阅读说明：本技术 无机纳米复合聚醚多元醇的制备方法 (Preparation method of inorganic nano composite polyether polyol ) 是由 程铸洪 高伟伟 李海东 姜男 于 2021-08-30 设计创作，主要内容包括：本发明涉及一种无机纳米复合聚醚多元醇的制备方法,属于聚醚多元醇改性技术领域。所述的无机纳米复合聚醚多元醇的制备方法,以无机纳米二氧化硅与含硅氧烷聚醚多元醇为原料,二者在水溶液中通过高温搅拌反应并进行脱水、脱醇处理得到所述的无机纳米复合聚醚多元醇；所述的含硅氧烷聚醚多元醇由硅烷偶联剂与起始剂复配,在催化剂作用下,与环氧烷烃进行聚合反应得到。本发明设计科学合理,制备的产品可以应用在聚氨酯材料阻燃领域,同时制备的产品具有较高的强度和优良的储存稳定性以及抗冲击性。(The invention relates to a preparation method of inorganic nano composite polyether polyol, belonging to the technical field of polyether polyol modification. The preparation method of the inorganic nano composite polyether polyol takes inorganic nano silicon dioxide and siloxane-containing polyether polyol as raw materials, and the inorganic nano composite polyether polyol is obtained by stirring the inorganic nano silicon dioxide and the siloxane-containing polyether polyol at high temperature in an aqueous solution for reaction, dehydration and dealcoholization; the siloxane-containing polyether polyol is obtained by compounding a silane coupling agent and an initiator and carrying out polymerization reaction with alkylene oxide under the action of a catalyst. The invention has scientific and reasonable design, the prepared product can be applied to the flame retardant field of polyurethane materials, and the prepared product has higher strength, excellent storage stability and impact resistance.)

1. A preparation method of inorganic nano composite polyether polyol is characterized by comprising the following steps: inorganic nano silicon dioxide and siloxane-containing polyether polyol are used as raw materials, and are stirred and reacted at high temperature in an aqueous solution, and dehydration and dealcoholization treatment are carried out to obtain the inorganic nano composite polyether polyol;

the siloxane-containing polyether polyol is obtained by compounding a silane coupling agent and an initiator and carrying out polymerization reaction with alkylene oxide under the action of a catalyst.

2. The method of producing an inorganic nanocomposite polyether polyol according to claim 1, characterized in that: the particle size of the inorganic nano silicon dioxide is less than 0.1 μm.

3. The method of producing an inorganic nanocomposite polyether polyol according to claim 1, characterized in that: the silane coupling agent is a modified aminosilane coupling agent.

4. The method of producing an inorganic nanocomposite polyether polyol according to claim 1, characterized in that: the initiator is a mixture of more than two of propylene glycol, diethylene glycol, water, glycerol, sorbitol or sucrose.

5. The method of producing an inorganic nanocomposite polyether polyol according to claim 1, characterized in that: the catalyst is organic amine catalyst.

6. The method of producing an inorganic nanocomposite polyether polyol according to claim 1, characterized in that: the amount of the raw materials for preparing the siloxane-containing polyether polyol is as follows:

7. the method of producing an inorganic nanocomposite polyether polyol according to claim 1, characterized in that: the polymerization temperature is 80-105 ℃, and the reaction time is 2-4 h.

8. The method of producing an inorganic nanocomposite polyether polyol according to claim 1, characterized in that: the used raw materials are as follows:

50-70% of siloxane-containing polyether polyol;

10-30% of inorganic nano silicon dioxide;

20-40% of water.

9. The method of producing an inorganic nanocomposite polyether polyol according to claim 1, characterized in that: the high-temperature stirring reaction temperature is 80-85 ℃, and the reaction time is 2-2.5 h.

10. The method of producing an inorganic nanocomposite polyether polyol according to claim 1, characterized in that: the dehydration and dealcoholization treatment method comprises the steps of heating at the temperature of 105 ℃ and 110 ℃ for 1.0-1.5 h.

Technical Field

The invention relates to a preparation method of inorganic nano composite polyether polyol, belonging to the technical field of polyether polyol modification.

Background

Polyurethane, namely carbamate, is one of six synthetic materials, and has excellent heat insulation, corrosion resistance, impact resistance and other properties, and the preparation and processing method is simple and convenient and easy to operate, so that the polyurethane is widely applied to the fields of buildings, heat preservation, machinery, automobile manufacturing, medical treatment, electronics and the like and is the first of various materials.

Most of the molecular structures of polyurethane materials are urethane segments. Most common polyurethane materials are easy to combust in air, and a large amount of toxic gas and smoke dust are generated in the combustion process, which causes great economic loss and casualties, so that the application of the polyurethane in certain fields with relatively high requirements on flame retardance is limited.

At present, the method for improving the flame retardant property of polyurethane is mainly a method of adding an organic flame retardant, but the method not only can cause the reduction of the strength and the processing property of materials, but also the added organic flame retardant component can often release highly toxic gas at high temperature, thereby causing greater harm to organisms and environment.

Inorganic materials are non-combustible or difficult-combustible intrinsic flame-retardant materials, and in recent years, methods for improving the flame retardance of the materials by adding the inorganic materials into polyurethane materials are more, but the method of physical mixing addition cannot prepare stable products in advance, so that the requirements on construction sites are higher, and the performances of obtained products are not ideal. The polyether polyol is one of main raw materials for producing the polyurethane material, and the production process is relatively simple and environment-friendly, and the reaction conditions are mild. In recent years, there are many studies on modifying polyether polyol to achieve structural flame retardance of polyurethane materials, but most of the modification methods belong to the category of adding organic flame retardant components physically or chemically as mentioned above, and no inorganic composite polyether polyol product is currently circulated in the market.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the preparation method of the inorganic nano composite polyether polyol is scientific and reasonable in design, the prepared product can be applied to the field of polyurethane material flame retardance, and the prepared product has high strength and excellent storage stability.

The preparation method of the inorganic nano composite polyether polyol is relatively simple, and the inorganic nano silicon dioxide is bonded with the polyether polyol structure in a covalent bond mode, so that the flame retardant effect of the body is achieved, and the preparation method has important significance for the development of flame retardant polyether polyol.

The preparation method of the inorganic nano composite polyether polyol takes inorganic nano silicon dioxide and siloxane-containing polyether polyol as raw materials, and the inorganic nano composite polyether polyol is obtained by stirring the inorganic nano silicon dioxide and the siloxane-containing polyether polyol at a high temperature in an aqueous solution for reaction, dehydration and dealcoholization;

the siloxane-containing polyether polyol is obtained by compounding a silane coupling agent and an initiator and carrying out polymerization reaction with alkylene oxide under the action of a catalyst.

The particle size of the inorganic nano-silica is below 0.1 μm, and industrial hydrophilic nano-silica produced by a gas phase method, also called fumed silica, is preferably A150, V15, LM150 and HL-150.

The silane coupling agent is a modified aminosilane coupling agent, and preferably one or two of A-1100, A-1110, A-1120 and A1130.

Preferably, the initiator is a mixture of two or more of propylene glycol, diethylene glycol, water, glycerol, sorbitol, or sucrose.

Preferably, the catalyst is an organic amine catalyst.

Preferably, the siloxane-containing polyether polyol starting materials are prepared in the following amounts:

based on the total mass of the four substances as 100 percent.

Preferably, the polymerization temperature is 80-105 ℃ and the reaction time is 2-4 h.

Preferably, the raw materials are used in the following amounts:

50-70% of siloxane-containing polyether polyol;

10-30% of inorganic nano silicon dioxide;

20-40% of water.

Based on the total mass of the three substances as 100 percent.

Preferably, the high-temperature stirring reaction temperature is 80-85 ℃, and the reaction time is 2-2.5 h.

Preferably, the dehydration and dealcoholization treatment method is carried out at the temperature of 105 ℃ and the temperature of 110 ℃ for 1.0-1.5 h.

The preparation method of the inorganic nano composite polyether polyol comprises the following steps:

(1) preparation of the siloxane-containing polyether polyol:

according to different theoretically designed functionalities and hydroxyl values, a silane coupling agent, an initiator and a catalyst are subjected to polymerization reaction with propylene oxide under certain conditions according to a set proportion to generate siloxane-containing polyether polyol;

(2) according to different contents of inorganic nano-silica, stirring the siloxane-containing polyether polyol synthesized in the step (1), nano-silica and water according to a set proportion at a high temperature under a certain condition, and carrying out dehydration and dealcoholization treatment to obtain the inorganic nano-composite polyether polyol.

In the step (1), the stirring speed is preferably 10 to 25 r/min.

In the step (1), the influence of the type selection of the silane coupling agent and the initiator on the polyether indexes is different, and polyether polyols with different index ranges can be synthesized according to the requirements.

In step (1), the catalyst includes, but is not limited to, N-dimethylcyclohexylamine, N-dimethylbenzylamine, pentamethyldiethylenetriamine, N ' -tetramethylalkylenediamine, triethylamine, triethylenediamine, N ' -diethylpiperazine, DMEA, DBU, N ' -dimethylpyridine, and the like.

The invention uses silane coupling agent containing amino and polyol as co-initiator, under the action of catalyst, initiates propylene oxide polymerization reaction to obtain polyether polyol containing siloxane, then siloxane in the polyether polyol can generate chemical reaction with silicon-oxygen bond on the surface of inorganic nano silicon dioxide under a certain condition, and inorganic components and polyether structure are chemically bonded to obtain polyether polyol with different indexes and silicon dioxide content. The polyether polyol synthesized by the method contains inorganic flame-retardant components in the structure, so that the polyurethane foam obtained in downstream application has good flame-retardant performance, higher strength and dimensional stability.

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

(1) according to the invention, the inorganic structure is connected with the organic structure of polyether in a chemical bond manner, so that inorganic flame-retardant components enter the structure of polyurethane, the flame-retardant property of polyurethane foam plastic is improved, and secondary damage to an organism caused by virulent gas generated at high temperature due to the addition of an organic flame retardant is avoided;

(2) the inorganic nano composite polyether polyol synthesized by the method has good storage stability, and compared with the physically added inorganic flame retardant component, the inorganic nano composite polyether polyol has good storage stability and lower requirements on foaming processing equipment, and can be processed and produced according to the conventional construction process;

(3) the polyurethane foam plastic prepared by the polyether polyol prepared by the method has good dimensional stability, higher strength and impact resistance.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.

The starting materials used in the examples are all commercial products.

Example 1

(1) Accurately weighing silane coupling agent A-1110165 g, glycerol 145g, sorbitol 120g and N, N-dimethylcyclohexylamine catalyst 9g, adding into a reaction kettle, slowly dropwise adding 400g of propylene oxide into the reaction kettle through a pressure container, stirring at the speed of 18r/min, and carrying out polymerization reaction at the temperature of 100 ℃ to obtain the siloxane-containing polyether polyol.

(2) 500g of siloxane-containing polyether polyol, 15090 g g of nano-silica A and 160g of deionized water are added into a three-neck flask equipped with a thermometer, a reflux condenser and a nitrogen protection device. Placing on a magnetic heating stirrer, stirring at 45r/min, reacting at 85 deg.C for 2h, heating to 105 deg.C, vacuum dehydrating, dealcoholizing for 1.5h, and making into yellowish transparent to slightly turbid uniform liquid.

Example 2

(1) Accurately weighing silane coupling agent A-1100150 g, glycerol 70g, diethylene glycol 80g, sucrose 123g and N, N-dimethylbenzylamine catalyst 10g, adding into a reaction kettle, slowly dripping 450g of propylene oxide into the reaction kettle through a pressure container at a stirring speed of 18r/min, and carrying out polymerization reaction at 100 ℃ to obtain siloxane-containing polyether polyol with yellow uniform appearance.

(2) 600g of siloxane-containing polyether polyol, 600g of nano-silica V15180 g and 230g of deionized water are added into a three-neck flask which is provided with a thermometer, a reflux condenser and a nitrogen protection device. Placing on a magnetic heating stirrer, stirring at 45r/min, reacting at 85 deg.C for 2h, heating to 105 deg.C, vacuum dehydrating, dealcoholizing for 1.5h, and making into yellowish transparent to slightly turbid uniform liquid.

Example 3

(1) Accurately weighing 12g of a silane coupling agent A-1120225 g, 160g of propylene glycol, 180g of sucrose and triethylamine catalyst, adding into a reaction kettle, slowly dropwise adding 500g of propylene oxide into the reaction kettle through a pressure container, stirring at 18r/min, and carrying out polymerization reaction at 100 ℃ to obtain the siloxane-containing polyether polyol.

(2) 600g of siloxane-containing polyether polyol, 600g of nano-silica LM 150200 g and 200g of deionized water are added into a three-neck flask equipped with a thermometer, a reflux condenser and a nitrogen protection device. Placing on a magnetic heating stirrer, stirring at 45r/min, reacting at 85 deg.C for 2h, heating to 105 deg.C, vacuum dehydrating, dealcoholizing for 1.5h to obtain inorganic nanometer composite polyether polyol which is light yellow transparent to slightly turbid uniform liquid.

Example 4

(1) Accurately weighing silane coupling agent A1130200 g, diethylene glycol 160g, sucrose 180g and pentamethyldiethylenetriamine catalyst 12g, adding into a reaction kettle, slowly dripping 480g of propylene oxide into the reaction kettle through a pressure container, stirring at 18r/min, and carrying out polymerization reaction at 100 ℃ to obtain the siloxane-containing polyether polyol.

(2) 500g of siloxane-containing polyether polyol, 500g of nano silicon dioxide HL-150200 g and 200g of deionized water are added into a three-neck flask provided with a thermometer, a reflux condenser tube and a nitrogen protection device. Placing on a magnetic heating stirrer, stirring at 45r/min, reacting at 85 deg.C for 2h, heating to 105 deg.C, vacuum dehydrating, dealcoholizing for 1.5h to obtain inorganic nanometer composite polyether polyol which is light yellow transparent to slightly turbid uniform liquid.

Comparative example 1

Adding nano-silica LM 150100 g, 80g of glycerol, 30g of diethylene glycol, 110g of sucrose and 8g of organic amine catalyst into a reaction kettle, slowly dropwise adding 620g of propylene oxide into the reaction kettle through a pressure container, stirring at 18r/min, carrying out polymerization reaction at 100 ℃, discharging materials after the reaction is finished, and obtaining polyether polyol which is light yellow turbid liquid in appearance and contains a large amount of white suspended particles.

The conventional polyether polyol was a light yellow transparent to slightly cloudy homogeneous liquid, and the polyether polyol prepared in comparative example 1 was pale yellow turbid in appearance and had a large amount of white suspended matter, and could not be used next.

In comparative example 1, the polyether polyol containing siloxane in the structure is not prepared in advance, but inorganic nano silica is directly added into a polymer system for polyether synthesis reaction, and compared with the example, inorganic components cannot be introduced into the polyether polyol, so that the inorganic phase and the organic phase cannot be compatible to precipitate white solid, and further detection and use cannot be performed.

Comparative example 2

Adding 265g of cane sugar, 140g of diethylene glycol and 11g of organic amine catalyst into a reaction kettle, slowly and dropwise adding 690g of propylene oxide into the reaction kettle through a pressure container, stirring at 18r/min, carrying out polymerization reaction at 100 ℃, discharging materials after the reaction is finished, and obtaining the polyether polyol which is light yellow transparent liquid in appearance.

Comparative example 3

Accurately weighing and adding a silane coupling agent A1130180 g, 62g of diethylene glycol, 98g of sucrose and 8g of organic amine catalyst into a reaction kettle, slowly dropwise adding 505g of propylene oxide into the reaction kettle through a pressure container, stirring at the speed of 18r/min, and carrying out polymerization reaction at the temperature of 100 ℃ to obtain the siloxane-containing polyether polyol.

The polyether polyols obtained in example 1, example 2, example 3 and example 4 and comparative example 1, comparative example 2 and comparative example 3 were subjected to hydroxyl value and viscosity tests, respectively, and the test results are shown in table 1.

TABLE 1 hydroxyl number, viscosity results for polyether polyols obtained in examples 1-4 and comparative examples 2-3

Performance of	Example 1	Example 2	Example 3	Example 4	Comparative example 1	Comparative example 2	Comparative example 3
								Hydroxyl value/mgKOH/g	350	340	338	310	Fail to test	437	390
viscosity/mPa. multidot.s (25 ℃ C.)	4520	5830	7500	8200	Fail to test	3560	4030

The polyether is compounded into combined materials according to a certain proportion, and the combined materials are mixed with PM200 according to a ratio of 1:1.2 respectively for foaming to prepare polyurethane foam, and the foam performance, the combined material proportion and the foam performance result are shown in table 2.

TABLE 2 examples 1-4 and comparative examples 2, 3 corresponding combination mix ratios and foam performance results

As can be seen from tables 1 and 2, the inorganic nanocomposite polyether polyol prepared by the invention has high flame retardancy, and the polyurethane foam prepared from the polyether polyol has high strength and dimensional stability.