A fluorine-containing polyurethane material and preparation method thereof

Abstract

The present invention belongs to the field of polyurethane processing technology and provides a fluorinated polyurethane material and a preparation method thereof. The present invention involves subjecting waste polyurethane powder to an alcoholysis reaction with a fluorinated diol, an alcoholysis agent, an alcoholysis promoter, and an alcoholysis catalyst. Fluorinated groups are grafted onto the polyether polyol. The use of the fluorinated diol imparts a more complete cellular structure to the polyurethane material. The fluorinated polyether polyol is then mixed with a foam stabilizer, a polymerization catalyst, a blowing agent, and a black material, followed by a polymerization reaction. This fully foamed cellular structure is further stabilized, complete, and uniformly and densely distributed. The polyurethane material also possesses a robust skeleton and an excellent cross-linked structure, resulting in a fluorinated polyurethane material with excellent compressive strength and low thermal conductivity. Results from the examples show that the fluorinated polyurethane material prepared by the present invention has a compressive strength of 0.44 MPa, a thermal conductivity of 0.013 W / m·K, and a water absorption of 0.55%.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane processing, in particular to a fluorine-containing polyurethane material and a preparation method thereof. Background Art

[0002] As the sixth largest synthetic material, polyurethane is widely used in automobiles, refrigerator manufacturing, transportation, civil engineering, shoes, synthetic leather, fabrics, aviation, medical care, petrochemicals and other fields.

[0003] Numerous scholars and researchers are currently researching methods for recycling and repurposing waste polyurethane. These methods generally include landfilling, incineration, physical crushing, thermal treatment, and chemical treatment. Landfilling can cause soil and water pollution; incineration can cause air pollution; physical crushing can only be used as a filler material, with limited utility value; and thermal treatment produces various toxic gases. In comparison, chemical treatment is an ideal recycling method for effectively recovering waste polyurethane.

[0004] Fluorinated polyurethane is a polymer material with unique properties. Since Lovelace's invention of the first patent for fluorinated polyurethane in 1958, its synthesis has attracted widespread attention and become a hot topic in polyurethane research. Recycling waste polyurethane to produce fluorinated polyurethane offers high-value recovery. However, the introduction of fluorine can lead to a decrease in the mechanical properties of the polyurethane material. Therefore, the preparation of fluorinated polyurethane with excellent compressive strength has become a pressing technical challenge in this field. Summary of the Invention

[0005] The object of the present invention is to provide a fluorine-containing polyurethane material and a preparation method thereof. The fluorine-containing polyurethane material prepared by the preparation method provided by the present invention has excellent compressive strength and lower thermal conductivity.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing a fluorine-containing polyurethane material, comprising the following steps:

[0008] (1) mixing a fluorinated diol, an alcoholysis agent, an alcoholysis co-agent, and an alcoholysis catalyst and dissolving the mixture to obtain a degradation agent;

[0009] (2) mixing the degradation agent obtained in step (1) with waste polyurethane powder and performing alcoholysis reaction to obtain fluorinated polyether polyol;

[0010] (3) The fluorinated polyether polyol obtained in step (2) is mixed with a foam stabilizer, a polymerization catalyst, a foaming agent and a black material, and then subjected to polymerization reaction to obtain a fluorinated polyurethane material.

[0011] Preferably, the fluorine-containing diol in step (1) comprises a two-step fluorine-containing diol or a one-step fluorine-containing diol.

[0012] Preferably, in step (1), the mass ratio of the fluorinated diol to the alcoholysis agent, the alcoholysis co-agent, and the alcoholysis catalyst is (3-10):(25-40):(20-40):(1-2).

[0013] Preferably, the particle size of the waste polyurethane powder in step (2) is 1 to 2 mm.

[0014] Preferably, the waste polyurethane powder in step (2) comprises one or more of polyester-type waste polyurethane powder, polyether-type waste polyurethane powder and castor oil-type polyurethane powder.

[0015] Preferably, in step (2), the mass ratio of waste polyurethane powder to degradation agent is 1:(0.9-1.5).

[0016] Preferably, the temperature of the alcoholysis reaction in step (2) is 130-220° C., and the time of the alcoholysis reaction is 1-5 h.

[0017] Preferably, in step (3), the mass ratio of the fluorinated polyether polyol to the foam stabilizer, polymerization catalyst, foaming agent, and black material is (20-30): (7.5-20): (0.5-1): (15-30): (40-50).

[0018] Preferably, the polymerization reaction temperature in step (3) is 10-40° C., and the polymerization reaction time is 20-30 min.

[0019] The present invention also provides a fluorine-containing polyurethane material prepared by the preparation method described in the above technical solution.

[0020] The present invention provides a preparation method of a fluorine-containing polyurethane material, comprising the following steps: (1) mixing a fluorine-containing diol, an alcoholysis agent, an alcoholysis co-agent and an alcoholysis catalyst, and dissolving the mixture to obtain a degradation agent; (2) mixing the degradation agent obtained in step (1) with waste polyurethane powder, and performing an alcoholysis reaction to obtain a fluorine-containing polyether polyol; and (3) mixing the fluorine-containing polyether polyol obtained in step (2) with a foam stabilizer, a polymerization catalyst, a foaming agent and a black material, and performing a polymerization reaction to obtain a fluorine-containing polyurethane material. The present invention comprises first preparing a degradation agent by combining a fluorinated diol, an alcoholysis agent, an alcoholysis co-agent, and an alcoholysis catalyst. This is then subjected to an alcoholysis reaction with waste polyurethane powder, recycling the waste polyurethane while grafting fluorinated groups onto the polyether polyol. Furthermore, the use of the fluorinated diol imparts extremely low surface energy, excellent water and oil repellency, and a more complete pore structure to the polyurethane material, thereby improving the compressive strength of the fluorinated polyurethane material. Finally, the fluorinated polyether polyol is mixed with a foam stabilizer, a polymerization catalyst, a blowing agent, and a black material, followed by a polymerization reaction. This fully foams the fluorinated polyurethane material, resulting in a stable, complete pore structure with uniform and dense pore distribution, a robust skeleton, and an excellent cross-linked structure. This results in a fluorinated polyurethane material with excellent compressive strength and low thermal conductivity. The results of the examples show that the fluorinated polyurethane material prepared by the present invention has a compressive strength of 0.44 MPa, a thermal conductivity of 0.013 W / m·K, and a water absorption of 0.55%. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 IR spectra of the fluorinated polyether polyol in Example 5 of the present invention and the polyether polyol in Comparative Example 1;

[0022] Figure 2 This is a SEM image of the fluorine-containing polyurethane material prepared in Example 5 of the present invention;

[0023] Figure 3 for Figure 2 SEM image after 2x magnification;

[0024] Figure 4 This is a SEM image of the fluorine-containing polyurethane material prepared in Example 10 of the present invention;

[0025] Figure 5 for Figure 4 SEM image after 2x magnification. DETAILED DESCRIPTION

[0026] The present invention provides a method for preparing a fluorine-containing polyurethane material, comprising the following steps:

[0027] (1) mixing a fluorinated diol, an alcoholysis agent, an alcoholysis co-agent, and an alcoholysis catalyst and dissolving the mixture to obtain a degradation agent;

[0028] (2) mixing the degradation agent obtained in step (1) with waste polyurethane powder and performing alcoholysis reaction to obtain fluorinated polyether polyol;

[0029] (3) The fluorinated polyether polyol obtained in step (2) is mixed with a foam stabilizer, a polymerization catalyst, a foaming agent and a black material, and then subjected to polymerization reaction to obtain a fluorinated polyurethane material.

[0030] The present invention prepares a degradation agent by mixing a fluorinated diol, an alcoholysis agent, an alcoholysis co-agent, and an alcoholysis catalyst and then dissolving the mixture. The degradation agent is then subjected to an alcoholysis reaction with waste polyurethane powder, thereby achieving complete alcoholysis of the waste polyurethane and efficient recycling of the waste polyurethane.

[0031] The fluorinated diols in the present invention have a stable structure, excellent weather resistance and heat stability, low intermolecular forces, and low interfacial molecular forces. By adding the fluorinated diols, polyurethane materials can be endowed with extremely low surface energy and excellent water and oil repellency. Furthermore, the fluorinated polyurethane materials prepared using the fluorinated diols have a more complete pore structure with uniform and dense pore distribution, resulting in improved compressive strength and lower thermal conductivity. In the present invention, the fluorinated diols preferably include two-step fluorinated diols or one-step fluorinated diols, and more preferably two-step fluorinated diols.

[0032] In the present invention, the two-step method for preparing fluorinated diol preferably comprises the following steps:

[0033] 1) mixing diisocyanate and fluorocarbon alcohol and performing a grafting reaction to obtain perfluoroalkyl isocyanate;

[0034] 2) The perfluoroalkyl isocyanate obtained in step 1) and the diolamine are mixed and subjected to a substitution reaction to obtain a two-step fluorinated diol.

[0035] The present invention preferably mixes a diisocyanate and a fluorocarbon alcohol and conducts a grafting reaction to obtain a perfluoroalkyl isocyanate. The present invention grafts a fluorine-containing group onto the isocyanate by mixing the diisocyanate and the fluorocarbon alcohol and then conducting a grafting reaction. In the present invention, the mixing atmosphere is preferably nitrogen.

[0036] In the present invention, the diisocyanate is preferably heated before the fluorocarbon alcohol is added. In the present invention, the heating temperature is preferably 50-60°C, more preferably 50-55°C. The present invention does not specifically limit the heating time, as long as the diisocyanate is completely dissolved.

[0037] In the present invention, the diisocyanate preferably includes an aromatic diisocyanate or an aliphatic diisocyanate. In the present invention, the aromatic diisocyanate preferably includes one or more of toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-isocyanatophthalene diphenyl ether, 4,4'-methylenebis(phenyl isocyanate), hexamethylene diisocyanate, dimethylbiphenyl diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate and 3,3'-dimethylbiphenyl-4,4'-diisocyanate. In the present invention, the aliphatic diisocyanate preferably includes one or more of methylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate. The present invention does not particularly limit the source of the diisocyanate; commercially available products known to those skilled in the art may be used.

[0038] In the present invention, the fluorocarbon alcohol preferably includes F(CF2) m (CH2) n OH, m=1~12, n=1~6, m=0~10, n=1~6 and F(CF2) m CH=CH(CH2) n OH, m=1 to 12, n=1 to 6. The present invention has no particular limitation on the source of the fluorocarbon alcohol, and commercially available products known to those skilled in the art can be used.

[0039] In the present invention, the grafting reaction temperature is preferably 60-80°C, more preferably 65-78°C; the grafting reaction time is preferably 2-3 hours, more preferably 2-2.5 hours. In the present invention, the grafting reaction temperature and time are preferably controlled within the above ranges to improve yield. In the present invention, the grafting reaction atmosphere is preferably nitrogen.

[0040] After obtaining the perfluoroalkyl isocyanate, the present invention preferably mixes the perfluoroalkyl isocyanate with a diolamine and performs a substitution reaction to obtain a two-step fluorinated diol.

[0041] In the present invention, the diolamine is preferably heated before adding the perfluoroalkyl isocyanate. In the present invention, the heating temperature is preferably ≤ 10°C. In the present invention, the perfluoroalkyl isocyanate is preferably added at a temperature ≤ 15°C.

[0042] The present invention has no particular limitation on the mixing method of the perfluoroalkyl isocyanate and the diolamine, and any mixing method well known to those skilled in the art may be used.

[0043] In the present invention, the diolamine preferably includes one or more of diethanolamine, dipropanolamine, dihexanolamine, 1-aminopropanediol, diethanolaminomethylamine, diethanolaminoethylamine, and diethanolaminopropylamine, and more preferably one or more of diethanolamine, dihexanolamine, diethanolaminomethylamine, and diethanolaminopropylamine. The present invention does not particularly limit the source of the diolamine, and commercially available products known to those skilled in the art can be used.

[0044] In the present invention, the mass ratio of the diisocyanate, fluorocarbon alcohol and diolamine is preferably (20-30): (40-50): (10-20), more preferably (25-27): (45-47): (15-18).

[0045] In the present invention, the temperature of the substitution reaction is preferably 15-20°C, more preferably 18-20°C; the time of the substitution reaction is preferably 2-3 hours, more preferably 2-2.5 hours. In the present invention, the temperature and time of the substitution reaction are preferably controlled within the above ranges to ensure complete reaction and reduce the formation of by-products.

[0046] After the substitution reaction is completed, the product of the substitution reaction is preferably washed, filtered, and dried in sequence to obtain a two-step fluorinated diol. The washing, filtering, and drying procedures are not particularly limited in the present invention and may be performed using washing, filtering, and drying techniques well known to those skilled in the art. In the present invention, the washing agent used is preferably toluene.

[0047] The fluorinated diol prepared by the above preparation method contains a fluorinated group and a rigid six-ring ring, has good chemical stability and structural rigidity, and can improve the waterproof performance, thermal stability and mechanical properties of polyurethane materials.

[0048] In the present invention, the one-step method for preparing fluorinated diol preferably comprises the following steps:

[0049] a) mixing dimethylolcarboxylic acid, fluorocarbon alcohol and a solvent to obtain a mixture;

[0050] b) mixing the mixture obtained in step a) with a catalyst and performing an esterification reaction to obtain a one-step fluorine-containing diol.

[0051] In the present invention, dimethylolcarboxylic acid, fluorocarbon alcohol and a solvent are preferably mixed to obtain a mixture.

[0052] The present invention does not specifically limit the manner in which the dimethylolcarboxylic acid, fluorocarbon alcohol, and solvent are mixed, and any mixing method known to those skilled in the art may be employed. In the present invention, the mixing temperature is preferably 100 to 105° C. In the present invention, the mixing atmosphere is preferably nitrogen.

[0053] In the present invention, the dimethylol carboxylic acid preferably includes one or more of 2,2-dimethylol propionic acid and 2,2-dimethylol butyric acid. The present invention has no particular limitation on the source of the dimethylol carboxylic acid, and commercially available products known to those skilled in the art can be used.

[0054] In the present invention, the fluorocarbon alcohol preferably includes F(CF2) m (CH2) n OH, m=1~12, n=1~6, m=0~10, n=1~6 and F(CF2) m CH=CH(CH2) n OH, m=1 to 12, n=1 to 6. The present invention has no particular limitation on the source of the fluorocarbon alcohol, and commercially available products known to those skilled in the art can be used.

[0055] In the present invention, the solvent preferably includes toluene, acetone, ethyl acetate or chloroform.

[0056] In the present invention, the mass ratio of the dihydroxymethylcarboxylic acid, fluorocarbon alcohol and solvent is preferably (2-8): (4-12): (10-40), more preferably (2-3): (7-8): (20-22).

[0057] After obtaining the mixture, the present invention preferably mixes the mixture with a catalyst and performs an esterification reaction to obtain a one-step fluorine-containing diol.

[0058] The present invention has no particular limitation on the manner of mixing the mixture and the catalyst, and any mixing manner well known to those skilled in the art may be used.

[0059] In the present invention, the catalyst preferably comprises one or more of concentrated sulfuric acid, p-toluenesulfonic acid and thionyl chloride. The present invention has no particular limitation on the source of the catalyst, and commercially available products known to those skilled in the art can be used.

[0060] In the present invention, the mass ratio of the mixture to the catalyst is preferably 100:(0.3-0.7), more preferably 100:(0.4-0.6).

[0061] In the present invention, the temperature of the esterification reaction is preferably 110-130° C., more preferably 110-120° C.; the time of the esterification reaction is preferably 3-5 h, more preferably 3-4 h.

[0062] After the esterification reaction is completed, the product of the esterification reaction is preferably washed and filtered in sequence to obtain a one-step fluorinated diol. The washing and filtering procedures are not particularly limited in the present invention; washing and filtering techniques familiar to those skilled in the art may be employed. In the present invention, the cleaning agent used for the washing is preferably water. In the present invention, the filtration is preferably performed under reduced pressure.

[0063] The fluorinated diol prepared by the above preparation method contains a fluorinated group and has good chemical stability, and can give the polyurethane material good waterproof performance, thermal stability and mechanical properties.

[0064] In the present invention, the alcoholysis agent preferably includes ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,3-propanediol, 1,2-propanediol, 1,8-octanediol, 1,9-nonanediol, dipropylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, pentanediol, butynediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, sorbitol, hydroxyethyl cellulose, sucrose, GR-63 The alcoholysis agent may be selected from the group consisting of propylene glycol, diethylene glycol, 1,2-butanediol, 1,3-butanediol, dipropylene glycol, diethylene glycol, pentanediol, butynediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, GR-635C, GR-4110A, GR-4110G, GRA-6360, and PEDA-1500. ...cyclopentanediol, GR-635C, GR-4110A, GR-4110G, GRA-6360, and PEDA-1500. The alcoholysis agent of the present invention is used to undergo alcohol ester exchange reaction with the carbamate bond in the polyurethane molecule, thereby generating a long-chain polyol.

[0065] In the present invention, the co-alcoholysis agent preferably includes one or more of ethanolamine, diethanolamine, triethanolamine, 3-propanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, cyclohexylamine, tertiary amine, ethylene glycol, sodium hydroxide, potassium hydroxide, potassium hydroxide alkoxide and sodium hydroxide alkoxide, more preferably one or more of diethanolamine, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine and cyclohexylamine. The present invention has no particular limitation on the source of the co-alcoholysis agent, and commercially available products well known to those skilled in the art can be used. The use of the co-alcoholysis agent in the present invention is conducive to improving the efficiency of the alcoholysis reaction and shortening the time of the alcoholysis reaction.

[0066] In the present invention, the alcoholysis catalyst preferably comprises one or more of potassium hydroxide, sodium hydroxide, and a DMC catalyst, more preferably one or more of potassium hydroxide and a DMC catalyst. The present invention does not particularly limit the source of the alcoholysis catalyst; commercially available products familiar to those skilled in the art may be used. In the present invention, the use of the alcoholysis catalyst facilitates the alcoholysis reaction, resulting in complete alcoholysis of the waste polyurethane.

[0067] In the present invention, the mass ratio of the fluorinated diol to the alcoholysis agent, the alcoholysis co-agent, and the alcoholysis catalyst is preferably (3-10):(25-40):(20-40):(1-2), and more preferably (3-7):(25-30):(20-30):(1-1.5). In the present invention, the mass ratio of the fluorinated diol to the alcoholysis agent, the alcoholysis co-agent, and the alcoholysis catalyst is preferably controlled within the above range to ensure the hydroxyl value and viscosity of the degradation product.

[0068] The present invention has no particular limitation on the mixing method of the fluorinated diol, the alcoholysis agent, the alcoholysis co-agent and the alcoholysis catalyst, and any mixing method well known to those skilled in the art may be used.

[0069] In the present invention, the dissolution temperature is preferably 100-130° C., more preferably 120-130° C.; the dissolution time is preferably 0.5-2 h, more preferably 1-1.5 h. In the present invention, the dissolution is preferably carried out under stirring.

[0070] After obtaining the degradation agent, the present invention mixes the degradation agent with waste polyurethane powder and then conducts an alcoholysis reaction to obtain a fluorinated polyether polyol. The present invention combines waste polyurethane powder with the degradation agent and then conducts an alcoholysis reaction, causing the carbamate bonds in the polyurethane molecules to undergo an alcohol transesterification reaction with the alcoholysis agent to produce a long-chain polyol, while simultaneously introducing a fluorinated group to obtain the fluorinated polyether polyol.

[0071] In the present invention, the waste polyurethane powder preferably has a particle size of 1 to 2 mm. The present invention preferably uses waste polyurethane powder with a particle size meeting these requirements, as this facilitates complete alcoholysis of the waste polyurethane and enables its recycling. In the present invention, the waste polyurethane powder is preferably obtained by crushing waste polyurethane foam. The crushing process is not particularly limited in the present invention; any crushing technique known to those skilled in the art can be employed.

[0072] In the present invention, the waste polyurethane foam is preferably cleaned and dried before being crushed. Oil or impurities on the surface of the waste polyurethane are preferably removed by cleaning and drying. The cleaning and drying procedures are not particularly limited in the present invention, and cleaning and drying techniques familiar to those skilled in the art may be employed.

[0073] The preparation method provided by the present invention is applicable to the processing of various waste polyurethane powders. In the present invention, the waste polyurethane powder preferably includes one or more of polyester-type waste polyurethane powder, polyether-type waste polyurethane powder, and castor oil-type polyurethane powder, and more preferably one or more of polyester-type waste polyurethane powder and polyether-type waste polyurethane powder.

[0074] In the present invention, the mass ratio of the waste polyurethane powder to the degradation agent is preferably 1:(0.9-1.5), more preferably 1:(0.9-1.1). In the present invention, the mass ratio of the waste polyurethane powder to the degradation agent is preferably controlled within the above range, which is conducive to sufficient degradation of the waste polyurethane.

[0075] In the present invention, the alcoholysis reaction temperature is preferably 130-220°C, more preferably 200-220°C; the alcoholysis reaction time is preferably 1-5 hours, more preferably 2-4 hours. In the present invention, the alcoholysis reaction time and temperature are preferably controlled within the above ranges to ensure that the main product of the alcoholysis reaction is a polyol.

[0076] After obtaining the fluorinated polyether polyol, the present invention mixes the fluorinated polyether polyol with a foam stabilizer, a polymerization catalyst, a blowing agent, and a black material, and then conducts a polymerization reaction to obtain a fluorinated polyurethane material. The present invention obtains a fluorinated polyurethane material having a robust skeleton, an excellent cross-linked structure, and a uniformly dense cell distribution, exhibiting excellent compressive strength and low thermal conductivity by mixing the fluorinated polyether polyol with the foam stabilizer, a polymerization catalyst, a blowing agent, and a black material, and then conducting a polymerization reaction.

[0077] In the present invention, the foaming agent preferably includes one or more of monofluorodichloroethane, dichlorofluoroethane, 1,1,1-trifluorodichloroethane, monochlorodifluoromethane, cyclopentane, isopentane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 1,1,1,2-tetrafluoroethane, and water, and more preferably one or more of dichlorofluoroethane, monochlorodifluoromethane, isopentane, and 1,1,1,3,3-pentafluoropropane. The present invention does not particularly limit the source of the foaming agent, and commercially available products familiar to those skilled in the art can be used. In the present invention, the foaming agent is used for foaming to give the fluorine-containing polyurethane material a cellular structure.

[0078] In the present invention, the polymerization catalyst preferably includes tris (dimethylaminopropyl) hexahydrotriazine, dimethylethanolamine, N, N, N', N", N"-pentamethyldiethylenetriamine, triethylenediamine, cyclohexylamine, N, N-dimethylpiperazine, triethylenediamine, dimethylaminoethyl ether, pentamethyldiethylenetriamine, 2,2'-dimorpholine diethyl ether, N, N-dimethylbenzylamine, N, N', N"-tetramethyl-1,6-hexanediamine, methyldiethanolamine, N, N, N'-trimethylaminoethylethanolamine, triethylamine, 1,2-dimethylimidazole, tetramethylethylenediamine , N,N-dimethylethanolamine, N,N-diethylethanolamine, dimethylaminoethoxyethanol, N,N,N′,N′-tetramethyl-1,3-propylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine and one or more of an organic tin catalyst, more preferably triethylenediamine, triethylenediamine, dimethylaminoethyl ether, N,N′,N"-tetramethyl-1,6-hexanediamine, methyldiethanolamine, 1,2-dimethylimidazole, tetramethylethylenediamine, N,N-diethylethanolamine, dimethylaminoethoxyethanol and one or more of an organic tin catalyst. The present invention has no special limitation on the source of the polymerization catalyst, and a commercially available product well known to those skilled in the art can be used. In the present invention, the polymerization catalyst is used to catalyze the reaction of a fluorinated polyether polyol with a black material.

[0079] In the present invention, the foam stabilizer preferably includes one or more of silicone oil L-600, silicone oil SE-232, silicone oil CGY-5, silicone oil DC-193, silicone oil SC-154, silicone oil SC-155, silicone oil SD-601, C12 tertiary amine, dodecyldimethyl tertiary amine, tetradecyldimethyl tertiary amine, and dimethylsiloxane, and more preferably includes one or more of silicone oil L-600, silicone oil DC-193, silicone oil SC-155, and tetradecyldimethyl tertiary amine. The present invention does not specifically limit the source of the foam stabilizer; commercially available products familiar to those skilled in the art can be used. In the present invention, the foam stabilizer is used to stabilize the foam, thereby imparting to the fluorinated polyurethane material a stable, intact cell structure, thereby achieving improved compressive strength and lower thermal conductivity.

[0080] In the present invention, the black material preferably includes one of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and polyphenyl polymethylene polyisocyanate, more preferably diphenylmethane diisocyanate or toluene diisocyanate. In the present invention, the diphenylmethane diisocyanate preferably includes one or more of MDI-100LL, MDI-100HL, MR-200, M200, 44V20, M20S, and 5005, more preferably one or more of MDI-100LL, MR-200, M200, and M20S. In the present invention, the toluene diisocyanate preferably includes TDI-80 / 20 or TDI-100, more preferably TDI-80 / 20. The present invention does not particularly limit the source of the black material, and commercially available products familiar to those skilled in the art can be used. The black material in the present invention is used to react with a fluorinated polyether polyol to form a fluorinated polyurethane material.

[0081] In the present invention, the mass ratio of the fluorinated polyether polyol to the foam stabilizer, polymerization catalyst, blowing agent, and black material is preferably (20-30):(7.5-20):(0.5-1):(15-30):(40-50), and more preferably (20-27):(7.5-15):(0.5-0.7):(15-20):(40-45). In the present invention, it is preferred to control the mass ratio of the fluorinated polyether polyol to the foam stabilizer, polymerization catalyst, blowing agent, and black material within the above range, which is beneficial for obtaining a fluorinated polyurethane material with high compressive strength and low thermal conductivity.

[0082] The present invention has no particular limitation on the manner of mixing the fluorinated polyether polyol with the foam stabilizer, polymerization catalyst, blowing agent and black material, and any mixing manner well known to those skilled in the art may be used.

[0083] In the present invention, the polymerization reaction temperature is preferably 10-40°C, more preferably 20-30°C; the polymerization reaction time is preferably 20-30 minutes, more preferably 25-30 minutes. In the present invention, the polymerization reaction temperature and time are preferably controlled within the above ranges, which is conducive to obtaining a polyurethane rigid foam with uniform cell distribution, a robust cell skeleton, and a high closed-cell ratio.

[0084] The present invention prepares a degradation agent by firstly preparing a fluorine-containing diol, an alcoholysis agent, an alcoholysis co-agent and an alcoholysis catalyst, then performs an alcoholysis reaction with waste polyurethane powder, and simultaneously grafts a fluorine-containing group onto the polyether polyol while recovering the waste polyurethane. Finally, the fluorine-containing polyether polyol is mixed with a foam stabilizer, a polymerization catalyst, a foaming agent and a black material, and then performs a polymerization reaction. While fully foaming, the fluorine-containing polyurethane material can have a stable and complete pore structure, and the pores are evenly and densely distributed, and the material has a thick skeleton and an excellent cross-linking structure, thereby obtaining a fluorine-containing polyurethane material with excellent compressive strength and low thermal conductivity.

[0085] The present invention also provides a fluorine-containing polyurethane material prepared by the preparation method described in the above technical solution. The fluorine-containing polyurethane material provided by the present invention has excellent compressive strength and low thermal conductivity.

[0086] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0087] Example 1

[0088] (1) 50 parts of polyester-type waste polyurethane foam are washed and dried, and then crushed into 1-2 mm powder, i.e., polyester-type waste polyurethane powder;

[0089] (2) adding 3 parts of two-step fluorinated diol, 25 parts of ethylene glycol, 20 parts of diisopropanolamine, and 1 part of KOH into a reactor, stirring and dissolving at 130° C. for 1.5 hours, then adding 50 parts of polyester type waste polyurethane powder obtained in step (1), raising the temperature to 200° C. for alcoholysis reaction for 2 hours, and cooling to room temperature to obtain fluorinated polyether polyol; wherein the mass ratio of the two-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 3:25:20:1, and the ratio of the mass of the polyester type waste polyurethane powder to the total mass of the two-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 1:0.98;

[0090] Among them, the preparation method of the two-step fluorinated diol is:

[0091] 1) Reactor No. 1 equipped with a thermometer and a stirring device was purged with nitrogen and nitrogen was continuously purged during the reaction. 25 parts of xylylene diisocyanate were added to reactor No. 1, stirred, and heated to 55° C. until completely dissolved. 45 parts of 1H,1H-perfluoro-1-nonanol were slowly added to the reactor, and then the temperature was raised to 78° C. and the reaction was carried out for 2 hours to obtain a perfluoroalkyl isocyanate.

[0092] 2) Reactor No. 2 equipped with a thermometer and a stirring device was cleaned with nitrogen and nitrogen was continuously passed through during the reaction. 15 parts of dihexanolamine were added to Reactor No. 2, stirred, and maintained at a temperature of 10° C. After the dihexanolamine was completely dissolved, the temperature was raised to 15° C., the perfluoroalkyl isocyanate obtained in step 1) was added, and the temperature was raised to 20° C. for reaction for 2.5 hours. The reaction was then washed with toluene, filtered, and dried to obtain a fluorinated diol; wherein the mass ratio of xylylene diisocyanate, 1H,1H-perfluoro-1-nonanol, and dihexanolamine was 25:45:15;

[0093] (3) Take 20 parts of the fluorinated polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of an organic tin catalyst, and 15 parts of dichlorofluoroethane in sequence, stir evenly, and then add 40 parts of diphenylmethane diisocyanate (the mass ratio of the fluorinated polyether polyol to silicone oil L-600, the organic tin catalyst, dichlorofluoroethane, and diphenylmethane diisocyanate is 20:7.5:0.5:15:40), stir rapidly, and let it stand to foam naturally to obtain a fluorinated polyurethane material.

[0094] Example 2

[0095] (1) 50 parts of polyester-type waste polyurethane foam are washed and dried, and then crushed into 1-2 mm powder, i.e. polyester-type waste polyurethane powder;

[0096] (2) 3.4 parts of two-step fluorinated diol, 25 parts of 1,3-butanediol, 20 parts of cyclohexylamine, and 1 part of KOH were added to a reactor, stirred and dissolved at 130° C. for 1.5 hours, and then 50 parts of the polyester type waste polyurethane powder obtained in step (1) were added, the temperature was raised to 200° C. for alcoholysis reaction for 2 hours, and cooled to room temperature to obtain a fluorinated polyether polyol; wherein the mass ratio of the two-step fluorinated diol, 1,3-butanediol, cyclohexylamine, and KOH was 3.4:25:20:1, and the mass ratio of the polyester type waste polyurethane powder to the total mass of the two-step fluorinated diol, 1,3-butanediol, cyclohexylamine, and KOH was 1:0.988;

[0097] Among them, the two-step method for preparing fluorinated diols is:

[0098] 1) Reactor No. 1 equipped with a thermometer and a stirring device was purged with nitrogen and continuously purged with nitrogen during the reaction. 27 parts of diphenylmethane diisocyanate were added to Reactor No. 1, stirred, and heated to 55° C. until completely dissolved. 40 parts of 1H,1H-perfluorooctyl-1-ol were slowly added to the reactor, and then the temperature was raised to 78° C. and reacted for 2 hours to obtain a perfluoroalkyl isocyanate.

[0099] 2) Reactor No. 2, which is equipped with a thermometer and a stirring device, is cleaned with nitrogen and continuously purged with nitrogen during the reaction. 17 parts of dihexanolamine are added to reactor No. 2 with stirring and the temperature is maintained at 10°C. After the dihexanolamine is completely dissolved, the temperature is raised to 15°C, and the perfluoroalkyl isocyanate obtained in step 1) is added. The temperature is then raised to 20°C and reacted for 2.5 hours. The reaction is then washed with toluene, filtered, and dried to obtain a fluorinated diol; wherein the mass ratio of diphenylmethane diisocyanate, 1H,1H-perfluorooctyl-1-ol, and dihexanolamine is 27:40:17;

[0100] (3) Take 20 parts of the fluorinated polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of an organic tin catalyst, and 15 parts of dichlorofluoroethane in sequence, stir evenly, add 40 parts of diphenylmethane diisocyanate (the mass ratio of the fluorinated polyether polyol to silicone oil L-600, the organic tin catalyst, dichlorofluoroethane, and diphenylmethane diisocyanate is 20:7.5:0.5:15:40), stir rapidly, and let it stand for natural foaming to obtain a fluorinated polyurethane material.

[0101] Example 3

[0102] (1) 50 parts of polyester-type waste polyurethane foam are washed and dried, and then crushed into 1-2 mm powder, i.e. polyester-type waste polyurethane powder;

[0103] (2) adding 4 parts of two-step fluorinated diol, 25 parts of diethylene glycol, 20 parts of N,N-diethylethanolamine, and 1 part of NaOH into a reactor, stirring and dissolving at 120° C. for 1.5 hours, then adding 50 parts of polyester type waste polyurethane powder obtained in step (1), raising the temperature to 200° C. for alcoholysis reaction for 2 hours, and cooling to room temperature to obtain fluorinated polyether polyol; wherein the mass ratio of the two-step fluorinated diol, diethylene glycol, N,N-diethylethanolamine, and KOH is 4:25:20:1, and the mass ratio of the polyester type waste polyurethane powder to the total mass of the two-step fluorinated diol, diethylene glycol, N,N-diethylethanolamine, and KOH is 1:1;

[0104] Among them, the preparation method of the two-step fluorinated diol is:

[0105] 1) Reactor No. 1, equipped with a thermometer and a stirring device, was purged with nitrogen and continuously purged with nitrogen during the reaction. 20 parts of hexamethylene diisocyanate were added to Reactor No. 1, stirred, and heated to 55° C. until completely dissolved. 45 parts of 1H,1H,2H,2H-perfluorohexan-1-ol were slowly added to the reactor, and the temperature was raised to 70° C. for reaction for 3 hours to obtain a perfluoroalkyl isocyanate.

[0106] 2) Reactor No. 2, which is equipped with a thermometer and a stirring device, is cleaned with nitrogen and continuously purged with nitrogen during the reaction. 20 parts of dihexanolamine are added to reactor No. 2, stirred, and maintained at a temperature of 10° C. After the dihexanolamine is completely dissolved, the temperature is raised to 15° C., the perfluoroalkyl isocyanate obtained in step 1) is added, and the temperature is raised to 20° C. for reaction for 2.5 hours. The mixture is then washed with toluene, filtered, and dried to obtain a fluorinated diol; wherein the mass ratio of hexamethylene diisocyanate, 1H,1H,2H,2H-perfluorohexan-1-ol, and dihexanolamine is 20:45:20;

[0107] (3) Take 20 parts of the fluorinated polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of organotin catalyst, and 15 parts of monochlorodifluoromethane in sequence, stir evenly, and then add 40 parts of polyphenyl polymethylene polyisocyanate (the mass ratio of fluorinated polyether polyol and silicone oil L-600, organotin catalyst, monochlorodifluoromethane, and polyphenyl polymethylene polyisocyanate is 20:7.5:0.5:15:40), stir rapidly, and let it stand for natural foaming to obtain a fluorinated polyurethane material.

[0108] Example 4

[0109] (1) 50 parts of polyether type waste polyurethane foam are washed and dried, and then crushed into 1-2 mm powder, i.e., polyether type waste polyurethane powder;

[0110] (2) adding 3.25 parts of two-step fluorinated diol, 25 parts of ethylene glycol, 20 parts of diisopropanolamine, and 1 part of KOH into a reactor, stirring and dissolving at 130° C. for 1.5 hours, then adding 50 parts of the polyether type waste polyurethane powder obtained in step (1), raising the temperature to 200° C. for alcoholysis reaction for 2 hours, and cooling to room temperature to obtain a fluorinated polyether polyol; wherein the mass ratio of the two-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 3.25:25:20:1, and the ratio of the mass of the polyester type waste polyurethane powder to the total mass of the two-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 1:0.985;

[0111] Wherein, the preparation method of fluorinated diol is:

[0112] 1) Reactor No. 1 equipped with a thermometer and a stirring device was purged with nitrogen and nitrogen was continuously purged during the reaction. 30 parts of xylylenediisocyanate were added to reactor No. 1, stirred, and heated to 50° C. until completely dissolved. 50 parts of 1H,1H-perfluorooctyl-1-ol were slowly added to the reactor, and the temperature was raised to 70° C. for reaction for 2 h to obtain a perfluoroalkyl isocyanate.

[0113] 2) Reactor No. 2, which is equipped with a thermometer and a stirring device, is cleaned with nitrogen and continuously purged with nitrogen during the reaction. 20 parts of dihexanolamine are added to reactor No. 2, stirred, and maintained at a temperature of 10° C. After the dihexanolamine is completely dissolved, the temperature is raised to 15° C., the perfluoroalkyl isocyanate obtained in step 1) is added, and the temperature is raised to 20° C. for reaction for 2.5 hours. The reaction is then washed with toluene, filtered, and dried to obtain a fluorinated diol; wherein the mass ratio of xylylene diisocyanate, 1H,1H-perfluorooctyl-1-ol, and dihexanolamine is 30:50:20;

[0114] (3) Take 20 parts of the fluorinated polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of an organic tin catalyst, and 15 parts of dichlorofluoroethane in sequence, stir evenly, and then add 40 parts of diphenylmethane diisocyanate (the mass ratio of the fluorinated polyether polyol to silicone oil L-600, the organic tin catalyst, dichlorofluoroethane, and diphenylmethane diisocyanate is 20:7.5:0.5:15:40), stir rapidly, and let it stand to foam naturally to obtain a fluorinated polyurethane material.

[0115] Example 5

[0116] (1) 50 parts of polyether type waste polyurethane foam are washed and dried, and then crushed into 1-2 mm powder, i.e., polyether type waste polyurethane powder;

[0117] (2) adding 4 parts of two-step fluorinated diol, 25 parts of ethylene glycol, 20 parts of diisopropanolamine, and 1 part of KOH into a reactor, stirring and dissolving at 130° C. for 1.5 hours, then adding 50 parts of the polyether type waste polyurethane powder obtained in step (1), raising the temperature to 200° C. for alcoholysis reaction for 2 hours, and cooling to room temperature to obtain a fluorinated polyether polyol; wherein the mass ratio of the two-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 4:25:20:1, and the ratio of the mass of the polyester type waste polyurethane powder to the total mass of the two-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 1:1;

[0118] Wherein, the preparation method of fluorinated diol is:

[0119] 1) Reactor No. 1, equipped with a thermometer and a stirring device, was purged with nitrogen and continuously purged with nitrogen during the reaction. 25 parts of isophorone diisocyanate were added to Reactor No. 1, stirred, and heated to 55° C. until completely dissolved. 45 parts of perfluoro-tert-butyl alcohol were slowly added to the reactor, and then the temperature was raised to 80° C. and the reaction was carried out for 2 hours to obtain a perfluoroalkyl isocyanate.

[0120] 2) Reactor No. 2, which is equipped with a thermometer and a stirring device, is cleaned with nitrogen and continuously purged with nitrogen during the reaction. 10 parts of dihexanolamine are added to Reactor No. 2, stirred, and maintained at a temperature of 10° C. After the dihexanolamine is completely dissolved, the temperature is raised to 15° C., the perfluoroalkyl isocyanate obtained in step 1) is added, and the temperature is raised to 20° C. for reaction for 2.5 hours. The mixture is then washed with toluene, filtered, and dried to obtain a fluorinated diol; wherein the mass ratio of isophorone diisocyanate, perfluoro-tert-butyl alcohol, and dihexanolamine is 25:45:10;

[0121] (3) Take 20 parts of the fluorinated polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of an organic tin catalyst, and 15 parts of dichlorofluoroethane in sequence, stir evenly, add 40 parts of diphenylmethane diisocyanate (the mass ratio of the fluorinated polyether polyol to silicone oil L-600, the organic tin catalyst, dichlorofluoroethane, and diphenylmethane diisocyanate is 20:7.5:0.5:15:40), stir rapidly, and let it stand for natural foaming to obtain a fluorinated polyurethane material.

[0122] Figure 1 IR spectra of the fluorinated polyether polyol in this embodiment and the polyether polyol in comparative example 1. Figure 1 It can be seen that at 1220cm -1 The stretching vibration peak of -CF bond appears at 1070cm -1 The integral area of ​​COC increases significantly, which is due to the fact that the two-step fluorinated diol has COC.

[0123] Figure 2 This is the SEM image of the fluorine-containing polyurethane material prepared in this example. Figure 3 for Figure 2 SEM image after 2 times magnification. Figure 2 and Figure 3 It can be seen that the fluorine-containing polyurethane material prepared by the present invention has a complete pore structure, the pore structure is regular hexagonal, and the skeleton is thick, the cross-linking structure is excellent, and the pore distribution is more uniform and denser. This good geometric structure and uniform pore distribution can enable the fluorine-containing polyurethane material to obtain better compressive strength and lower thermal conductivity.

[0124] Example 6

[0125] (1) 50 parts of polyester-type waste polyurethane foam are washed and dried, and then crushed into 1-2 mm powder, i.e., polyester-type waste polyurethane powder;

[0126] (2) adding 6 parts of one-step fluorinated diol, 25 parts of ethylene glycol, 20 parts of diisopropanolamine, and 1.8 parts of KOH into a reactor, stirring and dissolving at 130° C. for 1.5 hours, then adding 50 parts of the polyester type waste polyurethane powder obtained in step (1), raising the temperature to 200° C. for alcoholysis reaction for 2 hours, and cooling to room temperature to obtain a fluorinated polyether polyol; wherein the mass ratio of the one-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 6:25:20:1.8, and the ratio of the mass of the polyester type waste polyurethane powder to the total mass of the one-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 1:1.056;

[0127] The one-step preparation method of the fluorinated diol comprises the following steps: purging a reactor equipped with a thermometer and a stirring device with nitrogen and continuously flowing nitrogen during the reaction; mixing 2 parts of 2,2-dimethylolpropionic acid, 8 parts of 1H,1H-perfluoro-1-nonanol, and 30 parts of ethyl acetate to obtain a mixture; adding the mixture and a catalyst, p-toluenesulfonic acid, into a reactor, stirring, and heating to 115°C for 2 hours to obtain a product, wherein the mass ratio of the mixture to the catalyst is 100:0.4; and then washing, filtering under reduced pressure, and drying in sequence to obtain the one-step fluorinated diol; wherein the mass ratio of 2,2-dimethylolpropionic acid, 1H,1H-perfluoro-1-nonanol, and ethyl acetate is 2:8:30;

[0128] (3) Take 20 parts of the fluorinated polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of an organic tin catalyst, and 15 parts of dichlorofluoroethane in sequence, stir evenly, and then add 40 parts of diphenylmethane diisocyanate (the mass ratio of the fluorinated polyether polyol to silicone oil L-600, the organic tin catalyst, dichlorofluoroethane, and diphenylmethane diisocyanate is 20:7.5:0.5:15:40), stir rapidly, and let it stand to foam naturally to obtain a fluorinated polyurethane material.

[0129] Example 7

[0130] (1) 50 parts of polyester-type waste polyurethane foam are washed and dried, and then crushed into 1-2 mm powder, i.e., polyester-type waste polyurethane powder;

[0131] (2) adding 3 parts of one-step fluorinated diol, 25 parts of 1,3-butanediol, 20 parts of cyclohexylamine, and 1 part of KOH into a reactor, stirring and dissolving them at 130° C. for 1.5 hours, then adding 50 parts of the polyester type waste polyurethane powder obtained in step (1), raising the temperature to 200° C. for alcoholysis reaction for 2 hours, and cooling to room temperature to obtain a fluorinated polyether polyol; wherein the mass ratio of the one-step fluorinated diol, 1,3-butanediol, cyclohexylamine, and KOH is 3:25:20:1, and the mass ratio of the polyester type waste polyurethane powder to the total mass of the one-step fluorinated diol, 1,3-butanediol, cyclohexylamine, and KOH is 1:0.98;

[0132] The one-step preparation method of the fluorinated diol comprises the following steps: purging a reactor equipped with a thermometer and a stirring device with nitrogen and continuously flowing nitrogen during the reaction; mixing 2.3 parts of 2,2-dihydroxymethylbutyric acid, 8 parts of 1H,1H-perfluorooctyl-1-ol, and 30 parts of ethyl acetate to obtain a mixture; adding the mixture and a catalyst, p-toluenesulfonic acid, into a reactor, stirring, and heating to 115°C for 2 hours to obtain a product, wherein the mass ratio of the mixture to the catalyst is 100:0.4; and then washing, filtering under reduced pressure, and drying in sequence to obtain the one-step fluorinated diol; wherein the mass ratio of 2,2-dihydroxymethylbutyric acid, 1H,1H-perfluorooctyl-1-ol, and ethyl acetate is 2.3:8:30.

[0133] (3) Take 20 parts of the fluorinated polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of an organic tin catalyst, and 15 parts of dichlorofluoroethane in sequence, stir evenly, add 40 parts of diphenylmethane diisocyanate (the mass ratio of the fluorinated polyether polyol to silicone oil L-600, the organic tin catalyst, dichlorofluoroethane, and diphenylmethane diisocyanate is 20:7.5:0.5:15:40), stir rapidly, and let it stand for natural foaming to obtain a fluorinated polyurethane material.

[0134] Example 8

[0135] (1) 50 parts of polyester-type waste polyurethane foam are washed and dried, and then crushed into 1-2 mm powder, i.e., polyester-type waste polyurethane powder;

[0136] (2) 4 parts of one-step fluorinated diol, 25 parts of diethylene glycol, 20 parts of N,N-diethylethanolamine, and 1 part of NaOH were added to a reactor, stirred and dissolved at 120° C. for 1.5 hours, and then 50 parts of the polyester type waste polyurethane powder obtained in step (1) were added, the temperature was raised to 200° C. for alcoholysis reaction for 2 hours, and cooled to room temperature to obtain a fluorinated polyether polyol; wherein the mass ratio of the one-step fluorinated diol, diethylene glycol, N,N-diethylethanolamine, and KOH was 4:25:20:1, and the mass ratio of the polyester type waste polyurethane powder to the total mass of the one-step fluorinated diol, diethylene glycol, N,N-diethylethanolamine, and KOH was 1:1;

[0137] The preparation method of the fluorinated diol is as follows: a reactor equipped with a thermometer and a stirring device is cleaned with nitrogen and nitrogen is continuously supplied during the reaction; 2.5 parts of 2,2-dihydroxymethylbutyric acid, 8 parts of 1H,1H-1H,1H,2H,2H-perfluorohexan-1-ol and 30 parts of chloroform are mixed to obtain a mixture; the mixture and concentrated sulfuric acid as a catalyst are added to the reactor, stirred and heated to 120°C for reaction for 2 hours to obtain a product, wherein the mass ratio of the mixture to the catalyst is 100:0.5; and then the product is washed, filtered under reduced pressure and dried in sequence to obtain a one-step fluorinated diol; wherein the mass ratio of 2,2-dihydroxymethylbutyric acid, 1H,1H-1H,1H,2H,2H-perfluorohexan-1-ol and chloroform is 2.5:8:30;

[0138] (3) Take 20 parts of the fluorinated polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of organotin catalyst, and 15 parts of monochlorodifluoromethane in sequence, stir evenly, and then add 40 parts of polyphenyl polymethylene polyisocyanate (the mass ratio of fluorinated polyether polyol and silicone oil L-600, organotin catalyst, monochlorodifluoromethane, and polyphenyl polymethylene polyisocyanate is 20:7.5:0.5:15:40), stir rapidly, and let it stand for natural foaming to obtain a fluorinated polyurethane material.

[0139] Example 9

[0140] (1) 50 parts of polyether type waste polyurethane foam are washed and dried, and then crushed into 1-2 mm powder, i.e., polyether type waste polyurethane powder;

[0141] (2) adding 3 parts of one-step fluorinated diol, 25 parts of ethylene glycol, 20 parts of diisopropanolamine, and 1 part of KOH into a reactor, stirring and dissolving at 130° C. for 1.5 hours, then adding 50 parts of the polyether type waste polyurethane powder obtained in step (1), raising the temperature to 200° C. for alcoholysis reaction for 2 hours, and cooling to room temperature to obtain a fluorinated polyether polyol; wherein the mass ratio of the one-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 3:25:20:1, and the ratio of the mass of the polyester type waste polyurethane powder to the total mass of the one-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 1:0.98;

[0142] The one-step preparation method of the fluorinated diol comprises the following steps: purging a reactor equipped with a thermometer and a stirring device with nitrogen and continuously flowing nitrogen during the reaction; mixing 2.5 parts of 2,2-dimethylolpropionic acid, 9 parts of 1H,1H-perfluorooctyl-1-ol, and 30 parts of acetone to obtain a mixture; adding the mixture and concentrated sulfuric acid as a catalyst into a reactor, stirring, and heating to 120°C for reaction for 2 hours to obtain a product, wherein the mass ratio of the mixture to the catalyst is 100:0.3; and then washing, filtering under reduced pressure, and drying in sequence to obtain the one-step fluorinated diol; wherein the mass ratio of 2,2-dimethylolpropionic acid, 1H,1H-perfluorooctyl-1-ol, and acetone is 2.5:9:30.

[0143] (3) Take 20 parts of the fluorinated polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of an organic tin catalyst, and 15 parts of dichlorofluoroethane in sequence, stir evenly, and then add 40 parts of diphenylmethane diisocyanate (the mass ratio of the fluorinated polyether polyol to silicone oil L-600, the organic tin catalyst, dichlorofluoroethane, and diphenylmethane diisocyanate is 20:7.5:0.5:15:40), stir rapidly, and let it stand to foam naturally to obtain a fluorinated polyurethane material.

[0144] Example 10

[0145] (1) 50 parts of polyether type waste polyurethane foam are washed and dried, and then crushed into 1-2 mm powder, i.e., polyether type waste polyurethane powder;

[0146] (2) adding 3 parts of one-step fluorinated diol, 25 parts of ethylene glycol, 20 parts of diisopropanolamine, and 1 part of KOH into a reactor, stirring and dissolving at 130° C. for 1.5 hours, then adding 50 parts of the polyether type waste polyurethane powder obtained in step (1), raising the temperature to 200° C. for alcoholysis reaction for 2 hours, and cooling to room temperature to obtain a fluorinated polyether polyol; wherein the mass ratio of the one-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 3:25:20:1, and the ratio of the mass of the polyester type waste polyurethane powder to the total mass of the one-step fluorinated diol, ethylene glycol, diisopropanolamine, and KOH is 1:0.98;

[0147] The one-step preparation method of the fluorinated diol comprises the following steps: purging a reactor equipped with a thermometer and a stirring device with nitrogen and continuously flowing nitrogen during the reaction; mixing 3 parts of 2,2-dimethylolpropionic acid, 9 parts of perfluoro-tert-butanol, and 30 parts of ethyl acetate to obtain a mixture; adding the mixture and concentrated sulfuric acid as a catalyst into the reactor, stirring, and heating to 120°C for reaction for 2 hours to obtain a product, wherein the mass ratio of the mixture to the catalyst is 100:0.3; and then washing, filtering under reduced pressure, and drying in sequence to obtain the one-step fluorinated diol; wherein the mass ratio of 2,2-dimethylolpropionic acid, perfluoro-tert-butanol, and ethyl acetate is 3:9:30.

[0148] (3) Take 20 parts of the fluorinated polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of an organic tin catalyst, and 15 parts of dichlorofluoroethane in sequence, stir evenly, add 40 parts of diphenylmethane diisocyanate (the mass ratio of the fluorinated polyether polyol to silicone oil L-600, the organic tin catalyst, dichlorofluoroethane, and diphenylmethane diisocyanate is 20:7.5:0.5:15:40), stir rapidly, and let it stand for natural foaming to obtain a fluorinated polyurethane material.

[0149] Figure 4 This is the SEM image of the fluorine-containing polyurethane material prepared in this example. Figure 5 for Figure 4 SEM image after 2 times magnification. Figure 4 and Figure 5 It can be seen that the fluorine-containing polyurethane material prepared by the present invention has a complete pore structure, the pore structure is regular hexagonal, and the skeleton is thick, the cross-linking structure is excellent, and the pore distribution is more uniform and denser. This good geometric structure and uniform pore distribution can enable the fluorine-containing polyurethane material to obtain better compressive strength and lower thermal conductivity.

[0150] Comparative Example 1

[0151] (1) 50 parts of waste polyurethane foam were cleaned and dried, and then crushed into 1-2 mm powder;

[0152] (2) 25 parts of ethylene glycol, 20 parts of diisopropanolamine, and 1 part of catalyst KOH were added to a reactor, stirred and dissolved at 130° C. for 1.5 hours, and then 50 parts of the waste polyurethane powder obtained in step (1) were added, the temperature was raised to 200° C. and reacted for 2 hours, and cooled to room temperature to obtain a polyether polyol;

[0153] (3) Take 20 parts of the polyether polyol obtained in step (2), add 7.5 parts of silicone oil L-600, 0.5 parts of organic tin catalyst, and 15 parts of dichlorofluoroethane in sequence, stir evenly, add 40 parts of diphenylmethane diisocyanate, stir rapidly, and let it stand for natural foaming to obtain a polyurethane material.

[0154] Comparative Example 2

[0155] Take 20 parts of polyether polyol 4110, add 7.5 parts of silicone oil L-600, 0.5 parts of organic tin catalyst, and 15 parts of dichlorofluoroethane in sequence, stir evenly, add 40 parts of diphenylmethane diisocyanate, stir rapidly, and let it stand for natural foaming to obtain a polyurethane material.

[0156] Table 1 Performance test results of degradation products and polyurethane materials prepared in Examples 1 to 5 and Comparative Examples 1 to 2

[0157]

[0158] It can be seen from the above examples that the fluorine-containing polyurethane prepared by the preparation method provided by the present invention has excellent compressive strength and low thermal conductivity, with a compressive strength of 0.44 MPa, a thermal conductivity of 0.013 W / m·K, and a water absorption of 0.55%.

[0159] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a fluorine-containing polyurethane material, comprising the following steps: (1) mixing a fluorinated diol, an alcoholysis agent, an alcoholysis co-agent, and an alcoholysis catalyst and dissolving the mixture to obtain a degradation agent; (2) mixing the degradation agent obtained in step (1) with waste polyurethane powder and performing alcoholysis reaction to obtain fluorinated polyether polyol; (3) mixing the fluorinated polyether polyol obtained in step (2) with a foam stabilizer, a polymerization catalyst, a foaming agent, and a black material, and then performing a polymerization reaction to obtain a fluorinated polyurethane material; The fluorinated diol in step (1) is a one-step fluorinated diol; The one-step preparation method of fluorinated diol comprises the following steps: a) mixing dimethylolcarboxylic acid, fluorocarbon alcohol and a solvent to obtain a mixture; b) mixing the mixture obtained in step a) with a catalyst to carry out an esterification reaction, and after the esterification reaction is completed, washing and filtering the product of the esterification reaction in sequence to obtain a one-step fluorinated diol; The dihydroxymethyl carboxylic acid is one or more of 2,2-dihydroxymethyl propionic acid and 2,2-dihydroxymethyl butyric acid; The fluorocarbon alcohol is F(CF2) m (CH2) n OH, and F(CF2) m CH=CH(CH2) n One or more of OH; The F(CF2) m (CH2) n In OH, m = 1~12, n = 1~6; described In m=0~10, n=1~6; The F(CF2) m CH=CH(CH2) n In OH, m = 1~12, n = 1~6; In the step (1), the mass ratio of the fluorinated diol to the alcoholysis agent, the alcoholysis co-agent, and the alcoholysis catalyst is (3-10): (25-40): (20-40): (1-2); The mass ratio of the fluorinated polyether polyol to the foam stabilizer, the polymerization catalyst, the foaming agent, and the black material in the step (3) is (20-30): (7.5-20): (0.5-1): (15-30): (40-50).

2. The preparation method according to claim 1, characterized in that The particle size of the waste polyurethane powder in step (2) is 1-2 mm.

3. The preparation method according to claim 1, characterized in that The waste polyurethane powder in step (2) includes one or more of polyester-type waste polyurethane powder, polyether-type waste polyurethane powder and castor oil-type polyurethane powder.

4. The preparation method according to claim 1, characterized in that In the step (2), the mass ratio of waste polyurethane powder to degradation agent is 1:(0.9-1.5).

5. The preparation method according to claim 1, characterized in that The temperature of the alcoholysis reaction in step (2) is 130-220° C., and the time of the alcoholysis reaction is 1-5 hours.

6. The preparation method according to claim 1, characterized in that The polymerization reaction temperature in step (3) is 10-40° C., and the polymerization reaction time is 20-30 min.

7. The fluorine-containing polyurethane material prepared by the preparation method according to any one of claims 1 to 6.

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