阅读说明：本技术 一种回收利用废旧鞋底生产聚氨酯(pu)树脂的方法 (Method for producing Polyurethane (PU) resin by recycling waste soles ) 是由 黄福帅 杜江勇 于 2021-07-17 设计创作，主要内容包括：本发明涉及一种回收利用废旧鞋底生产聚氨酯(PU)树脂的方法,主要流程：废旧聚氨酯(PU)鞋底经除尘,剪切粉碎,装填,搅拌溶解,高温蒸馏,冷凝回收,过滤后得到聚醚/聚酯混合体。再加入某些化学试剂进行反应,并根据性能要求适时补加MDI和TDI中的一种或两种,然后进行搅拌聚合,最后经冷却得到新的聚氨酯树脂。本工艺采用废旧聚氨酯(PU)鞋底为原料即解决了废旧材料的处理问题,又使废弃物循环再生,同时大大降低了新的聚氨酯产品的生产成本,具有良好的经济效益和社会效益。(The invention relates to a method for producing Polyurethane (PU) resin by recycling waste soles, which mainly comprises the following steps: the polyether/polyester mixture is obtained by dedusting, shearing, crushing, filling, stirring, dissolving, distilling at high temperature, condensing, recycling and filtering the waste Polyurethane (PU) sole. Adding some chemical reagents for reaction, replenishing one or two of MDI and TDI according to the performance requirement, stirring for polymerization, and cooling to obtain the new polyurethane resin. The process adopts the waste Polyurethane (PU) sole as the raw material, thereby solving the problem of waste material treatment, recycling the waste, greatly reducing the production cost of new polyurethane products, and having good economic and social benefits.)

1. A method for producing Polyurethane (PU) resin by recycling waste soles is characterized by comprising the following steps:

the waste Polyurethane (PU) sole is subjected to dust removal, shearing and crushing, filling, stirring and dissolving, high-temperature distillation, condensation and recovery, and filtration to obtain a polyether/polyester mixture; adding some chemical reagents for reaction, replenishing one or two of MDI and TDI according to the performance requirement, stirring for polymerization, and cooling to obtain the new polyurethane resin.

2. The method for producing Polyurethane (PU) resin by recycling waste soles according to claim 1 is characterized by comprising the following steps:

(1) removing dust from waste materials: polyurethane (PU) sole, stripping off non-polyurethane part, removing impurity and dust;

(2) shearing and crushing: feeding the sole into a plastic crusher, and shearing and crushing, wherein the particle size is determined according to the aperture size of the reaction kettle and is smaller than the opening diameter of the reaction kettle;

(3) filling: putting the ground sole material into a reaction kettle without drying;

(4) stirring and dissolving: firstly, adding degradants 1 and 2 into a reaction kettle, starting stirring, and raising the temperature to be lower than 100 ℃ for 30-120 min; heating again, keeping the temperature at 120-250 ℃, and stirring for dissolving;

(5) high-temperature distillation: detecting the viscosity of the liquid in the reaction kettle, cooling to 80-200 ℃ after the viscosity meets the requirement, and distilling;

(6) condensation and recovery: the distilled liquid passes through a condensation recovery device to obtain the residual degrading agents 1 and 2;

(7) and (3) filtering: and after the liquid viscosity of the reaction kettle meets the requirement, cooling to below 80 ℃, and filtering to obtain a polyether/polyester mixture.

(8) Polymerization reaction: and injecting the polyether/polyester mixture, MDI/TDI, a catalyst, a chain extender, a foaming agent, a stabilizer and an antioxidant into a sole mold together, and carrying out foaming polymerization to obtain the novel polyurethane insole.

3. The method for recycling the Polyurethane (PU) resin produced by the waste shoe soles according to claim 2, wherein the degradation agent 1 is one of ethylene glycol or propylene glycol when stirring and dissolving; the degradation agent 2 is one of butanediol, diethylene glycol and pentanediol.

4. The method for producing Polyurethane (PU) resin by recycling waste soles according to claim 2, wherein the degradation agent is added in the following amounts (parts by mass): 100 parts of waste materials and 1-10-50 parts of a degrading agent; 2-30-100 parts of a degradation agent.

5. The method for producing Polyurethane (PU) resin by recycling waste shoe soles according to claim 2, wherein the viscosity is 200 to 5500 mPas/25 ℃ when the high temperature distillation is performed.

6. The method for producing Polyurethane (PU) resin by recycling waste shoe soles according to claim 2, wherein the viscosity is 800 to 8600mPa s/25 ℃ during the filtration.

7. The method for recycling the waste shoe soles to produce the Polyurethane (PU) resin according to claim 2, wherein the catalyst is one of tertiary amine catalysts such as triethylene diamine, diethanolamine and the like during the polymerization reaction; the chain extender is alcohol chain extenders such as ethylene glycol, butanediol, glycerol and the like; the foaming agent is water; the stabilizer is silicone oil and modified silicone oil; the antioxidant is poly (dipropylene glycol) phenyl phosphite.

8. The method for producing Polyurethane (PU) resin by recycling waste soles according to claim 2, wherein the polymerization reaction is carried out, and the method is characterized in that the mixture ratio of the components of the materials is (parts by mass): 100 parts of polyether/polyester mixture, 30-60 parts of MDI/TDI-and 0.1-2 parts of catalyst; 0.5-5 parts of chain extender, 1-20 parts of foaming agent and 0.1-1 part of stabilizer; 0.1-2 parts of antioxidant.

Technical Field

The invention belongs to the technical field of waste material recovery, and particularly relates to a method for producing Polyurethane (PU) resin by recycling waste soles.

Background

Polyurethane (PU) has stable chemical properties and excellent physical and mechanical functions due to its special chemical structure-repetitive characteristic group-NH-COO- (carbamate), and thus is widely used in the fields of wearing products, living goods, transportation vehicles, and aerospace. Due to its excellent chemical properties, the applied products cannot be easily handled after the service life is finished. Common treatment methods are incineration and burial; although the two methods can solve the problem in one time, the two methods often have corresponding negative effects.

Therefore, the invention develops and utilizes the waste polyurethane material to produce a new polyurethane product by recycling through a certain method based on the resource recycling application, thereby not only solving the treatment problem of the waste polyurethane material, but also greatly saving energy and creating new use value. And the product obtained by the method can also reduce the production cost of the product, and has good economic and social benefits.

Disclosure of Invention

The invention aims to effectively save cost and efficiently solve the problem of treatment of waste polyurethane. After the process is applied, the environmental problem caused by the waste polyurethane sole can be well solved, and good economic benefit and social benefit can be obtained.

In order to achieve the purpose, the invention adopts the following technical solutions:

the waste Polyurethane (PU) sole is subjected to dust removal, shearing and crushing, filling, stirring and dissolving, high-temperature distillation, condensation and recovery, and filtration to obtain a polyether/polyester mixture; adding some chemical reagents for reaction, replenishing one or two of MDI and TDI according to the performance requirement, stirring for polymerization, and cooling to obtain the new polyurethane resin.

The method for producing the Polyurethane (PU) resin by recycling the waste soles preferably comprises the following process steps:

(1) removing dust from waste materials: polyurethane (PU) sole, stripping off non-polyurethane part, removing impurity and dust;

(2) shearing and crushing: feeding the sole into a plastic crusher, and shearing and crushing, wherein the particle size is determined according to the aperture size of the reaction kettle and is smaller than the opening diameter of the reaction kettle;

(3) filling: putting the ground sole material into a reaction kettle without drying;

(4) stirring and dissolving: firstly, adding the degrading agents 1 and 2 into a reaction kettle, starting stirring, raising the temperature to be lower than 100 ℃, and keeping the time for 30-120 min; heating again, keeping the temperature at 120-250 ℃, and stirring for dissolving;

(5) high-temperature distillation: detecting the viscosity of the liquid in the reaction kettle, cooling to 80-200 ℃ after the viscosity meets the requirement, and distilling;

(6) condensation and recovery: the distilled liquid passes through a condensation recovery device to obtain the residual degrading agents 1 and 2;

(7) and (3) filtering: and after the liquid viscosity of the reaction kettle meets the requirement, cooling to below 80 ℃, and filtering to obtain a polyether/polyester mixture.

(8) Polymerization reaction: and (2) injecting 100 parts of polyether/polyester mixture, MDI/TDI, a catalyst, a chain extender, a foaming agent, a stabilizer and an antioxidant into a sole mold together, and carrying out foaming polymerization to obtain the novel polyurethane insole.

The method for producing the Polyurethane (PU) resin by recycling the waste soles preferably has the viscosity of 200-5500 mPa & s/25 ℃.

The method for producing the Polyurethane (PU) resin by recycling the waste soles preferably has the viscosity of 800-8600 mPa & s/25 ℃.

In the method for producing the Polyurethane (PU) resin by recycling the waste soles, preferably, the catalyst is one of tertiary amine catalysts such as triethylene diamine, diethanolamine and the like; the chain extender is alcohol chain extenders such as ethylene glycol, butanediol, glycerol and the like; the foaming agent is water; the stabilizer is silicone oil and modified silicone oil; the antioxidant is poly (dipropylene glycol) phenyl phosphite.

The method for producing the Polyurethane (PU) resin by recycling the waste soles preferably comprises the following components in parts by mass: 100 parts of polyether/polyester mixture, 30-60 parts of MDI/TDI-and 0.1-2 parts of catalyst; 0.5-5 parts of chain extender, 1-20 parts of foaming agent and 0.1-1 part of stabilizer; 0.1-2 parts of antioxidant.

Drawings

FIG. 1 is a flow chart of the method of the present invention;

Detailed Description

In order to make the aforementioned and other objects, features and advantages of the present invention more apparent, embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

The basic idea of the method of the invention is as follows: the waste Polyurethane (PU) sole is subjected to dust removal, shearing and crushing, filling, stirring and dissolving, high-temperature distillation, condensation and recovery, and filtration to obtain a polyether/polyester mixture; adding some chemical reagents for reaction, replenishing one or two of MDI and TDI according to the performance requirement, stirring for polymerization, and cooling to obtain the new polyurethane resin. Such manufacturing techniques and processes are readily implemented by those of ordinary skill in the art. The method specifically comprises the following steps:

(1) removing dust from waste materials: polyurethane (PU) sole, stripping off non-polyurethane part, removing impurity and dust;

(2) shearing and crushing: feeding the sole into a plastic crusher, and shearing and crushing, wherein the particle size is determined according to the aperture size of the reaction kettle and is smaller than the opening diameter of the reaction kettle;

(3) filling: putting 100 parts of the sole crushed material into a reaction kettle without drying;

(4) stirring and dissolving: firstly, adding 1 (ethylene glycol or propylene glycol) as a degradation agent, 10-50 parts and 30-100 parts of 2 (butanediol, diethylene glycol and pentanediol) into a reaction kettle, starting stirring, heating to a temperature lower than 100 ℃, and keeping the temperature for 30-120 min; heating again, keeping the temperature at 120-250 ℃, and stirring for dissolving;

(5) high-temperature distillation: detecting the viscosity of the liquid in the reaction kettle, cooling to 80-200 ℃ after the viscosity reaches 200-5500 mPa & s/25 ℃, and distilling;

(6) condensation and recovery: the distilled liquid passes through a condensation recovery device to obtain residual degradation agent 1 (one of ethylene glycol or propylene glycol) and residual degradation agent 2 (one of butanediol, diethylene glycol and pentanediol);

(7) and (3) filtering: and after the liquid viscosity of the reaction kettle is 800-8600 mPa & s/25 ℃, cooling to below 80 ℃, and filtering to obtain a polyether/polyester mixture.

(8) Polymerization reaction: 100 parts of polyether/polyester mixture, 30-60 parts of MDI/TDI, 0.1-2 parts of catalyst (one of tertiary amine catalysts such as triethylene diamine, diethanol amine and the like), 0.5-5 parts of chain extender (alcohols such as ethylene glycol, butanediol, glycerol and the like), 1-20 parts of foaming agent (water), 0.1-1 part of stabilizer (silicone oil and modified silicone oil) and 0.1-2 parts of antioxidant (poly (dipropylene glycol) phenyl phosphite ester) are injected into a sole mold together for foaming polymerization, and the novel polyurethane insole is obtained.

Detailed description of the preferred embodiments

(1) Removing dust from waste materials: polyurethane (PU) sole, stripping off non-polyurethane part, removing impurity and dust;

(2) shearing and crushing: feeding the sole into a plastic crusher, and shearing and crushing to obtain a product with the particle size of 35cm smaller than the opening diameter of the reaction kettle;

(3) filling: 100kg of ground sole materials are put into a reaction kettle without being dried, and the diameter of the opening of the reaction kettle is 40 cm;

(4) stirring and dissolving: firstly, adding 20kg of ethylene glycol and 65kg of butanediol into a reaction kettle, starting stirring, heating to 80 ℃, and keeping the temperature for 60 min; then heating, keeping the temperature at 185 ℃, stirring and dissolving;

(5) high-temperature distillation: detecting the viscosity of the liquid in the reaction kettle, cooling to 140 ℃ after the viscosity reaches 1100mPa & s/25 ℃, and distilling;

(6) condensation and recovery: the distilled liquid passes through a condensation recovery device to obtain the residual ethylene glycol and butanediol;

(7) and (3) filtering: and after the liquid viscosity of the reaction kettle is 3000 mPa.s/25 ℃, cooling to 60 ℃, and filtering to obtain a polyether/polyester mixture.

(8) Polymerization reaction: 50kg of polyether/polyester mixture, 20kg of MDI/TDI, 0.5kg of catalyst triethylene diamine, 2kg of chain extender glycerol, 5kg of foaming agent water, 0.25kg of stabilizer silicone oil and 1kg of antioxidant poly (dipropylene glycol) phenyl phosphite ester are injected into a sole mold together for foaming polymerization to obtain the novel polyurethane insole.

Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.