CN1308373C - Preparation method of fire retardant polymer polyether polyol and method for preparing block fire retardant polyurethane foam mateial therefrom - Google Patents

Abstract

A method for preparing a flame-retardant polymer polyether polyol and a method for preparing a block-shaped flame-retardant polyurethane foam material. The flame-retardant polymer polyether polyol is composed of general-purpose polyether polyol as the continuous phase, sub-nano ultrafine polymer particles of partially aminated diisocyanate-modified polyether polyol (dispersant) on the surface as the dispersed phase and two Phase composition of stable polymer colloidal dispersion system. It is prepared by reacting formaldehyde-urea-melamine-hexamethylenetetramine in polyether polyol at 65°C-98°C for 0.5-4 hours in the presence of the above-mentioned dispersant and drying. The product does not contain toxic and harmful substances such as phosphorus, halogen, styrene and acrylonitrile, and the process is simple and the cost is low. Combining this product with general-purpose polyether polyols and diisocyanate compounds in the presence of tertiary amines, organic metal catalysts, water, physical foaming agents and a small amount of silicone oil foam stabilizer, the flame-retardant Polyurethane foam. The material has good flame retardancy and mechanical properties.

Description

Preparation method of flame retardant polymer polyether polyol and method for preparing block flame retardant polyurethane foam material

technical field

The invention belongs to the field of polymer polyether polyol and its preparation and application, and in particular relates to a flame-retardant polymer polyether polyol and a method for preparing a block-shaped flame-retardant polyurethane foam material.

Background technique

Polyurethane foam is a high polymer with unique properties and versatile uses. It is based on polyether polyol and diisocyanate, mixed with a small amount of water, silicone surfactant, foaming agent, and formed under the combined action of organotin and tertiary amine catalysts. It can be used to make hard , semi-rigid and soft polyurethane foam, mainly used as shock-absorbing materials for seat cushions, cushions, interior parts and motorcycle saddles, etc., and can also be used to make sofas, mattresses, decorative materials and other civil uses product.

Polymer polyether polyols are usually the product of free radical dispersion polymerization of vinyl monomers in polyether polyols in the presence of dispersants. In the early 1970s, the vinyl monomers used in polymer polyether polyols were acrylonitrile. Its solid content (polymer content) is 5% to 25%, high viscosity, yellow color, and easy to cause heartburn and discoloration of polyurethane foam; in the mid-1980s, acrylonitrile and styrene mixed monomers were used to prepare polymer polyether polyols. The content is 20% to 30%, and the styrene content is more than 50%. In the early 1990s, some foreign companies successively launched polymer polyether polyols with a solid content of more than 40% and a viscosity lower than 5500mPa s (25°C). Such as the polymer polyether polyol disclosed in European patent Eur.Pat.Ep778,301; PCT.Int.Appl.Wo.97,15,605; PCT.Int.Appl.Wo.97,15,606, but these polymer polyether None of the polyols has flame retardancy, nor does the polyurethane foam prepared with them.

Polyurethane foam products are extremely flammable and difficult to flame-retardant. Most of the flame-retardant methods commonly used at present are to add flame retardants to the raw materials for the production of polyurethane. The flame retardants used mainly include reactive flame-retardant polyether polyols and non-reactive small Molecular flame retardants; reactive flame retardant polyether polyols are mainly phosphorus-containing chlorine polyether polyols, and polyurethane foams made from such polyether polyols have high cost and low bearing capacity; non-reactive small molecule flame retardants The main types of additives are liquid or solid compounds such as Sb ₂ O ₃ , melamines, phosphites and chlorides. Liquid non-reactive flame retardants are used, and the flame retardants gradually volatilize with the use of foam materials, and the flame retardant effect decrease and cause certain harm to the environment; the use of solid non-reactive flame retardants will significantly increase the viscosity of polyether polyols, increase the difficulty of the foaming process, reduce the open cell ratio of the foam, and make the density of the foam uneven . This kind of flame retardant is cumbersome to use, difficult to mix evenly, the dosage is large, and the flame retardant cost is high.

US Patents 4,214,055 and 3,953,393 use flame-retardant polymer polyols prepared by copolymerization of two or more mixed monomers in vinyl chloride, vinylidene chloride, styrene, and acrylonitrile, and use them to prepare flame-retardant polyurethane foams. However, homopolymers and copolymers of vinyl chloride and vinylidene chloride are usually thermally unstable, and toxic HCl gas is released during the foaming process, which is corrosive to foaming equipment; Japanese patent Jpn.Kokai.Tokyo.JP.0959 , The flame retardant used in the flame-retardant polymer polyol disclosed in 341 is polyvinyl chloride, which is also thermally unstable; Polyol, the polyurethane foam made of this kind of polymer polyol has certain flame retardancy, but tribromostyrene is difficult to synthesize, expensive and difficult to obtain.

Contents of the invention

One of the purposes of the present invention is to provide a preparation method of flame-retardant polymer polyether polyol, which is different from traditional free radical dispersion polymerization, but condensation polymerization, the flame-retardant polymer polyether polyol prepared by this method Polyol, with a small particle size of the dispersed phase polymer (0.1 micron to 0.85 micron), free of toxic and harmful substances such as phosphorus, halogen, styrene and acrylonitrile, green and environmentally friendly, and has a simple preparation process, low cost, and easy foaming Features.

The second object of the present invention is to provide a flame-retardant polyurethane block foaming method. The flame-retardant polyurethane foam prepared by this method has the characteristics of sub-nanometer dispersed phase polymer ultrafine particles reinforcement and flame retardancy. Therefore, the polyurethane Foam materials have high flame retardancy (oxygen value up to 28%) and high mechanical properties and indentation hardness.

The flame-retardant polymer polyether polyol of the present invention is made of general-purpose polyether polyol as the continuous phase, and the subnano polymer ultrafine particles of polyether polyol (dispersant) modified by aminated diisocyanate on the surface are dispersed. The polymer colloidal dispersion system composed of two phases and two phases.

The above-mentioned continuous phase is a general-purpose polyether polyol, that is, a polyether polyol formed by ring-opening polymerization of propylene oxide or ring-opening copolymerization of propylene oxide and ethylene oxide or ring-opening polymerization of propylene oxide and capped with ethylene oxide. , the functionality of its polyol is between 2 and 4, the hydroxyl value is between 36mgKOH/g and 70mgKOH/g, and the primary hydroxyl content is between 5% and 98%. Its polymerization method can adopt traditional anion ring opening Polymerization process and double metal cyanide catalyst polymerization process or a combination of both.

The above-mentioned dispersed phase of sub-nanometer polymer ultrafine particles is a "hair" polymer microsphere with an average particle diameter of 0.1 micron to 0.8 micron and partially aminated diisocyanate-modified polyether polyol on the surface.

Among the above-mentioned partially aminated diisocyanate-modified polyether polyols, the ether polyols refer to ring-opening polymerization of propylene oxide or ring-opening copolymerization of propylene oxide and ethylene oxide or ring-opening polymerization of propylene oxide, ethylene oxide The polyether polyol formed by capping with alkane has a polyol functionality between 2 and 4, a hydroxyl value between 19 mgKOH/g and 40 mgHO/g, and a primary hydroxyl content between 5% and 98%. The method can adopt the traditional anionic ring-opening polymerization process and the double metal cyanide catalyst polymerization process or a combination of the two; its diisocyanate is one of toluene diisocyanate, diphenylmethane diisocyanate or a mixture of the two; its amination It is the reaction of diamine and diisocyanate.

The above-mentioned polymer microspheres are polycondensates of formaldehyde, urea, melamine and hexamethylenetetramine.

The flame-retardant urethane foam of the present invention is based on the flame-retardant polymer polyether polyol of the present invention and diisocyanate compound in the presence of tertiary amine, organometallic catalyst, water, physical foaming agent, and a small amount of silicone oil foam stabilizer, It is made by block foaming process.

The above-mentioned diisocyanate compound is one or a mixture of toluene diisocyanate (T80/20), diphenylmethane diisocyanate (PAPI), the mixing ratio of the two is 65:35～100:0, preferably toluene Diisocyanate (T80/20), and the flame retardancy of flame retardant polyurethane foam is improved with the decrease of diisocyanate index.

The block foaming process mentioned above refers to box-type, vertical, horizontal and continuous foaming processes.

The manufacture method of flame-retardant polymer polyether polyol of the present invention is as follows:

Continuous phase-general polyether polyol, dispersant-partially aminated diisocyanate modified polyether polyol, nitrogen-containing monomer-urea, melamine, aldehyde-containing monomer-formaldehyde, and condensation reaction accelerator were added to the In a closed reactor with a stirrer and a temperature controller, the temperature is raised to the condensation reaction temperature, and after a constant temperature reaction at this temperature for a certain period of time, the volatile components are removed by vacuum drying to obtain a flame-retardant polymer polyether polyol .

The general-purpose polyether polyols mentioned above are polyether polyols formed by ring-opening polymerization of propylene oxide or ring-opening copolymerization of propylene oxide and ethylene oxide or ring-opening polymerization of propylene oxide and end-capping of ethylene oxide. The functionality is between 2 and 4, the hydroxyl value is between 36mgKOH/g and 70mgKOH/g, and the primary hydroxyl content is between 5% and 98%. The polymerization method can adopt the traditional anionic ring-opening polymerization process and double The amount of the metal cyanide catalyst polymerization process or the combination of the two is 100%-9000% of the sum of the nitrogen-containing monomer amount-urea and melamine, preferably 150%-2000%.

The above-mentioned formaldehyde is formaldehyde with a concentration of 25% to 45%, preferably a formaldehyde with a concentration of 37%. 400%, preferably 60% to 150%.

Above-mentioned nitrogen-containing monomer is urea, melamine, and the ratio of the mass of its urea, melamine is between 0: 100～100: 0, is preferably 100: 50; The sum of nitrogen-containing monomer consumption-urea, melamine quality is 2% to 60% of the mass of the entire reaction system, preferably 10% to 48%.

The above-mentioned condensation reaction accelerator is hexamethylenetetramine, p-toluenesulfonic acid, ammonia, formic acid, etc., preferably hexamethylenetetramine, and the amount of hexamethylenetetramine is the amount of nitrogen-containing monomer-urea 0.07% to 20% of the sum of mass of melamine

The above reaction temperature is the condensation reaction temperature, generally at 50°C to 100°C, preferably 65°C to 95°C, most preferably 75°C to 85°C

The above reaction time is 0.5 to 6 hours, preferably 1 to 4 hours, most preferably 2 to 4 hours.

The above-mentioned vacuum drying refers to drying at a certain temperature, generally 35°C to 100°C, preferably 40°C to 95°C; vacuum drying for a certain period of time, generally 1 to 12 hours, preferably 2 to 10 hours .

The above-mentioned dispersant-partially aminated diisocyanate-modified polyether polyol plays the role of dispersant in the synthesis of flame-retardant polymer polyether polyol, and its dosage is the sum of the nitrogen-containing monomer dosage-urea and melamine quality 0.5% to 150%, preferably 10% to 80%.

The preparation method of the polyether polyol modified by above-mentioned partially aminated diisocyanate is as follows:

Add polyether polyol, diisocyanate blocking agent, diisocyanate and tertiary amine into a closed reactor with stirrer and thermometer at 35°C to 45°C, and raise the temperature to 75°C to 85°C. After reacting at constant temperature for 4 to 6 hours, add diamine, then raise the temperature to 110°C to 125°C, and react for 0.5 to 3 hours. A partially aminated diisocyanate-modified polyether polyol is obtained.

The above-mentioned polyether polyol refers to the polyether polyol formed by the ring-opening polymerization of propylene oxide or the ring-opening copolymerization of propylene oxide and ethylene oxide or the ring-opening polymerization of propylene oxide and the capping of ethylene oxide. The functionality is between 2 and 4, the hydroxyl value is between 19mgKOH/g and 56mgHO/g, and the primary hydroxyl content is between 28% and 98%. The polymerization method can adopt the traditional anionic ring-opening polymerization process and bimetallic Cyanide catalyst polymerization process or a combination of both.

The above-mentioned diisocyanate blocking agent can be phenolic compounds, β-dicarbonyl compounds, oxime compounds, preferably oxime compounds, such as methyl ethyl ketone oxime.

The above-mentioned diisocyanate compound is one or a mixture of toluene diisocyanate and diphenylmethane diisocyanate, preferably toluene diisocyanate.

The above-mentioned tertiary amine is one of triethylamine, tripropylamine, tributylamine or a mixture of both and more than two, preferably triethylamine.

The above-mentioned diamine is one of ethylenediamine, propylenediamine, butylenediamine or a mixture of two or more of them, preferably ethylenediamine.

The molar ratio of the polyether polyol, toluene diisocyanate, ethylenediamine and triethylamine is 3:1:1:0.001 to 1:1::1:0.08.

The method for preparing flame-retardant polyurethane foam material with flame-retardant polymer polyether polyol of the present invention as raw material is as follows:

Mix the flame retardant polymer polyether polyol, polyether polyol, tertiary amine catalyst, organometallic catalyst, water, physical blowing agent and a small amount of silicone oil foam stabilizer respectively in the mixer, and then add diisocyanate compound at high speed Mixing, using box type, vertical and horizontal continuous foaming to prepare flame retardant polyurethane foam.

The above-mentioned small amount of silicone oil foam stabilizer is a silicone foam stabilizer, and its consumption (w/w) is 0.08% to 1.8% of polyether polyol, preferably 0.13% to 0.8%, and decreases with the amount of silicone oil foam stabilizer , the hardness and resilience of the flame-retardant polyurethane foam are increased.

The organotin catalysts mentioned above mainly include dibutyltin dilaurate, dibutyltin di-2-ethylhexanoate, dibutyltin diacetate, stannous octoate, stannous oleate and other common organotin catalysts.

The above-mentioned tertiary amine catalysts mainly include triethylenediamine, triethylamine, N, N, N', N'-tetramethyl-1,3,-butanediamine, N-ethylmorpholine, bis(β-dimethyl Commonly used tertiary amine catalysts such as base amine ethyl) ether.

The physical foaming agents mentioned above mainly include physical foaming agents such as dichloromethane, F ₁₁ , F ₁₂ , and F ₁₁₃ .

The above-mentioned diisocyanate compound is one or a mixture of toluene diisocyanate (T80/20), diphenylmethane diisocyanate (PAPI), the mixing ratio of the two is 65:35～100:0, preferably toluene Diisocyanate (T80/20), and the flame retardancy of flame retardant polyurethane foam is improved with the decrease of diisocyanate index.

The basic formula is as follows:

A component:

Ordinary polyether polyol: 30-70 parts

Water: 1 to 3 parts

Stannous octoate: 0.05～0.9 parts

Triethylenediamine: 0.05～0.9 parts

Silicone oil: 0.1～1.6 parts

The flame retardant polymer polyether polyol of the present invention: The rest of the flame retardant polymer polyether polyol of the present invention

Total 100 copies

B component:

Diisocyanate index: 95%～123%

Compared with the prior art, the present invention has the following advantages:

① The flame-retardant polymer polyether polyol does not contain toxic and harmful substances such as phosphorus, halogen, styrene, and acrylonitrile, and has the characteristics of simple preparation process, low cost, and easy foaming.

②The flame-retardant polyurethane foam prepared has the characteristics of sub-nanometer dispersed phase polymer ultrafine particles reinforcement and flame retardancy, so the polyurethane foam material has high flame retardancy (oxygen value can reach 28%) and high Mechanical properties and indentation hardness.

③ Partially aminated diisocyanate-modified polyether polyols act as dispersants in the synthesis of flame-retardant polymer polyether polyols, and act as foam stabilizers in the synthesis of flame-retardant polyurethane foam materials.

Description of drawings

Figure 1 is a comparison table of the synthesis of flame retardant polymer polyether polyol, foam formulation and flame retardant polyurethane foam performance.

Note in the figure: Dispersant I is partially aminated diisocyanate modified polyether polyol I.

Dispersant II is partially aminated diisocyanate modified polyether polyol II.

Performance A refers to the performance of flame-retardant polymer polyether polyol; stability/month refers to the time and month of natural storage without precipitation.

Performance B is the performance of foamed polyurethane foam.

Foaming basic formula (quality):

A component:

Ordinary polyether polyol: 39 parts

Water: 2.2 parts

Stannous octoate: 0.16 parts

Triethylenediamine: 0.16 parts

Silicone oil: 0.2 parts

The flame retardant polymer polyether polyol of the present invention: The rest of the flame retardant polymer polyether polyol of the present invention

Total 100 copies

B component:

Toluene diisocyanate index: 110%

specific implementation plan

The raw material of the embodiment of the present invention is as follows:

Polyether polyol N330: Glycerin or trimethylolpropane as the initiator, polyether polyol formed by ring-opening polymerization of propylene oxide and capped with 16% ethylene oxide, the polymerization method can adopt traditional anion ring-opening Polymerization process and double metal cyanide catalyst polymerization process or the combination of the two, the hydroxyl value is 34mgKOH/g-38mgKOH/g, and the primary hydroxyl content is between 60% and 85%.

Polyether polyol 6000: Glycerin or trimethylolpropane as the initiator, polyether polyol formed by ring-opening polymerization of propylene oxide and capped with 16% ethylene oxide, the polymerization method can adopt traditional anion ring-opening Polymerization process and double metal cyanide catalyst polymerization process or the combination of the two, the hydroxyl value is 26mgKOH/g-30mgKOH/g, and the primary hydroxyl content is between 60% and 85%.

Polyether polyol 551C: Glycerin or trimethylolpropane as the initiator, polyether polyol formed by ring-opening polymerization of propylene oxide and capped with 16% ethylene oxide, the polymerization method can adopt traditional anion ring-opening Polymerization process and double metal cyanide catalyst polymerization process or the combination of the two, the hydroxyl value is 54mgKOH/g-58mgKOH/g, and the primary hydroxyl content is between 50% and 85%.

Polyether polyol 3030: Glycerin or trimethylolpropane is used as the initiator, and polyether polyol is formed by ring-opening polymerization of propylene oxide. The polymerization method can adopt traditional anionic ring-opening polymerization process and double metal cyanide catalyst polymerization Process or the combination of the two, the hydroxyl value is 54mgKOH/g-58mgKOH/g, and the primary hydroxyl content is between 10% and 60%.

Polyether polyol 3031K: Glycerin or trimethylolpropane is used as the initiator, and polyether polyol is formed by ring-opening copolymerization of propylene oxide and ethylene oxide. The polymerization method can adopt traditional anionic ring-opening polymerization process and Double metal cyanide catalyst polymerization process or the combination of the two, the hydroxyl value is 54mgKOH/g-58mgKOH/g, and the primary hydroxyl content is between 15% and 80%.

Formaldehyde: Formaldehyde solution with a concentration of 37%

Example 1: At 40°C, 960 kilograms of polyether polyol N330, 17.4 kilograms of methyl ethyl ketoxime, 34.8 kilograms of toluene diisocyanate and triethylamine, 0.12 kilograms were added to a closed reactor with a stirrer and a thermometer, The temperature was raised to 80°C, and after constant temperature reaction at this temperature for 5 hours, 12 kg of ethylenediamine was added, and then the temperature was raised to 118°C, and reacted for 1 hour. Partially aminated diisocyanate modified polyether polyol I was obtained.

Embodiment 2: 6000, 600 kilograms of polyether polyols, 8.7 kilograms of methyl ethyl ketone oxime, 17.4 kilograms of toluene diisocyanate and triethylamine were added respectively at 40 ° C, and 0.06 kilograms were added in a closed reactor with a stirrer and a thermometer. The temperature was raised to 80°C, and after constant temperature reaction at this temperature for 5 hours, 6 kg of ethylenediamine was added, and then the temperature was raised to 118°C, and reacted for 1 hour. The partially aminated diisocyanate-modified polyether polyol II was obtained.

Embodiment 3: respectively general-purpose polyether polyol 3030, 500 kilograms, partially aminated diisocyanate modified polyether polyol 1, 69 kilograms, 221 kilograms of formaldehyde, 138 kilograms of urea, 69 kilograms of melamine, hexamethylene tetra Add 8.3 kg of amine into a closed 2000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at a constant temperature at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove volatile components, and obtain resistance For flame-retardant polymer polyether polyol, see Example 3 of the synthesis of flame-retardant polymer polyether polyol, foam formulation and performance comparison table of flame-retardant polyurethane foam.

Embodiment 4: respectively general-purpose polyether polyol 551C, 500 kilograms, partially aminated diisocyanate modified polyether polyol I, 69 kilograms, 221 kilograms of formaldehyde, 138 kilograms of urea, 69 kilograms of melamine, hexamethylene tetra Add 8.3 kg of amine into a closed 2000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at a constant temperature at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove volatile components, and obtain resistance For the flame-retardant polymer polyether polyol, see Example 4 of the synthesis of the flame-retardant polymer polyether polyol, the foaming formula and the performance comparison table of the flame-retardant polyurethane foam.

Embodiment 5: respectively general-purpose polyether polyol 3031K, 500 kilograms, partially aminated diisocyanate modified polyether polyol I, 69 kilograms, 221 kilograms of formaldehyde, 138 kilograms of urea, 69 kilograms of melamine, hexamethylene tetra Add 8.3 kg of amine into a closed 2000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at a constant temperature at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove volatile components, and obtain resistance For flame retardant polymer polyether polyol, see Example 5 of the synthesis of flame retardant polymer polyether polyol, foam formulation and performance comparison table of flame retardant polyurethane foam.

Example 6: 3030, 500 kilograms of general-purpose polyether polyols, 69 kilograms of partially aminated diisocyanate modified polyether polyols II, 221 kilograms of formaldehyde, 138 kilograms of urea, 69 kilograms of melamine, and 69 kilograms of hexamethylene tetrahydryl Add 8.3 kg of amine into a closed 2000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at a constant temperature at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove volatile components, and obtain resistance For the flame-retardant polymer polyether polyol, see Example 6 of the synthesis of the flame-retardant polymer polyether polyol, the foaming formula and the performance comparison table of the flame-retardant polyurethane foam.

Example 7: 500 kg of general-purpose polyether polyol 551C, 69 kg of partially aminated diisocyanate modified polyether polyol II, 221 kg of formaldehyde, 138 kg of urea, 69 kg of melamine, and 69 kg of hexamethylene tetra Add 8.3 kg of amine into a closed 2000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at a constant temperature at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove volatile components, and obtain resistance For flame-retardant polymer polyether polyol, see Example 7 of the synthesis of flame-retardant polymer polyether polyol, foam formulation and performance comparison table of flame-retardant polyurethane foam.

Embodiment 8: 500 kilograms of general-purpose polyether polyol 3031K, partially aminated diisocyanate modified polyether polyol II, 69 kilograms, 221 kilograms of formaldehyde, 138 kilograms of urea, 69 kilograms of melamine, hexamethylene tetra Add 8.3 kg of amine into a closed 2000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at a constant temperature at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove volatile components, and obtain resistance For flame-retardant polymer polyether polyol, see Example 8 of the synthesis of flame-retardant polymer polyether polyol, foam formulation and performance comparison table of flame-retardant polyurethane foam.

Comparative example 9: the feeding method is the same as example 1, and the charging amount is except that the adding amount of partly aminated diisocyanate modified polyether polyol I is 0 kilograms, and other adding amounts are the same as example 1, and the polymer polyether polyol obtained, The stability is not good, and it precipitates after five days of natural storage. See Example 9 of the synthesis of flame-retardant polymer polyether polyol, foaming formula and performance comparison table of flame-retardant polyurethane foam.

Comparative Example 10: The feeding method is the same as Example 4, and the feeding amount is 0 kg except that the adding amount of partially aminated diisocyanate-modified polyether polyol II is 0 kg, and the other adding amounts are the same as Example 4, and the polymer polyether polyol obtained, The stability is not good, and it precipitates after three days of natural storage. See Example 10 of the synthesis of flame-retardant polymer polyether polyol, foaming formula and performance comparison table of flame-retardant polyurethane foam.

Claims (15)

1. A preparation method of flame-retardant polymer polyether polyol, is characterized in that it is made up of following technology: The continuous phase-general polyether polyol, dispersant-partially aminated diisocyanate modified polyether polyol, nitrogen-containing monomer-urea, melamine, aldehyde-containing monomer-formaldehyde, and condensation reaction accelerator were added to the In a closed reactor equipped with a stirrer and a temperature controller, the temperature is raised to the condensation reaction temperature, and after a constant temperature reaction at this temperature, vacuum drying removes volatile components to obtain a flame-retardant polymer polyether polyol; general Polyether polyol is a polyether polyol formed by ring-opening polymerization of propylene oxide or ring-opening copolymerization of propylene oxide and ethylene oxide or ring-opening polymerization of propylene oxide and end-capping of ethylene oxide. The degree is between 2 and 4, the hydroxyl value is between 36mgKOH/g and 70mgKOH/g, and the primary hydroxyl content is between 5% and 98%. The polymerization method adopts the traditional anionic ring-opening polymerization process and double metal cyanide Catalyst polymerization process or the combination of the two, the dosage is 100% to 9000% of the sum of nitrogen-containing monomers—urea and melamine; formaldehyde is formaldehyde with a concentration of 25% to 45%, and its dosage is based on 37% formaldehyde concentration It is the amount of nitrogen-containing monomers—40% to 400% of the sum of the mass of urea and melamine; the nitrogen-containing monomers are urea and melamine, and the mass ratio of urea and melamine is between 0:100 and 100:0. The amount of monomers—the sum of the mass of urea and melamine is 2% to 60% of the mass of the entire reaction system; the condensation reaction accelerator is hexamethylenetetramine, p-toluenesulfonic acid, ammonia, formic acid, and other The dosage is 0.07%-20% of the sum of the nitrogen-containing monomers—urea and melamine. 2. According to the preparation method of flame-retardant polymer polyether polyol according to claim 1, it is characterized in that the reaction temperature is that the condensation reaction temperature is 50° C. to 100° C. 3. according to the preparation method of flame-retardant polymer polyether polyol according to claim 1, it is characterized in that the reaction time is 0.5～6 hours. 4. The preparation method of flame-retardant polymer polyether polyol according to claim 1, characterized in that vacuum drying refers to vacuum drying at a temperature of 35° C. to 100° C. for 1 to 12 hours. 5. according to the preparation method of flame-retardant polymer polyether polyol according to claim 1, it is characterized in that the polyether polyol modified by dispersant-part aminated diisocyanate is in the synthetic flame-retardant polymer polyether polyol It acts as a dispersant, and its dosage is 0.5% to 150% of the sum of the nitrogen-containing monomers—urea and melamine. 6. according to the preparation method of flame-retardant polymer polyether polyol according to claim 1, it is characterized in that being used for preparing the raw material intermediate of flame-retardant polymer polyether polyol-partially aminated diisocyanate modified polyether The preparation method of polyol is as follows: Add polyether polyol, diisocyanate blocking agent, diisocyanate and tertiary amine into a closed reactor with stirrer and thermometer at 35°C to 45°C, and raise the temperature to 75°C to 85°C. After reacting at constant temperature for 4-6 hours, add diamine, then raise the temperature to 110°C-125°C, and react for 0.5-3 hours to obtain partially aminated diisocyanate-modified polyether polyol. 7. according to the preparation method of flame-retardant polymer polyether polyol according to claim 6, it is characterized in that in the preparation method of the polyether polyol modified by above-mentioned partially aminated diisocyanate, polyether polyol refers to propylene oxide Polyether polyol formed by ring-opening polymerization or ring-opening copolymerization of propylene oxide and ethylene oxide or ring-opening polymerization of propylene oxide and capped with ethylene oxide, the polyol functionality is between 2 and 4, and the hydroxyl The value is between 36mgKOH/g and 70mgKOH/g, and the primary hydroxyl content is between 28% and 98%. The polymerization method adopts the traditional anion ring-opening polymerization process and double metal cyanide catalyst polymerization process or a combination of the two. 8. according to the preparation method of flame-retardant polymer polyether polyol according to claim 6, it is characterized in that in the preparation method of the polyether polyol modified by above-mentioned partially aminated diisocyanate, diisocyanate blocking agent is phenolic compound, β-dicarbonyl compounds, oxime compounds. 9. according to the preparation method of flame-retardant polymer polyether polyol according to claim 6, it is characterized in that in the preparation method of the polyether polyol modified by above-mentioned partially aminated diisocyanate, isocyanate compound is toluene diisocyanate , one of diphenylmethane diisocyanate or a mixture of both. 10. according to the preparation method of flame-retardant polymer polyether polyol according to claim 6, it is characterized in that in the preparation method of the polyether polyol modified by above-mentioned partially aminated diisocyanate, tertiary amine is triethylamine, tripropylamine , tributylamine. 11. according to the preparation method of flame-retardant polymer polyether polyol according to claim 6, it is characterized in that in the preparation method of the polyether polyol modified by above-mentioned partially aminated diisocyanate, dibasic amine is ethylenediamine, propylene glycol One or both of diamine and butylenediamine and a mixture of more than two. 12. according to the preparation method of flame-retardant polymer polyether polyol according to claim 6, it is characterized in that in the preparation method of the polyether polyol modified by above-mentioned partially aminated diisocyanate, polyether polyol, toluene diisocyanate, The molar ratio of ethylenediamine and triethylamine is 3:1:1:0.001 to 1:1::1:0.08. 13. A method for preparing block flame-retardant polyurethane foam according to claim 1, characterized in that it comprises the following processes: Mix flame retardant polymer polyether polyol, polyether polyol, tertiary amine catalyst, organometallic catalyst, water, physical blowing agent and a small amount of silicone oil foam stabilizer in a mixer, then add diisocyanate compound and mix at high speed , using box-type, vertical, and horizontal continuous foaming to obtain flame-retardant polyurethane foam. 14. according to the method for preparing block flame-retardant polyurethane foam material as claimed in claim 13, it is characterized in that above-mentioned small amount of silicone oil foam stabilizer is silicone foam stabilizer, and its consumption w/w is 0.08%～of polyether polyol 1.8%, and as the amount of silicone oil foam stabilizer decreases, the hardness and resilience of flame-retardant polyurethane foam increase. 15. According to the method for preparing block flame-retardant polyurethane foam material according to claim 13, it is characterized in that the above-mentioned diisocyanate compound is one or both of toluene diisocyanate T80/20, diphenylmethane diisocyanate PAPI The mixture, the mixing ratio of the two is 65:35-100:0, and as the diisocyanate index decreases, the flame retardancy of the prepared flame-retardant polyurethane foam increases.

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