WO2021114399A1

WO2021114399A1 - Method for preparing tire curing bladder

Info

Publication number: WO2021114399A1
Application number: PCT/CN2019/128108
Authority: WO
Inventors: 赵会岩; 赵海林; 范屏; 张学永; 刘涛
Original assignee: 永一橡胶有限公司
Priority date: 2019-12-12
Filing date: 2019-12-25
Publication date: 2021-06-17
Also published as: CN110713664A

Abstract

The present invention discloses a method for preparing a tire curing bladder, and relates to the technical field of tire curing bladder preparation. In the method for preparing a tire curing bladder in the present invention, raw materials comprise: 80-100 parts of a butyl rubber, 1-20 parts of a modified waste tire curing bladder material, 20-50 parts of carbon black, 8-10 parts of a vulcanized resin, 5.5-7.5 parts of castor oil, 2-4 parts of zinc oxide, 1-3 parts of stearic acid, and 3-5 parts of an accelerator. The preparation method comprises firstly carrying out a blending desulfurization and blending activation two-step modification treatment on the waste tire curing bladder material, and then carrying out internal mixing, mixing, injection and vulcanization on the waste tire curing bladder material and butyl rubber, so as to produce a new tire curing bladder. Compared with the prior art, in the present invention, the waste tire curing bladder is subjected to a modification treatment and then is applied to tire curing bladder processing again, and practice shows that the number of uses of the newly-manufactured tire curing bladder can reach 300-500 times.

Description

Method for preparing tire curing bladder

Technical field

The present invention relates to the technical field of preparation of tire curing bladder, in particular to a preparation method of tire curing bladder.

Background technique

The tire vulcanizing bladder acts as an inner mold in the tire vulcanization molding and can transfer the heat required for tire vulcanization. It can expand and contract and is easy to install and disassemble before and after use. Therefore, the tire vulcanization bladder is used in the molding and vulcanization of pneumatic tires. widely.

At present, the tire curing bladder can be used repeatedly 300-800 times. Because the tire curing bladder will repeatedly experience high temperature and high pressure during use, its various physical properties will decrease, especially after the number of uses reaches 700 to 800 times, the performance decline is serious and difficult to continue. use. The tire curing bladder used in the production of tires is increasing every year, and the waste tire curing bladder needs to find a good way to deal with it.

Summary of the invention

The present invention provides a method for preparing a tire curing bladder. The waste tire curing bladder is modified and applied in the processing of the tire curing bladder to solve the above technical problems.

The specific technical solution is a preparation method of tire curing bladder, the raw materials include: 80-100 parts of butyl rubber and 1-20 parts of modified waste tire curing bladder material, 20-50 parts of carbon black, 8 parts of vulcanized resin -10 parts, 5.5-7.5 parts of castor oil, 2-4 parts of zinc oxide, 1-3 parts of stearic acid, 3-5 parts of accelerator;

The general preparation method is as follows:

S1. Two-step modification treatment of the waste tire curing bladder. First, the waste tire curing bladder is cleaned, dried, and then crushed into 50-200 mesh pellets, and then 2,2'-dibenzamidodiphenyl bismuth is added. 0.3-0.8% of the sulfide is blended for desulfurization, blended for 30 minutes, and left for 8 hours; then 12-15% of a chlorine-containing modifier is added for blending activation to obtain a modified waste tire curing bladder material; The 2,2'-dibenzamidodiphenyl disulfide content and the content of the chlorine-containing modifier are calculated based on the weight of the waste tire curing bladder as 100%;

S2. Mix rubber in an internal mixer. First add half of the butyl rubber and modified waste tire vulcanization bladder to the internal mixer for banburying for 2-4 minutes, and then add the other half of the butyl rubber for banburying for 30-60 minutes. Seconds, then add carbon black, castor oil, zinc oxide, stearic acid, accelerant and banbury for 1-2 minutes, discharge the glue, and obtain a banbury film;

S3. Put the banbury film into an open mill, add vulcanized resin for mixing, thin through the triangle bag, press out the film, and cool the film naturally to room temperature;

S4. Add the film extruded in S3 to the feeding port of the injection vulcanizing machine, set the temperature of the injection machine to 60-90℃, and inject the rubber into the mold;

S5. Set the vulcanization temperature to 180-195℃, and the vulcanization time is 20-40min. After the vulcanization is completed, the vulcanization bladder is ejected.

After the new tire curing bladder is used to become a waste tire curing bladder, physical properties such as strength and elasticity will be reduced; when recycling these waste tire curing bladders, they need to be modified to enhance their surface activity. Part is added to the new butyl rubber and reused.

The waste tire curing bladder is crushed into granules. The 50-200 mesh pellet size is 0.074-0.335mm, and the specific surface area is greatly increased. In the modification treatment, the blending method can be used directly, and the waste tire curing bladder pellets can be mixed with The 2,2'-dibenzamidodiphenyl disulfide and the chlorine-containing modifier are fully contacted to complete the desulfurization and activation modification reaction.

Among them, in the present invention, 2,2'-dibenzamidodiphenyl disulfide is mainly used to desulfurize the waste tire curing bladder; the chlorine donor is used to modify the waste tire curing bladder pellets, and high content is selected. Modifiers with chlorine content have a more obvious modification effect; for example, the modification effect of activated carbon with a chlorine content of 3.1-3.4mg/g increases with the increase of the chlorine content.

Furthermore, in S1, the waste tire curing bladder pellets and the chlorine-containing modifier are stirred and blended, the stirring speed is 300-600 r/min, and the blending time is 15-30 min.

Further, the chlorine-containing modifier is one or more of chlorine-containing activated carbon, polyvinyl chloride, neoprene rubber, and chlorinated butyl rubber.

Furthermore, in S2, the initial temperature of banburying is 80°C, and the debinding temperature is 130°C.

Furthermore, in S3, the mill roll temperature was 80°C.

Further, the carbon black is N330, the accelerator is DM, and the vulcanized resin is an alkylphenol formaldehyde resin.

In blending modification, the modified waste tire vulcanization bladder material is first blended with part of the butyl rubber. During a certain period of time, under the action of stirring, the temperature will rise, and the waste tire vulcanization bladder material will undergo a modification reaction. Part of the butyl rubber and modified waste tire vulcanization bladder materials are first banned to facilitate uniform dispersion, and then the remaining butyl rubber, carbon black, castor oil, zinc oxide, stearic acid, accelerators and other small materials are added to dense Refining, and finally adding vulcanized resin for mixing to prevent premature vulcanization.

In addition, the main component of the tire curing bladder is butyl rubber, which has a regular molecular chain structure and good air tightness after vulcanization. The tire curing bladder will be scrapped once gas leakage occurs during use, and generally has not reached the recommended level. The physical properties of the tire curing bladder that is destroyed and discarded in advance are better in the number of times of use; and the physical properties of the tire curing bladder that reaches or exceeds the number of use are severely reduced. If the waste tire curing bladder can be sorted and recycled according to the number of times of use, for the waste tire curing bladder that is used less frequently, the amount of chlorine-containing modifier can be reduced during modification, or the raw material can be appropriately increased. The amount of waste tire vulcanization bladder material that has been subjected to sexual treatment, that is, the waste tire vulcanization bladder that has been used less frequently is more suitable for recycling and preparing new tire vulcanization bladder.

Compared with the prior art, in the present invention, the waste tire curing bladder is modified and applied again in the tire curing bladder processing. Practice shows that the newly produced tire curing bladder can be used up to 300-500 times.

Description of the drawings

Fig. 1 is a flow chart of a method for preparing a tire curing bladder according to a specific embodiment of the present invention.

Detailed ways

The specific implementation of the present invention will be described below with reference to the drawings and embodiments:

It should be noted that the structure, ratio, size, etc. shown in the drawings attached to this specification are only used to match the content disclosed in the specification for the understanding and reading of those familiar with this technology, and are not intended to limit the implementation of the present invention. The limiting conditions, any structural modification, proportional relationship, change or size adjustment, shall fall within the scope of the technical content disclosed in the present invention without affecting the effects and objectives that can be achieved by the present invention In the range.

At the same time, the terms such as "upper", "lower", "left", "right", "middle" and "one" cited in this specification are only for ease of description, not to limit the text. The scope of implementation of the invention, the change or adjustment of its relative relationship, shall be regarded as the scope of implementation of the invention without substantial changes to the technical content.

Example 1:

The process of preparing tire curing bladder is as follows:

S1. Modification of the vulcanization bladder of waste tires. The vulcanization bladder of waste tires is first washed, dried, and then crushed into 200 mesh pellets, and then 2,2'-dibenzamidodiphenyl disulfide 0.3% ( Parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) for blending and desulfurization, blending for 30 minutes, and parked for 8 hours; then adding 15% (parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) of chlorine Blending with chlorine-containing activated carbon with an amount of 3.1mg/g, stirring speed of 300r/min, and blending time of 30min, to obtain modified waste tire curing bladder material;

S2. Mix rubber with internal mixer. The initial temperature of banbury is 80℃. First add 50 parts of butyl rubber and 1 part of modified waste tire vulcanization bladder material to the internal mixer for banburying for 2 minutes, and then add 50 parts The butyl rubber is banned for 30 seconds, and then 50 parts of N330, 5.5 parts of castor oil, 2 parts of zinc oxide, 1 part of stearic acid, 3 parts of accelerator DM are added, banburying is carried out for 2 minutes, and the temperature is 130°C for discharging. Refining film

S3. Put the banbury film into an open mill, the roller temperature of the open mill is 80℃, add 8 parts of alkylphenol formaldehyde resin for mixing, thin through the triangle bag, press out the film, and cool the film naturally to room temperature;

S4. Add the film extruded in S3 to the feeding port of the injection vulcanizing machine, set the temperature of the injection machine to 70℃, and inject the rubber into the mold;

S5. Set the vulcanization temperature to 180°C, and the vulcanization time is 32min. After the vulcanization is completed, the vulcanization bladder is ejected.

Example 2:

The process of preparing tire curing bladder is as follows:

S1. Modification of the vulcanization bladder of waste tires. The vulcanization bladder of waste tires is cleaned and dried first, and then crushed into 50-200 mesh pellets, and then 2,2'-dibenzamidodiphenyl disulfide 0.8 is added. % (Parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) for blending and desulfurization, blending for 30 minutes, parked for 8 hours; then adding 12% (parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) Blending of chlorine-containing activated carbon with a chlorine content of 3.4 mg/g, a stirring speed of 600 r/min, and a blending time of 18 minutes, to obtain modified waste tire curing bladder materials;

S2: Mixing rubber with internal mixer. The initial temperature of internal mixing is 80℃. First add 50 parts of butyl rubber and 10 parts of modified waste tire vulcanization bladder material to the internal mixer for 3 minutes, and then add 50 parts. The butyl rubber is banned for 40 seconds, then 40 parts of N330, 6.5 parts of castor oil, 3 parts of zinc oxide, 2 parts of stearic acid, 4 parts of accelerator DM are added, and the banquet is for 1 minute. Refining film

S3. Put the banbury film into an open mill, the roller temperature of the open mill is 80℃, add 9 parts of alkylphenol formaldehyde resin for mixing, thin through the triangle bag, press out the film, and cool the film naturally to room temperature;

S4. Add the film pressed out in S3 to the feeding port of the injection vulcanizing machine, set the temperature of the injection machine to 75°C, and inject the rubber material into the mold;

S5. Set the vulcanization temperature to 185°C, the vulcanization time is 36min, the vulcanization is completed, and the vulcanization bladder is ejected.

Example 3:

The process of preparing tire curing bladder is as follows:

S1. Modification of the vulcanization bladder of waste tires. The vulcanization bladder of waste tires is cleaned and dried first, and then crushed into pellets of 50-200 mesh, and then 2,2'-dibenzamidodiphenyl disulfide 0.5 is added. % (Parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) for blending and desulfurization, blending for 30 minutes, and parked for 8 hours; then adding 15% (parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) The chlorine-containing activated carbon with a chlorine content of 3.3 mg/g is blended with polyvinyl chloride, the mass ratio of the chlorine-containing activated carbon to the polyvinyl chloride is 1:1, the stirring speed is 400r/min, and the blending time is 20min. Vulcanization bladder material for waste tires that have been treated sexually;

S2. Mixing rubber with internal mixer. The initial temperature of mixing is 80℃. First add 40 parts of butyl rubber and 20 parts of modified waste tire vulcanization bladder material to the internal mixer for 4 minutes, and then add 40 parts. The butyl rubber is banned for 60 seconds, then add 20 parts of N330, 7.5 parts of castor oil, 4 parts of zinc oxide, 3 parts of stearic acid, 5 parts of accelerator DM. Refining film

S3. Put the banbury film into an open mill, the roller temperature of the open mill is 80°C, add 10 parts of alkylphenol formaldehyde resin for mixing, thin through the triangle bag, press out the film, and cool the film naturally to room temperature;

S4. Add the film extruded in S3 to the feeding port of the injection vulcanizing machine, set the temperature of the injection machine to 90°C, and inject the rubber material into the mold;

S5. Set the vulcanization temperature to 195℃, and the vulcanization time is 20min. After the vulcanization is completed, the vulcanization bladder is ejected.

Example 4:

The process of preparing tire curing bladder is as follows:

S1. Modification of the vulcanization bladder of waste tires. The vulcanization bladder of waste tires is cleaned and dried first, and then crushed into 50-200 mesh pellets, and then 2,2'-dibenzamidodiphenyl disulfide 0.4 is added. % (Parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) for blending and desulfurization, blending for 30 minutes, parked for 8 hours; then adding 13% (parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) The polyvinyl chloride is blended, the stirring speed is 500r/min, and the blending time is 15min, to obtain the modified waste tire curing bladder material;

S2. Mixing rubber with internal mixer. The initial temperature of mixing is 80℃. First, add 45 parts of butyl rubber and 10 parts of modified waste tire vulcanization bladder material to the internal mixer for banburying for 2 minutes, and then add 45 parts. The butyl rubber is banned for 60 seconds, then 30 parts of N330, 6.5 parts of castor oil, 2 parts of zinc oxide, 2 parts of stearic acid, 4 parts of accelerator DM are added. Refining film

S4. Add the film extruded in S3 to the feeding port of the injection vulcanizing machine, set the temperature of the injection machine to 80°C, and inject the rubber material into the mold;

S5. Set the vulcanization temperature to 190℃, and the vulcanization time is 35min. After the vulcanization is completed, the vulcanization bladder is ejected.

Example 5:

The process of preparing tire curing bladder is as follows:

S1. Modification of the vulcanization bladder of waste tires. The vulcanization bladder of waste tires is cleaned and dried first, and then crushed into 50-200 mesh pellets, and then 2,2'-dibenzamidodiphenyl disulfide 0.6 is added. % (Parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) for blending and desulfurization, blending for 30 minutes, parked for 8 hours; then adding 14% (parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) The neoprene rubber is blended, the stirring speed is 350r/min, the blending time is 25min, and the modified waste tire curing bladder material is obtained;

S2. Mixing rubber with internal mixer. The initial temperature of mixing is 80℃. First add 50 parts of butyl rubber and 20 parts of modified waste tire vulcanization bladder material to the internal mixer for 4 minutes, and then add 50 parts. The butyl rubber is banned for 30 seconds, then 40 parts of N330, 7.5 parts of castor oil, 3 parts of zinc oxide, 2 parts of stearic acid, 3 parts of accelerator DM are added. Refining film

S4. Add the film pressed out in S3 to the feeding port of the injection vulcanizing machine, set the temperature of the injection machine to 85°C, and inject the rubber material into the mold;

S5. Set the vulcanization temperature to 185°C, and the vulcanization time is 40min. After the vulcanization is completed, the vulcanization bladder is ejected.

Example 6:

The process of preparing tire curing bladder is as follows:

S1. Modification of the vulcanization bladder of waste tires. The vulcanization bladder of waste tires is cleaned and dried first, and then crushed into 50-200 mesh pellets, and then 2,2'-dibenzamidodiphenyl disulfide 0.7 is added. % (Parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) for blending and desulfurization, blending for 30 minutes, and parked for 8 hours; then adding 15% (parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) The chlorinated butyl rubber is blended, the stirring speed is 450r/min, and the blending time is 30min, to obtain the modified waste tire curing bladder material;

S2. Mix rubber in an internal mixer. The initial temperature of banbury is 80℃. First, add 45 parts of butyl rubber and 20 parts of modified waste tire vulcanization bladder material to the internal mixer for 4 minutes, and then add 45 parts. The butyl rubber is banned for 45 seconds, and then 30 parts of N330, 6.5 parts of castor oil, 4 parts of zinc oxide, 3 parts of stearic acid, 4 parts of accelerator DM are added, banburying is carried out for 2 minutes, and the temperature is 130°C for discharging. Refining film

S5. Set the vulcanization temperature to 185°C, the vulcanization time is 35min, the vulcanization is completed, and the vulcanization bladder is ejected.

Example 7:

The process of preparing tire curing bladder is as follows:

S1. Modification of the vulcanization bladder of waste tires. The vulcanization bladder of waste tires is cleaned, dried, and then broken into 50-200 mesh pellets, and then 2,2'-dibenzamidodiphenyl disulfide 0.3 is added. % (Parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) for blending and desulfurization, blending for 30 minutes, and parked for 8 hours; then adding 15% (parts by weight, calculated based on the weight of the waste tire curing bladder as 100%) Polyvinyl chloride, neoprene rubber and chlorinated butyl rubber are blended. The mass ratio of polyvinyl chloride, neoprene rubber and chlorinated butyl rubber is 1:1:1; the stirring speed is 550r/min, and the blending time It is 27 minutes to obtain modified waste tire curing bladder material;

S2: Mixing rubber with internal mixer. The initial temperature of internal mixing is 80℃. First add 50 parts of butyl rubber and 10 parts of modified waste tire vulcanization bladder material to the internal mixer for 3 minutes, and then add 50 parts. The butyl rubber is banned for 55 seconds, then 40 parts of N330, 6.5 parts of castor oil, 3 parts of zinc oxide, 2 parts of stearic acid, 5 parts of DM accelerating agent are added, and banburying is carried out for 2 minutes at a temperature of 130°C to discharge the rubber. Refining film

For the film in Examples 1-7, the tensile strength>10.0MPa, the tearing strength>38.0kN/m, the elongation at break>350%, the hardness>72A; currently it is carried out with the vulcanization bladder model of agricultural tires. It can be used for 300-500 times.

Many other changes and modifications can be made without departing from the concept and scope of the present invention. It should be understood that the present invention is not limited to specific embodiments, and the scope of the present invention is defined by the appended claims.

Claims

A method for preparing a tire curing bladder, characterized in that:

The raw materials include: 80-100 parts of butyl rubber and 1-20 parts of modified waste tire curing bladder material, 20-50 parts of carbon black, 8-10 parts of vulcanized resin, 5.5-7.5 parts of castor oil, zinc oxide 2 -4 parts, 1-3 parts stearic acid, 3-5 parts accelerator;

The preparation method is as follows:

S1. Two-step modification treatment of the waste tire curing bladder. First, the waste tire curing bladder is cleaned, dried, and then crushed into 50-200 mesh pellets, and then 2,2'-dibenzamidodiphenyl bismuth is added. 0.3-0.8% of the sulfide is blended for desulfurization, blended for 30 minutes, and left for 8 hours; then 12-15% of a chlorine-containing modifier is added for blending activation to obtain a modified waste tire curing bladder material; The 2,2'-dibenzamidodiphenyl disulfide content and the content of the chlorine-containing modifier are calculated based on the weight of the waste tire curing bladder as 100%;

S2. Mix rubber in an internal mixer. First add half of the butyl rubber and modified waste tire vulcanization bladder to the internal mixer for banburying for 2-4 minutes, and then add the other half of the butyl rubber for banburying for 30-60 minutes. Seconds, then add carbon black, castor oil, zinc oxide, stearic acid, accelerant and banbury for 1-2 minutes, discharge the glue, and obtain a banbury film;

S3. Put the banbury film into an open mill, add vulcanized resin for mixing, thin through the triangle bag, press out the film, and cool the film naturally to room temperature;

S4. Put the film extruded in S3 into the feeding port of the injection vulcanizing machine, set the temperature of the injection machine to 60-90℃, and inject the rubber into the mold;

S5. Set the vulcanization temperature to 180-195℃, and the vulcanization time is 20-40min. After the vulcanization is completed, the vulcanizing bladder is ejected.
The method for preparing a tire curing bladder according to claim 1, wherein in S1, the waste tire curing bladder pellets and the chlorine-containing modifier are stirred and blended, and the stirring speed is 300-600r/min. The mixing time is 15-30min.
The method for preparing a tire curing bladder according to claim 1 or 2, wherein the chlorine-containing modifier is one of chlorine-containing activated carbon, polyvinyl chloride, neoprene rubber, and chlorinated butyl rubber. Kind or several kinds.
The method for preparing a tire curing bladder according to claim 3, wherein in S2, the initial temperature of banburying is 80°C, and the debinding temperature is 130°C.
The method for preparing a tire curing bladder according to claim 3, wherein in S3, the roller temperature of the open mill is 80°C.
The method for preparing a tire curing bladder according to claim 3, wherein the carbon black is N330, the accelerator is DM, and the curing resin is an alkylphenol formaldehyde resin.