CN106752122A - One kind nitridation carbon complex, its preparation method and application - Google Patents
One kind nitridation carbon complex, its preparation method and application Download PDFInfo
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- CN106752122A CN106752122A CN201611075046.5A CN201611075046A CN106752122A CN 106752122 A CN106752122 A CN 106752122A CN 201611075046 A CN201611075046 A CN 201611075046A CN 106752122 A CN106752122 A CN 106752122A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
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Abstract
The invention discloses a kind of azotized carbon nano piece and preparation method thereof, and the azotized carbon nano piece and polymer are compounded to form nitridation carbon complex.Nitridation carbon dust is ground, is added water and is obtained the suspension of carbonitride, be centrifuged, collect lower sediment, dried, obtain the nitridation carbon dust of preliminary ball milling；Solvent is added, the suspension that ultrasound obtains carbonitride is centrifuged ultrasound, and the upper strata dispersion liquid A for obtaining is centrifuged again, it is to obtain azotized carbon nano piece solution to collect upper strata dispersion liquid B.In dissolving a polymer in solvent, mix with azotized carbon nano piece, ultrasound, dry, that is, obtain carbonitride complex thin film.The nitridation carbon complex that the hydrogen bond that hydroxyl or acetyl group in amino in carbonitride and polymer are formed can stablize, improves the film forming for nitrogenizing carbon complex, and the addition of carbonitride improves the heat endurance of polymer, improves the fire protecting performance of polymer.
Description
Technical field
The present invention relates to high thermal stability material, fire proofing material field, and in particular to one kind nitridation carbon complex, its
Preparation method and application.
Background technology
With the development and the continuous expansion of application field of synthetic material industry, fire retardant chemical building material, electronic apparatus,
There are wide market prospects in the clothing, food, lodging and transportion -- basic necessities of life every field such as communications and transportation, space flight and aviation, household furniture, interior decoration.This
Outward, the field such as coalfield, oil field, forest extinguishing also promotes fire-retardant, extinguishing chemical production and develops faster.
Bromine phosphorus fire-retardant agent, especially bromide fire retardant, are extremely important and conventional fire retardant types.Although fire-retardant
The most frequently used halogenated flame retardant has other fire retardants unrivaled high efficiency of series in agent, but it is to environment and the danger of people
Evil is very important.Environmental issue is auxiliary agent development and application business's focus of attention, therefore, adjust the product knot of fire retardant
Structure, increases the emphasis for being developed into flame retardant area work of Efficient environment-friendlyflame flame retardant.
Engineering plastics are just developed rapidly in the 1950's.Although nylon 66 resin early in nineteen thirty-nine just
Succeed in developing and put into production, but it, mainly for the manufacture of synthetic fibers, was used until the fifties just breaks through pure fiber tradition at that time
On the way, plastics are manufactured by processing and forming.It is in later stage fifties polyformaldehyde and poly- carbonic acid that engineering plastics really obtain developing rapidly
After ester is succeeded in developing, their appearance has especially great meaning.Makrolon is with the transparent of excellent comprehensive performance
Engineering plastics, are widely used, and are one of engineering plastics with fastest developing speed, and in engineering plastics field, its yield and consumption figure are only secondary
Second is occupied in polyamide.20th century the mid-80 to succeed in developing TLCP be special engineering plastics development history
Upper another major event.Liquid crystal polymer excellent heat resistance, temperature in use up to more than 200 DEG C, with self-reinforcing, high intensity,
The characteristics such as high-modulus, chemical-resistant resistance, melt viscosity is low, convenient formation, has boundless application in electronics industry
Prospect.
Compared with general-purpose plastics, engineering plastics can reach at aspects such as mechanical performance, durability, corrosion resistance, heat resistances
Requirement higher, and process more convenient and alternative metal material.Engineering plastics be widely used in electric, automobile,
The industries such as building, office equipment, machinery, Aero-Space, to mould Dai Gang, to mould Dai Muyi as international popular trend.Engineering plastic
Material has turned into the most fast field of growth rate in world today's plastics industry, and its development is not only high to national pillar industry and modern times
New technological industry plays supporting role, while also promoting the adjustment of Transform of Traditional Industrial Equipment and product structure.
Graphite type carbon nitride (g-C3N4) it is the most stable of allotrope of carbonitride, the two-dimensional structure with stacking, due to
It has at a relatively high heat endurance, chemical stability, optically and electrically stability and cause increasing concern.g-
C3N4There is-NH more than needed in structure2With-NH, the number of these groups is with g-C3N4The reduction of condensation degree of dissolved and increase, and this
A little groups can act on forming hydrogen bond as avtive spot and other groups such as-SH ,-OH ,-COOH.g-C3N4And its derivative
All it is widely studied at aspects such as photoelectrocatalysis, decomposition aquatic products hydrogen, electrooptical device, bio-sensings, additionally, researcher is to g-
C3N4Compound composite material of birdsing of the same feather flock together has been also carried out research.
The content of the invention
Goal of the invention：In view of the shortcomings of the prior art, the technical problems to be solved by the invention are to provide a kind of carbonitride
Nanometer sheet, and it is combined with polymeric material, so as to improve the film forming of compound, heat endurance and fire protecting performance.
Technical scheme：To achieve these goals, one aspect of the present invention provides a kind of system of azotized carbon nano piece
Preparation Method, it is comprised the following steps：
(1) nitridation carbon dust is ground, then adds water and obtain the suspension of carbonitride；
(2) suspension of the carbonitride obtained to step (1) is centrifuged, and collects lower sediment, dries, and obtains preliminary ball
The nitridation carbon dust of mill；
(3) to solvent is added in the nitridation carbon dust of the preliminary ball milling, ultrasound is obtained ultrasound the suspension of carbonitride
It is centrifuged, is collected upper strata dispersion liquid A；
(4) the upper strata dispersion liquid A for obtaining step (3) is centrifuged obtains upper strata dispersion liquid B, the upper strata dispersion liquid B again
As azotized carbon nano piece solution.
In step (1), grinding is carried out in ball mill, in order to be fully ground to nitridation carbon dust, by ball milling
The rotating speed of machine is set to 20~2000rpm/min, and Ball-milling Time is set to 0.1~12h.
Another aspect of the present invention provides a kind of carbonitride as obtained in the preparation method of above-mentioned azotized carbon nano piece
Nanometer sheet.
Another aspect of the present invention provides a kind of nitridation carbon complex, and the nitridation carbon complex is azotized carbon nano piece
With the compound of polymer, azotized carbon nano piece is obtained by the preparation method of above-mentioned azotized carbon nano piece, and polymer contains hydroxyl
With one or two groups in acetyl group, mass ratio shared by carbonitride is 0.5%~10% in nitridation carbon complex.
Wherein, polymer is high molecular polymer, and high molecular polymer is cellulose acetate, makrolon, polypropylene, poly-
One or more in vinyl alcohol, polystyrene, polyamide, polyformaldehyde.
An additional aspect of the present invention provides a kind of method for preparing nitridation carbon complex, comprises the following steps：
(1) dissolve a polymer in solvent, obtain uniform solution, this solution is mixed with azotized carbon nano piece, ultrasound,
Obtain mixture；
(2) mixture obtained after step (1) treatment is poured in horizontal container, is dried, obtain nitrogenizing carbon complex
Film.
In order that azotized carbon nano piece is sufficiently formed hydrogen bond, selection redistilled water, acetone, ethanol, isopropyl with polymer
60 are set to as the solvent in step (1), by ultrasonic power one or more in alcohol, DMF~
100W, ultrasonic time is set to 6~16 hours.
Another aspect of the invention provides a kind of nitridation carbon complex in terms of high thermal stability material, fire proofing material
Application.
Beneficial effect：Compared with prior art, the present invention has advantages below：The present invention is prepared for azotized carbon nano piece,
The compound of azotized carbon nano piece and polymer solution can be effectively improved, especially the hydroxyl in the amino in carbonitride and polymer
The nitridation carbon complex that the hydrogen bond that base or acetyl group are formed can be stablized, improves the film forming of nitridation carbon complex, nitrogen
The addition for changing carbon improves the heat endurance of polymer, and this improves the fire protecting performance of polymer to a certain extent.
Brief description of the drawings
Fig. 1 is method of the embodiment 1 by water ultrasound, using the surface sweeping of carbonitride in the supernatant liquid being centrifugally separating to obtain
Electron microscope (SEM) image；
Fig. 2 is different content azotized carbon nano piece in experimental example 4, the nitridation that cellulose acetate (CA) is prepared as polymer
The TGA figures of carbon complex.
Specific embodiment
The preparation of the azotized carbon nano piece of embodiment 1
Azotized carbon nano piece is prepared according to following steps：Nitridation carbon dust is placed in grinding pot, distillation is added thereto to
Water, is closed the lid, then grinding pot is fixed on into ball milling in ball mill；The rotating speed of the ball mill is 300rpm/min, during grinding
Between be 5h；Then to adding distilled water flushing inwall to obtain the suspension of carbonitride in grinding pot, by the suspension of this carbonitride
It is transferred in centrifuge tube and the lower sediment for obtaining is centrifuged collects, drying obtains the nitridation carbon dust of preliminary ball milling.At the beginning of taking 1g
The nitridation carbon dust for walking ball milling is placed in bottle, is added thereto to 100mL acetone, tightens bottle cap, is sealed bottleneck and then is put in 100W
High power numerical control ultrasonic cleaner in 10~16h of ultrasound；Ultrasound terminates to obtain the suspension of carbonitride, by this carbonitride
Suspension is centrifuged in being transferred to centrifuge tube, and 15min is centrifuged under 3000rpm/min, and the upper strata dispersion liquid A for obtaining is collected,
Upper strata dispersion liquid A is centrifuged again again, the upper strata dispersion liquid B for obtaining is exactly azotized carbon nano piece solution, and azotized carbon nano piece is molten
The content of carbonitride is 0.12mg/mL in liquid.
The preparation of the azotized carbon nano piece of embodiment 2
Azotized carbon nano piece is prepared according to following steps：Nitridation carbon dust is placed in grinding pot, distillation is added thereto to
Water, is closed the lid, then grinding pot is fixed on into ball milling in ball mill；The rotating speed of the ball mill is 300rpm/min, and the time is
5h；Then to adding distilled water flushing inwall to obtain the suspension of carbonitride in grinding pot, the suspension of this carbonitride is shifted
The lower sediment for obtaining is centrifuged into centrifuge tube to collect, drying obtains the nitridation carbon dust of preliminary ball milling.By the preliminary balls of 2g
The nitridation carbon dust of mill is placed in bottle, is added thereto to 100mL acetone, tightens bottle cap, is sealed bottleneck and then is put in the height of 100W
10~16h of ultrasound in power numerical control ultrasonic cleaner；Ultrasound terminates to obtain the suspension of carbonitride, by the suspension of this carbonitride
Liquid is centrifuged in being transferred to centrifuge tube, and 15min is centrifuged under 3000rpm/min, and the upper strata dispersion liquid A for obtaining is collected, then
Upper strata dispersion liquid A is centrifuged again, and the upper strata dispersion liquid B for obtaining is exactly azotized carbon nano piece solution, in azotized carbon nano piece solution
The content of carbonitride is 0.18mg/mL.
The preparation of the azotized carbon nano piece of embodiment 3
Azotized carbon nano piece is prepared according to following steps：Nitridation carbon dust is placed in grinding pot, distillation is added thereto to
Water, is closed the lid, then grinding pot is fixed on into ball milling in ball mill；The rotating speed of the ball mill is 300rpm/min, and the time is
5h；Then to adding distilled water flushing inwall to obtain the suspension of carbonitride in grinding pot, the suspension of this carbonitride is shifted
The lower sediment for obtaining is centrifuged into centrifuge tube to collect, drying obtains the nitridation carbon dust of preliminary ball milling.By the preliminary balls of 3g
The nitridation carbon dust of mill is placed in bottle, is added thereto to 100mL acetone, tightens bottle cap, is sealed bottleneck and then is put in the height of 100W
10~16h of ultrasound in power numerical control ultrasonic cleaner；Ultrasound terminates to obtain the suspension of carbonitride, by the suspension of this carbonitride
Liquid is centrifuged in being transferred to centrifuge tube, and 15min is centrifuged under 3000rpm/min, and the upper strata dispersion liquid A for obtaining is collected, then
It is exactly azotized carbon nano piece solution, nitrogen in azotized carbon nano piece solution that upper strata dispersion liquid A is centrifuged the upper strata dispersion liquid B for obtaining again
The content for changing carbon is 0.24mg/mL.
Embodiment 4 is combined the preparation of different amounts of nitridation carbon complex
6 parts of cellulose acetates (CA) are taken, every part of cellulose acetate weight is 0.48g.By 6 parts of cellulose acetates in stirring
In the lower 18.72mL acetone being dissolved in respectively under normal temperature, mixing time is 2h, obtains 6 parts of mass percents containing cellulose acetate and is
2.5% cellulose acetate homogeneous phase solution.The content prepared in Example 1 is the azotized carbon nano piece solution of 0.12mg/mL,
The weight of azotized carbon nano piece in azotized carbon nano piece solution is set to be respectively 0,2.5mg, 5mg, 10mg, 20mg, 28mg, will be above-mentioned
Azotized carbon nano piece solution mixes with cellulose acetate homogeneous phase solution respectively under ultrasound, ultrasonic 6h, obtains nitrogenizing carbon complex
Solution, horizontal area is poured on for 60cm by carbonitride complex solution2Sheet glass on, be placed in again after degassing in baking oven do
Dry 24h, finally gives nitridation carbon complex, wherein in each sample the mass percentage content of carbonitride be respectively 0,0.5%,
1%th, 2%, 4%, 6%.Sample is designated as CA-0, CA-0.5, CA-1, CA-2, CA-4, CA-6 respectively.
The azotized carbon nano piece prepared in the method for acetone ultrasound can be prevented effectively from material in composite formation
The problem of the interface interaction inequality between carbonitride and cellulose acetate.Simultaneously in acetone system azotized carbon nano piece surface-
NH2, the hydroxyl of-NH and surface of cellulose acetate, acetyl group can well form strong hydrogen bond action, so as to carry acetate fiber
The heat endurance of element.
Nitridation carbon complex obtained above, the sample for taking 5mg are carried out into heat with thermal analyzer to its heat endurance respectively
Weight analysis are tested, and temperature test scope is 50~700 DEG C, and heating rate is 10 DEG C/min, and carrier gas is air, and air velocity is
100mL/min, has obtained the TGA figures of sample, as shown in Figure 2.The cellulose acetate for being compounded with carbonitride as shown in Figure 2 is thermally-stabilised
Property significantly improved than the cellulose acetate without carbonitride, wherein, in 50~200 DEG C of initial period, the initial heat point of sample
Solution temperature increases 28.7 DEG C；Within 200~700 DEG C of this stages, the heat decomposition temperature of the loss 60wt% of sample CA-1 is
559 DEG C, 258 DEG C of the heat decomposition temperature of the loss 60wt% than blank sample CA-0 improves 117%；The phase III 580~
700 DEG C, the carbon yield of the carbon yield of sample all than CA-0 is high.This shows that the compound of appropriate carbonitride can effectively improve acetic acid fibre
The heat endurance of element is tieed up, i.e. the cellulose acetate compound of carbonitride can be as fire proofing material.
Embodiment 5 is combined the preparation of different amounts of nitridation carbon complex
6 parts of makrolon are taken, every part of makrolon weight is 0.48g.6 parts of makrolon are dissolved in respectively under agitation
In 18.72mL chloroforms under normal temperature, jitter time is 2h, obtains the makrolon that mass percent containing makrolon is 2.5%
Homogeneous phase solution.The content prepared in Example 1 is the azotized carbon nano piece solution of 0.12mg/mL, makes azotized carbon nano piece molten
The weight of azotized carbon nano piece is respectively 0,2.5mg, 5mg, 10mg, 20mg, 28mg in liquid.By above-mentioned azotized carbon nano piece solution
Mix with makrolon homogeneous phase solution under ultrasound, ultrasonic agitation 6h obtains carbonitride complex solution, will nitrogenize carbon complex
Solution is poured on horizontal 60cm2It is placed in again on sheet glass, after degassing and 24h is dried in baking oven, finally gives nitridation carbon complex,
Wherein the mass percentage content of carbonitride is respectively 0,0.5%, 1%, 2%, 4%, 6% in each sample.Thermogravimetric analysis table
The compound heat endurance that can effectively improve makrolon of bright appropriate carbonitride, the i.e. polycarbonate compound of carbonitride can be with
As fire proofing material.
Embodiment 6 is combined the preparation of different amounts of nitridation carbon complex
6 parts of polypropylene are taken, every part of polypropylene weight is 0.48g.6 parts of polypropylene are dissolved under normal temperature respectively under agitation
18.72mL benzene in, jitter time is 2h, obtains the polypropylene homogeneous phase solution that mass percent containing polypropylene is 2.5%.Take reality
It is the azotized carbon nano piece solution of 0.12mg/mL to apply the content prepared in example 1, makes azotized carbon nano in azotized carbon nano piece solution
The weight of piece is respectively 0,2.5mg, 5mg, 10mg, 20mg, 28mg.By above-mentioned azotized carbon nano piece solution under ultrasound with poly- third
Alkene homogeneous phase solution mixes, and ultrasonic 6h obtains carbonitride complex solution, carbonitride complex solution is poured on into horizontal 60cm2
It is placed in again on sheet glass, after degassing and 24h is dried in baking oven, finally give nitridation carbon complex, is nitrogenized wherein in each sample
The mass percentage content of carbon is respectively 0,0.5%, 1%, 2%, 4%, 6%.Thermogravimetric analysis shows the compound of appropriate carbonitride
The polypropylene composite that polyacrylic heat endurance, i.e. carbonitride can be effectively improved can be as fire proofing material.
Claims (10)
1. a kind of preparation method of azotized carbon nano piece, it is characterised in that the preparation method is comprised the following steps：
(1) nitridation carbon dust is ground, then adds water and obtain the suspension of carbonitride；
(2) suspension of the carbonitride obtained to step (1) is centrifuged, and collects lower sediment, dries, and obtains preliminary ball milling
Nitridation carbon dust；
(3) to solvent is added in the nitridation carbon dust of the preliminary ball milling, ultrasound carries out the suspension that ultrasound obtains carbonitride
Centrifugation, collects upper strata dispersion liquid A；
(4) the upper strata dispersion liquid A for obtaining step (3) is centrifuged obtains upper strata dispersion liquid B again, and the upper strata dispersion liquid B is
Azotized carbon nano piece solution.
2. the preparation method of a kind of azotized carbon nano piece according to claim 1, it is characterised in that in step (1), grinding
Carried out in ball mill, the rotating speed of ball mill is 20~2000rpm/min, and Ball-milling Time is 0.1~12h.
3. a kind of azotized carbon nano piece, it is characterised in that the azotized carbon nano piece is as described in any one in claim 1-2
Preparation method be obtained.
4. a kind of nitridation carbon complex, it is characterised in that the nitridation carbon complex is azotized carbon nano piece and polymer is answered
Compound, preparation method of the azotized carbon nano piece as described in any one in claim 1-2 is obtained, and the polymer contains
One or two groups in hydroxyl and acetyl group, in the nitridation carbon complex mass ratio shared by carbonitride be 0.5%~
10%.
5. nitridation carbon complex according to claim 4, it is characterised in that the polymer is high molecular polymer.
6. nitridation carbon complex according to claim 5, it is characterised in that the high molecular polymer is acetate fiber
One or more in element, makrolon, polypropylene, polyvinyl alcohol, polystyrene, polyamide, polyformaldehyde.
7. it is a kind of prepare described in claim 4 nitridation carbon complex method, it is characterised in that the preparation method include with
Lower step：
(1) dissolve a polymer in solvent, obtain uniform solution, this solution is mixed with azotized carbon nano piece, ultrasound is obtained
Mixture；
(2) mixture that step (1) is obtained is poured in horizontal container, is dried, obtain carbonitride complex thin film.
8. method according to claim 7, it is characterised in that the solvent is redistilled water, acetone, ethanol, isopropyl
One or more in alcohol, DMF.
9. method according to claim 7, it is characterised in that the ultrasonic power is 60~100W, ultrasonic time is 6~
16 hours.
10. application of the nitridation carbon complex described in claim 4 in terms of high thermal stability material, fire proofing material.
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| CN109734060A (en) * | 2019-02-18 | 2019-05-10 | 东南大学 | Azotized carbon nano material and its preparation method and application |
| CN109908955A (en) * | 2019-04-01 | 2019-06-21 | 山东农业大学 | A kind of floating carbonitride/cellulose acetate flexible light catalytic porous film preparation method certainly |
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| CN113546665A (en) * | 2021-07-26 | 2021-10-26 | 广东工业大学 | Composite photocatalytic film for inhibiting growth of harmful microalgae and preparation method and application thereof |
| CN113735074A (en) * | 2021-08-31 | 2021-12-03 | 大韩道恩高分子材料(上海)有限公司 | Preparation method of inorganic nucleating agent for biodegradable material |
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| CN108384055A (en) * | 2018-02-14 | 2018-08-10 | 东华大学 | A kind of hybrid modification ammonium polyphosphate and preparation method thereof |
| CN109734060B (en) * | 2019-02-18 | 2020-12-25 | 东南大学 | Carbon nitride nano material and preparation method and application thereof |
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| CN109908955A (en) * | 2019-04-01 | 2019-06-21 | 山东农业大学 | A kind of floating carbonitride/cellulose acetate flexible light catalytic porous film preparation method certainly |
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| CN110632046A (en) * | 2019-09-11 | 2019-12-31 | 东南大学 | Carbon nitride paper-based fluorescence sensor for detecting polycyclic aromatic hydrocarbon and preparation method and application thereof |
| CN110632046B (en) * | 2019-09-11 | 2022-05-17 | 东南大学 | Carbon nitride paper-based fluorescence sensor and preparation method and application thereof |
| CN110994017A (en) * | 2020-01-03 | 2020-04-10 | 南京工业大学 | Nitride-enhanced polymer electrolyte, preparation method and long-life solid lithium ion battery |
| CN110994017B (en) * | 2020-01-03 | 2022-06-07 | 南京工业大学 | Nitride-enhanced polymer electrolyte, preparation method and long-life solid lithium ion battery |
| CN113354868A (en) * | 2021-06-17 | 2021-09-07 | 中山大学 | Phosphorus-doped polypyrrole-loaded carbon nitride nanocomposite and preparation method and application thereof |
| CN113546665A (en) * | 2021-07-26 | 2021-10-26 | 广东工业大学 | Composite photocatalytic film for inhibiting growth of harmful microalgae and preparation method and application thereof |
| CN113546665B (en) * | 2021-07-26 | 2024-03-12 | 广东工业大学 | Composite photocatalytic film for inhibiting growth of harmful microalgae and preparation method and application thereof |
| CN113735074A (en) * | 2021-08-31 | 2021-12-03 | 大韩道恩高分子材料(上海)有限公司 | Preparation method of inorganic nucleating agent for biodegradable material |
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