CN114085441A - Micro-nano regenerated gum base thermoplastic elastomer and preparation method thereof - Google Patents
Micro-nano regenerated gum base thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN114085441A CN114085441A CN202111446976.8A CN202111446976A CN114085441A CN 114085441 A CN114085441 A CN 114085441A CN 202111446976 A CN202111446976 A CN 202111446976A CN 114085441 A CN114085441 A CN 114085441A
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 136
- 239000005060 rubber Substances 0.000 claims abstract description 136
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 59
- 239000001301 oxygen Substances 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 238000004073 vulcanization Methods 0.000 claims abstract description 38
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000004014 plasticizer Substances 0.000 claims abstract description 24
- 241001441571 Hiodontidae Species 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003979 granulating agent Substances 0.000 claims description 9
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 229920004889 linear high-density polyethylene Polymers 0.000 claims description 3
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 3
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 3
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 claims description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011297 pine tar Substances 0.000 claims description 3
- 229940068124 pine tar Drugs 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 abstract description 6
- 239000010920 waste tyre Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L17/00—Compositions of reclaimed rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a micro-nano regenerated gum base thermoplastic elastomer and a preparation method thereof, wherein the raw material components comprise the following components in parts by weight: low mooney micro-oxygen reclaimed rubber: 60-80 parts; resin: 20-40 parts; a vulcanization system: 4-8 parts; compatibilizer: 2-10 parts; softening plasticizer: 2-8 parts; an anti-aging agent: 1-6 parts. The preparation method provided by the invention can use a large amount of low-cost reclaimed rubber, is simple to prepare, realizes high-valued recovery of waste tire rubber, realizes micro-nano dispersion of the reclaimed rubber in resin, has excellent interface compatibility between two phases, and can be used in dynamic working conditions.
Description
Technical Field
The invention belongs to the field of thermoplastic elastomer preparation methods, and particularly relates to a micro-nano reclaimed rubber-based thermoplastic elastomer and a preparation method thereof.
Background
As the biggest world tire production and consumption country in China, the continuous dynamic development of the automobile industry causes the quantity of waste tires to be increased sharply, and the black pollution is increasingly serious. The recycling of the waste rubber is a necessary choice under the policy of double carbon.
Thermoplastic elastomers have high elasticity of vulcanized rubber at use temperature and processability of thermoplastics at high temperature, and are third generation rubbers following natural and synthetic rubbers.
The reclaimed rubber is low molecular weight rubber which is processed by a three-dimensional cross-linked vulcanized rubber through physical and chemical actions and can be secondarily processed and vulcanized.
The thermoplastic elastomer prepared by blending the reclaimed rubber and the thermoplastic plastic can reduce environmental pollution and realize high-valued recycling of resources. However, the rubber powder used in the traditional rubber powder-based thermoplastic elastomer is particles which are difficult to disperse in millimeter scale, and the problems of difficult processing, poor dispersibility and the like exist in the processing and using processes.
Disclosure of Invention
The invention aims to provide a micro-nano regenerated gum base thermoplastic elastomer which has good mechanical property, excellent processing property, excellent flex fatigue resistance, economic value, environmental protection value and practical application value, and a preparation method thereof.
The invention is realized by the following technical scheme:
a micro-nano reclaimed rubber-based thermoplastic elastomer comprises the following raw material components in parts by weight:
low mooney micro-oxygen reclaimed rubber: 60-80 parts;
resin: 20-40 parts;
a vulcanization system: 4-8 parts;
compatibilizer: 2-10 parts;
softening plasticizer: 2-8 parts;
an anti-aging agent: 1-6 parts;
the low-Mooney-property micro-oxygen regenerated rubber is rubber powder regenerated by a dynamic micro-oxygen desulfurization method, and is specifically obtained by putting the rubber powder into a high-speed stirring and mixing tank, stirring for a certain time at the temperature of 180-240 ℃, and then cooling, wherein the sol content of the low-Mooney-property micro-oxygen regenerated rubber is more than 50%. Preferably, the stirring time is 3 to 6 minutes.
The inventor skillfully discovers that the low-Mooney micro-oxygen reclaimed rubber with the sol content of more than 60 percent can be reclaimed from tire rubber by a thermal oxidation method, the cross-linked network of the reclaimed rubber has high destruction degree, and good dispersion of micro-nano level can be formed in a resin system. Meanwhile, the low-Mooney micro-oxygen reclaimed rubber is prepared by an oxidation method, contains a large amount of polar functional groups on the surface and is well combined with polar fillers such as white carbon black and the like. In addition, the coated carbon black may be separated from the rubber network and has reinforcing properties. Improves the mechanical property and the processing property of the rare high-content regenerated rubber-based thermoplastic elastomer in the current research, improves the resource utilization rate and protects the environment.
According to the research of the inventor, the high-efficiency aerobic hydrolysis crosslinking of the tire rubber powder can be realized by regulating and controlling the time of thermal oxidation regeneration under the temperature condition of 180-240 ℃, and the low-Mooney micro-oxygen reclaimed rubber with high sol content is obtained. The temperature is continuously increased, the sol content of the reclaimed rubber is not greatly changed, but the energy consumption is increased; when the temperature is too low, the rubber powder is difficult to be subjected to decrosslinking. The time can be adjusted according to different temperatures, and the degradation degree of the reclaimed rubber is regulated and controlled by regulating and controlling the thermal oxidation degradation time of the rubber powder.
The above formulation parameters of the raw material components are selected because, according to the experimental results, when the content of the rubber phase represented by the low-Mooney micro-oxygen reclaimed rubber is 60 to 80 parts, the rubber phase and the plastic phase are uniformly mixed. The vulcanization system can realize a dynamic vulcanization process, and rubber particles are uniformly dispersed in a resin matrix under the action of high temperature and strong shearing force. Meanwhile, under the action of the compatibilizer, the compatibility of the rubber phase and the plastic phase is increased, and the mechanical property is also increased. The plasticizer can adjust the hardness of the product and improve the viscosity and the flexibility. If the content of the reclaimed rubber is too high, the rubber phase is agglomerated, the mechanical force is difficult to uniformly disperse, and the mechanical property and the processability are reduced.
Preferably, the Mooney viscosity of the low-Mooney micro-oxygen reclaimed rubber is 15-30.
Preferably, the rubber powder for preparing the low-Mooney micro-oxygen reclaimed rubber comprises full tire rubber powder of a radial tire.
Preferably, the resin is one or a mixture of more of linear low density polyethylene, high density polyethylene and polypropylene in any proportion.
Preferably, the vulcanization system is composed of sulfur, zinc oxide, stearic acid and an accelerator CZ, and the reclaimed rubber-based thermoplastic elastomer is prepared through dynamic vulcanization. The dynamic vulcanization process can improve the crosslinking density of the rubber phase, increase the interfacial interaction between two phases and improve the strength of the composite material.
Preferably, the compatibilizer is a maleic anhydride grafted polyolefin; the rubber phase and the plastic phase have different polarities and poor interfacial adhesion, and a compatibilizer is often used to reduce the interfacial tension of the two phases. The maleic anhydride can generate chemical action with hydroxyl on the surface of the reclaimed rubber, and the compatibility of the polyolefin and the resin matrix is good.
Preferably, the softening plasticizer is pine tar or coumarone resin, and the softening plasticizer can promote the uniform dispersion of the reclaimed rubber in the resin and improve the interface bonding force of the plastic phase and the resin phase.
Preferably, the anti-aging agent is anti-aging agent RD or anti-aging agent 4010 NA.
The invention also provides a preparation method of the micro-nano regenerated gum base thermoplastic elastomer, which comprises the following production processes:
according to the proportion, firstly, placing the low-Mooney-property micro-oxygen reclaimed rubber and a softening plasticizer in a high-speed mixer to be uniformly mixed in advance to obtain softened low-Mooney-property micro-oxygen reclaimed rubber; placing the resin and the compatibilizer in an internal mixer, controlling the temperature to be 150-180 ℃, and adding the softened low-Mooney micro-oxygen reclaimed rubber after the resin phase is fully melted; after the softened low-Mooney micro-oxygen reclaimed rubber is completely mixed, a vulcanization system and an anti-aging agent are added for vulcanization, and then the mixture is sliced or sent into a granulating agent for granulation for standby. In the dynamic vulcanization process, the reclaimed rubber is broken under the high shear action of the rotor and is uniformly dispersed in the resin phase in a micro-nano scale to complete phase inversion.
Preferably, the vulcanization time is 10 min.
Preferably, the rotor speed of the internal mixer is 60 rpm/min.
The temperature parameters are set in that the processing temperature of the resin matrix, namely PE and PP and the mixture thereof is 180 ℃, the reclaimed rubber is not degraded, and the vulcanization time is selected to be 10min because the torque of the mixture is basically unchanged after 10min according to the experimental result, namely the dynamic vulcanization process is completed.
The invention has the beneficial effects that:
according to the micro-nano regenerated rubber-based thermoplastic elastomer and the preparation method thereof, a large amount of low-cost regenerated rubber can be used, the preparation process is simple, and high-valued recovery of waste tire rubber is realized; the low-Mooney micro-oxygen reclaimed rubber realizes the dispersion of micro-nano degree in resin, the interface compatibility between two phases is excellent, and the obtained product has good processing performance and good physical and mechanical properties; the content of sol of the micro-nano reclaimed rubber is high, the gel is evolved from dozens of micrometers to micro-nano dimensions, the dynamic mechanical property, particularly the fatigue resistance, is better, the loss of the dispersion size of gel particles to the dynamic mechanical property is greatly reduced, the flex fatigue resistance is improved, the micro-nano reclaimed rubber base thermoplastic elastomer can be used in dynamic working conditions, the finally prepared micro-nano reclaimed rubber base thermoplastic elastomer has good performance, good mechanical property and excellent processing property, the flex fatigue resistance is excellent, the processing cost is low, the energy consumption is low, the high-valued recycling of waste tire rubber is realized, the double values of economy, environmental protection and practical application are realized, and the micro-nano reclaimed rubber base thermoplastic elastomer is worthy of popularization.
Detailed Description
A micro-nano reclaimed rubber-based thermoplastic elastomer comprises the following raw material components in parts by weight:
low mooney micro-oxygen reclaimed rubber: 60-80 parts;
resin: 20-40 parts;
a vulcanization system: 4-8 parts;
compatibilizer: 2-10 parts;
softening plasticizer: 2-8 parts;
an anti-aging agent: 1-6 parts.
The low-Mooney-property micro-oxygen regenerated rubber is rubber powder regenerated by a dynamic micro-oxygen desulfurization method, and is specifically obtained by putting the rubber powder into a high-speed stirring and mixing tank, stirring for a certain time at the temperature of 180-240 ℃, and then cooling, wherein the sol content of the low-Mooney-property micro-oxygen regenerated rubber is more than 50%. The stirring time is 3-6 minutes.
The Mooney viscosity of the low-Mooney micro-oxygen reclaimed rubber is 15-30.
The rubber powder for preparing the low-Mooney micro-oxygen reclaimed rubber comprises full tire rubber powder of a radial tire.
The resin is one or a mixture of more of linear low density polyethylene, high density polyethylene and polypropylene in any proportion.
The vulcanization system is composed of sulfur, zinc oxide, stearic acid and an accelerator CZ, and the reclaimed rubber-based thermoplastic elastomer is prepared through dynamic vulcanization. The dynamic vulcanization process can improve the crosslinking density of the rubber phase, increase the interfacial interaction between two phases and improve the strength of the composite material.
The compatibilizer is a maleic anhydride grafted polyolefin; the rubber phase and the plastic phase have different polarities and poor interfacial adhesion, and a compatibilizer is often used to reduce the interfacial tension of the two phases. The maleic anhydride can generate chemical action with hydroxyl on the surface of the reclaimed rubber, and the compatibility of the polyolefin and the resin matrix is good.
The softening plasticizer is pine tar and coumarone resin, and can promote the uniform dispersion of the reclaimed rubber in the resin and improve the interface bonding force of the plastic phase and the resin phase.
The anti-aging agent is anti-aging agent RD and anti-aging agent 4010 NA.
The preparation method of the micro-nano regenerated gum base thermoplastic elastomer comprises the following production processes:
according to the proportion, firstly, placing the low-Mooney-property micro-oxygen reclaimed rubber and a softening plasticizer in a high-speed mixer to be uniformly mixed in advance to obtain softened low-Mooney-property micro-oxygen reclaimed rubber; placing the resin and the compatibilizer in an internal mixer, controlling the temperature to be 150-180 ℃, and adding the softened low-Mooney micro-oxygen reclaimed rubber after the resin phase is fully melted; after the softened low-Mooney micro-oxygen reclaimed rubber is completely mixed, a vulcanization system and an anti-aging agent are added for vulcanization, and then the mixture is sliced or sent into a granulating agent for granulation for standby. The vulcanization time is 10 min.
The invention is further described below with reference to specific practical examples, but the invention can be implemented in different ways, which are defined and covered by the claims.
Example 1
A method for preparing a micro-nano regenerated gum base thermoplastic elastomer comprises the following steps:
low mooney micro-oxygen reclaimed rubber: 80 parts of a mixture;
resin: 20 parts of (1);
a vulcanization system: 8 parts of a mixture;
compatibilizer: 10 parts of (A);
softening plasticizer: 8 parts of a mixture;
an anti-aging agent: 6 parts.
Firstly, placing the low-Mooney-property micro-oxygen reclaimed rubber and a softening plasticizer in a high-speed mixer to be uniformly mixed in advance to obtain softened low-Mooney-property micro-oxygen reclaimed rubber; then the resin and the compatibilizer are placed in an internal mixer. The temperature of the internal mixer is set to be 150-180 ℃, and the rotating speed of a rotor is 60 rpm/min. Adding softened low-Mooney micro-oxygen reclaimed rubber after the resin phase is fully melted; after the softened low-Mooney micro-oxygen reclaimed rubber is completely mixed, a vulcanization system and an anti-aging agent are added, the mixing time is 10min, and then the mixture is sliced or sent into a granulating agent to be granulated for standby.
Example 2
A preparation method of a low-Mooney micro-oxygen regenerated rubber-based thermoplastic elastomer comprises the following steps:
low mooney micro-oxygen reclaimed rubber: 70 parts of (B);
resin: 30 parts of (1);
a vulcanization system: 6 parts of (1);
compatibilizer: 8 parts of a mixture;
softening plasticizer: 8 parts of a mixture;
an anti-aging agent: 6 parts.
Firstly, placing the low-Mooney-property micro-oxygen reclaimed rubber and a softening plasticizer in a high-speed mixer to be uniformly mixed in advance to obtain softened low-Mooney-property micro-oxygen reclaimed rubber; then the resin and the compatibilizer are placed in an internal mixer. The temperature of the internal mixer is set to be 150-180 ℃, and the rotating speed of a rotor is 60 rpm/min. Adding softened low-Mooney micro-oxygen reclaimed rubber after the resin phase is fully melted; after the softened low-Mooney micro-oxygen reclaimed rubber is completely mixed, a vulcanization system and an anti-aging agent are added, the mixing time is 10min, and then the mixture is sliced or sent into a granulating agent to be granulated for standby.
Example 3
A preparation method of a low-Mooney micro-oxygen regenerated rubber-based thermoplastic elastomer comprises the following steps:
low mooney micro-oxygen reclaimed rubber: 60 parts;
resin: 40 parts of a mixture;
a vulcanization system: 4 parts of a mixture;
compatibilizer: 8 parts of a mixture;
softening plasticizer: 6 parts of (1);
an anti-aging agent: 4 parts.
Firstly, placing the low-Mooney-property micro-oxygen reclaimed rubber and a softening plasticizer in a high-speed mixer to be uniformly mixed in advance to obtain softened low-Mooney-property micro-oxygen reclaimed rubber; then the resin and the compatibilizer are placed in an internal mixer. The temperature of the internal mixer is set to be 150-180 ℃, and the rotating speed of a rotor is 60 rpm/min. Adding softened low-Mooney micro-oxygen reclaimed rubber after the resin phase is fully melted; after the softened low-Mooney micro-oxygen reclaimed rubber is completely mixed, a vulcanization system and an anti-aging agent are added, the mixing time is 10min, and then the mixture is sliced or sent into a granulating agent to be granulated for standby.
Example 4
A preparation method of a low-Mooney micro-oxygen regenerated rubber-based thermoplastic elastomer comprises the following steps:
low mooney micro-oxygen reclaimed rubber: 50 parts of a mixture;
resin: 50 parts of a mixture;
a vulcanization system: 4 parts of a mixture;
compatibilizer: 10 parts of (A);
softening plasticizer: 8 parts of a mixture;
an anti-aging agent: 6 parts.
Firstly, placing the low-Mooney-property micro-oxygen reclaimed rubber and a softening plasticizer in a high-speed mixer to be uniformly mixed in advance to obtain softened low-Mooney-property micro-oxygen reclaimed rubber; then the resin and the compatibilizer are placed in an internal mixer. The temperature of the internal mixer is set to be 150-180 ℃, and the rotating speed of a rotor is 60 rpm/min. Adding softened low-Mooney micro-oxygen reclaimed rubber after the resin phase is fully melted; after the softened low-Mooney micro-oxygen reclaimed rubber is completely mixed, a vulcanization system and an anti-aging agent are added, the mixing time is 10min, and then the mixture is sliced or sent into a granulating agent to be granulated for standby.
Comparative example 1
The preparation method of the conventional Mooney regenerated rubber-based thermoplastic elastomer comprises the following steps:
conventional mooney reclaimed rubber: 70 parts of (B);
resin: 50 parts of a mixture;
a vulcanization system: 4 parts of a mixture;
compatibilizer: 10 parts of (A);
softening plasticizer: 8 parts of a mixture;
an anti-aging agent: 6 parts.
Firstly, putting conventional Mooney reclaimed rubber and a softening plasticizer into a high-speed mixer to be uniformly mixed in advance to obtain softened conventional Mooney reclaimed rubber; then the resin and the compatibilizer are placed in an internal mixer. The temperature of the internal mixer is set to be 150-180 ℃, and the rotating speed of a rotor is 60 rpm/min. Adding softened conventional Mooney reclaimed rubber after the resin phase is fully melted; and after the softened conventional Mooney reclaimed rubber is completely mixed, adding a vulcanization system and an anti-aging agent, mixing for 10min, and then discharging the mixture into a sheet or feeding the mixture into a granulating agent for granulation for later use.
Comparative example 2
The preparation method of the rubber powder-based thermoplastic elastomer comprises the following steps:
rubber powder: 70 parts of (B);
resin: 50 parts of a mixture;
a vulcanization system: 4 parts of a mixture;
compatibilizer: 10 parts of (A);
softening plasticizer: 8 parts of a mixture;
an anti-aging agent: 6 parts.
Firstly, putting the rubber powder and a softening plasticizer in a high-speed mixer to be uniformly mixed in advance to obtain softened rubber powder; then the resin and the compatibilizer are placed in an internal mixer. The temperature of the internal mixer is set to be 150-180 ℃, and the rotating speed of a rotor is 60 rpm/min. Adding softened rubber powder after the resin phase is fully melted; after the softened rubber powder is completely mixed, a vulcanization system and an anti-aging agent are added, the mixing time is 10min, and then the mixture is sliced or sent into a granulating agent to be granulated for standby.
The basic mechanical properties and processability tests are shown in table 1:
TABLE 1 test of mechanical and processing properties of micro-nano reclaimed rubber-based thermoplastic elastomer
The flex fatigue test results are shown in table 1.
Therefore, the micro-nano regenerated rubber base thermoplastic elastomer prepared by the invention has excellent mechanical property, obviously enhanced flex fatigue resistance of the product and good processing property, can consume a large amount of regenerated rubber, relieves the basic national conditions of the current stage and long-term rubber resource shortage of China, realizes the sustainable development of the rubber industry, leads the global rubber industry to realize greenization and high-valued application, and accelerates the realization of the targets of carbon peak reaching and carbon neutralization.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (10)
1. A micro-nano reclaimed rubber-based thermoplastic elastomer is characterized by comprising the following raw material components in parts by weight:
low mooney micro-oxygen reclaimed rubber: 60-80 parts;
resin: 20-40 parts;
a vulcanization system: 4-8 parts;
compatibilizer: 2-10 parts;
softening plasticizer: 2-8 parts;
an anti-aging agent: 1-6 parts;
the low-Mooney-property micro-oxygen regenerated rubber is rubber powder regenerated by a dynamic micro-oxygen desulfurization method, and is specifically obtained by putting the rubber powder into a high-speed stirring and mixing tank, stirring for a certain time at the temperature of 180-240 ℃, and then cooling, wherein the sol content of the low-Mooney-property micro-oxygen regenerated rubber is more than 50%.
2. The micro-nano regenerated gum base thermoplastic elastomer of claim 1, characterized in that: the Mooney viscosity of the low-Mooney micro-oxygen reclaimed rubber is 15-30.
3. The micro-nano regenerated gum base thermoplastic elastomer of claim 1, characterized in that: the rubber powder for preparing the low-Mooney micro-oxygen reclaimed rubber comprises full tire rubber powder of a radial tire.
4. The micro-nano regenerated gum base thermoplastic elastomer of claim 1, characterized in that: the resin is one or a mixture of more of linear low density polyethylene, high density polyethylene and polypropylene in any proportion.
5. The micro-nano regenerated gum base thermoplastic elastomer of claim 1, characterized in that: the vulcanization system is composed of sulfur, zinc oxide, stearic acid and an accelerator CZ, and the reclaimed rubber-based thermoplastic elastomer is prepared through dynamic vulcanization.
6. The micro-nano regenerated gum base thermoplastic elastomer of claim 1, characterized in that: the compatibilizer is a maleic anhydride grafted polyolefin.
7. The micro-nano regenerated gum base thermoplastic elastomer of claim 1, characterized in that: the softening plasticizer is pine tar or coumarone resin.
8. The micro-nano regenerated gum base thermoplastic elastomer of claim 1, characterized in that: the anti-aging agent is anti-aging agent RD and anti-aging agent 4010 NA.
9. The method for preparing a micro-nano regenerated gum base thermoplastic elastomer according to any one of claims 1 to 8, characterized in that: comprises the following processes: according to the proportion, firstly, placing the low-Mooney-property micro-oxygen reclaimed rubber and a softening plasticizer in a high-speed mixer to be uniformly mixed in advance to obtain softened low-Mooney-property micro-oxygen reclaimed rubber; placing the resin and the compatibilizer in an internal mixer, controlling the temperature to be 150-180 ℃, and adding the softened low-Mooney micro-oxygen reclaimed rubber after the resin phase is fully melted; after the softened low-Mooney micro-oxygen reclaimed rubber is completely mixed, a vulcanization system and an anti-aging agent are added for vulcanization, and then the mixture is sliced or sent into a granulating agent for granulation for standby.
10. The method for preparing the micro-nano regenerated gum base thermoplastic elastomer according to claim 9, characterized in that: the vulcanization time is 10 min.
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