A preparation method of modified polyacrylamide material

Abstract

The invention relates to the technical field of polymer materials, and discloses a method for preparing a modified polyacrylamide material. The invention adds acrylamide, alkenyl chitosan, methacryloyloxyethyl trimethylammonium chloride, and alkenyl-modified silicon-containing cyanuric chloride into deionized water, then continues to add azobisisobutyronitrile initiator, stirs evenly, introduces nitrogen protection, reacts, and then filters, washes, and dries after the reaction to obtain the modified polyacrylamide material. The nitrogen element in the invention can generate a flame-retardant gas when heated, which can not only dilute the concentration of flammable gas, but also limit the combustion of the substance. The silicon element can generate a glass-like substance on the surface of the material when heated, which isolates the material from transport and energy transfer. The boron element melts at high temperature to form a glass covering layer, which covers the surface of the burning object, isolates oxygen and heat, and achieves a flame retardant effect; the boron element and the chitosan structure have good antibacterial effect.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a method for preparing a modified polyacrylamide material. Background Art

[0002] Polyacrylamide is a general term for polymers obtained by copolymerization of acrylamide homopolymers or other monomers. It is one of the most widely used varieties of water-soluble polymers. The polyacrylamide structural unit contains amide groups, which can be easily obtained by grafting or cross-linking to obtain a variety of modified products. It is also widely used in water treatment, papermaking, textile and other industries, so the requirements for its performance are getting higher and higher. For example, patent CN115141377A discloses an antibacterial polyacrylamide material and a preparation method thereof. The polyacrylamide material provided by the present invention has good antibacterial properties, which expands the product field and application range of the polyacrylamide material, but its flame retardant effect is not improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies of the prior art, the present invention provides a method for preparing a modified polyacrylamide material, which has good flame retardant and antibacterial effects.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention provides the following technical solution: a method for preparing a modified polyacrylamide material, wherein the method for preparing the modified polyacrylamide material is:

[0007] (1) Add cyanuric chloride, triethylamine and acetone solvent into a reactor, stir evenly, and then add N-hydroxyethylpiperazine to the reactor, and react in a water bath at 0-2°C for 2-4 hours. Stir mechanically to allow the reaction to proceed fully. After the reaction is complete, filter, wash and dry to obtain intermediate 1.

[0008] (2) Add pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stir and disperse, continue to add intermediate 1, react at 75-90° C. for 6-9 hours, centrifuge after reaction, wash with ethanol, and dry to obtain pentaerythritol methyl silicate modified hydroxylated cyanuric chloride;

[0009] (3) adding 4-8 parts by weight of boric acid to an ether solvent, stirring and dispersing, and then adding 10-15 parts by weight of pentaerythritol methyl silicate modified hydroxylated cyanuric chloride thereto, reacting at 110-130° C. for 10-14 hours. After the reaction is completed, distilling under reduced pressure, filtering and drying are performed to obtain boric acid modified silicon-containing cyanuric chloride;

[0010] (4) Adding boric acid-modified silicon-containing cyanuric chloride and sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stirring and dispersing, reacting at 65-80°C for 12-16 hours, and then continuing to add 3-chloropropylene, reacting at 70-85°C for 6-10 hours, and then distilling under reduced pressure and filtering to obtain alkenyl-modified silicon-containing cyanuric chloride;

[0011] (5) Add acrylamide, olefinated chitosan, methacryloyloxyethyl trimethylammonium chloride, and olefin-modified silicon-containing cyanuric chloride into deionized water, and then continue to add azobisisobutyronitrile initiator, stir evenly, introduce nitrogen protection, react at 75-100°C for 6-10h, filter after completion, wash with water, and dry to obtain a modified polyacrylamide material.

[0012] Preferably, the mass ratio of cyanuric chloride, triethylamine and N-hydroxyethylpiperazine in (1) is 1:0.01-0.03:2.1-2.5.

[0013] Preferably, the mass ratio of pentaerythritol methyl silicate to intermediate 1 in (2) is 1.5-1.8:1.

[0014] Preferably, the mass ratio of the boric acid-modified silicon-containing cyanuric chloride, sodium 3-chloro-2-hydroxypropanesulfonate, and 3-chloropropylene in (4) is 1:1.1-1.3:0.8-1.2.

[0015] Preferably, the mass ratio of acrylamide, olefinic chitosan, methacryloyloxyethyl trimethyl ammonium chloride, olefinic modified silicon-containing cyanuric chloride, and azobisisobutyronitrile initiator in (5) is 1.6-2:1:1.2-1.4:1.1-1.2:0.02-0.03.

[0016] Preferably, the preparation method of the olefinated chitosan in (5) is:

[0017] S1. 7-12 parts by weight of chitosan was added to a dimethyl sulfoxide solvent to dissolve, heated in a water bath at 70-100°C, 4-8 parts by weight of 2,3-epoxypropyltrimethylammonium chloride was added at a constant pressure to react, and after the reaction, washed with anhydrous ethanol, dried, dialyzed, and concentrated to obtain quaternized chitosan;

[0018] S2. Add quaternized chitosan and acrylic acid to N,N-dimethylformamide solvent, stir evenly, then add p-toluenesulfonic acid catalyst, react at 80-115°C for 10-16h, and then distill under reduced pressure, filter and dry to obtain olefinated chitosan.

[0019] Preferably, the reaction time in S1 is 5-10 h.

[0020] Preferably, the mass ratio of quaternized chitosan, acrylic acid and p-toluenesulfonic acid catalyst in S2 is 1.2-1.4:1:0.01-0.03.

[0021] 3. Beneficial technical effects

[0022] The invention provides a modified polyacrylamide material by adding acrylamide, alkenyl chitosan, methacryloyloxyethyl trimethyl ammonium chloride and alkenyl-modified silicon-containing cyanuric chloride into deionized water, then adding azobisisobutyronitrile initiator thereto, stirring evenly, introducing nitrogen for protection, reacting, filtering after reaction, washing with water and drying.

[0023] The triazine group, nitrogen element, silicon element, boron element, and sodium sulfonate group contained in the modified polyacrylamide material all have good flame retardant effects. The nitrogen element can produce non-flammable gas when heated, which can not only dilute the concentration of flammable gas, but also take away some heat, further limiting the combustion of the material. When the silicon element is heated, it can produce a glass-like substance on the surface of the material, isolating the transport of substances and energy transfer. The boron element melts at high temperatures to form a glassy covering layer that covers the surface of the burning material, isolating oxygen and heat, and achieving a flame retardant effect; the boron element and chitosan structure have good antibacterial effects. DETAILED DESCRIPTION Example 1

[0024] (1) Add cyanuric chloride, triethylamine and acetone solvent into a reactor, stir evenly, and continue to add N-hydroxyethylpiperazine, wherein the mass ratio of cyanuric chloride, triethylamine and N-hydroxyethylpiperazine is 1:0.01:2.1, react in a water bath at 0°C for 2 hours, stir mechanically to allow for sufficient reaction, filter after completion, wash, and dry to obtain intermediate 1;

[0025] (2) adding pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stirring and dispersing, and continuously adding intermediate 1, wherein the mass ratio of pentaerythritol methyl silicate to intermediate 1 is 1.5:1, reacting at 75° C. for 6 h, centrifuging after reaction, washing with ethanol, and drying to obtain pentaerythritol methyl silicate-modified hydroxylated cyanuric chloride;

[0026] (3) adding 4 parts by weight of boric acid to an ether solvent, stirring and dispersing, and then adding 10 parts by weight of methyl silicate pentaerythritol modified hydroxylated cyanuric chloride thereto, reacting at 110° C. for 10 hours. After the reaction is completed, distilling under reduced pressure, filtering and drying are performed to obtain boric acid modified silicon-containing cyanuric chloride;

[0027] (4) Adding boric acid-modified silicon-containing cyanuric chloride and sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stirring and dispersing, reacting at 65°C for 12 hours, and then continuing to add 3-chloropropylene, wherein the mass ratio of boric acid-modified silicon-containing cyanuric chloride, sodium 3-chloro-2-hydroxypropanesulfonate, and 3-chloropropylene is 1:1.1:0.8, reacting at 70°C for 6 hours, and then distilling under reduced pressure and filtering to obtain alkenyl-modified silicon-containing cyanuric chloride;

[0028] (5) adding 7 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heating it in a water bath at 70° C., adding 4 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at constant pressure, reacting it for 5 hours, washing it with anhydrous ethanol after the reaction, drying it, dialyzing it, and concentrating it to obtain quaternized chitosan;

[0029] (6) adding quaternized chitosan and acrylic acid to N,N-dimethylformamide solvent, stirring evenly, and then adding p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of quaternized chitosan, acrylic acid, and p-toluenesulfonic acid catalyst is 1.2:1:0.01, reacting at 80°C for 10 hours, and then distilling under reduced pressure, filtering, and drying to obtain olefinated chitosan;

[0030] (7) Add acrylamide, alkenyl chitosan, methacryloyloxyethyl trimethyl ammonium chloride, and alkenyl-modified silicon-containing cyanuric chloride into deionized water, and then continue to add azobisisobutyronitrile initiator, wherein the mass ratio of acrylamide, alkenyl chitosan, methacryloyloxyethyl trimethyl ammonium chloride, alkenyl-modified silicon-containing cyanuric chloride, and azobisisobutyronitrile initiator is 1.6:1:1.2:1.1:0.02. Stir evenly, introduce nitrogen protection, react at 75°C for 6 hours, filter after reaction, wash with water, and dry to obtain a modified polyacrylamide material. Example 2

[0031] (1) Add cyanuric chloride, triethylamine and acetone solvent into a reactor, stir evenly, and continue to add N-hydroxyethylpiperazine, wherein the mass ratio of cyanuric chloride, triethylamine and N-hydroxyethylpiperazine is 1:0.03:2.5, react in a water bath at 2°C for 4 hours, stir mechanically to allow for full reaction, filter after completion, wash and dry to obtain intermediate 1;

[0032] (2) adding pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stirring and dispersing, and continuously adding intermediate 1, wherein the mass ratio of pentaerythritol methyl silicate to intermediate 1 is 1.8:1, reacting at 90° C. for 9 h, centrifuging after reaction, washing with ethanol, and drying to obtain pentaerythritol methyl silicate-modified hydroxylated cyanuric chloride;

[0033] (3) adding 8 parts by weight of boric acid to an ether solvent, stirring and dispersing, and then adding 15 parts by weight of methyl silicate pentaerythritol modified hydroxylated cyanuric chloride thereto, reacting at 130° C. for 14 hours. After the reaction is completed, distilling under reduced pressure, filtering and drying are performed to obtain boric acid modified silicon-containing cyanuric chloride;

[0034] (4) Adding boric acid-modified silicon-containing cyanuric chloride and sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stirring and dispersing, reacting at 80°C for 16 hours, and then continuing to add 3-chloropropylene, wherein the mass ratio of boric acid-modified silicon-containing cyanuric chloride, sodium 3-chloro-2-hydroxypropanesulfonate, and 3-chloropropylene is 1:1.3:1.2, reacting at 85°C for 10 hours, and then distilling under reduced pressure and filtering to obtain alkenyl-modified silicon-containing cyanuric chloride;

[0035] (5) adding 12 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heating it in a water bath at 100° C., adding 8 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at constant pressure, reacting it for 10 hours, washing it with anhydrous ethanol after the reaction, drying it, dialyzing it, and concentrating it to obtain quaternized chitosan;

[0036] (6) adding quaternized chitosan and acrylic acid to N,N-dimethylformamide solvent, stirring evenly, and then adding p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of quaternized chitosan, acrylic acid, and p-toluenesulfonic acid catalyst is 1.4:1:0.03, reacting at 115°C for 16 hours, and then distilling under reduced pressure, filtering, and drying to obtain olefinated chitosan;

[0037] (7) Add acrylamide, alkenyl chitosan, methacryloyloxyethyl trimethyl ammonium chloride, and alkenyl-modified silicon-containing cyanuric chloride into deionized water, and then continue to add azobisisobutyronitrile initiator, wherein the mass ratio of acrylamide, alkenyl chitosan, methacryloyloxyethyl trimethyl ammonium chloride, alkenyl-modified silicon-containing cyanuric chloride, and azobisisobutyronitrile initiator is 2:1:1.4:1.2:0.03. Stir evenly, introduce nitrogen protection, react at 100°C for 10 hours, filter after reaction, wash with water, and dry to obtain a modified polyacrylamide material. Example 3

[0038] (1) Add cyanuric chloride, triethylamine and acetone solvent into a reactor, stir evenly, and continue to add N-hydroxyethylpiperazine, wherein the mass ratio of cyanuric chloride, triethylamine and N-hydroxyethylpiperazine is 1:0.02:2.3, react in a water bath at 1°C for 3 hours, stir mechanically to allow for sufficient reaction, filter after completion, wash and dry to obtain intermediate 1;

[0039] (2) adding pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stirring and dispersing, and continuously adding intermediate 1, wherein the mass ratio of pentaerythritol methyl silicate to intermediate 1 is 1.7:1, reacting at 82° C. for 8 h, centrifuging after reaction, washing with ethanol, and drying to obtain pentaerythritol methyl silicate-modified hydroxylated cyanuric chloride;

[0040] (3) Add 6 parts by weight of boric acid to an ether solvent, stir and disperse, then add 12 parts by weight of methyl silicate pentaerythritol modified hydroxylated cyanuric chloride, react at 120° C. for 12 hours, and after the reaction is completed, perform vacuum distillation, filter and dry to obtain boric acid modified silicon-containing cyanuric chloride;

[0041] (4) Adding boric acid-modified silicon-containing cyanuric chloride and sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stirring and dispersing, reacting at 75°C for 14 hours, and then continuing to add 3-chloropropylene, wherein the mass ratio of boric acid-modified silicon-containing cyanuric chloride, sodium 3-chloro-2-hydroxypropanesulfonate, and 3-chloropropylene is 1:1.2:0.9, reacting at 80°C for 8 hours, and then distilling under reduced pressure and filtering to obtain alkenyl-modified silicon-containing cyanuric chloride;

[0042] (5) adding 11 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heating it in a water bath at 85° C., adding 6 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at constant pressure, reacting it for 7 hours, washing it with anhydrous ethanol after the reaction, drying it, dialyzing it, and concentrating it to obtain quaternized chitosan;

[0043] (6) adding quaternized chitosan and acrylic acid to N,N-dimethylformamide solvent, stirring evenly, and then adding p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of quaternized chitosan, acrylic acid, and p-toluenesulfonic acid catalyst is 1.3:1:0.02, reacting at 92°C for 13h, and then distilling under reduced pressure, filtering, and drying to obtain olefinated chitosan;

[0044] (7) Add acrylamide, alkenyl chitosan, methacryloyloxyethyl trimethyl ammonium chloride, and alkenyl-modified silicon-containing cyanuric chloride into deionized water, and then continue to add azobisisobutyronitrile initiator, wherein the mass ratio of acrylamide, alkenyl chitosan, methacryloyloxyethyl trimethyl ammonium chloride, alkenyl-modified silicon-containing cyanuric chloride, and azobisisobutyronitrile initiator is 1.8:1:1.3:1.15:0.025. Stir evenly, introduce nitrogen protection, react at 82°C for 8 hours, filter after reaction, wash with water, and dry to obtain a modified polyacrylamide material.

[0045] Comparative Example 1

[0046] Acrylamide, methacryloyloxyethyl trimethyl ammonium chloride, and alkenyl-modified silicon-containing cyanuric chloride are added to deionized water, and then azobisisobutyronitrile initiator is added thereto, wherein the mass ratio of acrylamide, methacryloyloxyethyl trimethyl ammonium chloride, alkenyl-modified silicon-containing cyanuric chloride, and azobisisobutyronitrile initiator is 1.8:1.3:1.15:0.025. Stir evenly, introduce nitrogen protection, react at 82°C for 8h, filter after reaction, wash with water, and dry to obtain a modified polyacrylamide material.

[0047] Comparative Example 2

[0048] Acrylamide, olefinated chitosan, and methacryloyloxyethyl trimethyl ammonium chloride are added to deionized water, and then azobisisobutyronitrile initiator is added thereto, wherein the mass ratio of acrylamide, olefinated chitosan, methacryloyloxyethyl trimethyl ammonium chloride and azobisisobutyronitrile initiator is 1.8:1:1.3:0.025, and the mixture is stirred evenly, nitrogen is introduced for protection, and the reaction is carried out at 82°C for 8 hours. After the reaction is completed, the mixture is filtered, washed with water, and dried to obtain a modified polyacrylamide material.

[0049] Use an oxygen index meter to test the limiting oxygen index of modified polyacrylamide materials; use a horizontal and vertical combustion instrument to test the combustion grade of modified polyacrylamide materials.

[0050] Table 1: Flame retardancy tests.

[0051] project Limiting oxygen index (%) Combustion level Example 1 31 V-0 Example 2 33 V-0 Example 3 32 V-0 Comparative Example 1 21 V-1 Comparative Example 2 20 V-1

[0052] It can be seen from Table 1 that the flame retardant effect of Examples 1-3 is better than that of Comparative Examples 1-2, which indicates that the modified polyacrylamide material prepared by the present invention has a good flame retardant effect.

[0053] Pipette 1 mL of 10 8 CFU / mL of Staphylococcus aureus was added to PBS buffer, and then diluted 10-fold to 10 5 CFU / mL, then add the material sample (1 cm×1cm×0.2mm), and then culture it in a constant temperature incubator at 37℃ with shaking for 24 h. After culture, add PBS buffer to dilute the bacterial solution 10 times in sequence, and then transfer 0.5 mL of the bacterial solution to the agar medium, and continue to culture it at 37℃ with shaking for 24 h. After culture, count the colonies and count the antibacterial rate.

[0054] Table 2: Antibacterial performance test.

[0055] project Antibacterial rate (%) Example 1 98.3 Example 2 99.6 Example 3 98.9 Comparative Example 1 84.5 Comparative Example 2 92.7

[0056] It can be seen from Table 2 that Examples 1-3 of the present invention have better antibacterial effects than Comparative Examples 1-2.

[0057] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a modified polyacrylamide material, characterized in that: The preparation method of the modified polyacrylamide material is: (1) Add cyanuric chloride, triethylamine and acetone solvent into a reactor, stir evenly, and then add N-hydroxyethylpiperazine to the reactor, and react in a water bath at 0-2°C for 2-4 hours. Stir mechanically to allow the reaction to proceed fully. After the reaction is complete, filter, wash and dry to obtain intermediate 1. (2) Add pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stir and disperse, continue to add intermediate 1, react at 75-90° C. for 6-9 hours, centrifuge after reaction, wash with ethanol, and dry to obtain pentaerythritol methyl silicate modified hydroxylated cyanuric chloride; (3) adding 4-8 parts by weight of boric acid to an ether solvent, stirring and dispersing, and then adding 10-15 parts by weight of pentaerythritol methyl silicate modified hydroxylated cyanuric chloride thereto, reacting at 110-130° C. for 10-14 hours. After the reaction is completed, distilling under reduced pressure, filtering and drying are performed to obtain boric acid modified silicon-containing cyanuric chloride; (4) Adding boric acid-modified silicon-containing cyanuric chloride and sodium 3-chloro-2-hydroxypropanesulfonate to N,N-dimethylformamide solvent, stirring and dispersing, reacting at 65-80°C for 12-16 hours, and then continuing to add 3-chloropropylene, reacting at 70-85°C for 6-10 hours, and then distilling under reduced pressure and filtering to obtain alkenyl-modified silicon-containing cyanuric chloride; (5) Add acrylamide, olefinic chitosan, methacryloyloxyethyl trimethyl ammonium chloride, and olefinic modified silicon-containing cyanuric chloride into deionized water, and then continue to add azobisisobutyronitrile initiator, stir evenly, pass nitrogen protection, react at 75-100°C for 6-10h, filter after completion, wash with water, and dry to obtain a modified polyacrylamide material; The preparation method of olefinated chitosan in (5) is as follows: S1. 7-12 parts by weight of chitosan was added to a dimethyl sulfoxide solvent to dissolve, heated in a water bath at 70-100°C, 4-8 parts by weight of 2,3-epoxypropyltrimethylammonium chloride was added at a constant pressure to react, and after the reaction, washed with anhydrous ethanol, dried, dialyzed, and concentrated to obtain quaternized chitosan; S2. Add quaternized chitosan and acrylic acid to N,N-dimethylformamide solvent, stir evenly, then add p-toluenesulfonic acid catalyst, react at 80-115°C for 10-16h, and then distill under reduced pressure, filter and dry to obtain olefinated chitosan.

2. The method for preparing the modified polyacrylamide material according to claim 1, characterized in that: The mass ratio of cyanuric chloride, triethylamine and N-hydroxyethylpiperazine in (1) is 1:0.01-0.03:2.1-2.

5.

3. The method for preparing the modified polyacrylamide material according to claim 1, characterized in that: The mass ratio of pentaerythritol methyl silicate to the intermediate 1 in (2) is 1.5-1.8:

1.

4. The method for preparing the modified polyacrylamide material according to claim 1, characterized in that: The mass ratio of the boric acid-modified silicon-containing cyanuric chloride, sodium 3-chloro-2-hydroxypropanesulfonate and 3-chloropropylene in (4) is 1:1.1-1.3:0.8-1.

2.

5. The method for preparing the modified polyacrylamide material according to claim 1, characterized in that: The mass ratio of acrylamide, olefinic chitosan, methacryloyloxyethyl trimethyl ammonium chloride, olefinic modified silicon-containing cyanuric chloride, and azobisisobutyronitrile initiator in (5) is 1.6-2:1:1.2-1.4:1.1-1.2:0.02-0.

03.

6. The method for preparing the modified polyacrylamide material according to claim 1, characterized in that: The reaction time in S1 is 5-10 hours.

7. The method for preparing the modified polyacrylamide material according to claim 1, characterized in that: The mass ratio of quaternized chitosan, acrylic acid and p-toluenesulfonic acid catalyst in S2 is 1.2-1.4:1:0.01-0.03.