A super-hydrophobic polymer composite material for tablecloth and preparation method thereof

Abstract

The invention discloses a super-hydrophobic polymer composite material for tablecloths and a preparation method thereof, and relates to the technical field of polymer materials. When preparing a super-hydrophobic polymer composite material for tablecloths, the present invention reacts diethanolamine with 1H, 1H, 2H, 2H-methacrylic acid-1H, 1H-perfluorooctyl ester to obtain a fluorinated diol monomer; soybean oil is sequentially reacted with glycerol and 1-(3-mercaptopropyl)-5,5-dimethylhydantoin to obtain a modified soybean oil-based polyol; isophorone diisocyanate, a fluorinated diol monomer, a modified soybean oil-based polyol, and 1,4-butene glycol are copolymerized to obtain polyurethane; polyurethane is calendered with a phosphorus-containing flame-retardant intermediate, and then chlorinated with a sodium hypochlorite aqueous solution to obtain a super-hydrophobic polymer composite material for tablecloths. The super-hydrophobic polymer composite material for tablecloths prepared by the present invention has excellent hydrophobic, antibacterial, flame-retardant and mechanical properties.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a super-hydrophobic polymer composite material for tablecloths and a preparation method thereof. Background Art

[0002] Tablecloths are mainly divided into decorative tablecloths and plastic tablecloths. Decorative tablecloths are mainly made of natural fibers, chemical fibers and their blended fabrics, with beauty as the primary condition and no certain functions; plastic tablecloths are mainly made of polymer materials such as polyvinyl chloride, polyurethane, polypropylene, etc., and have the characteristics of transparency, wear resistance, and economical affordability. With the development of the economy, people's living standards are also constantly improving. The demand for household items such as tablecloths is no longer limited to being cheap and usable, and attention is also paid to the environmental protection and health performance of household items. Based on this, the present invention proposes a super-hydrophobic polymer composite material for tablecloths, which uses soybean oil to replace a part of chemical raw materials, is more green and environmentally friendly, and at the same time gives the super-hydrophobic polymer composite material for tablecloths excellent antibacterial properties, so as to avoid the accumulation of stains and breeding of bacteria during the use of the tablecloths, which affects people's health. Summary of the invention

[0003] The object of the present invention is to provide a super-hydrophobic polymer composite material for tablecloth and a preparation method thereof, so as to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] The invention discloses a super-hydrophobic polymer composite material for tablecloths. The super-hydrophobic polymer composite material for tablecloths is prepared by copolymerizing isophorone diisocyanate, a fluorine-containing diol monomer, a modified soybean oil-based polyol and 1,4-butene diol to obtain polyurethane; reacting 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide with formic acid to obtain a phosphorus-containing flame-retardant intermediate; and calendering the polyurethane and the phosphorus-containing flame-retardant intermediate, and then chlorinating the composite material with a sodium hypochlorite aqueous solution to obtain the super-hydrophobic polymer composite material for tablecloths.

[0006] As an optimization, the fluorine-containing diol monomer is prepared by reacting diethanolamine with 1H,1H,2H,2H-methacrylic acid-1H,1H-perfluorooctyl ester.

[0007] As an optimization, the modified soybean oil-based polyol is prepared by reacting soybean oil with glycerol and 1-(3-mercaptopropyl)-5,5-dimethylhydantoin in sequence.

[0008] As an optimization, the 1-(3-mercaptopropyl)-5,5-dimethylhydantoin is prepared by reacting 5,5-dimethylhydantoin with 3-chloro-1-propanethiol.

[0009] A method for preparing a super-hydrophobic polymer composite material for tablecloths comprises the following preparation steps:

[0010] (1) Diethanolamine, sodium ethoxide and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(0.03-0.05):(20-24), stirred at 69-71°C and 300-500 r / min for 40-60 min under a nitrogen atmosphere, an equal molar amount of 1H,1H,2H,2H-methacrylic acid-1H,1H-perfluorooctyl ester is added with diethanolamine, the reaction is continued with stirring for 20-24 h, and dried at 3-5 Pa and 50-60°C for 7-8 h to obtain a fluorinated diol monomer;

[0011] (2) 5,5-dimethylhydantoin and 3-chloro-1-propanethiol were added in a molar ratio of 1:1 to tetrahydrofuran (20 to 24 times the mass of 5,5-dimethylhydantoin), and then triethylamine (0.03 to 0.05 times the mass of 5,5-dimethylhydantoin) was added, and the mixture was stirred at 50 to 60°C and 300 to 500 r / min for 3 to 4 hours, and dried at 3 to 5 Pa and 50 to 60°C for 7 to 8 hours to obtain 1-(3-mercaptopropyl)-5,5-dimethylhydantoin; soybean oil, glycerol, and lithium hydroxide were added in a mass ratio of 1:(0.2 to 0.3):(0.05 to 0.06). .07) are mixed evenly, stirred at 160-180°C, 300-500r / min for 3-4h, cooled to room temperature, extracted with n-hexane, and the organic phase is dried at 3-5Pa, 50-60°C for 7-8h to obtain soybean oil-based polyol; soybean oil-based polyol, 1-(3-mercaptopropyl)-5,5-dimethylhydantoin, and azobisisobutyronitrile are mixed evenly in a mass ratio of 1:(0.6-0.8):(0.03-0.05), stirred at 70-80°C, 300-500r / min for 3-4h to obtain modified soybean oil-based polyol;

[0012] (3) adding isophorone diisocyanate, fluorinated diol monomer, modified soybean oil-based polyol and 1,4-butene diol in a mass ratio of 1:(0.2-0.3):(0.2-0.3):(0.2-0.3) to N,N-dimethylformamide (20-24 times the mass of isophorone diisocyanate), stirring and reacting at 70-80° C. and 300-500 r / min under a nitrogen atmosphere, adding 1,6-hexanediol (0.06-0.08 times the molar amount of isophorone diisocyanate) to the reaction system every half an hour, monitoring the content of isocyanate groups, quenching the remaining isocyanate groups with anhydrous ethanol, cooling to room temperature, and drying at 5-7 Pa and 50-60° C. for 6-7 hours to obtain polyurethane;

[0013] (4) polyurethane, phosphorus-containing flame retardant intermediate, and azobisisobutyronitrile in a mass ratio of

[0014] 1: (0.10-0.12): (0.01-0.03) are mixed evenly, placed in a hot melt machine, stirred at 180-190° C. and 300-500 r / min for 10-20 min, and then sent to a calender for calendering to obtain a polyurethane film; the polyurethane film is immersed in a sodium hypochlorite aqueous solution with a mass fraction of 9-11%, and the pH is adjusted to 6.8-7.0 with a sulfuric acid aqueous solution with a mass fraction of 20-24%, ultrasonically treated for 1-2 h, taken out, and dried at 3-5 Pa and 50-60° C. for 7-8 h to obtain a super-hydrophobic polymer composite material for tablecloths.

[0015] As an optimization, the reaction process of the fluorinated diol monomer in step (1) is:

[0016]

[0017] As an optimization, the reaction process of 1-(3-mercaptopropyl)-5,5-dimethylhydantoin in step (2) is:

[0018]

[0019] As an optimization, the method for monitoring the content of isocyanate groups in the reaction system in step (3) is to detect the content of isocyanate groups in the reaction system by dibutyl amine-hydrochloric acid titration method, and stop adding 1,6-hexanediol when the content of unreacted isocyanate groups is less than 4-6% of the initial number of isocyanate groups.

[0020] As an optimization, the preparation method of the phosphorus-containing flame retardant intermediate in step (4) is as follows: under a nitrogen atmosphere, 30-40° C., 300-500 r / min stirring conditions, formic acid twice the molar amount of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide is uniformly added dropwise to 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide over a period of 50-60 min, washed with ether and deionized water for 3-5 times each, and dried at 3-5 Pa, 50-60° C. for 7-8 h to obtain the phosphorus-containing flame retardant intermediate;

[0021] The reaction process is:

[0022]

[0023] As an optimization, the process parameters of the calendering molding in step (4) are: setting the calender temperature to 150-160° C., the calendering speed to 50-60 m / min, and the pressure to 24-30 MPa.

[0024] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0025] When preparing the super-hydrophobic polymer composite material for tablecloth, the present invention comprises the following steps: reacting diethanolamine with 1H,1H,2H,2H-methacrylic acid-1H,1H-perfluorooctyl ester to obtain a fluorine-containing diol monomer; reacting 5,5-dimethylhydantoin with 3-chloro-1-propanethiol to obtain 1-(3-mercaptopropyl)-5,5-dimethylhydantoin; and reacting soybean oil with glycerol and 1-(3-mercaptopropyl)-5,5-dimethylhydantoin in sequence to obtain a modified soybean oil base. Polyol; copolymerizing isophorone diisocyanate, fluorinated diol monomer, modified soybean oil-based polyol and 1,4-butene diol to prepare polyurethane; reacting 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide with formic acid to prepare a phosphorus-containing flame retardant intermediate; calendering the polyurethane and the phosphorus-containing flame retardant intermediate, and then chlorinating with a sodium hypochlorite aqueous solution to prepare a super-hydrophobic polymer composite material for tablecloths.

[0026] First, diethanolamine is reacted with 1H,1H,2H,2H-methacrylic acid-1H,1H-perfluorooctyl ester to obtain a fluorinated diol monomer, which can participate in the polymerization reaction of polyurethane and introduce a large number of fluorine atoms on the side chain of the polyurethane molecule. The fluorine atoms have low reactivity and hydrophobicity, and can give the super-hydrophobic polymer composite material for tablecloths excellent hydrophobic properties; 5,5-dimethylhydantoin is reacted with 3-chloro-1-propanethiol to obtain 1-(3-mercaptopropyl)-5,5-dimethylhydantoin, and a thiol group is introduced into 1-(3-mercaptopropyl)-5,5-dimethylhydantoin; soybean oil is reacted with glycerol to obtain soybean oil-based polyol, and soybean oil-based polyol is reacted with 1-(3-mercaptopropyl)-5,5-dimethylhydantoin to obtain modified soybean oil. The thiol group on the oil-based polyol, 1-(3-mercaptopropyl)-5,5-dimethylhydantoin, reacts with the carbon-carbon double bond on the soybean oil-based polyol, and the modified soybean oil-based polyol participates in the copolymerization of polyurethane. The halamine precursor is grafted on the side chain of the polyurethane molecule. The halamine precursor is chlorinated to form a halamine structure. In the presence of water molecules, the N-Cl bond slowly decomposes to release hypohalous acid or hypohalogen radicals with strong oxidizing properties, which directly attack some groups in bacteria to denature proteins and inhibit enzyme metabolism, thereby achieving a bactericidal effect and giving the super-hydrophobic polymer composite material for tablecloths excellent antibacterial properties; once the oxidizing halogen is consumed, the NH bond can be converted into an N-Cl bond again by exposure to a diluted household bleach or a halogen releaser, thereby obtaining regeneration.

[0027] Secondly, isophorone diisocyanate, fluorinated diol monomer, modified soybean oil-based polyol, and 1,4-butene diol are copolymerized to prepare polyurethane, and a carbon-carbon double bond is introduced into the main chain of the polyurethane molecule; 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide is reacted with formic acid to prepare a phosphorus-containing flame retardant intermediate, and the phosphorus chlorine on 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide is converted into phosphorus Hydrogen; the polyurethane and the phosphorus-containing flame-retardant intermediate are calendered and then chlorinated with a sodium hypochlorite aqueous solution to obtain a super-hydrophobic polymer composite material for tablecloths; the phosphorus hydrogen on the phosphorus-containing flame-retardant intermediate can react with the carbon-carbon double bonds on the main chain of the polyurethane molecule to form a cross-linked network, which inhibits the relative slip between the polyurethane molecular chains and gives the super-hydrophobic polymer composite material for tablecloths excellent mechanical properties; at the same time, phosphorus element is introduced into the super-hydrophobic polymer composite material for tablecloths to give the super-hydrophobic polymer composite material for tablecloths excellent flame retardant properties. DETAILED DESCRIPTION

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] Example 1

[0030] A method for preparing a super-hydrophobic polymer composite material for tablecloths, the method for preparing the super-hydrophobic polymer composite material for tablecloths comprising the following preparation steps:

[0031] (1) Diethanolamine, sodium ethoxide and anhydrous ethanol were mixed uniformly in a mass ratio of 1:0.03:20, stirred at 69°C and 300 r / min for 60 min under a nitrogen atmosphere, and an equal molar amount of 1H,1H,2H,2H-methacrylic acid-1H,1H-perfluorooctyl ester was added with diethanolamine, and the reaction was continued with stirring for 24 h, and dried at 3 Pa and 50°C for 8 h to obtain a fluorinated diol monomer;

[0032] (2) 5,5-dimethylhydantoin and 3-chloro-1-propanethiol were added in a molar ratio of 1:1 to tetrahydrofuran (20 times the mass of 5,5-dimethylhydantoin), and then triethylamine (0.03 times the mass of 5,5-dimethylhydantoin) was added, and the mixture was stirred at 50°C and 300 r / min for 4 hours, and dried at 3 Pa and 50°C for 8 hours to obtain 1-(3-mercaptopropyl)-5,5-dimethylhydantoin; soybean oil, glycerol, and lithium hydroxide were added in a mass ratio of 1:0.2 :0.05 were mixed evenly, stirred at 160°C, 300r / min for 4h, cooled to room temperature, extracted with n-hexane, and the organic phase was dried at 3Pa, 50°C for 8h to obtain soybean oil-based polyol; soybean oil-based polyol, 1-(3-mercaptopropyl)-5,5-dimethylhydantoin, and azobisisobutyronitrile were mixed evenly at a mass ratio of 1:0.6:0.03, stirred at 70°C, 300r / min for 4h to obtain modified soybean oil-based polyol;

[0033] (3) adding isophorone diisocyanate, fluorinated diol monomer, modified soybean oil-based polyol, and 1,4-butene diol in a mass ratio of 1:0.2:0.2:0.2 to N,N-dimethylformamide (20 times the mass of isophorone diisocyanate), stirring and reacting at 70° C. and 300 r / min under a nitrogen atmosphere, adding 1,6-hexanediol (0.06 times the molar amount of isophorone diisocyanate) to the reaction system every half an hour, and detecting the isocyanate group concentration of the reaction system by dibutyl amine-hydrochloric acid titration method, stopping the addition of 1,6-hexanediol when the isocyanate group concentration is less than 4%, quenching the remaining isocyanate groups with anhydrous ethanol, cooling to room temperature, and drying at 5 Pa and 50° C. for 7 hours to obtain a polyurethane;

[0034] (4) Under nitrogen atmosphere, 30°C, 300 r / min stirring conditions, formic acid twice the molar amount of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide was uniformly added dropwise to 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide over a period of 50 min, washed with ether and deionized water for 3 times each, and dried at 3 Pa and 50°C for 8 h to obtain a phosphorus-containing flame retardant intermediate; polyurethane, phosphorus-containing flame retardant intermediate, and azobisisobutyronitrile were added in a mass ratio of 1: The polyurethane film was prepared by mixing the polyurethane film with a ratio of 1:0.10:0.01, placing the film in a hot melt machine, stirring the film at 180°C and 300 r / min for 20 min, and then sending the film to a calender for calendering. The calender temperature was set to 150°C, the calendering speed was set to 50 m / min, the pressure was set to 24 MPa, and the film was allowed to stand for 5 h to obtain a polyurethane film. The polyurethane film was immersed in a 9% sodium hypochlorite aqueous solution, the pH value was adjusted to 6.8 with a 20% sulfuric acid aqueous solution, and the film was ultrasonically treated for 1 h. The film was taken out and dried at 3 Pa and 50°C for 8 h to obtain a super-hydrophobic polymer composite material for tablecloths.

[0035] Example 2

[0036] A method for preparing a super-hydrophobic polymer composite material for tablecloths, the method for preparing the super-hydrophobic polymer composite material for tablecloths comprising the following preparation steps:

[0037] (1) Diethanolamine, sodium ethoxide and anhydrous ethanol were mixed uniformly in a mass ratio of 1:0.04:22, stirred at 70°C and 400 r / min for 50 min under a nitrogen atmosphere, and an equal molar amount of 1H,1H,2H,2H-methacrylic acid-1H,1H-perfluorooctyl ester was added with diethanolamine, and the reaction was continued with stirring for 22 h, and dried at 4 Pa ​​and 55°C for 7.5 h to obtain a fluorinated diol monomer;

[0038] (2) 5,5-dimethylhydantoin and 3-chloro-1-propanethiol were added in a molar ratio of 1:1 to tetrahydrofuran (22 times the mass of 5,5-dimethylhydantoin), and then triethylamine (0.04 times the mass of 5,5-dimethylhydantoin) was added, and the mixture was stirred at 55°C and 400 r / min for 3.5 hours, and dried at 4Pa and 55°C for 7.5 hours to obtain 1-(3-mercaptopropyl)-5,5-dimethylhydantoin; soybean oil, glycerol, and lithium hydroxide were added in a mass ratio of 1:0.25: 0.06 was mixed evenly, stirred at 170°C and 400r / min for 3.5h, cooled to room temperature, extracted with n-hexane, and the organic phase was dried at 4Pa and 55°C for 7.5h to obtain soybean oil-based polyol; soybean oil-based polyol, 1-(3-mercaptopropyl)-5,5-dimethylhydantoin and azobisisobutyronitrile were mixed evenly at a mass ratio of 1:0.7:0.04, stirred at 75°C and 400r / min for 3.5h to obtain modified soybean oil-based polyol;

[0039] (3) adding isophorone diisocyanate, fluorinated diol monomer, modified soybean oil-based polyol, and 1,4-butene diol in a mass ratio of 1:0.25:0.25:0.25 to N,N-dimethylformamide (22 times the mass of isophorone diisocyanate), stirring and reacting at 75° C. and 400 r / min under a nitrogen atmosphere, adding 1,6-hexanediol (0.07 times the molar amount of isophorone diisocyanate) to the reaction system every half an hour, and detecting the isocyanate group concentration of the reaction system by dibutyl amine-hydrochloric acid titration method, stopping the addition of 1,6-hexanediol when the isocyanate group concentration is less than 5%, quenching the remaining isocyanate groups with anhydrous ethanol, cooling to room temperature, and drying at 6 Pa and 55° C. for 6.5 hours to obtain a polyurethane;

[0040] (4) Under nitrogen atmosphere, 35°C, 400 r / min stirring conditions, formic acid twice the molar amount of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide was uniformly added dropwise to 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide over a period of 55 min, washed with ether and deionized water 4 times each, and dried at 4 Pa ​​and 55°C for 7.5 h to obtain a phosphorus-containing flame retardant intermediate; polyurethane, phosphorus-containing flame retardant intermediate, and azobisisobutyronitrile were added in a mass ratio of 1: The mixture was evenly mixed at a ratio of 0.11:0.02, placed in a hot melt machine, stirred at 185°C and 400 r / min for 15 min, and then sent to a calender for calendering. The calender temperature was set to 155°C, the calendering speed was 55 m / min, the pressure was 27 MPa, and the film was allowed to stand for 5.5 h to obtain a polyurethane film. The polyurethane film was immersed in a 10% by mass sodium hypochlorite aqueous solution, the pH was adjusted to 6.9 with a 22% by mass sulfuric acid aqueous solution, ultrasonically treated for 1.5 h, taken out, and dried at 4 Pa ​​and 55°C for 7.5 h to obtain a superhydrophobic polymer composite material for tablecloths.

[0041] Example 3

[0042] A method for preparing a super-hydrophobic polymer composite material for tablecloths, the method for preparing the super-hydrophobic polymer composite material for tablecloths comprising the following preparation steps:

[0043] (1) Diethanolamine, sodium ethoxide and anhydrous ethanol were mixed uniformly in a mass ratio of 1:0.05:24, stirred at 71°C and 500 r / min for 40 min under a nitrogen atmosphere, and an equal molar amount of 1H,1H,2H,2H-methacrylic acid-1H,1H-perfluorooctyl ester was added with diethanolamine, and the reaction was continued with stirring for 24 h, and dried at 5 Pa and 60°C for 7 h to obtain a fluorinated diol monomer;

[0044] (2) 5,5-dimethylhydantoin and 3-chloro-1-propanethiol were added in a molar ratio of 1:1 to tetrahydrofuran (24 times the mass of 5,5-dimethylhydantoin), and then triethylamine (0.05 times the mass of 5,5-dimethylhydantoin) was added, and the mixture was stirred at 60°C and 500 r / min for 3 h, and dried at 5 Pa and 60°C for 7 h to obtain 1-(3-mercaptopropyl)-5,5-dimethylhydantoin; soybean oil, glycerol, and lithium hydroxide were added in a mass ratio of 1:0.3. :0.07, mix evenly, stir and react at 180°C, 500r / min for 3h, cool to room temperature, extract with n-hexane, take the organic phase and dry at 5Pa, 60°C for 7h to obtain soybean oil-based polyol; soybean oil-based polyol, 1-(3-mercaptopropyl)-5,5-dimethylhydantoin and azobisisobutyronitrile are mixed evenly at a mass ratio of 1:0.8:0.05, stir and react at 80°C, 500r / min for 3h to obtain modified soybean oil-based polyol;

[0045] (3) adding isophorone diisocyanate, fluorinated diol monomer, modified soybean oil-based polyol, and 1,4-butene diol in a mass ratio of 1:0.3:0.3:0.3 to N,N-dimethylformamide (24 times the mass of isophorone diisocyanate), stirring and reacting at 80° C. and 500 r / min under a nitrogen atmosphere, adding 1,6-hexanediol (0.08 times the molar amount of isophorone diisocyanate) to the reaction system every half an hour, and detecting the isocyanate group concentration of the reaction system by dibutyl amine-hydrochloric acid titration method, stopping the addition of 1,6-hexanediol when the isocyanate group concentration is less than 6%, quenching the remaining isocyanate groups with anhydrous ethanol, cooling to room temperature, and drying at 7 Pa and 60° C. for 6 hours to obtain a polyurethane;

[0046] (4) Under nitrogen atmosphere, 40°C, 500 r / min stirring conditions, formic acid twice the molar amount of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide was uniformly added dropwise to 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide over a period of 60 minutes, washed with ether and deionized water for 5 times each, and dried at 5 Pa and 60°C for 7 hours to obtain a phosphorus-containing flame retardant intermediate; polyurethane, phosphorus-containing flame retardant intermediate, and azobisisobutyronitrile were added in a mass ratio of 1. 1:0.12:0.03 is mixed evenly, placed in a hot melt machine, stirred at 190°C and 500r / min for 10min, and then sent to a calender for calendering. The calender temperature is set to 160°C, the calendering speed is 60m / min, the pressure is 30MPa, and the polyurethane film is allowed to stand for 6h to obtain a polyurethane film; the polyurethane film is immersed in an aqueous solution of sodium hypochlorite with a mass fraction of 11%, the pH is adjusted to 7.0 with an aqueous solution of sulfuric acid with a mass fraction of 24%, ultrasonically treated for 2h, taken out, and dried at 5Pa and 60°C for 7h to obtain a superhydrophobic polymer composite material for tablecloths.

[0047] Comparative Example 1

[0048] The difference between the preparation method of the super-hydrophobic polymer composite material for tablecloths in Comparative Example 1 and Example 2 is that step (1) is not performed, and step (3) is modified as follows: isophorone diisocyanate, modified soybean oil-based polyol, and 1,4-butene diol are added to N,N-dimethylformamide with a mass ratio of 1:0.45:0.45 in a nitrogen atmosphere at 75°C and 400r / min to stir the reaction, and add 1,6-hexanediol with a molar amount of 0.07 times of isophorone diisocyanate to the reaction system every half an hour, and the isocyanate group concentration of the reaction system is detected by dibutyl amine-hydrochloric acid titration. When the isocyanate group concentration is less than 5%, stop adding 1,6-hexanediol, quench the remaining isocyanate groups with anhydrous ethanol, cool to room temperature, and dry at 6Pa, 55°C for 6.5h to obtain polyurethane. The remaining steps are the same as in Example 2.

[0049] Comparative Example 2

[0050] The preparation method of the super-hydrophobic polymer composite material for tablecloths in Comparative Example 2 is different from that in Example 2 in that step (2) is modified as follows: soybean oil, glycerol, and lithium hydroxide are uniformly mixed in a mass ratio of 1:0.25:0.06, stirred at 170° C. and 400 r / min for 3.5 h, cooled to room temperature, extracted with n-hexane, and the organic phase was dried at 4 Pa ​​and 55° C. for 7.5 h to obtain a modified soybean oil-based polyol. The remaining steps are the same as in Example 2.

[0051] Comparative Example 3

[0052] The preparation method of the super-hydrophobic polymer composite material for tablecloths in Comparative Example 3 differs from that in Example 2 only in step (3), and step (3) is modified as follows: adding isophorone diisocyanate, fluorinated diol monomer, and modified soybean oil-based polyol in a mass ratio of 1:0.45:0.45 to N, N-dimethylformamide 22 times the mass of isophorone diisocyanate, stirring and reacting at 75°C and 400r / min under a nitrogen atmosphere, adding 1,6-hexanediol 0.07 times the molar amount of isophorone diisocyanate to the reaction system every half an hour, and detecting the isocyanate group concentration of the reaction system by dibutylamine-hydrochloric acid titration, stopping the addition of 1,6-hexanediol when the isocyanate group concentration is less than 5%, quenching the remaining isocyanate groups with anhydrous ethanol, cooling to room temperature, and drying at 6Pa, 55°C for 6.5h to obtain polyurethane. The remaining steps are the same as in Example 2.

[0053] Comparative Example 4

[0054] The preparation method of the super-hydrophobic polymer composite material for tablecloths in Comparative Example 4 is different from that in Example 2 only in step (4), and step (4) is modified as follows: placing polyurethane in a hot melt machine, stirring at 185°C, 400r / min for 15min, and then sending it to a calender for calendering, setting the calender temperature to 155°C, the calendering speed to 55m / min, the pressure to 27MPa, and standing for 5.5h to obtain a polyurethane film; immersing the polyurethane film in a 10% sodium hypochlorite aqueous solution, adjusting the pH to 6.9 with a 22% sulfuric acid aqueous solution, ultrasonically treating for 1.5h, taking it out, and drying it at 4Pa, 55°C for 7.5h to obtain a super-hydrophobic polymer composite material for tablecloths. The remaining steps are the same as in Example 2.

[0055] Test Example 1

[0056] Hydrophobicity test

[0057] Test method: The water drop contact angles of the embodiments and comparative examples were tested using the sessile drop method on an OCA20 contact angle meter, with the water drop volume being 5 μL. The results are shown in Table 1.

[0058] Table 1

[0059]

[0060]

[0061] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 1, it can be found that the super-hydrophobic polymer composite material for tablecloth prepared by the present invention has good hydrophobic performance.

[0062] By comparison, the contact angles of Examples 1 to 3 are greater than the contact angle of Comparative Example 1, indicating that the fluorine-containing diol monomer is prepared by reacting diethanolamine with 1H,1H,2H,2H-methacrylic acid-1H,1H-perfluorooctyl ester. The fluorine-containing diol monomer can participate in the polymerization reaction of polyurethane, and introduce a large number of fluorine atoms on the side chains of polyurethane molecules. The fluorine atoms have low reactivity and hydrophobicity, and can give the super-hydrophobic polymer composite material for tablecloths excellent hydrophobic properties.

[0063] Test Example 2

[0064] Flame retardant performance test

[0065] Test method: The examples and comparative examples were prepared into standard specimens according to GB / T2406.2, and the limiting oxygen index of the standard specimens was tested. The results are shown in Table 2.

[0066] Table 2

[0067] Limiting oxygen index (%) Limiting oxygen index (%) Example 1 28.7 Comparative Example 1 28.6 Example 2 29.4 Comparative Example 2 29.2 Example 3 29.1 Comparative Example 3 28.9 Comparative Example 4 19.7

[0068] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 2, it can be found that the super-hydrophobic polymer composite material for tablecloth prepared by the present invention has good flame retardant properties.

[0069] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 4, indicating that the phosphorus-containing flame retardant intermediate is prepared by reacting 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide with formic acid, and the phosphorus chlorine on 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide is converted into phosphorus hydrogen; the polyurethane and the phosphorus-containing flame retardant intermediate are calendered, and the phosphorus hydrogen on the phosphorus-containing flame retardant intermediate can undergo addition reaction with the carbon-carbon double bond on the main chain of the polyurethane molecule, and the phosphorus element is introduced into the super-hydrophobic polymer composite material for tablecloths, so as to give the super-hydrophobic polymer composite material for tablecloths excellent flame retardant properties.

[0070] Test Example 3

[0071] Mechanical properties testing

[0072] Test method: The tensile strength of the examples and comparative examples was tested on an electronic universal testing machine according to GB / T1040.3. The results are shown in Table 3.

[0073] Table 3

[0074] Tensile strength(MPa) Tensile strength(MPa) Example 1 38.5 Comparative Example 1 37.9 Example 2 37.7 Comparative Example 2 38.2 Example 3 38.1 Comparative Example 3 28.3 Comparative Example 4 27.9

[0075] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 3, it can be found that the super-hydrophobic polymer composite material for tablecloth prepared by the present invention has good mechanical properties.

[0076] By comparison, the tensile strength of Examples 1 to 3 is greater than that of Comparative Examples 3 to 4, indicating that polyurethane is prepared by copolymerizing isophorone diisocyanate, fluorine-containing diol monomer, modified soybean oil-based polyol, and 1,4-butene diol, and carbon-carbon double bonds are introduced into the main chain of the polyurethane molecule; 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide is reacted with formic acid to prepare a phosphorus-containing flame retardant intermediate, and the phosphorus chlorine on 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide is converted into phosphorus hydrogen; polyurethane and the phosphorus-containing flame retardant intermediate are calendered, and the phosphorus hydrogen on the phosphorus-containing flame retardant intermediate can undergo addition reaction with the carbon-carbon double bonds on the main chain of the polyurethane molecule to form a cross-linked network, thereby inhibiting the relative slip between the polyurethane molecular chains, and giving the superhydrophobic polymer composite material for tablecloths excellent mechanical properties.

[0077] Test Example 4

[0078] Antimicrobial performance testing

[0079] Test method: The examples and comparative examples were cut into 10 mm × 10 mm samples and sterilized by ultraviolet irradiation for 3 h; the Escherichia coli strains were activated and prepared to a concentration of 3 × 10 4 cfu / ml bacterial suspension; put the sample into the bacterial suspension, shake at 300r / min for 5min at room temperature, take 1ml of the bacterial suspension and dilute it to 100 times, take 1ml of the diluted bacterial suspension and inoculate it into agar medium, culture it at 37℃ for 16h, count the colonies according to the method in GB / T15979, and calculate the antibacterial rate, antibacterial rate = (average colony count before sample shaking - average colony count after sample shaking) / average colony count before sample shaking × 100%. The results are shown in Table 4.

[0080] Table 4

[0081] Antibacterial rate (%) Antibacterial rate (%) Example 1 99.8 Comparative Example 1 99.7 Example 2 99.7 Comparative Example 2 74.3 Example 3 99.8 Comparative Example 3 99.8 Comparative Example 4 99.6

[0082] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 4, it can be found that the super-hydrophobic polymer composite material for tablecloth prepared by the present invention has good antibacterial properties.

[0083] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that 5,5-dimethylhydantoin is reacted with 3-chloro-1-propanethiol to prepare 1-(3-mercaptopropyl)-5,5-dimethylhydantoin, and a thiol group is introduced into 1-(3-mercaptopropyl)-5,5-dimethylhydantoin; soybean oil is reacted with glycerol to prepare soybean oil-based polyol, soybean oil-based polyol is reacted with 1-(3-mercaptopropyl)-5,5-dimethylhydantoin to prepare modified soybean oil-based polyol, and 1-(3-mercaptopropyl)-5,5-dimethylhydantoin is reacted with 1-(3-mercaptopropyl)-5,5-dimethylhydantoin to prepare modified soybean oil-based polyol. The thiol group on dimethyl hydantoin reacts with the carbon-carbon double bond on the soybean oil-based polyol to react with the modified soybean oil-based polyol in the copolymerization of polyurethane. The halamine precursor is grafted onto the side chain of the polyurethane molecule. The halamine precursor is chlorinated to form a halamine structure. In the presence of water molecules, the N-Cl bond slowly decomposes to release hypohalous acid or hypohalogen radicals with strong oxidizing properties, which directly attack some groups in bacteria to denature proteins and inhibit enzyme metabolism, thereby achieving a bactericidal effect and giving the super-hydrophobic polymer composite material for tablecloths excellent antibacterial properties.

[0084] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A super-hydrophobic polymer composite material for tablecloth, characterized in that: The super hydrophobic polymer composite material for tablecloth is prepared by copolymerizing isophorone diisocyanate, a fluorine-containing diol monomer, a modified soybean oil-based polyol, and 1,4-butene diol to obtain polyurethane; reacting 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide with formic acid to obtain a phosphorus-containing flame retardant intermediate; calendering the polyurethane and the phosphorus-containing flame retardant intermediate, and then chlorinating with a sodium hypochlorite aqueous solution to obtain the super hydrophobic polymer composite material for tablecloth; The modified soybean oil-based polyol is prepared by sequentially reacting soybean oil with glycerol and 1-(3-mercaptopropyl)-5,5-dimethylhydantoin; The 1-(3-mercaptopropyl)-5,5-dimethylhydantoin is prepared by reacting 5,5-dimethylhydantoin with 3-chloro-1-propanethiol; The fluorine-containing diol monomer is prepared by reacting diethanolamine with 1H,1H,2H,2H-methacrylic acid-1H,1H-perfluorooctyl ester.

2. A method for preparing the super-hydrophobic polymer composite material for tablecloth according to claim 1, characterized in that: The method comprises the following preparation steps: (1) Diethanolamine, sodium ethoxide and anhydrous ethanol were mixed uniformly in a mass ratio of 1:(0.03-0.05):(20-24), stirred at 69-71°C and 300-500 r / min for 40-60 min under a nitrogen atmosphere, and an equal molar amount of 1H,1H,2H,2H-methacrylic acid-1H,1H-perfluorooctyl ester was added to the mixture, and the reaction was continued with stirring for 20-24 h. The mixture was dried at 3-5 Pa and 50-60°C for 7-8 h to obtain a fluorinated diol monomer; (2) Add 5,5-dimethylhydantoin and 3-chloro-1-propanethiol in a molar ratio of 1:1 to tetrahydrofuran (20 to 24 times the mass of 5,5-dimethylhydantoin), then add triethylamine (0.03 to 0.05 times the mass of 5,5-dimethylhydantoin), stir at 50 to 60°C and 300 to 500 r / min for 3 to 4 hours, and dry at 3 to 5 Pa and 50 to 60°C for 7 to 8 hours to obtain 1-(3-mercaptopropyl)-5,5-dimethylhydantoin; add soybean oil, glycerol and lithium hydroxide in a mass ratio of 1:(0.2 to 0.3):(0.05 to 0 .07) are mixed evenly, stirred at 160-180°C and 300-500r / min for 3-4h, cooled to room temperature, extracted with n-hexane, and the organic phase is dried at 3-5Pa and 50-60°C for 7-8h to obtain soybean oil-based polyol; soybean oil-based polyol, 1-(3-mercaptopropyl)-5,5-dimethylhydantoin, and azobisisobutyronitrile are mixed evenly in a mass ratio of 1:(0.6-0.8):(0.03-0.05), stirred at 70-80°C and 300-500r / min for 3-4h to obtain modified soybean oil-based polyol; (3) Add isophorone diisocyanate, fluorinated diol monomer, modified soybean oil-based polyol and 1,4-butene diol in a mass ratio of 1:(0.2~0.3):(0.2~0.3):(0.2~0.3) to N,N-dimethylformamide (20~24 times the mass of isophorone diisocyanate), stir and react at 70~80°C and 300~500r / min under nitrogen atmosphere, add 1,6-hexanediol (0.06~0.08 times the molar amount of isophorone diisocyanate) to the reaction system every half an hour, monitor the content of isocyanate groups, quench the remaining isocyanate groups with anhydrous ethanol, cool to room temperature, and dry at 5~7Pa and 50~60°C for 6~7h to obtain polyurethane; (4) The polyurethane, phosphorus-containing flame retardant intermediate and azobisisobutyronitrile are mixed uniformly in a mass ratio of 1:(0.10-0.12):(0.01-0.03), placed in a hot melt machine, stirred at 180-190°C and 300-500 r / min for 10-20 min, and then sent to a calender for calendering to obtain a polyurethane film; the polyurethane film is immersed in a sodium hypochlorite aqueous solution with a mass fraction of 9-11%, the pH is adjusted to 6.8-7.0 with a sulfuric acid aqueous solution with a mass fraction of 20-24%, ultrasonically treated for 1-2 h, taken out, and dried at 3-5 Pa and 50-60°C for 7-8 h to obtain a superhydrophobic polymer composite material for tablecloths.

3. The method for preparing a super-hydrophobic polymer composite material for tablecloth according to claim 2, characterized in that: The reaction process of the fluorinated diol monomer in step (1) is: 。 4. The method for preparing a super-hydrophobic polymer composite material for tablecloth according to claim 2, characterized in that: The reaction process of 1-(3-mercaptopropyl)-5,5-dimethylhydantoin in step (2) is as follows: 。 5. The method for preparing a super-hydrophobic polymer composite material for tablecloth according to claim 2, characterized in that: The method for monitoring the content of isocyanate groups in the reaction system in step (3) is to detect the content of isocyanate groups in the reaction system by dibutyl amine-hydrochloric acid titration method, and stop adding 1,6-hexanediol when the content of unreacted isocyanate groups is less than 4-6% of the initial number of isocyanate groups.

6. The method for preparing a super-hydrophobic polymer composite material for tablecloth according to claim 2, characterized in that: The preparation method of the phosphorus-containing flame retardant intermediate in step (4) is as follows: under a nitrogen atmosphere, at 30-40° C. and under stirring conditions of 300-500 r / min, formic acid twice the molar amount of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide is uniformly added dropwise to 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide over a period of 50-60 min, washing with ether and deionized water for 3-5 times respectively, and drying at 3-5 Pa and 50-60° C. for 7-8 hours to obtain the phosphorus-containing flame retardant intermediate; The reaction process is: 。 7. The method for preparing a super-hydrophobic polymer composite material for tablecloth according to claim 2, characterized in that: The process parameters of the calendering molding in step (4) are: setting the calender temperature to 150-160° C., the calendering speed to 50-60 m / min, and the pressure to 24-30 MPa.

Images