Perfluorinated additive emulsion and preparation method thereof, polyether composition, rigid polyurethane foam and preparation method thereof

Abstract

The invention provides a perfluor additive emulsion and a preparation method thereof, the perfluor additive emulsion is obtained by uniformly dispersing a perfluor additive in polyether polyol, the polyether polyol is prepared from a mixed initiator, and the initiator contains a dispersing aid; the auxiliary dispersing agent at least comprises one of palm oil, soybean oil and castor oil. The combined polyether polyol prepared from the perfluorinated additive emulsion has high stability and is not easy to layer. And the prepared polyurethane rigid foam has the advantages of fine foam holes and low heat conductivity coefficient.

Description

Technical Field

[0001] The invention belongs to the field of foamed polyurethane materials, and specifically relates to a perfluorinated auxiliary agent emulsion and a preparation method thereof, a polyether composition, a polyurethane rigid foam and a preparation method thereof. Background Art

[0002] Rigid polyurethane (PU) foam plastic is one of the main varieties of polyurethane synthetic materials. It is a foam plastic made by the reaction of polyether polyol or polyester polyol with isocyanate to form a polyurethane main body, and the reaction of isocyanate with water or low-boiling-point chlorofluorocarbon foaming agent. It is a kind of low-density microporous polymer material with closed-cell structure and excellent comprehensive performance. As a heat preservation material for refrigerators, it has the advantages of low density, low thermal conductivity, high compressive strength, good adhesion and easy processing. So far, polyurethane rigid foam is not only widely used in the refrigeration industry, but also widely used in furniture, construction, packaging and insulation materials.

[0003] Polyurethane rigid foam is made by a series of chemical reactions of combined polyether polyols and isocyanates in the presence of certain catalysts, surfactants, foaming agents and other additives. Generally, before the reaction, the additives need to be added to the combined polyether polyols and mixed thoroughly to form a combined polyether. The combined polyether is then mixed evenly with the isocyanate by a high-pressure foaming machine and filled into the inner cavity of the refrigerator. Since refrigerator manufacturing is a continuous production, the raw material stability requirements are relatively high, which also leads to a cumbersome process for temporary performance changes and easy waste of raw materials.

[0004] The main properties of polyurethane rigid foam for refrigerators include demoulding performance, aging performance, thermal conductivity, etc. The requirements for raw materials for each performance are also inconsistent. For example, due to differences in laws and regulations in different countries and regions, the polyurethane rigid foam for refrigerator products is also different. For example, the EU prohibits the use of foaming agents with high GWP values, such as 134a and 245fa. At the same time, refrigerator products will also have different performance requirements. For example, some products require lower energy consumption, and polyurethane foam requires a lower thermal conductivity, resulting in an increase in production costs; some products even require flame retardant properties, which will lose the strength of polyurethane foam.

[0005] With the new EU energy consumption standards, higher and higher requirements are placed on the thermal conductivity of foams. The thermal conductivity of the CP system has been decreasing from the initial 19.5mw / mK to the latest requirement of 17.5mw / mK. Without changing the foaming agent, the thermal conductivity can only be reduced to about 18.0mw / mK by changing the polyether polyols, surfactants and catalysts. If further reduction is required, only perfluorinated additives can be used. The low surface tension characteristics of perfluorinated additives can improve the nucleation ability of polyurethane foam in the early stage of reaction, reduce the pore size, and thus reduce the thermal conductivity of the foam.

[0006] However, the mutual solubility of perfluorinated additives in combined polyethers is extremely poor. Without adjustment of the production process, the combined polyether containing the foaming agent will be stratified in just one hour after the addition of the perfluorinated additives, affecting the stability of the materials used on site by customers.

[0007] Therefore, how to keep the perfluorinated additives stable in the composite polyether has gradually become a difficult problem in the industry. Summary of the invention

[0008] In order to solve the problems existing in the prior art, the present invention provides a perfluorinated auxiliary agent emulsion and a preparation method thereof, which has good dispersibility in a polyether composition and will not delaminate even after being placed for a long time.

[0009] The invention also provides a polyether composition which has strong stability and can be placed at 0-50°C for 7 days without delamination. The polyether composition can be used for the preparation of polyurethane rigid foam.

[0010] The present invention also provides a polyurethane rigid foam and a preparation method thereof. The prepared foam has fine pores, low thermal conductivity and a small number of surface defects at the flow end.

[0011] In order to achieve the above invention objectives, the present invention adopts the following technical scheme: a perfluorinated additive emulsion, which is obtained by uniformly dispersing a perfluorinated additive in a polyether polyol, wherein the preparation raw material of the polyether polyol uses a mixed initiator, and the initiator contains a dispersant; the dispersant includes at least one of palm oil, soybean oil, and castor oil; preferably, the mass ratio of the dispersant in the polyether polyol is 20%-30%; and / or, the viscosity of the polyether polyol is 300-2000mpa.s (25°C), and the hydroxyl value is 250-450mg KOH / g.

[0012] In the present invention, the perfluorinated auxiliary agent is a perfluorinated olefin and / or a perfluorinated alkane; preferably, the mass ratio of the perfluorinated auxiliary agent to the dispersant is 1:(1-10).

[0013] In the present invention, the perfluorinated additive includes at least one of PF-5052, PF-5056, PF-5058, PF-5060, PF-7100, PF-188, and Noah 2100B.

[0014] In the present invention, the preparation method of the perfluorinated additive emulsion comprises the following steps: cooling the perfluorinated additive to below -10°C, cooling the polyether polyol to below 10°C, adding them into a stirring kettle according to the mass ratio, with a stirring rate of ≥2000r / min and a stirring time of ≥30min.

[0015] In the present invention, the polyether polyol in the perfluorinated auxiliary agent emulsion uses one or more of sucrose, sorbitol, propylene glycol, diethylene glycol and glycerol and a dispersant as a common initiator, KOH and / or alkaline amine organic matter as a catalyst, propylene oxide and / or ethylene oxide as a chain extender, and reacts at 120-160° C. for 8-12 hours. If KOH is a catalyst, phosphoric acid needs to be added to neutralize KOH after the reaction is completed, diatomaceous earth adsorbs metal salts, and the filter residue is filtered to obtain a polyether polyol containing a dispersant; if an alkaline amine organic matter is a catalyst, no post-treatment is required, and a polyether polyol containing a dispersant is directly obtained, and the viscosity is 300-1000 mpa.s and the hydroxyl value is 250-450 mg KOH / g.

[0016] The present invention also provides a polyether composition, comprising a perfluorinated auxiliary emulsion, a basic polyether polyol, an optional surfactant, a catalyst and water. Preferably, the perfluorinated auxiliary accounts for 0.5% to 4.0% by mass of the polyether composition.

[0017] As a preferred solution, in the polyether composition, the mass percentage of the perfluorinated additive emulsion in the polyether composition is 10%-50%; the mass percentage of the basic polyether polyol is 37.5%-86.3%; the mass percentage of the optional surfactant is 1.2%-4.0%; the mass percentage of the catalyst is 1.5%-5.5%; and the mass percentage of water is 1.0%-3.0%.

[0018] Preferably, the basic polyether polyol includes one or more of sucrose polyether polyol, sorbitol polyether polyol, o-toluenediamine polyether polyol, propylene glycol polyether polyol, diethylene glycol polyether polyol, glycerol polyether polyol, etc. Preferably, the sucrose polyether polyol is prepared by addition reaction of sucrose and propylene glycol as co-initiators with propylene oxide, and has a viscosity of 25000-45000 mpa.s and a hydroxyl value of 350-500 mgKOH / g.

[0019] Preferably, the sorbitol polyether polyol is prepared by using sorbitol and glycerol as initiators, performing a dehydration treatment before the reaction, and performing an addition reaction with propylene oxide, with a viscosity of 2000-15000 mpa.s and a hydroxyl value of 380-500 mgKOH / g.

[0020] Preferably, the toluenediamine polyether polyol is prepared by addition reaction of o-TDA as an initiator with propylene oxide, and has a viscosity of 300,000-500,000 mPa.s and a hydroxyl value of 490-610 mgKOH / g.

[0021] Preferably, the propylene glycol polyether polyol is prepared by addition reaction of propylene glycol as an initiator with propylene oxide, and has a viscosity of 20-500 mPa.s and a hydroxyl value of 100-350 mgKOH / g.

[0022] Preferably, the diethylene glycol polyether polyol is prepared by addition reaction of diethylene glycol as an initiator with propylene oxide, and has a viscosity of 20-500 mPa.s and a hydroxyl value of 100-350 mgKOH / g.

[0023] Preferably, the glycerol polyether polyol is prepared by addition reaction of glycerol as an initiator with propylene oxide, and has a viscosity of 100-1500 mPa.s and a hydroxyl value of 350-560 mgKOH / g.

[0024] Preferably, the surfactant is a silicon surfactant, preferably an organosilicon surfactant, most preferably one or more of L6863, L6900, Y16148, B8461, B8462, B8481, B84806, M-8805, M-8815, M-8830, M-8860, M-88310, M-88108, SD-613, SD-624, SD-625, SD-638, etc.;

[0025] Preferably, the combined catalyst comprises a plurality of pentamethyldiethylenetriamine, tetramethylhexanediamine, bis-dimethylaminoethyl ether, dimethylbenzylamine, dimethylcyclohexane, triethylenediamine, methylimidazole, potassium formate, potassium acetate, quaternary ammonium salt, tris(dimethylaminopropyl)hexahydrotriazine, etc.;

[0026] The present invention also provides a polyurethane rigid foam, which uses the above perfluorinated auxiliary emulsion. The raw materials for preparing the polyurethane rigid foam include a polyether composition, a foaming agent and a polyisocyanate, and the component contents thereof are as follows:

[0027] (a) polyether composition: 100 parts;

[0028] (b) Foaming agent: 12-32 parts

[0029] (c) Isocyanate: 120-170 parts

[0030] The foaming agent includes one or more of cyclopentane (CP), isopentane (IP), n-pentane (NP), n-butane (R600), isobutane (R600a), 1,1,1,3,3-pentafluoropropane (245fa), 1-chloro, 3,3,3-trifluoropropene (LBA), 1,1,1,2-tetrafluoroethane (134a), 1,1-difluoroethane (152a), 1,1,1,4,4,4-hexafluoro-2-butene (OP-1100), 1,3,3,3-tetrafluoropropene (GBA), etc.

[0031] The polyisocyanate is polymeric MDI, preferably polymeric MDI with an NCO content of 30 to 32%; more preferably, it is one or more of polymeric MDI Wanhua PM-200, polymeric MDI Wanhua PM-2010 and polymeric MDI Wanhua PM-400.

[0032] The specific preparation method of the polyurethane rigid foam is as follows:

[0033] 1) The perfluorinated additive and the polyether polyol containing the dispersant are mixed by a high-speed stirrer to obtain a perfluorinated additive emulsion, which is allowed to stand for defoaming and the temperature is controlled at 20-30°C;

[0034] 2) The base polyether polyol, the perfluorinated additive emulsion, the surfactant and the catalyst are uniformly mixed to obtain a composite polyether, and the temperature is controlled at 20-30° C.;

[0035] 3) The polyether composition and the foaming agent are mixed uniformly by a static premixing device to obtain a mixture B, which is transferred to a white material tank of a high-pressure foaming machine and the temperature is controlled at 15-20° C.;

[0036] 4) Mixture B and isocyanate are mixed evenly at the head of a foaming machine gun, and poured into a fixed closed mold to obtain the polyurethane rigid foam.

[0037] The conditions of the high pressure foaming process in step 4) are: material temperature 15-18°C, pressure 100-150 bar (gauge pressure); preferably material temperature 17°C, pressure 125 bar (gauge pressure), mold temperature 35-50°C, overfilling rate 15%-25%, demoulding time 130-300s.

[0038] Compared with the prior art, the present invention has the following advantages:

[0039] 1) The perfluorinated additive emulsion prepared by the present invention has a lot of storage stability. It can be placed at 0-50°C for one month without stratification. The polyether composition containing perfluorinated additives prepared by the emulsion also has strong stability. It can be placed at 0-50°C for 7 days without stratification.

[0040] 2) The polyurethane foam prepared by using the polyether composition containing the perfluorinated additive emulsion has finer pores and a lower foam thermal conductivity.

[0041] 3) The dispersant improves the stability of the perfluorinated additive in the combined polyether, and the number of bubbles on the surface of the prepared polyurethane rigid foam is small. DETAILED DESCRIPTION

[0042] The technical solution of the present invention is further illustrated by specific embodiments below, but the protection scope of the present invention is not limited thereto. Within the technical scope disclosed in the present invention, changes or replacements of the same or similar technical features should be covered within the protection scope of the present invention.

[0043] The manufacturers and models of the main test instruments in the embodiments of the present invention and the comparative examples are shown in Table 1:

[0044] Table 1 Manufacturers and models of main test instruments

[0045] Test Equipment model factory Thermal conductivity meter HC-074 EKO Equipment Compression strength machine 5Kn Proline Zwick / Roell High pressure foaming machine HK650 Hennecke Scanning electron microscopy SEM3100 Guoyi Quantum

[0046] The sources of the main materials and reagents of the embodiments of the present invention are shown in Table 2:

[0047] Table 2 Sources of main materials and reagents in Examples

[0048]

[0049]

[0050] Polyether polyol A: sucrose, palm oil, and propylene glycol are used as co-initiators, wherein the mass ratio of sucrose, palm oil, and propylene glycol is 7:2:1, and the content of palm oil is 20%. 3‰ KOH is added as a catalyst (mass ratio), placed in a reactor, and then propylene oxide is added, the mass ratio of propylene oxide to initiator is 15:10, and the addition reaction with propylene oxide is carried out at 120°C for 12 hours. After the reaction is completed, phosphoric acid needs to be added to neutralize KOH, diatomaceous earth is used to absorb metal salts, and the filter residue is filtered to remove the filter residue, and a polyether polyol containing a dispersant is obtained, with a viscosity of 830mpa.s and a hydroxyl value of 430mgKOH / g. It is calculated that the mass ratio of palm oil to the polyether polyol is 8%.

[0051] Perfluoro-additive emulsion A: Cool 2100B to -15°C, cool polyether polyol A containing palm oil to 5°C, and mix them evenly with a high-speed stirrer at a mass ratio of 2100B to palm oil of 1:1 to obtain perfluoro-additive emulsion A. Place the mixture in a 15°C thermostat. It is calculated that the mass ratio of 2100B in the emulsion is 7.4%.

[0052] Polyether polyol B: sorbitol, soybean oil, and glycerol are used as co-initiators, wherein the ratio of sorbitol, palm oil, and glycerol is 5:3:2, and the soybean oil content is 30%. Add 5‰ dimethylamine as a catalyst (mass ratio), place it in a reactor, and then add propylene oxide, the mass ratio of propylene oxide to initiator is 47:53, and react with propylene oxide at 140°C for 9 hours. The polyether polyol containing a dispersant is obtained, with a viscosity of 450mpa.s and a hydroxyl value of 320mgKOH / g. It is calculated that the mass ratio of soybean oil to the polyether polyol is 16%.

[0053] Perfluoro-additive emulsion B: Cool PF5056 to -10°C, cool polyether polyol B containing soybean oil to 5°C, and mix them with a high-speed stirrer at a mass ratio of PF-5056 to soybean oil of 1:8 to obtain perfluoro-additive emulsion B. Place it in a constant temperature box at 15°C. It is calculated that the mass ratio of PF5056 in the emulsion is 2%.

[0054] The polyether polyol A, polyether polyol B, polyether polyol C, polyether polyol D, polyether polyol E, polyether polyol F, polyether polyol G and polyether polyol H are all basic polyether polyols.

[0055] Polyether polyol C: Sucrose and propylene glycol are used as co-initiators to add propylene oxide to obtain a polyol with a viscosity of 1500 mPa.s and a hydroxyl value of 430 mgKOH / g.

[0056] Polyether polyol D: obtained by adding propylene oxide with sorbitol and glycerol as co-initiators, with a viscosity of 2100 mPa.s and a hydroxyl value of 420 mgKOH / g.

[0057] Polyether polyol E: Toluenediamine polyether polyol, prepared by addition reaction of o-TDA as initiator with propylene oxide, with a viscosity of 353000mpa.s and a hydroxyl value of 530mgKOH / g.

[0058] Polyether polyol F: prepared by addition reaction of propylene glycol as an initiator with propylene oxide, with a viscosity of 54 mPa.s and a hydroxyl value of 240 mgKOH / g.

[0059] Polyether polyol G: prepared by addition reaction of diethylene glycol as an initiator with propylene oxide, with a viscosity of 67 mPa.s and a hydroxyl value of 240 mgKOH / g.

[0060] Polyether polyol H: It is prepared by addition reaction of glycerol as an initiator with propylene oxide, with a viscosity of 350 mPa.s and a hydroxyl value of 450 mgKOH / g.

[0061] Example 1

[0062] A polyurethane rigid foam containing a perfluorinated additive emulsion, the raw materials are:

[0063] The mass ratio of the combined polyether, the foaming agent and the polyisocyanate is 100:13:141.25, specifically:

[0064] The composition of the combined polyether is as follows: 50 parts of perfluoro-auxiliary emulsion A (2100B content is 7.4%), 43.4 parts of basic polyether polyol, 2 parts of surfactant, 2.5 parts of combined catalyst, and 2.1 parts of water;

[0065] Foaming agent: CP 13 parts

[0066] Polyisocyanate: Wanhua PM200 141.25 parts.

[0067] The base polyether polyol includes: 25 parts of polyether polyol E and 18.4 parts of polyether polyol H.

[0068] Surfactant: B8481 2 parts (Evonik).

[0069] Combined catalyst: the foaming catalyst is bis-dimethylaminoethyl ether, the gelling catalyst is dimethylcyclohexylamine, the trimerization catalyst is tris(dimethylaminopropyl)hexahydrotriazine, bis-dimethylaminoethyl ether: dimethylcyclohexylamine: tris(dimethylaminopropyl)hexahydrotriazine = 1:3.1:1.2 (mass ratio).

[0070] The calculation shows that the mass proportion of the perfluoro additive 2100B in the combined polyether is 3.7%.

[0071] The preparation method of polyurethane rigid foam comprises the following steps:

[0072] 1) mixing the base polyether polyol, the perfluorinated additive emulsion A, the surfactant and the catalyst uniformly to obtain a composite polyether, and controlling the temperature at 20° C.;

[0073] 3) The combined polyether and the foaming agent are mixed uniformly by a static premixing device to obtain a mixture B, which is transferred to a white material tank of a high-pressure foaming machine and the temperature is controlled at 15° C.;

[0074] 4) Mixture B and isocyanate are mixed evenly at the head of a foaming machine gun, and poured into a fixed closed mold to obtain the polyurethane rigid foam.

[0075] The conditions of the high-pressure foaming process in step 4) are: material temperature 18°C, pressure 130 bar (gauge pressure), preferably material temperature 17°C, pressure 125 bar (gauge pressure), mold temperature 45°C, overfilling rate 15%, demoulding time 210s.

[0076] Example 2

[0077] In Example 1, the composition of the combined polyether is: 20 parts of perfluoro-auxiliary emulsion A (2100B content is 7.4%), 73.4 parts of basic polyether polyol;

[0078] The base polyether polyol comprises: 30 parts of polyether polyol A, 25 parts of polyether polyol E, and 18.4 parts of polyether polyol H;

[0079] The calculation shows that the mass proportion of the perfluoro additive 2100B in the combined polyether is 1.48%.

[0080] The types and contents of other blowing agents, polyisocyanates, surfactants, combined catalysts, water, and the method for preparing the polyurethane rigid foam are the same as those in Example 1.

[0081] Example 3

[0082] A polyurethane rigid foam containing a perfluorinated additive emulsion, the raw materials are:

[0083] The mass ratio of the combined polyether, the foaming agent and the polyisocyanate is 100:18:153.4, specifically:

[0084] The composition of the combined polyether is as follows: 20 parts of perfluoro-auxiliary emulsion B (PF-5056 content is 2%), 70.2 parts of basic polyether polyol, 4 parts of surfactant, 3.6 parts of combined catalyst, and 2.2 parts of water;

[0085] Foaming agent: CP 12 parts, LBA 6 parts

[0086] Polyisocyanate: Wanhua PM200 153.4 parts.

[0087] The base polyether polyol comprises: 20 parts of polyether polyol B, 45 parts of polyether polyol E, and 5.2 parts of polyether polyol H;

[0088] Surfactant: L6863 4 parts (Evonik).

[0089] Combined catalyst: the foaming catalyst is bis-dimethylaminoethyl ether, the gelling catalyst is dimethylcyclohexylamine, the trimerization catalyst is tris(dimethylaminopropyl)hexahydrotriazine, bis-dimethylaminoethyl ether: dimethylcyclohexylamine: quaternary ammonium salt = 1:3.1:1.2 (mass ratio).

[0090] The calculation shows that the mass proportion of the perfluorinated additive PF-5056 in the combined polyether is 0.4%.

[0091] The polyurethane foam preparation process is consistent with that in Example 1, and the overfilling rate is 25%.

[0092] Example 4

[0093] In Example 3, the combined polyether composition is: 40 parts of perfluorinated additive emulsion B (PF-5056 content is 2%), 50.2 parts of basic polyether polyol;

[0094] The base polyether polyol comprises: 45 parts of polyether polyol E and 5.2 parts of polyether polyol H;

[0095] The calculation shows that the mass proportion of the perfluorinated additive PF-5056 in the combined polyether is 0.8%.

[0096] The types and contents of other blowing agents, polyisocyanates, surfactants, combined catalysts, water, and the method for preparing the polyurethane rigid foam are the same as those in Example 3.

[0097] Comparative Example 1

[0098] In Example 1, 50 parts of the perfluorinated additive emulsion A is replaced by 50 parts of the polyether polyol A. The composite polyether does not contain a perfluorinated additive, and its raw materials and polyurethane foam preparation are the same as in Example 1.

[0099] Comparative Example 2

[0100] In Example 3, 40 parts of the perfluorinated additive emulsion B was replaced by 40 parts of polyether polyol B. The composite polyether did not contain a perfluorinated additive, and its raw materials and polyurethane foam were prepared in the same manner as in Example 3.

[0101] Comparative Example 3

[0102] In Example 1, 2100B was added to polyether polyol A without dispersant at a mass ratio of 7.4%, and after mixing, 50 parts of 2100B were used to replace 50 parts of perfluoro auxiliary emulsion A. The remaining raw materials and polyurethane foam preparation were the same as in Example 1.

[0103] The mass proportion of the perfluoro auxiliary agent 2100 in the combined polyether is 3.7%.

[0104] Table 3: Composition (parts by weight) and performance parameters of polyurethane rigid foam raw materials of Examples 1-4 and Comparative Examples 1-3

[0105]

[0106]

[0107] Note: Foam density, compression strength, thermal conductivity and dimensional stability are all measured according to national standards:

[0108] Foam core density test according to standard: GB / T 6343-2009;

[0109] Foam thermal conductivity test is in accordance with the standard: GB / T 10295-2008;

[0110] Foam compression strength test according to standard: GB / T 8813-2008;

[0111] Surface bubble standard: diameter ≥ 6cm is A + , 3cm≤diameter<6cm is A, 1A + =2A.

Claims

1. A perfluorinated additive emulsion, characterized in that: The perfluorinated additive is uniformly dispersed in a polyether polyol, wherein the preparation raw material of the polyether polyol uses a mixed initiator, and the initiator contains a dispersant; the dispersant includes at least one of palm oil, soybean oil, and castor oil; preferably, the mass ratio of the dispersant in the polyether polyol is 20%-30%; and / or the viscosity of the polyether polyol is 300-2000mpa.s (25°C), and the hydroxyl value is 250-450mgKOH / g.

2. The perfluorinated additive emulsion according to claim 1, characterized in that: The perfluorinated auxiliary agent is a perfluorinated olefin and / or a perfluorinated alkane; preferably, the mass ratio of the perfluorinated auxiliary agent to the dispersant is 1:(1-10).

3. The perfluorinated additive emulsion according to claim 2, characterized in that: The perfluorinated auxiliary agent includes at least one of PF-5052, PF-5056, PF-5058, PF-5060, PF-7100, PF-188, and Noah 2100B.

4. The method for preparing the perfluorinated additive emulsion according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: cooling the perfluorinated auxiliary agent to below -10°C, cooling the polyether polyol to below 10°C, adding them into a stirring kettle according to a mass ratio, with a stirring speed of ≥2000r / min and a stirring time of ≥30min.

5. A polyether composition, characterized in that The invention comprises the perfluorinated auxiliary emulsion according to any one of claims 1 to 3, a basic polyether polyol, an optional surfactant, a catalyst and water.

6. The polyether composition according to claim 5, characterized in that The base polyether polyol is selected from one or more of a polyether polyol with sucrose as the initiator, a polyether polyol with sorbitol as the initiator, a polyether polyol with glycerol as the initiator, a polyether polyol with o-TDA as the initiator, a polyether polyol with propylene glycol as the initiator, a polyether polyol with diethylene glycol as the initiator, or a polyether polyol with a mixed initiator; Preferably, the surfactant is a silicon-based surfactant, more preferably an organosilicon surfactant; Preferably, the catalyst comprises one or more of pentamethyldiethylenetriamine, tetramethylhexanediamine, bis-dimethylaminoethyl ether, dimethylbenzylamine, dimethylcyclohexane, triethylenediamine, methylimidazole, potassium formate, potassium acetate, quaternary ammonium salt, tris(dimethylaminopropyl)hexahydrotriazine.

7. The polyether composition according to claim 5 or 6, characterized in that The mass percentage of the perfluorinated auxiliary emulsion in the polyether composition is 10%-50%; the mass percentage of the basic polyether polyol is 37.5%-86.3%; the mass percentage of the optional surfactant is 1.2%-4.0%; the mass percentage of the catalyst is 1.5%-5.5%; and the mass percentage of water is 1.0%-3.0%.

8. A polyurethane rigid foam, characterized in that: Prepared by comprising the following components in parts by weight: The polyether composition according to any one of claims 5 to 7: 100 parts; Foaming agent: 12-32 parts Isocyanate: 120-170 parts.

9. The polyurethane rigid foam according to claim 8, characterized in that: The foaming agent is one or more of cyclopentane (CP), isopentane (IP), n-pentane (NP), n-butane (R600), isobutane (R600a), 1,1,1,3,3-pentafluoropropane (245fa), 1-chloro, 3,3,3-trifluoropropene (LBA), 1,1,1,2-tetrafluoroethane (134a), 1,1-difluoroethane (152a), 1,1,1,4,4,4-hexafluoro-2-butene (OP-1100), and 1,3,3,3-tetrafluoropropene (GBA); and / or, The isocyanate is polymeric MDI, preferably polymeric MDI with an NCO content of 30 to 32%; more preferably, it is one or more of polymeric MDI Wanhua PM-200, polymeric MDI Wanhua PM-2010 and polymeric MDI Wanhua PM-400.

10. The method for preparing a polyurethane rigid foam according to any one of claims 8 to 9, characterized in that: The following steps are involved: 1) mixing the base polyether polyol, the perfluorinated additive emulsion, the surfactant, the catalyst and water uniformly to obtain a polyether composition, and controlling the temperature at 20-30° C.; 2) The polyether composition and the foaming agent are mixed uniformly by a static premixing device to obtain a mixture B, which is transferred to a white material tank of a high-pressure foaming machine and the temperature is controlled at 15-20° C.; 3) Mixture B and isocyanate are mixed evenly at the head of a foaming machine gun, and poured into a fixed closed mold to obtain the polyurethane rigid foam; Preferably, in step 3), the material temperature is 15-18° C., the pressure is 100-150 bar (gauge pressure); and / or, the mold temperature is 35-50° C., the overfilling rate is 15%-25%, and the demoulding time is 130-300 s.

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