CN107459687B - Wide-temperature-range high-damping nano rubber composite material and preparation method thereof - Google Patents
Wide-temperature-range high-damping nano rubber composite material and preparation method thereof Download PDFInfo
- Publication number
- CN107459687B CN107459687B CN201610389303.6A CN201610389303A CN107459687B CN 107459687 B CN107459687 B CN 107459687B CN 201610389303 A CN201610389303 A CN 201610389303A CN 107459687 B CN107459687 B CN 107459687B
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- rubber
- parts
- nano tube
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A wide temperature range high damping nanometer rubber composite material and a preparation method thereof belong to the technical field of rubber preparation. The method is characterized in that the ternary integrated rubber containing the carbon nano tube is obtained by jointly coagulating a carbon nano tube aqueous solution and ternary integrated rubber latex of styrene, isoprene and butadiene; the nitrile rubber and the ternary integrated rubber containing the carbon nano tube are blended and co-vulcanized to obtain the rubber. The damping temperature range of the composite material with tan delta larger than 0.3 is-55.0-79.5 ℃. The rubber with different moduli and tan delta is obtained, a wider damping peak is obtained between two glass transition temperatures, and the interface action between polymer particles is enhanced by adding the filling material carbon nano tube, so that the glass transition temperature range of the rubber is widened while the damping value of the rubber material is improved.
Description
Technical Field
A wide temperature range high damping nanometer rubber composite material and a preparation method thereof belong to the technical field of rubber preparation.
Background
The macromolecule damping material is a new material developed, and the viscoelasticity of the macromolecule is utilized to absorb the energy of vibration, and the absorbed mechanical energy or acoustic energy is partially converted into heat energy and dissipated, so that the effect of reducing the amplitude or reducing the amplitude is achieved. The damping properties of a polymer are determined by its glass transition, where the damping value of the polymer is large, and the damping performance is usually evaluated by the height of its intrinsic dissipation peak and its span temperature range. The wide-temperature-range high-damping material is required to be at least in the temperature range of 60-80 ℃, and the damping factor tan delta is more than 0.3. Rubber is an ideal damping material, but the rubber elastomer damping material has the defects that the temperature range of the glass transition region of a single rubber variety is generally narrow and is only 20-40 ℃, and the temperature range is concentrated below room temperature. Therefore, it is required to widen the glass transition temperature range of the rubber while increasing the damping value of the rubber material.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides a wide-temperature-range high-damping nano rubber composite material with higher damping performance in wide frequency and wide temperature range and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the wide-temperature-range high-damping nano rubber composite material is characterized by comprising the following specific preparation steps of:
1) firstly, adding deionized water into a coagulator, adding 70-120 parts by weight of ammonium sulfate coagulation mother liquor into the coagulator, starting stirring, adding 10-20 parts by weight of carbon nano tube aqueous solution, and stirring for 5 min; then adding 80-99 parts by weight of ternary integrated rubber latex, adding a coagulant, and dehydrating and drying the coagulated ternary integrated rubber particles to obtain ternary integrated rubber containing carbon nano tubes; the coagulation temperature is 50-60 ℃, and the stirring speed is 300-400 r/min; the mass ratio of styrene to isoprene to butadiene in the ternary integrated rubber latex is 26-31: 16-20: 51-57, and the Mooney viscosity ML 1+4 at 100 ℃ is 55-70;
2) weighing 5-20 parts by weight of nitrile rubber and 80-95 parts by weight of the ternary integrated rubber containing the carbon nano tube prepared in the step 1), adding a processing aid, mixing in an internal mixer for 10-15 min, and then co-vulcanizing to obtain the rubber.
The existing methods for modifying the traditional rubber damping material mainly comprise blending, copolymerization, interpenetrating polymer networks and the like, and in recent years, people pay attention to the design of rubber molecular structures and microstructures by adopting chemical or physical methods or the construction of special damping mechanisms, and good effects are obtained. The carbon nano tube composite material has the advantages of large damping, high specific stiffness, low density, wide temperature and frequency limit interval and the like as a novel material, and the carbon nano tube added into the rubber material enhances the interface action among polymer particles, so that the material has higher damping performance in wide frequency and wide temperature range. The invention adopts ternary integrated rubber emulsion styrene-isoprene-butadiene (ESIBR) with dense lateral methyl and non-polarity in a molecular structure to be flocculated with carbon nano tube emulsion to prepare ternary integrated rubber containing carbon nano tubes, and then the ternary integrated rubber is blended with nitrile rubber with strong polarity to prepare ESIBR/CNT/NBR blend. The two rubbers with different glass transition temperatures are blended, the blending ratio is changed, not only the rubbers with different moduli and tan delta can be obtained, but also a wider damping peak is obtained between the two glass transition temperatures, and the interface action between polymer particles is enhanced by adding the filling material carbon nano tube, so that the glass transition temperature range of the rubbers is widened while the damping value of the rubber material is improved.
In order to achieve more uniform dispersion, the co-flocculation of carbon nanotubes and ESIBR is performed by first preparing the carbon nanotubes into an aqueous solution. The invention provides two preparation methods of modified carbon nanotube aqueous solutions:
1. when the carbon nanotube aqueous solution in the step 1) is a hydroxyl-modified carbon nanotube aqueous solution, the preparation steps are as follows:
1.1) adding the carbon nano tube into 1.8-2.0 mol/L sodium hydroxide aqueous solution, and stirring and dispersing to obtain carbon nano tube dispersion liquid;
1.2) pouring the carbon nano tube dispersion liquid into a stainless steel high-pressure reaction kettle, sealing, and reacting for 2-2.2 h at 180-185 ℃;
1.3) cooling to room temperature after the reaction is finished, then filtering with a polyvinylidene fluoride microporous filter membrane with the pore diameter of 0.45 mu m, washing with deionized water until the pH of the filtrate is =7, and washing with methanol for 2-3 times to obtain a filtrate; vacuum drying the filtrate at 40-45 deg.c; obtaining black carbon nanotube powder directly modified by hydroxyl;
1.4) dissolving the hydroxyl modified carbon nano-tube powder in water to obtain a hydroxyl modified carbon nano-tube aqueous solution.
2. When the carbon nanotube aqueous solution in the step 1) is a carboxyl modified carbon nanotube aqueous solution, the preparation steps are as follows:
2.1) dispersing the carbon nano tube in toluene by using ultrasonic waves, and then adding a toluene solution of azodiisobutyronitrile under the condition of continuous stirring; introducing nitrogen for 0.5 to 1 hour to remove oxygen, and reacting at 72 to 76 ℃ for 3.5 to 4.5 hours; washing the reaction product with toluene for 4-5 times, and then drying at 40-45 ℃ in vacuum; obtaining black azodiisobutyronitrile modified carbon nanotube powder;
2.2) dispersing the azodiisobutyronitrile modified carbon nano tube in a methanol solution of sodium hydroxide, and refluxing for 45-50 h at 60-62 ℃; after the reaction is finished, adjusting the pH value to be pH =3.0 by hydrochloric acid; washing the product with deionized water for 4-5 times, and vacuum drying at 40-45 ℃; obtaining black carboxyl modified carbon nanotube powder;
2.3) dissolving the carboxyl modified carbon nano tube powder in water to obtain a carboxyl modified carbon nano tube aqueous solution.
The preparation methods of the two modified carbon nanotube aqueous solutions can greatly improve the co-flocculation effect of the carbon nanotubes and the ESIBR, and the carbon nanotubes are uniformly dispersed in the composite material, so that the interface effect among polymer particles is better enhanced.
The invention also provides a preferable formula of the coagulation mother liquor and the coagulant, wherein the coagulation mother liquor in the step 1) is prepared by dissolving 20 parts by weight of ammonium sulfate in 50-100 parts by weight of desalted and deoxidized water. The coagulant in the step 1) is prepared by mixing 96-98 parts by mass of polyepichlorohydrin dimethylamine and 2-4 parts by mass of cellulose derivative, and then diluting the mixture with desalted and deoxygenated water until the solid content is 10-15%. Can ensure the flocculation effect of the ternary integrated rubber containing the carbon nano tube.
The nitrile rubber in the step 2) is an amorphous elastomer with the acrylonitrile content of 24-26%, and the Mooney viscosity ML100 ℃ of 1+4 of the nitrile rubber is 45-65.
The wide-temperature-range high-damping nano rubber composite material prepared by the preparation method comprises the following components in parts by weight: 5-20 parts of nitrile rubber, 80-95 parts of ternary integrated rubber containing carbon nano tubes, and the damping temperature range of the composite material with tan delta larger than 0.3 is-55.0-79.5 ℃.
Compared with the prior art, the wide-temperature-range high-damping nano rubber composite material has the beneficial effects that: the invention adopts ternary integrated rubber emulsion styrene-isoprene-butadiene (ESIBR) with dense lateral methyl and non-polarity in a molecular structure to be flocculated with carbon nano tube emulsion to prepare ternary integrated rubber containing carbon nano tubes, and then the ternary integrated rubber is blended with nitrile rubber with strong polarity to prepare ESIBR/CNT/NBR blend. The two rubbers with different glass transition temperatures are blended, the blending ratio is changed, not only the rubbers with different moduli and tan delta are obtained, but also a wider damping peak is obtained between the two glass transition temperatures, and the interface action between polymer particles is enhanced by adding the filling material carbon nano tube, so that the glass transition temperature range of the rubbers is widened while the damping value of the rubber material is improved. The damping temperature range is widened after the two rubbers with different glass transition temperatures are blended, the effective damping temperature range (tan delta is more than 0.3) reaches 134.5 ℃ (from minus 55.0 ℃ to 79.5 ℃), and the damping value of the rubber composite material is obviously increased by adding the carbon nano tube.
Detailed Description
The present invention is further illustrated by the following specific examples, of which example 1 is the most preferred.
Example 1
1) Preparing a hydroxyl modified carbon nanotube aqueous solution:
preparing a sodium hydroxide aqueous solution with the concentration of 2.0mol/L, weighing 2.5g of carbon nano tubes, adding into 50mL of the sodium hydroxide aqueous solution prepared above, and stirring and dispersing for 5 min; pouring the carbon nano tube dispersion liquid into a 50mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing and reacting for 2h at 180 ℃; after the reaction is finished, cooling to room temperature, filtering by using a polyvinylidene fluoride microporous filter membrane with the pore diameter of 0.45 mu m, washing by using deionized water until the pH of the filtrate is =7, and washing for 2 times by using methanol; vacuum drying the filtrate at 40 deg.C overnight; obtaining black carbon nanotube powder directly modified by hydroxyl; 5 parts of hydroxyl modified carbon nanotube powder is dissolved in 95 parts of water to obtain 5% of hydroxyl modified carbon nanotube aqueous solution;
2) preparation of a condensation mother solution: accurately weighing 20 parts by weight of ammonium sulfate, dissolving the ammonium sulfate in 80 parts by weight of desalted and deoxidized water to prepare a condensed mother solution for later use;
3) preparation of a coagulant: mixing 98.0 parts by mass of polyepichlorohydrin dimethylamine with 2.0 parts by mass of cellulose derivative, and diluting the mixture by using desalted and deoxidized water to obtain a solution with the solid content of 10 percent for later use;
4) the mass ratio of styrene to isoprene to butadiene in the ternary integrated rubber emulsion is S: I: B =28:18:54, and the Mooney viscosity ML100 ℃ (1 + 4) is 65; the nitrile rubber is an amorphous elastomer with the acrylonitrile content of 24-26%, and the Mooney viscosity ML100 ℃ (1 + 4) is 55;
5) adding deionized water into a coagulator, controlling the temperature of the deionized water at 55 ℃, adding 200ml of 20% ammonium sulfate solution into the coagulator, starting stirring, stirring at the rotating speed of 400r/min, adding 15 parts of carbon nano tube aqueous solution, and stirring for 5 min; adding 85 parts of ESIBR latex slowly, and dehydrating and drying the condensed ternary integrated rubber particles; weighing 10 parts of nitrile rubber and 90 parts of ternary integrated rubber containing carbon nano tubes, plasticating for 5 minutes, weighing 20 parts of carbon black and a certain amount of processing aid, mixing for 15 minutes in an internal mixer, and vulcanizing to obtain the rubber composite material.
Example 2
1) Preparing a hydroxyl modified carbon nanotube aqueous solution:
preparing a sodium hydroxide aqueous solution with the concentration of 1.8mol/L, weighing 2g of carbon nano tube, adding into 50mL of the sodium hydroxide aqueous solution prepared above, and stirring and dispersing for 5 min; pouring the carbon nano tube dispersion liquid into a 50mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing and reacting for 2.2h at 185 ℃; after the reaction is finished, cooling to room temperature, filtering by using a polyvinylidene fluoride microporous filter membrane with the pore diameter of 0.45 mu m, washing by using deionized water until the pH of the filtrate is =7, and washing for 3 times by using methanol; vacuum drying the filtrate at 45 deg.C overnight; obtaining black carbon nanotube powder directly modified by hydroxyl; 5 parts of hydroxyl modified carbon nanotube powder is dissolved in 95 parts of water to obtain 5% of hydroxyl modified carbon nanotube aqueous solution;
2) preparation of a condensation mother solution: accurately weighing 20 parts by weight of ammonium sulfate, dissolving the ammonium sulfate in 100 parts by weight of desalted and deoxidized water to prepare a condensed mother solution for later use;
3) preparation of a coagulant: mixing 96.0 parts by mass of polyepichlorohydrin dimethylamine and 4.0 parts by mass of cellulose derivative, and diluting the mixture by using desalted and deoxidized water to obtain a solution with the solid content of 10 percent for later use;
4) the mass ratio of styrene, isoprene and butadiene in the ternary integrated rubber emulsion is S: I: B =26:20:51, and the Mooney viscosity ML100 ℃ (1 + 4) is 55; the nitrile rubber is an amorphous elastomer with the acrylonitrile content of 24-26%, and the Mooney viscosity ML100 ℃ (1 + 4) is 65;
5) adding deionized water into a coagulator, controlling the temperature at 60 ℃, adding 200ml of 17% ammonium sulfate solution into the coagulator, starting stirring, stirring at the rotating speed of 300r/min, adding 20 parts of carbon nano tube aqueous solution, and stirring for 5 min; slowly adding 99 parts of SIBR latex, and dehydrating and drying the condensed ternary integrated rubber particles; weighing 15 parts of nitrile rubber and 85 parts of ternary integrated rubber containing carbon nano tubes, plasticating for 5 minutes, weighing 30 parts of carbon black and a certain amount of processing aid, mixing for 15 minutes in an internal mixer, and vulcanizing to obtain the rubber composite material.
Example 3
1) Preparing a hydroxyl modified carbon nanotube aqueous solution:
preparing a sodium hydroxide aqueous solution with the concentration of 2.0mol/L, weighing 3g of carbon nano tube, adding into 50mL of the sodium hydroxide aqueous solution prepared above, and stirring and dispersing for 5 min; pouring the carbon nano tube dispersion liquid into a 50mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing and reacting for 2h at 180 ℃; after the reaction is finished, cooling to room temperature, filtering by using a polyvinylidene fluoride microporous filter membrane with the pore diameter of 0.45 mu m, washing by using deionized water until the pH of the filtrate is =7, and washing for 2 times by using methanol; vacuum drying the filtrate at 40 deg.C overnight; obtaining black carbon nanotube powder directly modified by hydroxyl; 5 parts of hydroxyl modified carbon nanotube powder is dissolved in 95 parts of water to obtain 5% of hydroxyl modified carbon nanotube aqueous solution;
2) preparation of a condensation mother solution: accurately weighing 20 parts by weight of ammonium sulfate, dissolving the ammonium sulfate in 50 parts by weight of desalted and deoxidized water to prepare a condensed mother solution for later use;
3) preparation of a coagulant: mixing 98.0 parts by mass of polyepichlorohydrin dimethylamine with 2.0 parts by mass of cellulose derivative, and diluting the mixture by using desalted and deoxidized water to obtain a solution with the solid content of 10 percent for later use;
4) the mass ratio of styrene, isoprene and butadiene in the ternary integrated rubber emulsion is S: I: B =31:16:57, and the Mooney viscosity ML100 ℃ (1 + 4) is 70; the nitrile rubber is an amorphous elastomer with the acrylonitrile content of 24-26%, and the Mooney viscosity ML100 ℃ (1 + 4) is 65;
5) adding deionized water into a coagulator, controlling the temperature at 50 ℃, adding 200ml of 28.5% ammonium sulfate solution into the coagulator, starting stirring, stirring at the rotating speed of 400r/min, adding 10 parts of carbon nano tube aqueous solution, and stirring for 5 min; adding 80 parts of ESIBR latex slowly, and dehydrating and drying the condensed ternary integrated rubber particles; weighing 10 parts of nitrile rubber and 90 parts of ternary integrated rubber containing carbon nano tubes, plasticating for 5 minutes, weighing 20 parts of carbon black and a certain amount of processing aid, mixing for 15 minutes in an internal mixer, and vulcanizing to obtain the rubber composite material.
Example 4
1) Preparing a carboxyl modified carbon nano tube aqueous solution:
50mg of carbon nanotubes were ultrasonically (10min) dispersed in 50mL of toluene, and then 10mL of a toluene solution of Azobisisobutyronitrile (AIBN) (l.0g of AIBN dissolved in 10mL of toluene) was added with continuous stirring; introducing nitrogen for 0.5h, deoxidizing, and reacting for 4h at 75 ℃; washing the reaction product with toluene for 4-5 times, and vacuum drying at 40 deg.c overnight; obtaining black AIBN modified carbon nanotube powder;
dispersing 30mgAIBN modified carbon nano-tube in 50mL of methanol solution of sodium hydroxide (10mol/L), and refluxing for 48h at 60 ℃; after the reaction is finished, adjusting the pH value to be acidic pH =3.0 by hydrochloric acid; washing the product with deionized water for 4-5 times, and vacuum drying at 40 deg.C overnight; obtaining black carboxyl modified carbon nanotube powder; 5 parts of carboxyl modified carbon nanotube powder is dissolved in 95 parts of water to obtain 5% carboxyl modified carbon nanotube aqueous solution;
2) preparation of a condensation mother solution: accurately weighing 20 parts by weight of ammonium sulfate, dissolving the ammonium sulfate in 80 parts by weight of desalted and deoxidized water to prepare a condensed mother solution for later use;
3) preparation of a coagulant: mixing 98.0 parts by mass of polyepichlorohydrin dimethylamine with 2.0 parts by mass of cellulose derivative, and diluting the mixture by using desalted and deoxidized water to obtain a solution with the solid content of 10 percent for later use;
4) the mass ratio of styrene to isoprene to butadiene in the ternary integrated rubber emulsion is S: I: B =28:18:54, and the Mooney viscosity ML100 ℃ (1 + 4) is 55-70; the nitrile rubber is an amorphous elastomer with the acrylonitrile content of 24-26%, and the Mooney viscosity ML100 ℃ (1 + 4) is 45-65;
5) adding deionized water into a coagulator, controlling the temperature at 60 ℃, adding 220ml of 20% ammonium sulfate solution into the coagulator, starting stirring, stirring at the rotating speed of 350r/min, adding 5 parts of carbon nano tube aqueous solution, and stirring for 5 min; and slowly adding 95 parts of SIBR latex, and dehydrating and drying the condensed ternary integrated rubber particles. Weighing 20 parts of nitrile rubber, 80 parts of ternary integrated rubber containing carbon nano tubes, 40 parts of carbon black and a certain amount of processing aid, mixing for 15min in an internal mixer, and co-vulcanizing to obtain the rubber composite material.
Example 5
1) Preparing a carboxyl modified carbon nano tube aqueous solution:
50mg of carbon nanotubes were ultrasonically (10min) dispersed in 50mL of toluene, and then 10mL of a toluene solution of Azobisisobutyronitrile (AIBN) (l.0g of AIBN dissolved in 10mL of toluene) was added with continuous stirring; introducing nitrogen for 1h to remove oxygen, and reacting for 4.5h at 72 ℃; washing the reaction product with toluene for 4 times, and vacuum drying at 45 ℃ overnight; obtaining black AIBN modified carbon nanotube powder;
dispersing 30mgAIBN modified carbon nano-tube in 50mL of methanol solution of sodium hydroxide (10mol/L), and refluxing for 50h at 60 ℃; after the reaction is finished, adjusting the pH value to be acidic pH =3.0 by hydrochloric acid; washing the product with deionized water for 4 times, and vacuum drying at 45 ℃ overnight; obtaining black carboxyl modified carbon nanotube powder; 5 parts of carboxyl modified carbon nanotube powder is dissolved in 95 parts of water to obtain 5% carboxyl modified carbon nanotube aqueous solution;
2) preparation of a condensation mother solution: accurately weighing 20 parts by weight of ammonium sulfate, dissolving the ammonium sulfate in 80 parts by weight of desalted and deoxidized water to prepare a condensed mother solution for later use;
3) preparation of a coagulant: mixing 98.0 parts by mass of polyepichlorohydrin dimethylamine with 2.0 parts by mass of cellulose derivative, and diluting the mixture by using desalted and deoxidized water to obtain a solution with the solid content of 10 percent for later use;
4) the mass ratio of styrene to isoprene to butadiene in the ternary integrated rubber emulsion is S: I: B =28:18:54, and the Mooney viscosity ML100 ℃ (1 + 4) is 65; the nitrile rubber is an amorphous elastomer with the acrylonitrile content of 25 percent, and the Mooney viscosity ML100 ℃ (1 + 4) is 55;
5) adding deionized water into a coagulator, controlling the temperature at 60 ℃, adding 220ml of 20% ammonium sulfate solution into the coagulator, starting stirring, stirring at the rotating speed of 350r/min, adding 5 parts of carbon nano tube aqueous solution, and stirring for 5 min; and slowly adding 95 parts of SIBR latex, and dehydrating and drying the condensed ternary integrated rubber particles. Weighing 20 parts of nitrile rubber, 80 parts of ternary integrated rubber containing carbon nano tubes, 40 parts of carbon black and a certain amount of processing aid, mixing for 15min in an internal mixer, and co-vulcanizing to obtain the rubber composite material.
Example 6
1) Preparing a carboxyl modified carbon nano tube aqueous solution:
50mg of carbon nanotubes were ultrasonically (10min) dispersed in 50mL of toluene, and then 10mL of a toluene solution of Azobisisobutyronitrile (AIBN) (l.0g of AIBN dissolved in 10mL of toluene) was added with continuous stirring; introducing nitrogen for 0.5h to remove oxygen, and reacting for 3.5h at 76 ℃; washing the reaction product with toluene for 5 times, and vacuum drying at 40 ℃ overnight; obtaining black AIBN modified carbon nanotube powder;
dispersing 30mgAIBN modified carbon nano-tube in 50mL of methanol solution of sodium hydroxide (10mol/L), and refluxing for 45h at 62 ℃; after the reaction is finished, adjusting the pH value to be acidic pH =3.0 by hydrochloric acid; washing the product with deionized water for 5 times, and vacuum drying at 40 ℃ overnight; obtaining black carboxyl modified carbon nanotube powder; 5 parts of carboxyl modified carbon nanotube powder is dissolved in 95 parts of water to obtain 5% carboxyl modified carbon nanotube aqueous solution;
2) preparation of a condensation mother solution: accurately weighing 20 parts by weight of ammonium sulfate, dissolving the ammonium sulfate in 50 parts by weight of desalted and deoxidized water to prepare a condensed mother solution for later use;
3) preparation of a coagulant: mixing 98.0 parts by mass of polyepichlorohydrin dimethylamine with 2.0 parts by mass of cellulose derivative, and diluting the mixture by using desalted and deoxidized water to obtain a solution with the solid content of 10 percent for later use;
4) the mass ratio of styrene to isoprene to butadiene in the ternary integrated rubber emulsion is S: I: B =28:18:54, and the Mooney viscosity ML100 ℃ (1 + 4) is 65; the nitrile rubber is an amorphous elastomer with the acrylonitrile content of 26 percent, and the Mooney viscosity ML100 ℃ (1 + 4) is 55;
5) adding deionized water into a coagulator, controlling the temperature at 60 ℃, adding 220ml of 20% ammonium sulfate solution into the coagulator, starting stirring, stirring at the rotating speed of 350r/min, adding 5 parts of carbon nano tube aqueous solution, and stirring for 5 min; and slowly adding 95 parts of SIBR latex, and dehydrating and drying the condensed ternary integrated rubber particles. Weighing 20 parts of nitrile rubber, 80 parts of ternary integrated rubber containing carbon nano tubes, 40 parts of carbon black and a certain amount of processing aid, mixing for 15min in an internal mixer, and co-vulcanizing to obtain the rubber composite material.
TABLE 1 damping temp. range of ternary integrated rubber and nitrile rubber composite material
Note: t0.3: temperature range of tan delta > 0.3
Comparative example 1:
weighing 90 parts of styrene butadiene rubber SBR-1502, blending 10 parts of nitrile rubber in an internal mixer for 5 minutes, weighing 50 parts of carbon black and a certain amount of processing aid, blending in the internal mixer for 20 minutes, and then co-vulcanizing to obtain the rubber composite material.
Comparative example 2:
weighing 85 parts of styrene butadiene rubber SBR-1502, 15 parts of nitrile rubber, mixing and plastifying for 5 minutes in an internal mixer, weighing 50 parts of carbon black and a certain amount of processing aid, mixing for 20 minutes in the internal mixer, and co-vulcanizing to obtain the rubber composite material
Comparative example 3:
weighing 80 parts of styrene butadiene rubber and 20 parts of nitrile butadiene rubber, mixing and plasticating the mixture in an internal mixer for 5 minutes, weighing 50 parts of carbon black and a certain amount of processing aid, mixing the mixture in the internal mixer for 20 minutes, and then co-vulcanizing to obtain the rubber composite material.
TABLE 2 damping temperature range of styrene-butadiene rubber and nitrile rubber composite
As can be seen from the test results of the items of the examples and the comparative examples, the damping temperature range of the rubber composite material prepared by the ternary integrated rubber containing carbon nano tubes and the nitrile rubber in the examples is widened, the effective damping temperature range (tan delta > 0.3) reaches 134.5 ℃ (from-55.0 ℃ to 79.5 ℃), and the damping value is obviously increased.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of a wide temperature range high damping nanometer rubber composite material is characterized by comprising the following specific preparation steps:
1) firstly, adding deionized water into a coagulator, adding 70-120 parts by weight of ammonium sulfate coagulation mother liquor into the coagulator, starting stirring, adding 10-20 parts by weight of carbon nano tube aqueous solution, and stirring for 5 min; then adding 80-99 parts by weight of ternary integrated rubber latex, adding a coagulant, and dehydrating and drying the coagulated ternary integrated rubber particles to obtain ternary integrated rubber containing carbon nano tubes; the coagulation temperature is 50-60 ℃, and the stirring speed is 300-400 r/min; the mass ratio of styrene to isoprene to butadiene in the ternary integrated rubber latex is 26-31: 16-20: 51-57, and the Mooney viscosity ML 1+4 at 100 ℃ is 55-70;
2) weighing 5-20 parts by weight of nitrile rubber and 80-95 parts by weight of the ternary integrated rubber containing the carbon nano tube prepared in the step 1), adding a processing aid, mixing in an internal mixer for 10-15 min, and then co-vulcanizing to obtain the rubber.
2. The preparation method of the wide temperature range and high damping nanometer rubber composite material according to claim 1, characterized in that: the carbon nano tube aqueous solution in the step 1) is hydroxyl modified carbon nano tube aqueous solution.
3. The preparation method of the wide temperature range high damping nanometer rubber composite material according to claim 2, characterized in that: the preparation method of the hydroxyl modified carbon nanotube aqueous solution comprises the following steps:
3.1) adding the carbon nano tube into 1.8-2.0 mol/L sodium hydroxide aqueous solution, and stirring and dispersing to obtain carbon nano tube dispersion liquid;
3.2) pouring the carbon nano tube dispersion liquid into a stainless steel high-pressure reaction kettle, sealing, and reacting for 2-2.2 h at 180-185 ℃;
3.3) cooling to room temperature after the reaction is finished, then filtering with a polyvinylidene fluoride microporous filter membrane with the pore diameter of 0.45 mu m, washing with deionized water until the pH of the filtrate is =7, and washing with methanol for 2-3 times to obtain a filtrate; vacuum drying the filtrate at 40-45 deg.c; obtaining black carbon nanotube powder directly modified by hydroxyl;
3.4) dissolving the hydroxyl modified carbon nano-tube powder in water to obtain a hydroxyl modified carbon nano-tube aqueous solution.
4. The preparation method of the wide temperature range and high damping nanometer rubber composite material according to claim 1, characterized in that: the carbon nano tube aqueous solution in the step 1) is a carboxyl modified carbon nano tube aqueous solution.
5. The preparation method of the wide temperature range high damping nanometer rubber composite material according to claim 4, characterized in that: the preparation method of the carboxyl modified carbon nano tube aqueous solution comprises the following steps:
5.1) dispersing the carbon nano tube in toluene by using ultrasonic waves, and then adding a toluene solution of azodiisobutyronitrile under the condition of continuous stirring; introducing nitrogen for 0.5 to 1 hour to remove oxygen, and reacting at 72 to 76 ℃ for 3.5 to 4.5 hours; washing the reaction product with toluene for 4-5 times, and then drying at 40-45 ℃ in vacuum; obtaining black azodiisobutyronitrile modified carbon nanotube powder;
5.2) dispersing the azodiisobutyronitrile modified carbon nano tube in a methanol solution of sodium hydroxide, and refluxing for 45-50 h at 60-62 ℃; after the reaction is finished, adjusting the pH value to be pH =3.0 by hydrochloric acid; washing the product with deionized water for 4-5 times, and vacuum drying at 40-45 ℃; obtaining black carboxyl modified carbon nanotube powder;
and 5.3) dissolving the carboxyl modified carbon nano tube powder in water to obtain a carboxyl modified carbon nano tube aqueous solution.
6. The preparation method of the wide temperature range and high damping nanometer rubber composite material according to claim 1, characterized in that: the coagulation mother liquor in the step 1) is prepared by dissolving 20 parts by weight of ammonium sulfate in 50-100 parts by weight of desalted and deoxygenated water.
7. The preparation method of the wide temperature range and high damping nanometer rubber composite material according to claim 1, characterized in that: the coagulant in the step 1) is prepared by mixing 96-98 parts by mass of polyepichlorohydrin dimethylamine and 2-4 parts by mass of cellulose derivative, and then diluting the mixture with desalted and deoxygenated water until the solid content is 10-15%.
8. The preparation method of the wide temperature range and high damping nanometer rubber composite material according to claim 1, characterized in that: the nitrile rubber in the step 2) is an amorphous elastomer with the acrylonitrile content of 24-26%, and the Mooney viscosity ML100 ℃ of 1+4 of the nitrile rubber is 45-65.
9. The wide-temperature-range high-damping nano rubber composite material prepared by the preparation method according to any one of claims 1 to 8 is characterized by comprising the following components in parts by weight: 5-20 parts of nitrile rubber, 80-95 parts of ternary integrated rubber containing carbon nano tubes, and the damping temperature range of the composite material with tan delta larger than 0.3 is-55.0-79.5 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610389303.6A CN107459687B (en) | 2016-06-06 | 2016-06-06 | Wide-temperature-range high-damping nano rubber composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610389303.6A CN107459687B (en) | 2016-06-06 | 2016-06-06 | Wide-temperature-range high-damping nano rubber composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107459687A CN107459687A (en) | 2017-12-12 |
| CN107459687B true CN107459687B (en) | 2020-04-14 |
Family
ID=60545557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610389303.6A Active CN107459687B (en) | 2016-06-06 | 2016-06-06 | Wide-temperature-range high-damping nano rubber composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107459687B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047628A (en) * | 2017-12-27 | 2018-05-18 | 西南石油大学 | A kind of wide temperature domain damping elastic composite and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229724A (en) * | 2011-06-20 | 2011-11-02 | 华南理工大学 | Ternary rubber composite with wide temperature range and high damping property and preparation method thereof |
| CN103160056A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method of high-performance butadiene-styrene-isoprene powder polymer |
| CN103159963A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method of high-performance powdered nitrile rubber |
| CN105566514A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | Ternary integrated rubber latex agglomeration process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2949624A4 (en) * | 2013-01-24 | 2017-01-04 | Zeon Corporation | Carbon nanotube dispersion, method for manufacturing same, carbon nanotube composition, and method for manufacturing same |
-
2016
- 2016-06-06 CN CN201610389303.6A patent/CN107459687B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229724A (en) * | 2011-06-20 | 2011-11-02 | 华南理工大学 | Ternary rubber composite with wide temperature range and high damping property and preparation method thereof |
| CN103160056A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method of high-performance butadiene-styrene-isoprene powder polymer |
| CN103159963A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method of high-performance powdered nitrile rubber |
| CN105566514A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | Ternary integrated rubber latex agglomeration process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107459687A (en) | 2017-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104558708B (en) | Multifunctional rubber vulcanized rubber containing polyvinylpyrrolidone modified graphene oxide and preparation method thereof | |
| JP4727766B1 (en) | Unvulcanized rubber composition, method for producing the same, and pneumatic tire | |
| JP2008106099A (en) | Protein-degraded natural rubber, method for producing the same and composition containing the same | |
| CN106832261B (en) | A kind of High-performance graphene/nylon 6 nano-composite and preparation method thereof | |
| CN106118039A (en) | A kind of Graphene modified Pa 6 composite and preparation method thereof | |
| CN103804553B (en) | A kind of preparation method of Graphene/polyvinyl chloride composite materials | |
| Chen et al. | Greatly enhanced mechanical properties and heat distortion resistance of poly (L-lactic acid) upon compositing with functionalized reduced graphene oxide | |
| CN110183731B (en) | Preparation method of polyaniline modified nano carbon material | |
| CN104725687A (en) | Oil-extended and carbon nano tube and graphene oxide filled emulsion coagulating rubber and preparation method thereof | |
| CN105949536A (en) | {0><}0{>Preparation method of high-strength natural rubber (NR)/carbon nano tube (CNT) conductive composite film | |
| CN107459687B (en) | Wide-temperature-range high-damping nano rubber composite material and preparation method thereof | |
| JP6484145B2 (en) | Rubber composition manufacturing method and tire manufacturing method | |
| CN108424563A (en) | The high-performance rubber composite material and preparation method of nanofiber is drawn containing Kev | |
| CN110372941A (en) | A kind of high density polyethylene pipe and preparation method thereof | |
| CN110734587A (en) | Method for preparing nitrile rubber from modified carbon blacks | |
| CN110734590B (en) | Method for preparing emulsion polymerized styrene-butadiene rubber from ionic liquid and chitosan modified carbon black | |
| He et al. | Turning lignin into treasure: an innovative filler comparable to commercial carbon black for the green development of the rubber industry | |
| CN107814376A (en) | A kind of titania-doped coated carbon nano-tube composite material of selenium | |
| CN108219195B (en) | Graphene oxide compound for melt processing and preparation method thereof | |
| CN105732914B (en) | Preparation method of lignin-xanthan gum modified powder butadiene-acrylonitrile polymer | |
| CN108299697B (en) | Rubber, preparation method thereof, rubber composition and vulcanized rubber | |
| KR101264467B1 (en) | Method for coagulation of emulsion polymerization latex | |
| CN110734594A (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon blacks | |
| CN102093717A (en) | Sulfonated polyethersulfone/TiO2 nano composite material and preparation method thereof | |
| CN104072831A (en) | Oil-extended carbon-nanotubes-extended binary emulsion coprecipitation rubber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |