阅读说明：本技术 一种利用油污塑料制备再生胶的方法 (Method for preparing reclaimed rubber by using oil-contaminated plastic ) 是由 张俊锋 于国明 刘�东 张晓飞 刘德华 崔志峰 彭双华 于 2019-10-30 设计创作，主要内容包括：本发明公开了一种利用油污塑料制备再生胶的方法,属于材料再生技术领域。在制备过程中,先将熔盐加热熔融后加入电解槽中,再加入纳米二氧化钛、调节剂及废旧聚丙烯塑料,保温电解后,冷却,粉碎,得电解碎料；将所得电解碎料用水洗涤后,干燥,即得再生胶粉；其中调节剂为氧化石墨烯包覆引发剂,分散剂,和苯乙烯构成；氧化石墨烯包覆引发剂制备时,将引发剂和氧化石墨烯混合,并加入无水乙醇,混合后超声分散,再经减压蒸馏,干燥,球磨,得氧化石墨烯包覆引发剂。本发明制备过程可有效解决再生胶粉和废弃塑料的界面粘结性差引起的延展性下降的问题。(The invention discloses a method for preparing reclaimed rubber by using oil-contaminated plastics, belonging to the technical field of material regeneration. In the preparation process, firstly, the fused salt is heated and melted and then is added into an electrolytic cell, and then the nano titanium dioxide, the regulator and the waste polypropylene plastic are added, after heat preservation and electrolysis, the mixture is cooled and crushed to obtain crushed electrolytic material; washing the obtained electrolytic crushed materials with water, and drying to obtain regenerated rubber powder; wherein the regulator is composed of a graphene oxide coated initiator, a dispersant and styrene; when the graphene oxide coated initiator is prepared, the initiator and graphene oxide are mixed, absolute ethyl alcohol is added, ultrasonic dispersion is carried out after mixing, and then reduced pressure distillation, drying and ball milling are carried out to obtain the graphene oxide coated initiator. The preparation process can effectively solve the problem of ductility reduction caused by poor interface cohesiveness of the reclaimed rubber powder and the waste plastic.)

1. A method for preparing reclaimed rubber by using oil-contaminated plastics is characterized by comprising the following specific preparation steps:

(1) taking raw materials: taking a regulator, waste polypropylene plastic with oil stain content of 1-10%, nano titanium dioxide, waste tire rubber powder and molten salt;

(2) electrolysis: firstly, heating and melting molten salt, adding the molten salt into an electrolytic bath, adding nano titanium dioxide, a regulator and waste polypropylene plastics, carrying out heat preservation electrolysis, cooling and crushing to obtain an electrolyzed crushed material;

(3) removing impurities: and washing the obtained electrolytic crushed materials with water, and drying to obtain the regenerated rubber powder.

2. The method for preparing reclaimed rubber by using oil-contaminated plastic according to claim 1, wherein the regulator is prepared from the following raw materials in parts by weight: 5-10 parts of graphene oxide-coated initiator, 5-10 parts of dispersant and 100-120 parts of styrene.

3. The method for preparing reclaimed rubber by using oil-contaminated plastic according to claim 2, wherein in the graphene oxide-coated initiator, the mass ratio of the initiator to the graphene oxide is 1: 3-1: 10.

4. the method for preparing reclaimed rubber by using oil-contaminated plastic according to claim 3, wherein the preparation method of the graphene oxide coated initiator comprises the following steps:

according to the mass ratio of 1: 3-1: 10, mixing an initiator and graphene oxide, adding absolute ethyl alcohol with the mass being 10-20 times that of the graphene oxide, mixing, performing ultrasonic dispersion, performing reduced pressure distillation, drying, and performing ball milling to obtain the graphene oxide coated initiator.

5. The method for preparing reclaimed rubber by using oil-contaminated plastic according to claim 4, wherein the initiator is any one or more of dibenzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile.

6. The method for preparing reclaimed rubber by using oil-contaminated plastic according to claim 4, wherein the ball milling is as follows: according to the ball material mass ratio of 1: 20-1: adding 50 zirconia ball grinding beads, and carrying out ball milling and mixing for 1-5 h under the conditions that the rotation speed is 200-300 r/min and the revolution speed is 300-500 r/min.

7. The method for preparing reclaimed rubber by using oil-contaminated plastic according to claim 2, wherein the dispersing agent is any one or more of calcium stearate, magnesium stearate, zinc stearate, copper stearate, barium stearate, polyethylene glycol 200 and polyethylene glycol 400.

8. The method for preparing reclaimed rubber by using oil-contaminated plastic according to claim 1, wherein the molten salt is prepared from the following raw materials in parts by weight: 53 parts of potassium nitrate, 40 parts of sodium nitrite and 7 parts of sodium nitrate.

9. The method for preparing reclaimed rubber by using oil-contaminated plastic according to claim 1, wherein the heat-preservation electrolysis is as follows: and (3) taking a graphite rod as an electrode, and carrying out heat preservation electrolysis for 2-4 h under the conditions that the electrolysis temperature is 140-150 ℃ and the electrolysis voltage is 48-56V.

10. The method for preparing reclaimed rubber by using oil-contaminated plastic according to claim 1, wherein the raw materials are as follows: according to the weight parts, 5-10 parts of a regulator, 100-120 parts of waste polypropylene plastic with oil stain content of 1-10%, 4-8 parts of nano titanium dioxide, 100-150 parts of waste tire rubber powder and 500-1500 parts of molten salt are taken in sequence.

Technical Field

The invention discloses a method for preparing reclaimed rubber by using oil-contaminated plastics, belonging to the technical field of material regeneration.

Background

The waste rubber and plastic materials are recycled, waste materials are changed into valuable materials, the environmental pressure is relieved, certain environmental benefits and economic benefits are achieved, the application prospect is wide, and the development potential is huge.

The blending of rubber and plastic is a blending material which combines the dual characteristics of rubber and plastic by mixing the rubber and the plastic through a specific processing means and method. The two phases in the blend still maintain the respective characteristics, no new substances are generated after blending, and only the interfaces of the two phases form combination, which shows that the performances are complementary with each other. However, because the vulcanization temperature of rubber and the processing temperature of plastic are different, the rubber and the plastic have compatibility problems, so how to perfectly blend the rubber and the plastic and form good combination at the interface of two phases shows that the mutual performance complementation is the key point of the recycling of the blending of the rubber and the plastic.

At present, research researchers research the performance of a rubber-thermoplastic mixture formed by mixing waste tire rubber and waste polypropylene plastic, mainly research the influence of the addition amount of the regenerated rubber on the performance of the blend, and research results show that the mechanical performance of the mixture is basically unchanged when the content of the regenerated rubber reaches 30 percent, and the mechanical performance is obviously changed when the regenerated rubber is continuously added; when the addition amount is 40% or more, brittle fracture of the blend is liable to occur under impact load; as can be seen from the light microscope, when the amount of the reclaimed rubber in the mixture reaches 60%, the micro morphology of the reclaimed rubber is not changed, the reclaimed rubber is distributed on the continuous phase interface of the polypropylene plastic, and when the doping amount reaches 70%, the dispersed interface of the reclaimed rubber is increased in size and becomes a continuous phase. Generally speaking, when the content of the reclaimed rubber is 50-70%, the physical properties of the blend are optimal, but the performances such as viscosity and ductility are not ideal, mainly because the reclaimed rubber and the waste plastic are poor in viscosity at a phase interface and cannot be well combined to achieve the purpose of load transfer. Therefore, how to improve the interfacial adhesion between the recycled rubber and the plastic and make the product have good ductility is one of the technical problems to be solved urgently in the industry.

Disclosure of Invention

The invention mainly solves the technical problems that: aiming at the defects of poor ductility and insufficient mechanical properties of the recycled material caused by poor cohesiveness of the traditional recycled rubber-plastic material at the phase interface of the recycled rubber and the waste plastic, the method for preparing the recycled rubber by using the oil-contaminated plastic is provided.

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

a method for preparing reclaimed rubber by using oil-contaminated plastics comprises the following specific preparation steps:

sequentially taking 5-10 parts by weight of a regulator, 100-120 parts by weight of waste polypropylene plastic with oil stain content of 1-10%, 4-8 parts by weight of nano titanium dioxide, 100-150 parts by weight of waste tire rubber powder and 500-1500 parts by weight of molten salt, heating and melting the molten salt, adding the molten salt into an electrolytic cell, adding the nano titanium dioxide, the regulator and the waste polypropylene plastic, preserving heat, electrolyzing, cooling and crushing to obtain an electrolyzed crushed material;

and washing the obtained electrolytic crushed materials with water, and drying to obtain the regenerated rubber powder.

The beneficial technical effects are as follows: the technical scheme of the invention adopts the molten salt as the electrolyte to electrolyze the greasy dirt plastic and the rubber powder which need to be recovered, and the molten salt is present to form a molten eutectic with the non-conductive plastic and the rubber powder, so that the current in the electrolytic process acts on the rubber powder and the plastic, the disulfide bond in the rubber powder is broken, and the unstable part in the plastic is converted into a defect structure; after the electrolysis is finished, the molten salt can be dissolved in water and smoothly separated from the electrolyzed plastic and rubber powder, so that the subsequent treatment cannot be influenced;

in addition, the technical scheme of the invention introduces the nano titanium dioxide, and the nano titanium dioxide is added into the system before electrolysis, so that the nano titanium dioxide can further catalyze the degradation function of current on the unstable plastic part, and the unstable plastic part is converted into an active defect structure, thereby being beneficial to improving the reaction activity of the defect structure in the subsequent treatment process; moreover, the unique surface effect, volume effect and quantum size effect of the nano titanium dioxide can realize good modification on the defect part; thereby improving the mechanical property of the regenerated product;

the regulator is composed of the following raw materials in parts by weight: 5-10 parts of graphene oxide-coated initiator, 5-10 parts of dispersant and 100-120 parts of styrene.

In the graphene oxide-coated initiator, the mass ratio of the initiator to the graphene oxide is 1: 3-1: 10.

the preparation method of the graphene oxide coated initiator comprises the following steps:

according to the mass ratio of 1: 3-1: 10, mixing an initiator and graphene oxide, adding absolute ethyl alcohol with the mass being 10-20 times that of the graphene oxide, mixing, performing ultrasonic dispersion, performing reduced pressure distillation, drying, and performing ball milling to obtain the graphene oxide coated initiator.

The beneficial technical effects are as follows: according to the technical scheme, the initiator and the monomer styrene coated by the graphene oxide are introduced, the graphene oxide structure is provided with a hydrophobic region (conjugate region) and a hydrophilic region (carboxyl and hydroxyl), the hydrophobic initiator can be uniformly coated on an interlayer hydrophobic region by the graphene oxide under the action of ultrasonic, the structure is stable under the normal temperature condition and cannot play the activity of the initiator, but the internal initiator is gradually released along with the increase of the processing temperature in the electrolytic process, so that the styrene monomer and plastic defect parts are subjected to free radical polymerization, the plastic defect structure is reduced, the graphene oxide and the nano titanium dioxide are limited in a resin molecular chain structure, and the new molecular chain at the defect part is connected, the permanent physical entanglement with a rubber molecular chain can be realized, and the mechanical performance of the product is improved due to the formation of the physical entanglement, meanwhile, the interface bonding property of the plastic and the rubber is obviously improved, so that the ductility of the product is improved; moreover, the coating of the graphene oxide and the slow release of the initiator can ensure that the polymerization reaction is slow and mild, so that the initiator can be ensured to play a role in increasing molecular chains, the rubber and plastic molecular chains can form permanent physical entanglement, and the defects of the molecular chains caused by violent reaction can be avoided.

The initiator is any one or more of dibenzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile.

The ball milling is as follows: according to the ball material mass ratio of 1: 20-1: adding 50 zirconia ball grinding beads, and carrying out ball milling and mixing for 1-5 h under the conditions that the rotation speed is 200-300 r/min and the revolution speed is 300-500 r/min.

The dispersing agent is one or more of calcium stearate, magnesium stearate, zinc stearate, copper stearate, barium stearate, polyethylene glycol 200 and polyethylene glycol 400.

The molten salt is: molten salt having a melting point of less than 150 ℃.

The molten salt is prepared from the following raw materials in parts by weight: 53 parts of potassium nitrate, 40 parts of sodium nitrite and 7 parts of sodium nitrate.

The heat preservation electrolysis comprises the following steps: and (3) taking a graphite rod as an electrode, and carrying out heat preservation electrolysis for 2-4 h under the conditions that the electrolysis temperature is 140-150 ℃ and the electrolysis voltage is 48-56V.

Detailed Description

According to the mass ratio of 1: 3-1: 10, mixing an initiator and graphene oxide, adding absolute ethyl alcohol with the mass being 10-20 times that of the graphene oxide, mixing, performing ultrasonic dispersion for 45-60 min under the condition that the ultrasonic frequency is 45-60 kHz to obtain dispersion liquid, transferring the dispersion liquid into a rotary evaporator, performing reduced pressure distillation for 10-30 min under the conditions that the pressure is 400-500 mmHg and the temperature is 75-85 ℃ to obtain a concentrate, transferring the concentrate into a vacuum drying oven, and performing vacuum drying under the conditions that the temperature is 105-110 ℃ and the pressure is 60-80 Pa to obtain a dried material; and then transferring the dried material into a ball mill, wherein the mass ratio of the dried material to the ball material is 1: 20-1: adding zirconia ball grinding beads into the mixture 50, and performing ball milling and mixing for 1-5 hours under the conditions that the rotation speed is 200-300 r/min and the revolution speed is 300-500 r/min to obtain a graphene oxide coated initiator; the initiator is any one or more of dibenzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile;

according to the weight parts, sequentially taking 5-10 parts of graphene oxide coated initiator, 5-10 parts of dispersing agent and 100-120 parts of styrene, stirring and mixing for 1-3 hours at the rotating speed of 300-800 r/min by using a stirrer, and discharging to obtain a regulator; the dispersing agent is any one or more of calcium stearate, magnesium stearate, zinc stearate, copper stearate, barium stearate, polyethylene glycol 200 and polyethylene glycol 400;

according to the weight parts, sequentially taking 5-10 parts of a regulator, 100-120 parts of waste polypropylene plastic with oil stain content of 1-10%, 4-8 parts of nano titanium dioxide, 100-150 parts of waste tire rubber powder and 500-1500 parts of molten salt, heating and melting the molten salt, adding the molten salt into an electrolytic cell, adding the nano titanium dioxide, the regulator and the waste polypropylene plastic, taking a graphite rod as an electrode, carrying out heat preservation electrolysis for 2-4 h under the conditions that the electrolysis temperature is 140-150 ℃ and the electrolysis voltage is 48-56V, cooling and crushing to obtain electrolyzed crushed materials;

the molten salt is molten salt with the melting point lower than 150 ℃; the molten salt is prepared from the following raw materials in parts by weight: 53 parts of potassium nitrate, 40 parts of sodium nitrite and 7 parts of sodium nitrate;

and washing the obtained electrolytic crushed materials with water, and drying to obtain the regenerated rubber powder.