CN114874514A - Polybutadiene-based anti-slip wear-resistant rubber for soles and preparation method thereof - Google Patents
Polybutadiene-based anti-slip wear-resistant rubber for soles and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
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Abstract
The invention discloses a polybutadiene-based anti-slip wear-resistant rubber for soles and a preparation method thereof, wherein the rubber for the soles comprises the following components in parts by weight: 60 parts of polybutadiene rubber, 32-48 parts of thermoplastic elastomer SBS, 26-35 parts of modified boron-magnesium stone composite particles, 1.5-3.6 parts of terpene-phenol resin, 0.2-0.8 part of silane coupling agent, 1.2-1.8 parts of anti-aging agent, 2.3-4.6 parts of sulfur and 1.1-1.6 parts of accelerator. The rubber for the anti-slip and wear-resistant sole based on polybutadiene not only has wear resistance and skid resistance, but also has the advantages of light weight and strong elasticity, and in addition, the rubber is better improved in the aspect of aging resistance.
Description
Technical Field
The invention relates to the field of rubber elastomers, in particular to rubber for a non-slip wear-resistant sole based on polybutadiene and a preparation method thereof.
Background
The sole material is an important component of a shoe, and the quality of the sole material not only determines the performance of a pair of shoes, but also influences the comfort of a wearer. With the improvement of living standard and body-building consciousness, people pay more and more attention to the performance requirements of sole materials, and the sole is required to be antiskid and wear-resistant, and have multiple additional functions of light weight, softness, comfort and the like or be suitable for specific purposes. Rubber is a sole material of most of the current shoes due to relatively good wear resistance. However, although the rubber sole has better wear resistance and skid resistance, the rubber density is too high due to the addition of a large amount of reinforcing agents and fillers, and the sole is heavy to wear; in addition, the elasticity of the rubber sole is not good and the rubber sole is easy to age, so that the harder the shoe is, the worse the foot feeling is.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide rubber for a skid-proof and wear-resistant sole based on polybutadiene, which is light, soft and not easy to age, and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides a polybutadiene-based anti-slip wear-resistant rubber for soles, which comprises the following components in parts by weight:
60 parts of polybutadiene rubber, 32-48 parts of thermoplastic elastomer SBS, 26-35 parts of modified boron-magnesium stone composite particles, 1.5-3.6 parts of terpene-phenol resin, 0.2-0.8 part of silane coupling agent, 1.2-1.8 parts of anti-aging agent, 2.3-4.6 parts of sulfur and 1.1-1.6 parts of accelerator.
Preferably, the number average molecular weight of the thermoplastic elastomer SBS is 18000-20000.
Preferably, the particle size of the modified boromagnesite composite particles is 100-300 μm.
Preferably, the terpene phenol resin has a softening point of 125-150 ℃.
Preferably, the silane coupling agent is one of a silane coupling agent KH-792, a silane coupling agent KH-550 and a silane coupling agent KH-560.
Preferably, the antioxidant is one of antioxidant TMQ, antioxidant MB and antioxidant DNP.
Preferably, the promoter is promoter M or promoter TETD.
Preferably, the preparation method of the modified boromagnesite composite particle comprises the following steps:
firstly, maleic anhydride is used for sequentially carrying out Diels-Alder reaction, acylation reaction and condensation reaction to prepare a modifier;
secondly, activating the nano-boron magnesium stone by using vinyltrimethoxysilane to obtain nano-activated boron magnesium stone;
and thirdly, modifying the 1, 2-polybutadiene by using a modifier, and simultaneously adding the nano activated boron-magnesium stone to obtain the modified boron-magnesium stone composite particles.
Preferably, the molecular weight of the 1, 2-polybutadiene is 1000-2000.
Preferably, in the first step, the preparation method of the modifier comprises the following steps:
s1, weighing maleic anhydride and furan, mixing in a reaction container filled with acetone, fully stirring at room temperature for 16-24h, filtering out solids, washing with acetone for at least three times, and drying to obtain a compound A;
wherein the mass ratio of the maleic anhydride to the furan to the acetone is 2.2-3.6:3.7-4.4: 100;
s2, weighing the compound A and ethanol, mixing the compound A and the ethanol into a reaction container, placing a flask into an ice-water bath, fully stirring, dropwise adding 2-hydroxyethylamine into the flask, fully stirring again, removing the ice-water bath, assembling a condensation reflux device, heating to 65-85 ℃, stirring for 18-36h, cooling to room temperature, sealing the flask, storing in the dark at 0-4 ℃ for 6-10h, filtering out solids, washing with ethanol at 0-4 ℃, and drying to obtain a compound B;
wherein the mass ratio of the compound A to the 2-hydroxyethylamine to the ethanol is 1:0.3-0.6: 100;
s3, weighing a compound B, 4-dimethylaminopyridine and dichloromethane, mixing the compound B, 4-dimethylaminopyridine and dichloromethane into a reaction container, filling nitrogen into the reaction container to replace air, placing the reaction container in an ice-water bath condition, stirring for 0.5-1h, then dropwise adding 2-aminoacetyl chloride, stirring for 0.5-1h in the ice-water bath condition after dropwise adding, removing the ice-water bath, continuing stirring and reacting for 8-12h at room temperature, then washing with saturated sodium bicarbonate water and purified water in sequence, extracting and combining organic phases, and drying to remove a solvent to obtain a compound C;
wherein the mass ratio of the compound B, 2-aminoacetyl chloride, 4-dimethylaminopyridine and dichloromethane is 1:0.7-0.9:0.06-0.1: 50;
s4, mixing the compound C with toluene, placing the mixture in a reflux condensing device, heating to 120 ℃ under the protection of nitrogen, stirring for 3-6h, removing the solvent, and drying at 35-45 ℃ to obtain the modifier;
wherein the mass ratio of the compound C to the toluene is 1: 30-50.
Preferably, in the second step, the preparation method of the nano activated ascharite comprises the following steps:
weighing nano-boron magnesium stone, vinyl trimethoxy silane and deionized water, mixing, stirring at 45-55 deg.C for 4-6h, filtering to remove liquid, and drying to obtain nano-activated boron magnesium stone;
wherein the particle size of the nano boron magnesium stone is 300-800 nm; the mass ratio of the nano boron magnesium stone, the vinyl trimethoxy silane and the deionized water is 1:0.08-0.12: 10-20.
Preferably, in the third step, the preparation method of the modified boromagnesite composite particles comprises the following steps:
p1, weighing the modifier and acetanilide, mixing the modifier and the acetanilide in toluene, and stirring the mixture uniformly to form a modifier solution;
wherein the mass ratio of the modifier to the acetanilide to the toluene is 1:0.12-0.16: 10;
p2, weighing 1, 2-polybutadiene, nano activated boron magnesium stone and toluene, mixing the mixture into a reaction container, heating to 70-80 ℃, stirring uniformly, dropwise adding a modifier solution, stirring uniformly again, adding an initiator azobisisobutyronitrile, carrying out heat preservation reaction for 3-5 hours, precipitating by using anhydrous methanol, and drying under reduced pressure to obtain modified boron magnesium stone composite particles;
wherein the addition amount of the initiator is 2 to 5 percent of the mass of the 1, 2-polybutadiene; the mass ratio of the 1, 2-polybutadiene, the nano activated boron-magnesium stone, the modifier solution and the toluene is 1:1.2-1.8:3.4-5.8: 18-22.
In a second aspect, the invention provides a preparation method of rubber for a non-slip wear-resistant sole based on polybutadiene, which comprises the following steps:
step 1, weighing polybutadiene rubber and thermoplastic elastomer SBS, mixing into an internal mixer, and homogenizing to obtain a first mixture;
step 2, sequentially adding the weighed modified boron-magnesium stone composite particles, terpene-phenol resin, anti-aging agent and silane coupling agent into a mixing agent, then adding the first mixture, and uniformly mixing to obtain a second mixture;
and 3, adding the weighed sulfur and the accelerator into the second mixture, uniformly mixing, and placing on vulcanization equipment for vulcanization to obtain the rubber for the anti-slip wear-resistant sole based on polybutadiene.
Preferably, in the step 1, the temperature of the internal mixer is 100-.
Preferably, in the step 2, the mixing temperature is 80-120 ℃, the mixing pressure is 0.3-0.5MPa, the mixing time is 6-10min, and the second mixture is obtained after cooling after mixing.
Preferably, in the step 3, the mixing temperature is 80-100 ℃, the mixing pressure is 0.3-0.5MPa, and the mixing time is 3-5 min.
Preferably, in the step 3, the vulcanization temperature is 155-165 ℃, the vulcanization pressure is 15-25MPa, and the vulcanization time is 3-6 min.
The invention has the beneficial effects that:
1. the rubber for the anti-slip and wear-resistant sole based on polybutadiene not only has wear resistance and skid resistance, but also has the advantages of light weight and strong elasticity, and in addition, the rubber is better improved in the aspect of aging resistance.
2. In the invention, the polybutadiene rubber is used as a main raw material of the sole material and is obtained by polymerizing butadiene serving as a monomer. The thermoplastic elastomer SBS is a block copolymer of styrene and butadiene, has better compression deformation and rebound resilience, and can improve the rebound resilience of polybutadiene rubber by matching the polybutadiene rubber and the thermoplastic elastomer SBS, thereby improving the foot feel of the sole.
3. The self-made modified boron-magnesium stone composite particles are added as the filling reinforcing material, so that the defect of insufficient aging resistance after the polybutadiene rubber and the thermoplastic elastomer SBS are matched is overcome, the anti-tearing, anti-stretching and aging resistance of the shoe are well improved while the shoe can keep good elasticity, and the using amount of the modified boron-magnesium stone composite particles is greatly reduced compared with that of a conventional filling material (such as white carbon black) and is low in density, so that the modified boron-magnesium stone composite particles also have the advantages of light weight and good foot feel.
4. In addition, the invention also adds terpene phenol resin to improve the cohesive force of each raw material of the rubber sole; the silane coupling agent is used for improving the mutual fusion degree of the raw materials; the anti-aging agent is used for delaying rubber aging and prolonging the service life performance of rubber; the sulfur is used for vulcanizing rubber, so that rubber molecules are converted into a net structure from a linear structure; the accelerator is also a vulcanization accelerator, and is matched with sulfur to promote the activation of the sulfur, so that the crosslinking reaction of the vulcanizing agent and rubber molecules is accelerated.
5. In the process of preparing the modified boron-magnesium stone composite particles, the selected 1, 2-polybutadiene belongs to low-molecular-weight liquid polybutadiene, and the liquid polybutadiene contains double bonds, so that allylic hydrogen in molecular groups is relatively active and can be combined with a modifier for reaction. The bonding product contains unsaturated double bonds, has better curing and crosslinking properties in the subsequent vulcanization process, also contains various polar groups, has higher activity, and thus has stronger crosslinking properties with other compounds.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
The polybutadiene rubber used in the invention is cis-1, 4-polybutadiene rubber, and the polybutadiene rubber and the thermoplastic elastomer SBS both belong to products produced by the single mountain petrochemical company of China oil and gas Limited company.
Terpene phenol resin, i.e. terpene phenol resin, belongs to one of tackifying resins, and has the advantages of strong adhesive force, large cohesive force, good heat resistance and aging resistance.
White carbon black is a general term for white powdery X-ray amorphous silicic acid and silicate products, mainly referring to precipitated silica, fumed silica and ultrafine silica gel, and also including powdery synthetic aluminum silicate, calcium silicate, and the like.
The boromagnesite is a borate mineral, is white or grey-white and yellowish, has fibrous, columnar or platy crystals, can be gathered together or is fibrous or blocky, and has the advantages of high melting point, high chemical stability and high wear resistance.
In the traditional rubber sole industry, the most commonly used filling reinforcing agent is white carbon black, which has the advantages of better high temperature resistance and chemical stability, but white carbon black easily absorbs moisture in air, has poor dispersibility in the rubber mixing process, and is easy to harden rubber according to research, so that a certain softening agent, such as paraffin, tall oil and the like, must be added in the rubber refining process, but the addition of these materials not only makes the rubber heavier, but also affects the aging resistance of the rubber. The invention creatively abandons the traditional white carbon black filler, uses the boron-magnesia material as the base material, and prepares the modified boron-magnesia composite particles as the filler material.
The modifier is synthesized on the basis of maleic anhydride, firstly, furan and maleic anhydride are adopted to generate Diels-Alder reaction for protecting double bond groups to generate tetrahydrophthalic anhydride containing oxygen bridge bonds, namely a compound A; then, carrying out acylation reaction on the compound A and 2-hydroxyethylamine to generate an N-substituent compound B containing hydroxyl; then the acyl chloride and 2-amino acetyl chloride are subjected to condensation reaction, and acyl chloride groups and hydroxyl groups are combined to form ester groups to generate a compound C; and finally, under the condition of heating the solvent, removing furan groups to obtain the modifier, wherein the finally prepared modifier contains amino groups, ester groups and double-bond groups.
The specific process flow is as follows:
the invention is further described below with reference to the following examples.
Example 1
Polybutadiene-based anti-slip wear-resistant sole rubber comprises the following components in parts by weight:
60 parts of polybutadiene rubber, 40 parts of thermoplastic elastomer SBS, 30 parts of modified boromagnesite composite particles, 2.8 parts of terpene phenol resin, 1.5 parts of silane coupling agent KH-7920.5 parts of anti-aging agent TMQ, 3.8 parts of sulfur and 1.4 parts of accelerator M.
Wherein the number average molecular weight of the thermoplastic elastomer SBS is 18000-20000, the particle diameter of the modified boron-magnesium stone composite particle is 200 μm, and the softening point of the terpene-phenol resin is 135 ℃.
The preparation method of the modified boron magnesium stone composite particle comprises the following steps:
step one, preparing a modifier:
s1, weighing maleic anhydride and furan, mixing the maleic anhydride and the furan in a reaction container filled with acetone, wherein the mass ratio of the maleic anhydride to the furan to the acetone is 2.8:4.1:100, fully stirring the mixture for 20 hours at room temperature, filtering out solids, washing the solids for at least three times by using the acetone, and drying the solids to obtain a compound A;
s2, weighing the compound A and ethanol, mixing the compound A and the ethanol into a reaction container, placing a flask into an ice-water bath, fully stirring, dropwise adding 2-hydroxyethylamine into the flask, fully stirring again, removing the ice-water bath, assembling a condensation reflux device, heating to 75 ℃, stirring for 24 hours, cooling to room temperature, sealing the flask, storing in a dark place at 0-4 ℃ for 8 hours, filtering out solids, washing with ethanol at 0-4 ℃, and drying to obtain a compound B; wherein the mass ratio of the compound A to the 2-hydroxyethylamine to the ethanol is 1:0.4: 100;
s3, weighing a compound B, 4-dimethylaminopyridine and dichloromethane, mixing the compound B, 4-dimethylaminopyridine and dichloromethane into a reaction container, filling nitrogen into the reaction container to replace air, placing the reaction container in an ice-water bath condition, stirring for 0.5h, then dropwise adding 2-aminoacetyl chloride, stirring for 0.5h in the ice-water bath condition after dropwise adding, removing the ice-water bath, continuing stirring and reacting for 10h at room temperature, then washing with saturated sodium bicarbonate water and purified water in sequence, extracting and combining organic phases, and drying to remove a solvent to obtain a compound C; wherein the mass ratio of the compound B, 2-aminoacetyl chloride, 4-dimethylaminopyridine and dichloromethane is 1:0.8:0.08: 50;
s4, mixing the compound C with toluene, placing the mixture in a reflux condensing device, heating to 110 ℃ under the protection of nitrogen, stirring for 4 hours, removing the solvent, and drying at 40 ℃ to obtain a modifier; wherein the mass ratio of the compound C to the toluene is 1: 40.
Step two, preparing nano activated boron magnesium stone:
weighing nano-boron magnesium stone, vinyl trimethoxy silane and deionized water, mixing, stirring at 50 ℃ for 5h, filtering to remove liquid, and drying to obtain nano-activated boron magnesium stone; wherein the particle size of the nano-boron magnesium stone is 200-500 nm; the mass ratio of the nano boron magnesium stone, the vinyl trimethoxy silane and the deionized water is 1:0.1: 15.
Step three, preparing modified boron magnesium stone composite particles:
p1, weighing the modifier and acetanilide, mixing the modifier and the acetanilide in toluene, and stirring the mixture uniformly to form a modifier solution; wherein the mass ratio of the modifier to the acetanilide to the toluene is 1:0.14: 10;
p2, weighing 1, 2-polybutadiene, nano activated boron magnesium stone and toluene, mixing the mixture into a reaction container, heating to 75 ℃, stirring uniformly, dropwise adding a modifier solution, stirring uniformly again, adding an initiator azobisisobutyronitrile, carrying out heat preservation reaction for 4 hours, precipitating by using anhydrous methanol, and drying under reduced pressure to obtain modified boron magnesium stone composite particles; wherein the molecular weight of the 1, 2-polybutadiene is 1000-2000; the addition amount of the initiator is 3 percent of the mass of the 1, 2-polybutadiene; the mass ratio of the 1, 2-polybutadiene, the nano activated boron-magnesium stone, the modifier solution and the toluene is 1:1.5:4.6: 20.
The preparation method of the rubber for the anti-slip wear-resistant sole based on polybutadiene comprises the following steps:
step 1, weighing polybutadiene rubber and thermoplastic elastomer SBS, mixing the polybutadiene rubber and thermoplastic elastomer SBS into an internal mixer, wherein the temperature of the internal mixer is 110 ℃, the internal mixing homogenization time is 6min, and cooling to room temperature after internal mixing is finished to obtain a first mixture;
step 2, sequentially adding the weighed modified boron-magnesium stone composite particles, terpene-phenol resin, anti-aging agent and silane coupling agent into a mixing agent, then adding a first mixture, starting mixing, wherein the mixing temperature is 100 ℃, the mixing pressure is 0.4MPa, the mixing time is 8min, and cooling after mixing to obtain a second mixture;
step 3, adding the weighed sulfur and the accelerator into the second mixture for mixing, wherein the mixing temperature is 90 ℃, the mixing pressure is 0.4MPa, and the mixing time is 4 min; and (3) after mixing, putting the mixture on vulcanization equipment for vulcanization, wherein the vulcanization temperature is 160 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 4min, thus obtaining the rubber for the anti-slip wear-resistant sole based on polybutadiene.
Example 2
Polybutadiene-based anti-slip wear-resistant sole rubber comprises the following components in parts by weight:
60 parts of polybutadiene rubber, 32 parts of thermoplastic elastomer SBS, 26 parts of modified boron-magnesium stone composite particles, 1.5 parts of terpene-phenol resin, 1.2 parts of silane coupling agent KH-5500.2 parts, 1.2 parts of anti-aging agent MB, 2.3 parts of sulfur and 1.1 parts of accelerator M.
Wherein the number average molecular weight of the thermoplastic elastomer SBS is 18000-20000, the particle size of the modified boron-magnesium stone composite particle is 100 μm, and the softening point of the terpene-phenol resin is 125 ℃.
The preparation method of the modified boron-magnesium stone composite particle comprises the following steps:
step one, preparing a modifier:
s1, weighing maleic anhydride and furan, mixing the maleic anhydride and the furan in a reaction container filled with acetone, fully stirring the mixture for 16 hours at room temperature, filtering out solids, washing the solids with acetone for at least three times, and drying the solids to obtain a compound A; wherein the mass ratio of the maleic anhydride to the furan to the acetone is 2.2:3.7: 100;
s2, weighing the compound A and ethanol, mixing the compound A and the ethanol into a reaction container, placing a flask into an ice-water bath, fully stirring, dropwise adding 2-hydroxyethylamine into the flask, fully stirring again, removing the ice-water bath, assembling a condensation reflux device, heating to 65 ℃, stirring for 18 hours, cooling to room temperature, sealing the flask, storing in the dark at 0-4 ℃ for 6 hours, filtering out solids, washing with ethanol at 0-4 ℃, and drying to obtain a compound B; wherein the mass ratio of the compound A to the 2-hydroxyethylamine to the ethanol is 1:0.3: 100;
s3, weighing a compound B, 4-dimethylaminopyridine and dichloromethane, mixing the compound B, 4-dimethylaminopyridine and dichloromethane into a reaction container, filling nitrogen into the reaction container to replace air, placing the reaction container in an ice-water bath condition, stirring for 0.5h, then dropwise adding 2-aminoacetyl chloride, stirring for 0.5h in the ice-water bath condition after dropwise adding, removing the ice-water bath, continuing stirring at room temperature for reaction for 8h, then washing with saturated sodium bicarbonate water and purified water in sequence, extracting and combining organic phases, and drying to remove a solvent to obtain a compound C; wherein the mass ratio of the compound B, 2-aminoacetyl chloride, 4-dimethylaminopyridine and dichloromethane is 1:0.7:0.06: 50;
s4, mixing the compound C with toluene, placing the mixture in a reflux condensing device, heating to 100 ℃ under the protection of nitrogen, stirring for 3 hours, removing the solvent, and drying at 35 ℃ to obtain a modifier; wherein the mass ratio of the compound C to the toluene is 1: 30.
Step two, preparing nano activated boron magnesium stone:
weighing nano-boron magnesium stone, vinyl trimethoxy silane and deionized water, mixing, stirring at 45 ℃ for 4h, filtering to remove liquid, and drying to obtain nano-activated boron magnesium stone; wherein the particle size of the nano-boron magnesium stone is 200-500 nm; the mass ratio of the nano boron magnesium stone, the vinyl trimethoxy silane and the deionized water is 1:0.08: 10.
Step three, preparing modified boron magnesium stone composite particles:
p1, weighing the modifier and acetanilide, mixing the modifier and the acetanilide in toluene, and stirring the mixture uniformly to form a modifier solution; wherein the mass ratio of the modifier to the acetanilide to the toluene is 1:0.12: 10;
p2, weighing 1, 2-polybutadiene, nano activated boron magnesium stone and toluene, mixing the mixture into a reaction container, heating to 70 ℃, stirring uniformly, dropwise adding a modifier solution, stirring uniformly again, adding an initiator azobisisobutyronitrile, carrying out heat preservation reaction for 3 hours, precipitating by using anhydrous methanol, and drying under reduced pressure to obtain modified boron magnesium stone composite particles; wherein the molecular weight of the 1, 2-polybutadiene is 1000-2000; the addition amount of the initiator is 2 percent of the mass of the 1, 2-polybutadiene; the mass ratio of the 1, 2-polybutadiene, the nano activated boron-magnesium stone, the modifier solution and the toluene is 1:1.2:3.4: 18.
The preparation method of the rubber for the anti-slip wear-resistant sole based on polybutadiene comprises the following steps:
step 1, weighing polybutadiene rubber and thermoplastic elastomer SBS, mixing the polybutadiene rubber and thermoplastic elastomer SBS into an internal mixer, controlling the temperature of the internal mixer to be 100 ℃, controlling the internal mixing homogenization time to be 5min, and cooling to room temperature after the internal mixing is finished to obtain a first mixture;
step 2, sequentially adding the weighed modified boron-magnesium stone composite particles, terpene-phenol resin, anti-aging agent and silane coupling agent into a mixing agent, then adding a first mixture, starting mixing, wherein the mixing temperature is 80 ℃, the mixing pressure is 0.3MPa, the mixing time is 6min, and cooling after mixing to obtain a second mixture;
step 3, adding the weighed sulfur and the accelerator into the second mixture for mixing, wherein the mixing temperature is 80-100 ℃, the mixing pressure is 0.3MPa, and the mixing time is 3 min; and (3) placing the mixture on vulcanization equipment for vulcanization after mixing, wherein the vulcanization temperature is 155 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 3min, so that the rubber for the anti-slip wear-resistant sole based on polybutadiene is obtained.
Example 3
Polybutadiene-based anti-slip wear-resistant sole rubber comprises the following components in parts by weight:
60 parts of polybutadiene rubber, 48 parts of thermoplastic elastomer SBS, 35 parts of modified boron-magnesium stone composite particles, 3.6 parts of terpene-phenol resin, 1.8 parts of silane coupling agent KH-5600.8 parts of anti-aging agent DNP, 4.6 parts of sulfur and 1.6 parts of accelerator TETD.
Wherein the number average molecular weight of the thermoplastic elastomer SBS is 18000-20000, the particle diameter of the modified boron-magnesium stone composite particle is 300 μm, and the softening point of the terpene-phenol resin is 150 ℃.
The preparation method of the modified boron-magnesium stone composite particle comprises the following steps:
step one, preparing a modifier:
s1, weighing maleic anhydride and furan, mixing the maleic anhydride and the furan in a reaction container filled with acetone, fully stirring the mixture for 24 hours at room temperature, filtering out a solid, washing the solid with acetone for at least three times, and drying the solid to obtain a compound A; wherein the mass ratio of the maleic anhydride to the furan to the acetone is 3.6:4.4: 100;
s2, weighing the compound A and ethanol, mixing the compound A and the ethanol into a reaction container, placing a flask into an ice-water bath, fully stirring, dropwise adding 2-hydroxyethylamine into the flask, fully stirring again, removing the ice-water bath, assembling a condensation reflux device, heating to 85 ℃, stirring for 36 hours, cooling to room temperature, sealing the flask, storing in the dark at 0-4 ℃ for 10 hours, filtering out solids, washing with ethanol at 0-4 ℃, and drying to obtain a compound B; wherein the mass ratio of the compound A to the 2-hydroxyethylamine to the ethanol is 1:0.6: 100;
s3, weighing a compound B, 4-dimethylaminopyridine and dichloromethane, mixing the compound B, 4-dimethylaminopyridine and dichloromethane into a reaction container, filling nitrogen into the reaction container to replace air, placing the reaction container in an ice-water bath condition, stirring for 1h, then dropwise adding 2-aminoacetyl chloride, stirring for 1h in the ice-water bath condition after dropwise adding, removing the ice-water bath, continuing stirring at room temperature for reaction for 12h, then washing with saturated sodium bicarbonate water and purified water in sequence, extracting and combining organic phases, and drying to remove a solvent to obtain a compound C; wherein the mass ratio of the compound B, 2-aminoacetyl chloride, 4-dimethylaminopyridine and dichloromethane is 1:0.9:0.1: 50;
s4, mixing the compound C with toluene, placing the mixture in a reflux condensing device, heating to 120 ℃ under the protection of nitrogen, stirring for 6 hours, removing the solvent, and drying at 45 ℃ to obtain a modifier; wherein the mass ratio of the compound C to the toluene is 1: 50.
Step two, preparing nano activated boron magnesium stone:
weighing nano-boron magnesium stone, vinyl trimethoxy silane and deionized water, mixing, stirring at 55 ℃ for 6h, filtering to remove liquid, and drying to obtain nano-activated boron magnesium stone; wherein the particle size of the nano-boron magnesium stone is 200-500 nm; the mass ratio of the nano boron magnesium stone, the vinyl trimethoxy silane and the deionized water is 1:0.12: 20.
Step three, preparing modified boron magnesium stone composite particles:
p1, weighing the modifier and acetanilide, mixing the modifier and the acetanilide in toluene, and stirring the mixture uniformly to form a modifier solution; wherein the mass ratio of the modifier to the acetanilide to the toluene is 1:0.16: 10;
p2, weighing 1, 2-polybutadiene, nano activated boron magnesium stone and toluene, mixing the mixture into a reaction container, heating to 80 ℃, stirring uniformly, dropwise adding a modifier solution, stirring uniformly again, adding an initiator azobisisobutyronitrile, carrying out heat preservation reaction for 5 hours, precipitating by using anhydrous methanol, and drying under reduced pressure to obtain modified boron magnesium stone composite particles; wherein the molecular weight of the 1, 2-polybutadiene is 1000-2000; the addition amount of the initiator is 2-5% of the mass of the 1, 2-polybutadiene; the mass ratio of the 1, 2-polybutadiene, the nano activated boron-magnesium stone, the modifier solution and the toluene is 1:1.8:5.8: 22.
The preparation method of the rubber for the anti-slip wear-resistant sole based on polybutadiene comprises the following steps:
step 1, weighing polybutadiene rubber and thermoplastic elastomer SBS, mixing the polybutadiene rubber and thermoplastic elastomer SBS into an internal mixer, controlling the temperature of the internal mixer to be 120 ℃, controlling the internal mixing homogenization time to be 7min, and cooling to room temperature after the internal mixing is finished to obtain a first mixture;
step 2, sequentially adding the weighed modified boron-magnesium stone composite particles, terpene-phenol resin, anti-aging agent and silane coupling agent into a mixing agent, then adding a first mixture, starting mixing, wherein the mixing temperature is 120 ℃, the mixing pressure is 0.5MPa, the mixing time is 10min, and cooling after mixing to obtain a second mixture;
step 3, adding the weighed sulfur and the accelerator into the second mixture for mixing, wherein the mixing temperature is 100 ℃, the mixing pressure is 0.5MPa, and the mixing time is 5 min; and (3) after mixing, putting the mixture on vulcanization equipment for vulcanization, wherein the vulcanization temperature is 165 ℃, the vulcanization pressure is 25MPa, and the vulcanization time is 6min, thus obtaining the rubber for the anti-slip wear-resistant sole based on polybutadiene.
Comparative example 1
The difference between the polybutadiene-based anti-slip wear-resistant rubber for soles and the example 1 is that the preparation method of the modified boron-magnesium stone composite particles is different, and the preparation method of the modified boron-magnesium stone composite particles comprises the following steps:
step one, preparing nano activated boron magnesium stone:
weighing nano-boron magnesium stone, vinyl trimethoxy silane and deionized water, mixing, stirring at 50 ℃ for 5h, filtering to remove liquid, and drying to obtain nano-activated boron magnesium stone; wherein the particle size of the nano-boron magnesium stone is 200-500 nm; the mass ratio of the nano boron magnesium stone, the vinyl trimethoxy silane and the deionized water is 1:0.1: 15.
Step two, preparing modified boron magnesium stone composite particles:
p1, weighing acetanilide, mixing into toluene, and stirring to be uniform to form a modifier solution; wherein the mass ratio of the acetanilide to the toluene is 0.14: 10;
p2, weighing 1, 2-polybutadiene, nano activated boron magnesium stone and toluene, mixing the mixture into a reaction container, heating to 75 ℃, stirring uniformly, dropwise adding a modifier solution, stirring uniformly again, adding an initiator azobisisobutyronitrile, carrying out heat preservation reaction for 4 hours, precipitating by using anhydrous methanol, and drying under reduced pressure to obtain modified boron magnesium stone composite particles; wherein the molecular weight of the 1, 2-polybutadiene is 1000-2000; the addition amount of the initiator is 3 percent of the mass of the 1, 2-polybutadiene; the mass ratio of the 1, 2-polybutadiene, the nano activated boron-magnesium stone, the modifier solution and the toluene is 1:1.5:4.6: 20.
Comparative example 2
The difference between the polybutadiene-based anti-slip wear-resistant rubber for soles and the polybutadiene-based anti-slip wear-resistant rubber for soles in example 1 is that modified boron-magnesium stone composite particles are replaced by nano boron-magnesium stone.
Comparative example 3
The difference between the polybutadiene-based anti-slip wear-resistant rubber for soles and the polybutadiene-based anti-slip wear-resistant rubber for soles in example 1 is that modified boron-magnesium stone composite particles are not added.
The invention aims at the rubbers for soles prepared in example 1, comparative example 2 and comparative example 3 to carry out detection and comparison on performances, wherein the tensile strength and the elongation at break are detected according to the method of the standard GB/T528-one 2009; DIN abrasion detection is carried out according to a standard DIN-5351-1987, the heat aging treatment is carried out according to a standard GB/T3512-2014, the aging temperature is 80 ℃, and the aging time is 120 h; the ultraviolet aging treatment is carried out for 48h by referring to standard GB/T16585-2008, wavelength is 325nm and tritium lamp irradiation with power of 40W is carried out. The results are shown in table 1:
TABLE 1 comparison of the Properties of the rubbers for soles prepared by different methods
As can be seen from Table 1, the rubber for shoe soles prepared in example 1 had a hardness of 55 and a density of 1 g/cm 3 Compared with the traditional rubber sole, the rubber sole has the advantages of being lighter, higher in tensile strength and elongation at break, excellent in performance after thermal aging and ultraviolet aging, and lower in DIN abrasion, and has better mechanical property, wear resistance and aging resistance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The rubber for the anti-slip wear-resistant sole based on polybutadiene is characterized by comprising the following components in parts by weight:
60 parts of polybutadiene rubber, 32-48 parts of thermoplastic elastomer SBS, 26-35 parts of modified boron-magnesium stone composite particles, 1.5-3.6 parts of terpene-phenol resin, 0.2-0.8 part of silane coupling agent, 1.2-1.8 parts of anti-aging agent, 2.3-4.6 parts of sulfur and 1.1-1.6 parts of accelerator.
2. The polybutadiene-based rubber for anti-slip and wear-resistant soles according to claim 1, wherein the thermoplastic elastomer SBS has a number average molecular weight of 18000-20000, the modified boromagnesite composite particles have a particle size of 100-300 μm, and the terpene phenol resin has a softening point of 125-150 ℃.
3. The polybutadiene-based rubber for anti-slip and wear-resistant soles according to claim 1, wherein the silane coupling agent is one of a silane coupling agent KH-792, a silane coupling agent KH-550 and a silane coupling agent KH-560.
4. The rubber for non-slip wear-resistant soles based on polybutadiene according to claim 1, wherein the anti-aging agent is one of anti-aging agent TMQ, anti-aging agent MB and anti-aging agent DNP.
5. The rubber for anti-slip and wear-resistant soles based on polybutadiene as claimed in claim 1, wherein said accelerator is accelerator M or accelerator TETD.
6. The polybutadiene-based anti-slip wear-resistant sole rubber as claimed in claim 1, wherein the preparation method of the modified boromagnesite composite particles comprises the following steps:
firstly, maleic anhydride is used for sequentially carrying out Diels-Alder reaction, acylation reaction and condensation reaction to prepare a modifier;
secondly, activating the nano-boron magnesium stone by using vinyltrimethoxysilane to obtain nano-activated boron magnesium stone;
and thirdly, modifying the 1, 2-polybutadiene by using a modifier, and simultaneously adding the nano activated boron-magnesium stone to obtain the modified boron-magnesium stone composite particles.
7. The rubber for anti-slip and wear-resistant soles based on polybutadiene as claimed in claim 6, wherein in the first step, the modifier is prepared by the following steps:
s1, weighing maleic anhydride and furan, mixing in a reaction container filled with acetone, fully stirring at room temperature for 16-24h, filtering out solids, washing with acetone for at least three times, and drying to obtain a compound A;
s2, weighing the compound A and ethanol, mixing the compound A and the ethanol into a reaction container, placing a flask into an ice-water bath, fully stirring, dropwise adding 2-hydroxyethylamine into the flask, fully stirring again, removing the ice-water bath, assembling a condensation reflux device, heating to 65-85 ℃, stirring for 18-36h, cooling to room temperature, sealing the flask, storing in the dark at 0-4 ℃ for 6-10h, filtering out solids, washing with ethanol at 0-4 ℃, and drying to obtain a compound B;
s3, weighing a compound B, 4-dimethylaminopyridine and dichloromethane, mixing the compound B, 4-dimethylaminopyridine and dichloromethane into a reaction container, filling nitrogen into the reaction container to replace air, placing the reaction container in an ice-water bath condition, stirring for 0.5-1h, then dropwise adding 2-aminoacetyl chloride, stirring for 0.5-1h in the ice-water bath condition after dropwise adding, removing the ice-water bath, continuing stirring and reacting for 8-12h at room temperature, then washing with saturated sodium bicarbonate water and purified water in sequence, extracting and combining organic phases, and drying to remove a solvent to obtain a compound C;
s4, mixing the compound C with toluene, placing the mixture in a reflux condensing device, heating to 100-120 ℃ under the protection of nitrogen, stirring for 3-6h, removing the solvent, and drying at 35-45 ℃ to obtain the modifier.
8. The polybutadiene-based anti-slip and wear-resistant rubber for shoe soles according to claim 6, wherein in the second step, the preparation method of the nano activated boromagnesite comprises the following steps:
weighing nano-boron magnesium stone, vinyl trimethoxy silane and deionized water, mixing, stirring at 45-55 deg.C for 4-6h, filtering to remove liquid, and drying to obtain nano-activated boron magnesium stone.
9. The polybutadiene-based anti-slip and wear-resistant rubber for shoe soles according to claim 6, wherein in the third step, the modified boromagnesite composite particles are prepared by a method comprising the following steps of:
p1, weighing the modifier and acetanilide, mixing the modifier and the acetanilide in toluene, and stirring the mixture uniformly to form a modifier solution;
p2, weighing 1, 2-polybutadiene, nano activated boron magnesium stone and toluene, mixing the mixture into a reaction container, heating to 70-80 ℃, stirring uniformly, dropwise adding a modifier solution, stirring uniformly again, adding an initiator azobisisobutyronitrile, reacting for 3-5h while keeping the temperature, precipitating by using anhydrous methanol, and drying under reduced pressure to obtain the modified boron magnesium stone composite particles.
10. The preparation method of the rubber for the anti-slip and wear-resistant sole based on polybutadiene as claimed in any one of claims 1 to 9, characterized by comprising the following steps:
step 1, weighing polybutadiene rubber and thermoplastic elastomer SBS, mixing into an internal mixer, and homogenizing to obtain a first mixture;
step 2, sequentially adding the weighed modified boron-magnesium stone composite particles, terpene-phenol resin, anti-aging agent and silane coupling agent into a mixing agent, then adding the first mixture, and uniformly mixing to obtain a second mixture;
and 3, adding the weighed sulfur and the accelerator into the second mixture, uniformly mixing, and placing on vulcanization equipment for vulcanization to obtain the rubber for the anti-slip wear-resistant sole based on polybutadiene.
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