WO2018095221A1 - 一种通过不饱和羧酸盐补强的磁性橡胶及其制备方法 - Google Patents

一种通过不饱和羧酸盐补强的磁性橡胶及其制备方法 Download PDF

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WO2018095221A1
WO2018095221A1 PCT/CN2017/110103 CN2017110103W WO2018095221A1 WO 2018095221 A1 WO2018095221 A1 WO 2018095221A1 CN 2017110103 W CN2017110103 W CN 2017110103W WO 2018095221 A1 WO2018095221 A1 WO 2018095221A1
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rubber
magnetic
unsaturated carboxylate
parts
unsaturated
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陈玉坤
黄训辉
龚舟
曹黎明
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South China University of Technology SCUT
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

Definitions

  • the invention relates to a magnetic rubber, in particular to a soft magnetic magnetic rubber which is reinforced by an unsaturated carboxylate and has excellent mechanical properties and a preparation method thereof, and belongs to the technical field of functional polymer composite materials.
  • soft magnetic materials are widely used and popularized in the fields of electronic communication products and automotive parts, and are developing in the direction of high frequency, low loss, high temperature resistance, strong anti-interference and light weight.
  • the general ferromagnetic steel magnetic materials are limited in use in special occasions where the miniaturization and the shape of the molding are complicated due to the disadvantages of high density, hardness, and difficulty in processing and molding.
  • diversification and complexity of electronic and electrical equipment and some of its automotive parts It is difficult to make a micro-miniature, complex-shaped part of a general ferromagnetic steel, and it is easy to be broken even if it is used.
  • Magnetic rubber refers to a rubber material that has magnetic properties that can be utilized. It is generally a flexible magnetic material that has been finely prepared from magnetic powder, rubber, and compounding agent. The magnetic properties depend mainly on the type and amount of magnetic powder selected. Preparation process, etc. The powdered magnetic material is incorporated into an elastomeric polymer material such as rubber, and the resulting magnetic material is less likely to be broken. Magnetic rubber is soft and flexible, has good processing properties, and has various molecular structure changes. It has the characteristics that ferromagnetic steel cannot replace. The application research of magnetic rubber has become one of the hotspots in the research field of functional polymer materials.
  • Chinese invention patent application (CN102875854A) reports on a method for preparing high-strength magnetic rubber by using 110 phr of polymer (including natural rubber, neoprene, carboxylated nitrile rubber, PVC resin, phenolic resin, polyvinyl methyl ether, Polyethylene), 100 phr hard magnetic magnetic powder, 6 phr coupling agent, 16 phr sulfur vulcanizing agent and accelerator are first mixed uniformly; then added to the rubber mixing machine, rubberized at 170-180 ° C, and ground into a paste; Then, it is poured into a mold, cooled and solidified; finally, the cured sample is magnetized to obtain a product.
  • polymer including natural rubber, neoprene, carboxylated nitrile rubber, PVC resin, phenolic resin, polyvinyl methyl ether, Polyethylene
  • 100 phr hard magnetic magnetic powder 6 phr coupling agent, 16 phr sulfur vulcanizing
  • the silane coupling agent KH-570 in the formulation It can not effectively improve the compatibility between the magnetic powder and the rubber matrix and disperse the magnetic powder in the rubber matrix. Therefore, the tensile strength of the obtained rubber material is only 5.7 MPa, which cannot meet the requirements for some occasions with high strength requirements. .
  • the object of the present invention is to overcome the problems existing in the prior art, to provide a magnetic rubber reinforced by an unsaturated carboxylate and a preparation method thereof, and the obtained magnetic rubber has a tensile strength of 6.83 MPa or more and a tear strength of 13.98. Above MPa, the saturation magnetic induction intensity is 29.03 emu/g or more.
  • the unsaturated carboxylate of the present invention is one or more of zinc methacrylate, magnesium methacrylate, zinc acrylate and magnesium acrylate.
  • the unsaturated carboxylate of the present invention is one or more of zinc methacrylate, magnesium methacrylate, zinc acrylate and magnesium acrylate.
  • the unsaturated carboxylate structures contain double bonds, free radicals can be generated under the action of an initiator, thereby causing cross-linking and grafting reaction of rubber macromolecules, and the crosslinking of rubber is remarkably improved. Efficiency, crosslink density, and structural composition of the crosslinks are changed. Therefore, the unsaturated carboxylic acid salt of the prior art is usually used as a co-crosslinking agent for a peroxide vulcanizing agent, and it is usually used in an amount of from 1 to 3 phr (the amount of the rubber is 100 phr).
  • the unsaturated carboxylate is used as a reinforcing agent, a reaction compatibilizer and a co-crosslinking agent in an amount of 5 to 20 phr (the amount of the rubber is 100 phr).
  • the mechanism of action is: under the action of peroxide, the unsaturated carboxylate will undergo grafting and self-polymerization in the rubber matrix to form an ionic cross-linking bond, which will enhance the rubber and pull the rubber compound. The tensile strength and hardness are improved to some extent.
  • the compatibility of the magnetic powder with the rubber matrix is improved, the dispersion of the magnetic powder in the rubber matrix is improved, and the mechanical properties of the magnetic rubber are significantly improved without affecting the magnetic properties of the ferroferric oxide particles.
  • the magnetization curve and the hysteresis loop of the product are measured by vibrating the sample magnetometer, and the magnetic rubber mechanics obtained by the unsaturated carboxylate reinforcement is found.
  • the performance enhancement is very remarkable, the tensile strength can reach 6.83 MPa or more, and the comparative ratio (without adding unsaturated carboxylate) is increased by 2 to 6 times, and the tear strength is also greatly improved to 13.98 MPa or more.
  • the magnetic properties of the product of the invention are obviously improved while the mechanical properties are obviously improved, so that the magnetic rubber prepared by the invention can be applied to special occasions with high requirements on mechanical properties, and can make up for the lack of mechanical properties of some magnetic rubbers. Disadvantages.
  • the invention better solves how to significantly improve the mechanical properties of the magnetic rubber while maintaining the magnetic properties of the magnetic rubber.
  • a magnetic rubber reinforced by an unsaturated carboxylic acid salt the raw material composition of which is in parts by mass:
  • Micron-sized ferroferric oxide powder 70-100 parts
  • Vulcanizing agent 0.5 to 2.5 parts
  • Vulcanization accelerator 0.83 to 4.16 parts
  • the unsaturated carboxylate is one or more of zinc methacrylate, magnesium methacrylate, zinc acrylate and magnesium acrylate;
  • the vulcanizing agent is an alkyl peroxide
  • the micron-sized ferroferric oxide magnetic powder has a particle diameter of 0.1 to 5 um.
  • the vulcanization accelerator is one or more of triallyl cyanurate, triallyl isocyanurate and 1,2-polybutadiene;
  • the rubber is first masticized on the open mill, the unsaturated carboxylate is added, and the rubber is tapped, rolled, and triangled until the mixture is evenly mixed; then the ferroferric oxide powder is added to perform tapping. Winding, triangle; adding vulcanizing agent and vulcanization accelerator until the mixing is uniform, and the film is cooled and cooled to obtain a rubber compound; then the rubber is vulcanized and molded; finally, magnetization is performed to obtain a magnetic rubber.
  • the alkyl peroxide is dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1 One or more of 3-bis(tert-butylperoxy)hexane, benzoyl peroxide and 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexanekind.
  • the alkyl peroxide of the invention promotes the vulcanization of the rubber to form a crosslinked network under high temperature conditions, and also causes the unsaturated carboxylate to be grafted into the rubber macromolecular chain to form an ion crosslink bond, which makes the mechanical properties of the rubber Significantly enhanced; and the interaction between the metal ion clusters on the unsaturated carboxylate, the carbonyl group and the ferroferric oxide improves the phase of the ferroferric oxide magnetic powder and the rubber matrix without destroying the magnetic properties of the ferroferric oxide magnetic powder. Capacitance, and dispersion in the rubber matrix. This results in a tighter bond between the ferroferric oxide and the rubber matrix, thereby significantly improving the mechanical properties of the magnetic rubber.
  • the rubber in the magnetic rubber is one or more of natural rubber, nitrile rubber, styrene butadiene rubber and ethylene propylene rubber.
  • natural rubber nitrile rubber
  • styrene butadiene rubber styrene butadiene rubber
  • ethylene propylene rubber styrene butadiene rubber
  • different types of rubber may be used or combined.
  • the ferroferric oxide powder has a particle diameter of 0.2 to 4 um.
  • the raw material ratio composition is: N41 type NBR 100 parts, particle size 1 um ferroferric oxide powder 70 parts, zinc methacrylate 10 parts, dicumyl peroxide 1.5 parts and three Allyl isocyanurate 2.5 parts.
  • the number of times of the rubber mastication is 3-7 times; the addition of the unsaturated carboxylate, the addition of the ferroferric oxide magnetic powder or the addition of the vulcanizing agent and the vulcanization accelerator agent each time the rubber is tapped, rolled, and triangular
  • the number of times is 3-7 times.
  • the vulcanization molding comprises placing the rubber compound into a mold and vulcanizing the product into a product on a flat vulcanizer, wherein the vulcanization temperature is 140 to 175 ° C, and the vulcanization time is 10 to 60 min.
  • the magnetization is performed by placing the vulcanized molded blank into a magnetic field strength of 12,000 to 15000 Oe.
  • the line is magnetized and the magnetization time is 18 to 25 minutes.
  • the ferroferric oxide magnetic powder is dried in a vacuum environment at a temperature of 50 to 60 ° C for 2 to 6 hours before use; the weight ratio of the vulcanizing agent and the vulcanization accelerator is 1:1.2 to 1:1.8; Helps to remove moisture and ensure that the basic mechanical properties of the magnetic rubber are not affected.
  • the unsaturated carboxylic acid salt is added by direct addition; or the unsaturated carboxylic acid salt is added by in-situ formation; the in-situ formation method is added by adding metal during the rubber-coated roll at the open mill Or hydroxide and unsaturated carboxylic acid, in situ formation of unsaturated carboxylate, wherein the volume ratio of unsaturated carboxylic acid to metal oxide or hydroxide is 2.12 ⁇ 7.31:1; volume unit is ml; mass The unit is g; the unsaturated carboxylic acid is one or more of maleic acid, acrylic acid, methacrylic acid; the metal oxide or hydroxide is zinc oxide, magnesium oxide, magnesium hydroxide, One or more of aluminum hydroxide.
  • the unsaturated carboxylate will form an ionic crosslink bond in the rubber matrix under the action of the high temperature of the alkyl peroxide vulcanizing agent, and the interaction between the carbonyl group on the unsaturated carboxylate and the ferric oxide can improve the magnetic powder.
  • the preparation method of the magnetic rubber reinforced by the unsaturated carboxylate comprises the following steps:
  • Rubber At room temperature, the rubber is first masticated 3 to 7 times on the open mill; then the unsaturated carboxylate and ferroferric oxide magnetic powder are added one by one in order, and the tapping is performed 3 to 7 times respectively. , roll, triangle, until the mixing is uniform; finally add vulcanizing agent and vulcanization accelerator for mixing, 3 to 7 times of tapping, winding, triangle bag, until the mixing is uniform, filming, cooling , get the rubber mixture;
  • vulcanization molding the mixture is placed in a mold, and is vulcanized into a product on a flat vulcanizer, wherein the vulcanization temperature is 140 to 175 ° C, and the vulcanization time is 10 to 60 min;
  • the vulcanized molded blank is magnetized under the condition of a magnetic field strength of 12,000 to 15000 Oe, and the magnetization time is 18 to 25 minutes.
  • the temperature of the vulcanization molding in the step 2) is from 155 to 170 °C.
  • the magnetic powder used in the present invention is a micron-sized ferroferric oxide powder having high magnetic permeability, low coercive force, high saturation magnetic flux density and saturation magnetization, and low magnetic loss and electrical loss. Under the action of the external magnetic field, the easy magnetization axes of the magnetic particles in the rubber are easily aligned in the direction of the magnetic field, thereby obtaining a magnetic rubber having a high saturation magnetic flux density and saturation magnetization.
  • the particle size of the magnetic powder has a great influence on the magnetic rubber: the particle size of the magnetic powder is too small, that is, less than 100 nm, and the formation of the magnetic rubber is difficult because the magnetic powder is easy to agglomerate and requires chemical treatment to modify the surface, thereby causing complicated process and high cost; If the particle size is larger than 5 um, the coordination between the magnetic powder and the rubber is difficult, so that the rubber matrix cannot cover the entire surface of the magnetic powder, resulting in a lower saturation magnetic flux density and saturation magnetization.
  • the present invention has the following advantages:
  • the magnetic rubber of the present invention is combined with an alkyl peroxide vulcanizing agent by introducing an unsaturated carboxylic acid salt, and is tightly bonded to the rubber matrix by an ion crosslinking bond, and at the same time, a metal ion cluster in the ion crosslinking bond,
  • the carbonyl group interacts with the magnetic powder to improve the compatibility between the magnetic powder and the rubber matrix, and the dispersibility of the magnetic powder in the rubber matrix, so that the magnetic powder and the rubber matrix are more tightly combined, and the mechanical properties are significantly improved.
  • the tensile strength and tear strength of the magnetic rubber are increased by 2 to 6 times, which makes up for the shortcomings of the existing magnetic rubber.
  • the magnetic rubber produced by the invention has significant improvement in mechanical properties, and its magnetic properties are basically unchanged. It can be widely used in applications such as electronic appliances and automotive parts, which have high strength requirements and certain magnetic properties. field.
  • the processing method of the magnetic rubber of the invention is simple, the equipment used is generally used, less, and the cost is low.
  • Example 1 is a hysteresis diagram of the magnetic rubber obtained in Example 6 and Comparative Example 3.
  • Example 3 is a scanning electron micrograph of the magnetic rubber obtained in Example 4.
  • Example 4 is a scanning electron micrograph of the magnetic rubber obtained in Example 3.
  • Nitrile rubber was selected as the base rubber (Model N41, China National Petroleum Corporation, Lanzhou Petrochemical Company, acrylonitrile content of 28-30%).
  • the nitrile rubber (100g) was masticated 7 times on the mill; secondly, zinc methacrylate powder (5g) was added to the nitrile rubber, and the rubber was tapped, rolled, and triangled three times until mixing.
  • Nitrile rubber was selected as the base rubber (Model: Nandi 3655, Zhenjiang Nandi Chemical Co., Ltd., acrylonitrile content was 36%).
  • the nitrile rubber 100 g was masticated 6 times on an open mill;
  • zinc oxide powder (3.45 g) was added to the nitrile rubber while methacrylic acid (7.32 ml) was injected into the nitrile rubber with a syringe. , respectively, tapping, rolling, and triangleing for 4 times until the mixing is uniform; then adding the weighed and dried ferroferric oxide powder (85g), and also tapping, rolling, and triangleping 4 times each.
  • Nitrile rubber was selected as the base rubber (Model: Nandi 4155, Zhenjiang Nandi Chemical Co., Ltd., acrylonitrile content was 41%).
  • the natural rubber 100g was masticated five times on the mill;
  • magnesium methacrylate powder 15g was added to the natural rubber, and the rubber was tapped, rolled, and triangled five times until the mixture was uniform;
  • the weighed and dried ferroferric oxide magnetic powder 70g
  • the vulcanizing agent diisopropyl benzoate 1.8g
  • the vulcanization accelerator, triallyl isocyanurate (3.0 g) until the kneading was uniform; finally, the roll distance was adjusted to 0.6 cm, and the film was cooled.
  • the cooled mixture was placed in a mold, placed on a flat vulcanizer, and vulcanized at a temperature of 160 ° C for 22 min.
  • the rubber product obtained above is magnetized under the condition that the magnetic field strength is 15000 Oe, and the soft magnetic magnetic rubber is obtained after magnetization.
  • Nitrile rubber was selected as the base rubber (Model N41, China National Petroleum Corporation, Lanzhou Petrochemical Company, acrylonitrile content of 28-30%).
  • the nitrile rubber (100g) was masticated 7 times on the mill; secondly, zinc acrylate powder (10g) was added to the nitrile rubber, and the rubber was tapped, rolled, and triangled four times until the mixture was uniform; Then add the weighed and dried ferroferric oxide magnetic powder (70g), and then tap, roll and triangle three times until the mixing is uniform; then add the vulcanizing agent 2,5-dimethyl-2 , 5-bis(tert-butylperoxy)hexane (1.8 g) and vulcanization accelerator triallyl isocyanurate (3.0 g) until homogeneously kneaded; finally, the roll distance was adjusted to 0.4 cm.
  • the cooled mixture was placed in a mold, placed on a flat vulcanizer, and vulcanized at 170 ° C for 10 min.
  • the rubber product obtained above was subjected to magnetization under the condition that the magnetic field strength was 15,000 Oe, and after softening, a soft magnetic magnetic rubber was obtained.
  • Nitrile rubber was selected as the base rubber (Model: Nandi 3655, Zhenjiang Nandi Chemical Co., Ltd., acrylonitrile content was 36%).
  • the nitrile rubber (100 g) was firstly kneaded 6 times on an open mill; secondly, zinc oxide powder (1.73 g) was added to the nitrile rubber while methacrylic acid (3.67 ml) was injected into the nitrile rubber with a syringe. , respectively, tapping, rolling, and triangleing 5 times until the mixing is uniform; then adding the weighed and dried ferroferric oxide powder (70g), and also tapping, rolling, and triangleping 4 times each.
  • Nitrile rubber was selected as the base rubber (Model: Nandi 4155, Zhenjiang Nandi Chemical Co., Ltd., acrylonitrile content was 41%).
  • the natural rubber 100g was masticated five times on the mill;
  • the magnesium acrylate powder (10g) was added to the natural rubber, and the rubber was tapped, rolled, and triangled four times until the mixture was evenly mixed;
  • the vulcanization accelerator is triallyl isocyanurate (3.0 g) until the kneading was uniform; finally, the roll pitch was adjusted to 0.6 cm, and the film was cooled.
  • the cooled mixture was placed in a mold, placed on a flat vulcanizer, and vulcanized at a temperature of 160 ° C for 22 min.
  • the rubber product obtained above is magnetized under the condition that the magnetic field strength is 15000 Oe, and the soft magnetic magnetic rubber is obtained after magnetization.
  • Nitrile rubber was selected as the base rubber (Model N41, China National Petroleum Corporation, Lanzhou Petrochemical Company, acrylonitrile content of 28-30%).
  • the nitrile rubber (100g) was plasticized 7 times on the open mill; secondly, the weighed and dried ferroferric oxide powder (100g) was added, and the rubber was cut, rolled, and triangled three times until mixed. Uniformly; followed by the addition of the vulcanizing agent diisopropyl benzoate (1.5g) and the vulcanization accelerator isocyanurate isocyanate (2.5g) until the mixing is uniform; finally, the roll distance is adjusted to 0.4cm ,cool down.
  • the cooled mixture was placed in a mold, placed on a flat vulcanizer, and vulcanized at 170 ° C for 10 min.
  • the rubber product obtained above is magnetized under the condition that the magnetic field strength is 12000 Oe, and the soft magnetic magnetic rubber is obtained after magnetization.
  • Nitrile rubber was selected as the base rubber (Model: Nandi 3655, Zhenjiang Nandi Chemical Co., Ltd., acrylonitrile content was 36%).
  • the nitrile rubber (100g) was masticated 6 times on the open mill; secondly, the ferroferric oxide powder (85g) which was weighed and dried was added, and the rubber tapping, rolling and triangle were also carried out 4 times until mixing.
  • Nitrile rubber was selected as the base rubber (Model: Nandi 4155, Zhenjiang Nandi Chemical Co., Ltd., acrylonitrile content was 41%).
  • the natural rubber 100g
  • the ferroferric oxide powder 70g which has been weighed and dried is added, and the rubber is cut, rolled, and triangled five times until mixing. Uniform; then adding the vulcanizing agent diisopropyl benzoate (1.8g) and the vulcanization accelerator isocyanurate isocyanate (3.0g) until the mixing is uniform; finally, the roll distance is adjusted to 0.6cm, cool down.
  • the cooled mixture was placed in a mold, placed on a flat vulcanizer, and vulcanized at a temperature of 160 ° C for 22 min.
  • the rubber product obtained above is magnetized under the condition that the magnetic field strength is 15000 Oe, and the soft magnetic magnetic rubber is obtained after magnetization.
  • Table 1 Magnetic and physical properties of the magnetic rubber of the examples
  • Comparative example 1 Comparative example 2 Comparative example 3
  • Example 1 is a hysteresis diagram of the magnetic rubber obtained in Example 6 and Comparative Example 3.
  • Figure 1 is obtained by testing the vibrating sample magnetometer of the PPMS-9 comprehensive physical property measurement system.
  • Example 3 is a scanning electron micrograph of the magnetic rubber obtained in Example 4. 2 and 3, it can be clearly observed that the addition of the unsaturated carboxylate can improve the compatibility between the magnetic powder and the rubber matrix and increase the dispersion of the magnetic powder in the rubber matrix. 4 is a scanning electron micrograph of the magnetic rubber obtained in Example 3. 3 and 4, it can be observed that as the amount of the unsaturated carboxylic acid increases, the binding between the magnetic powder and the rubber matrix is tight, and the dispersibility of the magnetic powder in the rubber matrix becomes better.
  • Example 1 and Comparative Example 1 By comparison of the three groups of Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, it can be seen that the elongation at break is slightly increased after the addition of the unsaturated carboxylate. The increase is due to the improvement of the interface between the magnetic powder and the rubber matrix by the unsaturated carboxylate.
  • the magnetic rubber produced by the present invention has such excellent comprehensive properties, mainly in:
  • the magnetic properties of the magnetic rubber are uniform and stable due to the uniform dispersion of the ferroferric oxide magnetic powder in the rubber.
  • the unsaturated carboxylate undergoes self-polymerization and grafting reaction in the rubber matrix during the vulcanization process to form an ionic cross-linking bond, thereby improving the mechanical properties of the rubber.
  • a suitable particle size of ferroferric oxide magnetic powder is selected, so that the particle size is too large, which tends to cause a decrease in performance; and the magnetic powder particle size is too small, prone to agglomeration, and also leads to poor performance.

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Abstract

公开了一种通过不饱和羧酸盐补强的磁性橡胶及其制备方法；以质量份数计，该磁性橡胶的原料组成为：橡胶100份、微米级四氧化三铁磁粉70～100份、不饱和羧酸盐5～15份、硫化剂0.5～2.5份以及硫化促进剂0.83～4.16份；不饱和羧酸盐为甲基丙烯酸锌、甲基丙烯酸镁、丙烯酸锌和丙烯酸镁中的一种或多种；硫化剂为烷基过氧化物；所得的磁性橡胶的拉伸强度达6.83MPa以上、撕裂强度达13.98MPa以上、饱和磁感应强度达29.03emu/g以上。

Description

一种通过不饱和羧酸盐补强的磁性橡胶及其制备方法 技术领域
本发明涉及一种磁性橡胶，特别是涉及一种通过不饱和羧酸盐补强的、具有优异力学性能的软磁磁性橡胶及其制备方法；属于功能高分子复合材料技术领域。
背景技术
目前，软磁材料在电子通讯产品、车用零部件等领域有很大的应用与普及，并朝着高频化、低损耗、耐高温、抗干扰性强、轻量化方向发展。一般的铁磁钢类磁性材料因为密度大、坚硬、加工成型困难等缺点，使之在一些小型化、成型形状复杂精细的特殊场合下使用受到限制。而随着电子电器设备及其一些车用零部件日趋小型化、多样化、复杂化。一般的铁磁钢很难制成微小型、形状复杂精细的零件，即使做成了使用起来也容易碎裂。
磁性橡胶—是指具有可利用的磁学性质的橡胶材料，一般是由磁粉、橡胶和配合剂经过精细制备而成的柔性磁性材料，其磁性能主要取决于所选的磁粉的类型、用量以及制备工艺等。把粉末状磁性材料掺入橡胶等弹性体高分子材料中，制成的磁性材料就不易碎裂。磁性橡胶柔韧质轻、加工性能好、分子结构变化多样，具有铁磁钢无法取代的特性。磁性橡胶的应用研究已成为当今功能性高分子材料研究领域中的热点之一。通常，为了获得高的饱和磁通密度、饱和磁化强度和低的矫顽力，需要加大磁粉在橡胶中的填充量；但是，随着磁粉的填充量增加，磁性橡胶的力学性能往往会显著下降，一方面是由于磁粉与橡胶基体较差的相容性，另一方面则是因为磁粉在橡胶基体中易团聚，这导致在实际的应用中受限。虽然国内外有相关的文献报道：通过硅烷偶联剂、钛酸偶联剂等化学助剂对磁粉进行预处理或者对磁粉进行改性处理，从而改善磁粉与聚合物基体的相容性以及磁粉在聚合物基体中的分散性，进而提高磁性聚合物的力学性能。然而，由于预处理的工艺繁杂、周期长、成本高以及对高填充量的磁性聚合材料改善的效果不甚明显，导致在实际应用中难以推广。
中国发明专利申请(CN102875854A)报道了一种高强度磁性橡胶的制备方法，通过将110phr聚合物(包括天然橡胶、氯丁橡胶、羧基丁腈橡胶、PVC树脂、酚醛树脂、聚乙烯基甲醚、聚乙烯)、100phr硬磁磁粉、6phr偶联剂、16phr硫磺硫化剂及促进剂等先混合均匀后；再加入炼胶机，在170～180℃温度下炼胶，并磨合成膏块状；然后倒入模具中，冷却、固化；最后将固化后的样品进行充磁得到制品。但是，由于配方中的硅烷偶联剂KH-570 并不能有效地改善磁粉与橡胶基体之间的相容性以及使磁粉在橡胶基体中分散良好，因此所得橡胶材料的拉伸强度最高仅为5.7MPa，不能满足一些对强度要求较高的场合使用。
发明内容
本发明的目的在于克服现有技术存在的问题，提供一种通过不饱和羧酸盐补强的磁性橡胶及其制备方法，所得的磁性橡胶的拉伸强度达6.83MPa以上、撕裂强度达13.98MPa以上、饱和磁感应强度达29.03emu/g以上。
本发明不饱和羧酸盐为甲基丙烯酸锌、甲基丙烯酸镁、丙烯酸锌和丙烯酸镁中的一种或多种。目前在橡胶领域中，由于这些不饱和羧酸盐结构中含有双键，在引发剂的作用下可以产生自由基，从而引发橡胶大分子发生交联和接枝反应，明显提高了橡胶的交联效率、交联密度以及改变交联键的结构组成。所以，现有技术中不饱和羧酸盐通常作为过氧化物硫化剂的助交联剂使用，其用量通常是1～3phr(橡胶的用量为100phr)。
而在本发明中，不饱和羧酸盐是作为一种补强剂、反应增容剂和助交联剂使用，其用量为5～20phr(橡胶的用量为100phr)。其作用机理是：在过氧化物的作用下，不饱和羧酸盐会在橡胶基体中发生接枝和自聚合反应，形成离子交联键，对橡胶起到增强的作用，使胶料的拉伸强度、硬度有一定程度的提高。同时，通过不饱和羧酸盐中的金属离子簇、羰基与四氧化三铁磁粉之间的相互作用，从而提高了磁粉与橡胶基体的相容性、改善了磁粉在橡胶基体的分散，进而在不影响四氧化三铁粒子的磁性下显著提高磁性橡胶的力学性能。
本发明制成的混炼胶硫化成型后通过充磁，再通过振动样品磁强计来测量制品的磁化曲线和磁滞回线，发现通过不饱和羧酸盐补强所制得的磁性橡胶力学性能增强非常显著，其拉伸强度可达6.83MPa以上，较对比例(没有加入不饱和羧酸盐)提高2～6倍，而且撕裂强度也得到很大程度的提高、可达13.98MPa以上。本发明产品在力学性能明显得到提升的同时，磁学性能基本维持不变，使得本发明制备的磁性橡胶可以应用于对力学性能要求较高的特殊场合，能够弥补现在一些磁性橡胶力学性能不足的缺点。本发明较好地解决了如何在保持磁性橡胶的磁性性能不变的情况下显著提升磁性橡胶的力学性能。
本发明的上述技术目的是通过以下技术方案实现：
一种通过不饱和羧酸盐补强的磁性橡胶，以质量份数计，其原料配比组成为：
橡胶：100份；
微米级四氧化三铁磁粉：70～100份；
不饱和羧酸盐：5～15份；
硫化剂：0.5～2.5份；
硫化促进剂：0.83～4.16份；
所述不饱和羧酸盐为甲基丙烯酸锌、甲基丙烯酸镁、丙烯酸锌和丙烯酸镁中的一种或多种；
所述的硫化剂为烷基过氧化物；
微米级四氧化三铁磁粉的粒径为0.1～5um。
所述的硫化促进剂为氰脲酸三烯丙酯、异氰脲酸三烯丙酯和1,2-聚丁二烯中的一种或多种；
制备时，在室温条件下，在开炼机上先将橡胶塑炼，加入不饱和羧酸盐，进行割胶、打卷、打三角，至混炼均匀；再加入四氧化三铁磁粉，进行割胶、打卷、打三角；加入硫化剂和硫化促进剂剂，直至混炼均匀，出片、冷却，得混炼胶；然后混炼胶进行硫化成型；最后进行充磁，得磁性橡胶。
为进一步实现本发明目的，优选地，所述的烷基过氧化物为过氧化二异丙苯、2,5-二甲基-2,5-双(叔丁基过氧化)己烷、1,3-双(叔丁基过氧化)己烷、过氧化苯甲酰和1,1-二叔丁基过氧基-3,3,5-三甲基环己烷中的一种或多种。本发明烷基过氧化物在高温条件下促使橡胶硫化形成交联网络的同时，也引发不饱和羧酸盐接枝到橡胶大分子链上中形成离子交联键，这使得橡胶的力学性能得以显著加强；而且不饱和羧酸盐上的金属离子簇、羰基与四氧化三铁之间的相互作用在不破坏四氧化三铁磁粉的磁性下，改善了四氧化三铁磁粉与橡胶基体的相容性、以及在橡胶基体中的分散。这使得四氧化三铁与橡胶基体之间结合得更加紧密，从而显著改善该磁性橡胶的力学性能。
优选地，所述的磁性橡胶中的橡胶为天然橡胶、丁腈橡胶、丁苯橡胶和乙丙橡胶中的一种或多种。根据制品所应用场合的使用要求不同，如耐油、耐化学腐蚀性能、耐热、耐老化性能来选用不同类型的橡胶或将其复合使用。
优选地，所述的四氧化三铁磁粉的粒径为0.2～4um。
优选地，以质量份数计，其原料配比组成为：N41型NBR100份、粒径1um的四氧化三铁磁粉70份、甲基丙烯酸锌10份、过氧化二异丙苯1.5份和三烯丙基异氰脲酸酯2.5份。
优选地，所述橡胶塑炼的次数为3-7次；加入不饱和羧酸盐、加入四氧化三铁磁粉或加入硫化剂和硫化促进剂剂后每次的割胶、打卷、打三角的次数都为3-7次。
优选地，所述的硫化成型是将混炼胶放入模具中，在平板硫化仪上硫化成型为制品，其中硫化温度为140～175℃，硫化时间为10～60min。
优选地，所述的充磁是将硫化成型的坯件放入磁场强度为12000～15000Oe的条件下进 行充磁，充磁时间为18～25min。
优选地，所述的四氧化三铁磁粉在使用之前在50～60℃的温度下的真空环境干燥2～6h；所述硫化剂和硫化促进剂的重量比例为1:1.2～1:1.8；有助于排除出水分，确保磁性橡胶的基本力学性能不受影响。
所述不饱和羧酸盐采用直接添加法加入；或者是所述不饱和羧酸盐采用原位生成法加入；所述原位生成法加入是在橡胶包辊在开炼机时通过添加金属氧化物或氢氧化物和不饱和羧酸，原位生成不饱和羧酸盐，其中不饱和羧酸与金属氧化物或氢氧化物的体积质量比例为2.12～7.31:1；体积单位为ml；质量的单位为g；所述的不饱和羧酸为马来酸、丙烯酸、甲基丙烯酸中一种或多种；所述的金属氧化物或氢氧化物为氧化锌、氧化镁、氢氧化镁、氢氧化铝中一种或多种。不饱和羧酸盐在烷基过氧化物硫化剂于高温的作用下，会在橡胶基体中形成离子交联键，同时不饱和羧酸盐上的羰基与四氧化三铁的相互作用，改善磁粉在橡胶基体中的分布，从而使得四氧化三铁磁粉与橡胶基体结合得更加紧密，显著提升该磁性橡胶的力学性能。
所述的通过不饱和羧酸盐补强的磁性橡胶的制备方法，包括以下步骤：
1)炼胶：在室温条件下，在开炼机上先将橡胶塑炼3～7次；然后按照次序逐一加入不饱和羧酸盐和四氧化三铁磁粉，并分别进行3～7次的割胶、打卷、打三角包，直至混炼均匀；最后加入硫化剂和硫化促进剂剂进行混炼，进行3～7次的割胶、打卷、打三角包，直至混炼均匀，出片、冷却，得混炼胶；
2)硫化成型：将所述的混炼胶放入模具中，在平板硫化仪上硫化成型为制品，其中硫化温度为140～175℃，硫化时间为为10～60min；
3)充磁：将硫化成型的坯件放入磁场强度为12000～15000Oe的条件下进行充磁，充磁时间为18～25min。
优选步骤2)中硫化成型的温度为155～170℃。
本发明采用的磁粉为微米级四氧化三铁铁粉，具有高的磁导率、低的矫顽力、高的饱和磁通密度和饱和磁化强度以及低的磁损耗和电损耗。在外界磁场的作用下，橡胶中的磁性粒子的易磁化轴容易沿磁场方向排列取向，从而获得具有较高的饱和磁通密度和饱和磁化强度的磁性橡胶。磁粉的粒径对磁性橡胶影响较大：磁粉的粒径太小，即小于100nm，磁性橡胶的成型较为困难，因为磁粉易团聚、需要化学处理表面改性，从而导致工艺复杂化、成本提高；如果粒径较大，大于5um，磁粉和橡胶之间配合困难，导致橡胶基体就不能包覆全部磁粉表面，从而导致饱和磁通密度和饱和磁化强度较低。
相对于现有技术，本发明具有以下优点：
1、本发明的磁性橡胶通过引入不饱和羧酸盐，并与烷基过氧化物硫化剂配合，通过离子交联键的形式与橡胶基体紧密结合，同时离子交联键中的金属离子簇、羰基又与磁粉产生相互作用，改善了磁粉与橡胶基体中的相容性、以及磁粉在橡胶基体中的分散性，从而使得磁粉与橡胶基体的结合更加紧密，显著提升其力学性能，比对比例磁性橡胶的拉伸强度、撕裂强度均提升2～6倍，弥补了现有的磁性橡胶力学性能不足的缺点。
2、本发明制得的磁性橡胶在力学性能显著提升的同时，其磁学性能也基本保持不变，可广泛应用于电子电器以及车用零部件等对强度要求较高又具有一定磁性的应用领域。
3、本发明的磁性橡胶的加工工艺简单，使用的设备常用、较少，成本低。
附图说明
图1为实施例6和对比例3所得磁性橡胶的磁滞回曲线图。
图2为对比例3所得磁性橡胶的扫描电镜图。
图3为实施例4所得磁性橡胶的扫描电镜图。
图4为实施例3所得磁性橡胶的扫描电镜图。
具体实施方式
为更好地理解本发明，下面结合附图和实施例对本发明作进一步具体的说明，但是本发明实施方式不限于此。本发明实施例中有关的测试方法说明如下：
表1和表2中，拉伸性能按GB/T528-1998进行测试；直角撕裂强度按GB/T529-1999进行测试；饱和磁感应强度、磁滞回曲线通过振动样品磁强计(VSM)进行测试。
本发明实施例和对比例中扫描电镜图均通过荷兰飞利浦公司的XL-30FEG型扫描电子显微镜测量得到，其放大倍数均为10000倍。
实施例1
选取丁腈橡胶为基体橡胶(型号为N41，中国石油天然气股份有限公司，兰州石化分公司，丙烯腈含量为28～30％)。首先在开炼机上将丁腈橡胶(100g)塑炼7次；其次将甲基丙烯酸锌粉末(5g)加入到丁腈橡胶中，分别进行割胶、打卷、打三角各3次，直至混炼均匀；然后再加入称量好并干燥过的四氧化三铁磁粉(100g)，同样进行割胶、打卷、打三角各3次，直至混炼均匀；接着加入硫化剂过氧化二异丙苯(1.5g)和硫化促进剂异氰脲酸三烯丙酯(2.5g)，直至混炼均匀；最后，将辊距调至0.4cm出片、冷却。将冷却后的混炼放入模具内，然后放置于平板硫化仪上，在170℃的温度下硫化10min。将制得的橡胶制品放入磁场强度为12000Oe的条件下进行充磁，充磁后即得软磁磁性橡胶。
实施例2
选取丁腈橡胶为基体橡胶(型号为南帝3655，镇江南帝化工有限公司，丙烯腈含量为36％)。首先在开炼机上将丁腈橡胶(100g)塑炼6次；其次将氧化锌粉末(3.45g)加入到丁腈橡胶中的同时用注射器将甲基丙烯酸(7.32ml)注射入丁腈橡胶中，分别进行割胶、打卷、打三角各4次，直至混炼均匀；然后再加入称量好并干燥过的四氧化三铁磁粉(85g)，同样进行割胶、打卷、打三角各4次，直至混炼均匀；接着加入硫化剂2,5-二甲基-2,5-双(叔丁基过氧化)己烷(1.5g)和硫化促进剂异氰脲酸三烯丙酯(3.0g)，直至混炼均匀；最后，将辊距调至0.5cm出片、冷却。将冷却后的混炼放入模具内，然后放置于平板硫化仪上，在165℃的温度下硫化16min。将上述制得的橡胶制品放入磁场强度为12，000Oe的条件下进行充磁，充磁后即得软磁磁性橡胶。
实施例3
选取丁腈橡胶为基体橡胶(型号为南帝4155，镇江南帝化工有限公司，丙烯腈含量为41％)。首先在开炼机上将天然橡胶(100g)塑炼5次；其次将甲基丙烯酸镁粉末(15g)加入到天然橡胶中，分别进行割胶、打卷、打三角各5次，直至混炼均匀；然后再加入称量好并干燥过的四氧化三铁磁粉(70g)，同样进行割胶、打卷、打三角各5次，直至混炼均匀；接着加入硫化剂过氧化二异丙笨(1.8g)和硫化促进剂异氰脲酸三烯丙酯(3.0g)，直至混炼均匀；最后，将辊距调至0.6cm出片、冷却。将冷却后的混炼放入模具内，然后放置于平板硫化仪上，在160℃的温度下硫化22min。将上述制得的橡胶制品放入磁场强度为15000Oe的条件下进行充磁，充磁后即得软磁磁性橡胶。
实施例4
选取丁腈橡胶为基体橡胶(型号为N41，中国石油天然气股份有限公司，兰州石化分公司，丙烯腈含量为28～30％)。首先在开炼机上将丁腈橡胶(100g)塑炼7次；其次将丙烯酸锌粉末(10g)加入到丁腈橡胶中，分别进行割胶、打卷、打三角各4次，直至混炼均匀；然后再加入称量好并干燥过的四氧化三铁磁粉(70g)，同样进行割胶、打卷、打三角各3次，直至混炼均匀；接着加入硫化剂2,5-二甲基-2,5-双(叔丁基过氧化)己烷(1.8g)和硫化促进剂异氰脲酸三烯丙酯(3.0g)，直至混炼均匀；最后，将辊距调至0.4cm出片、冷却。将冷却后的混炼放入模具内，然后放置于平板硫化仪上，在170℃的温度下硫化10min。将上述制得的橡胶制品放入磁场强度为15，000Oe的条件下进行充磁，充磁后即得软磁磁性橡胶。
实施例5
选取丁腈橡胶为基体橡胶(型号为南帝3655，镇江南帝化工有限公司，丙烯腈含量为36％)。首先在开炼机上将丁腈橡胶(100g)塑炼6次；其次将氧化锌粉末(1.73g)加入到丁腈橡胶中的同时用注射器将甲基丙烯酸(3.67ml)注射入丁腈橡胶中，分别进行割胶、打卷、打三角各5次，直至混炼均匀；然后再加入称量好并干燥过的四氧化三铁磁粉(70g)，同样进行割胶、打卷、打三角各4次，直至混炼均匀；接着加入硫化剂过氧化二异丙笨(1.8g)和硫化促进剂异氰脲酸三烯丙酯(3.0g)，直至混炼均匀；最后，将辊距调至0.5cm出片、冷却。将冷却后的混炼放入模具内，然后放置于平板硫化仪上，在165℃的温度下硫化16min。将上述制得的橡胶制品放入磁场强度为15000Oe的条件下进行充磁，充磁后即得软磁磁性橡胶。
实施例6
选取丁腈橡胶为基体橡胶(型号为南帝4155，镇江南帝化工有限公司，丙烯腈含量为41％)。首先在开炼机上将天然橡胶(100g)塑炼5次；其次将丙烯酸镁粉末(10g)加入到天然橡胶中，分别进行割胶、打卷、打三角各4次，直至混炼均匀；然后再加入称量好并干燥过的四氧化三铁磁粉(77g)，同样进行割胶、打卷、打三角各3次，直至混炼均匀；接着加入硫化剂过氧化二异丙苯(1.8g)和硫化促进剂异氰脲酸三烯丙酯(3.0g)，直至混炼均匀；最后，将辊距调至0.6cm出片、冷却。将冷却后的混炼放入模具内，然后放置于平板硫化仪上，在160℃的温度下硫化22min。将上述制得的橡胶制品放入磁场强度为15000Oe的条件下进行充磁，充磁后即得软磁磁性橡胶。
对比例1
选取丁腈橡胶为基体橡胶(型号为N41，中国石油天然气股份有限公司，兰州石化分公司，丙烯腈含量为28～30％)。首先在开炼机上将丁腈橡胶(100g)塑炼7次；其次加入称量好并干燥过的四氧化三铁磁粉(100g)，同样进行割胶、打卷、打三角各3次，直至混炼均匀；接着加入硫化剂过氧化二异丙笨(1.5g)和硫化促进剂异氰脲酸三烯丙酯(2.5g)，直至混炼均匀；最后，将辊距调至0.4cm出片、冷却。将冷却后的混炼放入模具内，然后放置于平板硫化仪上，在170℃的温度下硫化10min。将上述制得的橡胶制品放入磁场强度为12000Oe的条件下进行充磁，充磁后即得软磁磁性橡胶。
对比例2
选取丁腈橡胶为基体橡胶(型号为南帝3655，镇江南帝化工有限公司，丙烯腈含量为36％)。首先在开炼机上将丁腈橡胶(100g)塑炼6次；其次加入称量好并干燥过的四氧化三铁磁粉(85g)，同样进行割胶、打卷、打三角各4次，直至混炼均匀；接着加入硫化剂 2,5-二甲基-2,5-双(叔丁基过氧化)己烷(1.5g)和硫化促进剂异氰脲酸三烯丙酯(3.0g)，直至混炼均匀；最后，将辊距调至0.5cm出片、冷却。将冷却后的混炼放入模具内，然后放置于平板硫化仪上，在165℃的温度下硫化16min。将上述制得的橡胶制品放入磁场强度为12，000Oe的条件下进行充磁，充磁后即得软磁磁性橡胶。
对比例3
选取丁腈橡胶为基体橡胶(型号为南帝4155，镇江南帝化工有限公司，丙烯腈含量为41％)。首先在开炼机上将天然橡胶(100g)塑炼5次；其次加入称量好并干燥过的四氧化三铁磁粉(70g)，同样进行割胶、打卷、打三角各5次，直至混炼均匀；接着加入硫化剂过氧化二异丙笨(1.8g)和硫化促进剂异氰脲酸三烯丙酯(3.0g)，直至混炼均匀；最后，将辊距调至0.6cm出片、冷却。将冷却后的混炼放入模具内，然后放置于平板硫化仪上，在160℃的温度下硫化22min。将上述制得的橡胶制品放入磁场强度为15000Oe的条件下进行充磁，充磁后即得软磁磁性橡胶。
表1：实施例的磁性橡胶的磁性能和物理性能情况表
Figure PCTCN2017110103-appb-000001
表2：对比例的磁性橡胶的磁性能和物理性能情况表
  对比例1 对比例2 对比例3
拉伸强度/MPa 2.76 2.65 2.51
撕裂强度/KN·m-1 9.12 8.98 8.86
饱和磁化强度/emu/g 37.74 35.16 31.74
断裂伸长率/％ 172.13 148.02 147.86
从上面的表1和表2实施例和对比例的检测结果可以看出，通过不饱和羧酸盐补强所制得的磁性橡胶其拉伸强度可达6.83MPa以上，其拉伸强度较对比例提高2～6倍，而且撕裂强度也得到很大程度的提高，可达13.98KN·m-1以上，而比较例1最好的测试结果才有9.12KN·m-1。同时，其饱和磁化强度达29.03emu/g以上。
通过实施例1和对比例1、实施例2和对比例2、实施例3和对比例3这三组的比较，可以看出实施例中的饱和磁化强度相比较于对应的对比例均有所稍稍下降。这是因为由于不饱和羧酸盐的加入，使得磁粉在磁性橡胶中的质量百分数有所降低。而在实施例6和对比例3中，磁粉在复合材料中质量百分数均为41.17％，其相对应的饱和磁化强度分别为31.73emu/g和31.74emu/g。图1为实施例6和对比例3所得磁性橡胶的磁滞回曲线图。图1通过PPMS-9型综合物性测量系统的振动样品磁强计测试得到。通过图1，也可以看出，实施例6和对比例3的磁滞回曲线基本完全重叠。这说明不饱和羧酸盐的添加，并未对磁性橡胶的饱和磁化强度产生影响，本发明制得的磁性橡胶的磁性性能主要取决于磁粉在复合材料的质量百分数。这也就说明只要保持磁粉在复合材料的质量百分数不变，添加适量的不饱和羧酸盐于橡胶基体中，即可制得一种兼具优异的力学性能和磁学性能的磁性橡胶。
图2为对比例3所得磁性橡胶的扫描电镜图。图3为实施例4所得磁性橡胶的扫描电镜图。通过图2和图3，可以明显地观察到，不饱和羧酸盐的添加能够改善磁粉与橡胶基体之间的相容性和提高磁粉在橡胶基体中的分散。图4为实施例3所得磁性橡胶的扫描电镜图。而通过图3和图4，可以观察到，随着不饱和羧酸的用量增加，磁粉与橡胶基体之间结合越紧密，同时磁粉在橡胶基体中的分散性也变得越好。
通过实施例1和对比例1、实施例2和对比例2、实施例3和对比例3这三组的比较，可以看出添加了不饱羧酸盐后，其断裂伸长率稍稍有所提升，这是因为不饱和羧酸盐对磁粉与橡胶基体的界面改善所致。
本发明所制得的磁性橡胶之所以具有如此优异的综合性能，主要在于：
1)通过不饱和羧酸盐中的金属离子簇、羰基与四氧化三铁磁粉之间强烈的相互作用，从而提高了磁粉与橡胶基体的相容性、改善了磁粉在橡胶基体的分散，进而在不影响四氧化三铁粒子的磁性下显著提高磁性橡胶的力学性能。同时，由于四氧化三铁磁粉在橡胶中的均匀分散，也使磁性橡胶的磁性均匀、稳定。
2)不饱和羧酸盐在过氧化物的作用下，在硫化过程中于橡胶基体发生自聚合和接枝反应，形成离子交联键，从而提高了橡胶的力学性能。
3)选取了适宜的粒径的四氧化三铁磁粉，因而粒径过大，容易导致性能下降；而磁粉粒径太小，容易发生团聚，也会导致性能不佳。

Claims (10)

  1. 一种通过不饱和羧酸盐补强的磁性橡胶，其特征在于，以质量份数计，其原料配比组成为：
    橡胶：100份；
    微米级四氧化三铁磁粉：70～100份；
    不饱和羧酸盐：5～15份；
    硫化剂：0.5～2.5份；
    硫化促进剂：0.83～4.16份；
    所述不饱和羧酸盐为甲基丙烯酸锌、甲基丙烯酸镁、丙烯酸锌和丙烯酸镁中的一种或多种；
    所述的硫化剂为烷基过氧化物；
    微米级四氧化三铁磁粉的粒径为0.1～5um；
    所述的硫化促进剂为氰脲酸三烯丙酯、异氰脲酸三烯丙酯和1,2-聚丁二烯中的一种或多种；
    制备时，在室温条件下，在开炼机上先将橡胶塑炼，加入不饱和羧酸盐，进行割胶、打卷、打三角，至混炼均匀；再加入四氧化三铁磁粉，进行割胶、打卷、打三角；加入硫化剂和硫化促进剂剂，直至混炼均匀，出片、冷却，得混炼胶；然后混炼胶进行硫化成型；最后进行充磁，得磁性橡胶。
  2. 根据权利要求1所述的通过不饱和羧酸盐补强的磁性橡胶，其特征在于，所述的烷基过氧化物为过氧化二异丙苯、2,5-二甲基-2,5-双(叔丁基过氧化)己烷、1,3-双(叔丁基过氧化)己烷、过氧化苯甲酰和1,1-二叔丁基过氧基-3,3,5-三甲基环己烷中的一种或多种。
  3. 根据权利要求1所述的通过不饱和羧酸盐补强的磁性橡胶，其特征在于，所述的磁性橡胶中的橡胶为天然橡胶、丁腈橡胶、丁苯橡胶和乙丙橡胶中的一种或多种。
  4. 根据权利要求1所述的通过不饱和羧酸盐补强的磁性橡胶，其特征在于，所述的四氧化三铁磁粉的粒径为0.2～4um。
  5. 根据权利要求1所述的通过不饱和羧酸盐补强的磁性橡胶，其特征在于，以质量份数计，其原料配比组成为：N41型NBR100份、粒径1um的四氧化三铁磁粉70份、甲基 丙烯酸锌10份、过氧化二异丙苯1.5份和三烯丙基异氰脲酸酯2.5份。
  6. 根据权利要求1所述的通过不饱和羧酸盐补强的磁性橡胶，其特征在于，所述橡胶塑炼的次数为3-7次；加入不饱和羧酸盐、加入四氧化三铁磁粉或加入硫化剂和硫化促进剂剂后每次的割胶、打卷、打三角的次数都为3-7次。
  7. 根据权利要求1所述的通过不饱和羧酸盐补强的磁性橡胶，其特征在于，所述的硫化成型是将混炼胶放入模具中，在平板硫化仪上硫化成型为制品，其中硫化温度为140～175℃，硫化时间为10～60min。
  8. 根据权利要求1所述的通过不饱和羧酸盐补强的磁性橡胶，其特征在于，所述的充磁是将硫化成型的坯件放入磁场强度为12,000～15,000Oe的条件下进行充磁，充磁时间为18～25min。
  9. 根据权利要求1所述的通过不饱和羧酸盐补强的磁性橡胶，其特征在于，所述的四氧化三铁磁粉在使用之前在50～60℃的温度下的真空环境干燥2～6h；所述硫化剂和硫化促进剂的重量比例为1:1.2～1:1.8；
    所述不饱和羧酸盐采用直接添加法加入；或者是所述不饱和羧酸盐采用原位生成法加入；所述原位生成法加入是在橡胶包辊在开炼机时通过添加金属氧化物或氢氧化物和不饱和羧酸，原位生成不饱和羧酸盐，其中不饱和羧酸与金属氧化物或氢氧化物的体积质量比例为2.12～7.31:1；体积单位为ml；质量的单位为g；所述的不饱和羧酸为马来酸、丙烯酸、甲基丙烯酸中一种或多种；所述的金属氧化物或氢氧化物为氧化锌、氧化镁、氢氧化镁、氢氧化铝中一种或多种。
  10. 权利要求1所述的通过不饱和羧酸盐补强的磁性橡胶的制备方法，其特征在于包括以下步骤：
    1)炼胶：在室温条件下，在开炼机上先将橡胶塑炼3～7次；然后按照次序逐一加入不饱和羧酸盐和四氧化三铁磁粉，并分别进行3～7次的割胶、打卷、打三角包，直至混炼均匀；最后加入硫化剂和硫化促进剂剂进行混炼，进行3～7次的割胶、打卷、打三角包，直至混炼均匀，出片、冷却，得混炼胶；
    2)硫化成型：将所述的混炼胶放入模具中，在平板硫化仪上硫化成型为制品，其中硫化温度为140～175℃，硫化时间为为10～60min；
    3)充磁：将硫化成型的坯件放入磁场强度为12,000～15,000Oe的条件下进行充磁，充磁时间为18～25min。
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