Environment-friendly high-elasticity foaming material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of preparation of polyurethane plastic materials, in particular to an environment-friendly high-elasticity foaming material as well as a preparation method and application thereof. The preparation method of the foaming material comprises the following steps: perfluorooctyl sulfonyl fluoride and diaminopropyl polydimethylsiloxane are subjected to a reaction, and fluorine-containing polydimethylsiloxane is obtained; the preparation method comprises the following steps: reacting 3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propanohydrazide with terephthalic diisothiocyanate to obtain isothiocyanate modified hindered phenol; the isothiocyanate modified hindered phenol reacts with primary amine at the terminal position of a fluorine-containing polydimethylsiloxane molecule through an isothiocyanate group to obtain an intermediate, and the intermediate is subjected to a desulfurization reaction to obtain a modifier; the preparation method comprises the following steps: reacting diisocyanate with polyether polyol, polyester polyol and natural polyol to obtain a component A, and stirring and mixing polyether polyol, a bio-based chain extender, a modifier, a catalyst and a foaming agent to obtain a component B; stirring and mixing the component A and the component B, and foaming to obtain the environment-friendly high-elasticity foaming material.

Description

Technical Field

[0001] This invention relates to the field of polyurethane plastic material preparation technology, specifically to an environmentally friendly, highly elastic foaming material, its preparation method, and its application. Background Technology

[0002] As a professional sports field material, synthetic running tracks require excellent wear resistance and elasticity. They typically undergo a foaming process to enhance shock absorption. The foamed structure effectively absorbs the impact of athletes' landings, reducing the risk of knee and ankle injuries. The raw materials for manufacturing synthetic running tracks mainly include polyurethane and rubber granules. A mixture of polyurethane and rubber granules produces a hybrid synthetic running track, entirely made of polyurethane. Without rubber granules, a fully synthetic running track is produced. Compared to the hybrid type, the fully synthetic type offers better wear resistance, higher elasticity, and stronger shock absorption. However, the extensive use of polyurethane leads to reliance on petrochemical products and poor environmental performance. Furthermore, synthetic running tracks exposed to the open environment for extended periods are prone to aging and damage, reducing their lifespan. Therefore, it is necessary to modify the polyurethane material to improve its anti-aging properties.

[0003] Chinese patent CN105131568B discloses a polyurethane foam for all-plastic running tracks and its preparation method. It improves the anti-aging performance of polyurethane materials by adding anti-aging agents. However, the improvement ability is reduced due to problems such as uneven dispersion between the anti-aging agent and the polyurethane matrix and easy migration of anti-aging agents with small molecular structures.

[0004] In addition, for polyester-based polyurethanes, it is also necessary to improve their hydrolysis resistance. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an environmentally friendly, highly elastic foaming material, its preparation method, and its application, thereby solving the problem that the anti-aging and anti-hydrolysis properties of polyurethane plastic materials in existing technologies need to be improved.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing an environmentally friendly, highly elastic foamed material includes the following steps:

[0008] Step 1: After mixing perfluorooctyl sulfonyl fluoride with toluene, diamine propyl polydimethylsiloxane is added dropwise. After the addition is complete, the temperature is raised to react. After the reaction is completed, the mixture is distilled under reduced pressure to obtain fluorinated polydimethylsiloxane.

[0009] Step 2: Add 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine and terephthalic diisothiocyanate to ethanol and react. After the reaction is complete, cool, filter, recrystallize, and dry to obtain isothiocyanate-modified hindered phenol.

[0010] Isothiocyanate-modified hindered phenol and fluorinated polydimethylsiloxane were added to toluene and reacted. After the reaction was completed, the precipitate was collected, filtered, washed, and dried to obtain the intermediate.

[0011] Step 3: Mix the intermediate, mercuric oxide, chloroform, and deionized water, react them, and after the reaction is complete, separate and purify them, then dry them to obtain the modifier.

[0012] Step 4: Mix diisocyanate with polyether polyol, polyester polyol and natural polyol, react, cool after reaction, discharge to obtain component A;

[0013] The polyether polyol, bio-based chain extender, modifier, catalyst and foaming agent are stirred and mixed to obtain component B;

[0014] Step 5: After mixing component A and component B, pour the mixture into a mold for foaming to obtain an environmentally friendly and highly elastic foamed material.

[0015] Preferably, in step one, the molar ratio of perfluorooctyl sulfonyl fluoride and diaminopropyl polydimethylsiloxane is 1:(1-1.05), and the reaction conditions are to raise the temperature to 50-60℃ and maintain the temperature at 50-60℃ for 2-3 hours.

[0016] Preferably, the amount of toluene added is 3-5 times the combined mass of perfluorooctyl sulfonyl fluoride and diaminopropyl polydimethylsiloxane, and the diaminopropyl polydimethylsiloxane is added under stirring at room temperature for 30-50 minutes.

[0017] Preferably, the molecular formula of the diaminopropyl polydimethylsiloxane is: H2N(CH2)3((CH3)2SiO)8(CH3)2Si(CH2)3NH2.

[0018] Preferably, in step two, when preparing isothiocyanate-modified hindered phenol, the molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine and terephthalic acid diisothiocyanate is 1:(1-1.05), and the reaction conditions are to react at 85-95℃ for 4-5 hours.

[0019] Preferably, the amount of ethanol added is 10-15 times the combined mass of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine and p-phenylenediisothiocyanate.

[0020] Preferably, in step two, when preparing the intermediate, the mass ratio of isothiocyanate-modified hindered phenol, fluorinated polydimethylsiloxane, and toluene is (48.4-50.8):(125-131):(800-1200), and the reaction conditions are to react at 70-90℃ for 6-8 hours.

[0021] Preferably, in step three, the mass ratio of the intermediate, mercuric oxide, chloroform, and deionized water is (173.4-181.8):(130.2-136.5):(4035-4230):(2705-2835), and the reaction is carried out under the condition of stirring at room temperature for 45-50 hours.

[0022] Preferably, in step four, when preparing component A, the molar ratio of the isocyanate group in the diisocyanate molecule to the total amount of hydroxyl groups in the polyether polyol, polyester polyol, and natural polyol molecules is (1.5-2):1, and the reaction conditions are to react at 80-90℃ for 3-4 hours.

[0023] Preferably, the molar ratio of the polyether polyol, polyester polyol, and natural polyol is 7:2:1.

[0024] Preferably, the diisocyanate includes hexamethylene diisocyanate (HDI) and isoflurane diisocyanate (IPDI), the polyether polyol includes polytetrahydrofuran ether diol (PTMEG), the polyester polyol includes polycarbonate diol (PCDL), and the natural polyol includes castor oil (a triglyceride compound formed by three molecules of ricinoleic acid and one molecule of glycerol through an ester bond).

[0025] Preferably, the molar ratio of hexamethylene diisocyanate and isoflurone diisocyanate is 1:1.

[0026] Preferably, in step four, when preparing component B, the mass ratio of polyether polyol, bio-based chain extender, modifier, catalyst and foaming agent is (20-30):(6-8):(5-7):(0.5-1):(1-3);

[0027] The polyether polyol is the same as the polyether polyol used to prepare component A. The bio-based chain extender includes bio-based 1,4-butanediol. The catalyst includes stannous octoate. The foaming agent includes deionized water.

[0028] Preferably, in step five, the mass ratio of component A to component B is 100:(40-50), and the foaming conditions are foaming at a temperature of 80-100℃ for 5-10 minutes.

[0029] The present invention also discloses an environmentally friendly and highly elastic foamed material prepared by the above-described method.

[0030] An application of an environmentally friendly, highly elastic foam material as described above.

[0031] Preferably, the application includes the application on polyurethane plastic running tracks, specifically including splicing the above-mentioned environmentally friendly and highly elastic foamed material (i.e., pre-formed polyurethane running track material) onto the base surface.

[0032] Preferably, the application in polyurethane plastic running tracks may further include mixing component A and component B, then pouring the mixture on-site and foaming it into shape.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] In this invention, the main material used to prepare the foaming material is entirely polyurethane, without any rubber particles. It is a fully plastic polyurethane foaming material with high elasticity and high wear resistance. When used to prepare plastic running tracks, it has excellent shock absorption performance and durability.

[0035] The polyurethane in this invention is prepared by reacting diisocyanate with polyether polyol, polyester polyol, natural polyol, and bio-based chain extender. The presence of polyether polyol can endow polyurethane with good flexibility and achieve high elasticity, while the presence of polyester polyol can endow polyurethane with good mechanical strength and achieve high strength. The natural polyol is castor oil, which is an environmentally friendly renewable biological raw material. Castor oil molecules contain three hydroxyl functional groups, which can form a three-dimensional network structure when reacting with isocyanate, further enhancing the strength of the polyurethane material. Compared with petrochemical chain extenders, bio-based chain extenders have significant advantages in terms of environmental protection due to the renewable nature of raw materials and the low carbonization of the production process. In addition, the foaming agent for polyurethane foaming is deionized water, which has excellent environmental friendliness compared with traditional chlorofluorocarbon foaming agents.

[0036] The modifier in this invention is prepared by reacting perfluorooctyl sulfonyl fluoride, diaminopropyl polydimethylsiloxane, terephthalic acid diisothiocyanate, and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl hydrazine. The introduction of organofluorine compounds and siloxane molecular chains can effectively improve the hydrophobic properties of polyurethane materials, reduce water penetration into the polyurethane materials, and avoid phenomena such as blistering, delamination, or degumming in running tracks. The introduction of hindered phenolic antioxidants can effectively improve the antioxidant aging resistance of polyurethane materials. The hindered phenolic antioxidant 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl hydrazine is linked by chemical bonding, and the fluorinated polydimethylsiloxane molecular chains are connected to the polyurethane... The entanglement between molecular chains not only improves the dispersion uniformity between the hindered phenolic antioxidant and the polyurethane matrix, but also effectively prevents the migration of the hindered phenolic antioxidant. The two isothiocyanate groups on the terephthalic diisothiocyanate molecule react with the amino groups on the 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine molecule and the amino groups at the terminal positions of the fluorinated polydimethylsiloxane molecule, respectively, to achieve chemical bonding between the hindered phenolic antioxidant and the fluorinated polydimethylsiloxane molecule. During the preparation of the modifier, the thiourea generated by the reaction of the isothiocyanate groups and the amino groups undergoes a desulfurization reaction to form a carbodiimide structure, which can effectively improve the hydrolysis resistance of polyester polyurethane and further enhance the durability of polyurethane-based foam materials. Attached Figure Description

[0037] Figure 1 This is a schematic diagram of the reaction between perfluorooctyl sulfonyl fluoride and diaminepropyl polydimethylsiloxane to prepare fluorinated polydimethylsiloxane in this invention.

[0038] Figure 2 This is a schematic diagram of the reaction between 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine and terephthalic acid diisothiocyanate to prepare isothiocyanate-modified hindered phenols in this invention.

[0039] Figure 3 This is a schematic diagram of the reaction between fluorinated polydimethylsiloxane and isothiocyanate-modified hindered phenol to prepare intermediates in this invention.

[0040] Figure 4 This is a schematic diagram illustrating the conversion of an intermediate into a modifier in this invention;

[0041] Figure 5 This is a schematic diagram of the reaction between castor oil and diisocyanate in this invention. Detailed Implementation

[0042] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0043] Example 1

[0044] This embodiment discloses a method for preparing an environmentally friendly, highly elastic foamed material, including the following steps:

[0045] Step 1: After mixing perfluorooctyl sulfonyl fluoride and toluene, diaminopropyl polydimethylsiloxane is added dropwise. The molar ratio of perfluorooctyl sulfonyl fluoride to diaminopropyl polydimethylsiloxane is 1:1. The amount of toluene added is 3 times the sum of the masses of perfluorooctyl sulfonyl fluoride and diaminopropyl polydimethylsiloxane. The dropwise addition conditions of diaminopropyl polydimethylsiloxane are: at room temperature, under stirring at 100 r / min, for 30 min. After the dropwise addition is completed, the temperature is raised to 50℃ and maintained at 50℃ for 3 h. After the reaction is completed, the mixture is distilled under reduced pressure to obtain fluorinated polydimethylsiloxane.

[0046] Step 2: Add 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazide and terephthalic diisothiocyanate to ethanol. The molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazide to terephthalic diisothiocyanate is 1:1. The amount of ethanol added is 10 times the combined mass of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazide and terephthalic diisothiocyanate. Reflux the mixture at 85°C for 5 hours. After the reaction is complete, cool to room temperature, filter, and recrystallize using a mixed solvent of chloroform and petroleum ether (volume ratio of chloroform and petroleum ether is 1:1). Dry the crystals in a vacuum drying oven at 50°C for 12 hours to obtain isothiocyanate-modified hindered phenol.

[0047] Isothiocyanate-modified hindered phenol and fluorinated polydimethylsiloxane were added to toluene in a mass ratio of 48.4:125:800. The mixture was reacted at 70°C for 8 hours. After the reaction was completed, three times the mass of toluene was added to deionized water for precipitation. The mixture was filtered, and the residue was washed three times with ethanol and then dried in a vacuum drying oven at 50°C for 12 hours to obtain an intermediate.

[0048] Step 3: Mix the intermediate, mercuric oxide, chloroform, and deionized water in a mass ratio of 173.4:130.2:4035:2705. Stir the mixture at room temperature for 45 hours. After the reaction is complete, the chloroform layer turns black. Filter the mixture until the filtrate becomes clear. Dry the mixture with CaCl2 for 2 hours, then filter it again. Evaporate the solvent from the filtrate under reduced pressure and recrystallize it with ethyl acetate. Place the crystals in a vacuum drying oven at 50°C for 12 hours to obtain the modifier.

[0049] Step 4: Mix hexamethylene diisocyanate, isoflurone diisocyanate, polytetrahydrofuran ether diol, polycarbonate diol, and castor oil, and react at 80°C for 4 hours. After the reaction is completed, cool and discharge the material to obtain component A.

[0050] The molar ratio of the isocyanate groups in hexamethylene diisocyanate and isoflurone diisocyanate molecules to the total amount of hydroxyl groups in polytetrahydrofuran ether diol, polycarbonate diol, and castor oil molecules is 1.5:1.

[0051] The molar ratio of polytetrahydrofuran ether glycol, polycarbonate glycol, and castor oil is 7:2:1;

[0052] The molar ratio of hexamethylene diisocyanate to isoflurane diisocyanate is 1:1;

[0053] Polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate and deionized water were stirred and mixed to obtain component B;

[0054] The mass ratio of polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate, and deionized water is 20:6:5:0.5:1; the polytetrahydrofuran ether diol is the same as the polytetrahydrofuran ether diol used to prepare component A.

[0055] Step 5: Mix component A and component B evenly at room temperature and stirring speed of 3000 r / min, then pour into a mold for foaming. The mass ratio of component A to component B is 100:40. The foaming condition is to foam at 80℃ for 10 min to obtain an environmentally friendly and highly elastic foamed material.

[0056] Example 2

[0057] This embodiment discloses a method for preparing an environmentally friendly, highly elastic foamed material, including the following steps:

[0058] Step 1: After mixing perfluorooctyl sulfonyl fluoride and toluene, diaminopropyl polydimethylsiloxane is added dropwise. The molar ratio of perfluorooctyl sulfonyl fluoride to diaminopropyl polydimethylsiloxane is 1:1.05. The amount of toluene added is 5 times the sum of the masses of perfluorooctyl sulfonyl fluoride and diaminopropyl polydimethylsiloxane. The dropwise addition of diaminopropyl polydimethylsiloxane is carried out at room temperature with stirring at 100 r / min for 50 min. After the dropwise addition is completed, the temperature is raised to 60℃ and maintained at 60℃ for 2 h. After the reaction is completed, the mixture is distilled under reduced pressure to obtain fluorinated polydimethylsiloxane.

[0059] Step 2: Add 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazide and terephthalic diisothiocyanate to ethanol. The molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazide to terephthalic diisothiocyanate is 1:1.05. The amount of ethanol added is 15 times the combined mass of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazide and terephthalic diisothiocyanate. Reflux the mixture at 95°C for 4 hours. After the reaction is complete, cool to room temperature, filter, and recrystallize using a mixed solvent of chloroform and petroleum ether (volume ratio of chloroform and petroleum ether is 1:1). Dry the crystals in a vacuum drying oven at 50°C for 12 hours to obtain isothiocyanate-modified hindered phenol.

[0060] Isothiocyanate-modified hindered phenol and fluorinated polydimethylsiloxane were added to toluene in a mass ratio of 50.8:131:1200. The mixture was reacted at 90°C for 6 hours. After the reaction was completed, three times the mass of toluene was added to deionized water for precipitation. The mixture was filtered, and the residue was washed three times with ethanol and then dried in a vacuum drying oven at 50°C for 12 hours to obtain an intermediate.

[0061] Step 3: Mix the intermediate, mercuric oxide, chloroform, and deionized water in a mass ratio of 181.8:136.5:4230:2835. Stir the mixture at room temperature for 50 hours. After the reaction is complete, the chloroform layer turns black. Filter the mixture until the filtrate becomes clear. Dry the mixture with CaCl2 for 2 hours, then filter it again. Evaporate the solvent from the filtrate under reduced pressure and recrystallize it with ethyl acetate. Place the crystals in a vacuum drying oven at 50°C for 12 hours to obtain the modifier.

[0062] Step 4: Mix hexamethylene diisocyanate, isoflurone diisocyanate, polytetrahydrofuran ether diol, polycarbonate diol, and castor oil, and react at 90°C for 3 hours. After the reaction is completed, cool and discharge the material to obtain component A.

[0063] The molar ratio of the isocyanate groups in hexamethylene diisocyanate and isoflurone diisocyanate molecules to the total amount of hydroxyl groups in polytetrahydrofuran ether diol, polycarbonate diol, and castor oil molecules is 2:1.

[0064] The molar ratio of polytetrahydrofuran ether glycol, polycarbonate glycol, and castor oil is 7:2:1;

[0065] The molar ratio of hexamethylene diisocyanate to isoflurane diisocyanate is 1:1;

[0066] Polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate and deionized water were stirred and mixed to obtain component B;

[0067] The mass ratio of polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate, and deionized water is 30:8:7:1:3; the polytetrahydrofuran ether diol is the same as the polytetrahydrofuran ether diol used to prepare component A.

[0068] Step 5: Mix component A and component B evenly at room temperature and stirring speed of 3000 r / min, then pour into a mold for foaming. The mass ratio of component A to component B is 100:50. The foaming condition is to foam at 100℃ for 5 minutes to obtain an environmentally friendly and highly elastic foamed material.

[0069] Example 3

[0070] This embodiment discloses a method for preparing an environmentally friendly, highly elastic foamed material, including the following steps:

[0071] Step 1: After mixing perfluorooctyl sulfonyl fluoride and toluene, diaminopropyl polydimethylsiloxane is added dropwise. The molar ratio of perfluorooctyl sulfonyl fluoride to diaminopropyl polydimethylsiloxane is 1:1.02. The amount of toluene added is 4 times the sum of the masses of perfluorooctyl sulfonyl fluoride and diaminopropyl polydimethylsiloxane. The dropwise addition of diaminopropyl polydimethylsiloxane is carried out at room temperature with stirring at 100 r / min for 40 min. After the dropwise addition is completed, the temperature is raised to 55℃ and maintained at 55℃ for 2.5 h. After the reaction is completed, the mixture is distilled under reduced pressure to obtain fluorinated polydimethylsiloxane.

[0072] Step 2: Add 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine and terephthalic diisothiocyanate to ethanol. The molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine to terephthalic diisothiocyanate is 1:1.02. The amount of ethanol added is 12 times the combined mass of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine and terephthalic diisothiocyanate. Reflux the mixture at 90°C for 4.5 h. After the reaction is complete, cool to room temperature, filter, and recrystallize using a mixed solvent of chloroform and petroleum ether (volume ratio of chloroform and petroleum ether is 1:1). Dry the crystals in a vacuum drying oven at 50°C for 12 h to obtain isothiocyanate-modified hindered phenol.

[0073] Isothiocyanate-modified hindered phenol and fluorinated polydimethylsiloxane were added to toluene in a mass ratio of 49.2:127:950. The mixture was reacted at 80°C for 7 hours. After the reaction was completed, three times the mass of toluene was added to deionized water for precipitation. The mixture was filtered, and the residue was washed three times with ethanol and then dried in a vacuum drying oven at 50°C for 12 hours to obtain an intermediate.

[0074] Step 3: Mix the intermediate, mercuric oxide, chloroform, and deionized water in a mass ratio of 176.2:132.3:4100:2750. Stir the mixture at room temperature for 48 hours. After the reaction is complete, the chloroform layer turns black. Filter the mixture until the filtrate becomes clear. Dry the mixture with CaCl2 for 2 hours, then filter it again. Evaporate the solvent from the filtrate under reduced pressure and recrystallize it with ethyl acetate. Place the crystals in a vacuum drying oven at 50°C for 12 hours to obtain the modifier.

[0075] Step 4: Mix hexamethylene diisocyanate, isoflurane diisocyanate, polytetrahydrofuran ether diol, polycarbonate diol, and castor oil, and react at 85°C for 3.5 hours. After the reaction is completed, cool and discharge the material to obtain component A.

[0076] The molar ratio of the isocyanate groups in hexamethylene diisocyanate and isoflurone diisocyanate molecules to the total amount of hydroxyl groups in polytetrahydrofuran ether diol, polycarbonate diol, and castor oil molecules is 1.65:1.

[0077] The molar ratio of polytetrahydrofuran ether glycol, polycarbonate glycol, and castor oil is 7:2:1;

[0078] The molar ratio of hexamethylene diisocyanate to isoflurane diisocyanate is 1:1;

[0079] Polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate and deionized water were stirred and mixed to obtain component B;

[0080] The mass ratio of polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate, and deionized water is 23:6.7:5.6:0.65:1.6; the polytetrahydrofuran ether diol is the same as the polytetrahydrofuran ether diol used to prepare component A.

[0081] Step 5: Mix component A and component B evenly at room temperature and stirring speed of 3000 r / min, then pour into a mold for foaming. The mass ratio of component A to component B is 100:43. The foaming conditions are foaming at 90℃ for 8 minutes to obtain an environmentally friendly and highly elastic foamed material.

[0082] Example 4

[0083] This embodiment discloses a method for preparing an environmentally friendly, highly elastic foamed material, including the following steps:

[0084] Step 1: After mixing perfluorooctyl sulfonyl fluoride and toluene, diaminopropyl polydimethylsiloxane is added dropwise. The molar ratio of perfluorooctyl sulfonyl fluoride to diaminopropyl polydimethylsiloxane is 1:1.03. The amount of toluene added is 4 times the sum of the masses of perfluorooctyl sulfonyl fluoride and diaminopropyl polydimethylsiloxane. The dropwise addition of diaminopropyl polydimethylsiloxane is carried out at room temperature with stirring at 100 r / min for 40 min. After the dropwise addition is completed, the temperature is raised to 55℃ and maintained at 55℃ for 2.5 h. After the reaction is completed, the mixture is distilled under reduced pressure to obtain fluorinated polydimethylsiloxane.

[0085] Step 2: Add 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine and terephthalic diisothiocyanate to ethanol. The molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine to terephthalic diisothiocyanate is 1:1.03. The amount of ethanol added is 13 times the combined mass of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine and terephthalic diisothiocyanate. Reflux the mixture at 90°C for 4.5 h. After the reaction is complete, cool to room temperature, filter, and recrystallize using a mixed solvent of chloroform and petroleum ether (volume ratio of chloroform and petroleum ether is 1:1). Dry the crystals in a vacuum drying oven at 50°C for 12 h to obtain isothiocyanate-modified hindered phenol.

[0086] Isothiocyanate-modified hindered phenol and fluorinated polydimethylsiloxane were added to toluene in a mass ratio of 50:129:1050. The mixture was reacted at 80°C for 7 hours. After the reaction was completed, three times the mass of toluene was added to deionized water for precipitation. The mixture was filtered, and the residue was washed three times with ethanol and then dried in a vacuum drying oven at 50°C for 12 hours to obtain an intermediate.

[0087] Step 3: Mix the intermediate, mercuric oxide, chloroform, and deionized water in a mass ratio of 179:134.4:4165:2790. Stir the mixture at room temperature for 48 hours. After the reaction is complete, the chloroform layer turns black. Filter the mixture until the filtrate becomes clear. Dry the mixture with CaCl2 for 2 hours, then filter it again. Evaporate the solvent from the filtrate under reduced pressure and recrystallize it with ethyl acetate. Place the crystals in a vacuum drying oven at 50°C for 12 hours to obtain the modifier.

[0088] Step 4: Mix hexamethylene diisocyanate, isoflurane diisocyanate, polytetrahydrofuran ether diol, polycarbonate diol, and castor oil, and react at 85°C for 3.5 hours. After the reaction is completed, cool and discharge the material to obtain component A.

[0089] The molar ratio of the isocyanate groups in hexamethylene diisocyanate and isoflurone diisocyanate molecules to the total amount of hydroxyl groups in polytetrahydrofuran ether diol, polycarbonate diol, and castor oil molecules is 1.8:1.

[0090] The molar ratio of polytetrahydrofuran ether glycol, polycarbonate glycol, and castor oil is 7:2:1;

[0091] The molar ratio of hexamethylene diisocyanate to isoflurane diisocyanate is 1:1;

[0092] Polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate and deionized water were stirred and mixed to obtain component B;

[0093] The mass ratio of polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate, and deionized water is 27:7.4:6.5:0.8:2.3; the polytetrahydrofuran ether diol is the same as the polytetrahydrofuran ether diol used to prepare component A.

[0094] Step 5: Mix component A and component B evenly at room temperature and stirring speed of 3000 r / min, then pour into a mold for foaming. The mass ratio of component A to component B is 100:47. The foaming conditions are foaming at 90℃ for 8 minutes to obtain an environmentally friendly and highly elastic foamed material.

[0095] Comparative Example 1

[0096] This comparative example discloses a method for preparing an environmentally friendly, highly elastic foamed material, comprising the following steps:

[0097] Step 1: Add 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazide and terephthalic diisothiocyanate to ethanol. The molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazide to terephthalic diisothiocyanate is 1:1. The amount of ethanol added is 10 times the combined mass of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazide and terephthalic diisothiocyanate. Reflux the mixture at 85°C for 5 hours. After the reaction is complete, cool to room temperature, filter, and recrystallize using a mixed solvent of chloroform and petroleum ether (volume ratio of chloroform and petroleum ether is 1:1). Dry the crystals in a vacuum drying oven at 50°C for 12 hours to obtain isothiocyanate-modified hindered phenol.

[0098] Isothiocyanate-modified hindered phenol and diaminopropyl polydimethylsiloxane were added to toluene in a mass ratio of 48.4:76.8:800. The mixture was reacted at 70°C for 8 hours. After the reaction was completed, three times the mass of deionized water was added to precipitate the mixture. The precipitate was filtered, and the residue was washed three times with ethanol and then dried in a vacuum drying oven at 50°C for 12 hours to obtain the intermediate.

[0099] Step 2: Mix the intermediate, mercuric oxide, chloroform, and deionized water in a mass ratio of 125.2:130.2:4035:2705. Stir the mixture at room temperature for 45 hours. After the reaction is complete, the chloroform layer turns black. Filter the mixture until the filtrate becomes clear. Dry the mixture with CaCl2 for 2 hours, then filter it again. Evaporate the solvent from the filtrate under reduced pressure and recrystallize it with ethyl acetate. Place the crystals in a vacuum drying oven at 50°C for 12 hours to obtain the modifier.

[0100] Step 3: Mix hexamethylene diisocyanate, isoflurone diisocyanate, polytetrahydrofuran ether diol, polycarbonate diol, and castor oil, and react at 80°C for 4 hours. After the reaction is completed, cool and discharge the material to obtain component A.

[0101] The molar ratio of the isocyanate groups in hexamethylene diisocyanate and isoflurone diisocyanate molecules to the total amount of hydroxyl groups in polytetrahydrofuran ether diol, polycarbonate diol, and castor oil molecules is 1.5:1.

[0102] The molar ratio of polytetrahydrofuran ether glycol, polycarbonate glycol, and castor oil is 7:2:1;

[0103] The molar ratio of hexamethylene diisocyanate to isoflurane diisocyanate is 1:1;

[0104] Polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate and deionized water were stirred and mixed to obtain component B;

[0105] The mass ratio of polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate, and deionized water is 20:6:5:0.5:1; the polytetrahydrofuran ether diol is the same as the polytetrahydrofuran ether diol used to prepare component A.

[0106] Step 4: Mix component A and component B evenly at room temperature and stirring speed of 3000 r / min, then pour into a mold for foaming. The mass ratio of component A to component B is 100:40. The foaming condition is to foam at 80℃ for 10 minutes to obtain an environmentally friendly and highly elastic foamed material.

[0107] Comparative Example 2

[0108] This comparative example discloses a method for preparing an environmentally friendly, highly elastic foamed material, comprising the following steps:

[0109] Step 1: After mixing perfluorooctyl sulfonyl fluoride and toluene, diaminopropyl polydimethylsiloxane is added dropwise. The molar ratio of perfluorooctyl sulfonyl fluoride to diaminopropyl polydimethylsiloxane is 1:1. The amount of toluene added is 3 times the sum of the masses of perfluorooctyl sulfonyl fluoride and diaminopropyl polydimethylsiloxane. The dropwise addition conditions of diaminopropyl polydimethylsiloxane are: at room temperature, under stirring at 100 r / min, for 30 min. After the dropwise addition is completed, the temperature is raised to 50℃ and maintained at 50℃ for 3 h. After the reaction is completed, the mixture is distilled under reduced pressure to obtain fluorinated polydimethylsiloxane.

[0110] Step 2: Fluorinated polydimethylsiloxane and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine were added to toluene. Phenylene diisocyanate was then added dropwise with stirring in an ice bath. The molar ratio of fluorinated polydimethylsiloxane, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine, and phenylene diisocyanate was 1:1:1. The amount of toluene added was 10 times the sum of the masses of fluorinated polydimethylsiloxane, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine, and phenylene diisocyanate. The dropwise addition of phenylene diisocyanate took 30 minutes. After the addition was complete, the mixture was reacted at 5°C for 5 hours. After the reaction was complete, the mixture was filtered, and the filter cake was recrystallized with chloroform. The recrystallized product was then dried in a vacuum drying oven at 50°C for 12 hours to obtain the modifier.

[0111] Step 3: Mix hexamethylene diisocyanate, isoflurone diisocyanate, polytetrahydrofuran ether diol, polycarbonate diol, and castor oil, and react at 80°C for 4 hours. After the reaction is completed, cool and discharge the material to obtain component A.

[0112] The molar ratio of the isocyanate groups in hexamethylene diisocyanate and isoflurone diisocyanate molecules to the total amount of hydroxyl groups in polytetrahydrofuran ether diol, polycarbonate diol, and castor oil molecules is 1.5:1.

[0113] The molar ratio of polytetrahydrofuran ether glycol, polycarbonate glycol, and castor oil is 7:2:1;

[0114] The molar ratio of hexamethylene diisocyanate to isoflurane diisocyanate is 1:1;

[0115] Polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate and deionized water were stirred and mixed to obtain component B;

[0116] The mass ratio of polytetrahydrofuran ether diol, bio-based 1,4-butanediol, modifier, stannous octoate, and deionized water is 20:6:5:0.5:1; the polytetrahydrofuran ether diol is the same as the polytetrahydrofuran ether diol used to prepare component A.

[0117] Step 4: Mix component A and component B evenly at room temperature and stirring speed of 3000 r / min, then pour into a mold for foaming. The mass ratio of component A to component B is 100:40. The foaming condition is to foam at 80℃ for 10 minutes to obtain an environmentally friendly and highly elastic foamed material.

[0118] In the above examples and comparative examples, the molecular formula of diaminopropyl polydimethylsiloxane is: H2N(CH2)3((CH3)2SiO)8(CH3)2Si(CH2)3NH2, the polytetrahydrofuran ether diol is PTMEG2000, that is, the molecular weight of polytetrahydrofuran ether diol is 2000, and the polycarbonate diol is PCDL2000, that is, the molecular weight of polycarbonate diol is 2000.

[0119] Test case

[0120] (1) Elasticity test: The rebound rate of the foamed material samples prepared in Examples 1-4 and Comparative Examples 1-2 was determined according to the standard GB / T6670-2008 "Determination of the rebound performance of flexible foamed polymer materials by falling ball method". The test results are shown in Table 1.

[0121] Table 1

[0122]

[0123] As shown in Table 1, the foam material prepared by this invention has high elasticity. The matrix material of the foam material of this invention is polyurethane. During the preparation of polyurethane, polyether polyol can impart good flexibility to polyurethane, making the polyurethane material highly elastic. At the same time, the introduction of polydimethylsiloxane molecular chains in the modifier can further improve the flexibility of the polyurethane material, thereby enhancing the elasticity of the foam material.

[0124] (2) Tensile strength test: The tensile strength of the foamed material samples prepared in Examples 1-4 and Comparative Examples 1-2 was determined according to the standard GB / T6634-2008 "Determination of Tensile Strength and Elongation at Break of Flexible Foamed Polymer Materials". The sample thickness was 15 mm and the tensile rate was 500 mm / min. The test results are shown in Table 2.

[0125] Table 2

[0126]

[0127] As shown in Table 2, the foam material prepared by this invention has high strength. The matrix material of the foam material of this invention is polyurethane. During the preparation of polyurethane, polyester polyol can impart good mechanical strength to polyurethane, giving the polyurethane material high strength. At the same time, castor oil with three hydroxyl functional groups reacts with isocyanate to give polyurethane a three-dimensional network structure, further enhancing the strength of the reinforced foam material.

[0128] (3) Antioxidant performance test: The foamed materials prepared in Examples 1-4 and Comparative Examples 1-2 were cut into dumbbell-shaped test samples as per standard GB / T528. The tensile strength retention rate of the test samples after thermo-oxidative aging at 140℃ for 1000h was measured. The test method was based on ISO527-2012, and the tensile rate was 5mm / min. The test results are shown in Table 3.

[0129] Table 3

[0130]

[0131] As shown in Table 3, the foam material prepared by this invention has good antioxidant aging resistance. The introduction of hindered phenolic antioxidants can effectively improve the antioxidant aging resistance of polyurethane materials. By chemically bonding the hindered phenolic antioxidant 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine, the entanglement between the fluorinated polydimethylsiloxane molecular chains and the polyurethane molecular chains improves the dispersion uniformity between the hindered phenolic antioxidants and the polyurethane matrix, further enhancing the antioxidant properties of the reinforced foam material.

[0132] (4) Hydrolysis resistance test: The foamed materials prepared in Examples 1-4 and Comparative Examples 1-2 were cut into dumbbell-shaped test samples as per standard GB / T528. After boiling in water at 120°C for 200 hours, the tensile strength retention rate of the test samples was measured. The test method was based on ISO527-2012, and the tensile rate was 5 mm / min. The test results are shown in Table 4.

[0133] Table 4

[0134]

[0135] As shown in Table 4, the foam material prepared by this invention exhibits excellent hydrolysis resistance. During the preparation of the modifier, the thiourea generated from the reaction of isothiocyanate groups and amino groups undergoes a desulfurization reaction to form a carbodiimide structure, which effectively improves the hydrolysis resistance of polyester-type polyurethane, thereby enhancing the hydrolysis resistance of the polyurethane-based foam material. Compared to Example 1, the modifier introduced in Comparative Example 2 did not form a carbodiimide, resulting in a significant decrease in hydrolysis resistance.

[0136] (5) Hydrophobicity test: The water contact angle of the surface of the foamed materials prepared in Examples 1-4 and Comparative Examples 1-2 in air was measured using a DSA100 contact angle measuring instrument from KRUSS GmbH, Germany. The test results are shown in Table 5.

[0137] Table 5

[0138] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Contact angle (°) 152 158 155 156 131 151

[0139] As shown in Table 5, the foam material prepared by this invention exhibits good hydrolysis resistance. During the preparation of the modifier, the introduction of organofluorine compounds and siloxane molecular chains effectively improves the hydrophobic properties of the polyurethane material. Compared to Example 1, in Comparative Example 1, no fluorine-containing compounds were introduced during the preparation of the modifier, resulting in a significant decrease in hydrophobic properties.

[0140] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing an environmentally friendly, highly elastic foamed material, characterized in that, Includes the following steps: Step 1: After mixing perfluorooctyl sulfonyl fluoride with toluene, diamine propyl polydimethylsiloxane is added dropwise. After the addition is complete, the temperature is raised to react. After the reaction is completed, the mixture is distilled under reduced pressure to obtain fluorinated polydimethylsiloxane. Step 2: Add 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine and terephthalic diisothiocyanate to ethanol and react. After the reaction is complete, cool, filter, recrystallize, and dry to obtain isothiocyanate-modified hindered phenol. Isothiocyanate-modified hindered phenol and fluorinated polydimethylsiloxane were added to toluene and reacted. After the reaction was completed, the precipitate was collected, filtered, washed, and dried to obtain the intermediate. Step 3: Mix the intermediate, mercuric oxide, chloroform, and deionized water, react them, and after the reaction is complete, separate and purify them, then dry them to obtain the modifier. Step 4: Mix diisocyanate with polyether polyol, polyester polyol and natural polyol, react, cool after reaction, discharge to obtain component A; The polyether polyol, bio-based chain extender, modifier, catalyst and foaming agent are stirred and mixed to obtain component B; Step 5: After mixing component A and component B, pour the mixture into a mold for foaming to obtain an environmentally friendly and highly elastic foamed material.

2. The method for preparing an environmentally friendly, highly elastic foamed material according to claim 1, characterized in that, In step one, the molar ratio of perfluorooctyl sulfonyl fluoride and diaminopropyl polydimethylsiloxane is 1:(1-1.05), and the reaction conditions are to raise the temperature to 50-60℃ and maintain the temperature at 50-60℃ for 2-3 hours.

3. The method for preparing an environmentally friendly, highly elastic foamed material according to claim 1, characterized in that, In step two, when preparing isothiocyanate-modified hindered phenol, the molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylhydrazine and terephthalic acid diisothiocyanate is 1:(1-1.05), and the reaction conditions are to react at 85-95℃ for 4-5 hours.

4. The method for preparing an environmentally friendly, highly elastic foamed material according to claim 1, characterized in that, In step two, when preparing the intermediate, the mass ratio of isothiocyanate-modified hindered phenol, fluorinated polydimethylsiloxane, and toluene is (48.4-50.8):(125-131):(800-1200), and the reaction conditions are to react at 70-90℃ for 6-8 hours.

5. The method for preparing an environmentally friendly, highly elastic foamed material according to claim 1, characterized in that, In step three, the mass ratio of the intermediate, mercuric oxide, chloroform, and deionized water is (173.4-181.8):(130.2-136.5):(4035-4230):(2705-2835), and the reaction is carried out under the condition of stirring at room temperature for 45-50 hours.

6. The method for preparing an environmentally friendly, highly elastic foamed material according to claim 1, characterized in that, In step four, when preparing component A, the molar ratio of the isocyanate group in the diisocyanate molecule to the total amount of hydroxyl groups in the polyether polyol, polyester polyol, and natural polyol molecules is (1.5-2):1, and the reaction conditions are to react at 80-90℃ for 3-4 hours. The diisocyanate includes hexamethylene diisocyanate and isoflurone diisocyanate, the polyether polyol includes polytetrahydrofuran ether diol, the polyester polyol includes polycarbonate diol, and the natural polyol includes castor oil.

7. The method for preparing an environmentally friendly, highly elastic foamed material according to claim 1, characterized in that, In step four, when preparing component B, the mass ratio of polyether polyol, bio-based chain extender, modifier, catalyst and foaming agent is (20-30):(6-8):(5-7):(0.5-1):(1-3); The polyether polyol is the same as the polyether polyol used to prepare component A. The bio-based chain extender includes bio-based 1,4-butanediol. The catalyst includes stannous octoate. The foaming agent includes deionized water.

8. The method for preparing an environmentally friendly, highly elastic foamed material according to claim 1, characterized in that, In step five, the mass ratio of component A to component B is 100:(40-50), and the foaming condition is to foam at a temperature of 80-100℃ for 5-10 minutes.

9. An environmentally friendly, highly elastic foamed material prepared by the method for preparing the environmentally friendly, highly elastic foamed material as described in any one of claims 1-8.

10. An application of the environmentally friendly, highly elastic foamed material as described in claim 9.

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