A method for producing polyacrylate rubber using waste plastic runway powder

Abstract

The present invention discloses a method for producing polyacrylate rubber using waste plastic runway powder. First, the waste plastic runway is crushed and subjected to size screening; then the waste plastic runway powder is pretreated to form a porous structure framework material; finally, the prepared porous structure framework material is placed in an acrylate monomer containing an organometal, a certain amount of initiator is added, and after heating and polymerization, an elastic polyacrylate rubber modified with waste plastic runway powder is obtained. By pretreating the waste plastic runway powder to obtain a porous structure framework material with a large surface area, the present invention can introduce reactive functional groups on its inner and outer surfaces, enabling reversible interaction with the polyacrylate containing an organometal, thereby endowing the material with self-healing properties. At the same time, the modification of the polyacrylate rubber is achieved by adding the waste plastic runway powder, improving the tensile properties and processing properties and endowing it with self-healing performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of materials, and specifically relates to a method for producing polyacrylate rubber by using waste plastic runway powder. Background Art

[0002] With the development of science and technology and the increasing attention paid to sports by people, the quality, comfort, etc. of sports venues are constantly improving, and they have gradually developed from the previous grasslands, lands, and cinder tracks to the current plastic runways. Most of the sports venues in current universities are plastic runways. According to statistics from the Ministry of Education, there are more than about 3,000 universities, colleges, and secondary vocational schools in China, and about 200,000 primary and secondary schools. Cumulatively, the market capacity of plastic runways in domestic universities will reach 215 million square meters, and the quantity is very large. No matter what kind of plastic runway, after being used for a certain number of years and experiencing wind, sun, rain, and exposure, it will undergo a certain degree of powdering, cracking, and aging. Along with the production and consumption process of plastic runways, a huge amount of waste plastic runway waste has also been generated. There are two traditional treatment methods for waste plastic runways, one is landfill and the other is incineration. The former wastes precious land resources and will also cause huge environmental pressure due to pollutants seeping into the soil, while the latter will cause serious air pollution.

[0003] Acrylate rubber has excellent heat resistance, oxidation resistance, weather resistance, and oil resistance. At the same time, acrylate rubber has significant advantages in mechanical properties and processing properties compared with fluororubber and silicone rubber, and the price is relatively low. In recent years, special seals, hydraulic hoses, cable sheaths, etc. based on acrylate rubber have been widely used in fields such as automobiles and aerospace, showing its increasingly important commercial value.

[0004] Therefore, it is of great significance to produce polyacrylate rubber by using waste plastic runway powder, which not only realizes the recycling of waste materials, saves resources and energy, but also reduces the environmental protection pressure. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for producing polyacrylate rubber by using waste plastic runway powder to solve the problems raised in the above background art. The present invention uses waste plastic runway powder to produce polyacrylate rubber, which not only realizes the recycling of resources but also alleviates the environmental protection pressure; at the same time, the addition of waste plastic runway powder realizes the modification of polyacrylate rubber, improving its tensile properties and processing properties. In addition, the preparation method of the present invention is simple, highly operable, and the process conditions are easy to control.

[0006] The method for producing polyacrylate rubber by using waste plastic runway powder of the present invention includes the following steps:

[0007] S1. Preparation of waste plastic runway powder: Crush the waste plastic runway and perform size screening;

[0008] S2. Pretreat the waste plastic runway powder, including swelling, copolymerization, and freeze-drying processes to form a porous structure framework material;

[0009] S3. Place the prepared porous structure framework material in an acrylate monomer containing organometal, add a certain amount of free radical initiator, and obtain a modified polyacrylate rubber of waste plastic runway powder with elasticity and self-healing properties after heating and polymerization.

[0010] Preferably, in step S1, after washing the waste plastic runway with distilled water and drying it, break it with a high-speed crusher and sieve to select powder with a diameter less than or equal to 1 mm.

[0011] Preferably, in step S2:

[0012] The swelling is to add the waste plastic runway powder to the acrylate monomer mixture for swelling. The mass ratio of the waste plastic runway powder to the acrylate monomer mixed solution is 1:10 to 1:20, and swell at room temperature for 8 h. Then take out the swollen waste plastic runway powder, and save the remaining mixture for later use. The acrylate monomers are selected from methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, etc.

[0013] The copolymerization is to place the swollen plastic runway powder in a mixed solvent of water and ethanol containing acrylic acid. The mass ratio of the swollen plastic runway powder to acrylic acid is 2:1. Add an appropriate amount of crosslinking agent and photoinitiator, and form a copolymer hydrogel through photoinitiated polymerization; specifically include the following steps: Take a certain amount of waste plastic runway powder swollen by the acrylate monomer mixture and acrylic acid and disperse them in a certain amount of mixed solvent of water and ethanol, then add an appropriate amount of crosslinking agent and photoinitiator, wrap the container with tin foil to keep it away from light, and stir for 2 h. The stirring speed is controlled at 500 revolutions per minute to obtain a prepolymer solution; then weigh a certain amount of the prepolymer solution into a polytetrafluoroethylene mold, place the mold in a closed dark box, and irradiate it with a 365 nm ultraviolet curing lamp for 2 h under nitrogen protection to obtain a copolymer hydrogel.

[0014] The crosslinking agent includes polyethylene glycol diacrylate, etc., and the mass of the crosslinking agent is 3.3 wt% of the mass of acrylic acid; the photoinitiator is selected from photoinitiator 1173, photoinitiator 2959, photoinitiator 819, etc., and the mass of the photoinitiator is 1.0 wt% of the mass of acrylic acid.

[0015] The mass ratio of water to ethanol in the water and ethanol mixed solvent is 3:1.

[0016] The freeze drying is to freeze dry the copolymer hydrogel under the conditions of -50°C and -0.1MPa to form a skeleton material with a porous structure.

[0017] Preferably, in step S3: the acrylate monomer is selected from n-butyl acrylate, n-hexyl acrylate, isooctyl acrylate, n-dodecyl acrylate, etc.; the organic metal is selected from zinc acetate, copper stearate, iron isooctanoate, etc., and the mass of the organic metal is 2-5wt% of the mass of the acrylate monomer; the free radical initiator is selected from azobisisobutyronitrile, azobisisoheptylnitrile, benzoyl peroxide, etc., and the mass of the free radical initiator is 0.5-1.2wt% of the mass of the acrylate monomer.

[0018] Preferably, step S3 comprises the following steps:

[0019] The porous structural skeleton material obtained in step 2 is placed in a reaction vessel, and appropriate amounts of free radical initiators, organic metals and acrylate monomers are also added thereto, with the mass ratio of the porous structural skeleton material to the acrylate monomer being 1:1 to 1:10. After sealing, the temperature is raised to 100°C for condensation reflux reaction for 8 hours, and then placed in an oven for further reaction at 60°C for 24 hours.

[0020] The beneficial effects of the present invention are embodied in:

[0021] The present invention utilizes waste plastic track powder to produce polyacrylate rubber, which realizes resource recycling and reuse while alleviating the pressure of environmental protection. At the same time, the addition of waste plastic track powder realizes the modification of polyacrylate rubber, improves its tensile properties and processing properties, and gives it self-repairing properties. In addition, the preparation method for producing polyacrylate rubber provided by the present invention is simple, highly operable, and the process conditions are easy to control, which is conducive to promotion and application. DETAILED DESCRIPTION

[0022] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention, and should not be construed as limitations within the scope of protection of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the art without making creative work are within the scope of protection of the present invention.

[0023] All substances listed in the examples of the present invention are commercially available and easily available.

[0024] Embodiment 1:

[0025] The waste plastic track was washed and dried with distilled water, crushed with a high-speed crusher, and sieved to obtain powder with a diameter of 1 mm.

[0026] 100 g of waste plastic runway powder was placed in 1200 g of butyl acrylate and 600 g of 2-hydroxyethyl acrylate for swelling, that is, swelling at room temperature for 8 h. Subsequently, the swollen waste plastic runway powder was taken out, and the remaining mixed solution was stored for later use. The swollen waste plastic runway powder and 50 g of acrylic acid were dispersed in 200 g of a water and ethanol mixed solution (mass ratio of water to ethanol is 3:1), then 1.65 g of polyethylene glycol diacrylate and 0.5 g of photoinitiator 1173 were added. The container was wrapped with tin foil to keep it away from light, and stirred for 2 h. The stirring speed was controlled at 500 revolutions per minute to obtain a prepolymer solution. Then the prepolymer solution was placed in a polytetrafluoroethylene mold, and the mold was placed in a sealed dark box. Under nitrogen protection, it was irradiated with a 365 nm ultraviolet curing lamp for 2 h, and then placed in a freeze dryer for freeze drying for 8 h to obtain a porous structure of the skeleton material.

[0027] The above-prepared porous structure of the skeleton material and 600 g of butyl acrylate were added to a reaction vessel, then 3 g of azobisisobutyronitrile and 12 g of zinc acetate were added thereto, and the temperature was raised to 100 °C for reflux condensation reaction for 8 h. Subsequently, it was placed in a vacuum drying oven and reacted at 60 °C for another 24 h.

[0028] Example 2:

[0029] The waste plastic runway was washed with distilled water, dried, and then crushed by a high-speed crusher. After sieving, the powder with a diameter of 1 mm was selected.

[0030] 200 g of waste plastic runway powder was placed in 2400 g of ethyl acrylate and 1200 g of methyl methacrylate for swelling, that is, swelling at room temperature for 8 h. Subsequently, the swollen waste plastic runway powder was taken out, and the remaining mixed solution was stored for later use. The swollen waste plastic runway powder and 100 g of acrylic acid were dispersed in 800 g of a water and ethanol mixed solution (mass ratio of water to ethanol is 3:1), then 3.3 g of dipropylene glycol diacrylate and 1.0 g of photoinitiator 2959 were added. The container was wrapped with tin foil to keep it away from light, and stirred for 2 h. The stirring speed was controlled at 500 revolutions per minute to obtain a prepolymer solution. Then the prepolymer solution was placed in a polytetrafluoroethylene mold, and the mold was placed in a sealed dark box. Under nitrogen protection, it was irradiated with a 365 nm ultraviolet curing lamp for 2 h, and then placed in a freeze dryer for freeze drying for 8 h to obtain a porous structure of the skeleton material.

[0031] The above-prepared skeleton material containing waste plastic runway powder and 1200 g of 2-ethylhexyl acrylate were added to a reaction vessel, then 6 g of azobisisoheptonitrile and 24 g of zinc stearate were added thereto, and the temperature was raised to 100 °C for reflux condensation reaction for 8 h. Subsequently, it was placed in a vacuum drying oven and reacted at 60 °C for another 24 h.

[0032] Example 3:

[0033] The waste plastic runway was washed with distilled water, dried, crushed by a high-speed crusher, and sieved to select powders with a diameter of 1 mm.

[0034] 300 g of the waste plastic runway powder was placed in 3600 g of butyl acrylate and 1800 g of methyl acrylate for swelling, that is, swelling for 8 h at room temperature. Subsequently, the swollen waste plastic runway powder was taken out, and the remaining mixed solution was stored for later use. The swollen waste plastic runway powder, 150 g of acrylic acid, and 30 g of N-allylmethylamine were dispersed in 1200 g of a water and ethanol mixed solution (the mass ratio of water to ethanol was 3:1). Then, 4.95 g of ethylene glycol dimethacrylate and 1.5 g of photoinitiator 1173 were added. The container was wrapped with tin foil to keep it away from light and stirred for 2 h. The stirring speed was controlled at 500 revolutions per minute to obtain a prepolymer solution. Then, the prepolymer solution was placed in a polytetrafluoroethylene mold, and the mold was placed in a closed dark box. It was irradiated with a 365 nm ultraviolet curing lamp for 2 h under nitrogen protection, and then placed in a freeze dryer for freeze drying for 8 h to obtain a porous structure skeleton material.

[0035] The above-prepared skeleton material containing waste plastic runway powder and 1800 g of ethyl acrylate were added to a reaction vessel. Then, 9 g of benzoyl peroxide and 36 g of iron isooctanoate were added thereto, and the temperature was raised to 100 °C for reflux condensation reaction for 8 h. Subsequently, it was placed in a vacuum drying oven and reacted at 60 °C for another 24 h.

[0036] Example 4:

[0037] The waste plastic runway was washed with distilled water, dried, crushed by a high-speed crusher, and sieved to select powders with a diameter of 1 mm.

[0038] 400 g of the waste plastic runway powder was placed in 4800 g of butyl acrylate and 2400 g of methyl methacrylate for swelling, that is, swelling for 8 h at room temperature. Subsequently, the swollen waste plastic runway powder was taken out, and the remaining mixed solution was stored for later use. After the swelling was completed, it was dispersed in 1600 g of a water and ethanol mixed solution (the mass ratio of water to ethanol was 3:1) together with 200 g of acrylic acid. Then, 6.6 g of polyethylene glycol diacrylate and 2.0 g of photoinitiator 819 were added. The container was wrapped with tin foil to keep it away from light and stirred for 2 h. The stirring speed was controlled at 500 revolutions per minute to obtain a prepolymer solution. Then, the prepolymer solution was placed in a polytetrafluoroethylene mold, and the mold was placed in a closed dark box. It was irradiated with a 365 nm ultraviolet curing lamp for 2 h under nitrogen protection, and then placed in a freeze dryer for freeze drying for 8 h to obtain a porous structure skeleton material.

[0039] Add the above-prepared skeleton material containing waste plastic runway powder and 2400 g of ethyl acrylate into a reaction vessel, then add 12 g of azobisisobutyronitrile and 48 g of iron isooctanoate into it, heat up to 100 °C and carry out a condensation reflux reaction for 8 h, and then place it in a vacuum drying oven and continue the reaction at 60 °C for 24 h.

[0040] Example 5:

[0041] Wash the waste plastic runway with distilled water, dry it, crush it with a high-speed crusher, and sieve to select powder with a diameter of 1 mm.

[0042] Place 100 g of waste plastic runway powder in 1200 g of butyl acrylate and 600 g of 2-hydroxyethyl acrylate for swelling, that is, swell at room temperature for 8 h, then take out the swollen waste plastic runway powder, and keep the remaining mixed solution for later use. Disperse the swollen plastic runway powder and 50 g of acrylic acid in 400 g of a water and ethanol mixed solution (the mass ratio of water to ethanol is 3:1), then add 1.65 g of polyethylene glycol diacrylate and 0.5 g of photoinitiator 1173, wrap the container with tin foil to keep it away from light, and stir for 2 h, and control the stirring speed at 500 revolutions per minute to obtain a prepolymer solution. Then place the prepolymer solution in a polytetrafluoroethylene mold, place the mold in a sealed dark box, irradiate it with a 365 nm ultraviolet curing lamp under nitrogen protection for 2 h, and then place it in a freeze dryer for freeze drying for 8 h to obtain a skeleton material with a porous structure.

[0043] Add the above-prepared skeleton material with a porous structure and 1000 g of butyl acrylate into a reaction vessel, then add 3 g of azobisisobutyronitrile and 12 g of zinc acetate into it, heat up to 100 °C and carry out a condensation reflux reaction for 8 h, and then place it in a vacuum drying oven and continue the reaction at 60 °C for 24 h.

[0044] Example 6:

[0045] Wash the waste plastic runway with distilled water, dry it, crush it with a high-speed crusher, and sieve to select powder with a diameter of 1 mm.

[0046] 200 g of waste plastic runway powder was swollen in 2400 g of ethyl acrylate and 1200 g of methyl methacrylate, that is, swollen at room temperature for 8 h. Subsequently, the swollen waste plastic runway powder was taken out, and the remaining mixed solution was stored for later use. The swollen plastic runway powder and 100 g of acrylic acid were dispersed in 800 g of a water and ethanol mixed solution (the mass ratio of water to ethanol was 3:1), then 3.3 g of dipropylene glycol diacrylate and 1.0 g of photoinitiator 2959 were added. The container was wrapped with tin foil to keep it away from light and stirred for 2 h, and the stirring speed was controlled at 500 revolutions per minute to obtain a prepolymer solution. Then the prepolymer solution was placed in a polytetrafluoroethylene mold, and the mold was placed in a sealed dark box. Under nitrogen protection, it was irradiated with a 365 nm ultraviolet curing lamp for 2 h, and then placed in a freeze dryer for freeze drying for 8 h to obtain a porous structure skeleton material.

[0047] The above-prepared skeleton material containing waste plastic runway powder and 2000 g of 2-ethylhexyl acrylate were added to a reaction vessel, then 6 g of 2,2'-azobis(2-methylheptanenitrile) and 24 g of zinc stearate were added thereto, and the temperature was raised to 100 °C for reflux condensation reaction for 8 h. Subsequently, it was placed in a vacuum drying oven and reacted at 60 °C for another 24 h.

[0048] Comparative Example 1:

[0049] 120 g of butyl acrylate, 2-hydroxyethyl acrylate and 50 g of acrylic acid were dispersed in 400 g of a water and ethanol mixed solution (the mass ratio of water to ethanol was 3:1), then 1.65 g of polyethylene glycol diacrylate and 0.5 g of photoinitiator 1173 were added. The container was wrapped with tin foil to keep it away from light and stirred on a magnetic stirrer for 2 h, and the stirring speed was controlled at 500 revolutions per minute to obtain a prepolymer solution. Then the prepolymer solution was placed in a polytetrafluoroethylene mold, and the mold was placed in a sealed dark box. Under nitrogen protection, it was irradiated with a 365 nm ultraviolet curing lamp for 2 h, and then placed in a freeze dryer for freeze drying for 8 h to obtain a porous structure skeleton material.

[0050] The above-prepared skeleton material and 600 g of butyl acrylate were added to a reaction vessel, then 3 g of 2,2'-azobis(2-methylheptanenitrile) and 12 g of zinc acetate were added thereto, and the temperature was raised to 100 °C for reflux condensation reaction for 8 h. Subsequently, it was placed in a vacuum drying oven and reacted at 60 °C for another 24 h.

[0051] Comparative Example 2:

[0052] The waste plastic runway was washed with distilled water, dried, crushed with a high-speed crusher, and sieved to select powder with a diameter of 1 mm.

[0053] 100 g of untreated waste plastic runway powder and 600 g of butyl acrylate were added to a reaction vessel, and then 3 g of azobisisobutyronitrile was added thereto. The temperature was raised to 100 °C and the reaction was carried out under reflux condensation for 8 h. Subsequently, it was placed in a vacuum drying oven and the reaction was continued at 60 °C for 24 h.

[0054] Performance test standards and methods: Using an electronic universal material testing machine, according to the international standard for elastomer performance testing GBT528-2009, tensile tests were carried out at a strain rate of 200 mm / min, and the average value was taken after measuring three times.

[0055] Mechanical property repair test: The standard spline was cut in half with a blade, and then the cross-sections were completely contacted, and then the change in the mechanical strength of the spline after 24 h was tested. The self-healing efficiency (%) was defined as the ratio of the maximum tensile strength of the repaired spline to the initial maximum tensile strength of the spline.

[0056] Mechanical tests were carried out on the prepared polyacrylate rubber, and the results are shown in Table 1.

[0057] Table 1 shows the performance of the materials prepared in the examples and comparative examples.

[0058] Tensile strength / MPa Elongation at break / % Self-healing efficiency / % Example 1 6.81 632.51 85.37 Example 2 7.32 590.36 84.81 Example 3 8.92 402.59 84.35 Example 4 10.81 326.98 84.02 Example 5 6.34 869.25 83.69 Example 6 6.02 962.89 83.18 Comparative example 1 5.60 798.32 87.23 Comparative example 2 5.73 769.21 0

[0059] From the comparison of the performance of the materials prepared in the above Examples 1-6 and comparative examples, it can be seen that compared with Comparative Example 1, the tensile strength of Example 1 increased, indicating that the performance of the polyacrylate rubber modified by adding waste plastic runway powder was improved, and it had self-healing properties. Compared with Comparative Example 2, the tensile strength of Example 1 increased significantly and it had self-healing properties, indicating that the pretreated waste plastic runway powder was more beneficial to the improvement of the performance of polyacrylate rubber. Comparing Example 1, Example 2, Example 3, and Example 4, as the amount of waste plastic runway powder increased, the tensile strength increased and the elongation at break decreased. Comparing Example 1 with Example 5 and Example 6, the elongation at break increased, indicating that when the amount of waste plastic runway powder was fixed, increasing the mass of the soft monomer could obtain a polyacrylate rubber composite with higher toughness. In summary, it is feasible to produce polyacrylate rubber using waste plastic runway powder, and at the same time, the resource recycling of waste plastic runways is realized.

[0060] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple deformations can be made to the technical solutions of the present invention, including any combination of specific technical features in any way. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods. However, these simple deformations and combinations are equally regarded as the content disclosed by the present invention and all fall within the scope of protection of the present invention.

Claims

1. A method for producing polyacrylate rubber using waste plastic runway powder, characterized in that It includes the following steps: S1. Prepare waste plastic runway powder: Crush the waste plastic runway and conduct size screening; S2. Pretreat the waste plastic runway powder, including swelling, copolymerization and freeze-drying processes to form a porous structure framework material; S3. Place the prepared porous structure framework material in an acrylate monomer containing organometal, add a certain amount of free radical initiator, and obtain a polyacrylate rubber modified with waste plastic runway powder with elasticity and self-healing properties after heating and polymerization; In step S2: The swelling is to add the waste plastic runway powder into the acrylate monomer mixed solution for swelling. The mass ratio of the waste plastic runway powder to the acrylate monomer mixed solution is 1:10 to 1:20, and swell at room temperature for 8 h; The copolymerization is to place the swollen plastic runway powder in a mixed solvent of water and ethanol containing acrylic acid, add a crosslinking agent and a photoinitiator, and form a copolymer hydrogel through photoinitiated polymerization; The freeze-drying is to freeze-dry the copolymer hydrogel under the conditions of -50°C and -0.1 MPa to form a porous structure framework material.

2. The method according to claim 1, wherein: In step S1, after washing the waste plastic runway with distilled water and drying it, break it with a high-speed crusher and sieve to select powder with a diameter less than or equal to 1 mm.

3. The method according to claim 1, wherein: In step S2, the acrylate monomer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, and 2-hydroxyethyl acrylate.

4. The method according to claim 1, wherein: In step S2, take a certain amount of waste plastic runway powder swollen by the acrylate monomer mixed solution and acrylic acid, disperse them in a certain amount of mixed solvent of water and ethanol, then add an appropriate amount of crosslinking agent and photoinitiator, wrap the container with tin foil to keep it away from light, and stir for 2 h. The stirring speed is controlled at 500 revolutions per minute to obtain a prepolymer solution; then weigh a certain amount of the prepolymer solution into a polytetrafluoroethylene mold, place the mold in a closed dark box, and irradiate it with a 365 nm ultraviolet curing lamp for 2 h under nitrogen protection to obtain a copolymer hydrogel.

5. The method according to claim 1 or 4, wherein: The mass ratio of the swollen plastic runway powder to acrylic acid is 2:

1.

6. The method according to claim 1 or 4, wherein: The mass ratio of water to ethanol in the water and ethanol mixed solvent is 3:

1.

7. The method according to claim 1, characterized in that Step S3 includes the following steps: Place the porous structure framework material obtained in step 2 in a reaction vessel, and also add an appropriate amount of free radical initiator, organometal and acrylate monomer. The mass ratio of the porous structure framework material to the acrylate monomer is 1:1 to 1:

10. After sealing, heat up to 100°C for reflux reaction for 8 h, and then place it in an oven and continue to react at 60°C for 24 h.