CN1295266C - Preparation method of fire retardant high activity polymer polyether polyol and method for preparing high elastic resilience fire retardant golyurethane soft foam material therefrom - Google Patents

Abstract

A method for preparing a flame-retardant high-activity polymer polyether polyol and a method for preparing a high-resilience flame-retardant polyurethane flexible foam material. Flame-retardant high-activity polymer polyether polyol is composed of general-purpose high-activity polyether polyol as the continuous phase, and sub-nano ultrafine polymer particles of partially aminated diisocyanate-modified polyether polyol on the surface as the dispersed phase. A stable polymer colloidal dispersion composed of two phases. Formaldehyde-urea-melamine-hexamethylenetetramine is prepared by reacting formaldehyde-urea-melamine-hexamethylenetetramine in high activity polyether polyol at 65°C-98°C for 0.5-4 hours and drying. It does not contain toxic and harmful substances such as phosphorus, halogen, styrene and acrylonitrile, and has a simple process and low cost. In the presence of the above product and diisocyanate compound in the presence of a tertiary amine catalyst, an organometallic catalyst, water, a crosslinking agent and a silicone oil foam stabilizer, the flame-retardant high-resilience polyurethane foam is prepared by cold molding and free foaming , has high flame retardancy.

Description

Preparation method of flame-retardant high-activity polymer polyether polyol and method for preparing high-resilience flame-retardant polyurethane soft 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 method for preparing a flame-retardant high-activity polymer polyether polyol and a method for preparing a high-resilience flame-retardant polyurethane flexible 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. The solid content (polymer content) is 5% to 25%, high viscosity, yellow color, and easy to cause discoloration of polyurethane foam; At 20% to 30%, the styrene content is above 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 European Patent Eur.Pat.Ep778,301; PCT.Int.Appl.Wo.97,15,605; PCT.Int.Appl.Wo.97,15,606 disclosed polymer polyether polyols, but these polymer polyether polyols Alcohols do not have flame retardancy, and the polyurethane foam prepared with them does not have flame retardancy either.

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 high-activity polymer polyether polyol, which is different from traditional free radical dispersion polymerization, but condensation-dispersion polymerization, and the flame-retardant high-activity polyol prepared by this method The active polymer polyether polyol has high activity, the particle size of the dispersed phase polymer is small (0.1 micron to 0.5 micron), and it does not contain toxic and harmful substances such as phosphorus, halogen, styrene and acrylonitrile. It is green and environmentally friendly, and has a preparation process Simple, low cost, easy to foam and so on.

The second object of the present invention is to provide a method for cold molding and foaming of flame-retardant high-resilience polyurethane. The high-resilience flame-retardant polyurethane foam prepared by this method has sub-nanometer dispersed phase polymer ultrafine particles for reinforcement, flame retardancy Flammable properties, so the polyurethane foam has high flame retardancy (oxygen value up to 28%) and high resilience and dent hardness.

The flame-retardant high-activity polymer polyether polyol of the present invention is a sub-nanometer polymer made of a general-purpose high-activity polyether polyol as the continuous phase and aminated diisocyanate-modified polyether polyol (dispersant) on the surface. Ultrafine particles are composed of dispersed phase and polymer colloid dispersion system composed of two phases.

The above-mentioned high-activity polyether polyol for continuous phase is a polyether polyol formed by ring-opening polymerization of propylene oxide and capping of ethylene oxide. The functionality of the polyol is between 2 and 4, and the hydroxyl value is 19mgKOH/ g to 36mgKOH/g, the primary hydroxyl content is between 65% and 98%, and its polymerization method can adopt the traditional anion ring-opening polymerization process and double metal cyanide catalyst polymerization process or a combination of the two.

The above-mentioned dispersed phase of sub-nanometer polymer ultrafine particles is "hair" polymer microspheres with an average particle diameter of 0.1 micron to 0.5 micron and partially aminated diisocyanate-modified polyether polyols grafted on the surface.

The mass ratio of the continuous phase to the dispersed phase is 98:2-30:70.

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 19mgKOH/g and 38mgHO/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 high-resilience urethane foam of the present invention is based on the flame-retardant high-activity polymer polyether polyol of the present invention, general-purpose high-activity polyether polyol and diisocyanate compound in tertiary amine, organic metal catalyst, water, physical hair In the presence of a foaming agent and a small amount of silicone oil foam stabilizer, it is made by cold molding foaming and free process.

The above-mentioned diisocyanate compound is one or a mixture of toluene diisocyanate (T80/20), diphenylmethane diisocyanate (PAPI), toluene diisocyanate (T80/20), diphenylmethane diisocyanate (PAPI) two The mixing ratio is 50:50 to 100:0, preferably toluene diisocyanate (T80/20), and the flame retardancy of the flame retardant polyurethane foam is improved with the decrease of the diisocyanate index.

The block foaming process mentioned above is cold molding foaming and free foaming process.

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

The continuous phase - general high activity polyether polyol, dispersant - partially aminated diisocyanate modified polyether polyol, nitrogen-containing monomer - urea, melamine, aldehyde-containing monomer - formaldehyde, and condensation reaction accelerator Add it into a closed reactor with a stirrer and a temperature controller to raise the temperature to the condensation reaction temperature. After a constant temperature reaction at this temperature for a certain period of time, vacuum dry to remove volatile components, and add general-purpose high-activity polyether Polyols, obtain flame retardant highly active polymer polyether polyols.

The general-purpose high-activity polyether polyols mentioned above and the added general-purpose high-activity polyether polyols are polyether polyols formed by ring-opening polymerization of propylene oxide and capping with ethylene oxide, and the functionality of the polyols is between 2 and 4. Among them, the hydroxyl value is between 19mgKOH/g and 38mgKOH/g, and the primary hydroxyl content is between 65% and 98%. The polymerization method can adopt the traditional anionic ring-opening polymerization process and double metal cyanide catalyst polymerization process or both Combination; the amount of the added general-purpose high-activity polyether polyol is 100% to 9000% of the sum of the nitrogen-containing monomer amount-urea and melamine, preferably 150%-2000%; the added general-purpose high-activity polyether The mass ratio of the polyol to the added general-purpose high-activity polyether polyol is 100:0-100:1000.

The above-mentioned formaldehyde is formaldehyde with a concentration of 25% to 45%, preferably formaldehyde with a concentration of 37%. 400%, preferably 50% to 200%.

Above-mentioned nitrogenous monomer is urea, melamine, and the ratio of its urea, melamine quality is between 0: 100～100:0, is preferably 100:50; Nitrogenous monomer consumption-the sum of urea, melamine quality is 2% to 60% of the mass of the entire reaction system except for the added general-purpose high-activity polyether polyol, 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 the mass of melamine.

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

The above reaction time is 0.5 to 6 hours, preferably 1 to 5 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 high-activity polymer polyether polyol, and its dosage is the amount of nitrogen-containing monomer—the quality of urea and melamine 0.5% to 150% of the sum, 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 38mgKOH/g, and the primary hydroxyl content is between 5% 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 or a mixture of two or more of triethylamine, tripropylamine and tributylamine, preferably triethylamine.

The above-mentioned diamines are one or a mixture of two or more of ethylenediamine, propylenediamine and butylenediamine, preferably ethylenediamine.

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

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

In the mixer, mix the flame-retardant high-activity polymer polyether polyol, high-activity polyether polyol, amine catalyst, delayed amine catalyst, water, crosslinking agent and silicone oil foam stabilizer, and then add diisocyanate compound. Mixing, injecting into molds or free foaming makes flame retardant polyurethane foam.

Above-mentioned silicone oil foam stabilizer is one or more than one silicone foam stabilizer, its consumption (w/w) is 0.08%～1.3% of polyether polyol, preferably 0.2%～1.2%

The above-mentioned tertiary amine catalyst is triethylenediamine, triethylamine, N, N, N', N'-tetramethyl-1,3,-butanediamine, N-ethylmorpholine, bis(β-dimethyl One or more tertiary amine catalysts in base amine ethyl) ether, diisopropanolamine, etc.

The above-mentioned diisocyanate compound is one or a mixture of toluene diisocyanate (T80/20) and diphenylmethane diisocyanate (PAPI). The mixing ratio of the two is toluene diisocyanate (T80/20): diphenylmethane diisocyanate (PAPI) in the range of 100:0 to 70:30, preferably 80:20.

The above-mentioned crosslinking agent is one or a mixture of glycerol, trimethylolpropane, diethanolamine, and triethanolamine. The basic formula is as follows:

The basic formula is as follows:

A component

Ordinary high activity polyether polyol: 0～70 parts

Water: 1 to 3 parts

Delayed amine catalyst: 0.1～0.3 parts

Triethylenediamine: 0.1～0.5 parts

Silicone oil: 0.7～1.2 parts

Cross-linking agent 1～2.5 parts

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

Total 100 copies

B component

Diisocyanate index: 100～115

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.

Description of drawings

Figure 1 is a comparison table of the synthesis of flame-retardant high-activity polymer polyether polyol, foaming formula and flame-retardant high-resilience polyurethane foam performance.

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

Performance A is the performance of flame retardant high active polymer polyether polyol.

Stability/month refers to the time of natural storage without precipitation, months.

Performance B is the performance of foamed polyurethane foam.

Basic formula for foaming:

A component

Ordinary high activity polyether polyol: 0 parts

water; 2 parts

Delayed amine catalyst (EPS102): 0.1 parts

Triethylenediamine (DABACO A331v): 0.3 parts

Silicone oil (DC5365): 1.1 parts

Glycerin 1.5 parts

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

Total 100 copies

B component

Toluene diisocyanate index: 102%

Detailed ways

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

Highly active 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 use traditional anion Polymerization process and double metal cyanide catalyst polymerization process or the combination of the two, the hydroxyl value is 34mgKOH/g-36mgKOH/g, and the primary hydroxyl content is between 60% and 85%.

Formaldehyde: Formaldehyde solution with a concentration of 37%

Preparation of partially aminated diisocyanate modified polyether polyols:

Embodiment 1: at 40 ℃, polyether polyol N330, 960 kilograms, 17.4 kilograms of methyl ethyl ketone oxime, 34.8 kilograms of toluene diisocyanate and triethylamine, 0.12 kilograms are added in the airtight reactor that has stirrer, thermometer, make The temperature was raised to 80°C, and after a 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 the reaction was carried out for 1 hour. A partially aminated diisocyanate-modified polyether polyol is obtained.

Embodiment 2: the general-purpose highly active polyether polyol N330, 550 kilograms, partially aminated diisocyanate modified polyether polyol, 61 kilograms, 197 kilograms of formaldehyde, 123 kilograms of urea, 61 kilograms of melamine, hexamethylene Add 5 kg of tetramine and 120 kg of water into a closed 3,000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove it. Volatile components, add high activity polyether polyol N330, 580 kg, obtain flame retardant high activity polymer polyether polyol, see the synthesis of flame retardant high activity polymer polyether polyol, foaming formula and flame retardant high Resilience polyurethane foam performance comparison table embodiment 2.

Embodiment 3: the general-purpose highly reactive polyether polyol N330, 550 kilograms, partially aminated diisocyanate modified polyether polyol, 61 kilograms, 197 kilograms of formaldehyde, 123 kilograms of urea, 61 kilograms of melamine, hexamethylene Add 5 kg of tetramine and 120 kg of water into a closed 3,000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove it. Volatile components, add high activity polyether polyol N330, 380 kg, obtain flame retardant high activity polymer polyether polyol, see synthesis of flame retardant high activity polymer polyether polyol, foaming formula and flame retardant high Resilience polyurethane foam performance comparison table embodiment 3.

Embodiment 4: the general-purpose highly active polyether polyol N330, 550 kilograms, partially aminated diisocyanate modified polyether polyol, 61 kilograms, 197 kilograms of formaldehyde, 123 kilograms of urea, 61 kilograms of melamine, hexamethylene Add 5 kg of tetramine and 120 kg of water into a closed 3,000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove it. Volatile components, add high activity polyether polyol N330, 180 kg, obtain flame retardant high activity polymer polyether polyol, see synthesis of flame retardant high activity polymer polyether polyol, foaming formula and flame retardant high Resilience polyurethane foam performance comparison table embodiment 4.

Embodiment 5: the general-purpose highly active polyether polyol N330, 550 kilograms, partially aminated diisocyanate modified polyether polyol, 51 kilograms, 197 kilograms of formaldehyde, 123 kilograms of urea, 61 kilograms of melamine, hexamethylene Add 5 kg of tetramine and 120 kg of water into a closed 3,000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove it. Volatile components, add high activity polyether polyol N330, 580 kg, obtain flame retardant high activity polymer polyether polyol, see the synthesis of flame retardant high activity polymer polyether polyol, foaming formula and flame retardant high Resilience polyurethane foam performance comparison table embodiment 5.

Embodiment 6: the general-purpose highly active polyether polyol N330, 550 kilograms, partially aminated diisocyanate modified polyether polyol, 41 kilograms, 197 kilograms of formaldehyde, 123 kilograms of urea, 61 kilograms of melamine, hexamethylene Add 5 kg of tetramine and 120 kg of water into a closed 3,000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove it. Volatile components, add high activity polyether polyol N330, 580 kg, obtain flame retardant high activity polymer polyether polyol, see the synthesis of flame retardant high activity polymer polyether polyol, foaming formula and flame retardant high Resilience polyurethane foam performance comparison table embodiment 6.

Embodiment 7: The general-purpose highly active polyether polyol N330, 550 kilograms, partially aminated diisocyanate modified polyether polyol, 31 kilograms, 197 kilograms of formaldehyde, 123 kilograms of urea, 61 kilograms of melamine, hexamethylene Add 5 kg of tetramine and 120 kg of water into a closed 3,000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove it. Volatile components, add high activity polyether polyol N330, 580 kg, obtain flame retardant high activity polymer polyether polyol, see the synthesis of flame retardant high activity polymer polyether polyol, foaming formula and flame retardant high Resilience polyurethane foam performance comparison table embodiment 7.

Embodiment 8: the general-purpose highly reactive polyether polyol N330, 550 kg, partially aminated diisocyanate modified polyether polyol, 21 kg, 197 kg of formaldehyde, 123 kg of urea, 61 kg of melamine, and hexamethylene Add 5 kg of tetramine and 120 kg of water into a closed 3,000-liter reactor with a stirrer and a thermometer, raise the temperature to 80°C, react at this temperature for 4 hours, and vacuum dry at 92°C for 4 hours to remove it. Volatile components, add high activity polyether polyol N330, 580 kg, obtain flame retardant high activity polymer polyether polyol, see the synthesis of flame retardant high activity polymer polyether polyol, foaming formula and flame retardant high Resilience polyurethane foam performance comparison table embodiment 8.

Example 9 (comparative example): the feeding method is the same as example 1, and the charging amount is except that the adding amount of part aminated diisocyanate modified polyether polyol I is 0 kilograms, and other adding amounts are the same as example 1, and the polymer polyether obtained Polyols have poor stability and precipitate after natural storage for three days. See Example 9 of the synthesis of flame-retardant high-activity polymer polyether polyols, foaming formulations, and performance comparison table of flame-retardant high-resilience polyurethane foams.

Claims (17)

1. A method for preparing flame-retardant high-activity polymer polyether polyol, which is characterized in that it is made of general-purpose high-activity polyether polyol as continuous phase, surface grafting part aminated diisocyanate modified polyether polyol Nanopolymer ultrafine particles are composed of a dispersed phase and a polymer colloidal dispersion system composed of two phases. The continuous phase is a general-purpose high-activity polyether polyol is a polyether polyol formed by ring-opening polymerization of propylene oxide and capped with ethylene oxide. Alcohol, the functionality of its polyol is between 2 and 4, the hydroxyl value is between 19mgKOH/g and 36mgKOH/g, the primary hydroxyl content is between 65% and 98%, and its polymerization method adopts traditional anion ring opening Polymerization process and double metal cyanide catalyst polymerization process or a combination of the two, the average particle size of the dispersed phase of sub-nano polymer ultrafine particles grafted with partially aminated diisocyanate-modified polyether polyol on the surface is between 0.1 micron and 0.5 micron Between, the mass ratio of the continuous phase to the dispersed phase is 98:2 to 30:70. 2. according to the preparation method of flame-retardant highly active polymer polyether polyol according to claim 1, it is characterized in that subnano polymer ultrafine particle is the condensation polymer of formaldehyde and urea, melamine, hexamethylenetetramine. 3. a method for preparing flame-retardant high-activity polymer polyether polyol according to claim 1, characterized in that it consists of the following processes: The continuous phase-general-purpose high-activity polyether polyol, dispersant-partially aminated diisocyanate modified polyether polyol, nitrogen-containing monomer-urea, melamine, aldehyde-containing monomer-formaldehyde, and condensation reaction accelerator Add it into a closed reactor with a stirrer and a temperature controller, raise the temperature to a condensation reaction temperature of 65°C to 95°C, and react at this temperature for 2 to 4 hours; vacuum dry at 92°C for 4 hours, Remove volatile components, and then add general-purpose high-activity polyether polyol to obtain flame-retardant high-activity polymer polyether polyol. 4. according to the preparation method of flame-retardant high activity polymer polyether polyol according to claim 3, it is characterized in that above-mentioned general high activity polyether polyol and the general high activity polyether polyol added are propylene oxide ring-opening polymerization 1. The polyether polyol formed by capping with ethylene oxide has a polyol functionality between 2 and 4, a hydroxyl value between 19mgKOH/g and 38mgKOH/g, and a primary hydroxyl content of 65% to 98%. Between, its polymerization method can adopt traditional anionic ring-opening polymerization process and double metal cyanide catalyst polymerization process or the combination of both; 100%-9000% of the sum, the mass ratio of added general-purpose high-activity polyether polyol to added general-purpose high-activity polyether polyol is 100:0-100:1000. 5. according to the preparation method of flame-retardant high activity polymer polyether polyol described in claim 3, it is characterized in that above-mentioned formaldehyde is the formaldehyde of concentration at 25%～45%, and its consumption is nitrogen-containing monomer in terms of 37% formaldehyde concentration. Body dosage - 40% to 400% of the sum of the mass of urea and melamine. 6. according to claim 3 described flame-retardant highly active polymer polyether polyol preparation method, it is characterized in that above-mentioned nitrogen-containing monomer is urea, melamine, and the ratio of the mass of its urea, melamine is at 0: 100～100: Between 0, the amount of nitrogen-containing monomers - the sum of the mass of urea and melamine is 2% to 60% of the mass of the entire reaction system except for the added general-purpose high-activity polyether polyol. 7. according to the preparation method of flame-retardant high activity polymer polyether polyol described in claim 3, it is characterized in that above-mentioned condensation reaction accelerator is hexamethylenetetramine, p-toluenesulfonic acid, ammoniacal liquor, formic acid, its six times The amount of methyltetramine is 0.07% to 20% of the sum of the amount of nitrogen-containing monomers-urea and melamine 8. according to the preparation method of flame-retardant high-activity polymer polyether polyol according to claim 3, it is characterized in that the polyether polyol of a part of above-mentioned dispersant aminated diisocyanate modification is in synthetic flame-retardant high-activity polymer polyol The ether polyol acts as a dispersant, and its dosage is 0.5% to 150% of the sum of the nitrogen-containing monomer—urea and melamine. 9. According to the preparation method of flame-retardant high-activity polymer polyether polyol according to claim 3, it is characterized in that the preparation method of a partially aminated diisocyanate-modified polyether polyol is as follows: at 35° C. to 45° C. Add polyether polyol, diisocyanate blocking agent, diisocyanate and tertiary amine into a closed reactor with a stirrer and a thermometer at ℃, raise the temperature to 75℃～85℃, and react at this temperature for 4～ After 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. 10. according to the preparation method of flame-retardant high active polymer polyether polyol according to claim 9, it is characterized in that in the preparation method of the polyether polyol modified by above-mentioned partially aminated diisocyanate, polyether polyol refers to ring 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 polyol functionality of which is between 2 and 4 Among them, the hydroxyl value is between 19mgKOH/g and 38mgKOH/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 metal cyanide catalyst polymerization process or both combined. 11. according to the preparation method of flame-retardant highly active polymer polyether polyol according to claim 9, it is characterized in that in the preparation method of the polyether polyol modified by above-mentioned partially aminated diisocyanate, diisocyanate blocking agent can be phenol Compounds, β-dicarbonyl compounds, oxime compounds. 12. according to the preparation method of flame-retardant highly active polymer polyether polyol according to claim 9, it is characterized in that in the preparation method of the polyether polyol modified by above-mentioned partial amination diisocyanate, diisocyanate compound is One or a mixture of toluene diisocyanate and diphenylmethane diisocyanate. 13. according to the preparation method of flame-retardant highly active polymer polyether polyol according to claim 9, 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, or a mixture of two or more of them. 14. According to the preparation method of the flame-retardant high-activity polymer polyether polyol according to claim 9, it is characterized in that in the preparation method of the polyether polyol modified by the above-mentioned partially aminated diisocyanate, the diamine is ethylenediamine , propylenediamine, butylenediamine or a mixture of two or more. 15. according to claim 9 described flame-retardant highly active polymer polyether polyol preparation method, it is characterized in that in the preparation method of the polyether polyol modified by above-mentioned partially aminated diisocyanate, polyether polyol, toluene di The molar ratio of isocyanate, ethylenediamine and triethylamine is between 3:1:1:0.001～1:1::1:0.08. 16. A method for preparing high-resilience polyurethane flame-retardant flexible foam according to claim 1, characterized in that it comprises the following processes: In the mixer, mix the flame-retardant high-activity polymer polyether polyol, high-activity polyether polyol, amine catalyst, delayed amine catalyst, water, crosslinking agent and silicone oil foam stabilizer, and then add diisocyanate compound. Mixing, injecting into molds or free foaming makes flame retardant polyurethane foam. 17. According to the method for preparing high-resilience polyurethane flame-retardant flexible foam material according to claim 16, it is characterized in that the above-mentioned diisocyanate compound is one or both of toluene diisocyanate T80/20 and diphenylmethane diisocyanate PAPI The mixture of the two, the mixing ratio of toluene diisocyanate T80/20: diphenylmethane diisocyanate PAPI is 100:0 ~ 70:30.

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