WO2022056687A1 - High-functionality polyether polyol and preparation method therefor - Google Patents

Abstract

A high-functionality polyether polyol and a preparation method therefor. The preparation method facilitates reducing or eliminating the influence of a low-functionality initiator on product production. The preparation method for the high-functionality polyether polyol comprises the following steps: adding a polyether polyol solvent and an initiator into a reaction vessel, adding an alkylene oxide into the reaction vessel in the presence of a catalyst, and performing a ring-opening polymerization reaction between the alkylene oxide and the initiator in an inert gas atmosphere to generate the high-functionality polyether polyol. The initiator comprises a high-functionality initiator and optionally a low-functionality initiator.

Description

A kind of high-functionality polyether polyol and preparation method thereof technical field

The invention relates to a preparation method of a high-functionality polyether polyol, and belongs to the technical field of polyether polyol preparation.

Background technique

Polyurethane foam is widely used in refrigerator, cold chain, pipeline, construction and other industries due to its excellent thermal insulation properties. Polyether polyol is one of the indispensable raw materials for the production of polyurethane, and its composition directly affects the application performance of polyurethane foam. High-functionality polyether polyols play an important role in combining polyether polyols because high-functionality polyether polyols can produce a high degree of crosslinking with isocyanates, accelerate foam curing, and have foams with high strength and good dimensional stability. status. Commonly used high-functionality polyether polyol initiators are solid raw materials such as sucrose, sorbitol, and pentaerythritol. In order to meet product quality and production efficiency, it is difficult to directly react with alkylene oxide. The low-molecular-weight liquid starter dissolves the solid feedstock, allowing the dissolved high-functionality starter to react with the alkylene oxide. When the amount of small molecular starter is small, the solubility is low, and it is easy to form solid residues. When the amount of small molecule initiator is large, the reaction ratio of small molecules and alkylene oxide is high, which reduces the functionality of polyether products and sacrifices Product performance.

CN106146823A discloses a preparation method of pure crystalline sorbitol polyether polyol. The pure sorbitol polyether polyol can be obtained by directly reacting sorbitol and propylene oxide under the catalysis of potassium hydroxide. Due to the difficulty of the direct reaction, the initial pressure of the reaction is 0.4-0.7MPa, and the pressure is high, indicating that the reaction vessel contains too much propylene oxide and the reaction rate is low. High pressure and high content of propylene oxide have greater safety. Hidden danger, it is difficult to apply in industrial production.

CN104072748A discloses a preparation method of sucrose-type polyether polyol. The method uses sucrose as an initiator, 1,3-dimethyl-2-imidazolidinone DMI for solvation, and KOH as a catalyst. The method can prepare high-functionality sugar ethers, and ensure that the sugars are fully reacted. Due to the use of organic solvents, recycling and processing are required to increase environmental protection burdens.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a high-functionality polyether polyol and a preparation method thereof.

Based on the preparation method of the present invention, it is beneficial to reduce or eliminate the influence of low-functionality starter on product production, for example, it is beneficial to avoid the formation of solid residues or reduce the amount of solid residues due to dissolved solid raw materials under the condition of reducing the amount of low-functionality starter used. The effect on the functionality of polyether products caused by excessive introduction of low-functionality initiators.

The present invention provides the following technical solutions in order to achieve its purpose:

The invention provides a preparation method of high-functionality polyether polyol. A polyether polyol solvent and an initiator are added into a reaction vessel, and in the presence of a catalyst, alkylene oxide is added into the reaction vessel, and in an inert gas atmosphere The alkylene oxide and the initiator are subjected to ring-opening polymerization reaction to generate the high-functionality polyether polyol; the initiator includes a high-functionality initiator and an optional low-functionality initiator;

Wherein, the high-functionality initiator is an initiator whose functionality is not less than 4;

The low-functionality initiator is an initiator whose functionality is less than 4;

The catalyst is a combination of one or more of an alkali metal catalyst and an amine catalyst; when the catalyst comprises the alkali metal catalyst, before the alkylene oxide is put into the reaction system, the alkali metal catalyst is Put into the reaction system and mix evenly with the initiator and the polyether polyol solvent; when the catalyst contains the amine catalyst, before the alkylene oxide is put into the reaction system, part of the amine The catalyst is added to the reaction system and mixed evenly with the initiator and the polyether polyol solvent, and the remaining amine catalyst and the alkylene oxide are pre-mixed uniformly and then put into the reaction system. In the preparation method of the present invention, the catalyst used may be an alkali metal catalyst, or an amine catalyst, or a catalyst formed by a combination of an alkali metal catalyst and an amine catalyst.

In some embodiments, the high-functionality starter includes sucrose, trehalose, mannitol, maltitol, isomalt, xylitol, sorbitol, cyclohexanol, pentaerythritol, dipentaerythritol, polyglycerol, ethyl acetate One or more of diamine, phenylenediamine, toluenediamine, melamine, and bis-trimethylolpropane.

In some embodiments, the low-functionality starter includes water, glycerol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, cyclopentanediol, hexanediol One or more of alcohol, cyclohexanediol, dodecanediol, ethanolamine, diethanolamine, and triethanolamine.

In some embodiments, the mass ratio of the high-functionality initiator, the low-functionality initiator, and the polyether polyol solvent is 100:0-100:10-500. The determination of the consumption of alkylene oxide can be determined by those skilled in the art according to the conventional technical knowledge that they have mastered. It is well known to those skilled in the art that the consumption of alkylene oxide is related to the target hydroxyl value of the product, according to the initial raw material used. The hydroxyl value and the desired product target hydroxyl value can determine the amount of alkylene oxide.

In some embodiments, the amount of the catalyst used is 0.01 of the total mass of the high-functionality initiator, the low-functionality initiator, the polyether polyol solvent, the alkylene oxide, and the catalyst. %-1%, such as 0.01%, 0.05%, 0.1%, 0.5%, 1%, etc.

In some embodiments, when the catalyst comprises the amine catalyst, before the alkylene oxide is put into the reaction system, 20%-60% of the total mass of the amine catalyst (eg 20%, 30%, 40%, 50%, 60%, etc.) of the amine catalyst is added into the reaction system and mixed with the initiator and the polyether polyol solvent evenly, and the remaining amine catalyst and the alkylene oxide are preliminarily mixed. After mixing evenly, it is put into the reaction system.

The remaining amine catalyst and the alkylene oxide are premixed uniformly in a closed inert atmosphere.

In some embodiments, the feeding conditions of the alkylene oxide include: after the temperature of the reaction system is raised to 80-100°C (eg, 80°C, 90°C, 100°C, etc.), the alkylene oxide is added dropwise to In the reaction system, the reaction temperature is controlled to 90-140°C (for example, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, etc.), specifically, during the dropwise addition of alkylene oxide, the reaction pressure is increased. Controlled within 0.4MPa. After the alkylene oxide feeding is completed, the curing is carried out; in some embodiments, the curing temperature is controlled to be 100-140 °C (for example, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C), and the curing pressure remains unchanged ( For example, when the pressure remains unchanged within 10-15 minutes), the reaction ends; specifically, in some examples, for example, after aging for 2-3 hours, the pressure can be maintained within 10-15 minutes.

In some embodiments, the alkali metal catalyst includes one or more of potassium hydroxide and sodium hydroxide.

In some embodiments, the amine catalyst includes dimethylamine, trimethylamine, triethylamine, dipropylamine, tripropylamine, N,N-dimethylcyclohexylamine, N-methyl-N-ethylcyclohexyl Amine, N-methyl-N-propylcyclohexylamine, N,N-diethylcyclohexylamine, triethylenediamine, N,N-dimethyloctadecylamine, N-methyldiethanolamine, 2-Dimethylethanolamine, 1,4-Dimethylpiperazine, N,N-Dimethylpiperazine, N,N-Dimethylbenzylamine, N,N-Xylidine, Dodecyl Dimethyl tertiary amine, bis(dimethylaminoethyl) ether, imidazole, N-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethylimidazole, 4-methylimidazole , 2-ethyl-4-methylimidazole, 1-(3-aminopropyl)imidazole, N-methylmorpholine, N-ethylmorpholine, pyridine, 2-aminopyridine, 4-aminopyridine, 4 -One or more of dimethylaminopyridine and 2,6-diaminopyridine.

In some embodiments, the alkylene oxide is one or more of ethylene oxide, propylene oxide, and butylene oxide, preferably propylene oxide.

In some embodiments of the present invention, the high-functionality polyether polyol has a functionality of not less than 4 and a hydroxyl value of 200-600 mgKOH/g.

In the present invention, the polyether polyol solvent refers to the polyether polyol used as a solvent, and the specific type of polyether polyol is not particularly limited, and can be composed of one or more of polyols and polyamines. A starter, or a starter composed of one or more of polyols and polyamines and water or vegetable oil or water and vegetable oil, and the finished polyether polyol obtained by reacting with alkylene oxide. Polyols or polyamines such as sucrose, trehalose, mannitol, maltitol, isomalt, xylitol, sorbitol, cyclohexanol, pentaerythritol, dipentaerythritol, polyglycerol, phenylenediamine, toluenediamine, melamine , Trimethylolpropane, Bistrimethylolpropane, Glycerin, Ethylene Glycol, Diethylene Glycol, Propylene Glycol, Dipropylene Glycol, Tripropylene Glycol, Butylene Glycol, Pentane Glycol, Cyclopentane Glycol, Hexylene Glycol, Cyclohexanediol, dodecanediol, ethylenediamine, ethanolamine, diethanolamine, triethanolamine, etc., and other polyols and polyamines not limited to the above types. The specific preparation process of the polyether polyol as a solvent is not limited, and conventional processes in the technical field such as alkali catalysis and amine catalysis can be used, and other processes, such as preparation by the method provided by the present invention, can also be used.

As is well known to those skilled in the art, in the preparation method of polyether polyol, the polyether polyol can be directly obtained by degassing after the reaction; , the specific process operation of neutralization and refining is conventional in this area, and this is not limited. For example, phosphoric acid and water can be added to the crude polyether product, and neutralization reaction can be carried out, then add magnesium aluminum silicate adsorbent, dehydration, The polyether polyol product was obtained by filtration.

In some embodiments, in the process of preparing the high-functionality polyether polyol, the high-functionality initiator, optional low-functionality initiator, polyether polyol solvent and catalyst (catalyst according to It is an amine catalyst or an alkali metal catalyst and is fed according to the feeding method described above) after adding the closed reaction vessel, start stirring, uniformly mix the reaction materials, replace the gas in the reactor with an inert gas such as nitrogen, vacuumize, and Under certain conditions, the alkylene oxide is put into the ring-opening polymerization reaction, and the reaction is degassed after the reaction. The "certain condition" means that the temperature of the reaction system is raised to 80-100 ° C, and then the alkylene oxide is added dropwise to the reaction system; in the process of feeding the alkylene oxide, the reaction temperature is controlled to 90 °C. -140°C, the alkylene oxide is matured after feeding, and the aging temperature is controlled to 100-140°C until the pressure remains unchanged.

The present invention also provides a high-functionality polyether polyol prepared based on the above-mentioned preparation method.

The technical scheme provided by the invention has the following beneficial effects:

(1) To provide a method for preparing a high-functionality polyether polyol, the high-functionality polyether polyol is, for example, a polyether polyol with a functionality of not less than 4, and the hydroxyl value is, for example, 200-600 mgKOH/g.

(2) Using polyether polyol as a solvent, on the one hand, it is used to disperse and dissolve the high-functionality solid starter, so that the amount of the low-functionality starter can be reduced, and the functional effect of the low-functionality starter on the product can be reduced or eliminated. In addition, the formation of solid residues can be avoided by reducing or not using low-functionality initiators; on the other hand, the polyether polyol solvent does not need to be recycled and can be used directly as a product, which is more environmentally friendly. need.

(3) In the preferred version, the present invention uses trehalose as the starting agent for the first time, and has the same functionality as sucrose. Under high temperature, trehalose has stronger stability than sucrose, and Maillard reaction is not easy to occur. The appearance of polyether products provides a new direction for the synthesis of high-functionality polyether polyols.

(4) The present invention can adopt an alkali metal catalyst, or an amine catalyst, or a catalyst system formed by a combination of an alkali metal catalyst and an amine catalyst. According to the action mechanism of the catalyst, the present invention sets different addition modes to optimize the catalytic efficiency. The alkali metal catalyst takes potassium hydroxide as an example, and its catalytic mechanism is that potassium hydroxide reacts with the polyol initiator to form potassium alkoxide and water, and the highly active potassium alkoxide acts on the alkylene oxide to carry out ring-opening polymerization; The alkali metal catalyst is added to the reaction equipment, and it is mixed with the starting agent. The reaction mechanism of amine catalysts is that the amine reacts with alkylene oxide to form a ring-opening active intermediate, and the highly active intermediate continues to react with the polyol initiator, and then undergoes chain extension polymerization. At the same time, in order to match the substrate concentration, it is necessary to ensure the initial The catalyst concentration is not zero; in the present invention, part of the amine catalyst is added to the reaction equipment to mix with the initiator and the solvent evenly, and part is added to the alkylene oxide storage tank to be mixed with the alkylene oxide, thereby effectively increasing the contact area between the catalyst and the alkylene oxide , to improve the catalytic efficiency; and the amine catalyst is easy to deactivate at high temperature for a long time. By mixing the amine catalyst with the alkylene oxide, fresh catalyst can be continuously replenished when the alkylene oxide is added dropwise to maintain the reaction efficiency. The injection of oxyalkane keeps the catalyst concentration from being overly diluted. Therefore, the catalyst addition method based on the present invention, especially the addition method of the amine catalyst, can effectively improve the production efficiency.

detailed description

In order to better understand the technical solutions of the present invention, the content of the present invention is further described below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

The used polyether polyol solvent of embodiment and comparative example is as follows:

Polyether polyol A: using sucrose and glycerol as starting agents, using potassium hydroxide as catalyst, and reacting with propylene oxide at 110 ° C, wherein the mass ratio of sucrose, glycerol, potassium hydroxide and propylene oxide is 100: 40:2:427. The obtained crude polyether is subjected to acid neutralization and purification treatment, that is, at 80° C., 0.6 parts of phosphoric acid and 6 parts of water are added to 100 parts (the following parts all refer to parts by weight) of the crude polyether, and 0.2 parts of silicic acid are added after the reaction for 30 minutes. The magnesium-aluminum adsorbent was stirred for 20 minutes, dehydrated for 1 hour, then heated to 115 °C for 1 hour, and filtered to obtain polyether polyol A with a functionality of 5 and a hydroxyl value of 360 mgKOH/g.

Polyether polyol B: take ten polyglycerol, diethylene glycol as starting agent, potassium hydroxide as catalyst, react with propylene oxide at 110 ° C, wherein ten polyglycerol, diethylene glycol, potassium hydroxide , The mass ratio of propylene oxide is 100:21:0.8:126. The obtained crude polyether is subjected to acid neutralization and purification treatment, that is, at 80° C., 0.6 parts of phosphoric acid and 6 parts of water are added to 100 parts (the following parts all refer to parts by weight) of the crude polyether, and 0.2 parts of silicic acid are added after the reaction for 30 minutes. The magnesium-aluminum adsorbent was stirred for 20 minutes, dehydrated for 1 hour, then heated to 115 °C for 1 hour, and filtered to obtain the polyether polyol B with a functionality of 6 and a hydroxyl value of 450 mgKOH/g.

Polyether polyol C: using sucrose and diethylene glycol as starting agents, using potassium hydroxide as catalyst, and reacting with propylene oxide at 110 ° C, wherein sucrose, diethylene glycol, potassium hydroxide, propylene oxide The mass ratio of 100:31:1.5:173. The obtained crude polyether is subjected to acid neutralization and purification treatment, that is, at 80° C., 0.9 parts of phosphoric acid and 6 parts of water are added to 100 parts (the following parts all refer to parts by weight) of the crude polyether, and 0.2 parts of silicic acid are added after the reaction for 30 minutes. The magnesium-aluminum adsorbent was stirred for 20 min, dehydrated for 1 h, then heated to 115 °C for 1 h, and filtered to obtain the polyether polyol C with a functionality of 5 and a hydroxyl value of 540 mgKOH/g.

Polyether polyol D: using sucrose and diethylene glycol as starting agents, using potassium hydroxide as catalyst, and reacting with propylene oxide at 110 ° C, wherein sucrose, diethylene glycol, potassium hydroxide, propylene oxide The mass ratio of 100:31:2.3:337. The obtained crude polyether is subjected to acid neutralization and purification treatment, that is, at 80° C., 0.9 parts of phosphoric acid and 6 parts of water are added to 100 parts (the following parts all refer to parts by weight) of the crude polyether, and 0.2 parts of silicic acid are added after the reaction for 30 minutes. The magnesium-aluminum adsorbent was stirred for 20 minutes, dehydrated for 1 hour, then heated to 115 °C for 1 hour, and filtered to obtain the polyether polyol D with a functionality of 5 and a hydroxyl value of 350 mgKOH/g.

Sucrose, glycerol, sorbitol, pentaerythritol, potassium hydroxide, N-methylimidazole, 4-methylimidazole, N,N-dimethylcyclohexylamine, triethylamine: Sinopharm Chemical Reagent Co., Ltd.;

Trehalose: Dezhou Huiyang Biotechnology Co., Ltd.;

Propylene oxide: Wanhua Chemical Co., Ltd.

Test Methods for Properties of Polyether Polyols:

Determination of hydroxyl value of polyether polyol: GB/T 12008.3-2009;

Viscosity determination of polyether polyol: GB/T10008.7-2010;

pH determination of polyether polyols: GB/T9724-2007;

The pressure involved in the following examples and comparative examples refers to gauge pressure unless otherwise specified.

Example 1

In a 5L stainless steel autoclave (ie, a reaction kettle) equipped with a stirrer, a heating temperature control device, a cooling device, and a pressure sensor, add 685 g of sucrose, 80 g of glycerol, 20 g of water, 600 g of polyether polyol A, and 6 g of potassium hydroxide. , 1 g of N-methylimidazole, start stirring, uniformly mix the reaction materials, replace with nitrogen 5 times, and evacuate to a pressure of -0.09MPa;

4 g of N-methylimidazole was added to propylene oxide, mixed under nitrogen atmosphere to obtain propylene oxide material, for subsequent use;

When the temperature of the reaction kettle rises to 100 ° C, start to drip propylene oxide material, the reaction temperature is controlled to 120 ° C, and the pressure is controlled within 0.4 MPa, after the dropwise addition of 2030 g of propylene oxide, the feeding is completed, and it is matured at 120 ° C. After the pressure remained constant for 10 minutes, vacuum was applied to obtain the crude polyether product. Add 11g phosphoric acid and 150g water to the crude polyether at 80°C, add 6g magnesium aluminum silicate adsorbent after 30min of reaction, stir for 20min, dehydrate for 1h, then heat up to 115°C for 1h dehydration, filter to obtain polyether polyol product .

The indexes of the synthesized polyether polyols are listed in Table 1.

Example 2

In a 5L stainless steel autoclave (that is, a reaction kettle) equipped with a stirrer, a heating temperature control device, a cooling device, and a pressure sensor, 550 g of sorbitol, 530 g of polyether polyol B, N,N-dimethylcyclohexane were added. Amine 7.9g, start stirring, uniformly mix the reaction materials, replace with nitrogen 5 times, and evacuate until the pressure is -0.09MPa;

5.7 g of N,N-dimethylcyclohexylamine was added to propylene oxide, and mixed uniformly under nitrogen atmosphere to obtain propylene oxide material, which was used for subsequent use;

When the temperature of the reaction kettle rises to 90 ℃, start to drip propylene oxide material, the reaction temperature is controlled to 115 ℃, and the pressure is controlled within 0.4MPa, after the dropwise addition of 1837g of propylene oxide, the feeding is completed, and it is matured at 120 ℃. Until the pressure remains unchanged within 10 minutes, the polyether polyol product is obtained by degassing.

The indexes of the synthesized polyether polyols are listed in Table 1.

Example 3

In a 5L stainless steel autoclave (ie, a reaction kettle) equipped with a stirrer, a heating temperature control device, a cooling device, and a pressure sensor, 707 g of pentaerythritol, 77 g of polyether polyol C, and 3.5 g of N,N-dimethylcyclohexylamine were added. g, replace with nitrogen for 5 times, evacuate to a pressure of -0.09MPa, turn on stirring, and evenly mix the reaction materials;

5.3 g of triethylamine was added to propylene oxide, and mixed uniformly under nitrogen atmosphere to obtain propylene oxide material, which was used for subsequent use;

When the temperature of the reaction kettle rises to 90 ℃, start to drip propylene oxide material, the reaction temperature is controlled to 110 ℃, and the pressure is controlled within 0.35MPa, the feeding is finished after 1434g of propylene oxide is added dropwise, and it is ripened at 115 ℃, and the ripening is completed. Until the pressure remains unchanged within 10 minutes, the polyether polyol product is obtained by degassing.

The indexes of the synthesized polyether polyols are listed in Table 1.

Example 4

In a 5L stainless steel autoclave (ie, a reaction kettle) equipped with a stirrer, a heating temperature control device, a cooling device, and a pressure sensor, 569 g of trehalose containing two molecules of crystal water, 400 g of polyether polyol D400 g, and N-methyl 3.2 g of imidazole, start stirring, uniformly mix the reaction materials, replace with nitrogen 5 times, and evacuate to a pressure of -0.09MPa;

6.5 g of 4-methylimidazole was added to propylene oxide, and mixed uniformly under nitrogen atmosphere to obtain propylene oxide material, which was used for subsequent use;

When the temperature of the reaction kettle rises to 100 ° C, start to drip propylene oxide material, the reaction temperature is controlled to 120 ° C, and the pressure is controlled within 0.4 MPa, after the dropwise addition of 2064 g of propylene oxide, the feeding is completed, and it is matured at 120 ° C. Until the pressure remains unchanged within 10 minutes, the polyether polyol product is obtained by degassing. The indexes of the synthesized polyether polyols are listed in Table 1.

Comparative Example 1

In a 5L stainless steel autoclave equipped with a stirrer, heating temperature control device, cooling device, and pressure sensor, add 685g of sucrose, 80g of glycerol, 20g of water, 6g of potassium hydroxide, and 1g of N-methylimidazole, start stirring, and mix evenly The reaction material was replaced with nitrogen for 5 times, and the pressure was evacuated to -0.09MPa;

4 g of N-methylimidazole was added to propylene oxide, mixed under nitrogen atmosphere to obtain propylene oxide material, for subsequent use;

When the temperature of the reaction kettle rises to 100 ° C, start to drip propylene oxide material, the reaction temperature is controlled to 120 ° C, and the pressure is controlled within 0.4 MPa, after the dropwise addition of 2030 g of propylene oxide, the feeding is completed, and it is matured at 120 ° C. After the pressure remained constant for 10 minutes, vacuum was applied to obtain the crude polyether product. Add 11g phosphoric acid and 140g water to the crude polyether at 80°C, add 5.7g magnesium aluminum silicate adsorbent after 30min of reaction, stir for 20min, dehydrate for 1h, then heat up to 115°C for dehydration for 1h, filter to obtain polyether polyol product.

The indexes of the synthesized polyether polyols are listed in Table 1.

Comparative Example 2

In a 5L stainless steel autoclave equipped with a stirrer, a heating temperature control device, a cooling device and a pressure sensor, 550 g of sorbitol, 530 g of polyether polyol B, and 13.6 g of N,N-dimethylcyclohexylamine were added, and stirring was started. Mix the reaction materials uniformly, replace with nitrogen for 5 times, evacuate to the pressure of -0.09MPa, when the temperature of the reaction kettle rises to 90 ℃, start to drip propylene oxide, control the reaction temperature to 115 ℃, and control the pressure within 0.4MPa , after adding 1837g of propylene oxide dropwise, the feeding is completed, and it is matured at 120 ° C until the pressure remains unchanged within 10 minutes, and the polyether polyol product is obtained by degassing.

The indexes of the synthesized polyether polyols are listed in Table 1.

Comparative Example 3

In a 5L stainless steel autoclave equipped with a stirrer, a heating temperature control device, a cooling device and a pressure sensor, 707g of pentaerythritol, 77g of polyether polyol C77g, and 3.5g of N,N-dimethylcyclohexylamine were added, and the stirring was started. Mix the reaction materials, replace with nitrogen 5 times, evacuate to the pressure of -0.09MPa, inject 5.3g of triethylamine into the reaction kettle, when the temperature of the reaction kettle rises to 90 ℃, start to drip propylene oxide, and the reaction temperature is controlled to 110 ℃, and the pressure was controlled within 0.35MPa, 1434g of propylene oxide was added dropwise, and the feeding was completed, and the mixture was aged at 115°C until the pressure remained unchanged within 10 minutes, and the polyether polyol product was obtained by degassing.

The indexes of the synthesized polyether polyols are listed in Table 1.

Table 1 embodiment and comparative example make polyether polyol index table

In Table 1, the "reaction time" refers to the time period from the start of the dropwise addition of propylene oxide to the time in the reaction kettle, and the time period from when the time is stopped when the aging is completed.

As can be seen from Table 1, both the reaction systems of Comparative Example 1 and Example 1 used lower proportions of low-functionality initiators. However, the main difference between Comparative Example 1 and Example 1 was that no polyether polyol solvent was used. , the resulting product has a dark color and solid residual sugar in the crude polyether, and the required reaction time is also longer. Compared with Example 2, Comparative Example 2, under the same conditions, did not add a part of the amine catalyst to the propylene oxide, but directly added all the amine catalysts to the reaction system before the propylene oxide was fed. The reaction time is significantly prolonged, which affects the production efficiency. Similarly, compared with Example 3, Comparative Example 3 did not add a part of the amine catalyst to the propylene oxide, which also significantly increased the reaction time. Compared with Example 1, the product of Example 4 has better appearance and lighter color, indicating that trehalose is more stable than sucrose, and the degree of side reactions causing discoloration is lower.

Those skilled in the art will appreciate that some modifications or adaptations of the present invention may be made under the teachings of this specification. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims (11)

1. A method for preparing a high-functionality polyether polyol, characterized in that a polyether polyol solvent and an initiator are added to a reaction vessel, and in the presence of a catalyst, alkylene oxide is added to the reaction vessel, and in an inert gas atmosphere wherein the alkylene oxide and the initiator undergo a ring-opening polymerization reaction to form the high-functionality polyether polyol; the initiator includes a high-functionality initiator and an optional low-functionality initiator ;

   Wherein, the high-functionality initiator is an initiator whose functionality is not less than 4;

   The low-functionality initiator is an initiator whose functionality is less than 4;

   The catalyst is a combination of one or more of an alkali metal catalyst and an amine catalyst; when the catalyst comprises the alkali metal catalyst, before the alkylene oxide is put into the reaction system, the alkali metal catalyst is Put into the reaction system and mix evenly with the initiator and the polyether polyol solvent; when the catalyst contains the amine catalyst, before the alkylene oxide is put into the reaction system, part of the amine The catalyst is added to the reaction system and mixed evenly with the initiator and the polyether polyol solvent, and the remaining amine catalyst and the alkylene oxide are pre-mixed uniformly and then put into the reaction system.
2. The preparation method according to claim 1, wherein the high-functionality starting agent comprises sucrose, trehalose, mannitol, maltitol, isomalt, xylitol, sorbitol, cyclohexanol, One or more of pentaerythritol, bis-pentaerythritol, polyglycerol, ethylenediamine, phenylenediamine, toluenediamine, melamine, and bis-trimethylolpropane.
3. The preparation method according to claim 1 or 2, wherein the low-functionality starter comprises water, glycerol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, One or more of pentanediol, cyclopentanediol, hexanediol, cyclohexanediol, dodecanediol, ethanolamine, diethanolamine, and triethanolamine.
4. The preparation method according to any one of claims 1-3, wherein the mass ratio of the high-functionality initiator, the low-functionality initiator, and the polyether polyol solvent is 100: 0-100: 10-500.
5. The preparation method according to claim 4, wherein the catalyst is used in the amount of the high-functionality initiator, the low-functionality initiator, the polyether polyol solvent, the epoxy resin 0.01%-1% of the total mass of alkane and the catalyst.
6. The preparation method according to any one of claims 1-5, wherein when the catalyst comprises the amine catalyst, before the alkylene oxide is put into the reaction system, the total mass of the amine catalyst is 20%-60% of the amine catalyst is added to the reaction system and mixed evenly with the initiator and the polyether polyol solvent, and the remaining amine catalyst and the alkylene oxide are pre-mixed uniformly before into the reaction system.
7. The preparation method according to any one of claims 1-6, wherein the remaining amine catalyst and the alkylene oxide are pre-mixed uniformly in a closed inert atmosphere.
8. The preparation method according to any one of claims 1-7, wherein the feeding conditions of the alkylene oxide include: the temperature of the reaction system is raised to 80-100° C., and then the alkylene oxide is dropped It is added to the reaction system, and the reaction temperature is controlled to be 90-140° C., and the alkylene oxide is matured after the feeding of the alkylene oxide is completed.
9. The preparation method according to any one of claims 1-8, wherein the alkali metal catalyst comprises one or more of potassium hydroxide and sodium hydroxide;

   And/or, the amine catalyst includes dimethylamine, trimethylamine, triethylamine, dipropylamine, tripropylamine, N,N-dimethylcyclohexylamine, N-methyl-N-ethylcyclohexylamine , N-methyl-N-propylcyclohexylamine, N,N-diethylcyclohexylamine, triethylenediamine, N,N-dimethyloctadecylamine, N-methyldiethanolamine, 2 - Dimethylethanolamine, 1,4-dimethylpiperazine, N,N-dimethylpiperazine, N,N-dimethylbenzylamine, N,N-xylidine, dodecyldi Methyl tertiary amine, bis(dimethylaminoethyl) ether, imidazole, N-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethylimidazole, 4-methylimidazole, 2-ethyl-4-methylimidazole, 1-(3-aminopropyl)imidazole, N-methylmorpholine, N-ethylmorpholine, pyridine, 2-aminopyridine, 4-aminopyridine, 4- One or more of dimethylaminopyridine and 2,6-diaminopyridine;

   And/or, the alkylene oxide is one or more of ethylene oxide, propylene oxide, and butylene oxide, preferably propylene oxide.
10. The preparation method according to any one of claims 1-9, wherein the high-functionality polyether polyol has a functionality of not less than 4 and a hydroxyl value of 200-600 mgKOH/g.
11. A high-functionality polyether polyol, characterized in that, it is prepared by the preparation method described in any one of claims 1-10.