CN106009449B - A kind of high temperature resistant and oil resistant thermoplastic vulcanizate and preparation method thereof - Google Patents
A kind of high temperature resistant and oil resistant thermoplastic vulcanizate and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种耐高温耐油热塑性硫化胶及其制备方法。按质量份数计，其主要原料组成：橡胶100份，氟塑料20‑90份，抗水解剂5‑20份，硫化剂0.5‑5份，硫化助剂0.5‑5份。制备时，将橡胶、抗水解剂在室温下混合均匀，再与氟塑料在180℃～300℃机械剪切条件下共混，混合均匀后出料冷却至室温，再与硫化剂、硫化助剂均匀混合；最后通过双螺杆挤出机进行动态硫化制得热塑性硫化胶。本发明的热塑性硫化胶，具有制备工艺简单，无需增容剂，相态结构精细，力学性能优异，硬度较低，耐高温、耐油性能优良，可回收利用的特点。可替代传统的热塑性橡胶应用于汽车胶管、电线电缆绝缘层、工具手柄等。
The invention discloses a high-temperature and oil-resistant thermoplastic vulcanizate and a preparation method thereof. In parts by mass, the main raw materials are composed of 100 parts of rubber, 20-90 parts of fluoroplastics, 5-20 parts of anti-hydrolysis agent, 0.5-5 parts of vulcanizing agent, and 0.5-5 parts of vulcanization aid. During preparation, the rubber and anti-hydrolysis agent are mixed uniformly at room temperature, and then blended with fluoroplastics under the condition of mechanical shearing at 180℃～300℃. After mixing uniformly, the material is discharged and cooled to room temperature. Uniform mixing; finally, the thermoplastic vulcanizate is obtained by dynamic vulcanization through a twin-screw extruder. The thermoplastic vulcanizate of the invention has the characteristics of simple preparation process, no need for a compatibilizer, fine phase structure, excellent mechanical properties, low hardness, excellent high temperature resistance and oil resistance, and can be recycled. It can replace traditional thermoplastic rubber in automotive hoses, wire and cable insulation, tool handles, etc.
Description
Technical Field
The invention relates to a high-temperature-resistant oil-resistant thermoplastic vulcanized rubber dynamically vulcanized and a preparation method thereof, belonging to the field of processing of high polymer materials.
Background
Thermoplastic vulcanizate is a special thermoplastic elastomer obtained by dynamic vulcanization reaction processing technology. When a small amount of plastic phase and a large amount of rubber are melt blended, the rubber is chemically crosslinked under the action of a crosslinking agent, the viscosity is increased, so that under the action of high-temperature mechanical shearing, the rubber-plastic blend is subjected to phase inversion, a large amount of rubber phase is crushed into micron (or nanometer) particles and uniformly dispersed in the small amount of plastic phase, and a special sea-island structure is formed after the rubber is crosslinked. The special structure enables the thermoplastic vulcanized rubber to have high elasticity and flexibility of the traditional rubber, and also has the performance of thermoplasticity processing and recycling of plastics, and the thermoplastic vulcanized rubber gradually replaces the traditional thermosetting rubber.
In recent years, with the development of industries such as aerospace, automobiles, and machinery, higher requirements are being placed on the performance of rubber products, and with the reduction of non-renewable resources such as petroleum, materials are required to be developed in the direction of environmental protection and recyclability. The traditional oil-resistant rubber products generally use nitrile rubber, chloroprene rubber and the like, the products cannot be recycled, and the oil resistance, particularly the oil resistance at high temperature, is more and more difficult to meet the requirements of industrial development. The ethylene vinyl acetate rubber, the ethylene acrylate rubber and the acrylate rubber have the characteristics of high temperature resistance and oil resistance, and the flame retardant property of the material is also improved due to the existence of the side ester group. The fluoroplastic has the advantages of high-temperature resistance, oil resistance and insulation performance, natural flame-retardant material and excellent wear resistance. Therefore, the rubber and the thermoplastic vulcanizate are prepared into the thermoplastic vulcanizate with the rubber dispersed in the fluoroplastic matrix by a dynamic vulcanization method, and the thermoplastic vulcanizate has excellent performances of high temperature resistance, oil resistance, insulation, wear resistance and the like. Patent CN 102690479A discloses a dynamically crosslinked polyamide/ethylene vinyl acetate rubber thermoplastic elastomer and a preparation method thereof, wherein the polyamide, the ethylene vinyl acetate rubber, a compatilizer and a peroxide crosslinking agent are added into an internal mixer, an open mill or a screw extruder at the blending temperature of 170-240 ℃ and are blended for 8-15 minutes, and the dynamically vulcanized polyamide/ethylene vinyl acetate rubber thermoplastic elastomer can be obtained. Because the compatibility of polyamide and ethylene vinyl acetate rubber is poor, a compatibilizer needs to be added, so that the cost is increased, the preparation process is more complicated, and the prepared thermoplastic elastomer is difficult to realize a fine microstructure; moreover, polyamide is easily hydrolyzed, which limits the application field of the prepared material. Patent CN 103059401A discloses an oil-resistant thermoplastic elastomer and a preparation method thereof, firstly, ethylene vinyl acetate (EVM) and a vulcanizing agent are mixed according to the mass ratio of 1000: 0.1-5 at the temperature of 30-200 ℃ to prepare master batch; discharging the master batch, cooling to normal temperature and crushing; and uniformly mixing the crushed masterbatch with Ethylene Vinyl Acetate (EVA), dynamically vulcanizing at 140-250 ℃ for 1-5 minutes, and discharging to obtain the oil-resistant thermoplastic elastomer. Because the high temperature resistance and oil resistance of the EVA are poor, the high temperature resistance and oil resistance of the prepared thermoplastic elastomer are poor, and the actual use requirement cannot be met. Patent CN 103396639a discloses a dynamically vulcanized fluoroplastic/fluororubber/silicone rubber thermoplastic elastomer and a preparation method thereof, wherein fluoroplastic, fluororubber, acid absorbent, silicone rubber and interface modifier are uniformly mixed at 175-330 ℃, and then a crosslinking agent and a crosslinking assistant are added under high-speed shearing to dynamically vulcanize a rubber phase to obtain a product. The compatibility of the fluoroplastic and the silicon rubber is extremely poor, so that expensive fluororubber is added as a compatibilizer, and the oil resistance of the silicon rubber is poor, so that the prepared thermoplastic vulcanized rubber has the problems of not fine microstructure, non-ideal performance and higher cost.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant oil-resistant thermoplastic vulcanized rubber and a preparation method thereof, aiming at the defects of the prior art and products. The rubber (ethylene vinyl acetate rubber, ethylene acrylate rubber or acrylate rubber) and the fluoroplastic selected by the invention have the characteristics of high temperature resistance and oil resistance, and the compatibility of the rubber and the fluoroplastic is good without adding a compatibilizer. The thermoplastic vulcanized rubber prepared by adopting the technology of rubber-plastic blending and dynamic vulcanization has the characteristics of simple preparation process, fine phase structure, excellent mechanical property, lower hardness, excellent high temperature resistance and oil resistance and recyclability.
The technical scheme of the invention is to provide a high-temperature-resistant oil-resistant thermoplastic vulcanized rubber which mainly comprises the following components in parts by weight:
the rubber is one of ethylene vinyl acetate rubber (the content of vinyl acetate is 40-80%), ethylene acrylate rubber (the content of methyl acrylate is 8-40%) or acrylate rubber.
The fluoroplastic is one of polyvinyl fluoride, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene or perfluoroethylene propylene.
The hydrolysis-resistant agent is a conventional hydrolysis-resistant agent, such as polycarbodiimide (PCD-50 for short).
The vulcanizing agent is one of di-tert-butylperoxydiisopropylbenzene, dicumyl peroxide or dibenzoyl peroxide; the vulcanizing assistant is one of triallyl isocyanurate (TAIC) or triallyl cyanurate (TAC).
The high-temperature-resistant oil-resistant thermoplastic vulcanized rubber comprises the following components in percentage by mass:
0.5-5 parts of oxidant;
5-20 parts of plasticizer;
1-5 parts of an anti-aging agent;
the antioxidant is conventional antioxidant, such as hindered phenol antioxidant 1010; the antioxidant is conventional antioxidant, such as 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD); the plasticizer is a conventional plasticizer, such as paraffin oil.
The invention also provides a preparation method of the high-temperature-resistant oil-resistant thermoplastic vulcanized rubber, which is characterized by comprising the following steps of:
(1) rubber and plastic premixing: at normal temperature, uniformly mixing the rubber and the anti-hydrolysis agent; mixing with fluoroplastic at 180-300 deg.c and cooling to room temperature; at normal temperature, uniformly mixing the rubber-plastic premix with a vulcanizing agent and an auxiliary vulcanizing agent to obtain a rubber-plastic premix;
(2) dynamic vulcanization: and (2) placing the rubber-plastic premix obtained in the step (1) into a double-screw extruder, and dynamically vulcanizing at the temperature of 200-330 ℃ and the rotating speed of 300-700 rpm to obtain the high-temperature-resistant oil-resistant thermoplastic vulcanizate.
The rubber (ethylene vinyl acetate rubber, ethylene acrylate rubber or acrylate rubber) and the fluoroplastic selected by the invention not only have extremely high temperature resistance and oil resistance, but also have stronger dipole-dipole interaction between carbonyl groups contained in the rubber and fluorine atoms contained in the fluoroplastic, so that the two have better compatibility, and a compatibilizer is not required to be added. The thermoplastic vulcanized rubber prepared by adopting the rubber-plastic premixing and dynamic vulcanization technology has the characteristic of excellent oil resistance, and also has excellent oil resistance at high temperature, on one hand, the main chain of the fluoroplastic molecular chain serving as a substrate is of a carbon-carbon single bond structure, the side group contains polar fluorine atoms, and the fluoroplastic has crystallinity, when the temperature is lower than the melting point of the fluoroplastic molecular chain, the crystal lattice of the fluoroplastic molecular chain is not damaged, and a solvent is difficult to permeate into a compact crystal lattice; on the other hand, the main chain of the rubber molecule as the dispersed phase does not contain double bonds, and the side groups contain polar ester groups. In addition, the thermoplastic vulcanized rubber has the characteristics of simple preparation process, fine phase structure, excellent mechanical property, lower hardness, recyclability and the like. The thermoplastic vulcanized rubber can replace the traditional thermoplastic rubber to be applied to automobile rubber tubes, wire and cable insulation layers, tool handles and the like, and has novelty, creativity and practicability.
Drawings
FIG. 1 is a graph showing the change in mechanical properties before and after the oil resistance test in example 2, wherein 1 is a tensile curve before the oil resistance test and 2 is a tensile curve after the oil resistance test. Tests show that after the thermoplastic vulcanizate is soaked in IRM903 standard oil for 72 hours at the temperature of 125 ℃, the tensile strength and the elongation at break of the thermoplastic vulcanizate are
Less than 10% change indicates that the thermoplastic vulcanizate has excellent oil resistance at high temperatures.
FIG. 2. phase structure diagram of example 2, showing the fine microstructure of the thermoplastic vulcanizate produced.
The invention is further described with reference to the following examples:
Detailed Description
The tensile strength and elongation at break in the examples were determined in accordance with the standards GB/T528-2009 and GB/T528-2009, respectively. The high temperature resistance and the oil resistance are measured according to the standard GB/T1690-2010.
Example 1:
the raw materials comprise the following components in parts by weight:
the preparation process of the thermoplastic vulcanized rubber comprises the following steps:
(1) rubber and plastic blending: at room temperature, uniformly mixing the acrylate rubber and the PCD-50 by using an open mill; mixing with dried polyvinyl fluoride and antioxidant 1010 in an internal mixer at 200 ℃, uniformly mixing, discharging and cooling to room temperature; at room temperature, uniformly mixing the rubber-plastic premix with RD, paraffin oil, di-tert-butylperoxydiisopropylbenzene and triallyl cyanurate in an open mill to obtain a rubber-plastic premix;
(2) dynamic vulcanization: the rubber-plastic premix was placed in a twin-screw extruder (HTS-40, the same shall apply hereinafter) and dynamically vulcanized at a screw temperature of 220 ℃ and a rotational speed of 300rpm to obtain a high-temperature-resistant oil-resistant thermoplastic vulcanizate.
TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Example 2:
the raw materials comprise the following components in parts by weight:
the preparation process of the thermoplastic vulcanized rubber comprises the following steps:
(1) rubber and plastic blending: at room temperature, uniformly mixing ethylene vinyl acetate rubber and PCD-50 by using an open mill; mixing the polyvinylidene fluoride powder with the dried polyvinylidene fluoride and the antioxidant 1010 in an internal mixer at 180 ℃, uniformly mixing, discharging and cooling to room temperature; at room temperature, uniformly mixing the rubber-plastic premix with RD, paraffin oil, dicumyl peroxide and triallyl isocyanurate in an open mill to obtain a rubber-plastic premix;
(2) dynamic vulcanization: and (3) placing the rubber-plastic premix in a double-screw extruder, setting the screw temperature at 200 ℃ and the rotation speed at 700rpm, and dynamically vulcanizing to obtain the high-temperature-resistant oil-resistant thermoplastic vulcanizate.
TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Example 3:
the raw materials comprise the following components in parts by weight:
the preparation process of the thermoplastic vulcanized rubber comprises the following steps:
(1) rubber and plastic blending: at normal temperature, uniformly mixing ethylene vinyl acetate rubber and PCD-50 by using an open mill; mixing with ethylene-tetrafluoroethylene copolymer and antioxidant 1010 in an internal mixer at 300 ℃, discharging and cooling to room temperature after uniform mixing; at room temperature, uniformly mixing the rubber-plastic premix with RD, paraffin oil, di-tert-butylperoxydiisopropylbenzene and triallyl cyanurate in an open mill to obtain a rubber-plastic premix;
(2) dynamic vulcanization: and (3) placing the rubber-plastic premix in a double-screw extruder, setting the screw temperature at 330 ℃ and the rotating speed at 500rpm, and dynamically vulcanizing to obtain the high-temperature-resistant oil-resistant thermoplastic vulcanizate.
TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Example 4:
the raw materials comprise the following components in parts by weight:
the preparation process of the thermoplastic vulcanized rubber comprises the following steps:
(1) rubber and plastic blending: at normal temperature, uniformly mixing ethylene vinyl acetate rubber (the content of vinyl acetate is 60%) and PCD-50 by using an open mill; mixing with dried ethylene-chlorotrifluoroethylene copolymer and antioxidant 1010 in an internal mixer at 260 ℃, uniformly mixing, discharging and cooling to room temperature; at room temperature, uniformly mixing the rubber-plastic premix with RD, paraffin oil, dicumyl peroxide and triallyl isocyanurate in an open mill to obtain a rubber-plastic premix;
(2) dynamic vulcanization: and (3) placing the rubber-plastic premix in a double-screw extruder, setting the screw temperature at 270 ℃, the rotating speed at 400rpm, and dynamically vulcanizing to obtain the high-temperature-resistant oil-resistant thermoplastic vulcanizate.
TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Example 5:
the raw materials comprise the following components in parts by weight:
the preparation process of the thermoplastic vulcanized rubber comprises the following steps:
(1) rubber and plastic blending: at normal temperature, uniformly mixing ethylene acrylate rubber (the content of methyl acrylate is 35 percent) and PCD-50 by using an open mill; mixing with dried polychlorotrifluoroethylene and antioxidant 1010 in an internal mixer at 260 ℃, discharging and cooling to room temperature after uniform mixing; uniformly mixing the rubber-plastic premix with RD, paraffin oil, dibenzoyl peroxide and triallyl cyanurate in an open mill at room temperature to obtain a rubber-plastic premix;
(2) dynamic vulcanization: and (3) placing the rubber-plastic premix in a double-screw extruder, setting the screw temperature at 240 ℃ and the rotating speed at 500rpm, and dynamically vulcanizing to obtain the high-temperature-resistant oil-resistant thermoplastic vulcanizate.
TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Example 6:
the raw materials comprise the following components in parts by weight:
the preparation process of the thermoplastic vulcanized rubber comprises the following steps:
(1) rubber and plastic blending: at room temperature, uniformly mixing ethylene acrylate rubber (the content of methyl acrylate is 10%) and PCD-50 by using an open mill; mixing with dried fluorinated ethylene propylene and antioxidant 1010 in an internal mixer at 280 ℃, uniformly mixing, discharging and cooling to room temperature; at room temperature, uniformly mixing the rubber-plastic premix with RD, paraffin oil, dibenzoyl peroxide and triallyl isocyanurate in an open mill to obtain a rubber-plastic premix;
(2) dynamic vulcanization: and (3) placing the rubber-plastic premix in a double-screw extruder, setting the screw temperature at 300 ℃ and the rotating speed at 600rpm, and dynamically vulcanizing to obtain the high-temperature-resistant oil-resistant thermoplastic vulcanizate.
TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
TABLE 1 physical Properties of thermoplastic vulcanizates
The data in the table 1 show that the high-temperature-resistant oil-resistant thermoplastic vulcanizate prepared by the invention has excellent oil resistance at high temperature, has lower hardness and smooth extrusion surface, and is a material with very excellent high-temperature-resistant oil resistance.
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| CN115304876B (en) * | 2022-08-05 | 2023-07-28 | 宁波博思特高分子材料科技有限公司 | High-elasticity TPV composite material and preparation method thereof |
| CN115490952A (en) * | 2022-10-09 | 2022-12-20 | 道恩高材(北京)科技有限公司 | A kind of fluorine rubber/fluoroplastic thermoplastic vulcanizate and preparation method thereof |
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