CN112223578A - Method for preparing high-toughness strontium ferrite/PPS injection molding granules through in-situ polymerization - Google Patents

Method for preparing high-toughness strontium ferrite/PPS injection molding granules through in-situ polymerization Download PDF

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CN112223578A
CN112223578A CN202011059855.3A CN202011059855A CN112223578A CN 112223578 A CN112223578 A CN 112223578A CN 202011059855 A CN202011059855 A CN 202011059855A CN 112223578 A CN112223578 A CN 112223578A
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magnetic powder
strontium ferrite
toughening agent
toughening
injection molding
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CN112223578B (en
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蔡伟
李荣耀
郑精武
乔梁
车声雷
应耀
李旺昌
余靓
陈海波
沈森琪
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Hangzhou Qianshi Technology Co ltd
Zhejiang University of Technology ZJUT
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Hangzhou Qianshi Technology Co ltd
Zhejiang University of Technology ZJUT
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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
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • 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
    • B29B9/12—Making granules characterised by structure or composition
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
    • H01F1/11—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
    • H01F1/113—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles in a bonding agent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing

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  • Power Engineering (AREA)
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  • Medicinal Chemistry (AREA)
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Abstract

The invention discloses a method for preparing high-toughness PPS-based strontium ferrite injection molding granules, which comprises the following steps: firstly, synthesizing a toughening agent by a hydrothermal method, adhering strontium ferrite to the surface of the toughening agent in an in-situ polymerization mode, centrifuging, washing and drying to obtain a toughening master batch; and secondly, mixing the toughening master batch obtained in the first step with strontium ferrite magnetic powder and a high-molecular adhesive, and then extruding and granulating the mixture by a double-screw extruder. The invention mixes the precursor of the synthetic toughening agent with the magnetic powder in the solvent in advance, obtains the toughening master batch through in-situ polymerization, and then mixes the toughening master batch with the rest magnetic powder and the macromolecular adhesive to extrude and granulate.

Description

Method for preparing high-toughness strontium ferrite/PPS injection molding granules through in-situ polymerization
Technical Field
The invention belongs to the field of bonded permanent magnet materials, and particularly relates to a high-toughness strontium ferrite injection molding granule and a preparation method thereof.
Background
With the continuous progress of technology, industries such as instruments, household appliances, electronic information, and automobile industries, and electronic components required for the industries, are all being developed in the direction of light weight, precision, miniaturization, low cost, high performance, and low power consumption. The strontium ferrite has a series of advantages of low price of raw materials, excellent oxidation resistance, higher coercive force and magnetic energy product, uniaxial magnetocrystalline anisotropy and the like, and is widely applied to industries such as automobiles, electronics, microwaves, magneto-optical and the like.
Compared with sintered magnets, the injection molding bonded magnet can be molded at one time, products with complex shapes and without subsequent processing can be produced, due to the fact that the bonded magnet added with the binder has certain plasticity, the processing of the products is simple due to the improvement of the fluidity, the production and assembly cost is low, and the large-scale automatic production in factories can be achieved. At present, the strontium ferrite permanent magnetic material is widely prepared industrially by an injection molding method, i.e. strontium ferrite magnetic powder, a high molecular binder and other additives are mixed and granulated according to a certain proportion, and then the prepared granules are directly prepared into a magnetic device by an injection molding machine under a proper process.
Polyphenylene Sulfide (PPS) is a thermoplastic engineering plastic with excellent comprehensive performance, so that a strontium ferrite magnet using the polyphenylene sulfide as a polymer binder has the advantages of outstanding thermal stability, excellent chemical stability, creep resistance, rigidity, electric insulation, processing formability and the like. In some previous patents, for example, CN102504534A directly blends unmodified PPS with magnetic powder, and the obtained composite material often has the disadvantages of large brittleness and poor impact resistance, and cannot meet the requirements of high-performance products.
The mechanical property of PPS can be obviously improved by adding the toughening agent, but if the magnetic powder, the adhesive and the toughening agent are simply mixed and extruded for granulation, the distribution of the magnetic powder in two phases is very uneven, and if the magnetic powder is only distributed in the PPS phase, the proportion of the magnetic powder to effectively bond resin is reduced, which inevitably affects the property of the composite material. In patent CN105885415, a toughening agent, a lubricant and a polymer binder are mixed and granulated in advance by a two-step method, so that the toughness of the composite magnet is improved to a certain extent, but there is a great room for improvement.
If the magnetic powder and the toughening agent are simply mixed by a double-screw extruder and the like, the problem that the magnetic powder is difficult to uniformly disperse exists in the mixing process under the condition that the filling proportion of the magnetic powder is high (such as 83-88%), and the processability and mechanical index of the obtained toughening master batch are poor.
The maximum magnetic energy product of the ferrite/PPS composite material on the market is 14.3KJ/m3The following. In addition, when the magnetic energy product reaches 14KJ/m3The mechanical impact property is 7KJ/m at left and right levels2The following. The magnetic property is too low to meet the requirements of high power or miniaturization, and the product cracking and the like can be caused due to low mechanics.
The invention mixes the magnetic powder and the toughening agent in advance in a mode of in-situ polymerization to obtain toughening master batch, and then mixes the toughening master batch, the magnetic powder and the adhesiveThe PPS/strontium ferrite magnetic composite material is prepared by extrusion granulation, and the preparation method of two-step granulation ensures that the magnetic powder can be uniformly distributed in the PPS and the toughening agent, improves the interface combination effect of two phases, and the magnetic powder can effectively transfer and disperse stress under the condition of uniform distribution as a disperse phase, and finally obtains the composite plastic magnetic granules with excellent performance (the maximum magnetic energy product is 15.52 KJ/m)3Meanwhile, the mechanical impact property is 8.77KJ/m2)。
Disclosure of Invention
The invention aims to mix magnetic powder and a toughening agent in advance, and enables the magnetic powder to be uniformly distributed in a PPS matrix phase and a modified toughening agent simultaneously through a preparation mode of step-by-step mixing and two-step granulation, and provides a PPS-based strontium ferrite injection molding granule material with high toughness and a preparation method of the granule.
The technical scheme for solving the problems comprises the following steps: a preparation method of in-situ polymerization high-toughness strontium ferrite injection molding granules comprises the following steps:
(1) adding strontium ferrite magnetic powder into a toughening agent precursor solution, adding a dispersing agent and an initiator, and hydrothermally synthesizing a triblock toughening agent, wherein the strontium ferrite magnetic powder is deposited on the surface of the toughening agent in situ, the mass fraction of the strontium ferrite magnetic powder is a, and the value range of a is 83-88%. (ii) a
(2) Mixing strontium ferrite magnetic powder with a high-molecular adhesive and the toughening agent synthesized in situ in the step (1), and extruding and granulating by a double-screw extruder to obtain high-toughness strontium ferrite/PPS injection molding granules; the mass fraction of the strontium ferrite magnetic powder in the granules is a, the mass fraction of the high molecular adhesive is b, the value range of b is 10.8-15.3%, and the balance is the toughening agent; the screw rotation speed is 150rad/min, the feeder rotation speed is 14rad/min, and the temperature of each barrel is 265-.
In some embodiments, the polymer binder is polyphenylene sulfide (PPS), but is not limited thereto.
The toughening agent precursor comprises ethylene, methyl acrylate and glycidyl methacrylate. The strontium ferrite magnetic powder does not participate in chemical reaction in a polymerization system, so that whether the strontium ferrite magnetic powder is added into the precursor solution or not does not influence the parameters of component proportion, reaction temperature, reaction time and the like of copolymerization reaction.
In some preferred embodiments, the magnetic powder is strontium ferrite magnetic powder treated by a surface treatment agent, and has a plurality of active sites, so that the strontium ferrite magnetic powder can be effectively connected with other components. The surface treatment agent may be a chelate type titanate coupling agent or the like, but is not limited thereto.
Compared with the conventional mixing method, the PPS-based/strontium ferrite granules prepared by step-by-step material mixing and two-step granulation have the following benefits:
according to the invention, the E-MA-GMA is used as a toughening agent to modify a strontium ferrite/PPS system, the step-by-step mixing and two-step granulation methods do not change the proportion of strontium ferrite magnetic powder, the density of the obtained granules is not changed, the flowability of the granules is improved under the condition of high powder filling, and the magnetic performance corresponding to the granules is improved. In addition, because the magnetic powder and the toughening agent are mixed in advance, the magnetic powder can be better distributed in the PPS phase and the toughening agent phase at the same time, and the magnetic powder is uniformly dispersed in the PPS and the toughening agent as a dispersion phase, so that the stress can be effectively transferred and dispersed, and after the mixing mode is changed, the magnetic powder is simultaneously distributed in the two phases to improve the interface bonding effect of the elastomer phase and the PPS phase, so that the toughness of the material is improved to a certain extent.
Drawings
FIG. 1a is a microscopic surface topography of a standard spline section in a conventional mixing manner; FIG. 1b is a microscopic surface topography of a standard sample strip cross section in a manner of mixing the magnetic powder toughening agent in advance;
FIG. 2 is a flow chart of a step-by-step mixing and two-step granulating and mixing process.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
In order to achieve the single-factor comparison effect, 1) the strontium ferrite magnetic powder used in the following examples and comparative examples is the magnetic powder treated by the same method, and the surface treatment method is as follows:
firstly, dissolving chelate titanate coupling agent ethylene glycol dititanate (KR-212S) in acetone to prepare a dilute solution, adding strontium ferrite magnetic powder into a reaction kettle, stirring and dispersing, taking out and drying the magnetic powder for later use.
2) In the following examples and comparative examples, the monomers in the monomer solution of the toughening agent are ethylene, methyl acrylate, and glycidyl methacrylate, the dispersing agent is hydroxypropyl methylcellulose, and the initiator is benzoyl peroxide, and the mass ratios are as follows: 88:6.8:5.2, reaction temperature of 90 and reaction time of 7 h.
In the examples and comparative examples of the present invention, the surface treatment method of the strontium ferrite magnetic powder, the polymerization method of the toughening agent, and the selection of the polymer binder are merely the same examples used for comparison, and those skilled in the art can adopt other surface treatment methods without any doubt, so that the surface of the strontium ferrite magnetic powder has more active sites, and adopt other monomers and auxiliaries, and adaptively adjust the polymerization ratio and reaction conditions, so as to obtain the triblock toughening agent.
Example 1
The granular material comprises the following components in percentage by mass:
strontium ferrite magnetic powder 830g
Polyphenylene sulfide 153g
Modified toughening agent 17g
According to the formula, 83g of strontium ferrite magnetic powder is added into a monomer solution containing a synthetic toughening agent, the toughening agent is hydrothermally synthesized under the action of an initiator, the magnetic powder is adhered to the surface of the toughening agent in an in-situ polymerization mode, and an obtained sample is centrifuged, washed and dried to obtain a toughening master batch; the mass ratio of the finally obtained toughened master batch magnetic powder to the toughening agent is 83: 17;
747g of strontium ferrite magnetic powder, 153g of polyphenylene sulfide and 100g of toughening master batch are uniformly mixed, and then are extruded and granulated by a double-screw extruder to obtain magnetic granules, wherein the rotating speed of the screw is 150rad/min, the rotating speed of the feeding machine is 10rad/s, and the temperature of each heating section of the double-screw extruder is 260 ℃, 295 and 295 ℃ from a feeding hole to a discharging hole.
And (3) preparing the finally prepared granules into standard test samples by an injection molding machine, wherein the temperature of each heating section of the injection molding machine is 270 ℃, 270 ℃ and 310 ℃ from a feed inlet to a discharge outlet in sequence. The performance test is carried out according to the standards of GB/T1043.1-2008, GB/T9341-2008, GB/T3217-2013 and the like, and the results are shown in the following table 1.
Comparative example 1:
the granular material comprises the following components in percentage by mass:
strontium ferrite magnetic powder 830g
Polyphenylene sulfide 153g
Modified toughening agent 17g
Hydrothermally synthesizing a toughening agent in a monomer solution of the toughening agent under the action of an initiator;
according to the formula, 830g of strontium ferrite magnetic powder, 153g of polyphenylene sulfide and 17g of synthetic toughening agent are directly mixed together, and are extruded and granulated through a double-screw extruder to obtain magnetic granules, wherein the rotating speed of the screw is 150rad/min, the rotating speed of the feeder is 10rad/s, and the temperature of each heating section of the double-screw extruder is 260 ℃, 295 and 295 ℃ from a feeding hole to a discharging hole in sequence.
And (3) preparing the finally prepared granules into standard test samples by an injection molding machine, wherein the temperature of each heating section of the injection molding machine is 270 ℃, 270 ℃ and 310 ℃ from a feed inlet to a discharge outlet in sequence. The performance test is carried out according to the standards of GB/T1043.1-2008, GB/T9341-2008, GB/T3217-2013 and the like, and the results are shown in the following table 1.
Comparing the sectional scanning electron microscope images of the samples in the embodiment 1 and the comparative example 1, the magnetic powder in the two samples is coated by the PPS well, and the difference is that the form of the elastomer is slightly changed, and the elastomer in the sample in the common mixing mode shown in the figure 1 is elliptical, the interface with the PPS is clear, and a certain gap exists. In the sample obtained by changing the mixing mode as shown in fig. 2, the elastomer has large deformation and is tightly combined with the PPS matrix, and the surface is rough, so that magnetic powder is distributed in the elastomer phase. The magnetic powder is simultaneously distributed in the two phases, so that the interface bonding effect of the elastomer phase and the PPS phase is improved to a certain extent, and the toughness of the composite material is obviously improved.
Example 2
The granular material comprises the following components in percentage by mass:
strontium ferrite magnetic powder 840g
Polyphenylene sulfide 144g
Modified toughening agent 16g
According to the formula, firstly, 84g of strontium ferrite magnetic powder is added into a monomer solvent containing a synthetic toughening agent, the toughening agent is hydrothermally synthesized under the action of an initiator, the magnetic powder is adhered to the surface of the toughening agent in an in-situ polymerization mode, and an obtained sample is centrifuged, washed and dried to obtain a toughening master batch; the mass ratio of the finally obtained toughened master batch magnetic powder to the toughening agent is 84: 16;
756g of strontium ferrite magnetic powder, 144g of polyphenylene sulfide and 100g of toughening master batch are uniformly mixed, and then are extruded and granulated by a double-screw extruder to obtain magnetic granules, wherein the rotating speed of the screw is 150rad/min, the rotating speed of the feeding machine is 10rad/s, and the temperature of each heating section of the double-screw extruder is 260 ℃, 295 and 295 ℃ from a feeding hole to a discharging hole.
And (3) preparing the finally prepared granules into standard test samples by an injection molding machine, wherein the temperature of each heating section of the injection molding machine is 270 ℃, 270 ℃ and 310 ℃ from a feed inlet to a discharge outlet in sequence. The performance test is carried out according to the standards of GB/T1043.1-2008, GB/T9341-2008, GB/T3217-2013 and the like, and the results are shown in the following table 1.
Comparative example 2:
the granular material comprises the following components in percentage by mass:
strontium ferrite magnetic powder 840g
Polyphenylene sulfide 144g
Modified toughening agent 16g
Hydrothermally synthesizing a toughening agent in a monomer solution of the toughening agent under the action of an initiator;
according to the formula, 840g of strontium ferrite magnetic powder, 144g of polyphenylene sulfide and 16g of synthesized E-MA-GMA are directly mixed, and are extruded and granulated through a double-screw extruder to obtain magnetic granules, wherein the rotating speed of the screw is 150rad/min, the rotating speed of the feeder is 10rad/s, and the temperature of each heating section of the double-screw extruder is 260 ℃, 295 and 295 ℃ from a feeding hole to a discharging hole.
And (3) preparing the finally prepared granules into standard test samples by an injection molding machine, wherein the temperature of each heating section of the injection molding machine is 270 ℃, 270 ℃ and 310 ℃ from a feed inlet to a discharge outlet in sequence. The performance test is carried out according to the standards of GB/T1043.1-2008, GB/T9341-2008, GB/T3217-2013 and the like, and the results are shown in the following table 1.
Example 3
The granular material comprises the following components in percentage by mass:
strontium ferrite magnetic powder 880g
Polyphenylene sulfide 108g
12g of modified toughening agent
According to the formula, firstly, 88g of strontium ferrite magnetic powder is added into a monomer solvent containing a synthetic toughening agent, the toughening agent is hydrothermally synthesized under the action of an initiator, the magnetic powder is adhered to the surface of the toughening agent in an in-situ polymerization mode, and an obtained sample is centrifuged, washed and dried to obtain a toughening master batch; the mass ratio of the toughened master batch magnetic powder to the toughening agent which is finally obtained is 88: 12;
792g of strontium ferrite magnetic powder, 108g of polyphenylene sulfide and 100g of toughening master batch are uniformly mixed, and then are extruded and granulated through a double-screw extruder to obtain magnetic granules, wherein the rotating speed of the screw is 150rad/min, the rotating speed of the feeding machine is 10rad/s, and the temperature of each heating section of the double-screw extruder is 260 ℃, 295 and 295 ℃ from a feeding hole to a discharging hole.
And (3) preparing the finally prepared granules into standard test samples by an injection molding machine, wherein the temperature of each heating section of the injection molding machine is 270 ℃, 270 ℃ and 310 ℃ from a feed inlet to a discharge outlet in sequence. The performance test is carried out according to the standards of GB/T1043.1-2008, GB/T9341-2008, GB/T3217-2013 and the like, and the results are shown in the following table 1.
Comparative example 3:
the granular material comprises the following components in percentage by mass:
strontium ferrite magnetic powder 880g
Polyphenylene sulfide 108g
12g of modified toughening agent
Hydrothermally synthesizing a toughening agent in a monomer solution of the toughening agent under the action of an initiator;
according to the formula, 880g of strontium ferrite magnetic powder, 108g of polyphenylene sulfide and 12g of synthesized E-MA-GMA are directly mixed, and are extruded and granulated through a double-screw extruder to obtain magnetic granules, wherein the rotating speed of the screw is 150rad/min, the rotating speed of the feeder is 10rad/s, and the temperature of each heating section of the double-screw extruder is 260 ℃, 295 and 295 ℃ from a feeding hole to a discharging hole.
And (3) preparing the finally prepared granules into standard test samples by an injection molding machine, wherein the temperature of each heating section of the injection molding machine is 270 ℃, 270 ℃ and 310 ℃ from a feed inlet to a discharge outlet in sequence. The performance test is carried out according to the standards of GB/T1043.1-2008, GB/T9341-2008, GB/T3217-2013 and the like, and the results are shown in the following table 1.
Comparative example 4
The granular material comprises the following components in percentage by mass:
strontium ferrite magnetic powder 880g
Polyphenylene sulfide 108g
12g of modified toughening agent
Although granulation was also carried out by the two-stage process, unlike example 1, the toughening masterbatch was prepared in a higher proportion of powder than the final pellet. Firstly, 108g of strontium ferrite magnetic powder is added into a monomer solvent containing a synthetic toughening agent, the toughening agent is hydrothermally synthesized under the action of an initiator, the magnetic powder is adhered to the surface of the toughening agent in an in-situ polymerization mode, and an obtained sample is centrifuged, washed and dried to obtain a toughening master batch; the mass ratio of the finally obtained toughening master batch magnetic powder to the toughening agent is 108: 12;
772g of strontium ferrite magnetic powder, 108g of polyphenylene sulfide and 120g of toughening master batch are uniformly mixed, and then are extruded and granulated by a double-screw extruder to obtain magnetic granules, wherein the rotating speed of the screw is 150rad/min, the rotating speed of the feeding machine is 10rad/s, and the temperature of each heating section of the double-screw extruder is 260 ℃, 295 and 295 ℃ from a feeding hole to a discharging hole.
And (3) preparing the finally prepared granules into standard test samples by an injection molding machine, wherein the temperature of each heating section of the injection molding machine is 270 ℃, 270 ℃ and 310 ℃ from a feed inlet to a discharge outlet in sequence. The performance test is carried out according to the standards of GB/T1043.1-2008, GB/T9341-2008, GB/T3217-2013 and the like, and the results are shown in the following table 1.
Comparative example 5
The granular material comprises the following components in percentage by mass:
strontium ferrite magnetic powder 880g
Polyphenylene sulfide 108g
12g of modified toughening agent
Although granulation was also carried out by the two-stage process, unlike example 1, the proportion of powder in the preparation of the toughening masterbatch was lower than the proportion of powder in the granules finally obtained. Specifically, firstly, 36g of strontium ferrite magnetic powder is added into a monomer solvent containing a synthetic toughening agent, the toughening agent is hydrothermally synthesized under the action of an initiator, the magnetic powder is adhered to the surface of the toughening agent in an in-situ polymerization mode, and an obtained sample is centrifuged, washed and dried to obtain a toughening master batch; the mass ratio of the finally obtained toughened master batch magnetic powder to the toughening agent is 36: 12;
844g of strontium ferrite magnetic powder, 108g of polyphenylene sulfide and 48g of toughening master batch are uniformly mixed, and then are extruded and granulated by a double-screw extruder to obtain magnetic granules, wherein the rotating speed of the screw is 150rad/min, the rotating speed of the feeding machine is 10rad/s, and the temperature of each heating section of the double-screw extruder is 260 ℃, 295 and 295 ℃ from a feeding hole to a discharging hole.
And (3) preparing the finally prepared granules into standard test samples by an injection molding machine, wherein the temperature of each heating section of the injection molding machine is 270 ℃, 270 ℃ and 310 ℃ from a feed inlet to a discharge outlet in sequence. The performance test is carried out according to the standards of GB/T1043.1-2008, GB/T9341-2008, GB/T3217-2013 and the like, and the results are shown in the following table 1.
Comparative example 6
The granular material comprises the following components in percentage by mass:
strontium ferrite magnetic powder 880g
Polyphenylene sulfide 108g
12g of modified toughening agent
Although granulation was also carried out by the two-stage process, unlike example 1, the proportion of powder in the preparation of the toughening masterbatch was lower than the proportion of powder in the granules finally obtained. Firstly, adding 5g of strontium ferrite magnetic powder into a monomer solvent containing a synthetic toughening agent, hydrothermally synthesizing the toughening agent under the action of an initiator, adhering the magnetic powder to the surface of the toughening agent in an in-situ polymerization mode, centrifuging, washing and drying an obtained sample to obtain a toughening master batch; the mass ratio of the finally obtained toughening master batch magnetic powder to the toughening agent is 5: 12;
and after 875g of strontium ferrite magnetic powder, 108g of polyphenylene sulfide and 17g of toughening master batch are uniformly mixed, extruding and granulating by a double-screw extruder to obtain magnetic granules, wherein the rotating speed of the screw is 150rad/min, the rotating speed of the feeder is 10rad/s, and the temperature of each heating section of the double-screw extruder is 260 ℃, 295 and 295 ℃ from a feeding hole to a discharging hole in sequence.
And (3) preparing the finally prepared granules into standard test samples by an injection molding machine, wherein the temperature of each heating section of the injection molding machine is 270 ℃, 270 ℃ and 310 ℃ from a feed inlet to a discharge outlet in sequence. The performance test is carried out according to the standards of GB/T1043.1-2008, GB/T9341-2008, GB/T3217-2013 and the like, and the results are shown in the following table 1.
Comparative example 7:
the granular material comprises the following components in percentage by mass:
strontium ferrite magnetic powder 880g
Polyphenylene sulfide 108g
Toughening agent 12g
Hydrothermally synthesizing a toughening agent in a monomer solution of the toughening agent under the action of an initiator;
according to the formula, firstly, 88g of strontium ferrite magnetic powder and 12g of E-MA-GMA are mixed, and then the mixture is extruded and granulated by a double-screw extruder to obtain toughening master batch; the rotating speed of the screw is 150rad/min, the rotating speed of the feeder is 14rad/min, and the temperature of each heating section of the double-screw extruder is 180 ℃, 225 ℃ and 225 ℃ from the feed inlet to the discharge outlet in sequence.
792g of strontium ferrite magnetic powder, 108g of polyphenylene sulfide and 100g of toughening master batch are uniformly mixed, and then are extruded and granulated through a double-screw extruder to obtain magnetic granules, wherein the rotating speed of the screw is 150rad/min, the rotating speed of the feeding machine is 10rad/s, and the temperature of each heating section of the double-screw extruder is 260 ℃, 295 and 295 ℃ from a feeding hole to a discharging hole.
And (3) preparing the finally prepared granules into standard test samples by an injection molding machine, wherein the temperature of each heating section of the injection molding machine is 270 ℃, 270 ℃ and 310 ℃ from a feed inlet to a discharge outlet in sequence. The performance test is carried out according to the standards of GB/T1043.1-2008, GB/T9341-2008, GB/T3217-2013 and the like, and the results are shown in the following table 1.
Table 1 components and test results in each example
Figure BDA0002711987820000081
Figure BDA0002711987820000091
The experimental results show that the magnetic performance of the composite magnet is improved along with the increase of the content of the magnetic powder, but the mechanical property is continuously reduced, and the mechanical property and the magnetic property of the composite magnet can not be improved simultaneously by simply changing the proportion of the powder. The mechanical property of the composite material can be improved by using the modified toughening agent under the condition of not changing the proportion of the magnetic powder, but the performance improvement of the material is not very obvious under the condition of conventional mixing, and the addition of the toughening agent also relates to the problems of uniform distribution of the magnetic powder in two phases and the compatibility of an interface between the two phases.
From the experimental results, the same magnetic powder ratio is observed, and the mechanical properties, especially the impact strength and the bending strain, of the examples 1,2 and 3 are obviously improved compared with the comparative examples 1,2 and 3, because the two-step granulation mode of mixing the magnetic powder with the toughening agent in advance solves the problems of uneven distribution of the magnetic powder in the toughening agent phase and the adhesive phase and poor bonding effect of the interface of the toughening agent phase and the adhesive phase.
In addition, under the condition of low powder filling (examples 1 and 2 and comparative examples 1 and 2), the influence of two different mixing modes on the flowability of the granules is small, the magnetic performance is basically not changed, but under the condition of high powder filling (example 3 and comparative example 3), the flowability of the granules is greatly reduced, but the flowability of a two-step method is superior to that of a one-step method, the requirements of subsequent injection molding and orientation can be met, and the magnetic performance is improved compared with that of the one-step method.
From the results of example 3 and comparative examples 4, 5 and 6, it is seen that the properties of the composite material are best when the powder ratio in the toughening masterbatch is consistent with the powder ratio in the final granules. When the proportion of the magnetic powder is higher or lower than that of the final granular material magnetic powder during preparation of the toughening master batch, the performance of the composite material is reduced, although the two-step method is adopted, the distribution uniformity of the granular material magnetic powder obtained according to different proportions is different from that of the granular material prepared according to the same proportion, and the magnetic powder is excessively distributed in a toughening agent phase, so that the toughening agent and PPS are prevented from acting, and the toughening effect of the toughening agent on PPS is reduced; the magnetic powder is excessively distributed in the PPS phase, so that the flowability of the granular material is reduced, the actual integral magnetic powder proportion is unchanged, and the magnetic performance is reduced.
From the results of example 3 and comparative example 7, the mixing method of in-situ polymerization in the hydrothermal process is better than the mixing method of a twin-screw extruder, and particularly, under the condition that the filling proportion of the magnetic powder is higher (88%), compared with the solid-melt mixing method of an extruder, the magnetic powder in the solution can achieve better dispersion effect, and the finally obtained magnet has better performance.
It should be noted that the components of the granule and the above examples are not intended to limit the present invention, and the present invention is not limited to the above examples, and all the components are within the scope of the present invention as long as the requirements of the present invention are met.

Claims (4)

1. A method for preparing high-toughness strontium ferrite/PPS injection molding granules by in-situ polymerization is characterized by comprising the following steps:
(1) adding strontium ferrite magnetic powder into a toughening agent precursor solution, adding a dispersing agent and an initiator, and hydrothermally synthesizing a triblock toughening agent, wherein the strontium ferrite magnetic powder is deposited on the surface of the toughening agent in situ, the mass fraction of the strontium ferrite magnetic powder is a, and the value range of a is 83-88%;
(2) mixing strontium ferrite magnetic powder with a high-molecular adhesive and the toughening agent synthesized in situ in the step (1), and extruding and granulating by a double-screw extruder to obtain high-toughness strontium ferrite/PPS injection molding granules; the mass fraction of the strontium ferrite magnetic powder in the granules is a, the mass fraction of the high molecular adhesive is b, the value range of b is 10.8-15.3%, and the balance is the toughening agent; the screw rotation speed is 150rad/min, the feeder rotation speed is 14rad/min, and the temperature of each barrel is 265-.
2. The method for preparing high-toughness strontium ferrite injection-molded particles according to claim 1, wherein the polymer binder is polyphenylene sulfide (PPS).
3. The method for preparing the high-toughness strontium ferrite injection-molded particle material according to claim 1, wherein the toughening agent precursor comprises ethylene, methyl acrylate and glycidyl methacrylate.
4. The method for preparing high-toughness strontium ferrite injection molding particles according to claim 1, wherein the magnetic powder is strontium ferrite magnetic powder treated by a surface treatment agent.
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CN115160784A (en) * 2022-08-12 2022-10-11 山东产研明泉新材料研究院有限公司 Preparation method of in-situ polymerized high-toughness samarium-iron-nitrogen injection molded granules

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CN1770337A (en) * 2005-09-16 2006-05-10 华南理工大学 Method for preparing bonded permanent ferrite by direct injection forming after in-situ polymerization
CN111378282A (en) * 2019-12-09 2020-07-07 赣州能之光新材料有限公司 PPS-based permanent magnet composite material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN1770337A (en) * 2005-09-16 2006-05-10 华南理工大学 Method for preparing bonded permanent ferrite by direct injection forming after in-situ polymerization
CN111378282A (en) * 2019-12-09 2020-07-07 赣州能之光新材料有限公司 PPS-based permanent magnet composite material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115160784A (en) * 2022-08-12 2022-10-11 山东产研明泉新材料研究院有限公司 Preparation method of in-situ polymerized high-toughness samarium-iron-nitrogen injection molded granules

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