CN111171402A - Rubber basketball outer skin and preparation method thereof - Google Patents

Rubber basketball outer skin and preparation method thereof Download PDF

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Publication number
CN111171402A
CN111171402A CN202010052505.8A CN202010052505A CN111171402A CN 111171402 A CN111171402 A CN 111171402A CN 202010052505 A CN202010052505 A CN 202010052505A CN 111171402 A CN111171402 A CN 111171402A
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rubber
mixing
parts
modified attapulgite
basketball
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陈侯灿
陈公湖
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Zhangzhou Huafei Sports Goods Co ltd
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Zhangzhou Huafei Sports Goods Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0033—Use of organic additives containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B41/00—Hollow inflatable balls
    • A63B41/08—Ball covers; Closures therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2407/00—Characterised by the use of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention relates to a rubber basketball outer skin and a preparation method thereof, wherein the rubber basketball outer skin is prepared from the following raw materials in parts by weight: 10-20 parts of natural rubber, 40-60 parts of butadiene rubber, 2-5 parts of sodium polyacrylate, 3-5 parts of polyurethane adhesive, 2-5 parts of water, 10-15 parts of polyethylene glycol, 15-20 parts of carbon black, 15-20 parts of zinc oxide, 10-20 parts of modified attapulgite, 0.5-0.8 part of N, N-di-N-butyl nickel dithiocarbamate, 0.2-0.8 part of sulfur, 1-1.2 parts of an accelerator and 2-4 parts of a foaming agent.

Description

Rubber basketball outer skin and preparation method thereof
Technical Field
The invention relates to a rubber basketball outer skin and a preparation method thereof.
Background
The rubber basketball mainly comprises an inner tube, a yarn winding layer, a middle tire layer and an outer skin covering the periphery of the middle tire layer from inside to outside, and a ball nozzle is further arranged on the basketball. The outer skin of the traditional rubber basketball is poor in weather resistance, the basketball is easy to deform and the outer skin of the basketball is easy to crack and embrittle along with the change of weather and time, the wear resistance and the scratch resistance of the basketball are poor, the surface of the basketball is easy to wear after the basketball is used for a period of time, and the service life of the basketball is shortened; in addition, a player may generate a lot of sweat on the palm during playing, and the hand with sweat may affect the touch feeling (e.g., feel sticky) when holding or beating the basketball, thereby affecting the performance of the player.
Disclosure of Invention
The invention aims to provide a rubber basketball outer skin which has good wear resistance and weather resistance and can absorb sweat on hands of a user and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: the rubber basketball outer skin is prepared from the following raw materials in parts by weight: 10-20 parts of natural rubber, 40-60 parts of butadiene rubber, 2-5 parts of sodium polyacrylate, 3-5 parts of polyurethane adhesive, 2-5 parts of water, 10-15 parts of polyethylene glycol, 15-20 parts of carbon black, 15-20 parts of zinc oxide, 10-20 parts of modified attapulgite, 0.5-0.8 part of N, N-di-N-butyl nickel dithiocarbamate, 0.2-0.8 part of sulfur, 1-1.2 parts of accelerator and 2-4 parts of foaming agent.
The preparation method of the rubber basketball outer skin comprises the following process steps:
step (1) preparation of a water-absorbent resin solution: mixing and heating sodium polyacrylate, polyurethane adhesive and water to obtain water-absorbent resin solution;
step (2) preparing modified attapulgite;
preparing a sizing material in step (3): mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, and then adding the mixture into an internal mixer for mixing to obtain a rubber material;
step (4) preparing main glue: adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer for mixing to obtain a main rubber;
step (5) preparing the rubber basketball outer skin material: adding the main rubber obtained in the step (4), a foaming agent and sulfur into an open mill for mixing to obtain a rubber basketball outer skin material;
and (6) extruding, calendering and cutting the rubber basketball outer skin material obtained in the step (5) to obtain the rubber basketball outer skin.
Compared with the prior art, the invention has the advantages that:
1. the rubber basketball outer skin has excellent weather resistance, wear resistance and scratch resistance, and the properties of the basketball outer skin do not change too much even along with the change of climate and service time, so that a basketball made of the basketball outer skin is not easy to deform, and the phenomena of cracking, embrittlement, cracking and abrasion are not easy to occur on the surface.
2. A basketball constructed from the basketball cover of the present invention has the same degree of bounce and grip as a conventional basketball, but is softer to the touch.
3. In addition, the basketball outer skin can absorb sweat on the palm of a basketball user, and provides excellent touch feeling for the user.
Detailed Description
The present invention will be described in detail with reference to the following examples:
the rubber basketball outer skin is prepared from the following raw materials in parts by weight: 10-20 parts of natural rubber, 40-60 parts of butadiene rubber, 2-5 parts of sodium polyacrylate, 3-5 parts of polyurethane adhesive, 2-5 parts of water, 10-15 parts of polyethylene glycol, 15-20 parts of carbon black, 15-20 parts of zinc oxide, 10-20 parts of modified attapulgite, 0.5-0.8 part of N, N-di-N-butyl nickel dithiocarbamate, 0.2-0.8 part of sulfur, 1-1.2 parts of accelerator and 2-4 parts of foaming agent.
The accelerator is preferably a mixture obtained by mixing zinc ethyl phenyl dithiocarbamate, dibenzothiazyl disulfide and an accelerator TMTD according to a weight ratio of 5:3: 2.
The foaming agent is one or a mixture of several of azodicarbonamide, 4' -oxo-bis-benzenesulfonyl hydrazide and p-toluene sulfonyl hydrazide.
The preparation method of the rubber basketball outer skin comprises the following process steps:
step (1) preparation of a water-absorbent resin solution: mixing and heating sodium polyacrylate, polyurethane adhesive and water to obtain water-absorbent resin solution;
step (2) preparing modified attapulgite;
preparing a sizing material in step (3): mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, and then adding the mixture into an internal mixer for mixing to obtain a rubber material;
step (4) preparing main glue: adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer for mixing to obtain a main rubber;
step (5) preparing the rubber basketball outer skin material: adding the main rubber obtained in the step (4), a foaming agent and sulfur into an open mill for mixing to obtain a rubber basketball outer skin material;
extruding, rolling and cutting the rubber basketball outer skin material obtained in the step (5) to obtain the rubber basketball outer skin;
the modified attapulgite and the water-absorbent resin solution can improve the water absorption performance of the basketball outer skin, and the modified attapulgite can also cover the friction performance of the basketball outer skin to improve the holding power of the basketball.
The specific method of the step (1) is as follows: mixing sodium polyacrylate, polyurethane adhesive and water uniformly, stirring and heating at 125-130 deg.C for 20-30 min.
The specific operation method of the step (2) is as follows:
step 1) preparation of acid-modified attapulgite: roasting the attapulgite at 750-800 ℃ for 4-5h, putting the attapulgite into a 10-15% hydrochloric acid solution for soaking for 3-4h, taking out the attapulgite, and drying the attapulgite until the water content is 2-3% to obtain acid modified attapulgite;
step 2) preparing a compound coupling agent: mixing a silane coupling agent Kh560 and maleic anhydride in a weight ratio of 1:2-4 to obtain a compound coupling agent;
step 3) preparing coupling agent modified attapulgite: adding a compound coupling agent into the acid-modified attapulgite obtained in the step 1), wherein the addition amount of the compound coupling agent is 4-6 wt% of the mass of the acid-modified attapulgite, then putting the mixture into a heating type kneader, mixing and stirring the mixture at a stirring speed of 50r/min, slowly heating the mixture while stirring the mixture, and stirring the mixture at a constant temperature for 2-3 hours when the temperature is raised to 80-90 ℃ to obtain the coupling agent-modified attapulgite;
step 4) adding stearic acid into the coupling agent modified attapulgite obtained in the step 3), wherein the addition amount of the stearic acid is 1.0-1.2 wt% of the mass of the acid modified attapulgite, continuously stirring and heating to 95 ℃ by using a heating type kneader, stirring at constant temperature for 1-2h, and discharging; and then, drying the discharged material, controlling the drying temperature at 50-60 ℃, conveying the material to a disc type grinding machine when the material is dried until the water content is less than 0.5%, and grinding the material into powder of 50-60 meshes to obtain the modified attapulgite.
The specific operation method of the step (3) is as follows: and (2) mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, adding into an internal mixer, and mixing for 15-20min at 70-80 ℃ to obtain a rubber material.
The specific operation method of the step (4) is as follows:
adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer, and mixing for 15-20min at 80-85 ℃ to obtain a main rubber;
the specific operation method of the step (5) is as follows:
and (3) adding the main rubber obtained in the step (4), the foaming agent and sulfur into an open mill, and mixing for 20-30min at the temperature of 80-85 ℃ to obtain the rubber basketball outer skin material.
The invention is explained in more detail below with reference to specific examples:
the first embodiment is as follows:
the rubber basketball outer skin is prepared from the following raw materials: 10kg of natural rubber, 60kg of butadiene rubber, 2kg of sodium polyacrylate, 5kg of polyurethane adhesive, 5kg of water, 15kg of polyethylene glycol, 15kg of carbon black, 20kg of zinc oxide, 10kg of modified attapulgite, 0.5kg of N, N-di-N-butyl nickel dithiocarbamate, 0.2kg of sulfur, 1kg of accelerator and 2kg of foaming agent.
The accelerator is a mixture obtained by mixing zinc ethylphenyl dithiocarbamate, dibenzothiazyl disulfide and accelerator TMTD according to the weight ratio of 5:3:2, wherein the weights of the zinc ethylphenyl dithiocarbamate, the dibenzothiazyl disulfide and the accelerator TMTD are respectively 0.5kg, 0.3kg and 0.2 kg;
the foaming agent is azodicarbonamide.
The preparation method of the rubber basketball outer skin comprises the following process steps:
step (1) preparation of a water-absorbent resin solution: and uniformly mixing weighed sodium polyacrylate, polyurethane adhesive and water, and then stirring and heating at 125 ℃ for 30 min.
Step (2) preparing modified attapulgite:
step 1) preparation of acid-modified attapulgite: roasting the attapulgite at 750 ℃ for 5h, then putting the attapulgite into a 10% hydrochloric acid solution for soaking for 4h, fishing out the attapulgite, and drying the attapulgite until the water content is 2% to obtain acid-modified attapulgite;
step 2) preparing a compound coupling agent: mixing a silane coupling agent Kh560 and maleic anhydride in a weight ratio of 1:2 to obtain a compound coupling agent;
step 3) preparing coupling agent modified attapulgite: adding a compound coupling agent into the acid-modified attapulgite obtained in the step 1), wherein the addition amount of the compound coupling agent is 4 wt% of the mass of the acid-modified attapulgite, then putting the mixture into a heating kneader, mixing and stirring, wherein the stirring speed is 50r/min, slowly heating while stirring, and stirring at a constant temperature for 3 hours when the temperature is raised to 80 ℃ to obtain the coupling agent-modified attapulgite;
step 4) adding stearic acid into the coupling agent modified attapulgite obtained in the step 3), wherein the addition amount of the stearic acid is 1.0 wt% of the mass of the acid modified attapulgite, continuously stirring by using a heating type kneader and heating to 95 ℃, stirring at constant temperature for 1h, and discharging; and then, drying the discharged material, controlling the drying temperature at 50 ℃, conveying the material to a disc type grinding machine when the material is dried until the water content is less than 0.5%, and grinding the material into powder of 60 meshes to obtain the modified attapulgite.
Preparing a sizing material in step (3): and (2) mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, adding into an internal mixer, and mixing for 20min at 70 ℃ to obtain a sizing material.
Step (4) preparing main glue: adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer, and mixing for 20min at 80 ℃ to obtain a main rubber; the accelerator is a mixture of zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and an accelerator TMTD mixed in advance.
Step (5) preparing the rubber basketball outer skin material: and (3) adding the main rubber obtained in the step (4), the foaming agent and sulfur into an open mill, and mixing for 30min at 80 ℃ to obtain the rubber basketball outer skin material.
And (6) extruding, calendering and cutting the rubber basketball outer skin material obtained in the step (5) to obtain the rubber basketball outer skin.
Example two:
the rubber basketball outer skin is prepared from the following raw materials: 10kg of natural rubber, 60kg of butadiene rubber, 2kg of sodium polyacrylate, 5kg of polyurethane adhesive, 2kg of water, 15kg of polyethylene glycol, 15kg of carbon black, 20kg of zinc oxide, 15kg of modified attapulgite, 0.5kg of N, N-di-N-butyl nickel dithiocarbamate, 0.2kg of sulfur, 1kg of accelerator and 2kg of foaming agent.
The accelerator is preferably a mixture obtained by mixing zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and accelerator TMTD in a weight ratio of 5:3:2, namely the weights of the zinc ethylphenyldithiocarbamate, the dibenzothiazyl disulfide and the accelerator TMTD are respectively 0.5kg, 0.3kg and 0.2 kg;
the foaming agent is azodicarbonamide.
The preparation method of the rubber basketball outer skin comprises the following process steps:
step (1) preparation of a water-absorbent resin solution: and uniformly mixing weighed sodium polyacrylate, polyurethane adhesive and water, and then stirring and heating at 125 ℃ for 30 min.
Step (2) preparing modified attapulgite:
step 1) preparation of acid-modified attapulgite: roasting the attapulgite at 750 ℃ for 5h, then putting the attapulgite into a 10% hydrochloric acid solution for soaking for 4h, fishing out the attapulgite, and drying the attapulgite until the water content is 2% to obtain acid-modified attapulgite;
step 2) preparing a compound coupling agent: mixing a silane coupling agent Kh560 and maleic anhydride in a weight ratio of 1:2 to obtain a compound coupling agent;
step 3) preparing coupling agent modified attapulgite: adding a compound coupling agent into the acid-modified attapulgite obtained in the step 1), wherein the addition amount of the compound coupling agent is 4 wt% of the mass of the acid-modified attapulgite, then putting the mixture into a heating kneader, mixing and stirring, wherein the stirring speed is 50r/min, slowly heating while stirring, and stirring at a constant temperature for 3 hours when the temperature is raised to 80 ℃ to obtain the coupling agent-modified attapulgite;
step 4) adding stearic acid into the coupling agent modified attapulgite obtained in the step 3), wherein the addition amount of the stearic acid is 1.0 wt% of the mass of the acid modified attapulgite, continuously stirring by using a heating type kneader and heating to 95 ℃, stirring at constant temperature for 1h, and discharging; and then, drying the discharged material, controlling the drying temperature at 50 ℃, conveying the material to a disc type grinding machine when the material is dried until the water content is less than 0.5%, and grinding the material into powder of 60 meshes to obtain the modified attapulgite.
Preparing a sizing material in step (3): and (2) mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, adding into an internal mixer, and mixing for 20min at 70 ℃ to obtain a sizing material.
Step (4) preparing main glue: adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer, and mixing for 20min at 80 ℃ to obtain a main rubber; the accelerator is a mixture of zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and an accelerator TMTD mixed in advance.
Step (5) preparing the rubber basketball outer skin material: and (3) adding the main rubber obtained in the step (4), the foaming agent and sulfur into an open mill, and mixing for 30min at 80 ℃ to obtain the rubber basketball outer skin material.
And (6) extruding, calendering and cutting the rubber basketball outer skin material obtained in the step (5) to obtain the rubber basketball outer skin.
Example three:
the rubber basketball outer skin is prepared from the following raw materials: 10kg of natural rubber, 60kg of butadiene rubber, 2kg of sodium polyacrylate, 5kg of polyurethane adhesive, 5kg of water, 15kg of polyethylene glycol, 20kg of carbon black, 20kg of zinc oxide, 15kg of modified attapulgite, 0.5kg of N, N-di-N-butyl nickel dithiocarbamate, 0.2kg of sulfur, 1kg of accelerator and 2kg of foaming agent.
The accelerator is preferably a mixture obtained by mixing zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and accelerator TMTD in a weight ratio of 5:3:2, namely the weights of the zinc ethylphenyldithiocarbamate, the dibenzothiazyl disulfide and the accelerator TMTD are respectively 0.5kg, 0.3kg and 0.2 kg;
the foaming agent is azodicarbonamide.
The preparation method of the rubber basketball outer skin comprises the following process steps:
step (1) preparation of a water-absorbent resin solution: and uniformly mixing weighed sodium polyacrylate, polyurethane adhesive and water, and then stirring and heating at 125 ℃ for 30 min.
Step (2) preparing modified attapulgite:
step 1) preparation of acid-modified attapulgite: roasting the attapulgite at 750 ℃ for 5h, then putting the attapulgite into a 10% hydrochloric acid solution for soaking for 4h, fishing out the attapulgite, and drying the attapulgite until the water content is 2% to obtain acid-modified attapulgite;
step 2) preparing a compound coupling agent: mixing a silane coupling agent Kh560 and maleic anhydride in a weight ratio of 1:2 to obtain a compound coupling agent;
step 3) preparing coupling agent modified attapulgite: adding a compound coupling agent into the acid-modified attapulgite obtained in the step 1), wherein the addition amount of the compound coupling agent is 4 wt% of the mass of the acid-modified attapulgite, then putting the mixture into a heating kneader, mixing and stirring, wherein the stirring speed is 50r/min, slowly heating while stirring, and stirring at a constant temperature for 3 hours when the temperature is raised to 80 ℃ to obtain the coupling agent-modified attapulgite;
step 4) adding stearic acid into the coupling agent modified attapulgite obtained in the step 3), wherein the addition amount of the stearic acid is 1.0 wt% of the mass of the acid modified attapulgite, continuously stirring by using a heating type kneader and heating to 95 ℃, stirring at constant temperature for 1h, and discharging; and then, drying the discharged material, controlling the drying temperature at 50 ℃, conveying the material to a disc type grinding machine when the material is dried until the water content is less than 0.5%, and grinding the material into powder of 60 meshes to obtain the modified attapulgite.
Preparing a sizing material in step (3): and (2) mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, adding into an internal mixer, and mixing for 20min at 70 ℃ to obtain a sizing material.
Step (4) preparing main glue: adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer, and mixing for 20min at 80 ℃ to obtain a main rubber; the accelerator is a mixture of zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and an accelerator TMTD mixed in advance.
Step (5) preparing the rubber basketball outer skin material: and (3) adding the main rubber obtained in the step (4), the foaming agent and sulfur into an open mill, and mixing for 30min at 80 ℃ to obtain the rubber basketball outer skin material.
And (6) extruding, calendering and cutting the rubber basketball outer skin material obtained in the step (5) to obtain the rubber basketball outer skin.
Example four:
the rubber basketball outer skin is prepared from the following raw materials: 15kg of natural rubber, 45kg of butadiene rubber, 3kg of sodium polyacrylate, 4kg of polyurethane adhesive, 3kg of water, 12kg of polyethylene glycol, 20kg of carbon black, 15kg of zinc oxide, 20kg of modified attapulgite, 0.6kg of N, N-di-N-butyl nickel dithiocarbamate, 0.5kg of sulfur, 1kg of accelerator and 3kg of foaming agent.
The accelerator is preferably a mixture obtained by mixing zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and accelerator TMTD in a weight ratio of 5:3:2, namely the weights of the zinc ethylphenyldithiocarbamate, the dibenzothiazyl disulfide and the accelerator TMTD are respectively 0.5kg, 0.3kg and 0.2 kg;
the foaming agent is azodicarbonamide.
The preparation method of the rubber basketball outer skin comprises the following process steps:
step (1) preparation of a water-absorbent resin solution: and uniformly mixing weighed sodium polyacrylate, polyurethane adhesive and water, and then stirring and heating at the temperature of 128 ℃ for 25 min.
Step (2) preparing modified attapulgite:
step 1) preparation of acid-modified attapulgite: roasting the attapulgite at 760 ℃ for 4.5h, soaking in 15% hydrochloric acid solution for 3.5h, taking out, and drying until the water content is 2.5% to obtain acid-modified attapulgite;
step 2) preparing a compound coupling agent: mixing a silane coupling agent Kh560 and maleic anhydride in a weight ratio of 1:3 to obtain a compound coupling agent;
step 3) preparing coupling agent modified attapulgite: adding a compound coupling agent into the acid-modified attapulgite obtained in the step 1), wherein the addition amount of the compound coupling agent is 5 wt% of the mass of the acid-modified attapulgite, then putting the mixture into a heating kneader, mixing and stirring the mixture at a stirring speed of 50r/min, slowly heating the mixture while stirring the mixture, and stirring the mixture at a constant temperature for 2.5 hours when the temperature is raised to 85 ℃ to obtain the coupling agent-modified attapulgite;
step 4) adding stearic acid into the coupling agent modified attapulgite obtained in the step 3), wherein the addition amount of the stearic acid is 1.2 wt% of the mass of the acid modified attapulgite, continuously stirring by using a heating type kneader and heating to 95 ℃, stirring at constant temperature for 1.5h, and discharging; and then, drying the discharged material, controlling the drying temperature at 55 ℃, conveying the material to a disc type grinding machine when the material is dried until the water content is less than 0.5%, and grinding the material into powder of 60 meshes to obtain the modified attapulgite.
Preparing a sizing material in step (3): and (2) mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, adding into an internal mixer, and mixing for 18min at 75 ℃ to obtain a rubber material.
Step (4) preparing main glue: adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer, and mixing for 18min at 83 ℃ to obtain a main rubber; the accelerator is a mixture of zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and an accelerator TMTD mixed in advance.
Step (5) preparing the rubber basketball outer skin material: and (3) adding the main rubber obtained in the step (4), the foaming agent and sulfur into an open mill, and mixing for 25min at 83 ℃ to obtain the rubber basketball outer skin material.
And (6) extruding, calendering and cutting the rubber basketball outer skin material obtained in the step (5) to obtain the rubber basketball outer skin.
Example five:
the rubber basketball outer skin is prepared from the following raw materials: 20kg of natural rubber, 40kg of butadiene rubber, 3kg of sodium polyacrylate, 3kg of polyurethane adhesive, 5kg of water, 10kg of polyethylene glycol, 18kg of carbon black, 15kg of zinc oxide, 18kg of modified attapulgite, 0.8kg of N, N-di-N-butyl nickel dithiocarbamate, 0.8kg of sulfur, 1.2kg of accelerator and 4kg of foaming agent.
The accelerator is preferably a mixture obtained by mixing zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and accelerator TMTD in a weight ratio of 5:3:2, wherein the weights of the zinc ethylphenyldithiocarbamate, the dibenzothiazyl disulfide and the accelerator TMTD are respectively 0.6kg, 0.36kg and 0.24 kg;
the foaming agent is p-toluenesulfonyl hydrazide.
The preparation method of the rubber basketball outer skin comprises the following process steps:
step (1) preparation of a water-absorbent resin solution: and uniformly mixing weighed sodium polyacrylate, polyurethane adhesive and water, and then stirring and heating at the temperature of 130 ℃ for 20 min.
Step (2) preparing modified attapulgite:
step 1) preparation of acid-modified attapulgite: roasting the attapulgite at 800 ℃ for 4h, soaking in 15% hydrochloric acid solution for 3h, taking out, and drying until the water content is 3% to obtain acid-modified attapulgite;
step 2) preparing a compound coupling agent: mixing a silane coupling agent Kh560 and maleic anhydride in a weight ratio of 1:4 to obtain a compound coupling agent;
step 3) preparing coupling agent modified attapulgite: adding a compound coupling agent into the acid-modified attapulgite obtained in the step 1), wherein the addition amount of the compound coupling agent is 6 wt% of the mass of the acid-modified attapulgite, then putting the mixture into a heating kneader, mixing and stirring the mixture at a stirring speed of 50r/min, slowly heating the mixture while stirring the mixture, and stirring the mixture at a constant temperature for 2 hours when the temperature is raised to 90 ℃ to obtain the coupling agent-modified attapulgite;
step 4) adding stearic acid into the coupling agent modified attapulgite obtained in the step 3), wherein the addition amount of the stearic acid is 1.1 wt% of the mass of the acid modified attapulgite, continuously stirring by using a heating type kneader and heating to 95 ℃, stirring at constant temperature for 2h, and discharging; and then, drying the discharged material, controlling the drying temperature at 60 ℃, conveying the material to a disc type grinding machine when the material is dried until the water content is less than 0.5%, and grinding the material into powder of 50 meshes to obtain the modified attapulgite.
Preparing a sizing material in step (3): and (2) mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, adding into an internal mixer, and mixing for 15min at 80 ℃ to obtain a sizing material.
Step (4) preparing main glue: adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer, and mixing for 15min at 85 ℃ to obtain a main rubber; the accelerator is a mixture of zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and an accelerator TMTD mixed in advance.
Step (5) preparing the rubber basketball outer skin material: and (3) adding the main rubber obtained in the step (4), the foaming agent and sulfur into an open mill, and mixing for 20min at 85 ℃ to obtain the rubber basketball outer skin material.
Extruding, rolling and cutting the rubber basketball outer skin material obtained in the step (5) to obtain the rubber basketball outer skin;
example six:
the rubber basketball outer skin is prepared from the following raw materials: 20kg of natural rubber, 40kg of butadiene rubber, 5kg of sodium polyacrylate, 3kg of polyurethane adhesive, 5kg of water, 10kg of polyethylene glycol, 20kg of carbon black, 18kg of zinc oxide, 18kg of modified attapulgite, 0.8kg of N, N-di-N-butyl nickel dithiocarbamate, 0.8kg of sulfur, 1.1kg of accelerator and 4kg of foaming agent.
The accelerator is preferably a mixture obtained by mixing zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and accelerator TMTD in a weight ratio of 5:3:2, wherein the weights of the zinc ethylphenyldithiocarbamate, the dibenzothiazyl disulfide and the accelerator TMTD are respectively 0.55kg, 0.33kg and 0.22 kg;
the foaming agent is azodicarbonamide.
The preparation method of the rubber basketball outer skin comprises the following process steps:
step (1) preparation of a water-absorbent resin solution: and uniformly mixing weighed sodium polyacrylate, polyurethane adhesive and water, and then stirring and heating at the temperature of 130 ℃ for 20 min.
Step (2) preparing modified attapulgite:
step 1) preparation of acid-modified attapulgite: roasting the attapulgite at 800 ℃ for 4h, soaking in 15% hydrochloric acid solution for 3h, taking out, and drying until the water content is 3% to obtain acid-modified attapulgite;
step 2) preparing a compound coupling agent: mixing a silane coupling agent Kh560 and maleic anhydride in a weight ratio of 1:4 to obtain a compound coupling agent;
step 3) preparing coupling agent modified attapulgite: adding a compound coupling agent into the acid-modified attapulgite obtained in the step 1), wherein the addition amount of the compound coupling agent is 6 wt% of the mass of the acid-modified attapulgite, then putting the mixture into a heating kneader, mixing and stirring the mixture at a stirring speed of 50r/min, slowly heating the mixture while stirring the mixture, and stirring the mixture at a constant temperature for 2 hours when the temperature is raised to 90 ℃ to obtain the coupling agent-modified attapulgite;
step 4) adding stearic acid into the coupling agent modified attapulgite obtained in the step 3), wherein the addition amount of the stearic acid is 1.1 wt% of the mass of the acid modified attapulgite, continuously stirring by using a heating type kneader and heating to 95 ℃, stirring at constant temperature for 2h, and discharging; and then, drying the discharged material, controlling the drying temperature at 60 ℃, conveying the material to a disc type grinding machine when the material is dried until the water content is less than 0.5%, and grinding the material into powder of 60 meshes to obtain the modified attapulgite.
Preparing a sizing material in step (3): and (2) mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, adding into an internal mixer, and mixing for 15min at 80 ℃ to obtain a sizing material.
Step (4) preparing main glue: adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer, and mixing for 15min at 85 ℃ to obtain a main rubber; the accelerator is a mixture of zinc ethylphenyldithiocarbamate, dibenzothiazyl disulfide and an accelerator TMTD mixed in advance.
Step (5) preparing the rubber basketball outer skin material: and (3) adding the main rubber obtained in the step (4), the foaming agent and sulfur into an open mill, and mixing for 20min at 85 ℃ to obtain the rubber basketball outer skin material.
Extruding, rolling and cutting the rubber basketball outer skin material obtained in the step (5) to obtain the rubber basketball outer skin;
the rubber basketball outer skins prepared in the first to sixth examples have good physical properties. The physical property testing data for the aged basketball skins obtained in examples one through six and the conventional rubber basketball skins at 105 deg.C for 24 hours are shown in Table 1 below:
TABLE 1 measurement data of aged physical Properties
Figure BDA0002371697050000111
Figure BDA0002371697050000121
As can be seen from the data in Table 1, the elongation at break, tensile strength, and 300% stress at break values before aging of the conventional rubber basketball skins are greatly changed from the corresponding values after aging (e.g., the elongation at break before aging is 751.93%, the elongation at break after aging is 783.50%, and the tensile strength before aging is 59.33kg/cm2While the tensile strength after aging was reduced to 23.85kg/cm2) The weather resistance of the traditional rubber basketball outer skin is not good; from the 300% stress at definite elongation of the conventional rubber basketball cover: the 300% stress at definite elongation before aging is only 10.56kg/cm2After aging, the amount of the water content was reduced to a lower level, namely 5.32kg/cm2The wear resistance of the conventional rubber basketball outer skin is also poor.
The change of the values of the basketball outer skins obtained in the first embodiment to the sixth embodiment of the invention is not large, and the elongation at break of the basketball outer skins obtained in the fourth embodiment is 751.60% before aging, and 755.32% after aging; the tensile strength before aging was 44.43kg/cm2And a tensile strength after aging of 46.13kg/cm2And the numerical value change before and after aging is not large, which shows that the basketball outer skin prepared by the invention has more excellent weather resistance compared with the traditional rubber basketball outer skinCan be used. In addition, it can be seen from the 300% stress at elongation before and after aging of the basketball cover made in accordance with the present invention that the basketball cover made in accordance with the present invention also has superior wear resistance as compared to conventional rubber basketball covers.
Testing the water absorption performance: 1uL of water was dropped from a 1uL syringe onto the outer surface of the basketball obtained in each example and onto the outer surface of a conventional rubber basketball, and then left to stand, and the time taken for the water stain to dry was recorded, and the test results are shown in Table 2 below:
TABLE 2 Water absorption Properties test results
Figure BDA0002371697050000122
By comprehensively considering the data in tables 1 and 2, the basketball outer skin obtained in the fourth embodiment of the invention has the best performance, and the basketball outer skin obtained in the fourth embodiment of the invention has stable performance, good weather resistance and excellent wear resistance, is moderate in hardness and elasticity before and after aging, and has the best moisture absorption performance, and the basketball outer skin obtained in the fourth embodiment is the best choice for manufacturing the basketball.
It should be noted that the above mentioned embodiments are only preferred embodiments of the present invention, and that those skilled in the art may make various changes, improvements and modifications without departing from the spirit of the present invention, and these changes, improvements and modifications should be construed as the protection scope of the present invention.

Claims (9)

1. A rubber basketball outer skin is characterized in that: the traditional Chinese medicine is prepared from the following raw materials in parts by weight: 10-20 parts of natural rubber, 40-60 parts of butadiene rubber, 2-5 parts of sodium polyacrylate, 3-5 parts of polyurethane adhesive, 2-5 parts of water, 10-15 parts of polyethylene glycol, 15-20 parts of carbon black, 15-20 parts of zinc oxide, 10-20 parts of modified attapulgite, 0.5-0.8 part of N, N-di-N-butyl nickel dithiocarbamate, 0.2-0.8 part of sulfur, 1-1.2 parts of accelerator and 2-4 parts of foaming agent.
2. The rubber basketball skin as defined in claim 1, wherein: the accelerator is a mixture obtained by mixing zinc ethyl phenyl dithiocarbamate, dibenzothiazyl disulfide and an accelerator TMTD according to a weight ratio of 5:3: 2.
3. The rubber basketball skin as defined in claim 1, wherein: the foaming agent is one or a mixture of several of azodicarbonamide, 4' -oxo-bis-benzenesulfonyl hydrazide and p-toluene sulfonyl hydrazide.
4. A method of making the rubber basketball skin of claim 1, wherein the rubber basketball skin is prepared by: the method comprises the following process steps:
step (1) preparation of a water-absorbent resin solution: mixing and heating sodium polyacrylate, polyurethane adhesive and water to obtain water-absorbent resin solution;
step (2) preparing modified attapulgite;
preparing a sizing material in step (3): mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, and then adding the mixture into an internal mixer for mixing to obtain a rubber material;
step (4) preparing main glue: adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer for mixing to obtain a main rubber;
step (5) preparing the rubber basketball outer skin material: adding the main rubber obtained in the step (4), a foaming agent and sulfur into an open mill for mixing to obtain a rubber basketball outer skin material;
and (6) extruding, calendering and cutting the rubber basketball outer skin material obtained in the step (5) to obtain the rubber basketball outer skin.
5. The method of making a rubber basketball skin as in claim 4, wherein: the specific method of the step (1) is as follows: mixing sodium polyacrylate, polyurethane adhesive and water uniformly, stirring and heating at 125-130 deg.C for 20-30 min.
6. The method of making a rubber basketball skin as in claim 4, wherein: the specific operation method of the step (2) is as follows:
step 1) preparation of acid-modified attapulgite: roasting the attapulgite at 750-800 ℃ for 4-5h, putting the attapulgite into a 10-15% hydrochloric acid solution for soaking for 3-4h, taking out the attapulgite, and drying the attapulgite until the water content is 2-3% to obtain acid modified attapulgite;
step 2) preparing a compound coupling agent: mixing a silane coupling agent Kh560 and maleic anhydride in a weight ratio of 1:2-4 to obtain a compound coupling agent;
step 3) preparing coupling agent modified attapulgite: adding a compound coupling agent into the acid-modified attapulgite obtained in the step 1), wherein the addition amount of the compound coupling agent is 4-6 wt% of the mass of the acid-modified attapulgite, then putting the mixture into a heating type kneader, mixing and stirring the mixture at a stirring speed of 50r/min, slowly heating the mixture while stirring the mixture, and stirring the mixture at a constant temperature for 2-3 hours when the temperature is raised to 80-90 ℃ to obtain the coupling agent-modified attapulgite;
step 4) adding stearic acid into the coupling agent modified attapulgite obtained in the step 3), wherein the addition amount of the stearic acid is 1.0-1.2 wt% of the mass of the acid modified attapulgite, continuously stirring and heating to 95 ℃ by using a heating type kneader, stirring at constant temperature for 1-2h, and discharging; and then, drying the discharged material, controlling the drying temperature at 50-60 ℃, conveying the material to a disc type grinding machine when the material is dried until the water content is less than 0.5%, and grinding the material into powder of 50-60 meshes to obtain the modified attapulgite.
7. The method of making a rubber basketball skin as in claim 4, wherein: the specific operation method of the step (3) is as follows: and (2) mixing the water-absorbent resin solution obtained in the step (1) with natural rubber, butadiene rubber and polyethylene glycol, adding into an internal mixer, and mixing for 15-20min at 70-80 ℃ to obtain a rubber material.
8. The method of making a rubber basketball skin as in claim 4, wherein: the specific operation method of the step (4) is as follows:
and (3) adding the rubber material obtained in the step (3), carbon black, zinc oxide, modified attapulgite, N-di-N-butyl nickel dithiocarbamates and an accelerator into an internal mixer, and mixing for 15-20min at 80-85 ℃ to obtain the main rubber.
9. The method of making a rubber basketball skin as in claim 4, wherein: the specific operation method of the step (5) is as follows:
and (3) adding the main rubber obtained in the step (4), the foaming agent and sulfur into an open mill, and mixing for 20-30min at the temperature of 80-85 ℃ to obtain the rubber basketball outer skin material.
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