CN110078911B

CN110078911B - Phosphate ester macromonomer and preparation method thereof, polymer polyol and preparation method thereof

Info

Publication number: CN110078911B
Application number: CN201910383143.8A
Authority: CN
Inventors: 刘洋; 鞠昌迅; 梁广荣; 李付国; 刘斌; 秦承群; 殷玲; 叶天; 宋新星
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2019-05-09
Filing date: 2019-05-09
Publication date: 2021-09-07
Anticipated expiration: 2039-05-09
Also published as: CN110078911A

Abstract

The invention discloses a phosphate ester macromonomer and a preparation method thereof, and polymer polyol and a preparation method thereof, wherein the phosphate ester macromonomer is prepared by adopting the reaction of the following raw materials: (a) a phosphorus-containing monomer, (b) a base polyether, (c) hydroxyethyl methacrylate. The preparation method only needs to mix phosphorus-containing monomer, hydroxyethyl methacrylate and basic polyether for reaction. The invention also provides a polymer polyol, which is prepared from the phosphate ester macromonomer by a prepolymerization method. The macromolecular monomer can be used as a stabilizer, the synthesis method is simple, convenient and feasible, the performance is excellent, and the prepared polymer polyol can effectively reduce the viscosity of the polymer polyol and has excellent stability.

Description

Phosphate ester macromonomer and preparation method thereof, polymer polyol and preparation method thereof

Technical Field

The invention relates to the field of preparation of a stabilizer and polymer polyol, in particular to a phosphate macromonomer and a preparation method thereof, and polymer polyol and a preparation method thereof.

Background

Since polymer polyols, which are the main raw materials for preparing polyurethane foams, have a wide range of applications, there is a great demand for polymer polyols in the market, and thus, there is an increasing demand for improvement in the properties and characteristics of polymer polyols. Although great progress has been made in the preparation of polymer polyols having high solids content and low viscosity, there still remains a great problem in high solids content and low viscosity and stability, and further improvement is needed. A number of related experiments have been performed in the art in order to improve the performance of stabilizers. Conclusion most of these methods also incorporate small amounts of unsaturation into the polyol to incorporate the reactive macromer stabilizer. As disclosed in US3652639, US3823201, "stabilizer precursors" (macromers) having a specific degree of reactive unsaturation are used to prepare polymer polyols, but the polymer polyols produced have a relatively low solids content. Later patents US5196476, EP0786480 disclose a process for preparing POP by a preformed stabilizer process, first a preformed stabilizer is prepared by reacting a free radical polymerization initiator with a macromer and an ethylenically unsaturated monomer, and then the preformed stabilizer is polymerized with the ethylenically unsaturated monomer in the presence of a polyether to prepare POP, which suffers from the disadvantage of high macromer usage (9 wt%) and high viscosity (8900 cp at 39.5% solids in the examples).

The existing polymer polyol products also have the problems of high viscosity, more product particles and larger polymer particles, and particularly, maleic anhydride or phthalic anhydride is frequently used in the preparation process of the stabilizer, so that the stabilizer is easy to sublimate to block a gas phase pipeline, the maintenance cost of the device is increased, and the device can be stopped in severe cases. Therefore, there is an urgent need for improvement in stabilizer to enhance the stability and other properties of the polymer polyol prepared.

Disclosure of Invention

The invention provides a phosphate ester macromonomer and a preparation method thereof, and polymer polyol and a preparation method thereof, wherein the macromonomer has the advantages of small viscosity and low use amount, and is suitable for being used as a dispersion stabilizer of the polymer polyol; and the polymer polyol prepared by using the polymer polyol as a raw material has low viscosity and excellent stability.

In order to solve the technical problems, the invention adopts the following technical scheme:

a phosphate ester macromonomer is prepared by adopting the reaction of the following raw materials:

(a) a phosphorus-containing monomer,

(b) a base polyether;

(c) hydroxyethyl methacrylate (HEMA):

preferably, the phosphorus-containing monomer is phosphoric acid or P₂O₅Wherein P is preferred₂O₅，

Further, wherein the molar ratio of the base polyether to the phosphorus-containing monomer is 1: 0.7-1:1.2, preferably 1: 0.8-1: 1.1;

the molar ratio of the base polyether to the hydroxyethyl methacrylate is 1: 1.8-1: 2.2, preferably 1: 1.9-1:2.1.

Further, the base polyether may be a trihydric or higher polyhydric alcohol, preferably a trihydric alcohol.

Further, the base polyether is one or more of polyester polyol or polyether polyol.

Further, the base polyether of the present invention is obtained by reacting a starting compound containing a plurality of active hydrogen atoms with one or more epoxides. Preferably, the starting compound having a plurality of active hydrogen atoms comprises one or more of glycerol, pentaerythritol, sorbitol, estolide, poly-estolide, xylitol, arabitol, mannitol, and the epoxide comprises one or more of ethylene oxide, propylene oxide and butylene oxide.

Further, the weight average molecular weight of the base polyether is 5000-.

The invention also provides a preparation method of the phosphate ester macromonomer, which comprises the following steps: mixing phosphorus-containing monomer, hydroxyethyl methacrylate (HEMA) and basic polyether, and reacting at the temperature of 100-150 ℃, preferably at the temperature of 120-140 ℃ for 1-5h, preferably 2-3h to obtain the phosphate macromonomer.

The invention also provides a polymer polyol comprising the following reaction raw materials:

(a1) a phosphate ester macromonomer;

(b1) a base polyol;

(c1) an ethylenically unsaturated monomer;

(d1) optionally a polymerization initiator;

(e1) optionally a chain transfer agent.

The phosphate ester macromonomer is the phosphate ester macromonomer described in the application or the phosphate ester macromonomer prepared by the preparation method;

the amount of the phosphate ester type macromonomer is 0.1-8 wt%, preferably 0.5-6 wt%, calculated by taking polymer polyol as a reference;

the amount of the base polyol is 30-90 wt%, preferably 40-70 wt%, calculated on the basis of the polymer polyol;

the amount of the ethylenically unsaturated monomer is 9-60 wt%, preferably 20-60 wt%, based on the total weight of the polymer polyol;

the amount of the polymerization initiator is 0.01-5 wt%, preferably 0.1-0.6 wt%, calculated by taking polymer polyol as a reference;

the amount of the chain transfer agent is 0.1-10 wt%, preferably 0.2-5 wt%, based on the polymer polyol.

Further, the base polyol is preferably polyether polyol, and the polyether polyol is obtained by ring-opening polymerization of one or more of polyols containing hydroxyl and having functionality of 2-6 serving as an initiator and ethylene oxide or a mixture of propylene oxide and ethylene oxide; preferably, the weight average molecular weight of the polyether polyol is 500-12000, the hydroxyl functionality is 2-6, and the content of the ethylene oxide is 2-20 wt% of the weight of the polyether polyol; more preferably, the polyether polyol has a weight average molecular weight of 1500 to 8000, a hydroxyl functionality of 3 to 5, and an ethylene oxide content of 5 to 15wt% based on the weight of the polyether polyol, and further preferably, the polyether polyol is produced by Wanhua chemical group, Inc

F3156 and/or

F3135。

Further, the ethylenically unsaturated monomers include one or more of aliphatic conjugated dienes, monovinylidene aromatic monomers, α, β -ethylenically unsaturated carboxylic acids and esters thereof, α, β -ethylenically unsaturated nitriles and amides, vinyl esters, vinyl ethers, vinyl ketones, vinyl and vinylidene halides, and a wide variety of other ethylenically unsaturated materials copolymerizable with the above monomer adducts or reactive monomers.

Preferably, the ethylenically unsaturated monomer is selected from butadiene, isoprene, styrene, alpha-methylstyrene, tert-butylstyrene, chlorostyrene, cyanostyrene, bromostyrene; one or more of acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate, itaconic acid, maleic anhydride, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, N- (dimethylaminomethyl) acrylamide, vinyl acetate;

further, the ethylenically unsaturated monomer is a monovinylidene aromatic monomer and/or an alpha, beta-ethylenically unsaturated nitrile, preferably styrene or acrylonitrile or a mixture of styrene and acrylonitrile with a molar ratio of 50: 50-99: 1, and particularly preferably a mixture of styrene and acrylonitrile with a molar ratio of 55: 45-80: 20.

Further, the polymerization initiator includes peroxides and/or azo compounds including alkyl hydroperoxides and aryl hydroperoxides, peroxyesters, peroxysulfates, perborates, percarbonates, and the like, preferably one or more of hydrogen peroxide, di-tert-butyl peroxide, tert-butyl peroxydiethylacetate, tert-butyl peroctoate, tert-butyl peroxyisobutyrate, tert-butyl peroxy 3, 5, 5-trimethylhexanoate, tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-amyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate (TBPEH), lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, Azobisisobutyronitrile (AIBN), 2 '-azobis- (2-methylbutyronitrile) (AMBN), diethyl 2, 2' -azobis (isobutyrate) (DEAB).

Further, the chain transfer agent includes isopropanol, ethanol, methanol, 1-butanol, 2-butanol, water, cyclohexane or mercaptan, wherein mercaptan and isopropanol are preferred.

The invention also provides a preparation method of the polymer polyol, which comprises the following steps:

1) adding phosphate macromonomer, part of ethylenic unsaturated monomer (10-40%), chain transfer agent and initiator into a batching kettle, uniformly mixing, and adding into a reaction kettle to prepare a prepolymer;

2) then, the prepolymer, the basic polyol, the residual ethylenically unsaturated monomer, the chain transfer agent and the initiator are uniformly mixed in a batching kettle and then added into a reaction kettle for reaction to obtain the polymer polyol.

Preferably, the temperature at which the polymer polyols of the present invention are prepared is influenced by the choice of initiator and reactor. The preparation temperature is generally from 80 ℃ to 160 ℃, preferably from 90 ℃ to 150 ℃, more preferably from 100 ℃ to 140 ℃.

Preferably, the amount of the part of the ethylenically unsaturated monomers added in the step 1) is 10% to 40% of the total mass of the ethylenically unsaturated monomers.

The ethylenically unsaturated monomers added in said step 1) and step 2) may be of different kinds. The preparation of the polymer polyols according to the invention can also be carried out by methods known to the person skilled in the art, for example as disclosed in CN 201310076260.2. The prepolymerization process of the present invention is preferably carried out by preparing a prepolymer from a phosphate macromonomer and a portion of ethylenically unsaturated monomers in the presence of a chain transfer agent, and reacting the prepolymer with a base polyol and the remainder of ethylenically unsaturated monomers to obtain a polymer polyol.

The invention has the following positive effects:

1) the polymer polyol prepared by the method has good stability, no blocky polymer is generated in the preparation process, the long-time operation can be maintained without cleaning a reaction device, and the production and operation cost is reduced; the prepared polymer polyol has low viscosity, good stability, uniform appearance of polymer particles and excellent fluidity.

2) The raw materials of the phosphate macromolecular monomer are all liquid, and sublimation does not exist; and the conversion rate of the prepared macromonomer is high, no post-treatment is needed, the preparation process is simple, the operation requirement is low, only the reaction temperature is needed to be reached, and the control is facilitated. Through adding basic polyether in the preparation of phosphate monomer, can increase the molecular weight of phosphate monomer, form macromolecular phosphate monomer, there is unsaturated double bond in the phosphate monomer, can participate in the free radical reaction, prepare polymer polyol as the stabilizer, the polyether chain segment of stabilizer can strengthen the compatibility between POP granule and the polyether of preparing in the POP granule, make POP have stronger stability, can also effectively reduce polymer polyol viscosity, and phosphorus-containing macromonomer has flame retardant properties, this phosphate monomer can form the gemini stabilizer, the structure that has two double bonds in the stabilizer molecule, has high unsaturation, can effectively reduce the stabilizer quantity, and make the polymer polyol of preparing have excellent stability.

Detailed Description

The method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims.

Example 1

Under the protection of nitrogen, a1 liter reactor equipped with a stirrer, a heater, a thermocouple, a condensation device with a water separator, an inlet and an outlet device was charged with a molar ratio of 1: 1: 1.9 phosphoric acid, base polyether polyol(s) ((

F3135, functionality of 3, hydroxyl value of 35, weight average molecular weight of 5000) and HEMA, uniformly mixing, maintaining the temperature at 110 ℃ for reaction for 3h, cooling to room temperature, and cooling to obtain a 1# phosphate macromonomer solution.

Example 2

Under the protection of nitrogen, a1 liter reactor equipped with a stirrer, a heater, a thermocouple, a condensation device with a water separator, an inlet and an outlet device was charged with a molar ratio of 1: 1.1: 1.95 phosphoric acid, base polyether polyol(s) ((

F3135) And HEMA, uniformly mixing, maintaining the temperature of 120 ℃ for reaction for 4h, cooling to room temperature, and cooling to obtain a 2# phosphate macromonomer solution.

Example 3

Under the protection of nitrogen, a1 liter reactor equipped with a stirrer, a heater, a thermocouple, a condensation device with a water separator, an inlet and an outlet device was charged with a molar ratio of 0.9: 1: 2.05 phosphoric acid, base polyether polyol(s) ((

F3135) And HEMA, uniformly mixing, maintaining the temperature of 120 ℃ for reaction for 4h, cooling to room temperature, and cooling to obtain a 3# phosphate macromonomer solution.

Example 4

Under the protection of nitrogen, a1 liter reactor provided with a stirrer, a heater, a thermocouple, a condensing device with a water separator, an inlet device and an outlet device is added, and the molar ratio of the mixture is 1: 1: 1.95 phosphoric acid, base polyether polyol(s) ((

F3160, functionality degree of 3, hydroxyl value of 26 and weight average molecular weight of 6500) and HEMA, uniformly mixing, maintaining the temperature of 120 ℃ for reaction for 4 hours, cooling to room temperature, and cooling to obtain a No. 4 phosphate macromonomer solution.

Comparative example 1

Polyol produced by Vanhua chemical group Ltd

120g of F3156 (functionality 3, hydroxyl number 56, weight average molecular weight 3000) were reacted with 3.2g of maleic anhydride at 115 ℃ for 5h, followed by 8g of ringAnd (3) capping with ethylene oxide, and reacting at 120 ℃ for 5 hours to obtain the 5# macromonomer.

Comparative example 2

Step 1)

Under nitrogen protection, in a1 liter reactor equipped with stirrer, heater, thermocouple, condensation device with water separator, inlet and outlet devices were added: 44.54g of methacrylic acid, 186g of a copolymer glycol of polyethylene oxide and propylene oxide having a weight average molecular weight of about 350 (EO/PO 5/2, molar ratio), 186g of a copolymer glycol of polyethylene oxide and propylene oxide having a weight average molecular weight of about 400 (EO/PO 2/5, molar ratio), 480g of toluene, 1.6g of hydroquinone, and 1.2g of t-butyl titanate were uniformly mixed, reacted at 110 ℃ for 4 hours, and then cooled to room temperature.

Step 2)

Adding 25.6g of initiator Benzoyl Peroxide (BPO) into the reaction liquid in the step 1), heating to 80 ℃ with stirring, and reacting for 2 h. And cooling to obtain the 6# macromonomer solution.

Example 5 preparation of prepolymer:

example 5-1

The prepolymer was prepared using a two-stage reactor system consisting of a Continuous Stirred Tank Reactor (CSTR) (first stage) and a plug flow reactor (second stage). The residence time in each reactor was about 60 minutes. The method comprises the steps of fully mixing isopropanol, a No. 1 phosphate macromonomer solution, an ethylenically unsaturated monomer and an initiator from a feeding tank through a static mixer, continuously feeding the mixture into a reactor through a feeding pipe, controlling the temperature of the reaction mixture to be 100 +/-5 ℃, controlling the pressure of the whole reaction process by a second-stage reactor through a pressure regulator, controlling the pressure to be 0.7 +/-0.05 Mpa, and finally cooling a preformed stabilizer through a cooler to enter a storage tank. The preformed 7# stabilizer was prepared from the raw materials and in the amounts indicated in Table 1.

In this example, the ethylenically unsaturated monomers are present in a molar ratio of 65: 35 of styrene and acrylonitrile.

Examples 5 and 2

Referring to the method of example 5-1, an 8# prepolymer was prepared according to the raw material ratios in Table 1, in this example, the molar ratio of ethylenically unsaturated monomers was 60: 40 of styrene and acrylonitrile. .

Examples 5 to 3

With reference to the method of example 5-1, a 9# prepolymer was prepared according to the raw material ratios in Table 1, in this example, the molar ratio of the ethylenically unsaturated monomers was 65: 35 of styrene and acrylonitrile.

Examples 5 to 4

Referring to the method of example 5-1, a 10# prepolymer was prepared according to the raw material ratios in Table 1, in this example, the molar ratio of ethylenically unsaturated monomers was 60: 40 of styrene and acrylonitrile. .

Comparative example 3: formulations are shown in Table 1, and 11# and 12# pre-formed stabilizers were obtained by the method of reference example 5-1, respectively.

TABLE 1 Pre-formed stabilizer formulations

Example 6 polymer polyol preparation:

the base polyol in this example was selected from polyols produced by Vanhua chemical group, Inc

F3135、

F3156、

F3160。

Example 6-1

Polymer polyols are prepared using a two-stage reactor system consisting of a Continuous Stirred Tank Reactor (CSTR) (first stage) and a plug flow reactor (second stage). The residence time in each reactor was about 60 minutes. Fully mixing the 7# preformed stabilizer, the basic polyol, the ethylenically unsaturated monomer, the isopropanol and the AIBN from a feeding tank through a static mixer, continuously feeding the mixture into a reactor through a feeding pipe, controlling the temperature of the reaction mixture to be 115 +/-5 ℃, controlling the pressure of the whole reaction process by a second-stage reactor through a pressure regulator, controlling the pressure to be 0.6 +/-0.05 Mpa, and cooling the final product through a cooler after two-stage vacuum demonomerization, and feeding the final product into a product tank. According to the raw materials and parts by weight shown in Table 2, 13# polymer polyol was prepared.

Example 6 to 2

In reference to the procedure of example 6-1, 14 to 16# polymer polyols were obtained, respectively.

Comparative example 4: the formulations are shown in Table 2, and 17# and 18# polymer polyols were obtained by the method of reference example 6-1, respectively.

TABLE 2 Polymer polyol formulations

As can be seen from the table, the polymer polyol prepared by using the phosphate macromonomer as the stabilizer has low viscosity and good fluidity. In comparative example 4, agglomeration and particles occurred during the preparation of No. 18 polymer polyol, and the agglomeration occurred on the stirring paddle, and the reaction could not be completed.

Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Claims

1. The phosphate ester macromonomer is characterized by being prepared by adopting the reaction of the following raw materials:

(a) a phosphorus-containing monomer,

(b) a base polyether which is a mixture of a polyether,

(c) hydroxyethyl methacrylate;

the phosphorus-containing monomer is phosphoric acid and P₂O₅One of (1);

the molar ratio of the base polyether to the phosphorus-containing monomer is 1: 0.7-1: 1.2;

the molar ratio of the base polyether to the hydroxyethyl methacrylate is 1: 1.8-1: 2.2.

2. the phosphate macromonomer of claim 1, wherein the phosphorus-containing monomer is P₂O₅。

3. The phosphate macromonomer of claim 1, wherein the molar ratio of the base polyether to the phosphorus-containing monomer is 1: 0.8-1: 1.1;

the molar ratio of the base polyether to the hydroxyethyl methacrylate is 1: 1.9-1:2.1.

4. The phosphate macromonomer of claim 1, wherein the base polyether is a trihydric or higher polyol.

5. The phosphate macromonomer of claim 1, wherein the base polyether is one or more polyether polyols.

6. The phosphate macromonomer of claim 1, wherein the base polyether is a triol.

7. A phosphate macromer according to claim 1, in which the base polyether is obtained by reacting a starting compound containing a plurality of active hydrogen atoms with one or more epoxides.

8. The phosphate macromonomer of claim 7, wherein the starting compound having a plurality of active hydrogen atoms comprises one or more of glycerol, pentaerythritol, sorbitol, xylitol, arabitol, and mannitol, and the epoxide comprises one or more of ethylene oxide, propylene oxide, and butylene oxide.

9. The phosphate macromonomer according to claim 1, wherein the base polyether has a weight average molecular weight of 5000-20000.

10. The phosphate macromonomer according to claim 9, wherein the weight average molecular weight of the base polyether is 8000 to 18000.

11. The phosphate macromonomer according to claim 10, wherein the base polyether has a weight average molecular weight of 10000 to 18000.

12. The method as claimed in claim 1, wherein the phosphorus-containing monomer, hydroxyethyl methacrylate and the base polyether are mixed and reacted at a temperature of 100 ℃ and 150 ℃ to obtain the phosphate macromonomer.

13. The method for preparing a phosphate macromonomer according to claim 12, wherein the reaction is carried out at 120-140 ℃.

14. A polymer polyol comprising the following reaction raw materials:

(a1) a phosphate ester-based macromonomer which is a polymer of a phosphoric acid ester-based macromonomer,

(b1) a base polyol which is a polyol of a polyol,

(c1) (ii) an ethylenically unsaturated monomer, wherein,

(d1) optionally a polymerization initiator, and optionally a polymerization initiator,

(e1) optionally a chain transfer agent;

the phosphate macromonomer is the phosphate macromonomer according to any one of claims 1 to 11 or the phosphate macromonomer prepared by the preparation method according to claim 12;

the amount of the phosphate ester type macromonomer is 0.1-8 wt%, calculated by taking polymer polyol as a reference;

the amount of the basic polyol is 30-90 wt%, calculated on the basis of the polymer polyol;

the dosage of the ethylenically unsaturated monomer is 9-60 wt%, calculated by taking the total weight of the polymer polyol as a reference;

the amount of the polymerization initiator is 0.01-5 wt%, calculated by taking polymer polyol as a reference;

the amount of the chain transfer agent is 0.1-10 wt%, calculated on the basis of polymer polyol.

15. The polymer polyol according to claim 14, wherein the amount of the phosphate-based macromonomer used is 0.5 to 6wt% based on the polymer polyol;

the amount of the basic polyol is 40-70 wt%, calculated on the basis of the polymer polyol;

the dosage of the olefinic unsaturated monomer is 20-60 wt%, calculated by taking the total weight of the polymer polyol as a reference;

the amount of the polymerization initiator is 0.1-0.6 wt%, calculated by taking polymer polyol as a reference;

the amount of the chain transfer agent is 0.2-5 wt% based on the polymer polyol.

16. The polymer polyol according to claim 14, wherein the base polyol is a polyether polyol obtained by ring-opening polymerization of ethylene oxide or a mixture of propylene oxide and ethylene oxide with one or more hydroxyl-containing polyols having a functionality of 2-6 as an initiator.

17. The polymer polyol of claim 16, wherein the polyether polyol has a weight average molecular weight of 500 to 12000, a hydroxyl functionality of 2 to 6, and the ethylene oxide is added in an amount of 2 to 20wt% based on the weight of the polyether polyol.

18. The polymer polyol of claim 17, wherein the polyether polyol has a weight average molecular weight of 1500 to 8000, a hydroxyl functionality of 3 to 5, and ethylene oxide is added in an amount of 5 to 15wt% based on the weight of the polyether polyol.

19. The polymer polyol of claim 18, wherein the polyether polyol is WANOL, manufactured by wawa chemical group limited^®F3156 and/or WANOL^®F3135。

20. The polymer polyol of claim 14 wherein said ethylenically unsaturated monomers comprise one or more of aliphatic conjugated dienes, monovinylidene aromatic monomers, α, β -ethylenically unsaturated carboxylic acids and esters thereof, α, β -ethylenically unsaturated nitriles and amides, vinyl ethers, vinyl ketones, vinyl and vinylidene halides.

21. The polymer polyol of claim 14 wherein said ethylenically unsaturated monomer comprises a vinyl ester.

22. The polymer polyol of claim 20, wherein said ethylenically unsaturated monomer is selected from the group consisting of butadiene, isoprene, styrene, α -methylstyrene, t-butylstyrene, chlorostyrene, cyanostyrene, bromostyrene; one or more of acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate, itaconic acid, maleic anhydride, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, N- (dimethylaminomethyl) acrylamide.

23. The polymer polyol of claim 21 wherein said ethylenically unsaturated monomer is vinyl acetate.

24. The polymer polyol of claim 20, wherein said ethylenically unsaturated monomer is a monovinylidene aromatic monomer and/or an α, β -ethylenically unsaturated nitrile.

25. The polymer polyol of claim 24, wherein the ethylenically unsaturated monomer is styrene or acrylonitrile or a mixture of styrene and acrylonitrile in a molar ratio of 50: 50 to 99: 1.

26. The polymer polyol of claim 25, wherein said ethylenically unsaturated monomer is a mixture of styrene and acrylonitrile in a molar ratio of 55: 45 to 80: 20.

27. The polymer polyol according to claim 14, wherein the polymerization initiator is a peroxide and/or an azo compound.

28. The polymer polyol of claim 27, wherein the peroxide is selected from the group consisting of alkyl and aryl hydroperoxides, persulfate, perborate, and percarbonate.

29. The polymer polyol of claim 27, wherein the peroxide is a peroxyester.

30. The polymer polyol according to claim 27, wherein the polymerization initiator is one or more selected from the group consisting of hydrogen peroxide, di-t-butyl peroxide, t-butyl peroxydiethylacetate, t-butyl peroxyoctoate, t-butyl peroxyisobutyrate, t-butyl peroxy3, 5, 5-trimethylhexanoate, t-butyl peroxybenzoate, t-butyl peroxypivalate, t-amyl peroxypivalate, t-butyl peroxy2-ethylhexanoate, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, azobisisobutyronitrile, 2 '-azobis- (2-methylbutyronitrile), and diethyl 2, 2' -azobis (isobutyrate).

31. The polymer polyol of claim 14, wherein the chain transfer agent comprises isopropanol, ethanol, methanol, 1-butanol, 2-butanol, water, or a mercaptan.

32. The polymer polyol of claim 31, wherein said chain transfer agents are mercaptans and isopropanol.

33. The method of preparing a polymer polyol according to claim 14, comprising the steps of:

1) uniformly mixing phosphate macromonomer, partial ethylenically unsaturated monomer, chain transfer agent and initiator, adding into a reaction kettle to prepare a prepolymer,

2) and then uniformly mixing the prepolymer, the basic polyol, the residual ethylenically unsaturated monomer, the chain transfer agent and the initiator, and adding the mixture into a reaction kettle for reaction to obtain the polymer polyol.

34. The method of claim 33, wherein the polymer polyol is prepared at a temperature of 80 ℃ to 160 ℃.

35. The method of claim 34, wherein the polymer polyol is prepared at a temperature of 90 ℃ to 150 ℃.

36. The method of claim 35, wherein the polymer polyol is prepared at a temperature of 100 ℃ to 140 ℃.

37. The method of claim 33, wherein the amount of the partially ethylenically unsaturated monomer added in step 1) is 10% to 40% of the total mass of the ethylenically unsaturated monomers.