CN117700625B - Rubber for toy tire and preparation method thereof - Google Patents

Rubber for toy tire and preparation method thereof Download PDF

Info

Publication number
CN117700625B
CN117700625B CN202311755941.1A CN202311755941A CN117700625B CN 117700625 B CN117700625 B CN 117700625B CN 202311755941 A CN202311755941 A CN 202311755941A CN 117700625 B CN117700625 B CN 117700625B
Authority
CN
China
Prior art keywords
rubber
parts
natural rubber
inorganic filler
agent
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
Application number
CN202311755941.1A
Other languages
Chinese (zh)
Other versions
CN117700625A (en
Inventor
徐厚发
徐春
刘菁
徐旷宇
徐雯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Houhua Rubber Technology Co ltd
Original Assignee
Dongguan Houhua Rubber Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dongguan Houhua Rubber Technology Co ltd filed Critical Dongguan Houhua Rubber Technology Co ltd
Priority to CN202311755941.1A priority Critical patent/CN117700625B/en
Publication of CN117700625A publication Critical patent/CN117700625A/en
Application granted granted Critical
Publication of CN117700625B publication Critical patent/CN117700625B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F253/00—Macromolecular compounds obtained by polymerising monomers on to natural rubbers or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • 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
    • C08K9/10—Encapsulated 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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)

Abstract

The invention relates to the technical field of rubber and discloses rubber for a toy tire and a preparation method thereof, wherein natural rubber, modified inorganic filler, reactive antibacterial agent, carbon black, anti-aging agent, sulfur and accelerator are used as raw materials, and the rubber is prepared through plasticating, mixing and vulcanization processes, wherein the addition of the modified inorganic filler can effectively utilize the synergistic effect of brucite and phosphate silane coupling agent, greatly enhance the flame retardant property of the natural rubber, and the reactive antibacterial agent can participate in the vulcanization process of the natural rubber, so that quaternary ammonium salt broad-spectrum antibacterial agent and rigid isocyanuric acid ring are introduced into the molecular chain of the natural rubber, thereby not only realizing the long-acting antibacterial effect of the natural rubber, but also being capable of being synergistically enhanced with the modified inorganic filler to strengthen the flame retardant property of the natural rubber, simultaneously improving the strength and other comprehensive properties of the natural rubber, and being beneficial to further application of the natural rubber in the toy tire.

Description

Rubber for toy tire and preparation method thereof
Technical Field
The invention relates to the technical field of rubber, in particular to rubber for toy tires and a preparation method thereof.
Background
In the age background of rapid economic development, the living standard of substances of children is gradually improved, and relatively large toys such as toy vehicles are gradually appeared in recent years, so that the toy vehicles have great attraction to children and also have certain influence on young people, and therefore, the toy vehicles are relatively rapid in recent years. The quality of performance of tires as components of toy vehicles that directly contact the ground can have a significant impact on the overall quality of the toy vehicle. The natural rubber is environment-friendly rubber, has good elasticity, can bear certain stretching and compression, has excellent corrosion resistance and can resist corrosion of various substances, so that the natural rubber can be used as a main material for preparing tires, but is of a linear structure and does not contain flame retardant elements, so that the natural rubber has poor flame retardant property and belongs to inflammables.
The invention patent publication No. CN105754168B discloses a high-strength oil-resistant modified natural rubber composite material, which is prepared by adopting organic montmorillonite, pentaerythritol phosphate, pentaerythritol, zinc borate and aluminum hydroxide for matching, and can endow the natural rubber composite material with excellent flame retardance. The invention patent publication No. CN111218039A discloses an antibacterial natural rubber, a preparation method and application thereof, and the hydrotalcite is endowed with good antibacterial performance by using hydrotalcite as a carrier of silver ions, but because of the incompatibility problem between an inorganic antibacterial agent and a natural rubber matrix, the hydrotalcite needs to be further modified by using beta-cyclodextrin, so that the technical scheme is slightly complicated. Therefore, the invention provides the natural rubber which has good antibacterial and flame-retardant properties and can be directly applied to manufacturing of toy tires.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides rubber for toy tires and a preparation method thereof, which solve the problem of poor flame retardant property and antibacterial property of natural rubber.
(II) technical scheme
A preparation method of rubber for toy tires comprises the following steps:
The first step, preparation of rubber plasticated:
adding natural rubber into an internal mixer, raising the temperature of a mixing chamber to 90-100 ℃, setting the rotating speed to 80-100r/min, mixing and plasticating for 5-10min, and standing for 8-12h to obtain a rubber plasticated material;
Secondly, preparing a rubber compound:
Adding the rubber plasticated into an open mill, sequentially adding modified inorganic filler, a reactive antibacterial agent, carbon black, an anti-aging agent, sulfur and an accelerator, and after the addition, carrying out trimming, triangular packaging and sheet thinning processes to obtain a rubber compounded material;
Thirdly, preparing rubber for the tire:
placing the rubber mixed material into a vulcanizing agent, setting the vulcanizing pressure to be 18-20MPa, vulcanizing for 10-20min at the vulcanizing temperature of 180-200 ℃, and forming to obtain the rubber for the tire;
The modified inorganic filler is a compound of phosphate silane coupling agent and brucite;
the structural formula of the reactive antibacterial agent is shown in the following figure:
as a further technical scheme of the invention, the preparation process of the rubber adopts the following raw materials in parts by weight: 70-80 parts of natural rubber, 1-4 parts of modified inorganic filler, 2-6 parts of reactive antibacterial agent, 15-25 parts of carbon black, 2-4 parts of anti-aging agent, 3-5 parts of sulfur and 1-3 parts of accelerator.
As a further technical scheme of the invention, the preparation method of the modified inorganic filler comprises the following steps:
Step one, preparation of a phosphate silane coupling agent:
Mixing chlorotriethoxysilane, 2-hydroxyethyl dimethyl phosphonate and tetrahydrofuran, stirring uniformly in a reaction kettle, starting nitrogen protection, dropwise adding a catalyst, keeping the temperature in the kettle at 50-60 ℃ after the catalyst is completely added, continuously stirring for 3-5 hours, discharging, separating out a solid material, and obtaining the phosphate silane coupling agent;
The chlorotriethoxysilane structure contains silicon-chlorine groups, and the 2-hydroxyethyl phosphonic acid dimethyl ester structure contains hydroxyl substituent groups, so that substitution reaction can be carried out with each other under the action of a catalyst to generate the silane coupling agent with a phosphate structure.
Step two, preparing modified inorganic filler:
placing the phosphate silane coupling agent and brucite into a high-speed mixer, adjusting the temperature in the mixer to 80-90 ℃, continuously stirring and mixing for 2-4 hours at the stirring rate of 300-500r/min, and cooling and discharging to obtain the modified inorganic filler.
Under the high temperature condition, the phosphate silane coupling agent can interact with brucite to modify the brucite, so as to form a brucite compound with the surface coated with the silane coupling agent, and the modified inorganic filler is prepared.
As a further technical scheme of the invention, in the first step, the catalyst is triethylamine, and the added mass of the triethylamine is 15-25% of the total mass of chlorotriethoxy and 2-hydroxyethyl dimethyl phosphonate.
As a further technical scheme of the invention, in the second step, the average grain size of the brucite is 1 mu m.
As a further technical scheme of the invention, the preparation method of the reactive antibacterial agent is as follows:
adding diallyl isocyanurate and toluene into a reaction kettle filled with nitrogen, starting stirring, continuously adding 2-chloroethyl trimethyl ammonium chloride into the reaction kettle after a uniform solution is formed, dropwise adding a sodium hydroxide solution into the reaction kettle after uniform mixing, introducing nitrogen, starting heating, keeping the temperature in the kettle to 60-70 ℃, stirring for 4-8 hours, cooling, discharging, and purifying to obtain the reactive antibacterial agent.
The diallyl isocyanurate structure contains secondary amine groups and can be substituted with substituted halogen groups in the 2-chloroethyl trimethyl ammonium chloride structure under the action of sodium hydroxide, so that the reactive antibacterial agent containing quaternary ammonium salt antibacterial groups, unsaturated alkenyl groups and rigid isocyanuric acid rings in the structure is prepared.
According to the further technical scheme of the invention, the mass ratio of the diallyl isocyanurate to the 2-chloroethyl trimethyl ammonium chloride is 1:0.75-0.8.
According to the further technical scheme of the invention, the mass fraction of the sodium hydroxide solution is 20-30%.
As a further technical scheme of the invention, the anti-aging agent is any one or a mixture of more than two of anti-aging agent 4010NA, anti-aging agent 4020 and anti-aging agent RD in any proportion; the accelerator is any one or a mixture of more than two of accelerator DZ, accelerator DM and accelerator CZ in any proportion.
The rubber for the toy tire is prepared by adopting the preparation method.
(III) beneficial technical effects
1. According to the invention, the modified inorganic filler is prepared by modifying brucite with the phosphate silane coupling agent, on one hand, the formed organic coating layer can effectively improve the dispersibility of brucite in natural rubber and avoid adverse effects caused by agglomeration of the brucite, on the other hand, the phosphate silane coupling agent contains silicon and phosphorus flame retardant elements, and can cooperate with the brucite to further effectively enhance the flame retardant property of the natural rubber, and the limit oxygen index of the prepared rubber can reach 34.1% through tests, so that the rubber has excellent flame retardant property.
2. The reactive antibacterial agent structure prepared by the invention contains unsaturated alkenyl functional groups, and can enter a natural rubber molecular chain in the vulcanization process, so that the quaternary ammonium salt antibacterial group and the rigid isocyanuric acid ring are introduced into the natural rubber, the quaternary ammonium salt antibacterial group has broad-spectrum antibacterial performance, the prepared rubber has good antibacterial performance, the precipitation phenomenon of the antibacterial agent can be avoided, and the long-acting antibacterial performance of the rubber is realized. In addition, the existence of the rigid isocyanuric acid ring can be used as a char forming agent, and the char forming agent and the modified inorganic filler are cooperated to enhance the flame retardant property of the natural rubber, and can also improve the comprehensive properties of the natural rubber such as strength and the like, thereby being beneficial to the further application of the rubber in toy tires.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a thermogravimetric analysis of brucite and modified inorganic fillers;
FIG. 2 is an infrared spectrum of a reactive antimicrobial agent.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. Preferred embodiments of the present invention are given below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
The rubber for the toy tire comprises the following raw materials in parts by weight: 70 parts of natural rubber, 1 part of modified inorganic filler, 2 parts of reactive antibacterial agent, 15 parts of carbon black, 2 parts of antioxidant 4010NA, 3 parts of sulfur and 1 part of accelerator DZ;
the preparation method of the rubber comprises the following steps:
The first step, preparation of rubber plasticated:
Adding natural rubber into an internal mixer, raising the temperature of a mixing chamber to 90 ℃, setting the rotating speed to 80r/min, mixing and plasticating for 5min, and standing for 8h to obtain a rubber plasticated product;
Secondly, preparing a rubber compound:
Adding a rubber plasticated material into an open mill, sequentially adding a modified inorganic filler, a reactive antibacterial agent, carbon black, an anti-aging agent 4010NA, sulfur and an accelerator DZ, and after the addition, carrying out trimming, triangular wrapping and sheet thinning processes to obtain a rubber compounded material;
Thirdly, preparing rubber for the tire:
the rubber mixed material is placed in a vulcanizing agent, the vulcanizing pressure is set to 18MPa, the vulcanization is carried out for 10min at the vulcanizing temperature of 180 ℃, and the rubber for the tire is obtained after molding.
The preparation method of the modified inorganic filler comprises the following steps:
Step one, preparation of a phosphate silane coupling agent:
Mixing 1.6g of chlorotriethoxysilane, 1.25g of dimethyl 2-hydroxyethyl phosphonate and tetrahydrofuran, stirring uniformly in a reaction kettle, starting nitrogen protection, dropwise adding 0.6g of triethylamine, keeping the temperature in the kettle at 60 ℃ after the catalyst is completely added, continuously stirring for 4 hours, discharging, separating out solid materials, and obtaining the phosphate silane coupling agent;
Step two, preparing modified inorganic filler:
placing 1.2g of phosphate silane coupling agent and 2g of brucite with the average particle size of 1 mu m into a high-speed mixer, adjusting the temperature in the mixer to 90 ℃, continuously stirring and mixing for 3 hours at the stirring rate of 500r/min, and cooling and discharging to obtain the modified inorganic filler.
FIG. 1 is a thermogravimetric analysis of brucite and modified inorganic filler, showing that the modification ratio of phosphate silane coupling agent to brucite in the modified inorganic filler is about 31.7%.
The preparation method of the reactive antibacterial agent is as follows:
Adding 1.8g of diallyl isocyanurate and toluene into a reaction kettle filled with nitrogen, starting stirring, continuously adding 1.4g of 2-chloroethyl trimethyl ammonium chloride into the reaction kettle after a uniform solution is formed, dripping 20mL of 30% sodium hydroxide solution into the reaction kettle after uniform mixing, introducing nitrogen after the addition, starting heating, keeping the temperature in the kettle to 65 ℃, keeping the temperature for 6 hours, cooling, discharging, and purifying to obtain the reactive antibacterial agent.
The structural formula of the reactive antibacterial agent is shown in the following figure:
Fig. 2 shows an infrared spectrum of the reactive antibacterial agent, and the analysis shows that the absorption peak at 3018cm -1 is a hydrocarbon stretching vibration peak at c=c, the absorption peaks at 2928cm -1 and 2883cm -1 are a exploratory stretching vibration peak at-CH 3 and-CH 2 -, the absorption peak at 1754cm -1 is a characteristic absorption peak of c=c, the absorption peak at 1701cm -1 is a characteristic absorption peak of c=o, and the absorption peak at 1406cm -1 is a characteristic absorption peak of c—n on the quaternary ammonium salt.
Example 2
The rubber for the toy tire comprises the following raw materials in parts by weight: 75 parts of natural rubber, 3 parts of modified inorganic filler prepared in the embodiment 1 of the invention, 5 parts of reactive antibacterial agent prepared in the embodiment 1 of the invention, 20 parts of carbon black, 4020 parts of anti-aging agent, 4 parts of sulfur and 2 parts of accelerator DM;
the preparation method of the rubber comprises the following steps:
The first step, preparation of rubber plasticated:
adding natural rubber into an internal mixer, raising the temperature of a mixing chamber to 95 ℃, setting the rotating speed to 90r/min, mixing and plasticating for 8min, and standing for 10h to obtain a rubber plasticated product;
Secondly, preparing a rubber compound:
Adding a rubber plasticated material into an open mill, sequentially adding the modified inorganic filler prepared in the embodiment 1 of the invention, the reactive antibacterial agent prepared in the embodiment 1 of the invention, carbon black, an anti-aging agent 4020, sulfur and an accelerator DM, and after the addition, carrying out trimming, triangular wrapping and sheet thinning processes to obtain a rubber compounded material;
Thirdly, preparing rubber for the tire:
The rubber mixed material is placed in a vulcanizing agent, the vulcanizing pressure is set to be 20MPa, the vulcanization is carried out for 15min at the vulcanizing temperature of 200 ℃, and the rubber for the tire is obtained after molding.
Example 3
The rubber for the toy tire comprises the following raw materials in parts by weight: 80 parts of natural rubber, 4 parts of modified inorganic filler prepared in the embodiment 1 of the invention, 6 parts of reactive antibacterial agent prepared in the embodiment 1 of the invention, 25 parts of carbon black, 4 parts of anti-aging agent RD, 5 parts of sulfur and 3 parts of accelerator CZ;
the preparation method of the rubber comprises the following steps:
The first step, preparation of rubber plasticated:
adding natural rubber into an internal mixer, raising the temperature of a mixing chamber to 100 ℃, setting the rotating speed to 100r/min, mixing and plasticating for 10min, and standing for 12h to obtain a rubber plasticated product;
Secondly, preparing a rubber compound:
Putting a rubber plasticated material into an open mill, sequentially adding the modified inorganic filler prepared in the embodiment 1 of the invention, the reactive antibacterial agent prepared in the embodiment 1 of the invention, carbon black, an anti-aging agent, sulfur and an accelerator, and after the addition, carrying out trimming, triangular packing and sheet thinning processes to obtain a rubber compounded material;
Thirdly, preparing rubber for the tire:
The rubber mixed material is placed in a vulcanizing agent, the vulcanizing pressure is set to be 20MPa, the vulcanization is carried out for 20min at the vulcanizing temperature of 200 ℃, and the rubber for the tire is obtained after molding.
Comparative example 1
The rubber for the toy tire comprises the following raw materials in parts by weight: 75 parts of natural rubber, 3 parts of brucite, 5 parts of the reactive antibacterial agent prepared in the embodiment 1 of the invention, 20 parts of carbon black, 4020 parts of an anti-aging agent, 4 parts of sulfur and 2 parts of an accelerator DM;
the preparation method of the rubber comprises the following steps:
The first step, preparation of rubber plasticated:
adding natural rubber into an internal mixer, raising the temperature of a mixing chamber to 95 ℃, setting the rotating speed to 90r/min, mixing and plasticating for 8min, and standing for 10h to obtain a rubber plasticated product;
Secondly, preparing a rubber compound:
Putting rubber plasticated into an open mill, sequentially adding brucite, the reactive antibacterial agent prepared in the embodiment 1 of the invention, carbon black, an anti-aging agent 4020, sulfur and an accelerator DM, and after the addition, carrying out trimming, triangular packing and sheet thinning processes to obtain a rubber compounded material;
Thirdly, preparing rubber for the tire:
The rubber mixed material is placed in a vulcanizing agent, the vulcanizing pressure is set to be 20MPa, the vulcanization is carried out for 15min at the vulcanizing temperature of 200 ℃, and the rubber for the tire is obtained after molding.
Comparative example 2
The rubber for the toy tire comprises the following raw materials in parts by weight: 75 parts of natural rubber, 5 parts of the reactive antibacterial agent prepared in the embodiment 1 of the invention, 20 parts of carbon black, 4020 parts of an anti-aging agent, 4 parts of sulfur and 2 parts of a promoter DM;
the preparation method of the rubber comprises the following steps:
The first step, preparation of rubber plasticated:
adding natural rubber into an internal mixer, raising the temperature of a mixing chamber to 95 ℃, setting the rotating speed to 90r/min, mixing and plasticating for 8min, and standing for 10h to obtain a rubber plasticated product;
Secondly, preparing a rubber compound:
Putting a rubber plasticated material into an open mill, sequentially adding the reactive antibacterial agent, carbon black, the anti-aging agent 4020, sulfur and the accelerator DM prepared in the embodiment 1 of the invention, and after the addition, carrying out trimming, triangular wrapping and sheet thinning processes to obtain a rubber compounded material;
Thirdly, preparing rubber for the tire:
The rubber mixed material is placed in a vulcanizing agent, the vulcanizing pressure is set to be 20MPa, the vulcanization is carried out for 15min at the vulcanizing temperature of 200 ℃, and the rubber for the tire is obtained after molding.
Comparative example 3
The rubber for the toy tire comprises the following raw materials in parts by weight: 75 parts of natural rubber, 3 parts of modified inorganic filler prepared in the embodiment 1 of the invention, 5 parts of diallyl isocyanurate, 20 parts of carbon black, 3 parts of anti-aging agent 4020, 4 parts of sulfur and 2 parts of accelerator DM;
the preparation method of the rubber comprises the following steps:
The first step, preparation of rubber plasticated:
adding natural rubber into an internal mixer, raising the temperature of a mixing chamber to 95 ℃, setting the rotating speed to 90r/min, mixing and plasticating for 8min, and standing for 10h to obtain a rubber plasticated product;
Secondly, preparing a rubber compound:
Putting a rubber plasticated material into an open mill, sequentially adding the modified inorganic filler, diallyl isocyanurate, carbon black, an anti-aging agent 4020, sulfur and an accelerator DM prepared in the embodiment 1 of the invention, and after the addition, carrying out trimming, triangular packing and sheet thinning processes to obtain a rubber compounded material;
Thirdly, preparing rubber for the tire:
The rubber mixed material is placed in a vulcanizing agent, the vulcanizing pressure is set to be 20MPa, the vulcanization is carried out for 15min at the vulcanizing temperature of 200 ℃, and the rubber for the tire is obtained after molding.
Comparative example 4
The rubber for the toy tire comprises the following raw materials in parts by weight: 75 parts of natural rubber, 20 parts of carbon black, 4020 parts of an anti-aging agent, 4 parts of sulfur and 2 parts of an accelerator DM;
the preparation method of the rubber comprises the following steps:
The first step, preparation of rubber plasticated:
adding natural rubber into an internal mixer, raising the temperature of a mixing chamber to 95 ℃, setting the rotating speed to 90r/min, mixing and plasticating for 8min, and standing for 10h to obtain a rubber plasticated product;
Secondly, preparing a rubber compound:
Putting the rubber plasticated into an open mill, sequentially adding carbon black, an anti-aging agent 4020, sulfur and an accelerator DM, and after the addition, carrying out trimming, triangular packing and sheet thinning processes to obtain a rubber compounded material;
Thirdly, preparing rubber for the tire:
The rubber mixed material is placed in a vulcanizing agent, the vulcanizing pressure is set to be 20MPa, the vulcanization is carried out for 15min at the vulcanizing temperature of 200 ℃, and the rubber for the tire is obtained after molding.
Performance detection
According to the standard QB/T2591-2003, staphylococcus aureus is selected as a test strain, and antibacterial performance test is carried out; tensile property testing is carried out according to the standard GB/T528-2009; according to GB/T2406.2-2009, limiting oxygen index test is carried out;
The test results are recorded in table 1 below:
TABLE 1 test results for examples 1-3 and comparative examples 1-4
Bacteriostatic rate/% Tensile Strength/MPa Limiting oxygen index/%
Example 1 99.5 121.9 33.8
Example 2 99.6 122.4 34.1
Example 3 99.2 122.0 33.9
Comparative example 1 99.0 120.7 27.1
Comparative example 2 99.2 116.1 24.8
Comparative example 3 62.9 119.0 33.5
Comparative example 4 60.8 95.7 24.3
As can be seen from the analysis of the test data in the table, the rubber prepared by adding the modified inorganic filler and the reactive antibacterial agent has excellent antibacterial performance, mechanical performance and flame retardant performance compared with the rubber prepared by not adding the modified inorganic filler and the reactive antibacterial agent. The comparative example 1 was modified by filling with unmodified brucite, and it was evident that the flame retardant properties were greatly reduced, and that slight agglomeration was possible, so that the mechanical properties were slightly reduced. Comparative example 2 was free of brucite, and the mechanical properties and flame retardant properties were further lowered. Comparative example 3 was modified with only diallyl isocyanurate, and showed poor antibacterial properties.
In view of the foregoing, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made herein without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.

Claims (10)

1. The preparation method of the rubber for the toy tire is characterized by comprising the following steps of:
the first step, preparation of rubber plasticated:
adding natural rubber into an internal mixer, raising the temperature of a mixing chamber to 90-100 ℃, setting the rotating speed to 80-100r/min, mixing and plasticating for 5-10min, and standing for 8-12h to obtain a rubber plasticated material;
secondly, preparing a rubber compound:
Adding the rubber plasticated into an open mill, sequentially adding modified inorganic filler, a reactive antibacterial agent, carbon black, an anti-aging agent, sulfur and an accelerator, and after the addition, carrying out trimming, triangular packaging and sheet thinning processes to obtain a rubber compounded material;
Thirdly, preparing rubber for the tire:
placing the rubber mixed material into a vulcanizing agent, setting the vulcanizing pressure to be 18-20MPa, vulcanizing for 10-20min at the vulcanizing temperature of 180-200 ℃, and forming to obtain the rubber for the tire;
The modified inorganic filler is a compound of phosphate silane coupling agent and brucite;
the structural formula of the reactive antibacterial agent is shown in the following figure:
2. the method for preparing the rubber for the toy tire according to claim 1, wherein the rubber is prepared from the following raw materials in parts by weight: 70-80 parts of natural rubber, 1-4 parts of modified inorganic filler, 2-6 parts of reactive antibacterial agent, 15-25 parts of carbon black, 2-4 parts of anti-aging agent, 3-5 parts of sulfur and 1-3 parts of accelerator.
3. The method for producing a rubber for a toy tire according to claim 2, wherein the method for producing the modified inorganic filler comprises the steps of:
Step one, preparation of a phosphate silane coupling agent:
Mixing chlorotriethoxysilane, 2-hydroxyethyl dimethyl phosphonate and tetrahydrofuran, stirring uniformly in a reaction kettle, starting nitrogen protection, dropwise adding a catalyst, keeping the temperature in the kettle at 50-60 ℃ after the catalyst is completely added, continuously stirring for 3-5 hours, discharging, separating out a solid material, and obtaining the phosphate silane coupling agent;
Step two, preparing modified inorganic filler:
placing the phosphate silane coupling agent and brucite into a high-speed mixer, adjusting the temperature in the mixer to 80-90 ℃, continuously stirring and mixing for 2-4 hours at the stirring rate of 300-500r/min, and cooling and discharging to obtain the modified inorganic filler.
4. A method for producing a rubber for a toy tire according to claim 3, wherein in the first step, the catalyst is triethylamine, and the mass of the triethylamine added is 15 to 25% of the total mass of chlorotriethoxy and dimethyl 2-hydroxyethyl phosphonate.
5. A method for producing a rubber for a toy tire according to claim 3, wherein in the second step, the average particle diameter of brucite is 1 μm.
6. The method for preparing rubber for toy tires according to claim 2, wherein the preparation method of the reactive antibacterial agent is as follows:
adding diallyl isocyanurate and toluene into a reaction kettle filled with nitrogen, starting stirring, continuously adding 2-chloroethyl trimethyl ammonium chloride into the reaction kettle after a uniform solution is formed, dropwise adding a sodium hydroxide solution into the reaction kettle after uniform mixing, introducing nitrogen, starting heating, keeping the temperature in the kettle to 60-70 ℃, stirring for 4-8 hours, cooling, discharging, and purifying to obtain the reactive antibacterial agent.
7. The method for producing a rubber for a toy tire according to claim 6, wherein the mass ratio of the diallyl isocyanurate to the 2-chloroethyltrimethylammonium chloride is 1:0.75-0.8.
8. The method for producing a rubber for a toy tire according to claim 6, wherein the mass fraction of the sodium hydroxide solution is 20 to 30%.
9. The method for producing a rubber for a toy tire according to claim 2, wherein the antioxidant is any one or a mixture of two or more of an antioxidant 4010NA, an antioxidant 4020 and an antioxidant RD in an arbitrary ratio; the accelerator is any one or a mixture of more than two of accelerator DZ, accelerator DM and accelerator CZ in any proportion.
10. A rubber for toy tires, characterized by being produced by the production method according to any one of claims 1 to 9.
CN202311755941.1A 2023-12-19 2023-12-19 Rubber for toy tire and preparation method thereof Active CN117700625B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311755941.1A CN117700625B (en) 2023-12-19 2023-12-19 Rubber for toy tire and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311755941.1A CN117700625B (en) 2023-12-19 2023-12-19 Rubber for toy tire and preparation method thereof

Publications (2)

Publication Number Publication Date
CN117700625A CN117700625A (en) 2024-03-15
CN117700625B true CN117700625B (en) 2024-05-10

Family

ID=90155056

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311755941.1A Active CN117700625B (en) 2023-12-19 2023-12-19 Rubber for toy tire and preparation method thereof

Country Status (1)

Country Link
CN (1) CN117700625B (en)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB646956A (en) * 1947-01-21 1950-11-29 Goodrich Co B F Improvements in or relating to the preparation of quaternary ammonium salts of n-phenyl-3, 5-diethyl-2-propyldihydropyridine
DE4202264A1 (en) * 1991-01-28 1992-07-30 Toyoda Gosei Kk Acrylic rubber compsn. for making tubes - contg. ethylene]-acrylic] acid ester] copolymer, epoxy-gp. contg. cpd. and isocyanuric acid and quat-ammonium cpd. as vulcanisation aids
EP0546564A1 (en) * 1991-12-13 1993-06-16 Toyoda Gosei Co., Ltd. Rubber laminates
JPH05202169A (en) * 1991-01-28 1993-08-10 Toyoda Gosei Co Ltd Acrylic rubber blend
JP2003192922A (en) * 2001-10-16 2003-07-09 Sekisui Chem Co Ltd Antistatic resin composition and antistatic composition
CN102786477A (en) * 2012-08-17 2012-11-21 上海师范大学 Hydroxy halogen amine compound containing quaternary ammonium salt functional group and preparation method and application thereof
CN108047521A (en) * 2017-11-04 2018-05-18 李景春 A kind of preparation method of compounded rubber pad
CN108948633A (en) * 2018-07-19 2018-12-07 芜湖桑乐金电子科技有限公司 One kind having the active Yoga mat of broad-spectrum antibacterial
CN109897185A (en) * 2019-03-18 2019-06-18 山东交通学院 A kind of side chain is containing vinyl and quaternary ammonium salt polysiloxanes and its synthetic method and the application in preparation antibacterial silicon rubber
CN111048261A (en) * 2019-10-21 2020-04-21 东莞福川精密工业股份有限公司 Anti-aging flame-retardant cable and processing technology
CN114573919A (en) * 2022-02-11 2022-06-03 南京利德东方橡塑科技有限公司 Flame-retardant environment-friendly light-color food-grade ethylene propylene diene monomer rubber composition and preparation method thereof
CN116218232A (en) * 2023-03-16 2023-06-06 常熟市斯泰普新材料有限公司 Antibacterial silicone rubber and preparation method thereof
CN116574341A (en) * 2023-07-12 2023-08-11 河北信泰新材料有限公司 Graphite composite polystyrene particle and preparation method thereof

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB646956A (en) * 1947-01-21 1950-11-29 Goodrich Co B F Improvements in or relating to the preparation of quaternary ammonium salts of n-phenyl-3, 5-diethyl-2-propyldihydropyridine
DE4202264A1 (en) * 1991-01-28 1992-07-30 Toyoda Gosei Kk Acrylic rubber compsn. for making tubes - contg. ethylene]-acrylic] acid ester] copolymer, epoxy-gp. contg. cpd. and isocyanuric acid and quat-ammonium cpd. as vulcanisation aids
JPH05202169A (en) * 1991-01-28 1993-08-10 Toyoda Gosei Co Ltd Acrylic rubber blend
EP0546564A1 (en) * 1991-12-13 1993-06-16 Toyoda Gosei Co., Ltd. Rubber laminates
JP2003192922A (en) * 2001-10-16 2003-07-09 Sekisui Chem Co Ltd Antistatic resin composition and antistatic composition
CN102786477A (en) * 2012-08-17 2012-11-21 上海师范大学 Hydroxy halogen amine compound containing quaternary ammonium salt functional group and preparation method and application thereof
CN108047521A (en) * 2017-11-04 2018-05-18 李景春 A kind of preparation method of compounded rubber pad
CN108948633A (en) * 2018-07-19 2018-12-07 芜湖桑乐金电子科技有限公司 One kind having the active Yoga mat of broad-spectrum antibacterial
CN109897185A (en) * 2019-03-18 2019-06-18 山东交通学院 A kind of side chain is containing vinyl and quaternary ammonium salt polysiloxanes and its synthetic method and the application in preparation antibacterial silicon rubber
CN111048261A (en) * 2019-10-21 2020-04-21 东莞福川精密工业股份有限公司 Anti-aging flame-retardant cable and processing technology
CN114573919A (en) * 2022-02-11 2022-06-03 南京利德东方橡塑科技有限公司 Flame-retardant environment-friendly light-color food-grade ethylene propylene diene monomer rubber composition and preparation method thereof
CN116218232A (en) * 2023-03-16 2023-06-06 常熟市斯泰普新材料有限公司 Antibacterial silicone rubber and preparation method thereof
CN116574341A (en) * 2023-07-12 2023-08-11 河北信泰新材料有限公司 Graphite composite polystyrene particle and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Bioaromatic-Associated Multifunctionality in Lignin-Containing Reversible Elastomers;Thys, M et al;ACS APPLIED POLYMER MATERIALS;20230727;第5卷(第8期);5846-5856 *
三烯丙基异氰尿酸酯的合成与表征;汪勇;赵卫平;吕建平;;精细化工;20160115(01);82-85 *

Also Published As

Publication number Publication date
CN117700625A (en) 2024-03-15

Similar Documents

Publication Publication Date Title
CN105330995B (en) A kind of environmental protection flame retardant bipeltate and preparation method thereof
KR101577651B1 (en) Novel cardanol based organic vulcanizing agent, manufacturing method of the same and rubber composition for tire using the same
CN111072973A (en) Phosphorus-containing POSS, preparation method thereof and application thereof in flame retardant
CN109786098B (en) Preparation method of flexible rubber neodymium-iron-boron magnet
CN109705634B (en) Attapulgite-based composite flame retardant modified by nitrogen-phosphorus-containing organic matter and preparation and application thereof
CN112251011A (en) Light-stable TPU composite material and preparation method thereof
CN117700625B (en) Rubber for toy tire and preparation method thereof
CN110218396B (en) UV printing rubber roller and preparation method thereof
CN114133523B (en) Polyurethane composition for light dynamic impact resistant new energy automobile battery box and preparation method thereof
CN112477310B (en) Thermoplastic resin composition and use thereof
CN111138736B (en) Zinc suboxide rubber composition and preparation method thereof
CN115160762B (en) Silane crosslinked SEBS-based halogen-free flame-retardant elastomer and preparation method thereof
CN112796111B (en) Method for synergistic flame-retardant gum dipping of high-strength polyester canvas
CN116731474A (en) High-temperature-resistant epoxy SMC resin composition and preparation method thereof
CN113214542A (en) Composite antimony trioxide flame retardant and preparation method thereof
CN118240177B (en) Production process of flame-retardant wear-resistant polyurethane composite material
CN109553770B (en) Bio-based flame-retardant polyamide 56 and preparation method thereof
CN114672078B (en) Modified rubber and preparation method thereof
CN103724704A (en) Tire tread rubber composition and tire using same
CN114213714B (en) Porous silicon-loaded anti-aging agent-silver ion compound, and preparation method and application thereof
CN115710390B (en) Low-rolling-resistance high-performance green flame-retardant rubber composite material and preparation method thereof
CN114561071B (en) Low-temperature-resistant nano silicon modified fluororubber composite material and preparation method thereof
KR20240156290A (en) Silyl-ether terminated polybutadiene
CN116178807A (en) Process for vulcanizing natural rubber by using composite zinc oxide
CN118420670A (en) Vegetable oil-based flame retardant and preparation method and application 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