阅读说明：本技术 一种废弃油脂基聚酯多元醇的环氧化制备方法 (Epoxidation preparation method of waste grease-based polyester polyol ) 是由 孙运强 韩志成 于 2020-06-09 设计创作，主要内容包括：本发明公开了一种废弃油脂基聚酯多元醇的环氧化制备方法,首先对废弃油脂进行预处理,除去杂质,然后经环氧化法得到环氧废弃油脂,与合成的低分子量植物基多元醇反应即可得到高分子量废弃油脂基多元醇。本发明的主要特点在于采用废弃油脂为原料,通过环氧化法制备废弃油脂基聚酯多元醇,不仅可以降低生产成本,更重要的是防止废弃油脂随意排放对环境的造成污染,为废弃油脂的再生利用提供新途径。本发明原料廉价易得、生产工艺简单,所得多元醇的羟基、酸值和环氧酯可调,所得多元醇的生物降解性良好,可在自然环境中自行降解,可广泛应用于可降解聚氨酯材料的制备,具有广阔的市场前景。(The invention discloses an epoxidation preparation method of waste grease-based polyester polyol. The method is mainly characterized in that the waste grease is used as a raw material, and the waste grease-based polyester polyol is prepared by an epoxidation method, so that the production cost can be reduced, more importantly, the pollution to the environment caused by random discharge of the waste grease is prevented, and a new way is provided for the recycling of the waste grease. The raw materials are cheap and easy to obtain, the production process is simple, the hydroxyl group, the acid value and the epoxy ester of the obtained polyol are adjustable, the biodegradability of the obtained polyol is good, the polyol can be automatically degraded in natural environment, the polyol can be widely applied to the preparation of degradable polyurethane materials, and the polyol has wide market prospect.)

1. An epoxidation preparation method of waste grease-based polyester polyol is characterized in that: the pretreatment of the waste grease comprises the following specific operation steps:

heating the waste oil to 60-80 ℃, filtering by using a sand core to remove solid impurities such as soil, food residues and the like in the waste oil, then removing water and volatile components in the oil in a heating and reduced pressure distillation mode at 30-60 ℃ until no bubbles are generated, finally adding acid clay for adsorption and decoloration, filtering to obtain treated oil, and pouring the treated oil into a bottle for later use.

2. An epoxidation preparation method of waste grease-based polyester polyol is characterized in that: the synthesis of the vegetable-based polyol comprises the following specific operation steps:

(1) synthesis of epoxy waste grease

Uniformly mixing organic acid, oxidant and catalyst according to the mass ratio of 1-5: 2-10: 0.1-2 to obtain a mixed reagent A, uniformly mixing the pretreated waste oil and phase transfer catalyst according to the mass ratio of 100: 1.5-5, and then placing the mixture into a water bath at 30-50 ℃ to stir and heat to obtain a mixed reagent B. Slowly dripping the mixed reagent A into the mixed reagent B at the temperature of 30-50 ℃, raising the temperature of the system to 50-90 ℃ after dripping, reacting for 0.5-8 hours, washing a product to be neutral after the reaction is finished, transferring the product to a rotary evaporator, and performing vacuum rotary evaporation at the temperature of 60-90 ℃ until no bubbles exist, thus obtaining the epoxy waste grease.

(2) Synthesis of low molecular weight vegetable-based polyol:

uniformly mixing the epoxy waste grease, the organic acid and the catalyst in the step (1) according to the mass ratio of 100: 1-5: 0.1-2, and reacting for 0.5-4 hours under the conditions of reflux condensation and nitrogen protection at 30-90 ℃. And after the reaction is finished, carrying out vacuum filtration at 80-140 ℃ until no bubbles exist, thus obtaining the low-molecular-weight plant-based polyol.

(3) Synthesis of high molecular weight plant-based polyol:

uniformly mixing the epoxy waste grease obtained in the step (1), the low-molecular-weight plant-based polyol in the step (2) and a catalyst according to a mass ratio of 100: 70-120: 0.1-2, reacting for 0.5-4 hours under the conditions of reflux condensation and nitrogen protection at 40-110 ℃, carrying out addition polymerization, repeatedly washing the obtained product with distilled water of 25 ℃ for multiple times after the reaction is finished, and carrying out vacuum dehydration to obtain the high-molecular-weight plant-based polyol.

3. The method for producing a waste oil-and-fat-based polyester polyol according to claim 2, wherein: the organic acid in the step (1) is one or a combination of formic acid, acetic acid, propionic acid or benzoic acid.

4. The method for producing a waste oil-and-fat-based polyester polyol according to claim 2, wherein: in the step (1), the oxidant is one or a combination of hydrogen peroxide, ozone and potassium permanganate.

5. The method for producing a waste oil-and-fat-based polyester polyol according to claim 2, wherein: the catalyst in the step (1) is one or a combination of more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.

6. The method for producing a waste oil-and-fat-based polyester polyol according to claim 2, wherein: the phase transfer catalyst in the step (1) is one or a combination of more of chain polyethylene glycol, tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride and cyclodextrin.

7. The method for producing a waste oil-and-fat-based polyester polyol according to claim 1, wherein: the waste oil comprises edible oil and swill oil which are not allowed to be used and are generated in the post-treatment process of catering and food processing factories, overdue oil and the like generated in the oil processing process.

The technical field is as follows:

the invention relates to the technical field of organic chemical synthesis, in particular to an epoxidation preparation method of waste grease-based polyester polyol.

Background art:

the oligomer polyether and polyester polyol are very important chemical intermediates and are widely applied to polyurethane synthesis. With the increasing demand of people on polyurethane products, the use amount of oligomer polyether and polyester polyol is also increased. In the past, most of main raw materials are derived from petrochemicals, so that the energy consumption is high, the pollution is heavy, and the dependence on the petrochemicals is strong. Petrochemicals are a non-renewable resource, with limited reserves and are rapidly decreasing. With the increasing exhaustion of petrochemical resources and the rising price of petroleum, it has become a necessary social trend to find a cheap, efficient and environmentally friendly renewable alternative raw material to prepare green polyol materials.

In recent years, the replacement of petrochemical resources by renewable resources has become a research hotspot in countries around the world. The yield of the vegetable oil is in the top of the world in China, and the vegetable oil has rich vegetable oil resources. The scientific researchers epoxidize various vegetable oils to obtain the epoxy vegetable oil. The epoxy vegetable oil has low volatility, good compatibility with resin, light resistance, good electrical property and good flexibility, and can improve the leakage resistance, milk extraction resistance and migration resistance of the high molecular polymer. In addition, the epoxy vegetable oil can be further opened under the action of a catalyst to form a hydroxyl compound, and the epoxy vegetable oil can be used for preparing polyol materials with different molecular weights and hydroxyl values and the like.

At present, millions of tons of waste vegetable oil are generated at home and abroad every year, and the waste vegetable oil is generally used as animal feed, but compared with other cheaper animal feed, the waste vegetable oil is not economical in processing and utilization. The environmental pollution, especially the illegal discharge, of the waste vegetable oil distributed in daily life and industrial production by people not only pollutes the environment, but also is a very large energy waste. Most of fatty acids contained in vegetable oil are unsaturated fatty acids, the position of double bonds is usually on a carbon atom at 10 or 9 position, the polymerization activity of the double bonds is low and is mostly non-conjugated double bonds, the chemical properties of most of vegetable oil are similar, the chemical modification mechanism is basically consistent, various modifications can be carried out on active groups such as ester groups, ester group alpha carbon, double bonds and the like on the molecular chain of the vegetable oil, and common modification methods comprise alcoholysis, epoxidation, ring opening of epoxy groups, esterification, double bond isomerization and the like. Wherein, the epoxidation method is superior to the simple production process, and the production process is easy to operate and is widely concerned.

The invention content is as follows:

the invention aims to solve the technical problem of providing a polyester polyol which is environment-friendly, simple in process, stable in performance and degradable, and is used for preparing degradable polyurethane.

1. The invention provides a pretreatment method of waste grease, which comprises the following specific operation steps:

heating the waste oil to 60-80 ℃, filtering by using a sand core, removing solid impurities such as soil, food residues and the like in the waste oil, then removing water and volatile components in the oil in a heating and reduced pressure distillation mode at 30-60 ℃ until no bubbles are generated, finally adding acid clay for adsorption and decoloration, filtering to obtain treated oil, and pouring the treated oil into a bottle for later use.

2. The invention provides an epoxidation synthesis method of plant-based polyol, which comprises the following specific operation steps:

(1) synthesis of epoxy waste grease

Uniformly mixing organic acid, oxidant and catalyst according to the mass ratio of 1-5: 2-10: 0.1-2 to obtain a mixed reagent A, uniformly mixing the pretreated waste oil and phase transfer catalyst according to the mass ratio of 100: 1.5-5, and then placing the mixture into a water bath at 30-50 ℃ to stir and heat to obtain a mixed reagent B. Slowly dripping the mixed reagent A into the mixed reagent B at the temperature of 30-50 ℃, raising the temperature of the system to 50-90 ℃ after dripping, reacting for 0.5-8 hours, washing a product to be neutral after the reaction is finished, transferring the product to a rotary evaporator, and performing vacuum rotary evaporation at the temperature of 60-90 ℃ until no bubbles exist, thus obtaining the epoxy waste grease.

(2) Synthesis of low molecular weight vegetable-based polyol:

uniformly mixing the epoxy waste grease, the organic acid and the catalyst in the step (1) according to the mass ratio of 100: 1-5: 0.1-2, and reacting for 0.5-4 hours under the conditions of reflux condensation and nitrogen protection at 30-90 ℃. And after the reaction is finished, carrying out vacuum filtration at 80-140 ℃ until no bubbles exist, thus obtaining the low-molecular-weight plant-based polyol.

(3) Synthesis of high molecular weight plant-based polyol:

uniformly mixing the epoxy waste grease obtained in the step (1), the low-molecular-weight plant-based polyol and the catalyst in the step (2) according to a certain mass ratio of 100: 70-120, reacting for 0.5-4 hours under the conditions of reflux condensation and nitrogen protection at 40-110 ℃, carrying out addition polymerization, repeatedly washing the obtained product with 25 ℃ distilled water for multiple times after the reaction is finished, and carrying out vacuum dehydration to obtain the high-molecular-weight plant-based polyol

3. The method comprises the following steps:

preferably, the organic acid in the step (1) is one or a combination of several of formic acid, acetic acid, propionic acid and benzoic acid;

preferably, the oxidant in the step (1) is one or a combination of hydrogen peroxide, ozone and potassium permanganate;

preferably, the catalyst in the step (1) is one or a combination of more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid;

preferably, the phase transfer catalyst in the step (1) is one or a combination of several of chain polyethylene glycol, tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride and cyclodextrin;

4. the invention provides an epoxidation preparation method of waste grease-based polyester polyol. The method for producing a waste oil-and-fat-based polyester polyol according to claim 1, comprising the steps of: the waste oil comprises edible oil and swill oil which are not allowed to be used and are generated in the post-treatment process of catering and food processing factories, overdue oil and the like generated in the oil processing process.

Compared with the background art, the invention has the advantages that: (1) the waste grease is adopted as a raw material, and the waste grease-based polyester polyol is prepared by an epoxidation method, so that waste can be changed into valuable, and the production cost is reduced; (2) the pollution to the environment caused by random discharge of the waste grease can be prevented, and a new way is provided for the recycling of the waste grease; (3) the production process is simple, the hydroxyl group, the acid value and the epoxy ester of the obtained polyol are adjustable, the biodegradability of the obtained polyol is good, and the polyol can be automatically degraded in natural environment; (4) can be widely applied to the preparation of degradable polyurethane materials and has wide market prospect.

The specific implementation mode is as follows:

the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a process are given, but the scope of the present invention is not limited to the following embodiments.

Example 1.

1. The invention provides a pretreatment method of waste grease, which comprises the following specific operation steps:

heating the waste grease to 60 ℃, filtering by using a sand core, removing solid impurities such as soil, food residues and the like in the waste grease, then removing water and volatile components in the grease by adopting a heating and reduced pressure distillation mode under the condition of 30 ℃ until no bubbles are generated, finally adding acid clay for adsorption and decoloration, filtering to obtain the treated grease, and pouring the treated grease into a bottle for later use.

2. The invention provides an epoxidation synthesis method of plant-based polyol, which comprises the following specific operation steps:

(1) synthesis of epoxy waste grease

Uniformly mixing formic acid, hydrogen peroxide and sulfuric acid according to the mass ratio of 1: 2: 0.1 to obtain a mixed reagent A, uniformly mixing the pretreated waste oil and chain polyethylene glycol according to the mass ratio of 100: 1.5, and then putting the mixture into a water bath at 30 ℃ to stir and heat to obtain a mixed reagent B. Slowly dripping the mixed reagent A into the mixed reagent B at the temperature of 30 ℃, raising the temperature of the system to 50 ℃ after dripping, reacting for 4 hours, washing a product to be neutral after the reaction is finished, transferring the product to a rotary evaporator, and performing vacuum rotary evaporation at the temperature of 60 ℃ until no bubbles exist, thus obtaining the epoxy waste grease.

(2) Synthesis of low molecular weight vegetable-based polyol:

uniformly mixing the epoxy waste grease, formic acid and sulfuric acid in the step (1) according to the mass ratio of 100: 1: 0.1, and reacting for 2 hours under the conditions of reflux condensation and nitrogen protection at 50 ℃. And after the reaction is finished, carrying out vacuum filtration at 8 ℃ until no bubbles exist, thus obtaining the low-molecular-weight plant-based polyol.

(3) Synthesis of high molecular weight plant-based polyol:

uniformly mixing the epoxy waste grease obtained in the step (1), the low-molecular-weight plant-based polyol and sulfuric acid in the step (2) according to a certain mass ratio of 100: 70: 0.5, reacting for 4 hours under the conditions of reflux condensation and nitrogen protection at 60 ℃, carrying out addition polymerization, repeatedly washing the obtained product with distilled water of 25 ℃ for multiple times after the reaction is finished, and carrying out vacuum dehydration to obtain the high-molecular-weight plant-based polyol.

Example 2.

1. The invention provides a pretreatment method of waste grease, which comprises the following specific operation steps:

heating the waste grease to 80 ℃, filtering by using a sand core, removing solid impurities such as soil, food residues and the like in the waste grease, then removing water and volatile components in the grease by adopting a heating and reduced pressure distillation mode under the condition of 40 ℃ until no bubbles are generated, finally adding acid clay for adsorption and decoloration, filtering to obtain the treated grease, and pouring the treated grease into a bottle for later use.

2. The invention provides an epoxidation synthesis method of plant-based polyol, which comprises the following specific operation steps:

(1) synthesis of epoxy waste grease

Uniformly mixing formic acid, hydrogen peroxide and phosphoric acid according to the mass ratio of 3: 4: 0.3 to obtain a mixed reagent A, uniformly mixing the pretreated waste oil and tetrabutylammonium bromide according to the mass ratio of 100: 2, and then putting the mixture into a water bath at 30-50 ℃ to stir and heat to obtain a mixed reagent B. Slowly dripping the mixed reagent A into the mixed reagent B at 40 ℃, raising the temperature of the system to 70 ℃ after dripping is finished, reacting for 3 hours, washing a product to be neutral after the reaction is finished, transferring the product to a rotary evaporator, and performing vacuum rotary evaporation at 65 ℃ until no bubbles exist, thus obtaining the epoxy waste grease.

(2) Synthesis of low molecular weight vegetable-based polyol:

uniformly mixing the epoxy waste grease, formic acid and phosphoric acid in the step (1) according to the mass ratio of 100: 2: 0.4, and reacting for 3.5 hours under the conditions of reflux condensation and nitrogen protection at 70 ℃. And after the reaction is finished, carrying out vacuum filtration at 100 ℃ until no bubbles exist, thus obtaining the low-molecular-weight plant-based polyol.

(3) Synthesis of high molecular weight plant-based polyol:

uniformly mixing the epoxy waste grease obtained in the step (1), the low-molecular-weight plant-based polyol and phosphoric acid in the step (2) according to a certain mass ratio of 100: 0.5, reacting for 3 hours under the conditions of reflux condensation and nitrogen protection at 65 ℃, carrying out addition polymerization, repeatedly washing the obtained product with distilled water of 25 ℃ for multiple times after the reaction is finished, and carrying out vacuum dehydration to obtain the high-molecular-weight plant-based polyol.

Example 3.

1. The invention provides a pretreatment method of waste grease, which comprises the following specific operation steps:

heating the waste grease to 65 ℃, filtering by using a sand core, removing solid impurities such as soil, food residues and the like in the waste grease, then removing water and volatile components in the grease by adopting a heating and reduced pressure distillation mode under the condition of 45 ℃ until no bubbles are generated, finally adding acid clay for adsorption and decoloration, filtering to obtain the treated grease, and pouring the treated grease into a bottle for later use.

2. The invention provides an epoxidation synthesis method of plant-based polyol, which comprises the following specific operation steps:

(1) synthesis of epoxy waste grease

Uniformly mixing acetic acid, ozone and sulfuric acid according to the mass ratio of 3: 4: 0.7 to obtain a mixed reagent A, uniformly mixing the pretreated waste oil and tetrabutylammonium bromide according to the mass ratio of 100: 2, and then putting the mixture into a water bath at 50 ℃ for stirring and heating to obtain a mixed reagent B. Slowly dripping the mixed reagent A into the mixed reagent B at 40 ℃, raising the temperature of the system to 75 ℃ after dripping is finished, reacting for 5 hours, washing a product to be neutral after the reaction is finished, transferring the product to a rotary evaporator, and performing vacuum rotary evaporation at 80 ℃ until no bubbles exist, thus obtaining the epoxy waste grease.

(2) Synthesis of low molecular weight vegetable-based polyol:

uniformly mixing the epoxy waste grease obtained in the step (1), acetic acid and sulfuric acid according to the mass ratio of 100: 2: 0.6, and reacting for 2.5 hours under the conditions of reflux condensation and nitrogen protection at 70 ℃. And after the reaction is finished, carrying out vacuum filtration at 120 ℃ until no bubbles exist, thus obtaining the low-molecular-weight plant-based polyol.

(3) Synthesis of high molecular weight plant-based polyol:

uniformly mixing the epoxy waste grease obtained in the step (1), the low-molecular-weight plant-based polyol and sulfuric acid in the step (2) according to a certain mass ratio of 100: 1, reacting for 4 hours under the conditions of reflux condensation and nitrogen protection at 80 ℃, carrying out addition polymerization, repeatedly washing the obtained product with distilled water of 25 ℃ for multiple times after the reaction is finished, and carrying out vacuum dehydration to obtain the high-molecular-weight plant-based polyol.

Example 4.

1. The invention provides a pretreatment method of waste grease, which comprises the following specific operation steps:

heating the waste grease to 80 ℃, filtering by using a sand core, removing solid impurities such as soil, food residues and the like in the waste grease, then removing water and volatile components in the grease by adopting a heating and reduced pressure distillation mode under the condition of 60 ℃ until no bubbles are generated, finally adding acid clay for adsorption and decoloration, filtering to obtain the treated grease, and pouring the treated grease into a bottle for later use.

2. The invention provides an epoxidation synthesis method of plant-based polyol, which comprises the following specific operation steps:

(1) synthesis of epoxy waste grease

Uniformly mixing formic acid, ozone and nitric acid according to the mass ratio of 2: 6: 0.7 to obtain a mixed reagent A, uniformly mixing the pretreated waste grease and tetrabutylammonium chloride according to the mass ratio of 100: 2, and then putting the mixture into a water bath at 50 ℃ for stirring and heating to obtain a mixed reagent B. Slowly dripping the mixed reagent A into the mixed reagent B at 50 ℃, raising the temperature of the system to 90 ℃ after dripping is finished, reacting for 8 hours, washing a product to be neutral after the reaction is finished, transferring the product to a rotary evaporator, and performing vacuum rotary evaporation at 90 ℃ until no bubbles exist, thus obtaining the epoxy waste grease.

(2) Synthesis of low molecular weight vegetable-based polyol:

uniformly mixing the epoxy waste grease, formic acid and nitric acid in the step (1) according to the mass ratio of 100: 3: 0.7, and reacting for 4 hours under the conditions of reflux condensation and nitrogen protection at 80 ℃. And after the reaction is finished, carrying out vacuum filtration at 140 ℃ until no bubbles exist, thus obtaining the low-molecular-weight plant-based polyol.

(3) Synthesis of high molecular weight plant-based polyol:

uniformly mixing the epoxy waste grease obtained in the step (1), the low-molecular-weight plant-based polyol and nitric acid in the step (2) according to a certain mass ratio of 100: 120: 2, reacting for 4 hours under the conditions of reflux condensation and nitrogen protection at 110 ℃, carrying out addition polymerization, repeatedly washing the obtained product with distilled water of 25 ℃ for multiple times after the reaction is finished, and carrying out vacuum dehydration to obtain the high-molecular-weight plant-based polyol.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Furthermore, it should be understood that although the present specification describes embodiments, this does not include only one embodiment, and such description is for clarity only, and those skilled in the art should be able to make the specification as a whole, and the embodiments may be appropriately combined to form other embodiments understood by those skilled in the art.