CN114479443A - Halogen-free flame retardant for thermoplastic polymer and preparation method thereof - Google Patents
Halogen-free flame retardant for thermoplastic polymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a halogen-free flame retardant for thermoplastic polymers, which comprises 60-90% of organic phosphinate, 5-20% of organosilicon flame retardant, 0.1-10% of inorganic silicon synergist and 0-10% of zinc-containing heat stabilizing compound by mass percent. The invention also provides a preparation method of the halogen-free flame retardant. The halogen-free flame retardant is corrosion-resistant and low-precipitation halogen-free flame retardant for thermoplastic polymers.
Description
Technical Field
The invention relates to the technical field of flame retardants for thermoplastic polymers, in particular to a halogen-free flame retardant for thermoplastic polymers and a preparation method thereof.
Background
Thermoplastic polymers such as nylon, polyester, polyphenylene ether, polyketone, etc. are widely used in a variety of industrial fields because of their excellent mechanical properties, chemical stability and thermal stability, but they are easily burned in the presence of a heat source, and thus it is generally necessary to add a flame retardant to impart corresponding flame retardant properties to them to meet industrial demands, such as in the fields of communications, electronics, electrical, rail transportation and automobiles.
The halogen flame retardant is the most used flame retardant in the world at present, and is favored due to the advantages of high flame retardant efficiency and moderate price. However, in view of the serious drawbacks of halogen flame retardants and the WEEE and RoHS directive of the European Union, many parts and products require no halogenation.
At present, the halogen-free flame retardant used for thermoplastic polymers mainly comprises red phosphorus, metal hydroxide, alkyl phosphinate and inorganic phosphinate. Wherein, red phosphorus can only be used for manufacturing dark products, and generates unpleasant odor in the processing process; the metal hydroxide has serious loss of comprehensive performance due to large addition amount; the inorganic hypophosphite has low price and simple synthesis process, but has low thermal stability, is easy to generate the phenomena of color change, scorching and even firing in the processing process, and can generate toxic gases such as phosphine and the like; melamine polyphosphate (MPP) synergistic Aluminum Diethylphosphinate (ADP) is a typical alkyl phosphinate flame retardant system, and due to the high phosphorus content and the synergistic action of phosphorus and nitrogen, the flame retardant system can realize high-efficiency flame retardance of the polymer, and does not generate toxic gases such as phosphine and the like in the high-temperature processing process, but has the following defects:
1) the two components react and decompose at high temperature to generate a small amount of acid gas, and the acid gas can not only cause material discoloration, but also corrode metal parts of processing equipment, thereby bringing about the problems of cost increase and production efficiency reduction;
2) the flame retardant is easy to separate out: when ADP and MPP are used in a damp and hot environment, the flame retardant is easy to migrate to the surface of a product, so that the flame retardant is unevenly distributed and lost, and finally, the flame retardance and the electrical property of the material are reduced, which is not accepted in the field of electronics and electricity. When the material contains MPP, mold scale is easy to generate in the injection molding process, and the production efficiency is reduced by stopping and cleaning the mold occasionally;
in recent years, the search for more efficient ADP (alkyl phosphinate) synergistic flame retardant systems has been an important direction of research.
Disclosure of Invention
In view of one or more of the problems in the prior art, according to one aspect of the present invention, there is provided a halogen-free flame retardant for thermoplastic polymers, comprising the following components by mass percent:
60 to 90 percent of organic phosphinate
5 to 20 percent of organic silicon flame retardant
0.1 to 10 percent of inorganic silicon synergist;
wherein the sum of the mass percentages of the components is 100%.
Optionally, 0-10% of a zinc-containing heat stabilizing compound is also included. The zinc-containing heat-stabilized compound has a stabilizing effect on the processing process of the halogen-free flame-retardant nylon polymer, can inhibit the corrosion of acidic substances released by the decomposition of the flame retardant on equipment, and can stabilize the color of a system; the zinc stabilizer belongs to inorganic substances, is equivalent to a filler, and is filled in an amorphous area of a polymer like a flame retardant. Because the PBT material has relatively low processing temperature, a zinc-containing heat-stable compound can not be added.
Optionally, the organic phosphinate is one or a combination of dialkyl aluminum phosphinate, dialkyl zinc phosphinate, dialkyl iron phosphinate and phenyl aluminum phosphinate.
Optionally, the organic phosphinate is aluminum diethylphosphinate.
Optionally, the organic phosphinate has an average particle size D50 satisfying 10 μ ι η < D50<50 μ ι η. The organic phosphinate is mainly distinguished from different specifications through particle size, and the smaller the particle size is, the finer the powder is, the higher the viscosity is, and the processing is not facilitated; the dispersion is not uniform due to the excessively large particle size, and the viscosity and the dispersion uniformity of the organic phosphinate are optimally balanced in the above particle size range when the glass of the halogen-free flame retardant for thermoplastic polymers is used.
Optionally, the organic silicon flame retardant is any one or a combination of polysiloxane, cage type silsesquioxane, hydroxyl silicone oil and silicone rubber.
Optionally, the organic silicon flame retardant is compounded by cage type silsesquioxane and hydroxyl silicone oil according to the mass ratio of (1-9):1, and the organic silicon flame retardant is compounded by cage type silsesquioxane and hydroxyl silicone oil according to the mass ratio of 1: 1.
Optionally, the inorganic silicon synergist is one or a combination of several of phyllosilicate, nano-silica and low-melting-point glass powder.
Optionally, the inorganic silicon-based synergist is nanosilicon dioxide.
Optionally, the zinc-containing thermal stabilizing compound comprises at least one of zinc borate, zinc oxide, zinc stannate.
Optionally, the zinc-containing heat stabilizing compound is zinc stannate.
Optionally, the zinc-containing thermally stable compound has an average particle size D50 satisfying 10 μ ι η < D50<50 μ ι η.
According to another aspect of the present invention, there is provided a method for preparing the halogen-free flame retardant for thermoplastic polymers, comprising:
weighing organic phosphinate, organic silicon flame retardant, inorganic silicon synergist and zinc-containing heat-stable compound according to the proportion, and uniformly mixing the materials by a high-speed mixer to obtain a powder flame retardant;
and (2) adopting a double-screw extruder, after the set temperature of each zone is stable, adding resin and an auxiliary agent from a main feeding hopper, feeding the powdery flame retardant from a side feeding port, adding glass fiber from a glass fiber port, and performing extrusion, granulation and drying to obtain the halogen-free flame-retardant polymer. The base resin is required to be modified due to lack of characteristics, such as flame retardant modification, reinforced modification, toughening modification, flame retardant reinforced modification and the like; the antioxidant plays a role in inhibiting thermal degradation and thermal aging of resin, and the lubricant plays two roles: firstly, various additives and resin are uniformly dispersed, and secondly, the processing process is smoother, and preferably, the additive amount of the additives is 0.1-1%.
In the halogen-free flame retardant for the thermoplastic polymer and the preparation method thereof, the organic silicon flame retardant can increase the dispersibility of the phosphorus flame retardant in the base material, so that the dosage of the diethyl aluminum phosphinate is reduced, the processing performance of the base material is improved, the influence of physical and mechanical properties is reduced, the corrosion and precipitation are relieved, and the halogen-free flame retardant is an ideal substitute for MPP. In addition, the inorganic silicon synergist can meet higher flame retardance.
The organosilicon flame retardant mainly comprises silicone oil, silicone resin, silicone rubber, organic silanol amide and the like. The organic silicon flame retardant has high efficiency, low toxicity, no pollution, less smoke, less influence on the use performance of resin and excellent flame retardant performance, so the organic silicon flame retardant is valued. The flame retardant mechanism is as follows: when the high molecular material is burnt, the-Si-O bond in the organic silicon molecule forms a-Si-C bond, and the generated white burning residue and carbide form a composite inorganic layer, so that the volatile generated by burning can be prevented from escaping, oxygen is prevented from contacting with the substrate, and the melt is prevented from dripping, thereby achieving the purpose of flame retardance.
The halogen-free flame retardant for the thermoplastic polymer comprises a phosphorus flame retardant, when the halogen-free flame retardant is used, phosphorus catalyzes and promotes the formation of carbon at high temperature, silicon increases the thermal stability of the carbon layers, so that the phosphorus/silicon synergistic flame retardant effect is exerted, and when siloxane is used for replacing silane, the phosphorus/silicon synergistic flame retardant effect is further enhanced, and the layered silicon dioxide formed by the degradation of the siloxane prevents the oxidation of the carbon layers, so that the stability of the carbon layers is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view of a flow chart of a method for preparing a halogen-free flame retardant for thermoplastic polymers according to the present invention;
FIG. 2 is a schematic representation of the corrosion test of the present invention.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
The halogen-free flame retardant for the thermoplastic polymer comprises, by mass, 60-90% of organic phosphinate, 5-20% of organosilicon flame retardant, 0.1-10% of inorganic silicon synergist, 0.1-10% of zinc-containing heat-stabilized compound.
FIG. 1 is a schematic diagram of a flow chart of a preparation method of the halogen-free flame retardant for thermoplastic polymers of the present invention, as shown in FIG. 1, the preparation method comprises:
step S1, weighing organic phosphinate, organosilicon flame retardant, inorganic silicon synergist and zinc-containing heat-stabilized compound according to the proportion, and uniformly mixing the materials by a high-speed mixer to obtain a powder flame retardant;
and step S2, adopting a double-screw extruder, adding resin and an auxiliary agent from a main feeding hopper after the set temperature of each zone is stable, feeding the powdery flame retardant from a side feeding port, adding glass fibers from a glass fiber port, and obtaining the halogen-free flame retardant polymer after extrusion, granulation and drying.
The halogen-free flame retardant and the preparation method thereof solve the defect of a phosphorus-nitrogen compound flame retardant system based on diethyl aluminum phosphinate of a thermoplastic polymer, and the halogen-free flame retardant is a flame retardant for the thermoplastic polymer and has the characteristics of high thermal stability, low migration, low precipitation, no corrosion to equipment and the like.
In the following examples, the halogen-free flame retardant for thermoplastic polymers was subjected to mechanical testing, flame retardancy testing, migration resistance testing and corrosion testing using the following methods, wherein:
mechanical testing, namely testing the tensile strength and the notch impact strength according to ISO527 and ISO179 testing standards;
flame retardant test, according to UL94V0 test standard test;
the migration resistance test is carried out, the prepared halogen-free flame-retardant glass fiber reinforced nylon sample is placed in a constant temperature and humidity box, the temperature is set to be 85 ℃, the relative humidity is 85%, and the state of the surface of the sample after 168 hours is observed visually;
and (3) corrosion testing, namely putting the prepared halogen-free flame-retardant glass fiber reinforced nylon material into a glass cup according to the graph shown in fig. 2, inserting a copper pipe in the middle of particles, putting the particles into a constant temperature and humidity box, setting the temperature to be 85 ℃ and the relative humidity to be 85%, and visually observing the corrosion state and the corrosion degree of the surface of the copper pipe after 168 hours: no corrosion, general and serious.
The following examples of the invention were carried out under the same conditions (temperature, screw geometry, injection molding parameters, etc.).
Comparative example 1
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
6 parts of MPP and 12 parts of Aluminum Diethylphosphinate (ADP) are applied to 41 parts of polyhexamethylene adipamide (PA 66 for short, Epstein Barr, EPR27) to prepare the halogen-free flame-retardant glass fiber reinforced PA66 powder flame retardant.
Granulating in a twin-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of halogen-free flame-retardant glass fiber reinforced PA66 to be 250-265 ℃, adding 10 parts of nylon resin (PA6), 0.3 parts of antioxidant 608, 0.2 parts of antioxidant 1098 and 0.5 parts of lubricant (silicone powder) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber port, starting a host machine and a feeder, and finishing the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material was injected in an injection molding machine to form standard samples specified by various test standards, and the obtained halogen-free flame-retardant glass fiber reinforced PA66 has the properties shown in Table 1.
Comparative example 2
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
3 parts of MPP and 15 parts of Aluminum Diethylphosphinate (ADP) are applied to 41 parts of polyhexamethylene adipamide (PA 66 for short, Epstein Barr, EPR27) to prepare the halogen-free flame-retardant glass fiber reinforced PA66 powder flame retardant.
Granulating in a twin-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of halogen-free flame-retardant glass fiber reinforced PA66 to be 250-265 ℃, adding 10 parts of nylon resin (PA6), 0.3 parts of antioxidant (608), 0.2 parts of antioxidant (1098) and 0.5 parts of lubricant (silicone powder) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber port, starting a host machine and a feeder, and finishing the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material was injected in an injection molding machine to form standard samples specified by various test standards, and the obtained halogen-free flame-retardant glass fiber reinforced PA66 has the properties shown in Table 1.
Comparative example 3
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
18 parts of diethyl aluminum phosphinate (ADP) is applied to 41 parts of polyhexamethylene adipamide (PA 66 for short, Hippon Hill Shenma, EPR27) to prepare the halogen-free flame-retardant glass fiber reinforced PA66 powder flame retardant.
Granulating in a twin-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of halogen-free flame-retardant glass fiber reinforced PA66 to be 250-265 ℃, adding 10 parts of nylon resin (PA6), 0.3 parts of antioxidant (608), 0.2 parts of antioxidant (1098) and 0.5 parts of lubricant (silicone powder) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber port, starting a host machine and a feeder, and finishing the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material was injected in an injection molding machine to form standard samples specified by various test standards, and the obtained halogen-free flame-retardant glass fiber reinforced PA66 has the properties shown in Table 1.
Comparative example 4
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
14 parts of diethyl aluminum phosphinate (ADP) and 2 parts of organic silicon are applied to 43 parts of polyhexamethylene adipamide (PA 66 for short, Hill-Poulten-Beck, EPR27) to prepare the halogen-free flame-retardant glass fiber reinforced PA66 powder flame retardant.
Granulating in a twin-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of halogen-free flame-retardant glass fiber reinforced PA66 to be 250-265 ℃, adding 10 parts of nylon resin (PA6), 0.3 parts of antioxidant (608), 0.2 parts of antioxidant (1098) and 0.5 parts of lubricant (silicone powder) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber port, starting a host machine and a feeder, and finishing the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material was injected in an injection molding machine to form standard samples specified by various test standards, and the obtained halogen-free flame-retardant glass fiber reinforced PA66 has the properties shown in Table 1.
Example 1
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
13 parts of diethyl aluminum phosphinate (ADP), 2 parts of organic silicon and 1 part of silicate are applied to 43 parts of polyhexamethylene adipamide (PA 66 for short, Eper mesa, EPR27) to prepare the halogen-free flame-retardant glass fiber reinforced PA66 powder flame retardant.
Granulating in a twin-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of the halogen-free flame-retardant glass fiber reinforced PA66 to be 250-265 ℃, adding 10 parts of nylon resin (PA6), 0.3 part of antioxidant (608), 0.2 part of antioxidant (1098) and 0.5 part of lubricant (silicone powder) into a hopper, adding a powder flame retardant into a side feeder, adding 30 parts of Glass Fiber (GF) into the side feeder through a glass fiber port, and starting a host machine and the feeder to finish the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material was injected in an injection molding machine to form standard samples specified by various test standards, and the obtained halogen-free flame-retardant glass fiber reinforced PA66 has the properties shown in Table 1.
Example 2
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
13 parts of diethyl aluminum phosphinate (ADP), 1 part of organic silicon, 1 part of silicate and 1 part of zinc stannate are applied to 43 parts of polyhexamethylene adipamide (PA 66 for short, Hippon Mare, EPR27) to prepare the halogen-free flame-retardant glass fiber reinforced PA66 powder flame retardant.
Granulating in a twin-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of halogen-free flame-retardant glass fiber reinforced PA66 to be 250-265 ℃, adding 10 parts of nylon resin (PA6), 0.3 parts of antioxidant (608), 0.2 parts of antioxidant (1098) and 0.5 parts of lubricant (silicone powder) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber port, starting a host machine and a feeder, and finishing the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material was injected in an injection molding machine to form standard samples specified by various test standards, and the properties of the obtained halogen-free flame-retardant glass fiber reinforced PA66 are shown in Table 1.
Example 3
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
13 parts of diethyl aluminum phosphinate (ADP), 1 part of organic silicon, 1 part of silicate and 1 part of zinc borate are applied to 43 parts of polyhexamethylene adipamide (PA 66 for short, Hippon Mare, EPR27) to prepare the halogen-free flame-retardant glass fiber reinforced PA66 powder flame retardant.
Granulating in a twin-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of halogen-free flame-retardant glass fiber reinforced PA66 to be 250-265 ℃, adding 10 parts of nylon resin (PA6), 0.3 parts of antioxidant (608), 0.2 parts of antioxidant (1098) and 0.5 parts of lubricant (silicone powder) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber port, starting a host machine and a feeder, and finishing the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material was injected in an injection molding machine to form standard samples specified by various test standards, and the obtained halogen-free flame-retardant glass fiber reinforced PA66 has the properties shown in Table 1.
Example 4
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
13 parts of diethyl aluminum phosphinate (ADP), 1 part of organic silicon, 1 part of silicate and 1 part of zinc oxide are applied to 43 parts of polyhexamethylene adipamide (PA 66 for short, Hippon Mare, EPR27) to prepare the halogen-free flame-retardant glass fiber reinforced PA66 powder flame retardant.
Granulating in a twin-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of halogen-free flame-retardant glass fiber reinforced PA66 to be 250-265 ℃, adding 10 parts of nylon resin (PA6), 0.3 parts of antioxidant (608), 0.2 parts of antioxidant (1098) and 0.5 parts of lubricant (silicone powder) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber port, starting a host machine and a feeder, and finishing the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried materials are injected into an injection molding machine to form standard samples specified by various test standards, and the performance of the obtained halogen-free flame-retardant glass fiber reinforced PA66 is shown in Table 1:
TABLE 1
From comparative examples 1 to 3, it can be seen that the amount of MPP is reduced and migration and corrosion are reduced but flame retardancy is reduced, from comparative example 4, it can be seen that replacing MPP with a silicone flame retardant alone reduces migration and corrosion but flame retardancy is reduced, and from example 1, the silicone flame retardant is compounded with an inorganic silicone-based synergist, without migration and corrosion, and achieves a flame retardancy rating of UL 94V-0.
Comparative example 5
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
6 parts of MPP and 14 parts of Aluminum Diethylphosphinate (ADP) are applied to 49 parts of polybutylene terephthalate (PBT, KH2085 for short) to prepare the halogen-free flame-retardant glass fiber reinforced PBT powder flame retardant.
Granulating in a double-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of the halogen-free flame-retardant glass fiber reinforced PBT to be 215-235 ℃, adding 0.2 part of antioxidant (1010), 0.3 part of antioxidant (608) and 0.5 part of lubricant (PETS) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber opening, and starting a host machine and a feeder to finish the extrusion granulation of the material. Sieving and drying the granulated materials.
(2) Application and testing of materials
The dried material is injected into an injection molding machine to form standard samples specified by various test standards, and the performance of the obtained halogen-free flame-retardant glass fiber reinforced PBT is shown in Table 2.
Comparative example 6
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
Applying 7 parts of MCA and 13 parts of Aluminum Diethylphosphinate (ADP) to 49 parts of polybutylene terephthalate (PBT, KH2085 for short) to prepare the halogen-free flame-retardant glass fiber reinforced PBT powder flame retardant.
Granulating in a double-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of the halogen-free flame-retardant glass fiber reinforced PBT to be 215-235 ℃, adding 0.2 part of antioxidant (1010), 0.3 part of antioxidant (608) and 0.5 part of lubricant (PETS) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber opening, and starting a host machine and a feeder to finish the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material is injected into an injection molding machine to form standard samples specified by various test standards, and the performance of the obtained halogen-free flame-retardant glass fiber reinforced PBT is shown in Table 2.
Comparative example 7
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
20 parts of Aluminum Diethylphosphinate (ADP) is applied to 49 parts of polybutylene terephthalate (PBT, KH2085 for short) to prepare the halogen-free flame-retardant glass fiber reinforced PBT powder flame retardant.
Granulating in a double-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of the halogen-free flame-retardant glass fiber reinforced PBT to be 215-235 ℃, adding 0.2 part of antioxidant (1010), 0.3 part of antioxidant (608) and 0.5 part of lubricant (PETS) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber opening, and starting a host machine and a feeder to finish the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material is injected into an injection molding machine to form standard samples specified by various test standards, and the performance of the obtained halogen-free flame-retardant glass fiber reinforced PBT is shown in Table 2.
Comparative example 8
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
16 parts of diethyl aluminum phosphinate (ADP) and 2 parts of organic silicon are applied to 51 parts of polybutylene terephthalate (PBT, KH2085 for short) to prepare the halogen-free flame-retardant glass fiber reinforced PBT powder flame retardant.
Granulating in a double-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of the halogen-free flame-retardant glass fiber reinforced PBT to be 215-235 ℃, adding 0.2 part of antioxidant (1010), 0.3 part of antioxidant (608) and 0.5 part of lubricant (PETS) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber opening, and starting a host machine and a feeder to finish the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material is injected into an injection molding machine to form standard samples specified by various test standards, and the performance of the obtained halogen-free flame-retardant glass fiber reinforced PBT is shown in Table 2.
Example 5
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
15 parts of diethyl aluminum phosphinate (ADP), 2 parts of organic silicon and 1 part of silicate are applied to 51 parts of polybutylene terephthalate (PBT, KH2085 for short) to prepare the halogen-free flame-retardant glass fiber reinforced PBT powder flame retardant.
Granulating in a double-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of the halogen-free flame-retardant glass fiber reinforced PBT to be 215-235 ℃, adding 0.2 part of antioxidant (1010), 0.3 part of antioxidant (608) and 0.5 part of lubricant (PETS) from a hopper, adding a powder flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber opening, and starting a host machine and a feeder to finish the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried material is injected into an injection molding machine to form standard samples specified by various test standards, and the performance of the obtained halogen-free flame-retardant glass fiber reinforced PBT is shown in Table 2.
Example 6
The halogen-free flame retardant for thermoplastic polymers is prepared by the following method, which comprises the following steps:
(1) extrusion granulation of materials
16 parts of diethyl aluminum phosphinate (ADP), 1 part of organic silicon and 1 part of silicate are applied to 51 parts of polybutylene terephthalate (PBT, KH2085 for short) to prepare the halogen-free flame-retardant glass fiber reinforced PBT powder flame retardant.
Granulating in a double-screw extruder with phi 36 and a length-diameter ratio of 40, setting the temperature of the halogen-free flame-retardant glass fiber reinforced PBT to 215-235 ℃, adding 0.2 part of antioxidant (1010), 0.3 part of antioxidant (608) and 0.5 part of lubricant (PETS) from a hopper, adding the powdery flame retardant from a side feeder, adding 30 parts of glass fiber (glass fiber, GF) through a glass fiber port, and starting a host machine and a feeder to finish the extrusion granulation of the material. Sieving and drying the granulated material.
(2) Application and testing of materials
The dried materials are injected into an injection molding machine to form standard samples specified by various test standards, and the performances of the obtained halogen-free flame-retardant glass fiber reinforced PBT are shown in Table 2:
TABLE 2
From comparison of comparative example 5 and comparative example 6, it can be seen that the use of MCA instead of MPP reduces the migration and corrosion, but does not meet the requirements of no migration and no corrosion; as can be seen from comparative example 7, the absence of MCA and MPP reduces the migration and corrosion, but does not meet the requirements of no migration and no corrosion, and reduces the flame retardant rating; from the comparative example 8, the organosilicon is adopted to replace MCA or MPP, so that the requirements of no migration and no corrosion are met, but the flame retardant grade is reduced; as can be seen from example 5, the organosilicon flame retardant compounded with the inorganic silicon synergist has no migration and corrosion and reaches the flame retardant rating of UL 94V-0.
As can be seen from tables 1 and 2, the flame retardant effect of the synergistic ADP of the organosilicon is not good, the inorganic silicon synergist can meet the requirement of higher flame retardance after being compounded, and the halogen-free flame retardant prepared by the preparation method has the characteristics of high thermal stability, no migration, no corrosion to equipment and the like; the halogen-free flame-retardant polymer added with the flame retardant has wide processing window, can reach UL94V-0 flame retardant grade, and does not precipitate or corrode equipment.
As described above, according to the embodiments of the present invention, various changes and modifications can be made by those skilled in the art without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The halogen-free flame retardant for the thermoplastic polymer is characterized by comprising the following components in percentage by mass:
2. halogen-free flame retardant for thermoplastic polymers according to claim 1, characterized in that the organic phosphinate is one or a combination of several of aluminum dialkylphosphinate, zinc dialkylphosphinate, iron dialkylphosphinate and aluminum phenylphosphinate, preferably the organic phosphinate is aluminum diethylphosphinate.
3. Halogen-free flame retardant for thermoplastic polymers according to claim 1, characterized in that the average particle size D50 of the organic phosphinate is 10 μm < D50<50 μm.
4. The halogen-free flame retardant for thermoplastic polymers according to claim 1, wherein the silicone-based flame retardant is any one or a combination of polysiloxane, cage type silsesquioxane and hydroxyl silicone oil.
5. The halogen-free flame retardant for thermoplastic polymers as claimed in claim 4, wherein the silicone flame retardant is compounded by cage type silsesquioxane and hydroxyl silicone oil according to a mass ratio of (1-9): 1.
6. The halogen-free flame retardant for thermoplastic polymers as claimed in claim 5, wherein the organic silicon flame retardant is compounded by cage type silsesquioxane and hydroxyl silicone oil according to the mass ratio of 1: 1.
7. The halogen-free flame retardant for thermoplastic polymers according to claim 1, wherein the inorganic silicon synergist is one or a combination of several of phyllosilicate, nano-silica and low-melting glass powder; preferably, the inorganic silicon-based synergist is nano-silica.
8. The halogen-free flame retardant for thermoplastic polymers according to claim 1, wherein the zinc-containing heat-stabilizing compound comprises at least one of zinc borate, zinc oxide, zinc stannate; preferably, the zinc-containing heat stabilizing compound is zinc stannate.
9. Halogen-free flame retardant for thermoplastic polymers according to claim 8 characterized in that the average particle size D50 of the zinc containing heat stabilized compound satisfies 10 μ ι η < D50<50 μ ι η.
10. A method for preparing the halogen-free flame retardant for thermoplastic polymers according to any of claims 1 to 9, comprising:
weighing organic phosphinate, organic silicon flame retardant, inorganic silicon synergist and zinc-containing heat-stable compound according to the proportion, and uniformly mixing the materials by a high-speed mixer to obtain a powder flame retardant;
granulating by adopting a double-screw extruder: after the set temperature of each heating zone of the extruder is stable, adding resin, antioxidant and lubricant from a main feeding hopper, feeding powder flame retardant from a side feeding port, adding glass fiber from a glass fiber port, and obtaining the halogen-free flame retardant polymer after extrusion, granulation and drying.
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| WO2024187808A1 (en) * | 2023-03-16 | 2024-09-19 | 江苏利思德新材料股份有限公司 | Granular halogen-free flame retardant, preparation method therefor, and use thereof |
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