Multi-layer vulcanization forming process of luminous rubber football

Abstract

The invention discloses a multi-layer vulcanization forming process of a luminous rubber football, and belongs to the technical field of rubber football preparation. The multi-layer vulcanization molding process of the luminous rubber football comprises the following steps: step (1), mixing composite rubber, a modified anti-aging agent and a vulcanizing agent by using an internal mixer and an open mill to prepare a rubber sheet; (2) preparing the rubber sheet into a ball bladder blank by using a forming machine, mounting a luminous carrier on the surface of the ball bladder blank, and heating and vulcanizing to obtain a luminous ball bladder; (3) the surface of the luminous bladder is wound with yarn, then the luminous bladder continues to be wrapped with the rubber sheet, the luminous bladder is put into a heatable football mold, and a formed football blank is obtained through vulcanization forming; and (4) the surface of the formed football blank is processed, and the luminous rubber football is obtained. The rubber football prepared by the method has excellent elasticity, self-repairing capability and ageing resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber football preparation, and in particular relates to a multi-layer vulcanization molding process of a luminous rubber football. Background Art

[0002] With the rapid development of materials science and manufacturing technology, rubber vulcanization technology is widely used to improve the performance of rubber products. Rubber vulcanization refers to the process of adding vulcanizing agents to cross-link rubber molecular chains under heating and pressurization conditions, thereby transforming the linear structure into a three-dimensional network structure. This process significantly enhances the strength, elasticity, wear resistance and corrosion resistance of rubber. In football manufacturing, the vulcanization process is used to form the inner liner and outer layer materials to ensure that the football has excellent elasticity and air tightness.

[0003] The invention patent with publication number CN 102462937 A discloses a fluorescent rubber football, which comprises a ball body, the ball body is made of rubber material, a vulcanized fluorescent light coating layer is provided on the outer surface of the ball body, the vulcanized fluorescent light coating layer is locally and spaced apart on the outer surface of the ball body and is vulcanized and connected to the ball body; since the vulcanized fluorescent light coating layer is provided on the outer surface of the ball body, the rubber football of the invention can emit fluorescence in weak light conditions, and is suitable for amateur athletes to carry out activities in poorly lit nights, under street lights, and on moonlit nights. At the same time, due to the luminous effect, the fun of the sport is increased. However, the wear resistance, self-repairing and anti-aging properties of the rubber football prepared by the method still have room for improvement. Summary of the invention

[0004] The purpose of the present invention is to provide a multi-layer vulcanization molding process for a luminous rubber football, so as to solve the technical problems of poor wear resistance, self-repairing ability and aging resistance of rubber footballs in the prior art.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The present invention provides a multi-layer vulcanization molding process for a luminous rubber football, comprising the following steps:

[0007] Step (1): using an internal mixer and an open mixer to mix the composite rubber, the modified antioxidant and the vulcanizing agent to prepare a film;

[0008] Step (2): using a molding machine to form a bladder embryo from the film, and installing a luminescent carrier on the surface of the bladder embryo, and heating and vulcanizing the luminescent bladder to obtain a luminescent bladder;

[0009] Step (3): Wrapping the surface of the luminous ball with yarn, then wrapping it with film, placing it in a heatable football mold, and vulcanizing it to obtain a molded football embryo;

[0010] Step (4): Processing the surface of the molded football embryo to obtain a luminous rubber football.

[0011] Preferably, the method for preparing the composite rubber comprises the following steps:

[0012] Q1: 1,6-hexanediol, 2,2'-dithiodibenzoic acid, p-toluenesulfonic acid and benzene are added to a container, heated and stirred to reflux, and after the reflux is completed, the liquid in the container is separated into layers, and the lower layer of liquid is washed, extracted, concentrated, and vacuum dried to obtain sulfur-containing ester diol;

[0013] Q2: Add terminal hydroxyl polybutylene glycol to a container, heat and evacuate, seal and stir, remove water, stop heating, cool, and obtain pretreated terminal hydroxyl polybutylene glycol. Then, add it and thioester diol to a container containing a condenser reflux tube, a mechanical stirrer and a thermometer, and then add dimethyl diphenyl diisocyanate. Heat and stir the reaction under a nitrogen atmosphere to obtain an intermediate.

[0014] Q3: Add triethanolamine to the container containing the intermediate, stir quickly, pour into a polytetrafluoroethylene mold, heat and vulcanize to obtain an elastomer;

[0015] Q4: Butyl rubber, styrene-butadiene rubber and elastomer are heated, mixed and stirred to obtain a composite rubber.

[0016] In the above process, the synthetic reaction formula of the elastomer is as follows:

[0017]

[0018] The results of mass spectrometry analysis of the sulfur-containing ester diols were: m / z: 506.18 (100.0%), 507.18 (30.0%), 508.18 (10.7%), 508.19 (4.0%), 509.18 (2.6%).

[0019] Preferably, in Q1, the molar ratio of 1,6-hexanediol, 2,2'-dithiodibenzoic acid and p-toluenesulfonic acid is (2-2.4): (1-1.2): (0.15-0.18), the heating stirring reflux temperature is 90-110°C, the reflux time is 20-24h, the lower layer of liquid is washed with benzene, the vacuum drying temperature is 70-90°C, and the time is 2-4h.

[0020] Preferably, in Q2, the average molecular weight of the terminal hydroxyl polybutylene glycol is 1000, the heating vacuum temperature is 100-120°C, the water removal pressure is 1-2MPa, the time is 2-3h, and the reaction is cooled to 80-85°C. The molar ratio of the pretreated terminal hydroxyl polybutylene glycol, the thioester diol and the dimethylbiphenyl diisocyanate is (1-1.3): (1-1.3): (3-3.9), the heating and stirring reaction temperature is 70-90°C, the time is 1-2h, and the rotation speed is 300-350rpm.

[0021] Preferably, in Q3, the molar ratio of triethanolamine to the intermediate is (1-1.4):(0.9-1.3), rapid stirring is performed for 3-5 minutes, the heating vulcanization temperature is 80-90°C, and the time is 8-10 hours; in Q4, the mass ratio of butyl rubber, styrene-butadiene rubber and elastomer is (20-30):(20-40):(8-10).

[0022] Preferably, the preparation method of the modified antioxidant comprises the following steps:

[0023] S1: adding p-phenylenediamine to a container containing anhydrous ethanol, stirring to dissolve, then adding dibutyltin dilaurate, adding allyl isothiocyanate to the container under stirring, heating to react, after the reaction is completed, filtering under reduced pressure, washing, and vacuum drying to obtain an intermediate product 1;

[0024] S2: adding 1-allyloxy-2,3-propylene oxide and 1-pentanethiol into a container, and then adding N,N-dimethylformamide and azobisisobutyronitrile, stirring for reaction, extracting, washing and drying to obtain an intermediate product 2;

[0025] S3: Add intermediate product 1 and intermediate product 2 to a container, add salicylic acid, heat to react, cool, add dichloromethane to dissolve, wash, rotary evaporate, and vacuum dry to obtain a modified antioxidant.

[0026] In the above process, the synthetic reaction formula of the modified antioxidant is as follows:

[0027]

[0028] The results of mass spectrometry analysis of intermediate product 1 are: m / z: 306.10 (100.0%), 307.10 (17.0%), 308.09 (9.1%), 308.10; the results of mass spectrometry analysis of intermediate product 2 are: m / z: 204.12 (100.0%), 205.12 (11.9%), 206.11 (4.5%); the results of mass spectrometry analysis of modified antioxidant are: m / z: 1122.57 (100.0%) ),1123.57(64.7%),1124.57(31.0%),1124.58(19.3%),1125.57(17.8%),1126.57(6.1%),1125.58(5.2%),1126.56(3.1%),1127.57(2.5%),1123.58(1.4%),1126.58(1.2%),1127.58(1.0%).

[0029] Preferably, in S1, the molar ratio of p-phenylenediamine to allyl isothiocyanate is (1-1.5):(2-3), the stirring time is 30-45 min, the heating reaction temperature is 50-60° C., and the reaction time is 3-5 h.

[0030] Preferably, in S2, the molar ratio of 1-allyloxy-2,3-propylene oxide to 1-pentanethiol is (1-1.9):(0.9-1.8), the stirring reaction time is 3-5 hours, and ethyl acetate is used for extraction.

[0031] Preferably, in S3, the molar ratio of intermediate product 1 to intermediate product 2 is (1-1.2):(4-5), the heating reaction temperature is 150-170°C, the time is 8-10h, washed with 1mol / L sodium bicarbonate aqueous solution and deionized water, and the vacuum drying temperature is 70-90°C, and the time is 8-10h.

[0032] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0033] 1. The present invention first uses 1,6-hexanediol, 2,2'-dithiodibenzoic acid, terminal hydroxyl polybutylene glycol, dimethylbiphenyl diisocyanate and triethanolamine as raw materials to prepare an elastomer, and mixes the elastomer, butyl rubber and styrene-butadiene rubber to prepare a composite rubber. Using the composite rubber as one of the raw materials for football can effectively improve the elasticity and self-repairing ability of football. Subsequently, p-phenylenediamine, allyl isothiocyanate, 1-allyloxy-2,3-propylene oxide and 1-pentanethiol are used as raw materials to prepare a modified antioxidant. Adding the modified antioxidant to the raw material of football can effectively improve the aging resistance of football and increase its service life.

[0034] 2. The present invention uses 1,6-hexanediol, 2,2'-dithiodibenzoic acid, terminal hydroxyl polybutylene glycol, dimethyl diphenyl diisocyanate and triethanolamine as raw materials to prepare an elastomer. The addition of the elastomer can effectively improve the elasticity and self-healing ability of the football. The soft segment contained in the elastomer is composed of low molecular weight polyols, which provides the flexibility and elasticity of the material. The hard segment contained in the elastomer is formed by the reaction of isocyanate and triethanolamine, which improves the strength and rigidity of the elastomer. When an external force acts on the elastomer, the soft segment can be deformed to absorb energy, while the hard segment maintains its overall structural stability. The interaction between the soft and hard segments makes the elastomer material have excellent elasticity and can quickly recover to its original shape after being subjected to external force; and the disulfide bonds contained in the elastomer have self-healing ability. When the elastomer material is damaged, the broken disulfide bonds can be reconnected through an exchange reaction, thereby repairing the physical damage and cracks of the material. In addition, the hydrogen bonds contained in the elastomer are also dynamic, which assists the repair of the elastomer to a certain extent. Therefore, when the elastomer is damaged by external force, the exchange reaction of disulfide bonds and the interaction of other non-covalent bonds can jointly promote the self-repair process of the material, allowing the football to recover quickly after damage and restore its original elasticity.

[0035] 3. The present invention uses p-phenylenediamine, allyl isothiocyanate, 1-allyloxy-2,3-propylene oxide and 1-pentanethiol as raw materials to prepare a modified antioxidant. The amino, thiourea and thiol groups contained in the modified antioxidant can interact with the rubber molecular chain to form stable chemical bonds and physical crosslinking points, thereby stabilizing the rubber molecular chain and reducing its degradation due to oxidation, thermal decomposition and the like. The existence of the interaction can also increase the rigidity of the rubber molecular chain and improve its tensile and tear resistance properties. The thiourea and phenolic hydroxyl groups contained in the modified antioxidant can also react with oxygen free radicals to inhibit the oxidation of the rubber molecular chain by oxygen free radicals, thereby reducing the breakage and crosslinking of the rubber molecular chain, allowing it to maintain its original elasticity and flexibility and increase its service life. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] Embodiment 1: This embodiment discloses a method for preparing a composite rubber, comprising the following steps:

[0038] Q1: 13 g 1,6-hexanediol, 16.9 g 2,2'-dithiodibenzoic acid, 1.4 g p-toluenesulfonic acid and 110 mL benzene were added to a container, heated and stirred at 100°C for 22 h, and after the reflux, the liquid in the container was separated into layers, and the lower layer was washed, extracted and concentrated with benzene, and vacuum dried at 80°C for 4 h to obtain sulfur-containing ester diol;

[0039] Q2: Add terminal hydroxyl polybutylene glycol with an average molecular weight of 1000 into a container, heat and evacuate at 110°C, seal and stir, remove water at 1MPa for 3h, stop heating, cool to 80°C, and obtain pretreated terminal hydroxyl polybutylene glycol. Subsequently, add 2.26g of pretreated terminal hydroxyl polybutylene glycol and 1.15g of thioester diol into a container containing a condenser reflux tube, a mechanical stirrer and a thermometer, and then add 1.79g of dimethylbiphenyl diisocyanate. Heat and stir at 90°C and 350rpm under a nitrogen atmosphere for 2h to obtain an intermediate.

[0040] Q3: Add 0.12g of triethanolamine to a container containing 2.43g of the intermediate, stir rapidly for 5 minutes, pour into a polytetrafluoroethylene mold, heat and vulcanize at 80°C for 10 hours to obtain an elastomer;

[0041] Q4: 25 g of butyl rubber, 30 g of styrene-butadiene rubber and 9 g of elastomer are heated, mixed and stirred to obtain a composite rubber.

[0042] This embodiment discloses a method for preparing a modified antioxidant, comprising the following steps:

[0043] S1: Add 0.69 g of p-phenylenediamine to a container containing 10 mL of anhydrous ethanol, stir and dissolve for 45 min, then add 0.2 mL of dibutyltin dilaurate, add 1.25 g of allyl isothiocyanate to the container under stirring, heat at 50°C for 4 h, and after the reaction is completed, filter under reduced pressure, wash, and vacuum dry to obtain intermediate 1;

[0044] S2: 1.77 g of 1-allyloxy-2,3-propylene oxide and 1.5 g of 1-pentanethiol were added to a container, followed by 5 mL of N,N-dimethylformamide and 0.02 g of azobisisobutyronitrile. After stirring for 4 h, the mixture was extracted with ethyl acetate, washed and dried to obtain an intermediate product 2.

[0045] S3: Add 11g of intermediate product 1 and 33.8g of intermediate product 2 into a container, add 0.1g of salicylic acid, heat to react at 150°C for 10h, cool, add 20mL of dichloromethane to dissolve, wash with 1mol / L sodium bicarbonate aqueous solution and deionized water, rotary evaporate, and vacuum dry at 80°C for 10h to obtain a modified antioxidant.

[0046] This embodiment discloses a multi-layer vulcanization molding process for a luminous rubber football, comprising the following steps:

[0047] Step (1): using an internal mixer and an open mixer to mix the composite rubber, the modified antioxidant and the vulcanizing agent to prepare a film;

[0048] Step (2): using a molding machine to form a bladder embryo from the film, and installing a luminescent carrier on the surface of the bladder embryo, and heating and vulcanizing the luminescent bladder to obtain a luminescent bladder;

[0049] Step (3): Wrapping the surface of the luminous ball with yarn, then wrapping it with film, placing it in a heatable football mold, and vulcanizing it to obtain a molded football embryo;

[0050] Step (4): Processing the surface of the molded football embryo to obtain a luminous rubber football.

[0051] Embodiment 2: This embodiment discloses a method for preparing a composite rubber, comprising the following steps:

[0052] Q1: 11.8 g 1,6-hexanediol, 15.3 g 2,2'-dithiodibenzoic acid, 1.3 g p-toluenesulfonic acid and 110 mL benzene were added to a container, heated and stirred at 100°C for 22 h, and after the reflux, the liquid in the container was separated into layers, and the lower layer was washed, extracted and concentrated with benzene, and vacuum dried at 80°C for 4 h to obtain sulfur-containing ester diol;

[0053] Q2: Add terminal hydroxyl polybutylene glycol with an average molecular weight of 1000 into a container, heat and evacuate at 110°C, seal and stir, remove water at 1MPa for 3h, stop heating, cool to 80°C, and obtain pretreated terminal hydroxyl polybutylene glycol. Subsequently, add 1.96g of pretreated terminal hydroxyl polybutylene glycol and 1.3g of thioester diol into a container containing a condenser reflux tube, a mechanical stirrer and a thermometer, and then add 1.55g of dimethylbiphenyl diisocyanate. Heat and stir at 90°C and 350rpm under a nitrogen atmosphere for 2h to obtain an intermediate.

[0054] Q3: Add 0.1 g of triethanolamine to a container containing 2.87 g of the intermediate, stir rapidly for 5 min, pour into a polytetrafluoroethylene mold, heat and vulcanize at 80 °C for 10 h to obtain an elastomer;

[0055] Q4: 30 g of butyl rubber, 20 g of styrene-butadiene rubber and 10 g of elastomer are heated, mixed and stirred to obtain a composite rubber.

[0056] This embodiment discloses a method for preparing a modified antioxidant, comprising the following steps:

[0057] S1: Add 0.55 g of p-phenylenediamine to a container containing 10 mL of anhydrous ethanol, stir and dissolve for 45 min, then add 0.2 mL of dibutyltin dilaurate, add 1.5 g of allyl isothiocyanate to the container under stirring, heat at 50°C for 4 h, and after the reaction is completed, filter under reduced pressure, wash, and vacuum dry to obtain intermediate 1;

[0058] S2: 1.22 g of 1-allyloxy-2,3-propylene oxide and 2 g of 1-pentanethiol were added to a container, followed by 5 mL of N,N-dimethylformamide and 0.02 g of azobisisobutyronitrile. After stirring for 4 h, the mixture was extracted with ethyl acetate, washed and dried to obtain an intermediate product 2.

[0059] S3: Add 12g of intermediate product 1 and 37.6g of intermediate product 2 into a container, add 0.1g of salicylic acid, heat to react at 150°C for 10h, cool, add 20mL of dichloromethane to dissolve, wash with 1mol / L sodium bicarbonate aqueous solution and deionized water, rotary evaporate, and vacuum dry at 80°C for 10h to obtain a modified antioxidant.

[0060] This embodiment discloses a multi-layer vulcanization molding process for a luminous rubber football, comprising the following steps:

[0061] Step (1): using an internal mixer and an open mixer to mix the composite rubber, the modified antioxidant and the vulcanizing agent to prepare a film;

[0062] Step (2): using a molding machine to form a bladder embryo from the film, and installing a luminescent carrier on the surface of the bladder embryo, and heating and vulcanizing the luminescent bladder to obtain a luminescent bladder;

[0063] Step (3): Wrapping the surface of the luminous ball with yarn, then wrapping it with film, placing it in a heatable football mold, and vulcanizing it to obtain a molded football embryo;

[0064] Step (4): Processing the surface of the molded football embryo to obtain a luminous rubber football.

[0065] Embodiment 3: This embodiment discloses a method for preparing a composite rubber, comprising the following steps:

[0066] Q1: 14.2 g 1,6-hexanediol, 18.4 g 2,2'-dithiodibenzoic acid, 1.5 g p-toluenesulfonic acid and 110 mL benzene were added to a container, heated and stirred at 100°C for 22 h, and after the reflux, the liquid in the container was separated into layers, and the lower layer was washed, extracted and concentrated with benzene, and vacuum dried at 80°C for 4 h to obtain sulfur-containing ester diol;

[0067] Q2: Add terminal hydroxyl polybutylene glycol with an average molecular weight of 1000 into a container, heat and evacuate at 110°C, seal and stir, remove water at 1MPa for 3h, stop heating, cool to 80°C, and obtain pretreated terminal hydroxyl polybutylene glycol. Subsequently, add 2.55g of the pretreated terminal hydroxyl polybutylene glycol and 1g of thioester diol into a container containing a condenser reflux tube, a mechanical stirrer and a thermometer, and then add 2.02g of dimethylbiphenyl diisocyanate. Heat and stir at 90°C and 350rpm under a nitrogen atmosphere for 2h to obtain an intermediate.

[0068] Q3: Add 0.14 g of triethanolamine to a container containing 1.99 g of the intermediate, stir rapidly for 5 min, pour into a polytetrafluoroethylene mold, heat and vulcanize at 80 °C for 10 h to obtain an elastomer;

[0069] Q4: 20 g of butyl rubber, 40 g of styrene-butadiene rubber and 8 g of elastomer are heated, mixed and stirred to obtain a composite rubber.

[0070] This embodiment discloses a method for preparing a modified antioxidant, comprising the following steps:

[0071] S1: Add 0.82 g of p-phenylenediamine to a container containing 10 mL of anhydrous ethanol, stir and dissolve for 45 min, then add 0.2 mL of dibutyltin dilaurate, add 1 g of allyl isothiocyanate to the container under stirring, heat at 50°C for 4 h, and after the reaction is completed, filter under reduced pressure, wash, and vacuum dry to obtain intermediate 1;

[0072] S2: 2.31 g of 1-allyloxy-2,3-propylene oxide and 1 g of 1-pentanethiol were added to a container, followed by 5 mL of N,N-dimethylformamide and 0.02 g of azobisisobutyronitrile. After stirring for 4 h, the mixture was extracted with ethyl acetate, washed and dried to obtain an intermediate product 2.

[0073] S3: Add 10g of intermediate product 1 and 30g of intermediate product 2 into a container, add 0.1g of salicylic acid, heat to react at 150°C for 10h, cool, add 20mL of dichloromethane to dissolve, wash with 1mol / L sodium bicarbonate aqueous solution and deionized water, rotary evaporate, and vacuum dry at 80°C for 10h to obtain a modified antioxidant.

[0074] This embodiment discloses a multi-layer vulcanization molding process for a luminous rubber football, comprising the following steps:

[0075] Step (1): using an internal mixer and an open mixer to mix the composite rubber, the modified antioxidant and the vulcanizing agent to prepare a film;

[0076] Step (2): using a molding machine to form a bladder embryo from the film, and installing a luminescent carrier on the surface of the bladder embryo, and heating and vulcanizing the luminescent bladder to obtain a luminescent bladder;

[0077] Step (3): Wrapping the surface of the luminous ball with yarn, then wrapping it with film, placing it in a heatable football mold, and vulcanizing it to obtain a molded football embryo;

[0078] Step (4): Processing the surface of the molded football embryo to obtain a luminous rubber football.

[0079] Embodiment 4: This embodiment discloses a method for preparing a composite rubber, comprising the following steps:

[0080] Q1: 12.4 g 1,6-hexanediol, 16.1 g 2,2'-dithiodibenzoic acid, 1.5 g p-toluenesulfonic acid and 110 mL benzene were added to a container, heated and stirred at 100°C for 22 h, and after the reflux, the liquid in the container was separated into layers, and the lower layer was washed, extracted and concentrated with benzene, and vacuum dried at 80°C for 4 h to obtain sulfur-containing ester diol;

[0081] Q2: Add terminal hydroxyl polybutylene glycol with an average molecular weight of 1000 into a container, heat and evacuate at 110°C, seal and stir, remove water at 1MPa for 3h, stop heating, cool to 80°C, and obtain pretreated terminal hydroxyl polybutylene glycol. Subsequently, add 2.11g of the pretreated terminal hydroxyl polybutylene glycol and 1.1g of thioester diol into a container containing a condenser reflux tube, a mechanical stirrer and a thermometer, and then add 1.67g of dimethylbiphenyl diisocyanate. Heat and stir at 90°C and 350rpm under a nitrogen atmosphere for 2h to obtain an intermediate.

[0082] Q3: Add 0.11 g of triethanolamine to a container containing 2.21 g of the intermediate, stir rapidly for 5 min, pour into a polytetrafluoroethylene mold, heat and vulcanize at 80 °C for 10 h to obtain an elastomer;

[0083] Q4: 22 g of butyl rubber, 25 g of styrene-butadiene rubber and 8.5 g of elastomer are heated, mixed and stirred to obtain a composite rubber.

[0084] This embodiment discloses a method for preparing a modified antioxidant, comprising the following steps:

[0085] S1: Add 0.62 g of p-phenylenediamine to a container containing 10 mL of anhydrous ethanol, stir and dissolve for 45 min, then add 0.2 mL of dibutyltin dilaurate, add 1.1 g of allyl isothiocyanate to the container under stirring, heat at 50°C for 4 h, and after the reaction is completed, filter under reduced pressure, wash, and vacuum dry to obtain intermediate 1;

[0086] S2: 1.45 g of 1-allyloxy-2,3-propylene oxide and 1.2 g of 1-pentanethiol were added to a container, followed by 5 mL of N,N-dimethylformamide and 0.02 g of azobisisobutyronitrile. After stirring for 4 h, the mixture was extracted with ethyl acetate, washed and dried to obtain an intermediate product 2.

[0087] S3: Add 10.5g of intermediate product 1 and 31.9g of intermediate product 2 into a container, add 0.1g of salicylic acid, heat to react at 150°C for 10h, cool, add 20mL of dichloromethane to dissolve, wash with 1mol / L sodium bicarbonate aqueous solution and deionized water, rotary evaporate, and vacuum dry at 80°C for 10h to obtain a modified antioxidant.

[0088] This embodiment discloses a multi-layer vulcanization molding process for a luminous rubber football, comprising the following steps:

[0089] Step (1): using an internal mixer and an open mixer to mix the composite rubber, the modified antioxidant and the vulcanizing agent to prepare a film;

[0090] Step (2): using a molding machine to form a bladder embryo from the film, and installing a luminescent carrier on the surface of the bladder embryo, and heating and vulcanizing the luminescent bladder to obtain a luminescent bladder;

[0091] Step (3): Wrapping the surface of the luminous ball with yarn, then wrapping it with film, placing it in a heatable football mold, and vulcanizing it to obtain a molded football embryo;

[0092] Step (4): Processing the surface of the molded football embryo to obtain a luminous rubber football.

[0093] Embodiment 5: This embodiment discloses a method for preparing a composite rubber, comprising the following steps:

[0094] Q1: 13.6 g 1,6-hexanediol, 17.6 g 2,2'-dithiodibenzoic acid, 1.3 g p-toluenesulfonic acid and 110 mL benzene were added to a container, heated and stirred at 100°C for 22 h, and after the reflux, the liquid in the container was separated into layers, and the lower layer was washed, extracted and concentrated with benzene, and vacuum dried at 80°C for 4 h to obtain sulfur-containing ester diol;

[0095] Q2: Add terminal hydroxyl polybutylene glycol with an average molecular weight of 1000 into a container, heat at 110°C, evacuate, seal and stir, remove water at 1MPa for 3h, stop heating, cool to 80°C to obtain pretreated terminal hydroxyl polybutylene glycol, then add 2.44g of pretreated terminal hydroxyl polybutylene glycol and 1.2g of thioester diol into a container containing a condenser reflux tube, a mechanical stirrer and a thermometer, then add 1.91g of dimethylbiphenyl diisocyanate, heat and stir at 90°C and 350rpm under a nitrogen atmosphere for 2h to obtain an intermediate;

[0096] Q3: Add 0.13 g of triethanolamine to a container containing 2.65 g of the intermediate, stir rapidly for 5 min, pour into a polytetrafluoroethylene mold, heat and vulcanize at 80 °C for 10 h to obtain an elastomer;

[0097] Q4: 28 g of butyl rubber, 35 g of styrene-butadiene rubber and 9.5 g of elastomer are heated, mixed and stirred to obtain a composite rubber.

[0098] This embodiment discloses a method for preparing a modified antioxidant, comprising the following steps:

[0099] S1: 0.76 g of p-phenylenediamine was added to a container containing 10 mL of anhydrous ethanol, and the mixture was stirred and dissolved for 45 min. Then, 0.2 mL of dibutyltin dilaurate was added, and 1.4 g of allyl isothiocyanate was added to the container under stirring conditions. The mixture was heated at 50° C. for 4 h. After the reaction was completed, the mixture was filtered under reduced pressure, washed, and dried in vacuo to obtain an intermediate product 1.

[0100] S2: 2.12 g of 1-allyloxy-2,3-propylene oxide and 1.7 g of 1-pentanethiol were added to a container, followed by 5 mL of N,N-dimethylformamide and 0.02 g of azobisisobutyronitrile. After stirring for 4 h, the mixture was extracted with ethyl acetate, washed and dried to obtain an intermediate product 2.

[0101] S3: Add 11.5g of intermediate product 1 and 35.7g of intermediate product 2 into a container, add 0.1g of salicylic acid, heat to react at 150°C for 10h, cool, add 20mL of dichloromethane to dissolve, wash with 1mol / L sodium bicarbonate aqueous solution and deionized water, rotary evaporate, and vacuum dry at 80°C for 10h to obtain a modified antioxidant.

[0102] This embodiment discloses a multi-layer vulcanization molding process for a luminous rubber football, comprising the following steps:

[0103] Step (1): using an internal mixer and an open mixer to mix the composite rubber, the modified antioxidant and the vulcanizing agent to prepare a film;

[0104] Step (2): using a molding machine to form a bladder embryo from the film, and installing a luminescent carrier on the surface of the bladder embryo, and heating and vulcanizing the luminescent bladder to obtain a luminescent bladder;

[0105] Step (3): Wrapping the surface of the luminous ball with yarn, then wrapping it with film, placing it in a heatable football mold, and vulcanizing it to obtain a molded football embryo;

[0106] Step (4): Processing the surface of the molded football embryo to obtain a luminous rubber football.

[0107] Comparative Example 1: Compared with Example 1, in the preparation process of the composite rubber in Comparative Example 1, no 2,2'-dithiodibenzoic acid is added, and other conditions remain unchanged.

[0108] Comparative Example 2: Compared with Example 1, in the preparation process of the modified antioxidant in Comparative Example 2, no p-phenylenediamine is added, and other conditions remain unchanged.

[0109] Comparative Example 3: Compared with Example 1, in Comparative Example 3, no elastomer is added during the preparation of the luminous rubber football, and other conditions remain unchanged.

[0110] Comparative Example 4: Compared with Example 1, in the preparation process of the luminous rubber football in Comparative Example 4, no modified antioxidant is added, and other conditions remain unchanged.

[0111] Experimental example: At room temperature, the obtained samples were cut into dumbbell shapes according to GB / T 528-2009 standard for testing, and the mechanical properties were tested using RG-2000 universal testing machine. The tensile speed during the test was 50 mm / min. At the same time, the obtained samples were cut into dumbbell shapes for tensile testing. The dumbbell-shaped samples were evenly cut into two halves using sharp cutters, vernier calipers, markers and other tools, and then the samples were realigned and connected for about 1 minute, and the results were recorded and packaged separately. The evaluation method of the self-repairing degree was expressed by the ultimate tensile strength at break, and the self-repairing efficiency = S1 / S0×100%, where S1 is the ultimate tensile strength at break of the repaired sample, and S0 is the ultimate tensile strength at break of the original sample. The obtained samples were placed in an oven at 100°C for thermal oxidative aging, and the mechanical properties of the samples before and after thermal oxidative aging were tested. The test results are shown in Table 1:

[0112] Table 1

[0113]

[0114]

[0115] From the test results in Table 1, it can be seen that the rubber footballs prepared in Examples 1-5 of the present invention have excellent self-repairing properties, elasticity and anti-aging properties. From the comparison between Comparative Example 1 and Examples 1-5, it can be seen that the addition of 2,2'-dithiodibenzoic acid can make the obtained rubber football have excellent self-repairing properties and elasticity; from the comparison between Comparative Example 2 and Examples 1-5, it can be seen that the addition of p-phenylenediamine can make the obtained rubber football have excellent anti-aging properties; from the comparison between Comparative Example 3 and Examples 1-5, it can be seen that the addition of an elastomer can make the obtained rubber football have excellent self-repairing properties and elasticity; from the comparison between Comparative Example 4 and Examples 1-5, it can be seen that the addition of a modified antioxidant can make the obtained rubber football have excellent anti-aging properties.

[0116] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0117] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A multi-layer vulcanization molding process for a luminous rubber football, characterized in that: The following steps are involved: Step (1): using an internal mixer and an open mixer to mix the composite rubber, a modified antioxidant and a vulcanizing agent to prepare a film; wherein the composite rubber is prepared from butyl rubber, styrene-butadiene rubber and an elastomer, and the modified antioxidant is prepared from p-phenylenediamine, allyl isothiocyanate, 1-allyloxy-2,3-propylene oxide and 1-pentanethiol as raw materials; Step (2): using a molding machine to form a bladder embryo from the film, and installing a luminescent carrier on the surface of the bladder embryo, and heating and vulcanizing the luminescent bladder to obtain a luminescent bladder; Step (3): Wrapping the surface of the luminous ball with yarn, then wrapping it with film, placing it in a heatable football mold, and vulcanizing it to obtain a molded football embryo; Step (4): Processing the surface of the molded football embryo to obtain a luminous rubber football.

2. The multi-layer vulcanization molding process of the luminous rubber football according to claim 1, characterized in that: The preparation method of the composite rubber comprises the following steps: Q1: 1,6-hexanediol, 2,2'-dithiodibenzoic acid, p-toluenesulfonic acid and benzene are added to a container, heated and stirred to reflux, and after the reflux is completed, the liquid in the container is separated into layers, and the lower layer of liquid is washed, extracted, concentrated, and vacuum dried to obtain sulfur-containing ester diol; Q2: Add terminal hydroxyl polybutylene glycol to a container, heat and evacuate, seal and stir, remove water, stop heating, cool, and obtain pretreated terminal hydroxyl polybutylene glycol. Then, add it and thioester diol to a container containing a condenser reflux tube, a mechanical stirrer and a thermometer, and then add dimethyl diphenyl diisocyanate. Heat and stir the reaction under a nitrogen atmosphere to obtain an intermediate. Q3: Add triethanolamine to the container containing the intermediate, stir quickly, pour into a polytetrafluoroethylene mold, heat and vulcanize to obtain an elastomer; Q4: Butyl rubber, styrene-butadiene rubber and elastomer are heated, mixed and stirred to obtain a composite rubber.

3. The multi-layer vulcanization molding process of the luminous rubber football according to claim 2, characterized in that: In the Q1, the molar ratio of 1,6-hexanediol, 2,2'-dithiodibenzoic acid and p-toluenesulfonic acid is (2-2.4): (1-1.2): (0.15-0.18), the heating stirring reflux temperature is 90-110°C, the reflux time is 20-24h, the lower layer of liquid is washed with benzene, the vacuum drying temperature is 70-90°C, and the time is 2-4h.

4. The multi-layer vulcanization molding process of the luminous rubber football according to claim 2, characterized in that: In the Q2, the average molecular weight of the terminal hydroxyl polybutylene glycol is 1000, the heating vacuum temperature is 100-120°C, the water removal pressure is 1-2MPa, the time is 2-3h, and the reaction is cooled to 80-85°C. The molar ratio of the pretreated terminal hydroxyl polybutylene glycol, the thioester diol and the dimethyl diphenyl diisocyanate is (1-1.3): (1-1.3): (3-3.9), the heating and stirring reaction temperature is 70-90°C, the time is 1-2h, and the rotation speed is 300-350rpm.

5. The multi-layer vulcanization molding process of the luminous rubber football according to claim 2, characterized in that: In the Q3, the molar ratio of triethanolamine to the intermediate is (1-1.4): (0.9-1.3), rapid stirring is performed for 3-5 minutes, the heating vulcanization temperature is 80-90°C, and the time is 8-10 hours; in the Q4, the mass ratio of butyl rubber, styrene-butadiene rubber and elastomer is (20-30): (20-40): (8-10).

6. The multi-layer vulcanization molding process of the luminous rubber football according to claim 1, characterized in that: The preparation method of the modified antioxidant comprises the following steps: S1: adding p-phenylenediamine to a container containing anhydrous ethanol, stirring to dissolve, then adding dibutyltin dilaurate, adding allyl isothiocyanate to the container under stirring, heating to react, after the reaction is completed, filtering under reduced pressure, washing, and vacuum drying to obtain an intermediate product 1; S2: adding 1-allyloxy-2,3-propylene oxide and 1-pentanethiol into a container, and then adding N,N-dimethylformamide and azobisisobutyronitrile, stirring for reaction, extracting, washing and drying to obtain an intermediate product 2; S3: Add intermediate product 1 and intermediate product 2 to a container, add salicylic acid, heat to react, cool, add dichloromethane to dissolve, wash, rotary evaporate, and vacuum dry to obtain a modified antioxidant.

7. The multi-layer vulcanization molding process of the luminous rubber football according to claim 6, characterized in that: In S1, the molar ratio of p-phenylenediamine to allyl isothiocyanate is (1-1.5):(2-3), the stirring time is 30-45 min, the heating reaction temperature is 50-60° C., and the reaction time is 3-5 h.

8. The multi-layer vulcanization molding process of the luminous rubber football according to claim 6, characterized in that: In S2, the molar ratio of 1-allyloxy-2,3-propylene oxide and 1-pentanethiol is (1-1.9): (0.9-1.8), the stirring reaction time is 3-5 hours, and ethyl acetate is used for extraction.

9. The multi-layer vulcanization molding process of the luminous rubber football according to claim 6, characterized in that: In the S3, the molar ratio of intermediate product 1 to intermediate product 2 is (1-1.2): (4-5), the heating reaction temperature is 150-170°C, the time is 8-10h, and it is washed with 1mol / L sodium bicarbonate aqueous solution and deionized water. The vacuum drying temperature is 70-90°C, and the time is 8-10h.

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