阅读说明：本技术 一种适用于连续挤出硫化的高膨胀率吸水橡胶及制备方法 (High-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization and preparation method thereof ) 是由 张勇 赵东阳 周尧 李郡 耿月 张鹏瑶 杨富民 于 2020-06-22 设计创作，主要内容包括：本发明公开了一种适用于连续挤出硫化的高膨胀率吸水橡胶及制备方法,包括以下重量份数的组分：天然橡胶70-150份、吸水树脂10-100份、补强体系20-100份、活性剂3-15份、偶联剂为0-5份、表面处理剂3-10份、增粘剂0-5份、防老剂0.5-5、硫化剂0.3-1份、促进剂0.5-1.5份；所述制备方法包括制备塑炼胶、制备混炼胶、制备混炼胶条、挤出橡胶材料的步骤。本发明具有优良的弹性、延伸性和膨胀止水性,且本发明的制备过程包括混炼和挤出硫化两个阶段,提高了吸水橡胶材料的生产效率和产品质量稳定性,降低了加工成本低,有利于提高市场竞争力。(The invention discloses a high-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization and a preparation method thereof, wherein the high-expansion-rate water-absorbing rubber comprises the following components in parts by weight: 70-150 parts of natural rubber, 10-100 parts of water-absorbing resin, 20-100 parts of reinforcing system, 3-15 parts of active agent, 0-5 parts of coupling agent, 3-10 parts of surface treating agent, 0-5 parts of tackifier, 0.5-5 parts of anti-aging agent, 0.3-1 part of vulcanizing agent and 0.5-1.5 parts of accelerator; the preparation method comprises the steps of preparing plasticated rubber, preparing mixed rubber strips and extruding the rubber material. The invention has excellent elasticity, extensibility and expansion water-stopping property, and the preparation process of the invention comprises two stages of mixing and extrusion vulcanization, thereby improving the production efficiency and the product quality stability of the water-absorbing rubber material, reducing the processing cost and being beneficial to improving the market competitiveness.)

1. A high-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization is characterized by comprising the following components in parts by weight:

70-150 parts of natural rubber, 10-100 parts of water-absorbing resin, 20-100 parts of reinforcing system, 3-15 parts of active agent, 0-5 parts of coupling agent, 3-10 parts of surface treating agent, 0-5 parts of tackifier, 0.5-5 parts of anti-aging agent, 0.3-1 part of vulcanizing agent and 0.5-1.5 parts of accelerator.

2. The high expansion water-absorbing rubber suitable for continuous extrusion vulcanization according to claim 1, wherein: the water-absorbing resin is polyacrylate.

3. The high expansion water-absorbing rubber suitable for continuous extrusion vulcanization according to claim 1, wherein: the reinforcing system is 20-50 parts of white carbon black, 0-25 parts of sapphirine and 0-25 parts of Kaiser.

4. The high expansion water-absorbing rubber suitable for continuous extrusion vulcanization according to claim 1, wherein: the activator is 3-10 parts of zinc oxide and 0.5-5 parts of stearic acid.

5. The high expansion water-absorbing rubber suitable for continuous extrusion vulcanization according to claim 1, wherein: the coupling agent is SI69, the surface treating agent is sodium dodecyl benzene sulfonate, and the tackifier is petroleum resin C5.

6. The high expansion water-absorbing rubber suitable for continuous extrusion vulcanization according to claim 1, wherein: the anti-aging agent comprises 6540.5-2.5 parts of protective wax and 0-2.5 parts of MB.

7. The high expansion water-absorbing rubber suitable for continuous extrusion vulcanization according to claim 1, wherein: the vulcanizing agent is sulfur, the accelerator is DM0.5-1.0 part and TT0-0.5 part.

8. The high-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization according to claim 1, which is characterized by comprising the following components in parts by weight:

70-100 parts of natural rubber, 30-100 parts of water-absorbing resin, 50-100 parts of reinforcing system, 5-15 parts of active agent, 0-4 parts of coupling agent, 5-10 parts of surface treating agent, 2-5 parts of tackifier, 1.5-5 parts of anti-aging agent, 0.5-1 part of vulcanizing agent and 1-1.5 parts of accelerator.

9. A method for preparing a high expansion water-absorbing rubber suitable for continuous extrusion vulcanization according to any one of claims 1 to 8, comprising two stages of mixing and extrusion vulcanization, and specifically comprising the following steps:

s1, preparing plasticated rubber: putting natural rubber into an internal mixer for plasticating, preparing plasticated rubber when the temperature reaches 140 ℃, and discharging the rubber for later use;

s2, preparing a rubber compound: putting the plasticated rubber prepared in the step S1 into an internal mixer, mixing the plasticated rubber in the internal mixer for 1 minute, then sequentially adding an active agent, a coupling agent, a surface treatment agent and a tackifier, and mixing the plasticated rubber for 1 to 2 minutes at the mixing temperature of between 70 and 120 ℃; then adding water-absorbent resin and reinforcing agent twice, mixing, preparing a section of rubber compound when the temperature reaches 120-140 ℃, and discharging rubber for later use;

s3, preparing a mixing rubber strip: cooling the mixed rubber prepared in the step S2 to 100 ℃ on an open mill, adding a vulcanizing agent and an accelerant, packaging and mixing for 1-2min, and thinly passing for three times to prepare a mixed rubber strip;

s4, extruding a vulcanized rubber material: placing the mixing rubber strip for more than 8 hours, placing the mixing rubber strip into a cold feed extruder for extrusion preforming, then sequentially performing high-temperature section, microwave section, hot air I and hot air disulfide molding, and then performing air cooling, rolling and other steps.

10. The method for preparing the high-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization according to claim 9, characterized in that: in the step S2, the rotor speed is 20-40r/min during mixing, and the mixing time is 5 minutes again.

Technical Field

The invention relates to the technical field of novel sealing materials, in particular to a high-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization and a preparation method thereof.

Background

The water-absorbing rubber material is a novel functional sealing waterproof material and is mainly applied to the fields of tunnels, water conservancy and the like which need to be sealed and waterproof. At present, most of water-absorbing rubber materials on the market have the problems of low water-absorbing speed, low tensile strength, small water-swelling rate and low swelling rate and tensile strength after repeated water immersion; and the existing commercial products have poor appearance, and the molded products have the defects of nonuniform quality, joint marks at joints, poor dimensional stability and the like.

The water-absorbing rubber material is applied to dams for sealing and stopping water, and has the most obvious requirements on the expansion rate and the water absorption speed after repeated water immersion: when the rainwater is much and the water level is high, the water-absorbing rubber absorbs water; when the rainwater is less and the water level is low, the water-absorbing rubber loses water; if the water absorption expansion rate is low, the water absorption rubber cannot make up the generated gap, and water seepage and water leakage of the dam can be caused; if the water absorption speed is low, the water absorption rubber is not expanded in the initial water contact process, the phenomena of poor sealing, water seepage and water leakage are easily caused, and the purpose of water stopping can be achieved until the water absorption rubber is expanded to block gaps.

Therefore, it is urgently needed to develop a water-absorbent rubber material with better stability, water-swelling rate, tensile strength, swelling rate after re-soaking and tensile strength.

Disclosure of Invention

The invention aims to solve the technical problem of providing a high-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization and a preparation method thereof, so as to solve the problems of unstable appearance size and quality of the existing product and low expansion rate of the water-absorbing rubber material after repeated water immersion, and further improve the expansion rate of the water-absorbing rubber material after repeated water immersion.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows.

A high-expansion-rate water-absorbent rubber suitable for continuous extrusion vulcanization comprises the following components in parts by weight:

70-150 parts of natural rubber, 10-100 parts of water-absorbing resin, 20-100 parts of reinforcing system, 3-15 parts of active agent, 0-5 parts of coupling agent, 3-10 parts of surface treating agent, 0-5 parts of tackifier, 0.5-5 parts of anti-aging agent, 0.3-1 part of vulcanizing agent and 0.5-1.5 parts of accelerator.

Further, the water-absorbing resin is polyacrylate.

Further, the reinforcing system comprises 20-50 parts of white carbon black, 0-25 parts of sapphirine and 0-25 parts of Kaiser.

Furthermore, the active agent is 3-10 parts of zinc oxide and 0.5-5 parts of stearic acid.

Further, the coupling agent is SI69, the surface treating agent is sodium dodecyl benzene sulfonate, and the tackifier is petroleum resin C5.

Further, the anti-aging agent comprises 6540.5-2.5 parts of protective wax and 2.5 parts of MB 0.

Further, the vulcanizing agent is sulfur, the accelerator is 0.5-1.0 part of DM and 0.5 part of TT0.

Further, the high-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization is characterized by comprising the following components in parts by weight:

70-100 parts of natural rubber, 30-100 parts of water-absorbing resin, 50-100 parts of reinforcing system, 5-15 parts of active agent, 0-4 parts of coupling agent, 5-10 parts of surface treating agent, 2-5 parts of tackifier, 1.5-5 parts of anti-aging agent, 0.5-1 part of vulcanizing agent and 1-1.5 parts of accelerator.

The invention also provides a preparation method of the high-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization, which comprises two stages of mixing and extrusion vulcanization, and specifically comprises the following steps:

s1, preparing plasticated rubber: putting natural rubber into an internal mixer for plasticating, preparing plasticated rubber when the temperature reaches 140 ℃, and discharging the rubber for later use;

s2, preparing a rubber compound: putting the plasticated rubber prepared in the step S1 into an internal mixer, mixing the plasticated rubber in the internal mixer for 1 minute, then sequentially adding an active agent, a coupling agent, a surface treatment agent and a tackifier, and mixing the plasticated rubber for 1 to 2 minutes at the mixing temperature of between 70 and 120 ℃; then adding water-absorbent resin and reinforcing agent twice, mixing, preparing a section of rubber compound when the temperature reaches 120-140 ℃, and discharging rubber for later use;

s3, preparing a mixing rubber strip: cooling the mixed rubber prepared in the step S2 to 100 ℃ on an open mill, adding a vulcanizing agent and an accelerant, packaging and mixing for 1-2min, and thinly passing for three times to prepare a mixed rubber strip;

s4, extruding a vulcanized rubber material: placing the mixing rubber strip for more than 8 hours, placing the mixing rubber strip into a cold feed extruder for extrusion preforming, then sequentially performing high-temperature section, microwave section, hot air I and hot air disulfide molding, and then performing air cooling, rolling and other steps.

Further, the rotor speed is 20 to 40r/min and the re-kneading time is 5 minutes when kneading is performed in the step S2.

Due to the adoption of the technical scheme, the technical progress of the invention is as follows.

The high-expansion-rate water-absorbent rubber material suitable for continuous extrusion vulcanization has good physical properties such as water-swelling rate, tensile strength, swelling rate after repeated water immersion, tensile strength and the like; the water absorption speed is high, and the water stopping efficiency is improved; the invention adopts the continuous extrusion vulcanization process for preparation, improves the production efficiency and the product quality stability of the water-absorbing rubber material, reduces the processing cost, and is beneficial to improving the market competitiveness.

Detailed Description

The invention provides a high-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization and a preparation method thereof, wherein the high-expansion-rate water-absorbing rubber comprises the following components in parts by weight: 70-150 parts of natural rubber, 10-100 parts of water-absorbing resin, 20-100 parts of reinforcing system, 3-15 parts of active agent, 0-5 parts of coupling agent, 3-10 parts of surface treating agent, 0-5 parts of tackifier, 0.5-5 parts of anti-aging agent, 0.3-1 part of vulcanizing agent and 0.5-1.5 parts of accelerator.

Wherein, the water-absorbing resin is polyacrylate, the reinforcing system is 20-50 parts of white carbon black, 0-25 parts of sapphirine and 0-25 parts of Kaiser, the active agent is 3-10 parts of zinc oxide and 0.5-5 parts of stearic acid, the coupling agent is SI69, the surface treating agent is sodium dodecyl benzene sulfonate, the tackifier is petroleum resin C5, the anti-aging agent is 6540.5-2.5 parts of protective wax, MB0-2.5 parts of vulcanizing agent is sulfur, the accelerator is DM0.5-1.0 part and TT0-0.5 part.

The main component of the water-absorbent resin in the invention is mainly hydrophilic groups, and the principle of water absorption is the superposition of chemical adsorption and physical adsorption. The hydrophilic group of the water-absorbing resin interacts with water molecules or forms a hydrated state due to molecular expansion caused by partial structure, so that the water-absorbing resin has ultrahigh water-absorbing performance, and the volume of the resin is remarkably expanded along with the increase of water absorption capacity.

The preparation method of the high-expansion-rate water-absorbing rubber suitable for continuous extrusion vulcanization comprises two stages of mixing and extrusion vulcanization, and specifically comprises the following steps:

s1, preparing plasticated rubber: and (3) putting the natural rubber into an internal mixer for plastication, preparing plasticated rubber when the temperature reaches 140 ℃, and discharging the rubber for later use.

S2, preparing a rubber compound: putting the plasticated rubber prepared in the step S1 into an internal mixer with the rotor rotating speed of 20-40r/min, mixing on the internal mixer for 1 minute, then sequentially adding an active agent, a coupling agent, a surface treating agent and a tackifier, and mixing for 1-2 minutes at the mixing temperature of 70-120 ℃; then adding the water-absorbing resin and the reinforcing agent twice, mixing for 5 minutes, preparing a section of rubber compound when the temperature reaches 120-140 ℃, and discharging the rubber for later use.

S3, preparing a mixing rubber strip: and (4) cooling the mixed rubber prepared in the step S2 to 100 ℃ on an open mill, adding a vulcanizing agent and an accelerator, packaging and mixing for 1-2min, and thinly passing for three times to prepare the mixed rubber strip.

S4, extruding a vulcanized rubber material: placing the mixing rubber strip for more than 8 hours, and then placing the mixing rubber strip into a cold feed extruder for extrusion preforming, wherein the extruder is set with the following process parameters: the temperature of the screw is 50-70 ℃, the temperature of the five sections of machine barrels is 50-80 ℃, the temperature of the machine head is 60-90 ℃, the rotating speed of the screw is 5-15r/min, and the extrusion speed is 1-3 m/min; then sequentially passing through a high-temperature section with the temperature of 180-.

In the preparation process of the rubber, the vulcanization starting stage is an induction stage, the sulfur, the activator and the accelerator are interacted firstly, so that the solubility of the activator in rubber is increased, the accelerator is activated, the accelerator and the sulfur are reacted to generate an intermediate product with higher activity, the activator and the accelerator play a synergistic effect, and then a rubber molecular chain is further initiated to generate a cross-linked rubber macromolecular free radical; and secondly, a crosslinking reaction stage, wherein crosslinkable free radicals or ions react with rubber molecular chains to generate crosslinking bonds.

In the water absorption process of the rubber prepared by the invention, the water absorption expansion force of the water absorption resin is greater than the binding force of the rubber network, and the rubber finally reaches balance along with the prolonging of time, and the expansion rate of the rubber tends to be stable. The more the amount of the resin is, the larger the water-swelling power is and the higher the swelling rate is. Under certain conditions, the movement or expansion of rubber molecular chains with too large crosslinking density is not easy, and the water absorption expansion force of rubber cannot overcome the binding force of a rubber network, so that the expansion rate is reduced; on the contrary, the swelling power of the water-absorbent resin with too low cross-linking density is larger than the network binding power, so that the swelling rate is reduced, meanwhile, the water-absorbent resin is easy to dissociate from the rubber network due to too large network gaps, so that the water-absorbent resin amount is reduced, the swelling power is smaller than the binding power, and finally the swelling rate is reduced, and the purpose of improving the swelling rate is achieved by controlling the using amounts of the coupling agent, the surfactant and the tackifier influencing the cross-linking density. Other auxiliary agents such as a vulcanization system, a reinforcing system and the like in the rubber are beneficial to improving the strength of the rubber, and the water absorption rate of the rubber can be improved by adding the active agent.

The present invention will be described in further detail with reference to specific examples.