阅读说明：本技术 一种生物质基聚酯多元醇的制备方法及用途 (Preparation method and application of biomass-based polyester polyol ) 是由 张龙 汤婉婷 于 2021-09-24 设计创作，主要内容包括：本发明采用高效催化技术,催化开环环氧大豆油制备生物质基聚酯多元醇,属于化工材料生物质高效利用技术领域。以环氧大豆油为原料,乙二醇为开环剂,衣康酸为催化剂,在带有搅拌装置、控温装置的反应釜中恒温120～150℃反应2～4h制得生物质基聚酯多元醇。所得生物基聚醚多元醇羟值为360.5-420.1mgKOH/g、含水率为0.15～0.25%,生物质基聚酯多元醇产品收率高达99.2%。由开环产物制备泡沫的压缩强度可达250～320kPa、表观密度为40.0～60.0kg/m～(3),尺寸收缩率1.53%,导热系数0.024W/m·K,整体综合性能与优于石油基聚氨酯硬质保温板国家标准(GB10800—1989、GBT8813-2008、GBT6343-2009)的指标要求,并且材料具有优良的降解性能。(The invention discloses a method for preparing biomass-based polyester polyol by catalyzing ring-opening epoxy soybean oil by adopting an efficient catalysis technology, and belongs to the technical field of efficient utilization of chemical material biomass. Epoxidized soybean oil is used as a raw material, ethylene glycol is used as a ring-opening agent, itaconic acid is used as a catalyst, and the biomass-based polyester polyol is prepared by reacting in a reaction kettle with a stirring device and a temperature control device at a constant temperature of 120-150 ℃ for 2-4 h. The hydroxyl value of the obtained biomass-based polyether polyol is 360.5-420.1mgKOH/g, the water content is 0.15-0.25%, and the yield of the biomass-based polyester polyol product is as high as 99.2%. The foam prepared from the ring-opening product has the compression strength of 250-320 kPa and the apparent density of 40.0-60.0 kg/m 3 Dimensional shrinkage of 1.53 percent and thermal conductivity of 0.024W/m.K, and integral synthesisThe composite performance is superior to the index requirements of national standards (GB 10800-1989, GBT8813-2008 and GBT 6343-2009) of petroleum-based polyurethane hard insulation boards, and the material has excellent degradation performance.)

1. A method for preparing biomass-based polyester polyol comprises the following steps: adding a certain mass of biomass raw material into a 1L stainless steel reaction kettle with a stirring device and a temperature control device, then adding a ring-opening agent accounting for 10-50% of the mass of the raw material and a catalyst accounting for 0.5-0.8% of the total mass of the ring-opening agent, uniformly mixing, and reacting at 120-150 ℃ for 2-4 h to obtain the biomass-based polyester polyol.

2. The method of claim, wherein the biomass-based polyester polyol is prepared by: the raw material is epoxidized soybean oil.

3. The method of claim, wherein the biomass-based polyester polyol is prepared by: the ring-opening agent is small molecular alcohols with active hydrogen atoms, such as ethanol, glycol, glycerol and the like.

4. The method of claim, wherein the biomass-based polyester polyol is prepared by: the dosage of the ring-opening agent is 10-50% of the mass of the raw materials.

5. The method of claim, wherein the biomass-based polyester polyol is prepared by: the catalyst is itaconic acid.

6. The method of claim, wherein the biomass-based polyester polyol is prepared by: the dosage of the catalyst is 0.5-0.8% of the total mass of the raw materials and the ring-opening agent.

7. The method of claim, wherein the biomass-based polyester polyol is prepared by: the reaction temperature is 120-150 ℃.

8. The method of claim, wherein the biomass-based polyester polyol is prepared by: the reaction time is 2-4 h.

9. The method according to any one of claims 1 to 8, use of the biomass-based polyester polyol obtained in the preparation of degradable rigid polyurethane insulation materials.

Technical Field

The invention relates to the technical field of new chemical materials and high-quality biomass utilization, in particular to a preparation method of biomass-based polyester polyol.

Background

Polyurethanes are a general term for macromolecular compounds containing repeating urethane groups in the main chain, obtained by reacting polyisocyanates with dihydroxy or polyhydroxy compounds. In recent years, with the increasing shortage of petroleum resources, a polyether polyol, which is one of main raw materials for synthesizing polyurethane, is coming to be on the market at an explosive price. And because the traditional polyurethane raw materials are completely from the petroleum industry, the products are difficult to degrade and recycle after being discarded, and the environment is seriously polluted. In order to relieve the excessive dependence on the increasingly exhausted petroleum resources and reduce the environmental pollution caused by the abandoned traditional polyurethane, the renewable natural plant polyol is used in the polyurethane industry, and the development of degradable biomass polyurethane materials becomes a hot point of domestic and foreign research. Soybean oil is a renewable natural resource and has become an extremely important industrial raw material, and the soybean oil contains ester groups and epoxy groups and is one of the most ideal raw materials for producing bio-based polyester polyol.

The ring-opening of epoxidized soybean oil is an important way for producing polyol, and the Liyan, etc. uses epoxidized soybean oil as raw material and uses methyl alcohol as ring-opening reagent to prepare the soybean oil polyol. In the reaction process, the soyabean oil alcohol with the required hydroxyl value (80-170 mgKOH/g) can be obtained by controlling the reaction time, the soyabean oil alcohol is partially substituted for the traditional polyether polyol and added into the formula, the polyurethane soft foamed plastic is prepared by foaming, and various mechanical property analyses are carried out on the polyurethane soft foamed plastic, so that the tensile strength of the product can reach more than 0.1MPa, and the elongation at break can reach more than 150%. .

The epoxidized soybean oil with different epoxy values is synthesized by using soybean oil, glacial acetic acid and hydrogen peroxide as raw materials and sulfuric acid as a catalyst. And 4 kinds of soybean polyol with hydroxyl values of 261mgKOH/g, 285mgKOH/g, 312mgKOH/g and 340mgKOH/g are prepared from the synthesized epoxidized soybean oil and diethanolamine through ring-opening addition reaction under the condition of using tetrafluoroboric acid as a catalyst.

The Mohei and the like synthesize the vegetable oil polyalcohol by ring-opening addition reaction by using epoxidized soybean oil and methanol as raw materials and acetone as a solvent. Under the conditions of the reaction temperature of 140 ℃ and the reaction time of 16h, the hydroxyl value of the product polyol is 177.4 mgKOH/g.

By integrating the existing polyol preparation technology, the soybean oil-based polyol ring-opened by methanol and diethanol amine generally has biotoxicity and is limited in the application field, ethylene glycol is used as a ring-opening agent in the invention, the ethylene glycol has no volatility and biotoxicity at normal temperature, and a catalyst adopts biomass organic acid of itaconic acid, so that the product has wide application field and better utilization value in the actual production.

Disclosure of Invention

Aiming at the problems, the invention provides a method for preparing biomass-based polyester polyol by using ring-opening epoxidized soybean oil, and the method has the technical characteristics that the process is simple to operate, the obtained biomass-based polyester polyol raw material is from plants, is environment-friendly and non-toxic, and meets the requirement of preparing a hard polyurethane thermal insulation material. In order to achieve the above object, the present invention adopts the following technical solutions: a method for preparing biomass-based polyester polyol comprises the following steps: adding a certain mass of biomass raw material into a stainless steel reaction kettle with a stirring device and a temperature control device, then adding a ring-opening agent accounting for 10-50% of the mass of the raw material and a catalyst accounting for 0.5-0.8% of the total mass of the ring-opening agent, uniformly mixing, and reacting at 120-150 ℃ for 2-4 h to obtain the biomass-based polyester polyol.

The raw material is epoxidized soybean oil.

The ring-opening agent is small molecular polyol with active hydrogen atoms such as ethylene glycol, glycerol and the like, and preferably ethylene glycol.

The dosage of the ring-opening agent is 10-50% of the mass of the raw materials, and preferably 35-40%.

The catalyst is itaconic acid.

The dosage of the catalyst is 0.5-0.8% of the total mass of the raw materials and the ring-opening agent, and preferably 0.6-0.75%.

The reaction temperature is 120-150 ℃, and preferably 120-130 ℃.

The reaction time is 2-4 h, preferably 2-3 h.

The rigid polyurethane foam product prepared from the liquefied product is environment-friendly and non-toxic, and still shows good service performance without adding any other petroleum-based polyether/ester polyol, the compression strength of the obtained biomass-based polyurethane rigid foam is 250-320 kPa, and the average apparent density is 55.0-60.0 kg/m³. The performance of the rigid polyurethane foam prepared by the product is shown to meet the requirements of national standards (GB/T6343-2009 and GB/T8813-2008).

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.

Example 1.

200g of epoxidized soybean oil, 80g of ethylene glycol and 1.5g of itaconic acid are sequentially added into a 500mL stainless steel reaction kettle provided with a stirring device and a temperature control device, and after uniform stirring and reaction at 120 ℃ for 3 hours, the biomass-based polyester polyol is obtained, and the hydroxyl value is determined to be 403.2mgKOH/g, and the water content is 0.23%.

Example 2.

400g of epoxidized soybean oil, 140g of ethylene glycol and 2.8g of itaconic acid are sequentially added into a 1L stainless steel reaction kettle provided with a stirring device and a temperature control device, uniformly stirred and reacted at 140 ℃ for 3 hours to obtain the biomass-based polyester polyol, and the hydroxyl value is determined to be 360.8mgKOH/g, and the water content is 0.18%.

Example 3.

And (2) sequentially adding 400g of epoxidized soybean oil, 150g of ethylene glycol and 2.0g of itaconic acid into a 1L stainless steel reaction kettle provided with a stirring device and a temperature control device, uniformly stirring, and reacting at 150 ℃ for 2.5h to obtain the biomass-based polyester polyol, wherein the hydroxyl value is determined to be 380.3mgKOH/g, and the water content is determined to be 0.24%.

Example 4.

And (2) sequentially adding 400g of epoxidized soybean oil, 160g of ethylene glycol and 3.0g of itaconic acid into a 1L stainless steel reaction kettle provided with a stirring device and a temperature control device, uniformly stirring, and reacting at 120 ℃ for 2.5 hours to obtain the biomass-based polyester polyol, wherein the hydroxyl value is determined to be 417.8mgKOH/g, and the water content is determined to be 0.21%.

EXAMPLE 5 mechanical Properties of rigid polyurethane foams prepared from the liquefied products

40.0g of the liquefied product of example 1 to 4, 0.1g of silicone oil L-580, 1.0g of water, and 0.02g of dibutyltin dilaurate as a catalyst were weighed and mixed in a 1L beaker, 50.0g of TDI was added thereto, and the mixture was stirred sufficiently until the system became homogeneous and foam rose, and then the stirring was stopped to allow free foaming at room temperature,and obtaining the flame-retardant rigid polyurethane foam after the foam is cured. The material has a compressive strength of 250 to 320kPa and an average apparent density of 55.0 to 60.0kg/m³. The performance of the rigid polyurethane foam prepared by the product is shown to meet the requirements of national standards (GB/T6343-2009 and GB/T8813-2008).

Example 6 mechanical Properties of rigid polyurethane foams prepared from the liquefied products

80.0g of the liquefied product of example 1 to 4, 0.18 g of silicone oil L-580, 1.8 g of water and 0.02g of dibutyltin dilaurate as a catalyst were weighed and mixed uniformly in a 2L beaker, 110.0g of TDI was added thereto, and the stirring was stopped when the system was sufficiently stirred uniformly and foam rose, and allowed to foam freely at room temperature, and after the foam was cured, a flame-retardant rigid polyurethane foam was obtained. The measured compression strength of the obtained biomass-based polyurethane rigid foam is 280-320 kPa, and the average apparent density is 58.0-60.0 kg/m³. The performance of the rigid polyurethane foam prepared by the product is shown to meet the requirements of national standards (GB/T6343-2009 and GB/T8813-2008).

Example 7 mechanical Properties of rigid polyurethane foams prepared from the liquefied products

Respectively weighing 20.0g of the liquefied product of the embodiment 1-4, 0.05g of silicone oil L-580, 0.3g of water and 0.02g of dibutyltin dilaurate serving as a catalyst in a 1L beaker, uniformly mixing, adding 23.0g of TDI, fully stirring until the system is uniform and foam rises, stopping stirring, allowing the system to freely foam at room temperature, and curing the foam to obtain the flame-retardant rigid polyurethane foam. The measured compression strength of the obtained biomass-based polyurethane rigid foam is 300-320 kPa, and the average apparent density is 58.4-60.0 kg/m³. The performance of the rigid polyurethane foam prepared by the product is shown to meet the requirements of national standards (GB/T6343-2009 and GB/T8813-2008).

Example 8 mechanical Properties of rigid polyurethane foams prepared from the liquefied products

20.0g of the liquefied product obtained in examples 1 to 4, 0.02g of silicone oil L-580, 0.2g of water, and 0.02g of dibutyltin dilaurate as a catalyst were weighed and mixed in a 500mL beaker, 23.0g of TDI was added thereto, and the mixture was stirred sufficiently until the system was homogeneousAnd when the foam rises uniformly, stopping stirring, allowing the foam to foam freely at room temperature, and curing the foam to obtain the flame-retardant rigid polyurethane foam. The measured compression strength of the obtained biomass-based polyurethane rigid foam is 270-320 kPa, and the average apparent density is 57.0-60.0 kg/m³. The performance of the rigid polyurethane foam prepared by the product is shown to meet the requirements of national standards (GB/T6343-2009 and GB/T8813-2008).

EXAMPLE 9 degradation Properties of the foam prepared

Taking the polyurethane foams of examples 5-8, cutting into cubes with edge lengths of about 10 mm, burying in soil for 45 days, the weight loss of the polyurethane foam is as high as 40.8%.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.