CN105348789A - Magnetic nylon composite and preparation method thereof - Google Patents
Magnetic nylon composite and preparation method thereof Download PDFInfo
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- CN105348789A CN105348789A CN201510909663.XA CN201510909663A CN105348789A CN 105348789 A CN105348789 A CN 105348789A CN 201510909663 A CN201510909663 A CN 201510909663A CN 105348789 A CN105348789 A CN 105348789A
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- coupling agent
- magneticsubstance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Developing Agents For Electrophotography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a magnetic nylon composite which is prepared from, 70 wt%-90 wt% of a magnetic material, 5wt%-15 wt% of nylon, 3 wt%-7 wt% of compatilizer and 0.5 wt%-1.5 wt% of an auxiliary; the total amount of all the components is 100%; the magnetic material is a magnetic material which is modified by a coupling agent and isobornyl methacrylate sequentially; the coupling agent is a composite coupling agent of a silane coupling agent and a titanate ester coupling agent. According to the magnetic nylon composite and the preparation method thereof, the composite coupling agent of the silane coupling agent and the titanate ester coupling agent and the isobornyl methacrylate are sequentially adopted to conduct modification treatment on the magnetic material, dispersibility of the magnetic material is promoted, the compatibility with the nylon material of the magnetic material is greatly improved, quite good dispersibility is achieved in the mixing process with the nylon material, and the prepared nylon material has magnetism and meanwhile obtains an excellent mechanical property.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of Magnetic nylon composite material and preparation method thereof.
Background technology
Magnetic product is of a great variety, is widely used, and play an important role in military equipment electronization and Hi-tech Industry Development, magnetic functional composite material is only one of them branch.Magnetic functional composite material is generally filled by powdered material and is formed, and volume content is 2 ~ 98%, and matrix can be metal, glass, polymkeric substance etc.Magnetic energy can be converted into mechanical energy by magnetic functional composite material, can be also magnetic energy by changes mechanical energy.From magnetic functional composite material composition, it is a kind of functional type material between macromolecular material and magneticsubstance, for this kind of material research we be referred to as boundary science or interdisciplinary science.
Magnetic functional composite material is a kind of novel high polymer functional materials that 20 century 70s grow up, and is one of the important foundation material in modern science and technology field.Magnetic functional composite material can be divided into structure-type and compound two kinds by composition, and structure-type magnetic functional composite material refers to that polymkeric substance itself has ferromagnetic magnet; Composite magnetic functional composite material refers to be processed and the magnet made for tackiness agent mixes to bond with magnetic powder with rubber or plastics.
The major advantage of magnetic functional composite material is: density is little, impact strength is large, the processing such as goods can carry out cutting, hole, weld, lamination and embossing, and can not be chipping when using.It can adopt the general working method of general plastics (as injection, mold pressing, extruding) to process, be easy to be processed into that dimensional precision is high, the goods of thin-walled, complicated shape, plastic band inserts goods, to electromagnetic equipment realize miniaturization, lightweight, precise treatment and high performance target play a part key, thus getting more and more as people are paid attention to, is a kind of up-and-coming basic function material.
But in rubber or plastic material, be mixed into magneticsubstance can affect the mechanical properties, the composite materials property of final preparation is poor, and this have impact on its market application foreground greatly.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of Magnetic nylon composite material and preparation method thereof, and the nylon composite materials of preparation has better mechanical property.
The invention provides a kind of Magnetic nylon composite material, comprising:
Each component total amount is 100%;
Described magneticsubstance is successively through the magneticsubstance of coupling agent, isobornyl methacrylate modification;
Described coupling agent is the composite coupler of silane coupling agent and titanate coupling agent.
Preferably, described magneticsubstance is strontium ferrite magnetic powder.
Preferably, described compatilizer is maleic anhydride graft POE.
Preferably, described auxiliary agent comprises:
Oxidation inhibitor 0.2wt% ~ 0.4wt%;
Lubricant 0.3wt% ~ 0.5wt%;
Coupling agent 0.2wt% ~ 0.4wt%;
Described oxidation inhibitor, lubricant, coupling agent total amount are 0.5wt% ~ 1.5wt%;
Described oxidation inhibitor is antioxidant 1010 or irgasfos 168, and described lubricant is N, N '-ethylene bis stearamide or copper silicon powder, and described coupling agent is the composite coupler of silane coupling agent and titanate coupling agent.
Preferably, described matrix material comprises:
Preferably, described matrix material also comprises:
The silicon nitrogen combustion inhibitor of 6wt% ~ 10wt%.
Preferably, described matrix material comprises:
Present invention also offers a kind of preparation method of above-mentioned nylon composite materials, comprising:
A) adopt the composite coupler of silane coupling agent and titanate coupling agent successively, isobornyl methacrylate carries out modification to magneticsubstance;
B) by proportioning, each raw material is mixed with modified magneticsubstance, mixing, extruding pelletization obtains nylon composite materials.
Preferably, described steps A) be specially:
A) magneticsubstance is dried 4 ~ 6h at 110 ~ 130 DEG C;
B) magneticsubstance after oven dry is added while stirring the composite coupler of silane coupling agent and titanate coupling agent successively, isobornyl methacrylate carries out modification.
Preferably, described step B) condition of extruding pelletization is:
Screw speed 340 turns/min, feeding rotating speed 350 turns/min, blank speed 450 turns/min.
Compared with prior art, the invention provides a kind of Magnetic nylon composite material, comprising: magneticsubstance 70wt% ~ 90wt%; Nylon 5wt% ~ 15wt%; Compatilizer 3wt% ~ 7wt%; Auxiliary agent 0.5wt% ~ 1.5wt%; Each component total amount is 100%; Described magneticsubstance is successively through the magneticsubstance of coupling agent, isobornyl methacrylate modification; Described coupling agent is the composite coupler of silane coupling agent and titanate coupling agent.The present invention adopts the composite coupler of silane coupling agent and titanate coupling agent successively, isobornyl methacrylate carries out modification to magneticsubstance, facilitate the dispersiveness of magneticsubstance, substantially increase the consistency of itself and nylon material, with nylon material mixing process, there is good dispersiveness, the nylon material of preparation, tool is magnetic while, have also obtained excellent mechanical property.
Embodiment
The invention provides a kind of Magnetic nylon composite material, comprising:
Each component total amount is 100%;
Described magneticsubstance is successively through the magneticsubstance of coupling agent, isobornyl methacrylate modification;
Described coupling agent is the composite coupler of silane coupling agent and titanate coupling agent.
The present invention adopts the composite coupler of silane coupling agent and titanate coupling agent successively, isobornyl methacrylate carries out modification to magneticsubstance, facilitate the dispersiveness of magneticsubstance, substantially increase the consistency of itself and nylon material, with nylon material mixing process, there is good dispersiveness, the nylon material of preparation, tool is magnetic while, have also obtained excellent mechanical property.
Magnetic nylon composite material provided by the invention comprises magneticsubstance, nylon, compatilizer and auxiliary agent.
Wherein, described magneticsubstance is successively through the magneticsubstance of coupling agent, isobornyl methacrylate (IBO) modification.
Described coupling agent is directly mix by silane coupling agent and titanate coupling agent the composite coupler produced.
The mass ratio of described silane coupling agent and titanate coupling agent is preferably 4:(5 ~ 7), in some embodiments of the invention, described ratio is 4:6.
The content of described magneticsubstance is 70wt% ~ 90wt%, and be preferably 78wt% ~ 87wt%, in some embodiments of the invention, its content is 87wt%.
In the present invention, described magneticsubstance is preferably magnetic, is more preferably strontium ferrite magnetic powder.The particle diameter of described magnetic is preferably 2000 ~ 3000 orders, is more preferably 2200 orders.
The present invention adopts the composite coupler of silane coupling agent and titanate coupling agent, isobornyl methacrylate carries out modification to magneticsubstance successively, facilitate the dispersiveness of magneticsubstance, and add the consistency of itself and nylon material, after nylon material compound, improve mechanical property and the luminance brightness of nylon material.
The content of described nylon is 5wt% ~ 15wt%, and be preferably 8wt% ~ 9wt%, in some embodiments of the invention, its content is 10wt%.
Nylon of the present invention is preferably nylon 6, and in some embodiments of the invention, described Nylon 6 is PA6 (1013B), and its tensile strength is 59.2MPa, and modulus in flexure is 15100MPa, and melt flow rate (MFR) is 15.9g/10min.
The content of described compatilizer is 3wt% ~ 7wt%, and be preferably 3wt% ~ 5wt%, in some embodiments of the invention, its content is 3wt%.
Described compatilizer is preferably grafting POE.In some embodiments of the invention, described compatilizer is maleic anhydride graft POE.
The present invention adopts above-mentioned compatilizer to carry out modification to nylon material, substantially increases the toughness of nylon material, after adding magneticsubstance, can not affect the mechanical property of material.
Described auxiliary agent content is 0.5wt% ~ 1.5wt%, and be preferably 0.7wt% ~ 1.2wt%, in some embodiments of the invention, its content is 1wt%.
The present invention is preferred, and described auxiliary agent comprises oxidation inhibitor, lubricant and coupling agent.
The content of described oxidation inhibitor is 0.2wt% ~ 0.4wt%, and be preferably 0.25wt% ~ 0.35wt%, in some embodiments of the invention, its content is 0.3wt%.
Described oxidation inhibitor is preferably antioxidant 1010, i.e. four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, or irgasfos 168, i.e. three [2.4-di-tert-butyl-phenyl] phosphorous acid ester.
Described lubricant content is 0.3wt% ~ 0.5wt%, and be preferably 0.35wt% ~ 0.45wt%, in some embodiments of the invention, its content is 0.4wt%.
Described lubricant is preferably EBS, i.e. N, N '-ethylene bis stearamide, or copper silicon powder.
Described coupling agent content is 0.2wt% ~ 0.4wt%, and be preferably 0.25wt% ~ 0.35wt%, in some embodiments of the invention, its content is 0.3wt%.
Described coupling agent is preferably the composite coupler of silane coupling agent and titanate coupling agent.The mass ratio of silane coupling agent and titanate coupling agent is preferably 4:(5 ~ 7), in some embodiments of the invention, described ratio is 4:6.
In the present invention, above-mentioned oxidation inhibitor, lubricant, coupling agent total amount are auxiliary agent content, i.e. 0.5wt% ~ 1.5wt%.
In some embodiments of the invention, the component of described matrix material is specially:
The present invention is preferred, and described matrix material also comprises silicon nitrogen combustion inhibitor.
The content of described fire retardant is 6wt% ~ 10wt%, and be preferably 7wt% ~ 9wt%, in some embodiments of the invention, its content is 8wt%.
Described silicon nitrogen combustion inhibitor is preferably the silicon nitrogen combustion inhibitor FS-950 of organosilane monomer by product synthesis.
In some embodiments of the invention, the component of described matrix material is specially:
The present invention with the addition of the magneticsubstance after silicon nitrogen combustion inhibitor and process in nylon material simultaneously, without the need to adopting Halogen phosphonium flame retardant, safety and environmental protection, fire retardant and magneticsubstance can be good at compatible simultaneously, play synergy, on the basis promoting material mechanical performance, greatly improve the flame retardant properties of material.
Present invention also offers a kind of preparation method of above-mentioned nylon composite materials, comprising:
A) adopt the composite coupler of silane coupling agent and titanate coupling agent successively, isobornyl methacrylate carries out modification to magneticsubstance;
B) by proportioning, each raw material is mixed with modified magneticsubstance, mixing, extruding pelletization obtains nylon composite materials.
Described steps A) modification is carried out to magneticsubstance be specially:
A) magneticsubstance is dried 4 ~ 6h at 110 DEG C ~ 130 DEG C, remove the excessive moisture that material is subsidiary, make its surface drying, the surface adhesion force that the later stage adds solubility composite coupler and isobornyl methacrylate is better.If do not dried, the surface attachment moisture of powder can affect and reduce the coated process of the activation of composite coupler to powder, and the synergistic effect of isobornyl methacrylate, thus greatly improves the overall performance of mixing material.
B) by the magneticsubstance high-speed stirring after drying, first add the composite coupler of silane coupling agent and titanate coupling agent, high speed processing 5 minutes simultaneously, then add isobornyl methacrylate and carry out mixed and modified.
The add-on of described coupling agent is preferably the 1wt% ~ 5wt% of magneticsubstance, and in some embodiments of the invention, described add-on is 3wt%.The add-on of described isobornyl methacrylate is preferably the 1wt% ~ 5wt% of magneticsubstance, and in some embodiments of the invention, described add-on is 2wt%.
Above-mentioned modification greatly reduces magneticsubstance and basal body interface sliding resistance at high temperature, is conducive to the magnetic aligning of magneticsubstance, to obtain high magnetic property.And improve the consistency of magnetic and nylon resin.
Carry out modified to magneticsubstance, each to itself and other raw material is mixed, obtain mixed resin, then mixed resin is added twin screw extruder, shear through twin screw extruder melting at 230 DEG C ~ 250 DEG C temperature, namely mixing, extruding pelletization obtain matrix material pellet.
The condition optimization of described extruding pelletization is: screw speed 340 turns/min, feeding rotating speed 350 turns/min, blank speed 450 turns/min.
In the present invention, described content is weight content.
The present invention there is no particular determination to above-mentioned each raw material sources, can be generally commercially available.
In order to further illustrate the present invention, below in conjunction with embodiment, Magnetic nylon composite material provided by the invention and preparation method thereof is described in detail.
Embodiment 1
100kg strontium ferrite magnetic powder (2200 order) is dried 4 hours at 120 DEG C; Then put into homogenizer to stir, the composite coupler 3Kg first adding 4:6 ratio silane coupling agent and titanate coupling agent in whipping process carries out surface treatment, then add the isobornyl methacrylate modification of 2kg, obtain the strontium ferrite magnetic powder of modification.
Embodiment 2
Batching:
Strontium ferrite magnetic powder 86wt% prepared by embodiment 1, NYLON610 wt%, maleic anhydride graft POE3wt%, antioxidant 1010 0.3wt%, EBS0.4wt%, the composite coupler 0.3wt% of silane coupling agent and titanate coupling agent.
Preparation method:
Proportioning raw material, mixes according to the above ratio, obtains mixed resin;
Mixed resin is added twin screw extruder, then shears through twin screw extruder melting at 230 DEG C ~ 250 DEG C temperature, namely mixing, extruding pelletization obtain carbon-fiber composite material pellet;
In extrusion, the screw speed of forcing machine is 340 turns/min, feeding rotating speed is 350 turns/min, blank speed is 450 turns/min.Produce after collecting and be Magnetic nylon composite material of the present invention.
After testing, the Magnetic nylon composite material of preparation has magnetic.
Detect its performance, the results are shown in Table 1, table 1 is that the mechanics of Magnetic nylon composite material sample prepared by the embodiment of the present invention and physicochemical property gather.
The mechanics of Magnetic nylon composite material sample prepared by table 1 embodiment of the present invention and physicochemical property gather
Embodiment 3
Batching:
Strontium ferrite magnetic powder 86wt% prepared by embodiment 1, NYLON610 wt%, maleic anhydride graft POE3wt%, irgasfos 168 0.3wt%, copper silicon powder 0.4wt%, the composite coupler 0.3wt% of silane coupling agent and titanate coupling agent.
Preparation method is with embodiment 1.
After testing, the Magnetic nylon composite material of preparation has magnetic.
Performance Detection is in table 1.
Embodiment 4
Batching:
Strontium ferrite magnetic powder 80wt% prepared by embodiment 1, nylon66 fiber wt%, maleic anhydride graft POE5wt%, antioxidant 1010 0.3wt%, EBS0.4wt%, the composite coupler 0.3wt% of silane coupling agent and titanate coupling agent, silicon nitrogen combustion inhibitor 8wt%.
Preparation method is with embodiment 1.
After testing, the Magnetic nylon composite material of preparation has magnetic.
Performance Detection is in table 1.
Embodiment 5
Strontium ferrite magnetic powder 86wt% prepared by embodiment 1, NYLON610 wt%, maleic anhydride graft POE3wt%, irgasfos 168 0.3wt%, copper silicon powder 0.4wt%, the composite coupler 0.3wt% of silane coupling agent and titanate coupling agent, silicon nitrogen combustion inhibitor 8wt%.
After testing, the Magnetic nylon composite material of preparation has magnetic.
Preparation method is with embodiment 1.
Performance Detection is in table 1.
From above-described embodiment, nylon material prepared by the present invention, tool is magnetic while, have also obtained excellent mechanical property and flame retardant properties.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a Magnetic nylon composite material, comprising:
Each component total amount is 100%;
Described magneticsubstance is successively through the magneticsubstance of coupling agent, isobornyl methacrylate modification;
Described coupling agent is the composite coupler of silane coupling agent and titanate coupling agent.
2. matrix material according to claim 1, is characterized in that, described magneticsubstance is strontium ferrite magnetic powder.
3. matrix material according to claim 1, is characterized in that, described compatilizer is maleic anhydride graft POE.
4. matrix material according to claim 1, is characterized in that, described auxiliary agent comprises:
Oxidation inhibitor 0.2wt% ~ 0.4wt%;
Lubricant 0.3wt% ~ 0.5wt%;
Coupling agent 0.2wt% ~ 0.4wt%;
Described oxidation inhibitor, lubricant, coupling agent total amount are 0.5wt% ~ 1.5wt%;
Described oxidation inhibitor is antioxidant 1010 or irgasfos 168, and described lubricant is N, N '-ethylene bis stearamide or copper silicon powder, and described coupling agent is the composite coupler of silane coupling agent and titanate coupling agent.
5. nylon composite materials according to claim 1, is characterized in that, comprising:
6. nylon composite materials according to claim 1, is characterized in that, also comprises:
The silicon nitrogen combustion inhibitor of 6wt% ~ 10wt%.
7. nylon composite materials according to claim 6, is characterized in that, comprising:
8. a preparation method for nylon composite materials described in any one of claim 1 ~ 7, comprising:
A) adopt the composite coupler of silane coupling agent and titanate coupling agent successively, isobornyl methacrylate carries out modification to magneticsubstance;
B) by proportioning, each raw material is mixed with modified magneticsubstance, mixing, extruding pelletization obtains nylon composite materials.
9. preparation method according to claim 8, is characterized in that, described steps A) be specially:
A) magneticsubstance is dried 4 ~ 6h at 110 ~ 130 DEG C;
B) magneticsubstance after oven dry is added while stirring the composite coupler of silane coupling agent and titanate coupling agent successively, isobornyl methacrylate carries out modification.
10. preparation method according to claim 8, is characterized in that, described step B) condition of extruding pelletization is:
Screw speed 340 turns/min, feeding rotating speed 350 turns/min, blank speed 450 turns/min.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114539768A (en) * | 2022-01-14 | 2022-05-27 | 滁州杰事杰新材料有限公司 | Nylon 11 composition and preparation method thereof |
CN115725180A (en) * | 2021-08-26 | 2023-03-03 | 安徽华米信息科技有限公司 | Ferromagnetic silicon rubber wrist strap core material and preparation method thereof |
WO2024021297A1 (en) * | 2022-07-28 | 2024-02-01 | 横店集团东磁股份有限公司 | Functional magnetic powder and method for preparing same, magnetic nylon masterbatch and method for preparing same, and magnetic plastic material |
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CN103709739A (en) * | 2013-12-16 | 2014-04-09 | 宁波博利隆复合材料科技有限公司 | Magnetic nylon composite material and preparation method thereof |
CN104194325A (en) * | 2014-09-17 | 2014-12-10 | 中山大学 | Preparing method of heat-conductive and injection-molded magnetic composite |
CN104231615A (en) * | 2014-09-28 | 2014-12-24 | 唐贵凤 | Magnetic nylon composite material and preparation method thereof |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN115725180A (en) * | 2021-08-26 | 2023-03-03 | 安徽华米信息科技有限公司 | Ferromagnetic silicon rubber wrist strap core material and preparation method thereof |
CN115725180B (en) * | 2021-08-26 | 2024-05-28 | 安徽华米健康科技有限公司 | Strong magnetic silicone rubber wristband core material and preparation method thereof |
CN114539768A (en) * | 2022-01-14 | 2022-05-27 | 滁州杰事杰新材料有限公司 | Nylon 11 composition and preparation method thereof |
CN114539768B (en) * | 2022-01-14 | 2023-06-16 | 滁州杰事杰新材料有限公司 | Nylon 11 composition and preparation method thereof |
WO2024021297A1 (en) * | 2022-07-28 | 2024-02-01 | 横店集团东磁股份有限公司 | Functional magnetic powder and method for preparing same, magnetic nylon masterbatch and method for preparing same, and magnetic plastic material |
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