阅读说明：本技术 一种密胺树脂基阻燃聚醚多元醇的制备方法 (Preparation method of melamine resin based flame-retardant polyether polyol ) 是由 张龙 李雪 于在乾 于 2019-10-22 设计创作，主要内容包括：本发明提供一种密胺树脂基聚醚多元醇的制备方法,涉及高分子领域,将三聚氰胺甲醛树脂与环氧丙烷在催化剂的条件下进行开环聚合而制成密胺树脂基阻燃聚醚多元醇。本发明以密胺树脂作为起始剂,可以制备高效阻燃性的含氮阻燃聚醚多元醇,对制成的密胺树脂基聚醚多元醇的性能进行检测,粘度为1500～2000mPa·s,含水量为0.2％～0.3％,羟值为350～390mgKOH/g。将合成的阻燃聚醚多元醇部分替代普通聚醚多元醇用于制备硬质聚氨酯泡沫可以达到离火自熄,测得硬质聚氨酯泡沫极限氧指数为30％左右；压缩强度为340kPa左右；泡沫密度为50kg·m<Sup>-3</Sup>左右；导热系数为0.025W·(m·K)<Sup>-1</Sup>左右。本发明无须外添加阻燃剂也能达到良好的阻燃效果。其制成的阻燃材料可应用于建筑、车辆内饰、家具等诸多方面。(The invention provides a preparation method of melamine resin-based polyether polyol, which relates to the field of high polymers and is prepared by ring-opening polymerization of melamine formaldehyde resin and propylene oxide under the condition of a catalyst. The melamine resin is used as an initiator, the nitrogen-containing flame-retardant polyether polyol with high-efficiency flame retardance can be prepared, and the performance of the prepared melamine resin-based polyether polyol is detected, wherein the viscosity is 1500-2000 mPa & s, the water content is 0.2-0.3%, and the hydroxyl value is 350-390 mgKOH/g. The synthesized flame-retardant polyether polyol partially replaces the common polyether polyol to be used for preparing the hard polyurethane foam, the hard polyurethane foam can be automatically extinguished after being away from fire, and the limit oxygen index of the hard polyurethane foam is measuredAbout 30 percent; the compressive strength is about 340 kPa; the foam density was 50 kg. m ‑3 Left and right; coefficient of thermal conductivity of 0.025W (m.K) ‑1 Left and right. The invention can achieve good flame-retardant effect without adding a flame retardant. The flame-retardant material prepared by the method can be applied to various aspects such as buildings, vehicle interior decorations, furniture and the like.)

1. A preparation method of melamine resin based flame retardant polyether polyol is characterized by comprising the following steps:

1) according to the mass ratio of 1: 1-2, weighing melamine resin and epoxypropane, adding the melamine resin and the epoxypropane into a reaction kettle, adding diethanol amine with the total mass of 1.0-2.0% of the raw materials into the reaction kettle, putting the materials into the reaction kettle, sealing the system, and using N₂The air in the kettle is replaced for three times, and N is introduced₂The pressure is 0.5-1 MPa, the reaction temperature is 100-140 ℃, after the reaction is carried out for 3-5 h, phosphorus pentoxide accounting for 8-10% of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 3-5 h;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 6-7 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.1-0.05 MPa to remove small molecules to obtain the flame-retardant polyether polyol;

3) cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

2. The method of preparing a melamine resin based flame retardant polyether polyol according to claim 1, comprising the steps of:

1) according to the mass ratio of 1: 1 weighing melamine resin and propylene oxide, adding into a reaction kettle, adding diethanolamine which accounts for 1.0 percent of the total mass of the raw materials into the reaction kettle, placing the materials into the reaction kettle, sealing the system, and adding N₂The air in the kettle is replaced for three times, and N is introduced₂The pressure is 0.5MPa, the reaction temperature is 100 ℃, after the reaction is carried out for 5 hours, phosphorus pentoxide accounting for 8 percent of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 3 hours;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 6 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.05 MPa to remove small molecules to obtain the flame-retardant polyether polyol;

3) cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

3. The method of preparing a melamine resin based flame retardant polyether polyol according to claim 1, comprising the steps of:

1) according to the mass ratio of 1: 1.25 adding melamine resin and propylene oxide into a reaction kettle, adding diethanolamine which accounts for 1.2 percent of the total mass of the raw materials into the reaction kettle, putting the materials into the reaction kettle, sealing the system, and adding N₂The air in the kettle is replaced for three times, and N is introduced₂The pressure is up to 0.6MPa, the reaction temperature is 110 ℃, after the reaction is carried out for 4 hours, phosphorus pentoxide accounting for 8.5 percent of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 4 hours;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 6.5 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.06 MPa to remove small molecules to obtain the flame-retardant polyether polyol;

3) cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

4. The method of preparing a melamine resin based flame retardant polyether polyol according to claim 1, comprising the steps of:

1) according to the mass ratio of 1: 1.5 weighing melamine resin and propylene oxide, adding into a reaction kettle, adding diethanolamine 1.5% of the total weight of the raw materials into the reaction kettle, placing the materials into the reaction kettle, sealing the system, and adding N₂The air in the kettle is replaced for three times, and N is introduced₂The pressure is up to 0.7MPa, the reaction temperature is 130 ℃, after the reaction is carried out for 3 hours, phosphorus pentoxide with the mass being 9 percent of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 5 hours;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 6.5 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.07 MPa to remove small molecules to obtain the flame-retardant polyether polyol;

3) cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

5. The method of preparing a melamine resin based flame retardant polyether polyol according to claim 1, comprising the steps of:

1) according to the mass ratio of 1: 1.75 melamine resin and propylene oxide were weighed and added to a reaction kettle, diethanolamine 1.8% by mass of the total amount of the raw materials was added to the reaction kettle, the materials were put into the reaction kettle and the system was sealed, and N was used₂The air in the kettle is replaced for three times, and N is introduced₂When the pressure is 0.8MPa and the reaction temperature is 130 ℃, after the reaction is carried out for 3.5 hours, phosphorus pentoxide accounting for 8-10 percent of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 4.5 hours;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 7 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.1 MPa to remove small molecules to obtain the flame-retardant polyether polyol;

3) cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

6. The method of preparing a melamine resin based flame retardant polyether polyol according to claim 1, comprising the steps of:

1) according to the mass ratio of 1: 2 weighing melamine resin and propylene oxide, adding into a reaction kettle, adding diethanolamine which accounts for 2.0 percent of the total mass of the raw materials into the reaction kettle, placing the materials into the reaction kettle, sealing the system, and using N₂The air in the kettle is replaced for three times, and N is introduced₂The pressure is up to 1MPa, the reaction temperature is 140 ℃, after the reaction is carried out for 4 hours, phosphorus pentoxide accounting for 8 to 10 percent of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 3 hours;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 7 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.1 MPa to remove small molecules to obtain the flame-retardant polyether polyol.

3) Cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

Technical Field

The invention relates to the technical field of high molecules, in particular to a preparation method of melamine resin based flame retardant polyether polyol.

Background

In recent years, building fire accidents frequently occur, great loss is brought to lives and properties of people, and the flame retardant property of the polyurethane rigid foam serving as an energy-saving and heat-insulating material for building exterior walls is particularly important. The rigid polyurethane foam has the excellent characteristics of unique heat insulation performance, light weight, high mechanical strength, simple construction and the like, and has the characteristics of sound insulation, cold resistance, heat resistance, corrosion resistance and the like, and is a heat insulation material with the lowest heat conductivity coefficient in the existing organic and inorganic materials. Therefore, the composite material is widely used as a heat insulation material for building outer walls, cold storages, pipelines, refrigerators, freezers and the like. However, the oxygen index of the polyurethane rigid foam which is not subjected to flame retardant treatment is about 17%, and the polyurethane rigid foam belongs to flammable materials, so that the flame retardant problem is particularly remarkable. The existing polyurethane rigid foam flame-retardant technology mainly adopts an additive flame retardant, and when the additive flame retardant is used in polyurethane rigid foam, the additive flame retardant is often separated out due to the migration to the surface along with the time, so that the phenomena of the reduction of the flame-retardant performance of the foam, even the flame retardance and the like are caused.

Currently, the flame retardant treatment of polyurethane materials is mainly divided into two types: one is an externally added flame retardant, and the other is to introduce a flame retardant element and an aromatic heterocyclic structure into a molecular structure. The former has the problems that the mechanical performance of the polyurethane material is obviously reduced when the addition amount is larger, the flame retardant performance is reduced because the flame retardant migrates, and the like, but the most extensive flame retardant technology is used when the flame retardant requirement of the polyurethane material is lower (the oxygen index is below 26%), and the latter is mainly realized by adding the polyol containing the flame retardant element or the heterocyclic structure and the reactive flame retardant into the formula of the polyurethane material, and has the advantages of lasting flame retardant performance and small influence on the mechanical performance. However, the flame retardant materials of the prior art are still limited in their application due to the drawbacks of flame retardant properties and mechanical properties.

Disclosure of Invention

Technical problem to be solved

In order to solve the problems that the application of the flame-retardant material in the prior art is still limited due to the defects of flame-retardant property and mechanical property, the invention provides a preparation method of melamine resin-based flame-retardant polyether polyol, melamine formaldehyde resin and propylene oxide are subjected to ring-opening polymerization under the condition of a catalyst to prepare the melamine resin-based flame-retardant polyether polyol, and the reaction type flame-retardant polyether polyol provided by the invention is also one of the preferable methods for improving the flame-retardant property of polyurethane foam.

(II) technical scheme

In order to achieve the purpose, the invention is realized by the following technical scheme:

a preparation method of melamine resin based flame retardant polyether polyol comprises the following steps:

1) according to the mass ratio of 1: 1-2, weighing melamine resin and epoxypropane, adding the melamine resin and the epoxypropane into a reaction kettle, adding diethanol amine with the total mass of 1.0-2.0% of the raw materials into the reaction kettle, putting the materials into the reaction kettle, sealing the system, and using N₂The air in the kettle is replaced for three times, and N is introduced₂The pressure is 0.5-1 MPa, the reaction temperature is 100-140 ℃, after the reaction is carried out for 3-5 h, phosphorus pentoxide accounting for 8-10% of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 3-5 h;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 6-7 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.1-0.05 MPa to remove small molecules to obtain the flame-retardant polyether polyol;

3) cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

Preferably, the method comprises the following steps:

1) according to the mass ratio of 1: 1 weighing melamine resin and propylene oxide, adding into a reaction kettle, adding diethanolamine which accounts for 1.0 percent of the total mass of the raw materials into the reaction kettle, placing the materials into the reaction kettle, sealing the system, and adding N₂The air in the kettle is replaced for three times, and N is introduced₂The pressure is 0.5MPa, the reaction temperature is 100 ℃, after the reaction is carried out for 5 hours, phosphorus pentoxide accounting for 8 percent of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 3 hours;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 6 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.05 MPa to remove small molecules to obtain the flame-retardant polyether polyol;

3) cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

Preferably, the method comprises the following steps:

1) according to the mass ratio of 1: 1.25 adding melamine resin and propylene oxide into a reaction kettle, adding diethanolamine which accounts for 1.2 percent of the total mass of the raw materials into the reaction kettle, putting the materials into the reaction kettle, sealing the system, and adding N₂The air in the kettle is replaced for three times, and N is introduced₂The pressure is up to 0.6MPa, the reaction temperature is 110 ℃, after the reaction is carried out for 4 hours, phosphorus pentoxide accounting for 8.5 percent of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 4 hours;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 6.5 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.06 MPa to remove small molecules to obtain the flame-retardant polyether polyol;

3) cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

Preferably, the method comprises the following steps:

1) according to the mass ratio of 1: 1.5 weighing melamine resin and propylene oxide, adding into a reaction kettle, adding diethanolamine 1.5% of the total weight of the raw materials into the reaction kettle, placing the materials into the reaction kettle, sealing the system, and adding N₂The air in the kettle is replaced for three times, and N is introduced₂The pressure is up to 0.7MPa, the reaction temperature is 130 ℃, after the reaction is carried out for 3 hours, phosphorus pentoxide with the mass being 9 percent of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 5 hours;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 6.5 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.07 MPa to remove small molecules to obtain the flame-retardant polyether polyol;

3) cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

Preferably, the method comprises the following steps:

1) according to the mass ratio of 1: 1.75 melamine resin and propylene oxide were weighed and added to a reaction kettle, diethanolamine 1.8% by mass of the total amount of the raw materials was added to the reaction kettle, and the materials were put inIn the reaction kettle, sealing the system, and using N₂The air in the kettle is replaced for three times, and N is introduced₂When the pressure is 0.8MPa and the reaction temperature is 130 ℃, after the reaction is carried out for 3.5 hours, phosphorus pentoxide accounting for 8-10 percent of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 4.5 hours;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 7 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.1 MPa to remove small molecules to obtain the flame-retardant polyether polyol;

3) cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

Preferably, the method comprises the following steps:

1) according to the mass ratio of 1: 2 weighing melamine resin and propylene oxide, adding into a reaction kettle, adding diethanolamine which accounts for 2.0 percent of the total mass of the raw materials into the reaction kettle, placing the materials into the reaction kettle, sealing the system, and using N₂The air in the kettle is replaced for three times, and N is introduced₂The pressure is up to 1MPa, the reaction temperature is 140 ℃, after the reaction is carried out for 4 hours, phosphorus pentoxide accounting for 8 to 10 percent of the total mass of the raw materials is added into the reaction kettle, and the reaction is continued for 3 hours;

2) after the reaction in the step 1) is finished, cooling and discharging, adjusting the pH value of the material to 7 by using diethanolamine, and then vacuumizing at 120 ℃ and-0.1 MPa to remove small molecules to obtain the flame-retardant polyether polyol.

3) Cooling the polyether polyol obtained in the step 2) to normal temperature to obtain a target object, and pouring the target object into a sealed container.

(III) advantageous effects

The invention provides a preparation method of melamine resin based polyether polyol, which has the advantages of short preparation period, simple process and low cost and is suitable for industrial production. The obtained flame-retardant polyether polyol is used for partially replacing common polyether polyol to prepare rigid polyurethane foam, has high flame retardance, and can achieve self-extinguishing after leaving fire. And the mechanical strength and other properties of the foam are not obviously reduced. Meanwhile, the high-nitrogen flame-retardant polyol has the characteristics of high flame-retardant efficiency, high thermal decomposition temperature, low toxicity, environmental friendliness and the like.

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, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.