CN111019040B - High-strength non-stick roll acrylate rubber, preparation method thereof and vulcanized rubber composition composed of high-strength non-stick roll acrylate rubber - Google Patents
High-strength non-stick roll acrylate rubber, preparation method thereof and vulcanized rubber composition composed of high-strength non-stick roll acrylate rubber Download PDFInfo
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Abstract
The invention relates to high-strength non-stick roller acrylic rubber, a preparation method thereof and a vulcanized rubber composition composed of the high-strength non-stick roller acrylic rubber, and belongs to the technical field of acrylic rubber. The high-strength non-stick roller acrylic rubber introduces functional monomers in the premixing process; during polymerization reaction, dropwise adding an ice-water mixture, and controlling the reaction temperature to be 48-55 ℃; the functional monomer is one or more of methacrylonitrile, acrylonitrile, styrene, hexafluorobutyl acrylate and dodecafluoroheptyl acrylate. The high-strength non-stick roller acrylic rubber disclosed by the invention is uniform and stable in quality, high in strength and non-stick roller performance and excellent in processing performance; the invention also provides a preparation method of the acrylate rubber, which has the advantages of simple and controllable process, safety, energy conservation and low cost; in addition, the invention also provides a vulcanized rubber composition without adding any anti-sticking roller auxiliary agent.
Description
Technical Field
The invention relates to high-strength non-stick roller acrylic rubber, a preparation method thereof and a vulcanized rubber composition composed of the high-strength non-stick roller acrylic rubber, and belongs to the technical field of acrylic rubber.
Background
Acrylate rubber (hereinafter referred to as ACM) is an elastomer obtained by copolymerizing acrylate as a main monomer, wherein a main chain of the elastomer is a saturated carbon chain, and a side group of the elastomer is a polar ester group. The special structure endows the material with a plurality of excellent characteristics, such as: the rubber has the advantages of heat resistance, aging resistance, oil resistance, ozone resistance, ultraviolet resistance and the like, mechanical properties and processing properties superior to those of fluororubber and silicone rubber, and heat resistance, aging resistance and oil resistance superior to those of nitrile rubber. The ACM is widely applied to various high-temperature and oil-resistant environments, and becomes a sealing material which is intensively developed and popularized in the automobile industry in recent years, in particular to a high-temperature-resistant oil seal, a crankshaft, a valve rod, a cylinder gasket, a hydraulic oil delivery pipe and the like for automobiles.
However, the existing acrylate rubber has more problems, such as severe temperature rise in the reaction process, easy implosion, high gel content of the acrylate rubber caused by the implosion, difficulty in powder eating, and poor product quality uniformity and stability. Meanwhile, the main method for synthesizing the acrylate rubber at the present stage is a method for dropwise adding the residual monomers, and the method has the disadvantages of long reaction time, low productivity and high cost, so that the acrylate rubber is high in price.
In addition, the acrylate rubber has the problems of low strength, difficult processing and the like, and along with the stricter and stricter requirements on the quality of sealing materials, the use limitation of low-strength acrylate rubber products is infinitely enlarged; at the same time, processing difficulties directly affect the productivity, which also limits the use of acrylate rubbers.
Patent CN1861678A provides a method for preparing a cold-resistant acrylic rubber which is easy to process, the acrylic rubber has excellent processing performance, the low-temperature brittleness can reach-35 ℃, but the low-temperature brittleness is achieved by adding N2The method for dripping the residual monomers in the atmosphere controls the reaction process, the process is complex, the optimal speed for dripping the residual monomers is difficult to control, namely the polymerization rate and the highest polymerization temperature of each batch are different, and the product performance of the product is unstable due to the factors.
Patent CN102807720A discloses a rubber formulation and its preparation method, wherein a single acrylate rubber is expensive, and easy to stick to roll or difficult to mix during mixing, in order to overcome these problems, it uses nitrile rubber to obtain an acrylate rubber mixture which can not stick to roll or fall off roll during preparation, but because of incorporating nitrile rubber, the usage temperature of the acrylate rubber mixture is only 150 ℃, which is much lower than the maximum usage temperature 175 ℃ to 210 ℃ of acrylate rubber.
Therefore, it is desirable to develop a production process of acrylate rubber, and more particularly, to a production process of acrylate rubber, which controls the reaction temperature of the production process of acrylate rubber to be about 50 ℃, completes the reaction in a one-step method, does not add any anti-sticking roller auxiliary agent, overcomes the characteristic that the roll is very stuck in the processing process of the prior acrylate rubber, and has the strength of 19MPa after being mixed with a matching system.
Disclosure of Invention
The invention aims to provide the high-strength non-stick roll acrylic rubber which is uniform and stable in quality, high in strength and non-stick roll performance and excellent in processability; the invention also provides a preparation method of the acrylate rubber, which has the advantages of simple and controllable process, safety, energy conservation and low cost; in addition, the invention also provides a vulcanized rubber composition without adding any anti-sticking roller auxiliary agent.
The high-strength non-stick roller acrylic rubber introduces functional monomers in the premixing process; during polymerization reaction, dropwise adding an ice-water mixture, and controlling the reaction temperature to be 48-55 ℃;
the functional monomer is one or more of methacrylonitrile, acrylonitrile, styrene, hexafluorobutyl acrylate and dodecafluoroheptyl acrylate.
The high-strength nonstick roller acrylic rubber comprises the following raw materials in percentage by mass:
the total amount of the monomers is 100 percent;
wherein: 80-99% of acrylate monomer
0.1-10% of crosslinking monomer
0.1-10% of functional monomer;
relative to the total amount of monomers:
1 to 10 percent of emulsifier
0.01-0.2% of molecular weight regulator;
initiator:
0.01 to 0.1 percent of oxidant
0.004-0.04% of reducing agent
100-250% of deionized water.
The acrylic ester monomer is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate or butyl methacrylate.
The crosslinking monomer is one or more of acrylic acid, methacrylic acid, butenedioic acid or butenedioic acid monoalkyl ester.
The preparation method of the high-strength non-stick roller acrylic rubber is characterized by comprising the following steps of:
(1) premixing: premixing an emulsifier, deionized water, an acrylate monomer, a crosslinking monomer, a functional monomer and a molecular weight regulator; the premixing temperature is strictly controlled at 50 +/-5 ℃, the premixing stirring speed is strictly controlled at 180-220rpm, and the premixing time is strictly controlled at 25-45 min;
(2) and (3) deoxidizing: introducing N directly into the reactor2The oxygen in the reactor is replaced, and the reactor is not required to be subjected to pressure reduction treatment by a vacuum pump, so that the time is effectively saved;
(3) and (3) initiation: when the temperature of the reactor is 30-45 ℃, adding a redox initiator into the reactor, and strictly controlling the stirring speed of the reactor at 20-80 rpm;
(4) reaction: when the temperature of the reactor begins to rise, adjusting the stirring speed to 180-220rpm, slowly dripping the ice-water mixture, and controlling the reaction temperature to be 48-55 ℃;
(5) aging: when the temperature in the reactor is not changed any more, adjusting the stirring speed to 10-150 rpm, adjusting the temperature of the reactor to 75-85 ℃, and preserving the heat for 1-3 h;
(6) demulsifying: after aging is finished, carrying out steam stripping treatment on the crude rubber particles, removing unreacted micromolecules, and then adding electrolyte into the crude rubber particles or carrying out freezing treatment on the crude rubber particles to achieve a demulsification effect, so as to obtain crude rubber particles;
(7) washing and drying: and repeatedly cleaning the crude rubber particles by using deionized water at the temperature of 50-70 ℃, and drying in a drying oven at the temperature of 80-90 ℃ for 12 hours to obtain the acrylate crude rubber.
The vulcanized rubber composition consisting of the acrylate rubber comprises the following raw materials: acrylate rubber, a filler, an anti-aging agent, a processing aid, a vulcanizing agent and a vulcanization accelerator.
Graphene oxide is added to the filler.
The anti-aging agent is one or more of an anti-aging agent KY405, an anti-aging agent MBZ and an anti-aging agent MB.
The processing aid is stearic acid, paraffin, microcrystalline wax and the like.
The vulcanizing agents are No. 1 vulcanizing agent, No. 3 vulcanizing agent, CLP5250 and the like.
The vulcanization accelerator is ACT55, DOTG and the like.
The preparation method of the vulcanized rubber comprises the following steps:
adding acrylate rubber into a double-roll open mill, sequentially adding a processing aid, an anti-aging agent and a filler, adding a vulcanizing agent and a vulcanization accelerator after powder feeding is finished, and performing triangular bag making on a double roll for 5 times and thin passing for 5 times. And taking out the slices and placing for 24 hours for later use. Carrying out first-stage vulcanization on a flat vulcanizing machine under the condition of 180 ℃ multiplied by 10 min; the second vulcanization is carried out in an oven, and the vulcanization condition is 180 ℃ multiplied by 4 h.
When the acrylic ester rubber (namely the crude acrylic ester rubber) is prepared, the ice-water mixture is slowly dripped, the emulsion polymerization reaction temperature is controlled to be 48-55 ℃, so that the reaction process is very mild, phenomena such as implosion and the like can not be generated, the process is safe and controllable, the productivity is not influenced, and the product performance is controllable; in the polymerization process, a proper amount of methacrylonitrile (0.5-4%), hexafluorobutyl acrylate (0.5-2%) and dodecafluoroheptyl acrylate (0.5-2%) is introduced, so that the problem of roller sticking of the acrylate rubber is solved, and the prepared acrylate rubber does not need to be additionally added with any roller sticking prevention aid in the processing process (the mechanism that the roller sticking is not caused by adding a functional monomer is that the functional monomer can increase the elasticity of ACM, increase the Mooney viscosity of rubber and reduce the viscosity); when the acrylate rubber (namely, raw acrylate rubber) is used for mixing to prepare vulcanized rubber, 2-4% of Graphene Oxide (GO) is added and mixed with a matching system, so that the strength of the prepared vulcanized rubber can reach 19MPa, and the sealing requirements of machinery such as automobiles and the like are met.
Compared with the prior art, the invention has the following beneficial effects:
(1) the acrylate rubber has uniform and stable quality, high strength, non-stick property and excellent processing performance;
(2) the preparation method of the acrylate rubber has the advantages of simple and controllable process, safety, energy conservation and low cost;
(3) when the acrylate rubber is used for preparing vulcanized rubber, no anti-sticking roller auxiliary agent is added, and the obtained vulcanized rubber has high strength and meets the sealing requirements of machinery such as automobiles and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
(1) Mixing and stirring 4 parts of emulsifier, 150 parts of deionized water, 42 parts of ethyl acrylate, 40 parts of butyl acrylate, 5 parts of methoxyethyl acrylate, 5 parts of ethoxyethyl acrylate, 0.5 part of acrylic acid, 1.5 parts of methacrylic acid, 2 parts of methacrylonitrile, 2 parts of hexafluorobutyl acrylate, 2 parts of dodecafluoroheptyl acrylate and 0.01 part of molecular weight regulator at 50 ℃, wherein the stirring speed is strictly controlled at 200rpm, and the stirring time is 30 min;
(2) deoxidizing, introducing N directly into the reactor2So as to replace the oxygen therein, and the vacuum pump is not needed to carry out decompression treatment on the reactor;
(3) when the temperature is 35 ℃, adding a redox initiator, 0.01 part of an oxidant and 0.004 part of a reducing agent into the reactor, and controlling the stirring speed to be 50 rpm;
(4) when the temperature of the reactor begins to rise, adjusting the stirring speed to 200rpm, slowly dropwise adding an ice-water mixture, and controlling the reaction temperature to be 50 ℃;
(5) when the temperature in the reactor does not change any more, recording the polymerization time, adjusting the stirring speed to 80rpm, adjusting the temperature of the reactor to 80 ℃, and preserving heat and aging for 2 hours;
(6) after aging, steam stripping treatment is carried out on the mixture, and 1LCaCl is added into the mixture after unreacted micromolecules are removed2Solution of CaCl2The concentration of the solution is 5 percent, and raw rubber particles are obtained;
(7) repeatedly cleaning the crude rubber particles with 65 ℃ deionized water, putting the crude rubber particles into a drying oven at 85 +/-5 ℃ after completely cleaning, and drying for 12h to obtain the acrylate crude rubber.
Example 2
(1) Mixing and stirring 4 parts of emulsifier, 150 parts of deionized water, 46 parts of ethyl acrylate, 40 parts of butyl acrylate, 5 parts of methoxyethyl acrylate, 5 parts of ethoxyethyl acrylate, 0.5 part of acrylic acid, 1.5 parts of methacrylic acid, 2 parts of methacrylonitrile and 0.01 part of molecular weight regulator at 45 ℃, wherein the stirring speed is strictly controlled at 200rpm, and the stirring time is 25 min;
(2) deoxidizing, introducing N directly into the reactor2So as to replace the oxygen therein, and the vacuum pump is not needed to carry out decompression treatment on the reactor;
(3) when the temperature is 45 ℃, adding a redox initiator, 0.01 part of an oxidant and 0.004 part of a reducing agent into the reactor, and controlling the stirring speed to be 50 rpm;
(4) when the temperature of the reactor begins to rise, adjusting the stirring speed to 200rpm, slowly dropwise adding an ice-water mixture, and controlling the reaction temperature to be 48 ℃;
(5) when the temperature in the reactor does not change any more, recording the polymerization time, adjusting the stirring speed to 10rpm, adjusting the temperature of the reactor to 80 ℃, and preserving the heat and aging for 2 hours;
(6) after aging, steam stripping treatment is carried out on the mixture, and 1LCaCl is added into the mixture after unreacted micromolecules are removed2Solution of CaCl2The concentration of the solution is 5 percent, and raw rubber particles are obtained;
(7) repeatedly cleaning the crude rubber particles with 65 ℃ deionized water, putting the crude rubber particles into a drying oven at 85 +/-5 ℃ after completely cleaning, and drying for 12h to obtain the acrylate crude rubber.
Example 3
(1) Mixing and stirring 4 parts of emulsifier, 150 parts of deionized water, 42 parts of ethyl acrylate, 40 parts of butyl acrylate, 5 parts of methoxyethyl acrylate, 5 parts of ethoxyethyl acrylate, 0.5 part of acrylic acid, 1.5 parts of methacrylic acid, 2 parts of hexafluorobutyl acrylate, 4 parts of dodecafluoroheptyl acrylate and 0.01 part of molecular weight regulator at 55 ℃, wherein the stirring speed is strictly controlled at 200rpm, and the stirring time is 45 min;
(2) deoxidizing, introducing N directly into the reactor2So as to replace the oxygen therein, and the vacuum pump is not needed to carry out decompression treatment on the reactor;
(3) when the temperature is 40 ℃, adding a redox initiator, 0.01 part of an oxidant and 0.004 part of a reducing agent into the reactor, and controlling the stirring speed at 50 rpm;
(4) when the temperature of the reactor begins to rise, adjusting the stirring speed to 200rpm, slowly dropwise adding an ice-water mixture, and controlling the reaction temperature to be 55 ℃;
(5) when the temperature in the reactor does not change any more, recording the polymerization time, adjusting the stirring speed to 150rpm, adjusting the temperature of the reactor to 80 ℃, and preserving the heat and aging for 2 hours;
(6) after aging, steam stripping treatment is carried out on the mixture, and 1LCaCl is added into the mixture after unreacted micromolecules are removed2Solution of CaCl2The concentration of the solution is 5 percent, and raw rubber particles are obtained;
(7) repeatedly cleaning the crude rubber particles with 65 ℃ deionized water, putting the crude rubber particles into a drying oven at 85 +/-5 ℃ after completely cleaning, and drying for 12h to obtain the acrylate crude rubber.
Comparative example 1
(1) Mixing and stirring 4 parts of emulsifier, 150 parts of deionized water, 48 parts of ethyl acrylate, 40 parts of butyl acrylate, 5 parts of methoxyethyl acrylate, 5 parts of ethoxyethyl acrylate, 0.5 part of acrylic acid, 1.5 parts of methacrylic acid and 0.01 part of molecular weight regulator at 50 ℃, wherein the stirring speed is strictly controlled at 200rpm, and the stirring time is 30 min;
(2) deoxidizing, introducing N directly into the reactor2So as to replace the oxygen therein, and the vacuum pump is not needed to carry out decompression treatment on the reactor;
(3) when the temperature is 35 ℃, adding a redox initiator, 0.01 part of an oxidant and 0.004 part of a reducing agent into the reactor, and controlling the stirring speed to be 50 rpm;
(4) when the temperature of the reactor begins to rise, adjusting the stirring speed to 200rpm, slowly dropwise adding an ice-water mixture, and controlling the reaction temperature to be 50 ℃;
(5) when the temperature in the reactor does not change any more, recording the polymerization time, adjusting the stirring speed to 80rpm, adjusting the temperature of the reactor to 80 ℃, and preserving heat and aging for 2 hours;
(6) after aging, steam stripping treatment is carried out on the mixture, and 1LCaCl is added into the mixture after unreacted micromolecules are removed2Solution of CaCl2The concentration of the solution is 5 percent, and raw rubber particles are obtained;
(7) repeatedly cleaning the crude rubber particles with 65 ℃ deionized water, putting the crude rubber particles into a drying oven at 85 +/-5 ℃ after completely cleaning, and drying for 12h to obtain the acrylate crude rubber.
Comparative example 2
(1) Mixing and stirring 4 parts of emulsifier, 150 parts of deionized water, 46 parts of ethyl acrylate, 40 parts of butyl acrylate, 5 parts of methoxyethyl acrylate, 5 parts of ethoxyethyl acrylate, 0.5 part of acrylic acid, 1.5 parts of methacrylic acid, 2 parts of methacrylonitrile and 0.01 part of molecular weight regulator at 45 ℃, wherein the stirring speed is strictly controlled at 200rpm, and the stirring time is 25 min;
(2) deoxidizing, introducing N directly into the reactor2So as to replace the oxygen therein, and the vacuum pump is not needed to carry out decompression treatment on the reactor;
(3) when the temperature is 35 ℃, adding a redox initiator, 0.01 part of an oxidant and 0.004 part of a reducing agent into the reactor, and controlling the stirring speed to be 50 rpm;
(4) when the temperature of the reactor begins to rise, adjusting the stirring speed to 200rpm, slowly dropwise adding an ice-water mixture, and controlling the reaction temperature to be 40 ℃;
(5) when the temperature in the reactor does not change any more, recording the polymerization time, adjusting the stirring speed to 80rpm, adjusting the temperature of the reactor to 80 ℃, and preserving heat and aging for 2 hours;
(6) after aging, steam stripping treatment is carried out on the mixture, and 1LCaCl is added into the mixture after unreacted micromolecules are removed2Solution of CaCl2The concentration of the solution is 5 percent, and raw rubber particles are obtained;
(7) repeatedly cleaning the crude rubber particles with 65 ℃ deionized water, putting the crude rubber particles into a drying oven at 85 +/-5 ℃ after completely cleaning, and drying for 12h to obtain the acrylate crude rubber.
Comparative example 3
(1) Mixing and stirring 4 parts of emulsifier, 150 parts of deionized water, 46 parts of ethyl acrylate, 40 parts of butyl acrylate, 5 parts of methoxyethyl acrylate, 5 parts of ethoxyethyl acrylate, 0.5 part of acrylic acid, 1.5 parts of methacrylic acid, 2 parts of methacrylonitrile and 0.01 part of molecular weight regulator at 55 ℃, wherein the stirring speed is strictly controlled at 200rpm, and the stirring time is 45 min;
(2) deoxidizing, introducing N directly into the reactor2To replace oxygen thereinGas, a vacuum pump is not needed for carrying out pressure reduction treatment on the reactor;
(3) when the temperature is 35 ℃, adding a redox initiator, 0.01 part of an oxidant and 0.004 part of a reducing agent into the reactor, and controlling the stirring speed to be 50 rpm;
(4) when the temperature of the reactor begins to rise, adjusting the stirring speed to 200rpm, and naturally raising the temperature;
(5) when the temperature in the reactor does not change any more, recording the polymerization time, adjusting the stirring speed to 80rpm, adjusting the temperature of the reactor to 80 ℃, and preserving the heat and aging for 2 hours.
(6) After aging, steam stripping treatment is carried out on the mixture, and 1LCaCl is added into the mixture after unreacted micromolecules are removed2Solution of CaCl2The concentration of the solution is 5 percent, and the raw rubber particles are obtained.
(7) Repeatedly cleaning the crude rubber particles with 65 ℃ deionized water, putting the crude rubber particles into a drying oven at 85 +/-5 ℃ after completely cleaning, and drying for 12h to obtain the acrylate crude rubber.
Preparation of vulcanized rubber:
according to the rubber vulcanization formula shown in Table 1, the acrylate rubbers obtained in examples 1 to 3 and comparative examples 1 to 3 were fed into a two-roll mill, and then the processing aid, the antioxidant and the filler were sequentially added, and after the powder was consumed, the vulcanizing agent and the vulcanization accelerator were added, and a triangular bag was formed on a two-roll mill for 5 times and thinly passed for 5 times. And taking out the slices and placing for 24 hours for later use. Carrying out first-stage vulcanization on a flat vulcanizing machine under the condition of 180 ℃ multiplied by 10 min; the second vulcanization is carried out in an oven, and the vulcanization condition is 180 ℃ multiplied by 4 h.
The following property tests were performed on vulcanizates prepared from the acrylate green rubbers prepared in examples 1-3 and comparative examples 1-3:
1, intrinsic viscosity test
Measuring by adopting a one-point method of an Ubbelohde viscometer, weighing 25 +/-0.5 mg of the product, putting the product into a 25mL volumetric flask to prepare an ACM acetone solution, dissolving for 24h, and testing after filtering. The solvent is acetone, the water bath temperature is 30 +/-0.1 ℃, and the intrinsic viscosity [ eta ] is obtained by a one-point method.
ηr＝t/t0 ηsp＝ηr-1 wherein:
ηr-relative viscosity, dimensionless;
t-time of flow of the polymer solution, s;
t 0-time of solvent efflux, s;
[ eta ] -intrinsic viscosity, dL/g;
c-concentration of polymer solution, g/dL. Wherein c is 4 m/dL. V25 ml, m is in g.
2, gel content test
Weight reduction method. Weighing 25 + -0.5 mg of product, placing into a 25ml volumetric flask, preparing ACM acetone solution, dissolving for 24h, filtering with a 120 mesh copper net, drying the insoluble substance to constant weight at 80 ℃, and calculating gel content (G%) according to weight loss method.
Ash content test of raw rubber
Acrylate rubber crude rubber part 1 of the measurement of rubber ash according to GBT 4498.1-2013: the muffle furnace method was used to test the raw rubber ash.
4, crude rubber volatile test
The acrylate rubber volatile component is tested according to the determination standard of GBT24131-2009 raw rubber volatile component content.
Mooney viscosity test
Acrylate rubber Mooney viscosity determination of unvulcanized rubber according to GBT1232.1-2016 part 1 with a disc shear viscometer: determination of Mooney viscosity the test was carried out.
6, scorch time test
The scorch time of the acrylate rubber was measured by a disk shear viscometer for measuring the initial vulcanization characteristics of the unvulcanized rubber of GBT 1233-2008.
7, hardness test
Hardness according to GBT531.1-2008 vulcanized rubber or thermoplastic rubber indentation hardness test method part 1: the shore durometer (shore hardness) test was performed.
8, mechanical properties
The mechanical properties were tested according to the determination of tensile stress strain properties of GBT528-2009 vulcanizates or thermoplastic rubbers.
Glass transition temperature test (Tg)
The glass transition temperature was measured by DSC method.
TABLE 1 rubber vulcanization formulation
The above dosage is measured by mass portion.
TABLE 21 # - -9# rubber vulcanization Performance test results
Note: ● is not sticky; general; delta bonding
Comparing formula 1# with formula 6#, it can be seen that when no functional monomer is added, the mooney viscosity of the acrylate rubber is low, the acrylate rubber is very sticky to a roller, the viscosity of the rubber is very high, and the mooney viscosity, the tensile strength at break and the elongation at break of the rubber are all improved after the functional monomer is added.
Comparing formulation 7# with formulation 4#, it can be seen that when the reaction temperature is low, the polymerization reaction is very slow, and the intrinsic viscosity, Mooney viscosity, and tensile strength at break are all very low, indicating that the acrylate rubber has a low molecular weight, a high volatile content, indicating that the reaction is insufficient.
Comparing formulas 1# and 8#, it can be seen that when the temperature is controlled without ice water, the polymerization time is very short, the formation of implosion is high, the rubber gel content is high, the rubber strength is low, and the volatile component is high, indicating that the reaction is insufficient.
Comparing formulas 1#, 2#, 3#, and 9#, it can be seen that the addition of GO can significantly enhance the tensile strength at break of rubber.
Claims (6)
1. A high-strength non-stick roller acrylic rubber is characterized in that: functional monomers are introduced in the premixing procedure; during the polymerization reaction, the reaction temperature is controlled to be 48-55 ℃;
the functional monomers are hexafluorobutyl acrylate and dodecafluoroheptyl acrylate;
the preparation method of the high-strength non-stick roller acrylic rubber comprises the following steps:
(1) premixing: premixing an emulsifier, deionized water, an acrylate monomer, a crosslinking monomer, a functional monomer and a molecular weight regulator; the premixing temperature is controlled to be 50 +/-5 ℃, the premixing stirring speed is controlled to be 180-220rpm, and the premixing time is controlled to be 25-45 min;
(2) and (3) deoxidizing: introducing N directly into the reactor2To displace oxygen therein;
(3) and (3) initiation: when the temperature of the reactor is 30-45 ℃, adding a redox initiator into the reactor, and controlling the stirring speed of the reactor to be 20-80 rpm;
(4) reaction: when the temperature of the reactor begins to rise, adjusting the stirring speed to 180-220rpm, dropwise adding an ice-water mixture, and controlling the reaction temperature to be 48-55 ℃;
(5) aging: when the temperature in the reactor is not changed any more, adjusting the stirring speed to 10-150 rpm, adjusting the temperature of the reactor to 75-85 ℃, and preserving the heat for 1-3 h;
(6) demulsifying: after aging is finished, carrying out steam stripping treatment on the rubber particles, removing unreacted micromolecules, and then adding electrolyte into the rubber particles or carrying out freezing treatment on the rubber particles to obtain raw rubber particles;
(7) washing and drying: repeatedly cleaning the raw rubber particles with deionized water, and drying after completely cleaning to obtain the acrylate raw rubber;
the high-strength nonstick roller acrylic rubber comprises the following raw materials in percentage by mass:
the total amount of the monomers is 100 percent;
wherein:
92-99% of acrylate monomer
0.1-10% of crosslinking monomer
0.1-6% of functional monomer;
relative to the total amount of monomers:
1 to 10 percent of emulsifier
0.01-0.2% of molecular weight regulator;
initiator:
0.01 to 0.1 percent of oxidant
0.004-0.04% of reducing agent
100-250% of deionized water.
2. The high strength roll-less acrylate rubber according to claim 1, wherein: the acrylate monomer is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate or butyl methacrylate.
3. The high strength roll-less acrylate rubber according to claim 1, wherein: the crosslinking monomer is one or more of acrylic acid, methacrylic acid, butenedioic acid or butenedioic acid monoalkyl ester.
4. The high strength roll-less acrylate rubber according to claim 1, wherein: in the step (7), repeatedly cleaning the raw rubber particles by using deionized water at 50-70 ℃; drying in a drying oven at 80-90 ℃ for 12 h.
5. A vulcanized rubber composition comprising the acrylate rubber according to any one of claims 1 to 4, wherein: the method comprises the following raw materials: acrylate rubber, a filler, an anti-aging agent, a processing aid, a vulcanizing agent and a vulcanization accelerator.
6. The vulcanized rubber composition according to claim 5, wherein: graphene oxide is added to the filler.
Priority Applications (1)
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| CN1861678A (en) * | 2006-05-19 | 2006-11-15 | 北京化工大学 | Preparation process of easy processing cold resisting type polyacrylate rubber |
| CN102167772A (en) * | 2011-01-20 | 2011-08-31 | 安徽大学 | Fluorine-containing easily processed acrylate rubber and preparation method thereof |
| CN110498881A (en) * | 2019-07-16 | 2019-11-26 | 九江杜威橡胶科技有限公司 | A kind of method of high intensity carboxyl type acrylic rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1861678A (en) * | 2006-05-19 | 2006-11-15 | 北京化工大学 | Preparation process of easy processing cold resisting type polyacrylate rubber |
| CN102167772A (en) * | 2011-01-20 | 2011-08-31 | 安徽大学 | Fluorine-containing easily processed acrylate rubber and preparation method thereof |
| CN110498881A (en) * | 2019-07-16 | 2019-11-26 | 九江杜威橡胶科技有限公司 | A kind of method of high intensity carboxyl type acrylic rubber |
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