CN108948423A - The halogen-free flame-retardant system and its application that the thio hypophosphites of dialkyl group list is cooperateed with organic phosphite - Google Patents
The halogen-free flame-retardant system and its application that the thio hypophosphites of dialkyl group list is cooperateed with organic phosphite Download PDFInfo
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Abstract
The invention discloses a kind of halogen-free flame-retardant system that the thio hypophosphites of dialkyl group list is cooperateed with organic phosphite, raw material composition includes: the thio hypophosphites 50~95% of dialkyl group list, organic phosphite 4~40% and zinc compound 1~10%；The thio hypophosphites of dialkyl group list, structural formula such as formula (I) or (II) are shown, in formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, carbon number is 1~6；M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m is 1~4.The halogen-free flame-retardant system have the characteristics that high fire-retardance, it is non-migratory, do not corrode equipment, be well adapted for fiberglass reinforced thermoplastic engineering plastic system, obtain excellent combination property halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic.
Description
Technical field
The present invention relates to the technical fields of fire retardant, and in particular to a kind of thio hypophosphites of dialkyl group list with it is organic phosphorous
The halogen-free flame-retardant system and its preparing the application in halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic that hydrochlorate cooperates with.
Background technique
Fiberglass reinforced thermoplastic engineering plastic is steady because having good rigidity and impact resistance, low warpage properties, high size
Qualitative, good appearance, easy processing molding and the performance characteristics such as recyclable and be widely used in field of electronics.?
The application in these fields proposes fire-retardant requirement to material, and thermoplastic engineering plastic is combustible material, compound with glass
Afterwards, due to the wick effect of glass, so that fiberglass reinforced engineering plastics are easier to burn.Therefore fiberglass reinforced engineering plastics are at this
A little fields are in application, need to solve the problems, such as fire-retardant, and the presence of wick effect makes its fire-retardant difficulty bigger.Here heat
Plastic engineering plastics refer mainly to polyester and nylon.
Currently, including the basic flame-retardant system of two classes for the fire-retardant of fiberglass reinforced thermoplastic engineering plastic: halogen system resistance
Combustion system and non-halogen fire-retardant system.Halogen system flame-retardant system is usually brominated flame-retardant collaboration antimony oxide, a large number of studies show that,
Fiberglass reinforced thermoplastic engineering plastic added with bromide fire retardant can produce thick smoke and the harmful substances such as hydrogen bromide in burning,
Human body can be caused to suffocate, secondly, the electrical insulating property of halogenated flame retardant is poor, in some fields using also restrained.Therefore, it is
Fiberglass reinforced thermoplastic engineering plastic is developed safe and environment-friendly, high performance halogen-free flame-retardant system and is had become a hot topic of research, in recent years
There is the novel halogen-free flame retardants or flame-retardant system applied to fiberglass reinforced thermoplastic engineering plastic.
It according to the literature, mainly include that two major classes are basic applied to the halogen-free flame retardants of fiberglass reinforced thermoplastic engineering plastic
System: one kind is red phosphorus；Another kind of is phosphorus nitrogen system flame-retardant system.For red phosphorus, although its good flame retardation effect, it faces two
Problem: first is that the color of red phosphorus, limits its scope of application, it is generally only to apply in black products；Second is that in process
In be easy to produce the violents in toxicity such as hydrogen phosphide, bring environmental protection and safety problem, therefore red phosphorus is not fiberglass reinforced engineering thermoplastic
The optimal selection of plastics.For phosphorus nitrogen system flame-retardant system, this is a kind of efficient flame-retardant system, has high flame retarding efficiency,
The some defects for avoiding red phosphorus are the hot spots studied at present.
Currently, with the most use, the phosphorus nitrogen compound system based on diethyl hypo-aluminum orthophosphate is answered, for example, diethyl time phosphorus
Sour aluminium compounding melamine Quadrafos (MPP) system can due to the synergistic effect of phosphorus content with higher and phosphorus nitrogen
To realize the highly effective flame-retardant to fiberglass reinforced thermoplastic engineering plastic, product color problem is also not present, while there is very high score
Temperature is solved, in the high temperature working processes of fiberglass reinforced thermoplastic engineering plastic, the hypertoxic gas such as hydrogen phosphide will not be generated.But it is right
In the phosphorus nitrogen compound system based on diethyl hypo-aluminum orthophosphate, however it remains some disadvantages are mainly manifested in:
It is decomposed first is that two kinds of components have certain reaction at high temperature, generates a small amount of acidic materials, these acids
Matter can generate corrosion to the metal parts of process equipment, need replacing component after a certain time, bring the increase and drop of cost
The problem of low production efficiency；Second is that nitrogenous compound MPP, there are certain precipitation, material is in injection molding process, injection molding one
After the product of cover half number, there can be deposit on mold, the presence of these deposits will affect the appearance of product, this is desirable
It stops work and clears up mold, can also reduce production efficiency, while this precipitation can also cause fire retardant to migrate to product surface, cause to hinder
Combustion agent is unevenly distributed and is lost, and finally makes the fire-retardant failure of material, there are security risks；Third is that additive amount is big, to material
Effect on Mechanical Properties is larger.
As a whole, it is applied to the flame-retardant system of fiberglass reinforced thermoplastic engineering plastic at present, there are color, has
Poisonous gas is easily precipitated, has the problems such as corrosion and reduction material mechanical performance, some are that fatal problem cannot then use, some are then
It is to lead to increased costs, efficiency reduction etc..Therefore, it is necessary to develop novel halogen-free flame-retardant system.
Summary of the invention
The present invention is directed to the existing phosphorus based on diethyl hypo-aluminum orthophosphate applied to fiberglass reinforced thermoplastic engineering plastic
The defect of nitrogen compounding flame retardant discloses a kind of Halogen that the thio hypophosphites of dialkyl group list is cooperateed with organic phosphite resistance
Combustion system, the halogen-free flame-retardant system have many advantages, such as high fire-retardance, it is non-migratory, do not corrode equipment, the Halogen prepared based on this
Flame-proof glass fibre enhances thermoplastic engineering plastic, can prepare the component or product of field of electronics.
Specific technical solution is as follows:
A kind of halogen-free flame-retardant system that the thio hypophosphites of dialkyl group list is cooperateed with organic phosphite, by weight percentage
Meter, raw material composition include:
The thio hypophosphites 50~95% of dialkyl group list；
Organic phosphite 4~40%；
Zinc compound 1~10%；
Shown in the thio hypophosphites of dialkyl group list, structural formula such as following formula (I) or following formula (II):
In formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, the carbon number of the straight chained alkyl or branched alkyl is 1
~6；
M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m be 1~
4。
The present invention uses the novel thio hypophosphite fire retardant of dialkyl group list, by cooperateing with organic phosphite, shape
Non-nitrogen containing compounding flame retardant is cooperateed at the multielement based on phosphorus sulphur, solves the existing compositional flame-retardant based on diethyl hypo-aluminum orthophosphate
The defects of system is perishable present in the flame-proof glass fibre enhancing thermoplastic engineering plastic, precipitation easy to migrate.The novel flame-retardant body
System can be well adapted for fiberglass reinforced thermoplastic engineering plastic material, the bittern-free flame-proof material being had excellent performance.
Preferably, in the general formula of the thio hypophosphites of dialkyl group list, R1、R2Independently selected from methyl, ethyl, positive third
Base, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl or isohesyl；M is selected from Mg, Ca, Al, Sn, Ti or Zn.
The invention also discloses a kind of preparation processes of the thio hypophosphites of dialkyl group list, to prepare dialkyl group list sulphur
For generation aluminum phosphate, specifically:
(1) the thio sodium hypophosphite solution of dialkyl group list is reacted in acid condition with aluminum sulfate solution, obtains dialkyl group
The suspension of single thio hypo-aluminum orthophosphate sediment；
(2) suspension will be filtered, washed and dry, pulverize at 120 DEG C to certain partial size, obtain dialkyl group list sulphur
For hypo-aluminum orthophosphate combustion inhibitor.
It wherein, can be by commercially available acquisition, or by the following method as the thio sodium hypophosphite of dialkyl group list of raw material
Preparation:
(a) reacting Acidic phosphates in the presence of the concentrated sulfuric acid with phosphorus pentasulfide can be generated the thio secondary phosphorus of dialkyl group list
Acid；
(b) the thio hypophosphorous acid of dialkyl group list is reacted with sodium hydroxide generates the thio sodium hypophosphite of dialkyl group list soluble easily in water
Salt.
The characteristics of dialkyl group list thio hypophosphites is phosphorus content height, and there are also the collaboration of element sulphur, good flame resistance, tools
There is a higher temperature of initial decomposition, water-soluble extremely low, resistance to migration is nonhygroscopic, is that a kind of novel can be applied to nylon, polyester etc.
In engineering plastics, especially in the engineering plastics of fiberglass reinforced.The thio hypophosphites of dialkyl group list is used alone, in certain applications
Field, flame retardant property still are apparent not enough, therefore also need and component is cooperateed with to compound, and can be only achieved fire-retardant requirement.
Inventors discovered through research that being added suitable organic in the presence of dialkyl group list thio hypophosphites
Phosphite, forms the non-nitrogen flame-retardant system based on phosphorus sulphur structure, which has preferable flame-retarding characteristic.
Shown in the general structure of the organic phosphite such as following formula (III) or following formula (IV):
In formula, R is selected from the linear fatty alkyl that aromatic radical or carbon number are 1~6, and Me is selected from zinc, calcium or magnesium；
Preferably, the organic phosphite is methylisothiouronium methylphosphite aluminium, ethyl phosphorous acid aluminium, and the molecular weight of R group is smaller,
Phosphorus content is higher, to fire-retardant more advantageous.
The organic phosphite the preparation method comprises the following steps: (1) organic phosphite hydrolyzes in acid condition, be made organic
Phosphorous acid；(2) organic phosphorous acid and metal hydroxides are in acid condition, in an aqueous medium, anti-in 150~180 DEG C of high pressures
It answers；(3) suspension is filtered, washed and is dry, pulverize at 200~240 DEG C to certain partial size.
The organic phosphite being prepared has very high thermal decomposition temperature, can assist with the thio hypophosphites of dialkyl group list
Same-action, while water-soluble low, resistance to migration.
Moreover, it has been found that introducing the zinc compound that a small amount of high temperature resistant is not precipitated in the above system, can be further improved
Corrosion-resistant and thermal stability, and anti-flammability is provided, there is not yet the problem of precipitation.Preferably, the zinc compound is selected from boron
Both sour zinc and/or zinc stannate have high decomposition temperature, water-soluble low, not migration precipitation.It can be assisted with phosphorus sulphur structure
Together, anti-flammability is improved, and there is suppression cigarette effect, reduces smoke density.
To further increase cooperative flame retardant effect, in the compound system, the thio hypophosphites of dialkyl group list be it is powdered,
Average grain diameter D50 is 20~50 μm；Organic phosphite be it is powdered, average grain diameter D50 be 20~50 μm；Zinc compound is
Powdered, average grain diameter D50 is 20~50 μm.
The invention also discloses the halogen-free flame-retardant glass fiber enhancing engineering thermoplastic modelings that the halogen-free flame-retardant system preparation is added
Material, by weight percentage, raw material composition includes:
The substrate is selected from polyamide or polyester.
The polyamide includes fatty polyamide, semiaromatic polyamide composition, such as nylon 6, nylon66 fiber, nylon MXD 6, Buddhist nun
Dragon 12 and the high-temperature nylons such as nylon 46,4T, 6T, 9T, 10T, 12T.
The polyester includes PBT or PET.
When the substrate is selected from polyamide, preferably raw material composition includes:
Further preferably, the raw material composition of the halogen-free flame-retardant system includes:
The thio hypophosphites 73~83% of dialkyl group list；
Organic phosphite 11~21%；
Zinc compound 2.5~6%.
Further preferably, the substrate is selected from PA66, and the organic phosphite is selected from methylisothiouronium methylphosphite aluminium, zinc compound choosing
From zinc borate；The thio hypophosphites of dialkyl group list is selected from the thio hypo-aluminum orthophosphate of diethyl list.
When the substrate is selected from polyester, raw material composition includes:
Further preferably, the raw material composition of the halogen-free flame-retardant system includes:
The thio hypophosphites 56~80% of dialkyl group list；
Organic phosphite 13~37%；
Zinc compound 3~7%.
Further preferably, the substrate is selected from PBT, and the organic phosphite is selected from methylisothiouronium methylphosphite aluminium, zinc compound choosing
From zinc borate；The thio hypophosphites of dialkyl group list is selected from the thio hypo-aluminum orthophosphate of diethyl list.
Thermoplastic engineering plastic is enhanced by the halogen-free flame-retardant glass fiber that above-mentioned formula is prepared, can reach UL94V0
(1.6mm) flame retardant rating, and have the advantages that not corrode equipment, without being precipitated.
The invention also discloses the preparation method of halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic, each raw material is blended
Afterwards, flame-retardant system is dispersed in substrate, then passes through band plus the twin-screw extrusion of glass fiber opening and fire retardant powder feed inlet
Machine, each component complete melt blending, and extruding pelletization in an extruder.
Compared with prior art, the present invention has the advantage that
The invention discloses the phosphorus sulphur multielement being made of the thio hypophosphites of dialkyl group list and organic phosphite collaborations
Compound non-nitrogen flame-retardant system, have many advantages, such as high fire-retardance, it is non-migratory, do not corrode equipment, may be used as fiberglass reinforced thermoplasticity work
The halogen-free flame-retardant system of engineering plastics, preparing the novel halogen-free flame-retardant glass fiber applied to electric and electronic field enhances engineering thermoplastic
Plastics proprietary material.
Specific embodiment
Raw material:
(1) preparation of the thio hypo-aluminum orthophosphate of diethyl list
The sulphur that the thio sodium hypophosphite aqueous solution 960g of diethyl list of compound concentration 20wt% and concentration are 30wt% respectively
Desalted water 1000g is added into reactor by sour aluminum water solution 228g, and the sulfuric acid solution 50g that concentration is 25wt%, heating is added
To 80 DEG C, starts to synchronize the thio sodium hypophosphite aqueous solution of dropwise addition diethyl list and aluminum sulfate solution in proportion into reaction kettle, obtain
It to the thio hypo-aluminum orthophosphate sediment of diethyl list, is added dropwise to complete within 2 hours, keeps the temperature 1 hour, be then filtered, washed, dry, obtain
The thio hypo-aluminum orthophosphate combustion inhibitor 166g (yield 95%) of diethyl list.
After tested, 345 DEG C of the initial decomposition temperature of product, solubility is 0.05% in water；
(2) MPP, Melapur 200 is purchased from BASF；
(3) zinc borate, Firebrake 500 are purchased from Borax；
(4) nylon66 fiber, EPR27, table mountain mind horse；
(5) glass, ECS301UW, Chongqing Polycomp International Co., Ltd；
(6) diethyl hypo-aluminum orthophosphate, 8003, Jiangsu Li Side new material Co., Ltd；
(7) antioxidant, 1098, BASF；
(8) silicone, middle indigo plant morning twilight；
(9) PBT, 211M, Changchun chemistry；
(10) methylisothiouronium methylphosphite aluminium, Jiangsu Li Side new material Co., Ltd.
Embodiment 1
Halogen-free flameproof compound system is applied in glass fiber enhanced nylon, follows these steps and test method investigates fire retardant
Performance.
(1) mixture of halogen-free flame-retardant system
The compounding flame retardant each component and other auxiliary agents for being added in machine and weighing up in advance according to the ratio are stirred in height, starts high-speed stirring
It mixes, stirs 10min, complete the mixture of powder, discharge.
(2) extruding pelletization of material
Buddhist nun is added after temperature stablizes 20min in predetermined temperature in each area's temperature setting of double screw extruder from hopper
Dragon, by adding glass fiber opening to be added, the powder of step (1) mixture is fed glass by powder charging aperture, starts host and feeder,
Complete the extruding pelletization of material.The material for having made grain is sent into feed bin by blast system, and dries.
(3) application and test of material
The material dried is molded by the standard sample of various testing standard defineds in injection molding machine, and carries out correlation
The test of material property.It is primarily upon following performance indicator:
Fire-retardant experiment
It is tested according to UL94V0 testing standard.
Resistance to migration experiment
The halogen-free flame-retardant glass fiber prepared is enhanced into nylon sample, is put into climatic chamber, is arranged 85 DEG C of temperature, relatively
Humidity 85%, the state of specimen surface of the visual observations after 168 hours.
Corrosion experiment
One metal block is set on die head, and high-temperature material passes through 25Kg material granulation in die head and metal block contact, test
The waste of metal afterwards, loss is higher, and corrosion resistance is poorer.Think that corrosion is acceptable if etching extent < 0.1%.
Mechanics Performance Testing
Tensile strength is tested by ASTM D638 and presses ASTM D256 impact strength.
Each material and proportion are shown in Table 1 in the present embodiment, and obtained testing of materials the results are shown in Table 1.
Embodiment 2
Implementation process is same as Example 1, keeps fire retardant systems total amount constant, adjusts the thio hypo-aluminum orthophosphate of diethyl list
With the ratio of methylisothiouronium methylphosphite aluminium.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Embodiment 3
Implementation process is same as Example 1, keeps fire retardant systems total amount constant, adjusts the thio hypo-aluminum orthophosphate of diethyl list
With the ratio of methylisothiouronium methylphosphite aluminium.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Embodiment 4
Implementation process is same as Example 1, keeps flame-retardant system total amount constant, and the thio hypo-aluminum orthophosphate accounting of diethyl list is protected
Hold constant, the ratio of other two components of adjustment.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 1
Implementation process is same as Example 1, in addition to using diethyl hypo-aluminum orthophosphate to replace the thio hypo-aluminum orthophosphate of diethyl list
Outside.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 2
Implementation process is same as Example 1, other than without using zinc borate.Other materials and proportion are shown in Table 1, obtained
Material the results are shown in Table 1.
Comparative example 3
Implementation process is same as Example 1, other than only using the thio hypo-aluminum orthophosphate of diethyl list and zinc borate, does not use
Methylisothiouronium methylphosphite aluminium.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 4
Implementation process is same as Example 1, other than only using the thio hypo-aluminum orthophosphate of diethyl list.Other materials and proportion
It is shown in Table 1, obtained material the results are shown in Table 1.
Comparative example 5
Implementation process is same as Example 1, in addition to flame-retardant system uses the compound system of diethyl hypo-aluminum orthophosphate and MPP.
Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Table 1
Embodiment 5
Implementation process is same as Example 1, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Embodiment 6
Implementation process is same as Example 2, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Embodiment 7
Implementation process is same as Example 3, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Embodiment 8
Implementation process is same as Example 4, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Comparative example 6
Implementation process is identical as comparative example 1, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Comparative example 7
Implementation process is identical as comparative example 2, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Comparative example 8
Implementation process is identical as comparative example 3, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Comparative example 9
Implementation process is identical as comparative example 4, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Comparative example 10
Implementation process is identical as comparative example 5, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Table 2
Claims (9)
1. a kind of halogen-free flame-retardant system that the thio hypophosphites of dialkyl group list is cooperateed with organic phosphite, which is characterized in that press
Weight percent meter, raw material composition include:
The thio hypophosphites 50~95% of dialkyl group list；
Organic phosphite 4~40%；
Zinc compound 1~10%；
Shown in the thio hypophosphites of dialkyl group list, structural formula such as following formula (I) or following formula (II):
In formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, the carbon number of the straight chained alkyl or branched alkyl is 1~6；
M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m is 1~4.
2. the halogen-free flameproof body that the thio hypophosphites of dialkyl group list according to claim 1 is cooperateed with organic phosphite
System, which is characterized in that the R1、R2Independently selected from methyl, ethyl, n-propyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl,
Isopentyl, n-hexyl or isohesyl；
The M is selected from Mg, Ca, Al, Sn, Ti or Zn.
3. the halogen-free flameproof that the thio hypophosphites of dialkyl group list according to claim 1 or 2 is cooperateed with organic phosphite
System, which is characterized in that the average grain diameter D50 of the thio hypophosphites of dialkyl group list is 20~50 μm.
4. the halogen-free flameproof body that the thio hypophosphites of dialkyl group list according to claim 1 is cooperateed with organic phosphite
System, which is characterized in that shown in the general structure of the organic phosphite such as following formula (III) or following formula (IV):
In formula, R is selected from the linear fatty alkyl that aromatic radical or carbon number are 1~6, and Me is selected from zinc, calcium or magnesium；
The average grain diameter D50 of the organic phosphite is 20~50 μm.
5. the halogen-free flameproof body that the thio hypophosphites of dialkyl group list according to claim 1 is cooperateed with organic phosphite
System, which is characterized in that the zinc compound is selected from zinc borate and/or zinc stannate, and average grain diameter D50 is 20~50 μm.
6. a kind of halogen-free flame-retardant glass fiber enhances thermoplastic engineering plastic, which is characterized in that including any according to claim 1~5
The halogen-free flame-retardant system, by weight percentage, raw material composition includes:
The substrate is selected from polyamide or polyester.
7. halogen-free flame-retardant glass fiber according to claim 6 enhances thermoplastic engineering plastic, which is characterized in that percentage by weight
Than meter, raw material composition includes:
The substrate is selected from polyamide；
The raw material of the halogen-free flame-retardant system forms
The thio hypophosphites 73~83% of dialkyl group list；
Organic phosphite 11~21%；
Zinc compound 2.5~6%.
8. halogen-free flame-retardant glass fiber according to claim 6 enhances thermoplastic engineering plastic, which is characterized in that percentage by weight
Than meter, raw material composition includes:
The substrate is selected from polyester；
The raw material of the halogen-free flame-retardant system forms
The thio hypophosphites 56~80% of dialkyl group list；
Organic phosphite 13~37%；
Zinc compound 3~7%.
9. enhancing thermoplastic engineering plastic according to any halogen-free flame-retardant glass fiber of claim 6~8, which is characterized in that institute
It states organic phosphite and is selected from methylisothiouronium methylphosphite aluminium, zinc compound is selected from zinc borate.
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| CN115073819A (en) * | 2022-06-15 | 2022-09-20 | 兰州瑞朴科技有限公司 | Aluminum phosphate salt flame retardant based on growth nucleus and preparation method and application thereof |
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