阅读说明：本技术 一种新型聚醚多元醇及制备方法和由其制备的聚氨酯泡沫 (Novel polyether polyol, preparation method thereof and polyurethane foam prepared from novel polyether polyol ) 是由 徐薇 马爱勤 王新宇 蔡仲铭 田苗 于 2021-09-01 设计创作，主要内容包括：本发明涉及一种新型聚醚多元醇及其制备方法和由其制备的聚氨酯泡沫。本发明所述的聚醚多元醇制备方法为：以三羟甲基氨基甲烷和羟基酪醇为起始剂,在碱性催化剂的作用下,与环氧烷烃开环聚合,制得所述聚醚多元醇。聚氨酯泡沫的原料包括质量比为100：10-13：110-130的组合聚醚、发泡剂和多异氰酸酯。本发明使用新型聚醚多元醇所得的聚氨酯泡沫,具有导热性能改善的优势,为聚醚多元醇和聚氨酯合成提供新的技术方案。(The present invention relates to a novel polyether polyol, a method for preparing the same, and a polyurethane foam prepared therefrom. The preparation method of the polyether polyol comprises the following steps: the polyether polyol is prepared by taking trihydroxymethyl aminomethane and hydroxytyrosol as initiators and performing ring-opening polymerization with alkylene oxide under the action of an alkaline catalyst. The polyurethane foam comprises the following raw materials in mass ratio of 100: 10-13: 110-130, a blowing agent and a polyisocyanate. The polyurethane foam obtained by using the novel polyether polyol has the advantage of improved heat-conducting property, and provides a new technical scheme for synthesizing the polyether polyol and the polyurethane.)

1. A method of preparing a polyether polyol comprising: uniformly mixing the tris (hydroxymethyl) aminomethane, the hydroxytyrosol and a catalyst, adding the alkylene oxide to carry out ring-opening polymerization reaction, and optionally carrying out neutralization and refining treatment to obtain the polyether polyol.

2. The method according to claim 1, wherein the mass ratio of tris (hydroxymethyl) aminomethane, hydroxytyrosol, alkylene oxide and catalyst is 100:10-100:280-800: 0.48-10.

3. The preparation method according to claim 1 or 2, wherein the catalyst is one or more of an alkali metal catalyst and an amine catalyst;

preferably, the alkali metal catalyst comprises one or more of cesium hydroxide, potassium hydroxide, sodium hydroxide, and the amine catalyst comprises dimethylamine, trimethylamine, dipropylamine, tripropylamine, N-dimethylcyclohexylamine, N-methyl-N-ethylcyclohexylamine, N-methyl-N-propylcyclohexylamine, N-diethylcyclohexylamine, N-dimethyloctadecylamine, pentamethyldiethylenetriamine, N-methyldiethanolamine, 2-dimethylethanolamine, 1, 4-dimethylpiperazine, N-dimethylbenzylamine, N-dimethylaniline, dodecyldimethyltertiary amine, imidazole, N-methylimidazole, 2-ethylimidazole, 4-methylimidazole, 2-ethyl-4-methylimidazole, sodium hydroxide, One or more of pyridine, 2-aminopyridine, 4-dimethylamino pyridine and 2, 6-diamino pyridine.

4. The production method according to any one of claims 1 to 3, wherein the alkylene oxide is one or more of ethylene oxide, propylene oxide and butylene oxide.

5. The method according to any one of claims 1 to 4, wherein the tris (hydroxymethyl) aminomethane and hydroxytyrosol are uniformly mixed with the catalyst in such a manner that: when the catalyst is solid, adding the catalyst, the tris (hydroxymethyl) aminomethane and the hydroxytyrosol into a closed reaction container, starting stirring, uniformly mixing reaction materials, replacing gas in the reactor with inert gas, and vacuumizing to negative pressure; when the catalyst is liquid, adding tris (hydroxymethyl) aminomethane and hydroxytyrosol into a reaction container, stirring, replacing with inert gas, vacuumizing to negative pressure, pumping in the catalyst under the condition of not introducing air, and mixing with the reaction materials.

6. The production method according to any one of claims 1 to 5, wherein the manner of charging the alkylene oxide comprises: adding a certain amount of alkylene oxide, wherein the adding amount is 5-10 wt% of the total amount of materials in the kettle, heating to 80-100 ℃, timing for 0.5-1h when the pressure in the kettle begins to drop, then continuously adding the alkylene oxide, controlling the reaction temperature to 90-140 ℃, keeping the whole reaction pressure less than or equal to 0.6MPa, and curing for 2-4h after the feeding is finished.

7. A polyurethane foam prepared from materials including a conjugate polyether, a blowing agent, and a polyisocyanate, wherein the polyether polyol of any one of claims 1-6 is included in the conjugate polyether;

preferably, the mass ratio of the combined polyether, the foaming agent and the polyisocyanate is 100: 10-13: 110-130;

preferably, the foaming agent is one or more of cyclopentane, HFC-245fa, HFC-134a, HFC-365a and LBA; the polyisocyanate is polymeric MDI.

8. The polyurethane foam according to claim 7, wherein the conjugate polyether comprises 90-95 parts of the polyether composition, 1.5-3.5 parts of the surfactant, 2-4 parts of the mixed catalyst, and 1-3 parts of water.

9. The polyurethane foam according to claim 8, wherein the polyether composition comprises, by mass: 5-15 parts of the polyether polyol of any one of claims 1-6, 20-55 parts of sucrose-and-glycerol initiated polyether polyol, 20-40 parts of toluene diamine polyether polyol, 5-12 parts of glycerol polyether polyol, 10-20 parts of sorbitol polyether polyol;

preferably, the sucrose and glycerol initiated polyether polyol is prepared by polymerization of sucrose and glycerol as initiators and propylene oxide, and has a hydroxyl value of 400-500mgKOH/g and a functionality of 4-6;

the toluene diamine polyether polyol is prepared by polymerizing toluene diamine serving as an initiator with propylene oxide, wherein the hydroxyl value is 380-440, and the functionality is 3-4;

the glycerol polyether polyol is prepared by polymerizing glycerol serving as an initiator and propylene oxide, and has a hydroxyl value of 180-250mgKOH/g and a functionality of 2-3;

the sorbitol polyether polyol is prepared by polymerizing sorbitol serving as an initiator and propylene oxide, and has a hydroxyl value of 400-460mgKOH/g and a functionality of 5-6.

10. The polyurethane foam of claim 8 or 9, wherein the surfactant is a silicone surfactant;

the mixed catalyst comprises a mixture of pentamethyldiethylenetriamine, tetramethylhexamethylenediamine, bis-dimethylaminoethyl ether, dimethylbenzylamine, dimethylcyclohexylamine, triethylenediamine, hexahydrotriazine, potassium acetate and dibutyltin dilaurate in any proportion.

Technical Field

The invention relates to polyether polyol, a preparation method thereof and polyurethane foam prepared from the polyether polyol, and belongs to the technical field of materials.

Background

Polyurethane materials are known as the fifth major plastic, and have wide applications in the fields of refrigerators, freezers, refrigerated trucks, heat insulation boards, pipeline heat preservation and the like due to low thermal conductivity and good dimensional stability. With the rapid development of the polyurethane industry, the standards of energy conservation and environmental protection are continuously improved, and the performance requirements on polyurethane materials are also gradually improved.

Polyether polyol is used as a basic raw material, and polyether polyols with different structures can be synthesized in a targeted manner by optimizing the molecular structure and the component proportion of the polyether polyol, so that the performance of polyurethane foam is improved, and the application requirements are met. Among common polyether polyols, sucrose-based polyether polyol accounts for a relatively high proportion in combined polyether polyol, and has the characteristic of high functionality, and the formed polyurethane foam has good dimensional stability and high foam strength, but the heat-conducting property is not outstanding. In order to respond to the national policy of energy saving and consumption reduction, the research of low conductor system needs to continuously attack.

Disclosure of Invention

The invention aims to provide a novel polyether polyol, which is developed from the viewpoint of optimizing the structure of the polyether polyol, and improves the heat-conducting property and the like of a hard polyurethane material.

In a first aspect of the present invention, a novel polyether polyol is provided.

The preparation method of the novel polyether polyol comprises the following steps: uniformly mixing trihydroxymethyl aminomethane, hydroxytyrosol and a catalyst in an inert atmosphere, adding alkylene oxide under a certain condition for ring-opening polymerization, degassing after the reaction is finished, and optionally performing neutralization and refining treatment to obtain the polyether polyol.

The catalyst is one or more of alkali metal catalyst and amine catalyst, the alkali metal catalyst comprises cesium hydroxide, potassium hydroxide, sodium hydroxide and the like, the amine catalyst comprises dimethylamine, trimethylamine, dipropylamine, tripropylamine, N-dimethylcyclohexylamine, N-methyl-N-ethylcyclohexylamine, N-methyl-N-propylcyclohexylamine, N-diethylcyclohexylamine, N-dimethyloctadecylamine, pentamethyldiethylenetriamine, N-methyldiethanolamine, 2-dimethylethanolamine, 1, 4-dimethylpiperazine, N-dimethylbenzylamine, N-dimethylaniline, dodecyl dimethyl tertiary amine, imidazole, N-methylimidazole, 2-ethylimidazole, sodium hydroxide and the like, the amine catalyst comprises N, N-diethylcyclohexylamine, N-dimethyloctadecylamine, pentamethyldiethylenetriamine, N-methyldiethanolamine, 2-dimethylethanolamine, 1, 4-dimethylpiperazine, N-dimethylbenzylamine, N-dimethyl-aniline, dodecyl dimethyl tertiary amine, imidazole, 2-methylimidazole, 2-ethylimidazole, N-ethyl imidazole, sodium hydroxide and the like, 4-methylimidazole, 2-ethyl-4-methylimidazole, pyridine, 2-aminopyridine, 4-dimethylaminopyridine, 2, 6-diaminopyridine and the like.

The alkylene oxide is one or more of ethylene oxide, propylene oxide and butylene oxide.

Generally, the mass ratio of the tris (hydroxymethyl) aminomethane, the hydroxytyrosol, the alkylene oxide and the catalyst is 100:10-100:280-800: 0.48-10.

In the solution of the present invention, there are two main ways of uniformly mixing in an inert atmosphere: adding the catalyst, tris (hydroxymethyl) aminomethane and hydroxytyrosol into a closed reaction container when the catalyst is solid, stirring, uniformly mixing the reaction materials, replacing the gas in the reactor with inert gas such as nitrogen for 3-5 times, and vacuumizing to negative pressure, wherein the pressure is less than or equal to-0.09 MPa; when the catalyst is liquid, adding tris (hydroxymethyl) aminomethane and hydroxytyrosol into a reaction container, stirring, replacing for 3-5 times with nitrogen, vacuumizing to negative pressure with the pressure less than or equal to-0.09 MPa, pumping in the catalyst under the condition of not introducing air, and mixing with the reaction materials.

In a further embodiment, the manner of charging the alkylene oxide specifically comprises: after the nitrogen replacement is finished, a certain amount of alkylene oxide is added, the adding amount is 5-10 wt% of the total amount of the materials in the kettle, the temperature is increased to 80-100 ℃, the pressure in the kettle begins to drop for 0.5-1h, then the alkylene oxide is continuously added dropwise, the reaction temperature is controlled to 90-140 ℃, the whole reaction pressure is less than or equal to 0.6MPa, and the aging is carried out for 2-4h after the feeding is finished.

The neutralization and refining process comprises the steps of adding acid and water into crude polyether polyol to carry out neutralization reaction, adding an adsorbent after the reaction is finished, and carrying out dehydration and filtration. The temperature of the neutralization process is 70-90 ℃, and the temperature of the dehydration process is 80-120 ℃. The acid is preferably phosphoric acid, and the adsorbent is one or more of magnesium silicate, aluminum silicate and magnesium aluminum silicate.

In a second aspect, the present invention relates to the use of the above-described novel polyether polyols for the preparation of polyurethane foams.

The polyurethane foam provided by the invention comprises the following preparation raw materials of combined polyether, a foaming agent and polyisocyanate, wherein the mass ratio of the combined polyether to the foaming agent to the polyisocyanate is 100: 10-13: 110-130;

the foaming agent is one or more of cyclopentane, HFC-245fa, HFC-134a, HFC-365a and LBA;

the polyisocyanate is polymeric MDI, typically polymeric MDI having an NCO content of 30 to 32%;

in the scheme of the invention, the combined polyether comprises 90-95 parts of polyether composition, 1.5-3.5 parts of surfactant, 2-4 parts of mixed catalyst and 1-3 parts of water;

further, the polyether composition comprises the following components in percentage by mass: 5-15 parts of novel polyether polyol, 20-55 parts of sucrose and glycerin initiated polyether polyol, 20-40 parts of toluene diamine polyether polyol, 5-12 parts of glycerin polyether polyol and 10-20 parts of sorbitol polyether polyol;

generally, the sucrose and glycerol initiated polyether polyol is prepared by polymerization of sucrose and glycerol as initiators and propylene oxide, and has a hydroxyl value of 400-500mgKOH/g and a functionality of 4-6;

the toluene diamine polyether polyol is prepared by polymerizing toluene diamine serving as an initiator with propylene oxide, wherein the hydroxyl value is 380-440, and the functionality is 3-4;

the glycerol polyether polyol is prepared by polymerizing glycerol serving as an initiator and propylene oxide, and has a hydroxyl value of 180-250mgKOH/g and a functionality of 2-3;

the sorbitol polyether polyol is prepared by polymerizing sorbitol serving as an initiator and propylene oxide, and has a hydroxyl value of 400-460mgKOH/g and a functionality of 5-6;

the surfactant is an organic silicon surfactant;

the mixed catalyst comprises a mixture of pentamethyldiethylenetriamine, tetramethylhexamethylenediamine, bis-dimethylaminoethyl ether, dimethylbenzylamine, dimethylcyclohexylamine, triethylenediamine, hexahydrotriazine, potassium acetate and dibutyltin dilaurate in any proportion.

The preparation method of the polyurethane foam mainly comprises the following steps:

1) weighing the polyether composition, the surfactant, the mixed catalyst and water in proportion, uniformly mixing, and cooling to 8-15 ℃ to obtain combined polyether;

2) cooling the foaming agent below 10 ℃, adding the foaming agent into the combined polyether, and uniformly mixing;

3) and mixing the combined polyether and the foaming agent mixture with polyisocyanate, and injecting the mixture into a mold for foaming to obtain the polyurethane foam.

Further, the material temperature in the step 3) is 17-21 ℃, and the constant temperature of the die is 30-40 ℃.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention adopts trihydroxymethyl aminomethane and hydroxytyrosol as initiators to prepare a novel polyether polyol. Compared with sucrose polyether polyol with similar hydroxyl value, the polyether polyol has lower viscosity, and is beneficial to improving the fluidity of prepared polyurethane foam.

(2) The molecular units of the trihydroxymethyl aminomethane and the hydroxytyrosol are smaller, which is helpful for obtaining smaller cell structural units, improving the cell density, introducing nitrogen elements and aromatic structures, being helpful for improving the rigidity of the cell structure and improving the closed cell rate, thereby improving the heat conductivity of the polyurethane foam. The polyurethane foam prepared by replacing sucrose-based polyether polyol with the polyether polyol initiated by the trihydroxymethyl aminomethane and the hydroxytyrosol has lower heat conductivity coefficient and better meets the requirements of energy conservation and low consumption.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention. 1. Test methods for testing properties of polyether polyols:

determination of the hydroxyl number of the polyether polyol: GB/T12008.3-2009;

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

determination of the moisture of the polyether polyol: GB/T22313-2008;

determination of the pH of the polyether polyol: GB/T9724-2007.

2. Test methods for testing foams:

foam core density test according to standard: GB/T6343-2009;

foam thermal conductivity test according to standard: GB/T10295-;

foam flow property test according to the standard: GB/T21332-;

foam demold expansion test according to standard: QB/JH.

Example 1

Adding 500g of tris (hydroxymethyl) aminomethane, 50g of hydroxytyrosol and 12g of potassium hydroxide into a 5L stainless steel autoclave provided with a stirrer, a heating temperature control device, a cooling device and a pressure sensor, starting stirring, uniformly mixing reaction materials, performing nitrogen displacement for 3 times, vacuumizing until the pressure is-0.09 MPa, dropwise adding 50g of propylene oxide, raising the temperature of the reaction kettle to 90 ℃, continuing dropwise adding the propylene oxide after the pressure in the reaction kettle begins to drop and timing for 0.5h, controlling the reaction temperature to be 110 ℃, controlling the pressure to be within 0.5MPa, controlling the reaction temperature to be 120 ℃ when 701g of the propylene oxide is dropwise added, dropwise adding the residual 1586g of the propylene oxide, controlling the pressure to be within 0.4MPa, curing at 120 ℃ for 2h after the feeding is finished, and then vacuumizing to obtain a crude polyether product. Adding 21g of phosphoric acid and 100g of water into the crude polyether at 80 ℃, reacting for 30min, adding 5g of magnesium aluminum silicate adsorbent, stirring for 20min, dehydrating for 1h, heating to 115 ℃, dehydrating for 1h, and filtering to obtain the polyether polyol.

The polyether polyol has the following properties:

appearance: light yellow liquid

Hydroxyl value: 426mgKOH/g

Viscosity: 7245mPa.s 25 deg.C

Moisture content: 0.13 percent

pH：9.75。

Example 2

Adding 500g of tris (hydroxymethyl) aminomethane and 250g of hydroxytyrosol into a 5L stainless steel autoclave provided with a stirrer, a heating temperature control device, a cooling device and a pressure sensor, performing nitrogen displacement for 3 times, vacuumizing to the pressure of-0.09 MPa, pumping 16g of N, N-dimethylcyclohexylamine, starting stirring, uniformly mixing reaction materials, dropwise adding 40g of propylene oxide, raising the temperature of the reaction kettle to 95 ℃, controlling the reaction temperature to be 110 ℃ and the pressure to be within 0.5 hour after timing 0.5 hour when the pressure in the reaction kettle begins to drop, controlling the reaction temperature to be 115 ℃ when the propylene oxide is dropwise added, dropwise adding the rest 1418g of propylene oxide, controlling the pressure to be within 0.4MPa, curing at 120 ℃ for 2 hours after the feeding is finished, and then performing vacuum pumping to obtain the polyether product.

The polyether polyol has the following properties:

appearance: light yellow liquid

Hydroxyl value: 458mgKOH/g

Viscosity: 12750mPa.s 25 deg.C

Moisture content: 0.05 percent

pH：10.20。

Example 3

Adding 500g of tris (hydroxymethyl) aminomethane and 500g of hydroxytyrosol into a 5L stainless steel autoclave provided with a stirrer, a heating temperature control device, a cooling device and a pressure sensor, performing nitrogen displacement for 3 times, vacuumizing to the pressure of-0.09 MPa, pumping 7g of N-methylimidazole, starting stirring, uniformly mixing reaction materials, dropwise adding 90g of propylene oxide, raising the temperature of the autoclave to 100 ℃, continuing dropwise adding the propylene oxide after the pressure in the autoclave begins to drop and timing for 0.5h, controlling the reaction temperature to be 130 ℃ and the pressure to be within 0.5MPa, controlling the reaction temperature to be 135 ℃ and dropwise adding the residual 1520g of propylene oxide when 867g of the propylene oxide is dropwise added, controlling the pressure to be within 0.4MPa, curing for 2h at 140 ℃ after the feeding is finished, and then vacuumizing to obtain the polyether product.

The polyether polyol has the following properties:

appearance: light yellow liquid

Hydroxyl value: 492mgKOH/g

Viscosity: 17060mPa.s 25 deg.C

Moisture content: 0.06 percent

pH：9.90。

Comparative example 1

Adding 500g of cane sugar, 202g of glycerol and 11g of potassium hydroxide into a 5L stainless steel autoclave provided with a stirrer, a heating temperature control device, a cooling device and a pressure sensor, starting stirring, uniformly mixing reaction materials, replacing 3 times with nitrogen, vacuumizing until the pressure is-0.09 MPa, dropwise adding 50g of propylene oxide, raising the temperature of the reaction kettle to 90 ℃, continuing dropwise adding the propylene oxide after timing 0.5h when the pressure in the reaction kettle begins to drop, controlling the reaction temperature to be 110 ℃, controlling the pressure to be within 0.5MPa, controlling the reaction temperature to be 120 ℃ when the propylene oxide is dropwise added to 512g, dropwise adding the residual 1146g of propylene oxide, controlling the pressure to be within 0.4MPa, curing at 120 ℃ for 2h after the feeding is finished, and then vacuumizing to obtain a crude polyether product. Adding 19.3g of phosphoric acid and 96g of water into the crude polyether at the temperature of 80 ℃, reacting for 30min, adding 5g of magnesium aluminum silicate adsorbent, stirring for 20min, dehydrating for 1h, then heating to 115 ℃, dehydrating for 1h, and filtering to obtain the polyether polyol.

The polyether polyol has the following properties:

appearance: yellow liquid

Hydroxyl value: 428mgKOH/g

Viscosity: 14340mPa.s 50 DEG C

Moisture content: 0.26 percent

pH：6.7。

Examples 4 to 7 and comparative example 2

Examples 4 to 7 and comparative example 2 are examples of rigid polyurethane foams. Rigid polyurethane foams of examples 4-7 and comparative example 2 were produced using the formulations of Table 1 below, wherein the formulations of the examples also contained a polyisocyanate (not shown in Table 1) in an amount of 1.2 times the amount of polyisocyanate based on the mass of the conjugate polyether.

Rigid polyurethane foams of examples 4-7 and comparative example 2 were prepared by the following method:

1) weighing the polyether composition, the surfactant, the mixed catalyst and water in proportion, uniformly mixing, and cooling to 10 ℃ to obtain combined polyether;

2) cooling the foaming agent to 8 ℃, adding the foaming agent into the combined polyether, and uniformly mixing;

3) the mixture is mixed with polyisocyanate (temperature controlled at 19 ℃) and processed by a high-pressure injection molding machine (Krauss Maffei RSC 16/16) at the speed of 180-220m/s, and then injected into a mold with constant temperature (35 ℃) for reaction, and expansion curing is carried out to form rigid polyurethane foam.

The rigid polyurethane foams prepared in examples 4 to 7 and comparative example 2 were subjected to the performance test, and the results of the performance test are shown in Table 2.

The raw materials are illustrated as follows:

polyether polyol A: toluenediamine is used as an initiator, and the hydroxyl value is 398 mgKOH/g;

polyether polyol B: glycerol is used as an initiator, and the hydroxyl value is 225 mgKOH/g;

polyether polyol C: sorbitol is used as an initiator, and the hydroxyl value is 430 mgKOH/g;

surfactant (b): l6863 silicone oil, produced by Meiji Co;

mixing the catalyst: the mass ratio of dibutyltin dilaurate to triethylene diamine to N, N-dimethyl cyclohexylamine is 1: 1.2: 1.2;

polyisocyanate: PM-200, produced by Wanhua chemical group, Inc.;

foaming agent CP: cyclopentane, ZiboXin Rong chemical science and technology Limited.

TABLE 1

TABLE 2

According to the foam test results, examples 4-7 had lower thermal conductivity and better flow and similar demold properties compared to comparative example 2, indicating that the tris and hydroxytyrosol initiated polyether polyols had superior thermal conductivity properties compared to sucrose based polyether polyols.

It will be understood by those skilled in the art that various modifications and changes may be made to the present invention without departing from the spirit and scope of the invention. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.