CN110066460B - Anti-blooming precipitation environment-friendly flame-retardant plastic master batch and preparation method thereof - Google Patents
Anti-blooming precipitation environment-friendly flame-retardant plastic master batch and preparation method thereof Download PDFInfo
- Publication number
- CN110066460B CN110066460B CN201910385001.5A CN201910385001A CN110066460B CN 110066460 B CN110066460 B CN 110066460B CN 201910385001 A CN201910385001 A CN 201910385001A CN 110066460 B CN110066460 B CN 110066460B
- Authority
- CN
- China
- Prior art keywords
- environment
- master batch
- blooming
- powder
- ammonium polyphosphate
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Abstract
The invention relates to the technical field of flame-retardant plastics, in particular to an anti-blooming environment-friendly flame-retardant plastic master batch and a preparation method thereof. Ammonium polyphosphate and melamine polyphosphate are compounded and micronized, an aluminum hydroxide coating film is coated on the surface of the micronized composite micro powder, silicone powder is formed in the coating film while the aluminum hydroxide coating film is formed, and then the silicone powder, filler, lubricating aid, silicone oil, polypropylene and compatilizer are extruded and granulated by a double screw to obtain the environment-friendly flame retardant plastic master batch preventing frost precipitation. The aluminum salt solution is converted into an aluminum hydroxide coating, and the dispersed silicone powder is stably coated on the surface of the ammonium polyphosphate in advance to endow the ammonium polyphosphate with excellent hydrophobicity, so that the dispersibility and compatibility of the flame retardant in plastics are enhanced, particularly, the silicone powder has good stability and non-migration, and the ammonium polyphosphate can be effectively prevented from being sprayed and separated out after being stably coated.
Description
Technical Field
The invention relates to the technical field of flame-retardant plastics, in particular to an anti-blooming environment-friendly flame-retardant plastic master batch and a preparation method thereof.
Background
Because plastics are mainly non-polar materials, and the flame retardant is generally filler or polar meltable substances, when the flame retardant is used for plastics, the compatibility of the flame retardant and the plastics is poor, and the flame retardant is easy to frost and separate out, so that the appearance glossiness of a product is influenced, and the strength of the plastic product is deteriorated. The plastic products with higher requirements on the flame retardant are generally electric products, more flame retardant needs to be added, and the appearance quality of the plastic products is seriously influenced by the precipitation of the flame retardant. In addition, along with the precipitation of the flame retardant, the flame retardant function of the plastic product is reduced.
Since polypropylene has excellent processability, it is used to replace high-grade engineering plastics by enhancing rigidity and strength, and is gradually applied in large scale in the fields of automobiles and household appliances. However, while polypropylene is easy to process, its flame retardancy is a problem. Usually, polypropylene has low fire-resistant temperature and is inflammable, and when a large amount of flame retardant is added, the flame retardant is easy to migrate and separate out in a polypropylene system due to poor compatibility of the flame retardant and the polypropylene. When the flame retardant is added into polypropylene for injection molding processing, the flame retardant is often separated out on the surface of an injection molding product due to the influence of heat. Producing a threadlike white strip that affects the appearance of the product. Some non-soluble, particulate flame retardants tend to migrate to the surface of the article to form a bloom, which directly affects the surface finish of the article. According to the prior art, the evolution of flame retardants is generally mitigated, mainly by increasing the interfacial compatibility of the flame retardants with the resin matrix. For example, the Chinese patent publication No. CN101891952B discloses a non-precipitation flame-retardant master batch, aiming at the defect that a brominated flame retardant is precipitated, the problem of precipitation of the flame retardant is solved by adding modified polyamide as a compatilizer. However, with the development of flame retardant technology, brominated flame retardants produce toxic and harmful gases during production, which pollute the environment and cause problems of production safety and high price.
Ammonium polyphosphate (APP) is a phosphorus and nitrogen special-effect intumescent inorganic flame retardant and has been applied in the fields of plastics, coatings and the like. The flame retardant P-N has high content of flame-retardant elements, good thermal stability, high flame-retardant efficiency and lasting flame-retardant performance. With the development of global flame retardants towards environmental protection and no halogenation, intumescent flame retardants with APP as the main raw material have become a hot spot for research and development. Therefore, ammonium polyphosphate is a preferred flame retardant. The ammonium polyphosphate has lower cost than a bromine flame retardant and is environment-friendly. However, when the brominated flame retardant is used for plastic products, the brominated flame retardant is more seriously separated out, and the ammonium polyphosphate is sensitive to water, so that when the brominated flame retardant is used for flame retardants of plastics of electric products, the flame retardant has the risk of deterioration in a humid environment. In addition, ammonium polyphosphate releases a certain amount of small molecules upon thermal processing of conventional plastics. Therefore, in order to promote the flame retardant application of ammonium polyphosphate in the field of plastics, the problems of heat resistance, water resistance and efflorescence precipitation of ammonium polyphosphate in plastics must be solved. And the problem of ammonium polyphosphate precipitation is difficult to fundamentally solve by adopting the existing single compatilizer technology.
Disclosure of Invention
Aiming at the defect that the ammonium polyphosphate as a plastic flame retardant has precipitation blooming, the invention provides an environment-friendly flame-retardant plastic master batch for preventing the precipitation blooming and a preparation method thereof in order to promote the ammonium polyphosphate flame retardant to be applied to plastic products in large amount. Aluminum hydroxide is coated on the surfaces of the ammonium polyphosphate and melamine polyphosphate composite micro powder and then modified, so that the water resistance and the heat resistance stability of the ammonium polyphosphate are enhanced, and the efflorescence precipitation is effectively prevented.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of an anti-blooming environment-friendly flame-retardant plastic master batch, which is characterized by comprising the following steps of:
(1) grinding the silicone powder and aluminum sulfate, and then adding deionized water to obtain aluminum sulfate composite liquid for dispersing the silicone powder for later use; wherein the mass ratio of the silicone powder to the aluminum sulfate to the deionized water is 1:5: 20;
(2) compounding ammonium polyphosphate and melamine polyphosphate in a mass ratio of 3:1, and processing by a fine machine to obtain composite micro powder with the particle size of less than 5 microns;
(3) adding the composite micro powder into a closed container, filling ammonia gas into the closed container, controlling the temperature of the container to be 35-45 ℃, stirring at a high speed, spraying the aluminum sulfate composite liquid obtained in the step (1) into the closed container by using a high-pressure spray gun, contacting the surface of the suspended composite micro powder with the aluminum sulfate composite liquid, and gradually dissolving the ammonia gas in water to form a weak alkali environment so as to promote the surface of the composite micro powder to form an aluminum hydroxide coating layer; discharging the materials from a closed container, and drying the materials in a fluidized bed at the temperature of 100-120 ℃ to obtain the composite modified ammonium polyphosphate fire retardant;
(4) adding 40-50 parts by weight of composite modified ammonium polyphosphate flame retardant, 5-10 parts by weight of filler, 0.5-1 part by weight of lubricating aid and 0.1-0.3 part by weight of silicone oil into a high-speed mixer, stirring at a high speed of 120 ℃ for 15-20min, then adding 15-20 parts by weight of polypropylene and 5-10 parts by weight of compatilizer, stirring at a low speed for 3-5min, mixing uniformly, discharging materials, feeding into a cold mixer, stirring at a low speed and cooling;
(5) and (3) feeding the material cooled in the step (4) into a double-screw extruder through a conveying pipeline, and performing extrusion granulation to obtain the anti-blooming environment-friendly flame-retardant plastic master batch.
Ammonium polyphosphate (APP) is an excellent flame retardant, and the flame retardant mechanism is that strong polyphosphoric acid dehydrating agent is generated after heated dehydration to promote the dehydration of the surface of organic matter to generate carbide, and the generated non-volatile phosphorus oxide and polyphosphoric acid are added to the surface of a base materialThe covering is carried out, and the nitrogen element is contained, so that gases such as carbon dioxide, nitrogen, ammonia gas and the like are released by thermal decomposition, and the gases are not easy to burn, and the supply of oxygen is blocked. Is a cheap and excellent environment-friendly halogen-free flame retardant. The general structural formula of the total ammonium polyphosphate (APP) of Nifeqing simple desluo is (NH4)(n+2)PnO(3n+1)When n is 10-20, the compound is easy to dissolve in water; n is 20-100, insoluble but sensitive to water.
Preferably, the ammonium polyphosphate in the step (2) is long-chain ammonium polyphosphate with n being more than 500, which is stable at the conventional plastic processing temperature, but begins to decompose into phosphoric acid and ammonia at the temperature of more than 300 ℃, and is further dehydrated to form polyphosphoric acid or polymetaphosphoric acid at the temperature of more than 300 ℃, so that the flame retardance is excellent.
Melamine polyphosphate (MPP) is an additive flame retardant with a wide application range, is generally white and fine powder, has a decomposition temperature of more than 300 ℃, shows excellent flame retardance through P-N cooperativity, and has the outstanding advantages of good thermal stability, water insolubility, small smoke generation and no moisture absorption. When used for plastics, the flame-retardant coating has excellent high-temperature-resistant processing performance, generates a foamy coke layer when being decomposed in an endothermic way, covers the surface of a combustion object, plays a role in isolating air, and vaporized melamine provides an inert gas source and can dilute the concentration of oxygen and combustible gas generated by the decomposition of high polymers, thereby achieving the purpose of flame retardance. The compound has excellent flame retardance when being matched with ammonium polyphosphate.
Preferably, the melamine phosphate in the step (2) is selected from commercially available melamine polyphosphate with the phosphorus content of more than 14% and the nitrogen content of more than 38%.
And (3) micronizing and compounding commercially available ammonium polyphosphate with large particle size and melamine polyphosphate into composite micro powder with particle size less than 5 μm by adopting a conventional micronizer in the step (2). In order to prevent material denaturation and agglomeration caused by high temperature during micronization treatment, a grinding type micronizer is carefully adopted. Preferably, the fine machine is a vortex airflow pulverizer.
Preferably, the high-speed stirring speed in the step (3) is 800-1200rpm, and the composite micro powder is preferably fully suspended so as to be fully contacted with the atomized aluminum sulfate composite liquid. In actual operation, in order to ensure that the composite micro powder is fully suspended, the adding amount of the composite micro powder in the closed container does not exceed 1/3 of the capacity of the closed container.
Preferably, in the step (3), ammonia gas is filled into the closed container, the ammonia gas environment of the closed container is maintained, the ammonia gas is continuously filled, the pressure of the ammonia gas is ensured to be 0.01MPa, and when the atomized aluminum sulfate composite liquid is sprayed, the ammonia gas is gradually dissolved in water and uniformly generates aluminum hydroxide, so that a uniform coating layer is formed on the surface of the ammonium polyphosphate and melamine polyphosphate composite micro powder; different from the direct addition of ammonia water, the direct addition of ammonia water can lead to the violent and rapid generation of aluminum hydroxide, and the uniform coating of micro powder is difficult.
Further preferably, the spraying amount of the aluminum sulfate composite liquid in the step (3) is controlled to be 0.5-1 time of the mass of the composite micro powder. In order to better ensure that the aluminum hydroxide coating layer is uniformly formed on the surface of the composite micro powder, the pressure of the high-pressure spray gun is 0.6-0.8 MPa.
Preferably, the filler in the step (4) is at least one of talcum powder, wollastonite powder, montmorillonite and mica powder.
Preferably, the lubricating assistant in the step (4) is one of polyethylene wax and stearic acid powder.
Preferably, the silicone oil in the step (4) is at least one of methyl trifluoro propyl silicone oil, methyl ethoxy silicone oil, methyl silicone oil and ethyl silicone oil; the excellent hydrophobicity of the modified composite ammonium polyphosphate flame retardant increases the compatibility of the modified composite ammonium polyphosphate flame retardant with resin, and is beneficial to reducing the precipitation of the flame retardant.
Preferably, the compatibilizer in the step (4) is one of maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene-octene copolymer and maleic anhydride grafted ethylene-propylene-diene copolymer.
Preferably, the high-speed stirring rotation speed in the step (4) is 400-900rpm, and the low-speed stirring rotation speed is 80-100 rpm.
Preferably, the double-screw extruder in the step (5) is a short-length-ratio counter-rotating double-screw extruder with the screw diameter of 45mm and the length-diameter ratio of 20: 1. The screw rod sets up 5 heating zones by feeding to the ejection of compact, and the temperature is in proper order: the 1 region is 100-120 ℃, the 2 region is 150-160 ℃, the 3 region is 180-190 ℃, the 4 region is 160-170 ℃ and the 5 region is 130-140 ℃; and (5) carrying out air-cooled die surface granulation. The double-screw extruder with short-long warp ratio and counter-rotating property can cut materials less, and the advanced decomposition of the compound modified ammonium polyphosphate flame retardant caused by high shear can be avoided.
The invention further provides the anti-blooming environment-friendly flame-retardant plastic master batch prepared by the method. In order to solve the defect that the ammonium polyphosphate is used as a flame retardant in plastics and has the frosting precipitation, the ammonium polyphosphate and the melamine polyphosphate are compounded and micronized, the surface of the micronized composite micro powder is coated to form an aluminum hydroxide coating, and the silicone powder is formed in the coating while the aluminum hydroxide coating is formed; on the other hand, the ammonium polyphosphate is coated by the aluminum hydroxide, so that the ammonium polyphosphate has increased moisture resistance and cannot be subjected to moisture deterioration when being used for electric appliance plastics; more importantly, the aluminum salt is converted into the aluminum hydroxide coating, and the dispersed silicone powder is stably coated on the surface of the ammonium polyphosphate in advance to endow the ammonium polyphosphate with excellent hydrophobicity, so that the dispersibility and compatibility of the flame retardant in plastics are enhanced, particularly, the silicone powder has good stability and non-migration, and the stable coated ammonium polyphosphate can effectively prevent the ammonium polyphosphate from blooming and separating out.
Compared with the method of directly adding the silicone powder to modify the ammonium polyphosphate, the method forms an aluminum hydroxide coating on the surface of the ammonium polyphosphate and melamine polyphosphate composite micro powder in the process of forming aluminum hydroxide from the aluminum salt, and stably coats the silicone powder on the surface of the ammonium polyphosphate and melamine polyphosphate composite micro powder. The compatibility of the composite micro powder and the plastic is greatly improved, and the blooming and precipitation are effectively inhibited; further, the coated aluminum hydroxide is a flame-retardant functional material, and the flame-retardant function is effectively exerted in a synergistic manner.
Compared with the prior art, the invention discloses an anti-blooming environment-friendly flame-retardant plastic master batch and a preparation method thereof, wherein the outstanding characteristics and excellent effects are as follows:
1. according to the invention, ammonium polyphosphate and melamine polyphosphate are compounded and micronized, an aluminum hydroxide coating is coated on the surface of the micronized composite micro powder, silicone powder is formed in the coating while the aluminum hydroxide coating is formed, and the ammonium polyphosphate and melamine polyphosphate composite micro powder are coated by the aluminum hydroxide, so that the ammonium polyphosphate has good heat resistance, is easy to be subjected to thermoplastic processing in a plastic system, and reduces the release of small molecules caused by thermal processing.
2. The invention increases the moisture resistance of the ammonium polyphosphate by coating with the aluminum hydroxide, and the ammonium polyphosphate is not affected with moisture and deteriorated when being used for electric appliance plastics.
3. According to the invention, aluminum salt is converted into aluminum hydroxide coating, and the dispersed silicone powder is stably coated on the surface of ammonium polyphosphate in advance, so that the ammonium polyphosphate is endowed with excellent hydrophobicity, thereby enhancing the dispersibility and compatibility of the flame retardant in plastics, particularly, the silicone powder has good stability and non-migration, and the stable coated ammonium polyphosphate can effectively prevent the ammonium polyphosphate from blooming and separating out.
4. The preparation method is simple, the process is easy to control, the effect is excellent, the preparation method is suitable for large-scale production, the obtained plastic flame-retardant master batch is suitable for being added into various plastics to improve the flame retardance and prevent the flame retardant from being frosted and separated out, and the use effect is particularly better in polypropylene and polyamide.
Drawings
FIG. 1: example 1 flame retardant masterbatch was used in scanning electron microscopy photographs of test panels made from PP injection molding.
FIG. 2 is a drawing: comparative example 1 flame retardant masterbatch was used for low scanning electron microscopy of test panels made from PP injection moulding.
FIG. 3: comparative example 1 flame retardant masterbatch was used for high power scanning electron microscopy of test panels made from PP injection moulding.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Grinding the silicone powder and aluminum sulfate, and then adding deionized water to obtain aluminum sulfate composite liquid for dispersing the silicone powder for later use; wherein the mass ratio of the silicone powder to the aluminum sulfate to the deionized water is 1:5: 20;
(2) compounding long-chain ammonium polyphosphate with n being more than 500 and commercially available melamine polyphosphate with phosphorus content being more than 14 percent and nitrogen content being more than 38 percent in a mass ratio of 3:1, and processing the mixture by a vortex airflow mill to obtain composite micro powder with particle size being less than 5 mu m;
(3) adding the composite micro powder into a closed container, ensuring that the adding amount of the composite micro powder in the closed container is not more than 1/3 of the capacity of the closed container, filling ammonia gas into the closed container, controlling the temperature of the container to be 45 ℃, stirring at a high speed of 800rpm, preferably fully suspending the composite micro powder, spraying the aluminum sulfate composite liquid obtained in the step (1) into the closed container by adopting a high-pressure spray gun at the pressure of 0.6MPa, contacting the surface of the suspended composite micro powder with the aluminum sulfate composite liquid, maintaining the ammonia gas environment of the closed container, continuously filling the ammonia gas, ensuring the ammonia gas pressure to be 0.01MPa, gradually dissolving the ammonia gas in water to form a weak alkali environment, and promoting the aluminum sulfate salt solution on the surface of the composite micro powder to form an aluminum; discharging materials from a closed container, and drying the materials in a fluidized bed at 100 ℃ to obtain the composite modified ammonium polyphosphate flame retardant; the spraying amount of the aluminum sulfate composite liquid is controlled to be 0.5 time of the mass of the composite micro powder;
(4) adding 40 parts by weight of composite modified ammonium polyphosphate flame retardant, 5 parts by weight of talcum powder, 0.5 part by weight of polyethylene wax and 0.1 part by weight of methyl trifluoro propyl silicone oil into a high-speed mixer, stirring at 100 ℃ and a stirring speed of 400rpm for 15min, then adding 15 parts by weight of polypropylene and 50 parts by weight of compatilizer maleic anhydride grafted polypropylene, stirring at a low speed of 80rpm for 3min, uniformly mixing, discharging materials, feeding into a cold mixer, stirring at a low speed, and cooling to room temperature;
(5) and (3) conveying the material cooled in the step (4) into a short-length channel ratio counter-rotating double-screw extruder with a screw diameter of 45mm and a length-diameter ratio of 20:1 through a conveying pipeline. The screw rod sets up 5 heating zones by feeding to the ejection of compact, and the temperature is in proper order: zone 1 120 deg.C, zone 2 150 deg.C, zone 3 180 deg.C, zone 4 160 deg.C, and zone 5 deg.C 140 deg.C; and extruding and granulating, and granulating by adopting an air-cooled die surface to obtain the anti-blooming environment-friendly flame-retardant plastic master batch.
Mixing the flame-retardant plastic master batch obtained in example 1 with PPK1708 resin in a mass ratio of 2: 10, uniformly mixing, and performing injection molding to obtain a flat plate test sample with the number of 1#, the injection molding temperature: zone 1 at 200 ℃; zone 2 at 210 ℃; zone 3 at 230 ℃; zone 4 at 240 ℃. The test board obtained was left at 80 ℃ for 24 hours, and the surface of the test board was observed by scanning electron microscopy, as shown in FIG. 1, the gloss of the board surface was good and no precipitates were formed.
Example 2
(1) Grinding the silicone powder and aluminum sulfate, and then adding deionized water to obtain aluminum sulfate composite liquid for dispersing the silicone powder for later use; wherein the mass ratio of the silicone powder to the aluminum sulfate to the deionized water is 1:5: 20;
(2) compounding long-chain ammonium polyphosphate with n being more than 500 and commercially available melamine polyphosphate with phosphorus content being more than 14 percent and nitrogen content being more than 38 percent in a mass ratio of 3:1, and processing the mixture by a vortex airflow mill to obtain composite micro powder with particle size being less than 5 mu m;
(3) adding the composite micro powder into a closed container, ensuring that the adding amount of the composite micro powder in the closed container is not more than 1/3 of the capacity of the closed container, filling ammonia gas into the closed container, controlling the temperature of the container to be 35 ℃, stirring at a high speed of 1200rpm, preferably fully suspending the composite micro powder, spraying the aluminum sulfate composite liquid obtained in the step (1) into the closed container by adopting a high-pressure spray gun at the pressure of 0.8MPa, contacting the surface of the suspended composite micro powder with the aluminum sulfate composite liquid, maintaining the ammonia gas environment of the closed container, continuously filling the ammonia gas, ensuring the ammonia gas pressure to be 0.01MPa, gradually dissolving the ammonia gas in water to form a weak alkali environment, and promoting the aluminum sulfate salt solution on the surface of the composite micro powder to form an aluminum; discharging materials from a closed container, and drying the materials in a fluidized bed at 120 ℃ to obtain a composite modified ammonium polyphosphate flame retardant; the spraying amount of the aluminum sulfate composite liquid is controlled to be 0.5 time of the mass of the composite micro powder;
(4) adding 50 parts by weight of composite modified ammonium polyphosphate flame retardant, 10 parts by weight of wollastonite powder, 1 part by weight of stearic acid and 0.2 part by weight of methyl silicone oil into a high-speed mixer, stirring at 120 ℃ and a stirring speed of 800rpm for 20min, then adding 20 parts by weight of polypropylene and 10 parts by weight of compatilizer maleic anhydride grafted polyethylene, stirring at a low speed of 100rpm for 5min, uniformly mixing, discharging materials, feeding into a cold mixer, and stirring at a low speed for cooling;
(5) and (3) conveying the material cooled in the step (4) into a short-length channel ratio counter-rotating double-screw extruder with a screw diameter of 45mm and a length-diameter ratio of 20:1 through a conveying pipeline. The screw rod sets up 5 heating zones by feeding to the ejection of compact, and the temperature is in proper order: zone 1 at 100 deg.C, zone 2 at 150 deg.C, zone 3 at 180 deg.C, zone 4 at 160 deg.C, and zone 5 at 140 deg.C; and extruding and granulating, and granulating by adopting an air-cooled die surface to obtain the anti-blooming environment-friendly flame-retardant plastic master batch.
Mixing the flame-retardant plastic master batch obtained in example 2 with PPK1708 resin in a mass ratio of 2: 10, uniformly mixing, and performing injection molding to obtain a flat plate test sample with the thickness of 1.6mm, wherein the serial number is No. 2, and the injection molding temperature is as follows: zone 1 at 200 ℃; zone 2 at 210 ℃; zone 3 at 230 ℃; zone 4 at 240 ℃. The test was carried out according to UL94-2006, using vertical combustion. The instrument adopts a UL94 horizontal and vertical combustion test box, and the flame retardant grade reaches V0 grade.
Example 3
(1) Grinding the silicone powder and aluminum sulfate, and then adding deionized water to obtain aluminum sulfate composite liquid for dispersing the silicone powder for later use; wherein the mass ratio of the silicone powder to the aluminum sulfate to the deionized water is 1:5: 20;
(2) compounding long-chain ammonium polyphosphate with n being more than 500 and commercially available melamine polyphosphate with phosphorus content being more than 14 percent and nitrogen content being more than 38 percent in a mass ratio of 3:1, and processing the mixture by a vortex airflow mill to obtain composite micro powder with particle size being less than 5 mu m;
(3) adding the composite micro powder into a closed container, ensuring that the adding amount of the composite micro powder in the closed container is not more than 1/3 of the capacity of the closed container, filling ammonia gas into the closed container, controlling the temperature of the container to be 45 ℃, stirring at a high speed of 1200rpm, preferably fully suspending the composite micro powder, spraying the aluminum sulfate composite liquid obtained in the step (1) into the closed container by adopting a high-pressure spray gun at the pressure of 0.8MPa, contacting the surface of the suspended composite micro powder with the aluminum sulfate composite liquid, maintaining the ammonia gas environment of the closed container, continuously filling the ammonia gas, ensuring the ammonia gas pressure to be 0.01MPa, gradually dissolving the ammonia gas in water to form a weak alkali environment, and promoting the aluminum sulfate salt solution on the surface of the composite micro powder to form an aluminum; discharging materials from a closed container, and drying the materials in a fluidized bed at 120 ℃ to obtain a composite modified ammonium polyphosphate flame retardant; the spraying amount of the aluminum sulfate composite liquid is controlled to be 0.8 time of the mass of the composite micro powder;
(4) adding 50 parts by weight of composite modified ammonium polyphosphate flame retardant, 5 parts by weight of mica powder, 0.5 part by weight of polyethylene wax and 0.3 part by weight of methyl ethoxy silicone oil into a high-speed mixer, stirring at 100 ℃ and a stirring speed of 900rpm for 20min, then adding 15 parts by weight of polypropylene and 5 parts by weight of compatilizer maleic anhydride grafted ethylene-octene copolymer, stirring at a low speed of 80rpm for 5min, mixing uniformly, discharging materials, feeding into a cold mixer, stirring at a low speed and cooling;
(5) and (3) conveying the material cooled in the step (4) into a short-length channel ratio counter-rotating double-screw extruder with a screw diameter of 45mm and a length-diameter ratio of 20:1 through a conveying pipeline. The screw rod sets up 5 heating zones by feeding to the ejection of compact, and the temperature is in proper order: zone 1 120 deg.C, zone 2 160 deg.C, zone 3 190 deg.C, zone 4 170 deg.C, and zone 5 deg.C, zone 140 deg.C; and extruding and granulating, and granulating by adopting an air-cooled die surface to obtain the anti-blooming environment-friendly flame-retardant plastic master batch.
Comparative example 1
(1) Adding aluminum sulfate into deionized water to obtain aluminum sulfate composite liquid for later use; wherein the mass ratio of the aluminum sulfate to the deionized water is 5: 20;
(2) compounding long-chain ammonium polyphosphate with n being more than 500 and commercially available melamine polyphosphate with phosphorus content being more than 14 percent and nitrogen content being more than 38 percent in a mass ratio of 3:1, and processing the mixture by a vortex airflow mill to obtain composite micro powder with particle size being less than 5 mu m;
(3) adding the composite micro powder into a closed container, ensuring that the adding amount of the composite micro powder in the closed container is not more than 1/3 of the capacity of the closed container, filling ammonia gas into the closed container, controlling the temperature of the container to be 45 ℃, stirring at a high speed of 800rpm, preferably fully suspending the composite micro powder, spraying the aluminum sulfate composite liquid obtained in the step (1) into the closed container by adopting a high-pressure spray gun at the pressure of 0.6MPa, contacting the surface of the suspended composite micro powder with the aluminum sulfate composite liquid, maintaining the ammonia gas environment of the closed container, continuously filling the ammonia gas, ensuring the ammonia gas pressure to be 0.01MPa, gradually dissolving the ammonia gas in water to form a weak alkali environment, and promoting the aluminum sulfate salt solution on the surface of the composite micro powder to form an aluminum; discharging materials from a closed container, and drying the materials in a fluidized bed at 100 ℃ to obtain the composite modified ammonium polyphosphate flame retardant; the spraying amount of the aluminum sulfate composite liquid is controlled to be 0.5 time of the mass of the composite micro powder;
(4) adding 40 parts by weight of composite modified ammonium polyphosphate flame retardant, 1 part by weight of silicone powder, 5 parts by weight of talcum powder, 0.5 part by weight of polyethylene wax and 0.1 part by weight of methyl trifluoropropyl silicone oil into a high-speed mixer, stirring at 100 ℃ and a stirring speed of 400rpm for 15min, then adding 15 parts by weight of polypropylene and 50 parts by weight of compatilizer maleic anhydride grafted polypropylene, stirring at a low speed of 80rpm for 3min, uniformly mixing, discharging materials, feeding into a cold mixer, stirring at a low speed, and cooling to room temperature;
(5) and (3) conveying the material cooled in the step (4) into a short-length channel ratio counter-rotating double-screw extruder with a screw diameter of 45mm and a length-diameter ratio of 20:1 through a conveying pipeline. The screw rod sets up 5 heating zones by feeding to the ejection of compact, and the temperature is in proper order: zone 1 120 deg.C, zone 2 150 deg.C, zone 3 180 deg.C, zone 4 160 deg.C, and zone 5 deg.C 140 deg.C; and extruding and granulating, and carrying out air-cooling die surface grain cutting to obtain the environment-friendly flame-retardant plastic master batch.
Compared with the embodiment 1, the comparative example 1 does not add the silicone powder into the aluminum sulfate liquid, but adds the silicone powder after forming the aluminum hydroxide coating, so that a single aluminum hydroxide coating is formed, and the silicone powder is not tightly coated on the surface of the composite micro powder, so that the flame retardant is easy to frost and separate out in the plastic.
Mixing the flame-retardant plastic master batch obtained in the comparative example 1 with PPK1708 resin in a mass ratio of 2: 10, uniformly mixing, and performing injection molding to obtain a flat plate test sample, wherein the number is 3#, and the injection molding temperature is as follows: zone 1 at 200 ℃; zone 2 at 210 ℃; zone 3 at 230 ℃; zone 4 at 240 ℃. The obtained test board is placed at 80 ℃ for 24h, the surface of the test board is observed by a scanning electron microscope, as shown in figure 2, the board surface has obviously precipitated crystal points, and through further enlarged observation, as shown in figure 3, the size of the precipitated crystal points is close to 5 mu m, and the glossiness and the smoothness of the plastic product are improved.
Claims (10)
1. A preparation method of an anti-blooming environment-friendly flame-retardant plastic master batch is characterized by comprising the following steps:
(1) grinding the silicone powder and aluminum sulfate, and then adding deionized water to obtain aluminum sulfate composite liquid for dispersing the silicone powder for later use; wherein the mass ratio of the silicone powder to the aluminum sulfate to the deionized water is 1:5: 20;
(2) compounding ammonium polyphosphate and melamine polyphosphate in a mass ratio of 3:1, and processing by a fine machine to obtain composite micro powder with the particle size of less than 5 microns;
(3) adding the composite micro powder into a closed container, filling ammonia gas into the closed container, controlling the temperature of the container to be 35-45 ℃, stirring at a high speed, spraying the aluminum sulfate composite liquid obtained in the step (1) into the closed container by using a high-pressure spray gun, contacting the surface of the suspended composite micro powder with the aluminum sulfate composite liquid, and gradually dissolving the ammonia gas in water to form a weak alkali environment so as to promote the surface of the composite micro powder to form an aluminum hydroxide coating layer; discharging the materials from a closed container, and drying the materials in a fluidized bed at the temperature of 100-120 ℃ to obtain the composite modified ammonium polyphosphate fire retardant;
(4) adding 40-50 parts by weight of composite modified ammonium polyphosphate flame retardant, 5-10 parts by weight of filler, 0.5-1 part by weight of lubricating aid and 0.1-0.3 part by weight of silicone oil into a high-speed mixer, stirring at a high speed of 120 ℃ for 15-20min, then adding 15-20 parts by weight of polypropylene and 5-10 parts by weight of compatilizer, stirring at a low speed for 3-5min, mixing uniformly, discharging materials, feeding into a cold mixer, stirring at a low speed and cooling;
(5) and (3) feeding the material cooled in the step (4) into a double-screw extruder through a conveying pipeline, and performing extrusion granulation to obtain the anti-blooming environment-friendly flame-retardant plastic master batch.
2. The preparation method of the anti-blooming environment-friendly flame-retardant plastic master batch according to claim 1, characterized by comprising the following steps: the structural general formula of the ammonium polyphosphate is (NH)4)n+2PnO3n+1And (3) selecting long-chain ammonium polyphosphate with n being more than 500 as the ammonium polyphosphate in the step (2).
3. The preparation method of the anti-blooming environment-friendly flame-retardant plastic master batch according to claim 1, characterized by comprising the following steps: the melamine polyphosphate in the step (2) is selected from commercially available melamine polyphosphate with the phosphorus content of more than 14 percent and the nitrogen content of more than 38 percent.
4. The preparation method of the anti-blooming environment-friendly flame-retardant plastic master batch according to claim 1, characterized by comprising the following steps: and (3) adopting a vortex airflow pulverizer as the fine machine in the step (2).
5. The preparation method of the anti-blooming environment-friendly flame-retardant plastic master batch according to claim 1, characterized by comprising the following steps: the high-speed stirring rotating speed in the step (3) is 800-1200rpm, and the adding amount of the composite micro powder in the closed container does not exceed 1/3 of the capacity of the closed container.
6. The preparation method of the anti-blooming environment-friendly flame-retardant plastic master batch according to claim 1, characterized by comprising the following steps: filling ammonia gas into the closed container, maintaining the ammonia gas environment of the closed container, and continuously filling the ammonia gas to ensure that the pressure of the ammonia gas is 0.01 MPa; the pressure of the high-pressure spray gun is 0.6-0.8 MPa.
7. The preparation method of the anti-blooming environment-friendly flame-retardant plastic master batch according to claim 1, characterized by comprising the following steps: the filler in the step (4) is at least one of talcum powder, wollastonite powder, montmorillonite and mica powder; the lubricating additive is one of polyethylene wax and stearic acid powder; the silicone oil is at least one of methyl trifluoro propyl silicone oil, methyl ethoxy silicone oil, methyl silicone oil and ethyl silicone oil; the compatilizer is one of maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene-octene copolymer and maleic anhydride grafted ethylene-propylene-diene copolymer.
8. The preparation method of the anti-blooming environment-friendly flame-retardant plastic master batch according to claim 1, characterized by comprising the following steps: in the step (4), the high-speed stirring rotating speed is 400-900rpm, and the low-speed stirring rotating speed is 80-100 rpm.
9. The preparation method of the anti-blooming environment-friendly flame-retardant plastic master batch according to claim 1, characterized by comprising the following steps: the double-screw extruder in the step (5) is a double-screw extruder with a screw diameter of 45mm and a length-diameter ratio of 20: 1; the screw rod sets up 5 heating zones by feeding to the ejection of compact, and the temperature is in proper order: the 1 region is 100-120 ℃, the 2 region is 150-160 ℃, the 3 region is 180-190 ℃, the 4 region is 160-170 ℃ and the 5 region is 130-140 ℃; and (5) carrying out air-cooled die surface granulation.
10. An environment-friendly flame-retardant plastic master batch preventing blooming and separating out is characterized in that: prepared by the process of any one of claims 1 to 9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910385001.5A CN110066460B (en) | 2019-05-09 | 2019-05-09 | Anti-blooming precipitation environment-friendly flame-retardant plastic master batch and preparation method thereof |
| PCT/CN2019/110473 WO2020224182A1 (en) | 2019-05-09 | 2019-10-10 | Environment-friendly flame-retardant plastic master batch capable of preventing from blooming and precipitation and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910385001.5A CN110066460B (en) | 2019-05-09 | 2019-05-09 | Anti-blooming precipitation environment-friendly flame-retardant plastic master batch and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110066460A CN110066460A (en) | 2019-07-30 |
| CN110066460B true CN110066460B (en) | 2020-05-01 |
Family
ID=67370518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910385001.5A Active CN110066460B (en) | 2019-05-09 | 2019-05-09 | Anti-blooming precipitation environment-friendly flame-retardant plastic master batch and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110066460B (en) |
| WO (1) | WO2020224182A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110066460B (en) * | 2019-05-09 | 2020-05-01 | 浙江麟祥塑业有限公司 | Anti-blooming precipitation environment-friendly flame-retardant plastic master batch and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1522551A1 (en) * | 2003-10-07 | 2005-04-13 | Clariant GmbH | Agglomerate flame retardants containing phosphorus |
| CN101880408A (en) * | 2010-06-25 | 2010-11-10 | 北京盛大华源科技有限公司 | Flame retardant and preparation method thereof |
| CN104194161A (en) * | 2014-09-29 | 2014-12-10 | 江苏力达塑料托盘制造有限公司 | Precipitation resistant, toughening and flame-retardant polypropylene composite material and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3728629A1 (en) * | 1987-08-27 | 1989-03-09 | Hoechst Ag | FLAME-RESISTANT POLYMERS |
| WO2016105554A1 (en) * | 2014-12-23 | 2016-06-30 | Jji Technologies, Llc | Novel fire-resistant compositions for the high temperature plastic materials |
| CN105489283A (en) * | 2015-12-31 | 2016-04-13 | 江苏亨通线缆科技有限公司 | Fire resistant cable for intelligent robot |
| CN106674768A (en) * | 2016-12-29 | 2017-05-17 | 南京璟仕汇新材料科技有限公司 | Ethylene propylene diene terpolymer low-smoke zero-halogen flame retardant soft rubber |
| CN106633897A (en) * | 2016-12-31 | 2017-05-10 | 铜陵华科电子材料有限公司 | Formula of halogen-free flame-retardant aid |
| CN107892771B (en) * | 2017-12-14 | 2020-12-04 | 和昌电业(肇庆)有限公司 | Cold-resistant low-smoke halogen-free flame-retardant cable material and preparation method thereof |
| CN110066460B (en) * | 2019-05-09 | 2020-05-01 | 浙江麟祥塑业有限公司 | Anti-blooming precipitation environment-friendly flame-retardant plastic master batch and preparation method thereof |
-
2019
- 2019-05-09 CN CN201910385001.5A patent/CN110066460B/en active Active
- 2019-10-10 WO PCT/CN2019/110473 patent/WO2020224182A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1522551A1 (en) * | 2003-10-07 | 2005-04-13 | Clariant GmbH | Agglomerate flame retardants containing phosphorus |
| CN101880408A (en) * | 2010-06-25 | 2010-11-10 | 北京盛大华源科技有限公司 | Flame retardant and preparation method thereof |
| CN104194161A (en) * | 2014-09-29 | 2014-12-10 | 江苏力达塑料托盘制造有限公司 | Precipitation resistant, toughening and flame-retardant polypropylene composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020224182A1 (en) | 2020-11-12 |
| CN110066460A (en) | 2019-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Synthesis of N-ethyl triazine–piperazine copolymer and flame retardancy and water resistance of intumescent flame retardant polypropylene | |
| Yang et al. | Synergistic and compatibilizing effect of octavinyl polyhedral oligomeric silsesquioxane nanoparticles in polypropylene/intumescent flame retardant composite system | |
| CN112250935B (en) | High-flame-retardant-grade low-smoke halogen-free material and preparation method and application thereof | |
| CN101280097A (en) | Nanometer flame-proof polyethylene glycol terephthalate engineering plastics and preparation thereof | |
| CN108250566A (en) | A kind of low warpage halogen-free expanded flame-retardant Long Glass Fiber Reinforced PP Composite and preparation method thereof | |
| CN110819009B (en) | High-melt-index halogen-free flame-retardant polypropylene material and preparation method thereof | |
| WO2017075855A1 (en) | Polypropylene-specific efficient halogen-free flame retardant masterbatch, preparation method therefor and use thereof | |
| JPWO2005061626A1 (en) | Flame retardant thermoplastic resin composition | |
| CN101747616A (en) | Modified polyphenyl ether material and preparation method thereof | |
| CN109370043B (en) | Low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA and preparation method thereof | |
| WO2023020452A1 (en) | Halogen-free flame-retardant polypropylene composition, and preparation method therefor and use thereof | |
| CN110066460B (en) | Anti-blooming precipitation environment-friendly flame-retardant plastic master batch and preparation method thereof | |
| CN113754902B (en) | Environment-friendly polyamide flame-retardant master batch and preparation method thereof | |
| CN111171542B (en) | High CTI flame-retardant polycarbonate alloy material and preparation method and application thereof | |
| CN102206406A (en) | Method for preparing transparent heat-resistance polylactic acid modification material | |
| EP4215575A1 (en) | Halogen-free flame-retardant compounded system having resistance to high heat and high shear and high flame resistance, and application thereof | |
| CA2048227A1 (en) | Process for incorporating additives in thermoplastic polymers | |
| CN110157096B (en) | Environment-friendly antistatic flame-retardant polypropylene material and preparation method thereof | |
| CN109897371B (en) | Precipitation-proof environment-friendly flame-retardant plastic master batch and preparation method thereof | |
| CN111690207A (en) | Production method of halogen-free flame-retardant master batch | |
| CN108250573B (en) | Thermo-oxidative aging resistant halogen-free environment-friendly flame-retardant polypropylene material and preparation method thereof | |
| CN108203527A (en) | A kind of high limit oxygen index (OI) halogen-free flameproof PP materials and preparation method thereof | |
| CN111138713A (en) | Stearylamine modified ammonium polyphosphate and preparation method and application thereof | |
| CN109233270A (en) | Utilize the halogen-free flame-retardant nylon 6 material and preparation method thereof of 6 waste silk of polyamide fibre production | |
| CN109265938A (en) | A kind of modified PBT material preparation method |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200413 Address after: 318014 1055 Gaoxin Road, Taizhou City, Zhejiang Province Applicant after: ZHEJIANG LINXIANG PLASTIC Co.,Ltd. Address before: 318000 No. 2-32, West Wang Village, Hong Jia street, Jiaojiang District, Taizhou, Zhejiang. Applicant before: Wang Jinqi |
|
| TA01 | Transfer of patent application right |