CN114806140A - Bio-based degradable plastic course - Google Patents
Bio-based degradable plastic course Download PDFInfo
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- CN114806140A CN114806140A CN202210555399.4A CN202210555399A CN114806140A CN 114806140 A CN114806140 A CN 114806140A CN 202210555399 A CN202210555399 A CN 202210555399A CN 114806140 A CN114806140 A CN 114806140A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the technical field of plastic runways, in particular to a bio-based degradable plastic runway, which comprises the following raw materials in parts by mass: 20-40 parts of degradable resin, 100-120 parts of modified polyurethane, 13-21 parts of polyether polyol, 35-48 parts of waste tire rubber, 30-40 parts of EPDM rubber particles, 10-15 parts of pigment, 5-12 parts of filler, 3-4 parts of thermal oxidation aging modifier and auxiliary agent. Compared with the prior art, the invention effectively improves the water resistance and the thermal-oxidative-aging resistance of the plastic track, has simple production process and low production cost, and is beneficial to advocating green environmental protection by adding a proper amount of degradable materials.
Description
Technical Field
The invention relates to the technical field of plastic runways, in particular to a bio-based degradable plastic runway.
Background
The plastic track is also named as all-weather track and field sports track and consists of polyurethane prepolymer, mixed polyether, waste tyre rubber, EPDM rubber grain or PU grain, pigment, assistant and stuffing. The plastic track has the characteristics of good flatness, high compressive strength, proper hardness and elasticity and stable physical performance, is beneficial to the exertion of the speed and the technology of athletes, effectively improves the sports performance and reduces the tumble injury rate.
However, when raining, a large amount of rainwater can permeate into the plastic track, so that the phenomenon of bulging is very serious, and the surface of the plastic track is easily subjected to thermal oxidation aging due to long-time insolation in summer at high temperature. Therefore, we propose a bio-based degradable plastic runway to solve the above problems.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a bio-based degradable plastic track.
A bio-based degradable plastic track is characterized by comprising the following raw materials in parts by mass: 20-40 parts of degradable resin, 100-120 parts of modified polyurethane, 13-21 parts of polyether polyol, 35-48 parts of waste tire rubber, 30-40 parts of EPDM rubber particles, 10-15 parts of pigment, 5-12 parts of filler, 3-4 parts of thermal oxidation aging modifier and auxiliary agent;
the polyether polyol is one of polyoxypropylene diol, polytetrahydrofuran diol, polyoxyethylene diol and polyoxyethylene triol;
the pigment is one of iron oxide red, iron oxide black, iron oxide blue and iron oxide yellow;
the auxiliary agent comprises 4-9 parts by mass of wetting dispersant, 6-8 parts by mass of vulcanizing agent, 3-5 parts by mass of plasticizer and 3-7 parts by mass of curing agent;
the filler comprises one of gypsum, kaolin, nano calcium carbonate and talcum powder.
Preferably, the degradable resin is a mixed resin composed of polylactic acid, polycaprolactone and polyhydroxybutyrate according to a mass ratio of 1:1: 1.
Preferably, the preparation method of the modified polyurethane is as follows:
step one, weighing toluene diisocyanate, polyether 210 and hydroxyl silicone oil, adding the weighed materials into a four-neck flask, controlling the temperature at 70-75 ℃, reacting for 4-5 hours, cooling to room temperature, adding 1, 4-butanediol, heating to 70-75 ℃, and reacting for 2-2.5 hours;
and step two, cooling to 55 ℃, adding dimethylolpropionic acid, heating to 70-75 ℃ for hydrophilic chain extension reaction for 3-3.2 hours, cooling to room temperature, adding triethylamine for neutralization until the pH value is 8, neutralizing for 30-40 minutes, and rapidly adding water for emulsification for 1-1.5 hours under high-speed stirring to obtain the modified polyurethane.
Preferably, the dosage ratio of the two times of the polytetrahydrofuran diol is 1:4, and the dosage of the hydroxyl silicone oil is 8 percent of the total amount of the polytetrahydrofuran diol.
Preferably, the preparation method of the thermal-oxidative aging modifier comprises the following steps:
and (3) mixing the main antioxidant and the auxiliary antioxidant, stirring uniformly, heating to 75-80 ℃, adding aniline, and continuously stirring until the main antioxidant and the auxiliary antioxidant are uniformly mixed to obtain the thermal-oxidative aging modifier.
Preferably, the main antioxidant is an antioxidant 245, the auxiliary antioxidant is an antioxidant 168, the mass ratio of the thermal oxidation aging modifier to the modified polyurethane is 3:100, and the mass ratio of the main antioxidant to the auxiliary antioxidant to the aniline is 5:2: 1.
Preferably, the wetting dispersant is polyoxyethylene alkyl ether, the vulcanizing agent is dicumyl peroxide, the plasticizer is dioctyl ester, and the curing agent is 2547.
A preparation method of a bio-based degradable plastic track comprises the following steps:
s1, weighing the waste tire rubber, and cutting the waste tire rubber into blocks to obtain waste tire rubber blocks for later use;
s2, weighing the degradable resin, the modified polyurethane, the polyether polyol, the waste tire rubber and the EPDM rubber particles, mixing the degradable resin, the modified polyurethane, the polyether polyol, the waste tire rubber and the EPDM rubber particles with the waste tire rubber block in the S1, and then putting the mixture into an internal mixer for mixing, wherein the mixing temperature is 100-110 ℃, the mixing time is 15-20 minutes, and a mixing mixture is obtained after mixing;
s3, adding the pigment, the filler and the wetting dispersant and the plasticizer in the auxiliary agent into the mixed mixture of S2, stirring and mixing, then carrying out secondary mixing, putting the mixture into a refining machine for refining after mixing, wherein the refining temperature is 85-90 ℃, and the refining time is 5-7 minutes, and obtaining a refined mixture after refining;
s4, putting the refined mixture into an extruder, adding a thermal oxidation aging modifier and a vulcanizing agent and a curing agent in the auxiliary agent at the same time, blending and extruding, then entering a hot air channel for vulcanizing, and cooling to obtain the plastic track material;
and S5, spreading the plastic runway material in the S4 on the primer, flattening, trimming and curing to obtain the plastic runway.
Preferably, the head temperature of the extruder during blending extrusion is 150-160 ℃, the extrusion speed is 2-3m/min, the vulcanization speed is 2-3m/min, and the temperature of the hot air channel is 100-180 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. in the invention, the polyurethane is modified by the organic silicon, the organic silicon chain segment is introduced into the main chain of the polyurethane, the organic silicon chain segment with hydrophobicity migrates and is enriched to the surface of the polyurethane, and the surface tension of the base material is effectively changed, thereby improving the water resistance of the plastic track.
2. In the invention, the thermal-oxidative aging modifier is prepared by adopting the antioxidant 245 as a main antioxidant, the antioxidant 168 as an auxiliary antioxidant and a small amount of aniline, and is added into the raw materials of the formula, so that the thermal-oxidative aging resistance of the plastic track can be effectively improved.
3. In the invention, the production process is simple, the production cost is low, and the addition of a proper amount of degradable materials can help to promote green environmental protection.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1:
a bio-based degradable plastic track comprises the following raw materials in parts by mass: 21 parts of degradable resin, 100 parts of modified polyurethane, 13 parts of polyoxypropylene diol, 35 parts of waste tire rubber, 30 parts of EPDM rubber particles, 10 parts of iron oxide red, 5 parts of talcum powder, 3 parts of thermal oxidation aging modifier, 4 parts of polyoxyethylene alkyl ether, 6 parts of dicumyl peroxide, 3 parts of dioctyl ester and 25473 parts of curing agent.
Example 2:
a bio-based degradable plastic track comprises the following raw materials in parts by mass: 30 parts of degradable resin, 110 parts of modified polyurethane, 17 parts of polyoxypropylene diol, 42 parts of waste tire rubber, 35 parts of EPDM rubber particles, 13 parts of iron oxide red, 8 parts of talcum powder, 3.3 parts of thermal oxidation aging modifier, 6.5 parts of polyoxyethylene alkyl ether, 7 parts of dicumyl peroxide, 4 parts of dioctyl ester and 25475 parts of curing agent.
Example 3:
a bio-based degradable plastic track comprises the following raw materials in parts by mass: 39 parts of degradable resin, 120 parts of modified polyurethane, 21 parts of polyoxypropylene diol, 48 parts of waste tire rubber, 40 parts of EPDM rubber particles, 15 parts of iron oxide red, 12 parts of talcum powder, 3.6 parts of thermal oxidation aging modifier, 9 parts of polyoxyethylene alkyl ether, 8 parts of dicumyl peroxide, 5 parts of dioctyl ester and 25477 parts of curing agent.
In examples 1-3 above:
firstly, the degradable resin is mixed resin consisting of polylactic acid, polycaprolactone and polyhydroxybutyrate according to the mass ratio of 1:1: 1; curing agent 2547 was produced from Guangzhou green protection New Material Co.
Secondly, the preparation method of the single-mass part modified polyurethane comprises the following steps:
step one, weighing 78.9g of toluene diisocyanate, 36.5g of polyether 210 and 43.0g of hydroxyl silicone oil, adding the weighed materials into a four-neck flask with a thermometer and a stirring device, controlling the temperature at 75 ℃, reacting for 5 hours, cooling to room temperature, adding 17.8g of 1, 4-butanediol, heating to 70 ℃, and reacting for 2 hours;
and step two, cooling to 55 ℃, adding 16.4g of dimethylolpropionic acid, heating to 70 ℃ for hydrophilic chain extension reaction for 3 hours, cooling to room temperature, adding triethylamine for neutralization until the pH value is 8, neutralizing for 30 minutes, and rapidly adding water at the rotating speed of 1200rpm for emulsification for 1 hour to obtain the modified polyurethane.
Thirdly, the preparation method of the thermal oxidation aging modifier with the single substance weight portion is as follows:
and (3) mixing 150g of the antioxidant 245 and 60g of the antioxidant 168, uniformly stirring, heating to 80 ℃, adding 30g of aniline, and continuously stirring until the mixture is uniformly mixed to obtain the thermal-oxidative aging modifier.
The specific process for preparing the bio-based degradable plastic track in the above examples 1-3 is as follows:
s1, weighing the waste tire rubber, and cutting the waste tire rubber into blocks to obtain waste tire rubber blocks for later use;
s2, weighing the degradable resin, the modified polyurethane, the polyether polyol, the waste tire rubber and the EPDM rubber particles, mixing the degradable resin, the modified polyurethane, the polyether polyol, the waste tire rubber and the EPDM rubber particles with the waste tire rubber block in the S1, and then putting the mixture into an internal mixer for mixing, wherein the mixing temperature is 110 ℃, the mixing time is 20 minutes, and a mixing mixture is obtained after mixing;
s3, adding the pigment, the filler and the wetting dispersant and the plasticizer in the auxiliary agent into the mixed mixture of S2, stirring and mixing, then carrying out secondary mixing, putting the mixture into a refiner for refining after mixing, wherein the refining temperature is 90 ℃ and the refining time is 5 minutes, and obtaining a refined mixture after refining;
s4, putting the refined mixture into an extruder, adding a vulcanizing agent and a curing agent in the thermal oxidation aging modifier and the auxiliary agent simultaneously, blending and extruding, wherein the temperature in the extruder is 120 ℃, the extrusion speed is 2m/min, then feeding the mixture into a hot air channel for vulcanizing, the vulcanization speed is 2m/min, the temperature of the hot air channel is 100 ℃, and cooling to obtain the plastic track material;
and S5, spreading the plastic runway material in the S4 on the primer, flattening, trimming and curing to obtain the plastic runway.
Test I, determination of water resistance of plastic track
Comparative example 1: compared with the example 1, the difference is that the polyurethane in the raw material is not modified;
comparative example 2: compared with the example 2, the difference is that the polyurethane in the raw material is not modified;
comparative example 3: compared with the example 3, the difference is that the polyurethane in the raw material is not modified;
test subjects: the plastic track of examples 1-3 and comparative examples 1-3;
the test method comprises the following steps: measuring the surface water contact angle of the plastic track at room temperature by using an OCA (optical contact angle instrument) series water contact angle instrument (produced by Dataphysics, Germany);
and (3) test results:
from the test results in the table above, it can be seen that:
in each test group, the surface water contact angle of the plastic track in the examples is much larger than that of the comparative example, but the surface water contact angles of the plastic track in the examples are larger than 90 degrees, that is, both belong to the category of hydrophobic materials, but the hydrophobic property of the plastic track in the examples is stronger.
Therefore, the polyurethane is modified by the organic silicon, so that the water resistance of the plastic track can be obviously improved.
Test II, determination of thermal oxidation aging resistance of plastic track
Comparative example 4: compared with example 1, the difference is that the thermal oxidation aging modifier is changed into antioxidant 245;
comparative example 5: compared with example 1, the difference is that the thermal oxidation aging modifier is changed into antioxidant 168;
comparative example 6: compared with example 1, the difference is that the 'thermal oxygen aging modifier' is not contained;
test subjects: the plastic racetracks of example 1 and comparative examples 4-6, and the conventional plastic racetracks;
the test method comprises the following steps: long-term aging test method of reference bituminous mixture (JTG E20-2011)
(1) Placing the plastic track in a test object in a 401A type aging box at 85 +/-3 ℃, and continuously heating for 5 days under the condition of forced ventilation;
(2) bonding the aged tensile test piece with the connector, and performing direct tensile test after the bonding is firm;
(3) the aging resistance index is determined from the stress to failure, strain to failure, and energy to break between aged and unaged urethane rubber particle mixtures.
And (3) test results:
from the test results in the table above, it can be seen that:
(1) the failure stress of example 1 is reduced by 7.6% after aging, the failure stress of comparative example 4 is reduced by 15.4% after aging, the failure stress of comparative example 5 is reduced by 18.8% after aging, the failure stress of comparative example 6 is reduced by 22.8% after aging, and the failure stress of the conventional plastic track is reduced by 22.4% after aging;
(2) the failure strain of example 1 was reduced by 33.3% after aging, the failure stress of comparative example 4 was reduced by 41.2% after aging, the failure stress of comparative example 5 was reduced by 43.8% after aging, the failure stress of comparative example 6 was reduced by 50.0% after aging, and the failure stress of the conventional plastic track was reduced by 53.3% after aging;
(3) the fracture energy of example 1 was reduced by 37.9% after aging, the fracture energy of comparative example 4 was reduced by 41.2% after aging, the fracture energy of comparative example 5 was reduced by 45.1% after aging, the fracture energy of comparative example 6 was reduced by 73.4% after aging, and the fracture energy of the conventional plastic track was reduced by 71.4% after aging;
from the above results, it can be seen that the failure stress, failure strain and fracture energy of examples 1 and comparative examples 4 to 5 are higher than those of the conventional plastic track, while the failure stress, failure strain and fracture of comparative example 6 are not much different from those of the conventional plastic track;
therefore, the effect of the antioxidant 168 is inferior to that of the antioxidant 245 in the improvement of the thermal-oxidative aging resistance of the plastic track, and the effect of the antioxidant 245 and the antioxidant 168 which are prepared by mixing the antioxidant 245 and the antioxidant 168 together and adding aniline for modification is better than that of the antioxidant 245 alone.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A bio-based degradable plastic track is characterized by comprising the following raw materials in parts by mass: 20-40 parts of degradable resin, 100-120 parts of modified polyurethane, 13-21 parts of polyether polyol, 35-48 parts of waste tire rubber, 30-40 parts of EPDM rubber particles, 10-15 parts of pigment, 5-12 parts of filler, 3-4 parts of thermal oxidation aging modifier and auxiliary agent;
the polyether polyol is one of polyoxypropylene diol, polytetrahydrofuran diol, polyoxyethylene diol and polyoxyethylene triol;
the pigment is one of iron oxide red, iron oxide black, iron oxide blue and iron oxide yellow;
the auxiliary agent comprises 4-9 parts by mass of wetting dispersant, 6-8 parts by mass of vulcanizing agent, 3-5 parts by mass of plasticizer and 3-7 parts by mass of curing agent;
the filler comprises one of gypsum, kaolin, nano calcium carbonate and talcum powder.
2. The bio-based degradable plastic runway according to claim 1, characterized in that the degradable resin is a mixed resin composed of polylactic acid, polycaprolactone and polyhydroxybutyrate according to a mass ratio of 1:1: 1.
3. The bio-based degradable plastic runway according to claim 1, characterized in that the preparation method of the modified polyurethane is as follows:
step one, weighing toluene diisocyanate, polyether 210 and hydroxyl silicone oil, adding the weighed materials into a four-neck flask, controlling the temperature at 70-75 ℃, reacting for 4-5 hours, cooling to room temperature, adding 1, 4-butanediol, heating to 70-75 ℃, and reacting for 2-2.5 hours;
and step two, cooling to 55 ℃, adding dimethylolpropionic acid, heating to 70-75 ℃ for hydrophilic chain extension reaction for 3-3.2 hours, cooling to room temperature, adding triethylamine for neutralization until the pH value is 8, neutralizing for 30-40 minutes, and rapidly adding water for emulsification for 1-1.5 hours under high-speed stirring to obtain the modified polyurethane.
4. The bio-based degradable plastic track according to claim 1, wherein the thermo-oxidative aging modifier is prepared by the following steps:
and (3) mixing the main antioxidant and the auxiliary antioxidant, stirring uniformly, heating to 75-80 ℃, adding aniline, and continuously stirring until the main antioxidant and the auxiliary antioxidant are uniformly mixed to obtain the thermal-oxidative aging modifier.
5. The bio-based degradable plastic track according to claim 4, wherein the primary antioxidant is an antioxidant 245, the secondary antioxidant is an antioxidant 168, the mass ratio of the thermal-oxidative aging modifier to the modified polyurethane is 3:100, and the mass ratio of the primary antioxidant, the secondary antioxidant and the aniline is 5:2: 1.
6. The biodegradable plastic track according to claim 1, wherein the wetting dispersant is polyoxyethylene alkyl ether, the vulcanizing agent is dicumyl peroxide, the plasticizer is dioctyl ester, and the curing agent is 2547.
7. The method for preparing a bio-based degradable plastic track according to any one of claims 1 to 6, comprising the following steps:
s1, weighing the waste tire rubber, and cutting the waste tire rubber into blocks to obtain waste tire rubber blocks for later use;
s2, weighing the degradable resin, the modified polyurethane, the polyether polyol, the waste tire rubber and the EPDM rubber particles, mixing the degradable resin, the modified polyurethane, the polyether polyol, the waste tire rubber and the EPDM rubber particles with the waste tire rubber block in the S1, and then putting the mixture into an internal mixer for mixing, wherein the mixing temperature is 100-110 ℃, the mixing time is 15-20 minutes, and a mixing mixture is obtained after mixing;
s3, adding the pigment, the filler and the wetting dispersant and the plasticizer in the auxiliary agent into the mixed mixture of S2, stirring and mixing, then carrying out secondary mixing, putting the mixture into a refining machine for refining after mixing, wherein the refining temperature is 85-90 ℃, and the refining time is 5-7 minutes, and obtaining a refined mixture after refining;
s4, putting the refined mixture into an extruder, adding a thermal oxidation aging modifier and a vulcanizing agent and a curing agent in the auxiliary agent at the same time, blending and extruding, then entering a hot air channel for vulcanizing, and cooling to obtain the plastic track material;
and S5, spreading the plastic runway material in the S4 on the primer, flattening, trimming and curing to obtain the plastic runway.
8. The method as claimed in claim 7, wherein the extruder has a head temperature of 150-160 ℃, an extrusion speed of 2-3m/min, a vulcanization speed of 2-3m/min, and a hot air channel temperature of 100-180 ℃.
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