |
| CN101078137A (en) * | 2007-06-29 | 2007-11-28 | 东华大学 | Lignin-base nano carbon fibre and preparation method thereof |
| CN101112980A (en) * | 2007-06-27 | 2008-01-30 | 东华大学 | Method for preparing nano carbon fibre by using polyacryl-nitrile (PAN) |
| CN102398902A (en) * | 2011-07-21 | 2012-04-04 | 中国地质大学（武汉） | Method for preparing carbon nano material by using natural endellite as formwork |
| CN104401965A (en) * | 2014-11-19 | 2015-03-11 | 中国科学院长春应用化学研究所 | Method for preparing carbon material |
-
2019
- 2019-03-28 CN CN201910244980.2A patent/CN110055625B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935637A (en) * | 2005-09-23 | 2007-03-28 | 清华大学 | Method for preparing carbon nano tube |
| CN1939838A (en) * | 2005-09-29 | 2007-04-04 | 鸿富锦精密工业（深圳）有限公司 | Production of carbon nano-tubes |
| CN1955112A (en) * | 2005-10-27 | 2007-05-02 | 鸿富锦精密工业（深圳）有限公司 | Preparation method of carbon nano-tube |
| CN101112980A (en) * | 2007-06-27 | 2008-01-30 | 东华大学 | Method for preparing nano carbon fibre by using polyacryl-nitrile (PAN) |
| CN101078137A (en) * | 2007-06-29 | 2007-11-28 | 东华大学 | Lignin-base nano carbon fibre and preparation method thereof |
| CN102398902A (en) * | 2011-07-21 | 2012-04-04 | 中国地质大学（武汉） | Method for preparing carbon nano material by using natural endellite as formwork |
| CN104401965A (en) * | 2014-11-19 | 2015-03-11 | 中国科学院长春应用化学研究所 | Method for preparing carbon material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333906A (en) * | 2020-03-26 | 2020-06-26 | 中国科学院化学研究所 | Preparation method of solid acid catalyst and carbon nanofiber |
| CN111333906B (en) * | 2020-03-26 | 2021-03-30 | 中国科学院化学研究所 | Preparation method of solid acid catalyst and carbon nanofiber |
| CN111501133A (en) * | 2020-05-28 | 2020-08-07 | 中国科学院化学研究所 | Carbon nanofiber based on inorganic structure template and preparation method thereof |
| CN111501133B (en) * | 2020-05-28 | 2021-05-25 | 中国科学院化学研究所 | Carbon nanofiber based on inorganic structure template and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110055625B (en) | 2022-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Design of healable epoxy composite based on β-hydroxyl esters crosslinked networks by using carboxylated cellulose nanocrystals as crosslinker | |
| CN107825621B (en) | Polymer-based micro/nano functional composite spherical powder and preparation method thereof | |
| CN106192048B (en) | Preparation method of graphene oxide modified polypropylene fiber | |
| JP5384405B2 (en) | Method for producing thermosetting composite material with high nanotube content | |
| CN110055625A (en) | A method of using galapectite as catalyst preparation carbon nano-fiber | |
| CN102561037B (en) | Benzoxazine-modified super-hydrophobic nano fiber membrane and preparation method thereof | |
| CN103108903B (en) | Nanoparticle pultrusion processing aide | |
| CN105463620B (en) | A kind of graphene/PET composite fibre and preparation method thereof | |
| Vijayan et al. | Liquid rubber and silicon carbide nanofiber modified epoxy nanocomposites: Volume shrinkage, cure kinetics and properties | |
| CN102181140B (en) | Carbon fiber silk waste reinforced polycarbonate composite material and preparation method of the carbon fiber silk waste reinforced polycarbonate composite material | |
| CN106698385A (en) | Method for preparing nanocarbon material in a discharge mode combining dielectric barrier discharge and arc discharge | |
| CN108046665A (en) | A kind of micro-nano composite hollow structure nano material modification high durability concrete material and preparation method thereof | |
| CN109399611A (en) | A kind of preparation method of carbon nanotube | |
| CN103088460B (en) | A kind of High-strength industrial polyester fiber and preparation method thereof | |
| CN104610705A (en) | Method for preparing carbon nanotube modified epoxy resin-based composite material | |
| CN105504713A (en) | Polylactic acid microspherical modified material for 3D printing and preparation method thereof | |
| CN102070877A (en) | Low-intensity magnetic field-induced ordered carbon nanotube/epoxy resin composite material and preparation method thereof | |
| CN101168616B (en) | Method for preparing polysaccharide nano particle grafting polyester modified polylactic acid material | |
| CN105646896B (en) | Nano particle grafting stereoblock PLA, preparation method and applications | |
| CN103480391A (en) | Preparation method for magnetic Fe3O4@ZnWO4 composite photocatalyst | |
| CN103232661B (en) | Preparation method of carbon nano tube/polyvinyl alcohol conductive composite material | |
| CN107603131A (en) | A kind of low energy consumption, the method for prepare with scale graphene filling master batch | |
| CN110724285A (en) | Polyaryletherketone composite powder and preparation method thereof | |
| CN104058401A (en) | Preparation method of porous carbon microspheres | |
| CN108559011A (en) | A kind of epoxy resin composite material 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 |