CN110804209A - Special modified basalt fiber for rubber and preparation method thereof - Google Patents

Special modified basalt fiber for rubber and preparation method thereof Download PDF

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Publication number
CN110804209A
CN110804209A CN201911256693.XA CN201911256693A CN110804209A CN 110804209 A CN110804209 A CN 110804209A CN 201911256693 A CN201911256693 A CN 201911256693A CN 110804209 A CN110804209 A CN 110804209A
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basalt fiber
parts
rubber
modified
zinc oxide
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申慧君
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Jieshou Xinyilong Machinery And Equipment Purchase And Sale Co Ltd
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Jieshou Xinyilong Machinery And Equipment Purchase And Sale Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention discloses a preparation method of special modified basalt fiber for rubber, and provides a rubber material prepared by adding the modified basalt fiber prepared by the embodiment of the invention, which has better wear resistance and better high temperature aging resistance,the deformation phenomenon does not occur after the high-temperature treatment. Acid treating basalt fiber with organic-inorganic mixed acid composed of citric acid, acetic acid and phosphoric acid to fully activate basalt fiber surface activity, and microwave mixing60The basalt surface activity is further excited by the Co-gamma ray irradiation treatment, so that the adsorbability is enhanced, the active sites are increased, and the subsequent attachment of nano zinc oxide is facilitated; the nano zinc oxide is modified by melamine, so that the compatibility of the nano zinc oxide and a rubber substrate can be enhanced, the adhesion modification of the nano zinc oxide on the surface of basalt fiber is promoted, the nano zinc oxide can be physically crosslinked with rubber molecules, the system structure is improved, and the modified rubber structure is more stable.

Description

Special modified basalt fiber for rubber and preparation method thereof
Technical Field
The invention belongs to the technical field of modified materials, and particularly relates to a special modified basalt fiber for rubber and a preparation method thereof.
Background
As an important component of a high polymer material, rubber has special functions irreplaceable by other materials in the aspects of tires, sealing materials and the like, and becomes an indispensable important substance in national economy and daily life. However, in the long-term application process, the rubber has poor wear resistance, is easy to wear and has short service life, so the rubber needs to be modified to enhance the wear resistance and the ageing resistance, and the common modified filler is carbon black which has poor dispersibility and is easy to agglomerate to cause the effects of good local wear resistance and poor local wear resistance.
Disclosure of Invention
Aiming at the problems, the invention aims to provide the special modified basalt fiber for the rubber and the preparation method thereof so as to improve the wear resistance and the ageing resistance of the rubber material.
The invention is realized by the following technical scheme:
the special modified basalt fiber for rubber is characterized by being prepared from the following raw materials in parts by weight:
20-30 parts of basalt fiber, 50-100 parts of mixed acid solution, 1-3 parts of sodium carboxymethylcellulose, 5-8 parts of glutamic acid, 5-10 parts of polyvinyl alcohol, 10-15 parts of silane coupling agent KH-5502-3, 10-15 parts of nano zinc oxide, 15-20 parts of epoxidized natural rubber, 5-10 parts of dihydroxy silicone oil and 3-4 parts of calcined kaolin.
Further, the preparation method comprises the following steps:
(1) the basalt fiber is pretreated by the following steps: adding basalt fiber into mixed acid solution, stirring at 40-43 deg.C and 200-300rpm for 20-30min, filtering, microwave treating the basalt fiber with microwave device, and adding the basalt fiber into the mixed acid solution60Irradiating for 5-9min in a Co-gamma ray irradiator, and taking out;
(2) adding the basalt fiber obtained in the step (1) into ethylene glycol, heating the system to 70-80 ℃, then adding sodium carboxymethylcellulose, glutamic acid, polyvinyl alcohol and a silane coupling agent KH-550, and then carrying out ultrasonic treatment for 30-40min under the ultrasonic condition of 300-500Hz to obtain a basalt fiber dispersion liquid;
(3) putting the nano zinc oxide into a calcining furnace, calcining at 386 ℃ of 350-76 ℃ for 20-30min, adding melamine when the temperature is reduced to 70-76 ℃, ball-milling in a ball mill for 30-60min until the mixture is naturally cooled, then putting the mixture into a pressure box, standing the mixture for 1-2h under 2.5-3MPa, then vacuumizing the mixture to-0.09 to-0.1 MPa, continuously standing the mixture for 2-3h, and finally decompressing and taking out the mixture to obtain the modified nano zinc oxide;
(4) and (3) putting the modified nano zinc oxide obtained in the step (3) into the basalt fiber dispersion liquid obtained in the step (2), stirring at 80-86 ℃ and 600-1000rpm for 30-50min, adding epoxidized natural rubber and dihydroxy silicone oil, continuously stirring for 30-40min, filtering, drying at 40-60 ℃ to obtain modified basalt fiber, cooling, filtering, washing with deionized water for 2-4 times, and drying at 40-50 ℃ to obtain the modified basalt fiber.
Further, the mixed acid solution in the step (1) is a mixed solution of citric acid, acetic acid and phosphoric acid, wherein the mass fraction of the citric acid is 2-3%, the mass fraction of the acetic acid is 5-8%, and the mass fraction of the phosphoric acid is 3-5%.
Further, the microwave treatment in the step (1) is specifically treatment at 600W of 500-.
Further, the step (1) is60The dosage rate of the Co-gamma ray treatment is 1.2-1.5 kGy/min.
Further, the roasted kaolin is kaolin which is roasted at the temperature of 350-420 ℃ for 40-60min, and the particle size of the kaolin is 10-50 mu m.
The invention has the beneficial effects that: the rubber material prepared by adding the modified basalt fiber prepared by the embodiment of the invention has good wear resistance, good high-temperature aging resistance, no deformation after high-temperature treatment, and is worthy of popularization. Acid treating basalt fiber with organic-inorganic mixed acid composed of citric acid, acetic acid and phosphoric acid to fully activate basalt fiber surface activity, and microwave mixing60Co-gamma ray irradiation treatment further activatesThe basalt surface activity enhances the adsorptivity, increases the active sites and is beneficial to the adhesion of the subsequent nano zinc oxide; the nano zinc oxide is modified by melamine, so that the compatibility of the nano zinc oxide and a rubber substrate can be enhanced, the adhesion modification of the nano zinc oxide on the surface of basalt fiber is promoted, the nano zinc oxide is adhered on the surface of the basalt fiber, on one hand, the nano zinc oxide can be physically crosslinked with rubber molecules, the system structure is improved, the modified rubber structure is more stable, the wear resistance is enhanced, on the other hand, the defects of uneven dispersion and easy agglomeration of the nano zinc oxide are improved, and the wear resistance and the high-temperature aging resistance of the obtained rubber material are enhanced; the existence of the glutamic acid can improve the dispersibility of the basalt fiber and the nano zinc oxide in the substrate, enhance the interface bonding force of the basalt fiber and the nano zinc oxide, and improve the mechanical property and the wear resistance of the rubber.
Detailed Description
The invention is illustrated by the following specific examples, which are not intended to be limiting.
Example 1
The special modified basalt fiber for rubber is characterized by being prepared from the following raw materials in parts by weight:
20 parts of basalt fiber, 50 parts of mixed acid solution, 1 part of sodium carboxymethylcellulose, 5 parts of glutamic acid, 5 parts of polyvinyl alcohol, 5 parts of silane coupling agent KH-5502, 10 parts of nano zinc oxide, 15 parts of epoxidized natural rubber, 5 parts of dihydroxy silicone oil and 3 parts of calcined kaolin.
Further, the preparation method comprises the following steps:
(1) the basalt fiber is pretreated by the following steps: adding basalt fiber into mixed acid solution, stirring at 40 deg.C and 200rpm for 20min, filtering, microwave treating the basalt fiber with microwave device, and adding the basalt fiber into the solution60Irradiating for 5min in a Co-gamma ray irradiator, and taking out;
(2) adding the basalt fiber obtained in the step (1) into ethylene glycol, heating the system to 70 ℃, then adding sodium carboxymethylcellulose, glutamic acid, polyvinyl alcohol and a silane coupling agent KH-550, and then carrying out ultrasonic treatment for 30min under the ultrasonic condition of 300Hz to obtain a basalt fiber dispersion liquid;
(3) placing the nano zinc oxide into a calcining furnace, calcining for 20min at 350 ℃, adding melamine when the temperature is reduced to 70 ℃, ball-milling for 30min in a ball mill until the mixture is naturally cooled, then placing the mixture into a pressure box, placing the pressure box for 1h at 2.5MPa, vacuumizing to-0.09 MPa, continuing to place for 2h, and finally decompressing and taking out the mixture to obtain modified nano zinc oxide;
(4) and (3) adding the modified nano zinc oxide obtained in the step (3) into the basalt fiber dispersion liquid obtained in the step (2), stirring at 80 ℃ and 600rpm for 30min, adding epoxidized natural rubber and dihydroxy silicone oil, continuing stirring for 30min, filtering, drying at 40 ℃ to obtain modified basalt fiber, cooling, filtering, washing with deionized water for 2 times, and drying at 40 ℃ to obtain the modified basalt fiber.
Further, the mixed acid solution in the step (1) is a mixed solution of citric acid, acetic acid and phosphoric acid, wherein the mass fraction of the citric acid is 2%, the mass fraction of the acetic acid is 5% and the mass fraction of the phosphoric acid is 3%.
Further, the microwave treatment in the step (1) is specifically a treatment at 500W for 4min, a treatment at 1000W for 2min, and then a treatment at 2000W for 3 min.
Further, the step (1) is60The dose rate for Co-gamma radiation treatment was 1.2 kGy/min.
Further, the roasted kaolin is kaolin which is roasted at 350 ℃ for 40min, and the particle size of the kaolin is 10 mu m.
Example 2
The special modified basalt fiber for rubber is characterized by being prepared from the following raw materials in parts by weight:
25 parts of basalt fiber, 70 parts of mixed acid solution, 2 parts of sodium carboxymethylcellulose, 7 parts of glutamic acid, 6 parts of polyvinyl alcohol, a silane coupling agent KH-5503, 12 parts of nano-zinc oxide, 18 parts of epoxidized natural rubber, 8 parts of dihydroxy silicone oil and 4 parts of calcined kaolin.
Further, the preparation method comprises the following steps:
(1) the basalt fiber is pretreated byProcessing: adding basalt fiber into mixed acid solution, stirring at 42 deg.C and 250rpm for 25min, filtering, microwave treating the basalt fiber with microwave device, and adding the basalt fiber into the solution60Irradiating for 7min in a Co-gamma ray irradiator, and taking out;
(2) adding the basalt fiber obtained in the step (1) into ethylene glycol, heating the system to 75 ℃, then adding sodium carboxymethylcellulose, glutamic acid, polyvinyl alcohol and a silane coupling agent KH-550, and then carrying out ultrasonic treatment for 35min under the ultrasonic condition of 400Hz to obtain a basalt fiber dispersion liquid;
(3) placing the nano zinc oxide into a calcining furnace, calcining for 25min at 376 ℃, adding melamine when the temperature is reduced to 73 ℃, ball-milling for 50min in a ball mill until the mixture is naturally cooled, then placing the mixture into a pressure box, placing the pressure box for 2h at 2.8MPa, vacuumizing to-0.095 MPa, continuing to place the mixture for 3h, and finally decompressing and taking out the mixture to obtain modified nano zinc oxide;
(4) and (3) adding the modified nano zinc oxide obtained in the step (3) into the basalt fiber dispersion liquid obtained in the step (2), stirring at 83 ℃ and 800rpm for 40min, adding epoxidized natural rubber and dihydroxy silicone oil, continuing stirring for 35min, filtering, drying at 50 ℃ to obtain modified basalt fiber, cooling, filtering, washing with deionized water for 3 times, and drying at 45 ℃ to obtain the modified basalt fiber.
Further, the mixed acid solution in the step (1) is a mixed solution of citric acid, acetic acid and phosphoric acid, wherein the mass fraction of citric acid is 3%, the mass fraction of acetic acid is 6% and the mass fraction of phosphoric acid is 4%.
Further, the microwave treatment in the step (1) is specifically at 550W for 5min, at 1100W for 3min, and then at 2200W for 5 min.
Further, the step (1) is60The dose rate for Co-gamma radiation treatment was 1.3 kGy/min.
Further, the roasted kaolin is kaolin which is roasted at 380 ℃ for 50min, and the particle size of the kaolin is 30 μm.
Example 3
The special modified basalt fiber for rubber is characterized by being prepared from the following raw materials in parts by weight:
30 parts of basalt fiber, 100 parts of mixed acid solution, 3 parts of sodium carboxymethylcellulose, 8 parts of glutamic acid, 10 parts of polyvinyl alcohol, 10 parts of silane coupling agent KH-5503, 15 parts of nano zinc oxide, 20 parts of epoxidized natural rubber, 10 parts of dihydroxy silicone oil and 4 parts of calcined kaolin.
Further, the preparation method comprises the following steps:
(1) the basalt fiber is pretreated by the following steps: adding basalt fiber into mixed acid solution, stirring at 43 deg.C and 300rpm for 30min, filtering, microwave treating the basalt fiber with microwave device, and adding the basalt fiber into the solution60Irradiating for 9min in a Co-gamma ray irradiator, and taking out;
(2) adding the basalt fiber obtained in the step (1) into ethylene glycol, heating the system to 80 ℃, then adding sodium carboxymethylcellulose, glutamic acid, polyvinyl alcohol and a silane coupling agent KH-550, and then carrying out ultrasonic treatment for 40min under the ultrasonic condition of 500Hz to obtain a basalt fiber dispersion liquid;
(3) putting the nano zinc oxide into a calcining furnace, calcining at 386 ℃ for 30min, adding melamine when cooling to 76 ℃, ball-milling in a ball mill for 60min until natural cooling, then putting into a pressure box, placing for 2h at 3MPa, then vacuumizing to-0.1 MPa, continuing to place for 3h, finally decompressing and taking out to obtain modified nano zinc oxide;
(4) and (3) adding the modified nano zinc oxide obtained in the step (3) into the basalt fiber dispersion liquid obtained in the step (2), stirring at 86 ℃ and 1000rpm for 50min, adding epoxidized natural rubber and dihydroxy silicone oil, continuing stirring for 40min, filtering, drying at 60 ℃ to obtain modified basalt fiber, cooling, filtering, washing with deionized water for 4 times, and drying at 50 ℃ to obtain the modified basalt fiber.
Further, the mixed acid solution in the step (1) is a mixed solution of citric acid, acetic acid and phosphoric acid, wherein the mass fraction of citric acid is 3%, the mass fraction of acetic acid is 8% and the mass fraction of phosphoric acid is 5%.
Further, the microwave treatment in the step (1) is specifically to treat for 6min at 600W, treat for 4min at 1200W, and then treat for 6min at 2500W.
Further, the step (1) is60The dose rate for Co-gamma radiation treatment was 1.5 kGy/min.
Further, the calcined kaolin is kaolin calcined at 420 ℃ for 60min, and the particle size of the calcined kaolin is 50 μm.
And (3) performance testing:
1) 80 parts of natural rubber and 10 parts of the materials obtained in the examples and the comparative examples are sent into an internal mixer for plastication, the materials are discharged when the temperature of the materials rises to 115 ℃ to obtain a base material, then 5 parts of sulfur powder and 5 parts of glycerol are added for mixing for 10min at 75 ℃, finally 2 parts of anti-aging agent are added for thin passing for 5 times, and extrusion molding is carried out.
The samples obtained in each example, comparative example and control group were subjected to the Akron abrasion test in accordance with GB/T1689-1998, the total stroke of the sample was 1.61km, and the mass of the rubber sample before and after abrasion was weighed by an electronic balance with an accuracy of 1mg, and the abrasion mass was obtained by subtracting the two masses.
The rubber obtained in each example was tested for tensile strength at break (. sigma.b 1/MPa) according to the method described in GB/T528-92, and then left at 180 ℃ for 12 hours, and the morphology of the rubber was observed, and the tensile strength at break (. sigma.b 1/MPa) of the heat-treated rubber was tested according to the method described in GB/T528-92.
The test results are shown in table 1:
TABLE 1
Abrasion quality (g) σb1/MPa Morphology after heat treatment σb1/MPa
Example 1 0.085 25.1 Is not deformed 25.0
Example 2 0.084 25.4 Is not deformed 25.3
Example 3 0.086 25.3 Is not deformed 25.2
As can be seen from Table 1, the rubber material prepared by adding the modified basalt fiber prepared by the embodiment of the invention has better wear resistance, better high-temperature aging resistance, no deformation phenomenon after high-temperature treatment, and is worthy of popularization.

Claims (5)

1. A preparation method of a special modified basalt fiber for rubber is characterized by comprising the following steps:
(1) the basalt fiber is pretreated by the following steps: adding basalt fiber into mixed acid solution, stirring at 40-43 deg.C and 200-300rpm for 20-30min, filtering, microwave treating the basalt fiber with microwave device, and adding the basalt fiber into the mixed acid solution60Irradiating for 5-9min in a Co-gamma ray irradiator, and taking out;
(2) adding the basalt fiber obtained in the step (1) into ethylene glycol, heating the system to 70-80 ℃, then adding sodium carboxymethylcellulose, glutamic acid, polyvinyl alcohol and a silane coupling agent KH-550, and then carrying out ultrasonic treatment for 30-40min under the ultrasonic condition of 300-500Hz to obtain a basalt fiber dispersion liquid;
(3) putting the nano zinc oxide into a calcining furnace, calcining at 386 ℃ of 350-76 ℃ for 20-30min, adding melamine when the temperature is reduced to 70-76 ℃, ball-milling in a ball mill for 30-60min until the mixture is naturally cooled, then putting the mixture into a pressure box, standing the mixture for 1-2h under 2.5-3MPa, then vacuumizing the mixture to-0.09 to-0.1 MPa, continuously standing the mixture for 2-3h, and finally decompressing and taking out the mixture to obtain the modified nano zinc oxide;
(4) adding the modified nano zinc oxide obtained in the step (3) into the basalt fiber dispersion liquid obtained in the step (2), stirring at 80-86 ℃ and 600-1000rpm for 30-50min, adding epoxidized natural rubber and dihydroxy silicone oil, continuously stirring for 30-40min, filtering, drying at 40-60 ℃ to obtain modified basalt fibers, cooling, filtering, washing with deionized water for 2-4 times, and drying at 40-50 ℃ to obtain the modified basalt fibers;
the components are prepared from the following components in parts by weight:
20-30 parts of basalt fiber, 50-100 parts of mixed acid solution, 1-3 parts of sodium carboxymethylcellulose, 5-8 parts of glutamic acid, 5-10 parts of polyvinyl alcohol, 10-15 parts of silane coupling agent KH-5502-3, 10-15 parts of nano zinc oxide, 15-20 parts of epoxidized natural rubber, 5-10 parts of dihydroxy silicone oil and 3-4 parts of calcined kaolin.
2. The method for preparing the modified basalt fiber special for rubber according to claim 1, wherein the mixed acid solution of step (1) is a mixed solution of citric acid, acetic acid and phosphoric acid, wherein the mass fraction of citric acid is 2-3%, the mass fraction of acetic acid is 5-8%, and the mass fraction of phosphoric acid is 3-5%.
3. The modified basalt fiber special for rubber as claimed in claim 1, wherein the microwave treatment in the step (1) is specifically at 600W of 500-.
4. The modified basalt fiber specially used for rubber according to claim 1, wherein the step (1) is performed by60The dosage rate of the Co-gamma ray treatment is 1.2-1.5 kGy/min.
5. The modified basalt fiber special for rubber as claimed in claim 1, wherein the calcined kaolin is kaolin calcined at 350-420 ℃ for 40-60min, and the particle size is 10-50 μm.
CN201911256693.XA 2019-12-07 2019-12-07 Special modified basalt fiber for rubber and preparation method thereof Withdrawn CN110804209A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087936A (en) * 2021-05-20 2021-07-09 哈尔滨工业大学 Fiber surface treatment method
CN114277567A (en) * 2021-12-30 2022-04-05 天津工业大学 Preparation method of kapok fiber loaded molybdenum disulfide based on gamma irradiation
CN115745502A (en) * 2022-11-23 2023-03-07 安徽理工大学 Preparation method of basalt fiber rubber cement soil

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087936A (en) * 2021-05-20 2021-07-09 哈尔滨工业大学 Fiber surface treatment method
CN113087936B (en) * 2021-05-20 2022-04-19 哈尔滨工业大学 Fiber surface treatment method
CN114277567A (en) * 2021-12-30 2022-04-05 天津工业大学 Preparation method of kapok fiber loaded molybdenum disulfide based on gamma irradiation
CN115745502A (en) * 2022-11-23 2023-03-07 安徽理工大学 Preparation method of basalt fiber rubber cement soil

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Application publication date: 20200218