CN112297278B - Preparation method of antimony trioxide PBT flame-retardant master batch - Google Patents
Preparation method of antimony trioxide PBT flame-retardant master batch Download PDFInfo
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- CN112297278B CN112297278B CN202011035457.8A CN202011035457A CN112297278B CN 112297278 B CN112297278 B CN 112297278B CN 202011035457 A CN202011035457 A CN 202011035457A CN 112297278 B CN112297278 B CN 112297278B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- 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
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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The preparation method of the antimony trioxide PBT flame-retardant master batch comprises the following steps: the preparation method of the antimony trioxide PBT flame-retardant master batch is characterized by comprising the following steps of: and (3) conveying the antimonous oxide powder and the carrier resin to a double-screw extruder in proportion through a weightlessness scale or directly conveying the antimonous oxide powder and the carrier resin to a high-speed stirrer, uniformly stirring, adding the mixed materials to the double-screw extruder, melting, plasticizing and extruding the materials in the screw extruder, granulating and forming the materials by a granulating device, and drying the materials to obtain a finished product. The method for preparing the antimony trioxide PBT flame-retardant master batch has the advantages of difficult blockage of a die head, low defective rate, high direct yield and low production cost; no dust is generated, and the environment is friendly; the prepared antimony trioxide PBT flame-retardant master batch has the antimony trioxide powder content of 70-90 percent and is particularly suitable for engineering plastic processing industry.
Description
Technical Field
The invention relates to a preparation method of flame-retardant master batch for engineering plastic processing, in particular to a method for preparing antimony trioxide powder into antimony trioxide PBT flame-retardant master batch.
Background
Due to the development of society and the progress of technology, plastics are increasingly used in construction, furniture, automobiles, traffic, aviation, aerospace, electric appliances and the like. Improving the flame retardant rating of plastics has become a very urgent issue. The PBT which is one of the five engineering plastics has high requirements on the corresponding flame retardant grade and flame retardant property, wherein the antimony trioxide series flame retardant master batch has the characteristics of high efficiency, low toxicity, environmental protection (cleaning) and the like, so that the use degree of the antimony trioxide series flame retardant master batch is higher and higher in China and countries and regions such as European Union, the United states, japanese and the like, and a plurality of users gradually use the antimony trioxide master batch as a substitute product of the antimony trioxide. The need to mastere PBT with antimony trioxide is also increasing.
However, because the PBT resin has the characteristics of high melting point, high temperature sensitivity, high crystallization speed, high hardness of crystallized materials and the like, the traditional master batch preparation process is difficult to meet the preparation requirements of the antimony oxide master batch of engineering plastics, so that corresponding researches are conducted aiming at the characteristics of high-melting-point crystal engineering plastics, a process suitable for preparing the antimony trioxide PBT master batch is developed, and the process is an important subject faced by the technicians in the field.
For a long time, the preparation process of the antimony trioxide PBT master batch is searched at home and abroad, but due to the related characteristics of the PBT, when a plurality of extrusion and pelleting modes which are common at present are used, the process has a certain degree of defects:
1. the underwater pelletizing system is characterized in that the cutter is used for pelletizing on the die surface, the underwater pelletizing system is cooled by water, but the pelletizing mode enables a cooling carrier to be in direct contact with the die surface, so that the die head temperature of a screw extruder is reduced, and the die head is easy to block and cannot be extruded and pelletized normally for a long time due to the fact that the temperature sensitivity of PBT resin to the die head is too high.
2. The die head temperature is not affected by the strand-cutting mode, normal extrusion operation can be realized, but in the subsequent strand-cutting operation process, the cooled antimony trioxide PBT master batch is very fragile in material due to the characteristics of PBT resin, the strand breakage phenomenon can occur in the strand-cutting process, the operation difficulty is increased, a large amount of crushed particles and powder can be produced, the particle types are not very regular after the strand-cutting, the defective rate is increased, the direct yield is reduced, the defective rate of the antimony trioxide PBT master batch produced by the strand is 3-4%, and the average direct yield is only 91.3%, so that the production cost is greatly increased.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art and provide the preparation method of the antimony trioxide PBT flame-retardant master batch, which has the antimony trioxide content of more than 70%, the PBT resin content of not more than 30%, the die head is not easy to block, the defective rate is low, the direct yield is high, and the production cost is low.
The technical scheme adopted for solving the technical problems is that the preparation method of the antimony trioxide PBT flame-retardant master batch comprises the following steps: and (3) conveying the antimony trioxide powder and the carrier resin to a double-screw extruder in proportion through a weightlessness scale or directly conveying the antimony trioxide powder and the carrier resin to a high-speed stirrer, uniformly stirring, adding the mixed materials into the double-screw extruder, melting, plasticizing and extruding the materials in the screw extruder, granulating and forming the materials by a granulating device, and drying the materials.
Further, the weight percentage of the antimony trioxide to the resin is as follows: 70-90% of antimonous oxide powder and 10-30% of carrier resin.
Further, the resin is polybutylene terephthalate, abbreviated as PBT.
Further, the temperature in the twin-screw extruder is 180 ℃ to 250 ℃.
Further, the aspect ratio of the twin-screw extruder is 32 to 48.
Further, the granulating equipment is water ring die surface hot cutting granulating equipment or air cooling die surface hot cutting granulating equipment.
Further, after the drying, iron is removed by an iron remover.
Further, the iron remover is a permanent magnet iron remover or an electromagnetic iron remover.
Further, the magnetic force of the permanent magnet iron remover or the electromagnetic iron remover is 0.3T-2.5T.
The invention has the following advantages after adopting the technical scheme: the antimony trioxide PBT flame-retardant master batch prepared by the method has the antimony trioxide content of more than or equal to 70 percent and the resin PBT content of less than or equal to 30 percent, and is prepared by conveying raw materials into a double-screw extruder through a weightlessness scale, or stirring by a high-speed stirrer, uniformly mixing, heating by the double-screw extruder, shearing, mixing and compressing by a screw, extruding by a die opening, granulating by granulating equipment, and preparing the granular master batch. The granulating is preferably hot-cutting granulating on the water ring die surface or hot-cutting granulating on the air cooling die surface, and the granulating method has the advantages that the cooling medium does not directly contact with the die head, so that the die head temperature is not influenced, the twin-screw extruder can normally extrude, the twin-screw extruder directly enters circulating water for cooling after granulating, only a small amount of particles are produced, no powder is basically produced, the yield and the direct yield of products are improved, and meanwhile, the yield of the products can be improved, and the manufacturing cost is reduced.
The equipment used in the invention is a weightlessness scale or high-speed stirrer, a double-screw extruder and granulating equipment, is common and easy to obtain, has simpler production process, lower labor intensity and stronger operability.
The antimony trioxide PBT flame-retardant master batch prepared by the method can be directly used as a granular flame-retardant master batch, and only a resin matrix material is required to be added, so that other additives are not needed, and the flame-retardant effect of powdery antimony trioxide is achieved in the flame-retardant material. After being mixed with the PBT resin material, the PBT resin material can be well dispersed with the resin matrix material. In addition, only two substances of antimony trioxide and PBT exist in the master batch, so that the application space of the antimony trioxide and PBT flame-retardant master batch is greatly increased, the use breadth of the antimony trioxide and PBT master batch is increased, meanwhile, the use of the master batch can improve the labor environment, reduce the pollution of dust to the environment, and the master batch has profound social benefits on the use of inorganic powder.
The preferred scheme of the invention adds the iron remover technology, removes magnetic substances in the technology product, further improves the product quality and is more beneficial to the use of downstream technology.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
70wt% of antimony trioxide and 30wt% of PBT resin are put into a high-speed stirrer to be stirred uniformly at a high speed for about 5 minutes, and the mixed materials are added into a mixture with an aspect ratio of 32: 1. in the double-screw extruder, the control temperature of the temperature zone of the double-screw extruder is respectively 150 ℃ in a conveying zone, 206 ℃ in a plasticizing zone, 225 ℃ in a melting zone and 231 ℃ in an extruding zone, the mixed materials are melted, plasticized and extruded in a charging barrel of the double-screw extruder, hot-cut and granulated through a water ring type die surface, dried, deironized and packaged, and finally the granular antimony trioxide master batch is prepared. The cost appearance is spherical particles, the particle sizes are basically consistent, and the content of the antimonous oxide is 70.2% as a result of chemical detection of the product. The defective rate is 0.6%, and the powder sample is basically absent. The yield thereof was found to be 96.1%.
Example 2
80 weight percent of antimonous oxide and 20 weight percent of resin are put into a high-speed stirrer to be stirred uniformly at high speed for about 10 minutes, and the mixed materials are added into a mixture with the length-diameter ratio of 40: 1. in the double-screw extruder, the control temperature of the extrusion temperature zone of the double screws is 220 ℃ in a conveying zone, 239 ℃ in a plasticizing zone, 245 ℃ in a melting zone, 248 ℃ in an extrusion zone, the mixed materials are melted, plasticized and extruded in a charging barrel of the reciprocating screw extruder, and then hot-cut granulation, drying, iron removal and packaging are carried out through an air cooling die surface, so that the granular antimony trioxide master batch is prepared. The appearance of the product is elliptic granular, the grain size is basically consistent, and the product is basically free of powder. The chemical detection result shows that the content of antimonous oxide is 80.15%, the defective rate is 0.8%, and the direct yield is 92.8%.
Example 3
80wt% antimony trioxide, 20wt% PBT resin is directly transferred to an aspect ratio of 48 by weight loss scale: in the double-screw extruder, the control temperature of the temperature zone of the double-screw extruder is 190 ℃ in a conveying zone, 226 ℃ in a plasticizing zone, 249 ℃ in a melting zone and 231 ℃ in an extruding zone, the mixed materials are melted, plasticized and extruded in a charging barrel of the double-screw extruder, hot-cut and granulated through a water ring type die surface, dried, iron-removed and packaged to prepare granular antimony trioxide master batches. The appearance of the finished product is elliptic granular, the grain sizes are basically consistent, and the finished product is basically free of powder. The chemical detection result shows that the content of the antimonous oxide is 80.06%, the defective rate is 0.7%, and the direct yield is 94.1%.
Example 4
90wt% antimony trioxide, 10% PBT resin is directly fed to an aspect ratio of 48 by weight loss: 1. in the double-screw extruder, the control temperature of the temperature zone of the double-screw extruder is 238 ℃ in a conveying zone, 206 ℃ in a plasticizing zone, 225 ℃ in a melting zone and 246 ℃ in an extruding zone, the mixed materials are melted, plasticized and extruded in a charging barrel of the double-screw extruder, hot-cut and granulated through an air cooling die surface, dried, iron-removed and packaged, and the granular antimony trioxide master batch is prepared. The cost appearance is oval granular, the grain size is basically consistent, and a small amount of powder sample is generated. The chemical detection result shows that the content of the antimonous oxide is 90.31%, the defective rate is 1.2%, and the direct yield of the product is 93.8%.
Claims (7)
1. The preparation method of the antimony trioxide PBT flame-retardant master batch is characterized by comprising the following steps of: delivering antimony trioxide powder and carrier resin to a double-screw extruder according to a proportion by weightlessness or directly delivering the antimony trioxide powder and the carrier resin to a high-speed stirrer, uniformly stirring, adding the mixed materials to the double-screw extruder, melting, plasticizing and extruding the materials in the screw extruder, granulating and molding the materials by granulating equipment, and drying the materials to obtain a finished product; the weight percentage of the antimony trioxide to the resin is as follows: 90% of antimony trioxide powder and 10% of carrier resin;
the resin is polybutylene terephthalate;
the granulating equipment is water ring die surface hot cutting granulating equipment or air cooling die surface hot cutting granulating equipment.
2. The process for preparing antimony trioxide PBT flame retardant master batch according to claim 1, wherein the temperature in the twin-screw extruder is 180 ℃ to 250 ℃.
3. The process for preparing a flame retardant masterbatch of antimony trioxide, PBT, according to any one of claims 1 to 2, characterized in that the twin-screw extruder has an aspect ratio of 32 to 48.
4. The method for preparing the antimony trioxide PBT flame retardant master batch according to claim 1 or 2, wherein the drying is further followed by iron removal by an iron remover.
5. The method for preparing the antimony trioxide PBT flame retardant master batch according to claim 3, wherein the drying is further followed by iron removal by an iron remover.
6. The method for preparing the antimony trioxide PBT flame retardant master batch according to claim 5, wherein the iron remover is a permanent magnet iron remover or an electromagnetic iron remover.
7. The method for preparing the antimony trioxide PBT flame retardant master batch according to claim 6, wherein the magnetic force of the permanent magnet iron remover or the electromagnetic iron remover is 0.3T-2.5T.
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| CN112297278B true CN112297278B (en) | 2024-03-08 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217756A (en) * | 2003-01-14 | 2004-08-05 | Mitsubishi Engineering Plastics Corp | Method for producing flame retardant resin composition |
| CN105111569A (en) * | 2015-10-11 | 2015-12-02 | 江苏五信新材料科技有限公司 | Preparation method of antimony trioxide flame-retardant master batch |
| CN106317594A (en) * | 2016-08-22 | 2017-01-11 | 益阳生力材料科技股份有限公司 | Halogen-free antimony trioxide flame-retardant master batches and preparation method thereof |
| KR20170038252A (en) * | 2015-09-30 | 2017-04-07 | (주)인테크놀로지 | Flame retardant master batch of expanded polystyrene with enhanced cell uniformity and flame-resistance, and a method of the manufacturing |
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- 2020-09-27 CN CN202011035457.8A patent/CN112297278B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217756A (en) * | 2003-01-14 | 2004-08-05 | Mitsubishi Engineering Plastics Corp | Method for producing flame retardant resin composition |
| KR20170038252A (en) * | 2015-09-30 | 2017-04-07 | (주)인테크놀로지 | Flame retardant master batch of expanded polystyrene with enhanced cell uniformity and flame-resistance, and a method of the manufacturing |
| CN105111569A (en) * | 2015-10-11 | 2015-12-02 | 江苏五信新材料科技有限公司 | Preparation method of antimony trioxide flame-retardant master batch |
| CN106317594A (en) * | 2016-08-22 | 2017-01-11 | 益阳生力材料科技股份有限公司 | Halogen-free antimony trioxide flame-retardant master batches and preparation method thereof |
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