CN107722350A - A kind of polyhydroxy silicon nitrogen type flame retardant and its preparation method and the application in anti-inflaming polyurethane hard foam material - Google Patents

Abstract

The invention discloses a polyhydroxyphenyl ring silicon nitrogen type flame retardant, which is characterized in that it has the following chemical structure: Wherein R is the following structural formula or its analogues _{: Wherein} R is one of the following structural formulas or its analogue: With the polyhydroxyphenyl ring silicon nitrogen type flame retardant of the present invention, polyether polyol, polyester polyol, polyisocyanate, catalyst, stabilizer, crosslinking agent, modified nano-oxide, flame retardant, distilled water as The main raw materials are mixed, stirred at high speed, foamed and matured to obtain full water foamed flame retardant rigid polyurethane material. The resulting all-water foamed flame-retardant polyurethane rigid foam has high mechanical properties and flame-retardant properties, with a density of 58.5-64.5kg/m ³ , a compressive strength of 0.405-0.45MPa, a tensile strength of 0.53-0.68MPa, and a limiting oxygen index of 28.5 ~34.5%.

Description

A kind of polyhydroxy silicon nitrogen type flame retardant and its preparation method and in flame retardant polyurethane rigid foam material application in

technical field

The invention relates to a silicon-nitrogen flame retardant and full water foamed rigid polyurethane foam.

Background technique

Polyurethane hard material is one of the most widely used polymer materials at present, with low density, high specific strength, excellent wear resistance, low thermal conductivity, and excellent shock absorption and sound absorption properties. The disadvantage of rigid polyurethane foam is that it is flammable and has poor high temperature resistance. When it comes into contact with a fire source, it will immediately produce flames, which poses a huge threat to human life and property, and greatly restricts its application. Reactive flame retardants participate in the polymerization reaction during the synthesis of polyurethane and combine flame retardant elements on the main chain or side chain of the material molecule, so that the prepared polyurethane material has flame retardant properties. This type of flame retardant is compatible with the matrix material. Good capacitance and high flame retardant efficiency. Phosphorus-based and silicon-based flame retardants have the advantages of high flame retardant efficiency, long-lasting and stable flame retardant effect, and low cost, while compounds with aromatic structure or heterocyclic structure can enhance the rigidity of the molecular chain of the material to a certain extent. Chinese published patent CN101906248A discloses a rigid polyurethane foam with high compressive strength and enhanced rigidity, which is made of aromatic compounds As a rigid structural component that enhances the compressive strength of polyurethane foam, this aromatic compound enhances the mechanical properties of the material, but does not greatly improve the flame retardancy of the material.

The preparation of rigid polyurethane foam generally uses low-boiling chlorofluorocarbons as blowing agents, such as CFC-F11, HFC-141b, and HFC-245fa. These fluorine-containing blowing agents all have a certain destructive effect on ozone, and Hydrocarbon blowing agents represented by pentane are toxic, flammable and explosive, and have harmful effects on the environment. In recent years, the foaming process using water as a foaming agent has begun to be widely studied. Water and isocyanate react to generate _CO2 as a foaming agent. The ozone decay index (ODP) is 0, and the foaming process is simpler and safer. However, compared with the physical foaming system, the material prepared by all-water foaming has disadvantages such as low strength, poor dimensional stability, and brittle foam. Some specific nano-oxides are modified, and the agglomeration phenomenon in the material disappears, which has good compatibility with the material, and also improves the tensile strength, wear resistance and anti-aging performance of the material to a certain extent, making the foam The body is not easy to be brittle.

The invention introduces flame retardant elements such as silicon and nitrogen into the molecular structure of the polyurethane material, and at the same time combines the rigid heat-resistant benzene ring structure to enhance the flame retardant performance of the rigid polyurethane material and the rigid cohesion of the molecular chain. The flame retardant process of silicon and nitrogen compounds acts on the condensed phase and gas phase of material combustion respectively, and has a certain two-phase synergistic flame retardant effect. Abandoning the use of chlorofluorocarbons as a physical blowing agent, using a full-water foaming system to prepare rigid polyurethane foam, and further adding modified nano-oxides to it, to a large extent overcomes the problem of full-water foaming polyurethane rigid materials Disadvantages such as low strength, poor dimensional stability, and brittle foam.

Contents of the invention

In order to solve the above-mentioned problems in the prior art, the present invention provides a fully water-foamed flame-retardant polyurethane rigid foam material and a preparation method thereof. On the one hand, the present invention utilizes the method of molecular design of chemical structure to prepare polyhydroxy benzene ring silicon nitrogen flame retardant, the presence of silicon nitrogen structure and benzene ring group enhances the flame retardancy and heat resistance of the material, on the other hand , using water with zero ODP value as a foaming agent, introducing modified nano-oxides, effectively improving the tensile strength, wear resistance and anti-aging properties of the material foam, and making the foam less brittle. In order to realize above object of the invention, the technical scheme that the present invention adopts is as follows:

A polyhydroxyphenyl ring silicon nitrogen type flame retardant, it has the following chemical structure:

Wherein R is _one of the following structural formulas:

R is one of the following structural formulas _:

A method for preparing the above-mentioned polyhydroxyphenyl ring silicon nitrogen type flame retardant, it carries out following reaction:

It includes the following steps:

Step 1. Under the condition of stirring at room temperature, dissolve p-hydroxybenzaldehyde in ethanol to form A solution, and dissolve the bisaminobenzene ring compound in ethanol to form B solution. Add B solution to A solution dropwise at 25-30°C. The dropping time is controlled within 1-2h. After the dropping is completed, the temperature is raised to 40-55°C and reacted for 2-4h to obtain a polyhydroxy compound containing a carbon-nitrogen double bond. The bisaminobenzene ring compound is the following 8 types One of the compounds:

Step 2. Under the protection of nitrogen, add the silicon-containing compound to the reaction system in the above step 1, and add the catalyst zinc chloride at the same time, raise the temperature of the reaction mixture to 70-85°C, react for 8-16h, and cool it to room temperature. Pour into petroleum ether and stir for 0.5-1.5h, filter out the solid product, wash with cold ethanol, and vacuum-dry at 50-75°C for 12-24h to obtain a polyhydroxyphenylcyclosilane-nitrogen flame retardant, the silicon-containing The compound is one of the following two compounds:

In the above method for preparing polyhydroxyphenylcyclic phosphorus nitrogen type flame retardants, the mass ratio of p-hydroxybenzaldehyde to ethanol in the A solution is 1:8-15, and the mass ratio of the bisaminobenzene ring compound to the ethanol in the B solution is The ratio is 1:5-10, the molar ratio of bisaminobenzene ring compound to p-hydroxybenzaldehyde is 1:2-2.5, the molar ratio of bisaminobenzene ring compound to silicon-containing compound is 1:3-3.5, and p-hydroxybenzene The mass ratio of formaldehyde to petroleum ether is 1:35-50, and the mass ratio of p-hydroxybenzaldehyde to zinc chloride is 1:0.02-0.05.

The application of the above-mentioned polyhydroxyphenylcyclosilane-nitrogen flame retardant in the preparation of full water foaming flame retardant polyurethane rigid foam material.

The above-mentioned all-water-foaming flame-retardant polyurethane rigid foam material contains two components A and B. By mass, the components in component A are: polyether polyol: 30-85 parts, polyester Polyol: 15-30 parts, stabilizer: 2-4 parts, catalyst: 0.5-3 parts, crosslinking agent: 0.5-1.5 parts, distilled water: 3-10 parts, modified nano-oxide: 2-10 parts, The above-mentioned polyhydroxyphenyl-silicon-phosphorus-nitrogen flame retardant: 5-12 parts; the number of components in component B is: polyisocyanate: 60-150 parts.

The above-mentioned all-water foaming flame-retardant polyurethane rigid foam material, the stabilizer in the A component is one or a combination of silicone foam stabilizers AK-8805, AK-8811, AK-8803, and AK-8832; The catalyst is triethylenediamine, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, ethylenediamine, cyclohexylamine, 1,3,5-tris(dimethylaminopropyl) One or more combinations of hexahydrotriazine and pentamethyldiethylenetriamine; the crosslinking agent is one or more combinations of trimethylolpropane, triethanolamine, diethanolamine, and glycerin; the poly Ether polyol is one or several kinds of polytetrahydrofuran polyol or polyoxypropylene polyol, the hydroxyl value is 420-480mgKOH/g, the viscosity is 2000-6000mPa.s (25℃); polyester polyol is aliphatic polyol One or more of ester polyols or aromatic polyester polyols, their hydroxyl value is 100-400mgKOH/g, and their viscosity is 2000-3000mPa.s (25°C); the polyisocyanate is polymethylene polyol Phenyl polyisocyanate (PAPI).

The above-mentioned all-water foaming flame-retardant polyurethane rigid foam material, the modified nano-oxide in the A component is obtained by modifying the nano-oxide with a coupling agent, wherein the nano-oxide is nano-titanium dioxide (TiO ₂ ), nano-dioxide Silicon oxide (SiO ₂ ), nano zinc oxide (ZnO), nano aluminum oxide (Al ₂ O ₃ ), nano antimony pentoxide (Sb ₂ O ₅ ), nano zirconia (ZrO ₂ ), nano cerium oxide (CeO ₂ ), nano-iron oxide (Fe ₂ O ₃ ), one or a combination of nano-ceramics, the coupling agent is one of silane coupling agent KH550 or titanate coupling agent 201, the coupling agent and nano-oxidation The mass ratio of the compound is 1:15-20, first configure an ethanol solution containing 2%-4% of the coupling agent, place the nano-oxide in the ethanol solution containing the coupling agent, stir for 0.5-1h and then filter, the filter cake is in Dry at 80-95°C for 2 hours to prepare modified nano-oxides.

A method for preparing the above-mentioned all-water foaming flame-retardant polyurethane rigid foam material, which is to mix polyether polyol and polyester polyol in component A and stir evenly at high speed, add other additives and stir evenly, and mix with component B Fully mixed by high-pressure foaming machine equipment, injected into a constant temperature sealed mold by the nozzle of the foaming machine, and obtained a flame-retardant polyurethane rigid foam material through a series of processes such as foaming, curing, and demoulding.

The invention prepares a flame-retardant polyurethane rigid foam based on full water foaming on the basis of synthesizing a silicon-nitrogen structure flame retardant. Introduce flame retardant elements such as silicon and nitrogen into the molecular structure of polyurethane materials, and at the same time combine the rigid heat-resistant benzene ring structure to enhance the flame retardant properties of rigid polyurethane materials and the rigidity of molecular chains. Abandoning the use of chlorofluorocarbons as a physical blowing agent, using a full-water foaming system to prepare rigid polyurethane foam, and further adding modified nano-oxides to it, to a large extent overcomes the problem of full-water foaming polyurethane rigid materials Disadvantages such as low strength, poor dimensional stability, and brittle foam. The beneficial effects of the present invention are as follows:

1. The present invention prepares flame-retardant polyurethane rigid foam, which does not contain harmful elements such as halogens, avoids the generation of toxic gas and a large amount of smoke during combustion, and the molecular chain structure contains a benzene ring structure with good thermal stability and flame-retardant silicon Nitrogen structure, which enhances the thermal stability and flame retardancy of rigid polyurethane;

2. The present invention is a flame-retardant polyurethane rigid foam based on full water foaming. Modified nano-oxides are introduced into it, which avoids the disadvantages of low strength, poor dimensional stability, and brittle foam of full water foaming polyurethane rigid materials. . The resulting all-water foamed flame-retardant polyurethane rigid foam has high mechanical properties and flame-retardant properties, with a density of 58.5-64.5kg/m ³ , a compressive strength of 0.405-0.45MPa, a tensile strength of 0.53-0.68MPa, and a limiting oxygen index of 285. ~345%.

detailed description

The following examples are used to illustrate the polyhydroxyphenylcyclosilyl nitrogen type flame retardant of the present invention and a kind of full water foaming flame retardant polyurethane rigid foam material and its preparation method. Examples are to further describe the present invention in detail, but they do not limit the present invention.

A kind of full water foaming flame-retardant polyurethane rigid foam material of the present invention is prepared according to the following method:

Weigh the polyols and various additives in component A according to the formula components, mix and stir evenly, and fully mix with component B through a high-pressure foaming machine, and the fully mixed components A and B are passed through a foaming machine gun The head is injected into a constant temperature sealed mold, and a flame-retardant polyurethane rigid foam material is obtained through a series of processes such as foaming, curing, and demoulding.

Example 1:

Preparation of flame retardant:

1. Under the condition of stirring at room temperature, 5.0g (0.041mol) p-hydroxybenzaldehyde was dissolved in 75g (95ml) ethanol solution to form A solution, and 3.0g (0.0164mol) 4,4'-diaminobiphenyl was dissolved in 30g (38ml) ) in ethanol solution to form B solution. Add B solution dropwise to A solution at 30°C. The time for dropping is controlled at 2h. Polyols;

2. Under the protection of nitrogen, add the silicon hydride trimethoxyhydrosilane to the mixing system in the above 1, and at the same time add 0.25 g of catalyst zinc chloride, raise the temperature of the reaction mixture to 85 ° C, react for 16 hours, and cool to room temperature It was poured into 250g (386ml) of petroleum ether and stirred for 1.5h, filtered to obtain a solid product, washed 5 times with cold ethanol solution, and vacuum-dried at 75°C for 24h to obtain a polyhydroxyphenylcyclosilane nitrogen-type flame retardant.

The structure of polyols containing carbon-nitrogen double bonds is:

Polyhydroxyphenyl ring silicon nitrogen type flame retardant compound structure is:

Preparation of modified nano oxides:

The mass ratio of silane coupling agent KH550 to nano-alumina is 1:20, configure a 4% ethanol solution containing a coupling agent, place the nano-alumina in the ethanol solution containing a coupling agent, stir for 1 hour and filter, the filter cake Dry at 95°C for 2 hours to prepare modified nano-alumina.

The formula components for preparing all-water foaming flame-retardant polyurethane rigid foam material are as follows:

Polyether polyol (hydroxyl value 470mgKOH/g, viscosity 3000mPa.s, HK4110, provided by Shandong Jining Huakai Resin Co., Ltd.): 85 parts

Polyester polyol (hydroxyl value 204mgKOH/g, viscosity 2000mPa.s, HK2054, provided by Shandong Jining Huakai Resin Co., Ltd.): 30 parts

AK-8803 (provided by Jiangsu Mesid Chemical Co., Ltd.): 4 copies

1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (Yutai County Haina Environmental Protection Technology Co., Ltd.): 3 parts

Trimethylolpropane (provided by Shandong Lianchuang Energy Saving New Materials Co., Ltd.): 1.5 parts

Polyhydroxyphenyl ring silicon nitrogen type flame retardant (self-made according to the above method): 12 parts

Modified nano-alumina (provided by Nanjing Tianxing New Material Co., Ltd.): 10 parts

Distilled water: 10 parts

Polymethylene polyphenyl polyisocyanate (provided by Zhengzhou Keyulong Chemical Products Co., Ltd.): 150 parts

Example 2:

Preparation of flame retardant:

1. Under the condition of stirring at room temperature, 5.0g (0.041mol) p-hydroxybenzaldehyde was dissolved in 40g ethanol solution to form A solution, and 0.0205mol3,3'-dimethoxy 4,4'-diaminobiphenyl was dissolved in 25g ethanol Solution B is formed in the solution, and solution B is added dropwise to solution A at 25°C. The dropping time is controlled at 1h. After the addition, the temperature is raised to 40°C and reacted for 2h to obtain a polyhydroxyl compound containing a carbon-nitrogen double bond. compound;

2. Under the protection of nitrogen, add the silicon hydride compound trimethoxyhydrosilane to the mixing system in the above 1, and at the same time add 0.1 g of catalyst zinc chloride, raise the temperature of the reaction mixture to 70 ° C, react for 8 hours, and cool to room temperature It was poured into 175g of petroleum ether and stirred for 0.5h, filtered to obtain a solid product, washed 5 times with cold ethanol solution, and vacuum-dried at 50°C for 12h to obtain a polyhydroxyphenylcyclosilane nitrogen-type flame retardant.

The structure of polyols containing carbon-nitrogen double bonds is:

Polyhydroxyphenyl ring silicon nitrogen type flame retardant compound structure is:

Preparation of modified nano oxides:

The mass ratio of titanate coupling agent 201 to nano-titanium dioxide is 1:15, configure an ethanol solution containing 2% of coupling agent, place nano-titanium dioxide in the ethanol solution containing coupling agent, stir for 0.5h and then filter. The cake was dried at 80° C. for 2 hours to obtain modified nano titanium dioxide.

The formula components for preparing all-water foaming flame-retardant polyurethane rigid foam material are as follows:

Polyether polyol (hydroxyl value 480mgKOH/g, viscosity 6000mPa.s, HK8205, provided by Shandong Jining Huakai Resin Co., Ltd.): 30 parts

Polyester polyol (hydroxyl value 400mgKOH/g, viscosity 2000mPa.s, HK3022, provided by Shandong Jining Huakai Resin Co., Ltd.): 15 parts

AK-8805 (provided by Jiangsu Mesid Chemical Co., Ltd.): 2 copies

Triethylenediamine (Yutai County Haina Environmental Protection Technology Co., Ltd.): 0.5 parts

Triethanolamine (provided by Shandong Lianchuang Energy Saving New Materials Co., Ltd.): 0.5 parts

Polyhydroxyphenyl ring silicon nitrogen type flame retardant (self-made according to the above method): 5 parts

Modified nano-titanium dioxide (provided by Nanjing Tianxing New Material Co., Ltd.): 2 parts

Distilled water: 3 parts

Polymethylene polyphenyl polyisocyanate (provided by Zhengzhou Keyulong Chemical Products Co., Ltd.): 60 parts

Example 3:

Preparation of flame retardant:

1. Under the condition of stirring at room temperature, 5.0g (0.041mol) p-hydroxybenzaldehyde is dissolved in 75g (95ml) ethanol solution to form A solution, and 0.0164mol3,3'-diaminophenyl sulfone is dissolved in 30g (38ml) ethanol solution to form B solution, add B solution to A solution dropwise at 30°C, the dropping time is controlled at 1h, after the dropwise addition is completed, the temperature is raised to 55°C, and reacted for 3h to obtain a polyhydroxy compound containing a carbon-nitrogen double bond;

2. Under the protection of nitrogen, add the silicon hydride compound trimethoxyhydrogensilane to the mixing system in the above 1, and at the same time add 0.25 g of catalyst zinc chloride, raise the temperature of the reaction mixture to 85 ° C, react for 10 h, and cool to room temperature. It was poured into 250g (386ml) of petroleum ether and stirred for 1.5h, filtered to obtain a solid product, washed 5 times with cold ethanol solution, and vacuum-dried at 75°C for 24h to obtain a polyhydroxyphenylcyclosilane nitrogen-type flame retardant.

The structure of polyols containing carbon-nitrogen double bonds is:

Polyhydroxyphenyl ring silicon nitrogen type flame retardant compound structure is:

Preparation of modified nano oxides:

The mass ratio of silane coupling agent KH550 to nano-zinc oxide is 1:20, configure a 4% ethanol solution containing coupling agent, place nano-alumina in the ethanol solution containing coupling agent, stir for 1 hour and filter, the filter cake Dry at 95° C. for 2 hours to prepare modified nano zinc oxide.

The formula components for preparing all-water foaming flame-retardant polyurethane rigid foam material are as follows:

Polyether polyol (hydroxyl value 420mgKOH/g, viscosity 2000mPa.s, HK4110G, provided by Shandong Jining Huakai Resin Co., Ltd.): 55 parts

Polyester polyol (hydroxyl value 100mgKOH/g, viscosity 3000mPa.s, HK2100, provided by Shandong Jining Huakai Resin Co., Ltd.): 30 parts

AK-8811 (provided by Jiangsu Mesid Chemical Co., Ltd.): 2 copies

Ethylenediamine (Yutai County Haina Environmental Protection Technology Co., Ltd.): 3 parts

Diethanolamine (provided by Shandong Lianchuang Energy Saving New Materials Co., Ltd.): 1.0 parts

Polyhydroxyphenyl ring silicon nitrogen type flame retardant (self-made according to the above method): 12 parts

Modified nano-zinc oxide (provided by Nanjing Tianxing New Material Co., Ltd.): 10 parts

Distilled water: 10 parts

Polymethylene polyphenyl polyisocyanate (provided by Zhengzhou Keyulong Chemical Products Co., Ltd.): 100 parts

Example 4:

Preparation of flame retardant:

1. Under the condition of stirring at room temperature, 5.0g (0.041mol) of p-hydroxybenzaldehyde was dissolved in 75g (95ml) of ethanol solution to form A solution, and 0.0164mol of 4,4'-diaminophenyl sulfone was dissolved in 30g (38ml) of ethanol solution to form B solution, add B solution to A solution dropwise at 30°C, the dropping time is controlled at 1h, after the dropwise addition is completed, the temperature is raised to 55°C, and reacted for 2h to obtain a polyhydroxy compound containing a carbon-nitrogen double bond;

2. Under the protection of nitrogen, add the silicon hydride compound trimethoxyhydrosilane to the mixing system in the above 1, and at the same time add 0.25 g of catalyst zinc chloride, raise the temperature of the reaction mixture to 80 ° C, react for 16 hours, and cool to room temperature. It was poured into 250g (386ml) of petroleum ether and stirred for 1.5h, filtered to obtain a solid product, washed 5 times with cold ethanol solution, and vacuum-dried at 75°C for 20h to obtain a polyhydroxyphenylcyclosilane nitrogen-type flame retardant.

The structure of polyols containing carbon-nitrogen double bonds is:

Polyhydroxyphenyl ring silicon nitrogen type flame retardant compound structure is:

Preparation of modified nano oxides:

The mass ratio of silane coupling agent KH550 to nano-silica is 1:15, configure a 3% ethanol solution containing coupling agent, place nano-alumina in the ethanol solution containing coupling agent, stir for 1 hour, filter, and filter The cake was dried at 95° C. for 2 hours to obtain modified nano-silica.

The formula components for preparing all-water foaming flame-retardant polyurethane rigid foam material are as follows:

Polyether polyol (hydroxyl value 430mgKOH/g, viscosity 3000mPa.s, HK8210, provided by Shandong Jining Huakai Resin Co., Ltd.): 65 parts

Polyester polyol (hydroxyl value 280mgKOH/g, viscosity 2000mPa.s, HK2043, provided by Shandong Jining Huakai Resin Co., Ltd.): 30 parts

AK-8832 (provided by Jiangsu Mesid Chemical Co., Ltd.): 4 copies

N, N-Dimethylbenzylamine (Yutai Haina Environmental Protection Technology Co., Ltd.): 3 parts

Glycerin (provided by Shandong Lianchuang Energy Saving New Material Co., Ltd.): 1.5 parts

Polyhydroxyphenyl ring silicon nitrogen type flame retardant (self-made according to the above method): 12 parts

Modified nano-silica (provided by Nanjing Tianxing New Material Co., Ltd.): 10 parts

Distilled water: 10 parts

Polymethylene polyphenyl polyisocyanate (provided by Zhengzhou Keyulong Chemical Products Co., Ltd.): 100 parts

Example 5:

Preparation of flame retardant:

1. Under stirring conditions at room temperature, 5.0g (0.041mol) of p-hydroxybenzaldehyde was dissolved in 75g (95ml) of ethanol solution to form A solution, and 0.0164mol of 4,4'-p-phenylenediamine was dissolved in 30g (38ml) of ethanol solution to form B solution, add B solution to A solution dropwise at 30°C, the dropping time is controlled at 2h, after the dropwise addition is completed, the temperature is raised to 55°C, and reacted for 4h to obtain a polyhydroxy compound containing a carbon-nitrogen double bond;

2. Under the protection of nitrogen, add the silicon hydride trimethoxyhydrosilane to the mixing system in the above 1, and at the same time add 0.25 g of catalyst zinc chloride, raise the temperature of the reaction mixture to 85 ° C, react for 16 hours, and cool to room temperature It was poured into 250g (386ml) of petroleum ether and stirred for 1.5h, filtered to obtain a solid product, washed 5 times with cold ethanol solution, and vacuum-dried at 75°C for 24h to obtain a polyhydroxyphenylcyclosilane nitrogen-type flame retardant.

The structure of polyols containing carbon-nitrogen double bonds is:

Polyhydroxyphenyl ring silicon nitrogen type flame retardant compound structure is:

Preparation of modified nano oxides:

The mass ratio of titanate coupling agent 201 to nanometer antimony pentoxide is 1:20, prepare a 4% ethanol solution containing a coupling agent, place nano-alumina in the ethanol solution containing a coupling agent, and stir for 1 hour After filtering, the filter cake was dried at 95° C. for 2 hours to obtain modified nanometer antimony pentoxide.

The formula components for preparing all-water foaming flame-retardant polyurethane rigid foam material are as follows:

Polyether polyol (hydroxyl value 470mgKOH/g, viscosity 3000mPa.s, HK4110, provided by Shandong Jining Huakai Resin Co., Ltd.): 75 parts

Polyester polyol (hydroxyl value 204mgKOH/g, viscosity 2000mPa.s, HK2054, provided by Shandong Jining Huakai Resin Co., Ltd.): 30 parts

AK-8803 (provided by Jiangsu Mesid Chemical Co., Ltd.): 4 copies

Cyclohexylamine (Yutai County Haina Environmental Protection Technology Co., Ltd.): 3 parts

Trimethylolpropane (provided by Shandong Lianchuang Energy Saving New Materials Co., Ltd.): 1.5 parts

Polyhydroxyphenyl ring silicon nitrogen type flame retardant (made by the above method): 10 parts

Modified nano antimony pentoxide (provided by Nanjing Tianxing New Material Co., Ltd.): 10 parts

Distilled water: 10 parts

Polymethylene polyphenyl polyisocyanate (provided by Zhengzhou Keyulong Chemical Products Co., Ltd.): 120 parts

Embodiment 6:

Preparation of flame retardant:

1. Under stirring condition at room temperature, 5.0g (0.041mol) p-Hydroxybenzaldehyde is dissolved in 75g (95ml) ethanol solution to form A solution, 0.0164mol3, 3' dimethyl 4, 4'-diphenylamine is dissolved in 30g ( 38ml) to form B solution in ethanol solution, add B solution to A solution dropwise at 30°C, and the dropping time is controlled at 2h. of polyols;

2. Under the protection of nitrogen, add the silicon hydride compound trimethoxyhydrogensilane to the mixing system in the above 1, and at the same time add 0.25 g of catalyst zinc chloride, raise the temperature of the reaction mixture to 85 ° C, react for 10 h, and cool to room temperature. It was poured into 250g (386ml) of petroleum ether and stirred for 1.5h, filtered to obtain a solid product, washed 5 times with cold ethanol solution, and vacuum-dried at 75°C for 24h to obtain a polyhydroxyphenylcyclosilane nitrogen-type flame retardant.

The structure of polyols containing carbon-nitrogen double bonds is:

The structure of the polyhydroxyphenyl ring silicon nitrogen type flame retardant compound is:

Preparation of modified nano oxides:

The mass ratio of silane coupling agent KH550 to nano zirconia is 1:20, configure an ethanol solution containing 4% coupling agent, place nano alumina in the ethanol solution containing coupling agent, stir for 1 hour and filter, the filter cake Dry at 95° C. for 2 hours to prepare modified nano zirconia.

The formula components for preparing all-water foaming flame-retardant polyurethane rigid foam material are as follows:

Polyether polyol (hydroxyl value 420mgKOH/g, viscosity 2000mPa.s, HK4110G, provided by Shandong Jining Huakai Resin Co., Ltd.): 85 parts

Polyester polyol (hydroxyl value 100mgKOH/g, viscosity 3000mPa.s, HK2100, provided by Shandong Jining Huakai Resin Co., Ltd.): 30 parts

AK-8805 (provided by Jiangsu Mesid Chemical Co., Ltd.): 4 copies

N, N-Dimethylbenzylamine (Yutai County Haina Environmental Protection Technology Co., Ltd.): 2 parts

Trimethylolpropane (provided by Shandong Lianchuang Energy Saving New Materials Co., Ltd.): 1.5 parts

Polyhydroxyphenyl ring silicon nitrogen type flame retardant (self-made according to the above method): 12 parts

Modified nano-zirconia (provided by Nanjing Tianxing New Material Co., Ltd.): 10 parts

Distilled water: 10 parts

Polymethylene polyphenyl polyisocyanate (provided by Zhengzhou Keyulong Chemical Products Co., Ltd.): 150 parts

Embodiment 7:

Preparation of flame retardant:

1. Under the condition of stirring at room temperature, 5.0g (0.041mol) p-hydroxybenzaldehyde was dissolved in 75g (95ml) ethanol solution to form A solution, and 0.0164mol 2-methyl 4,4'-diphenylamine was dissolved in 30g (38ml) ethanol Solution B is formed in the solution, and solution B is added dropwise to solution A at 25°C. The dropping time is controlled at 2h. After the addition, the temperature is raised to 55°C and reacted for 4h to obtain a polyhydroxyl compound containing a carbon-nitrogen double bond. compound;

2. Under the protection of nitrogen, add the silicon hydride trimethoxyhydrogensilane to the mixing system in the above 1, and at the same time add 0.25 g of catalyst zinc chloride, raise the temperature of the reaction mixture to 70 ° C, react for 16 hours, and cool to room temperature. It was poured into 250g (386ml) of petroleum ether and stirred for 1.5h, filtered to obtain a solid product, washed 5 times with cold ethanol solution, and vacuum-dried at 75°C for 24h to obtain a polyhydroxyphenylcyclosilane nitrogen-type flame retardant.

The structure of polyols containing carbon-nitrogen double bonds is:

Polyhydroxyphenyl ring silicon nitrogen type flame retardant compound structure is:

Preparation of modified nano oxides:

The mass-to-weight ratio of the silane coupling agent KH550 to the nano-cerium oxide is 1:20, configure an ethanol solution containing 4% of the coupling agent, place the nano-alumina in the ethanol solution containing the coupling agent, stir for 1 hour and then filter. The cake was dried at 95°C for 2 hours to obtain modified nano-cerium oxide.

The formula components for preparing all-water foaming flame-retardant polyurethane rigid foam material are as follows:

Polyether polyol (hydroxyl value 420mgKOH/g, viscosity 2000mPa.s, HK4110G, provided by Shandong Jining Huakai Resin Co., Ltd.): 75 parts

Polyester polyol (hydroxyl value 100mgKOH/g, viscosity 3000mPa.s, HK2100, provided by Shandong Jining Huakai Resin Co., Ltd.): 30 parts

AK-8832 (provided by Jiangsu Mesid Chemical Co., Ltd.): 4 copies

Pentamethyldiethylenetriamine (Yutai County Haina Environmental Protection Technology Co., Ltd.): 3 parts

Trimethylolpropane (provided by Shandong Lianchuang Energy Saving New Materials Co., Ltd.): 1.5 parts

Polyhydroxyphenyl ring silicon nitrogen type flame retardant (self-made according to the above method): 12 parts

Modified nano-cerium oxide (provided by Nanjing Tianxing New Material Co., Ltd.): 10 parts

Distilled water: 10 parts

Polymethylene polyphenyl polyisocyanate (provided by Zhengzhou Keyulong Chemical Products Co., Ltd.): 120 parts

Embodiment 8:

Preparation of flame retardant:

1. Under stirring conditions at room temperature, 5.0g (0.041mol) p-hydroxybenzaldehyde was dissolved in 40g ethanol solution to form A solution, 0.0205mol1,3-diphenylamine was dissolved in 25g ethanol solution to form B solution, and B was dissolved at 25°C The solution was added dropwise to the A solution, and the dropping time was controlled at 1 hour. After the dropping, the temperature was raised to 40°C, and the reaction was carried out for 2 hours to obtain a polyhydroxy compound containing a carbon-nitrogen double bond;

2. Under the protection of nitrogen, add the silicon hydrogen compound to the mixing system in the above 1, and add 0.1 g of zinc chloride catalyst at the same time, raise the temperature of the reaction mixture to 70 ° C, react for 8 hours, and pour it into 175 g of Stir in petroleum ether for 0.5h, filter to obtain a solid product, wash with cold ethanol solution for 5 times, and vacuum-dry at 50°C for 12h to obtain a polyhydroxyphenylcyclosilane nitrogen-type flame retardant.

The structure of polyols containing carbon-nitrogen double bonds is:

Polyhydroxyphenyl ring silicon nitrogen type flame retardant compound structure is:

Preparation of modified nano oxides:

The mass ratio of silane coupling agent KH550 to nano-iron oxide is 1:20, configure an ethanol solution containing 4% coupling agent, place nano-alumina in the ethanol solution containing coupling agent, stir for 1 hour and filter, the filter cake Dry at 95° C. for 2 hours to prepare modified nanometer iron oxide.

The formula components for preparing all-water foaming flame-retardant polyurethane rigid foam material are as follows:

Polyether polyol (hydroxyl value 430mgKOH/g, viscosity 3000mPa.s, HK8210, provided by Shandong Jining Huakai Resin Co., Ltd.): 65 parts

Polyester polyol (hydroxyl value 280mgKOH/g, viscosity 2000mPa.s, HK2043, provided by Shandong Jining Huakai Resin Co., Ltd.): 30 parts

AK-8811 (provided by Jiangsu Mesid Chemical Co., Ltd.): 4 copies

1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (Yutai County Haina Environmental Protection Technology Co., Ltd.): 3 parts

Trimethylolpropane (provided by Shandong Lianchuang Energy Saving New Materials Co., Ltd.): 1.5 parts

Polyhydroxyphenyl ring silicon nitrogen type flame retardant (self-made according to the above method): 12 parts

Modified nano-iron oxide (provided by Nanjing Tianxing New Material Co., Ltd.): 8 parts

Nano ceramics: 2 parts

Distilled water: 10 parts

Polymethylene polyphenyl polyisocyanate (provided by Zhengzhou Keyulong Chemical Products Co., Ltd.): 150 parts of the flame-retardant and mechanical properties of the full-water foamed flame-retardant polyurethane rigid foam material are tested, and the results are shown in Table 1:

Claims (8)

1. A kind of 1. polyhydroxy phenyl ring silicon nitrogen type flame retardant, it is characterized in that it has following chemical constitution：

   Wherein R₁For one kind of following structural formula：

   R₂For one kind of following two structural formulas：
2. A kind of 2. method of the polyhydroxy phenyl ring silicon nitrogen type flame retardant prepared described in claim 1, it is characterized in that it is including following Step：

   Step 1, under the conditions of being stirred at room temperature, parahydroxyben-zaldehyde is dissolved in ethanol and forms solution A, double amino benzene ring compounds are molten B solution is formed in ethanol, B solution is added dropwise in solution A at 25-30 DEG C, time for adding control is in 1-2h, dropwise addition knot 40-55 DEG C is warming up to after beam, 2-4h is reacted, obtains a kind of polyol containing carbon-to-nitrogen double bon, described double aminobenzenes Cycle compound is one kind in following 8 kinds of compounds：

   Under step 2, nitrogen protection, silicon-containing compound is added in the reaction system in above-mentioned steps 1, while add catalyst Zinc chloride, reactant mixture is warming up to 70-85 DEG C, reacts 8-16h, be cooled to after room temperature to be poured into petroleum ether and stir 0.5-1.5h, solid product is filtered out, then washed with cold ethanol, be dried in vacuo 12-24h in 50-75 DEG C, obtain polyhydroxy phenyl ring Silicon nitrogen type flame retardant, described silicon-containing compound are one kind in following two kinds of compounds：
3. 3. the method according to claim 2 for preparing polyhydroxy phenyl ring silicon nitrogen type flame retardant, it is characterized in that：Described A is molten The mass ratio of parahydroxyben-zaldehyde and ethanol is 1: 8-15 in liquid, the mass ratio of double amino benzene ring compounds and ethanol in B solution For 1: 5-10, the mol ratio of double amino benzene ring compounds and parahydroxyben-zaldehyde is 1: 2-2.5, and double amino benzene ring compounds are with containing The mol ratio of silicon compound is 1: 3-3.5, and the mass ratio of parahydroxyben-zaldehyde and petroleum ether is 1: 35-50, parahydroxyben-zaldehyde Mass ratio with zinc chloride is 1: 0.02-0.05.
4. 4. the polyhydroxy phenyl ring silicon nitrogen type flame retardant described in claim 1 is in full water foamed anti-inflaming polyurethane hard foam material is prepared Application.
5. 5. full water foamed anti-inflaming polyurethane hard foam material according to claim 4, it is characterized in that：It includes two kinds of groups of A, B Point, by mass, the component number in component A is：PPG：30-85 parts, PEPA：15-30 parts, stabilizer： 2-4 parts, catalyst：0.5-3 parts, crosslinking agent：0.5-1.5 parts, distilled water：3-10 parts, modified nano oxide compound：2-10 parts, on The polyhydroxy benzenes silicon Phosphorus-nitrogen flame retardant stated：5-12 parts；Component number in B component is：Polyisocyanates：60-150 parts.
6. 6. full water foamed anti-inflaming polyurethane hard foam material according to claim 4, it is characterized in that：It is stable in the component A Agent is organosilicon foam stabilizer AK-8805, AK-8811, AK-8803, AK-8832 one or more of combinations；Catalyst is three Ethylene diamine, N, N- dimethyl cyclohexyl amines, N, N- dimethyl benzylamines, ethylenediamine, cyclohexylamine, 1,3,5- tri- (dimethylamino-propyls) One or more of combinations of Hexahydrotriazine, pentamethyl-diethylenetriamine；Crosslinking agent is trimethylolpropane, triethanolamine, two One or more of combinations of monoethanolamine, glycerine；The PPG is that polytetrahydrofuran polyol or PPOX are more The one or more of first alcohol, hydroxyl value 420-480mgKOH/g, viscosity are 2000-6000mPa.s (25 DEG C)；PEPA is The one or more of aliphatic polyester polyols or aromatic polyester polyol, their hydroxyl value are 100-400mgKOH/g, are glued Spend for 2000-3000mPa.s (25 DEG C)；The polyisocyanates is poly methylene poly phenyl poly isocyanate (PAPI).
7. 7. full water foamed anti-inflaming polyurethane hard foam material according to claim 4, it is characterized in that：It is modified in the component A Nano-oxide is nano-oxide through obtained by coupling agent modified processing, wherein nano-oxide is nano titanium oxide (TiO₂), nano silicon (SiO₂), nano zine oxide (ZnO), nano aluminium oxide (Al₂O₃), nanometer antimony pentoxide (Sb₂O₅), nano zircite (ZrO₂), nano-cerium oxide (CeO₂), nano-sized iron oxide (Fe₂O₃), one kind of nano ceramics or several Kind combination, coupling agent is one kind of Silane coupling agent KH550 or titanate coupling agent 201, coupling agent and nano-oxide Mass ratio is 1: 15-20, first configures the ethanol solution of the 2%-4% containing coupling agent, and nano-oxide is placed in into the second containing coupling agent In alcoholic solution, filtered after stirring 0.5-1h, filter cake dries 2h at 80-95 DEG C, and modified nano oxide compound is made.
8. 8. a kind of preparation method of the full water foamed anti-inflaming polyurethane hard foam material described in claim 4, it is characterized in that：It is by A groups PPG and PEPA mixing high-speed stirred are uniform in point, add after other auxiliary agents stir, pass through with B component High-pressure foam machine equipment is sufficiently mixed, and is injected by foaming machine gun head in constant temperature sealed mold, foamed, curing, demoulding etc. A series of processes obtain anti-inflaming polyurethane hard foam material.