ANTIBACTERIAL POLYMER AND PREPARATION METHOD THEREOF

Abstract

An antibacterial polymer and a preparation method thereof are provided. The antibacterial polymer is obtained by polymerization of a polyol and a guanidine salt, and has the following structure:

##STR00001##

In the preparation method, non-toxic and non-irritating polyols are used as raw materials, wherein the non-toxic and non-irritating polyols are friendly to an environment and a human body.

Claims

1. An antibacterial polymer obtained by polymerization of a polyol and a guanidine salt, comprising the following structure: ##STR00004## wherein n=5-10, m=50-150; Y.sup.− is selected from the group consisting of Cl.sup.−, NO.sub.3.sup.−, HCO.sub.3.sup.−, CH.sub.3COO.sup.−, HSO.sub.4.sup.− and H.sub.2PO.sub.4.sup.− anion; X is a C5-C20 ester group or ether group containing 1-5 active unsaturated double bonds; and Z is H or X; the antibacterial polymer is prepared according to the following method: taking and adding 124 g of ethylene glycol and 260 g of guanidine nitrate to a reactor to obtain a resultant mixture, and mixing the resultant mixture evenly; adjusting pH of the resultant mixture to 5 under a protection of nitrogen; heating the resultant mixture to 120° C., and reacting for 3 hours; then adding 30 g of acrylic acid, and performing an esterification reaction for 1 hour; and then, terminating the esterification reaction.

2. An antibacterial polymer obtained by polymerization of a polyol and a guanidine salt, comprising the following structure: ##STR00005## wherein n=5-10, m=50-150; Y.sup.− is selected from the group consisting of Cl.sup.−, NO.sub.3.sup.−, HCO.sub.3.sup.−, CH.sub.3COO.sup.−, HSO.sub.4.sup.− and H.sub.2PO.sub.4.sup.− anion; X is a C5-C20 ester group or ether group containing 1-5 active unsaturated double bonds; Z is H or X; the antibacterial polymer is prepared according to the following method: taking and adding 152 g of propylene glycol and 254 g of guanidine carbonate to a reactor to obtain a resultant mixture, and mixing the resultant mixture evenly; adjusting a pH of the resultant mixture to 4 under a protection of nitrogen; heating the resultant mixture to 130° C., and reacting for 2.5 hours; then adding 25 g of methacrylic acid, and performing an esterification reaction for 1.5 hours; and then, terminating the esterification reaction.

3. An antibacterial polymer obtained by polymerization of a polyol and a guanidine salt comprising the following structure: ##STR00006## wherein n=5-10, m=50-150; Y.sup.− is selected from the group consisting of Cl.sup.−, NO.sub.3.sup.−, HCO.sub.3.sup.−, CH.sub.3COO.sup.−, HSO.sub.4.sup.− and H.sub.2PO.sub.4.sup.− anion; X is a C5-C20 ester group or ether group containing 1-5 active unsaturated double bonds; Z is H or X; the antibacterial polymer is prepared according to the following method: taking and adding 118 g of 1,6-hexanediol and 100 g of guanidine hydrochloride and adding to a reactor to obtain a resultant mixture, and mixing the resultant mixture evenly; adjusting a pH of the resultant mixture to 3 under a protection of nitrogen; heating the resultant mixture to 150° C., and reacting for 2 hours; then adding 20 g of epoxypropyl acrylate, and performing an esterification reaction for 2 hours; and then, terminating the esterification reaction.

Description

DETAILED DESCRIPTION

Example 1 Preparation of Antibacterial Masterbatch of the Present Application

[0020] 1.1 124 g of ethylene glycol and 260 g of guanidine nitrate are taken and added to a reactor and mixed evenly. pH is adjusted to 5 with hydrochloric acid under the protection of nitrogen. The resultant is heated to 120° C., reacted for 3 h, then added with 30 g of acrylic acid. An esterification reaction is performed for 1 h, and then the reaction is terminated. The product is granulated.

[0021] The molecular weight of the product is about 8,300, the thermal decomposition temperature thereof is about 340° C., and the infrared spectrum thereof shows a desired characteristic absorption peak.

[0022] 1.2 118 g of 1,6-hexanediol and 100 g of guanidine hydrochloride are taken and added to the reactor, and mixed evenly. pH is adjusted to 3 with hydrochloric acid under the protection of nitrogen. The resultant is heated to 150° C., reacted for 2 h, then added with 20 g of epoxypropyl acrylate. An esterification reaction is performed for 2 h, and then the reaction is terminated. The product is granulated.

[0023] The molecular weight of the product is about 11,500, the thermal decomposition temperature thereof is about 360° C., and the infrared spectrum thereof shows a desired characteristic absorption peak.

[0024] 1.3 152 g of propylene glycol and 254 g of guanidine carbonate are taken and added to the reactor and mixed evenly. pH is adjusted to 4 with hydrochloric acid under the protection of nitrogen. The resultant is heated to 130° C., reacted for 2.5 h, and then added with 25 g of methacrylic acid. An esterification reaction is performed for 1.5 h, and then the reaction is terminated. The product is granulated.

[0025] The molecular weight of the product is about 10,600, the thermal decomposition temperature is about 300° C., and the infrared spectrum shows a desired characteristic absorption peak.

Example 2 Preparation of PPR Injection Molding Material Using the Antibacterial Masterbatch of the Present Application

[0026] The specific preparation of the injection molding material is completed by the cooperative enterprise. The antibacterial masterbatch of CN1111556C is prepared according to Example 1 in the publication. The antibacterial masterbatch of the present application is prepared according to the method of Example 1. PP-R resin raw material particles, methyl phenyl silicone oil, polypropylene wax (molecular weight 12,000), and talc powder (3,000 mesh) are all conventional types purchased from Ningbo Zhenhai Best Plastics Co., Ltd. and Shanghai Yuxi Industrial Co., Ltd. An injection molding machine is a Yujiang YJ88 horizontal injection molding machine.

[0027] Material 1: every 100 parts by weight of PPR particles are added with 3 parts by weight of the antibacterial masterbatch of the present application (1.1), 0.2 part by weight of methyl phenyl silicone oil, 0.3 part by weight of polypropylene wax, and 1 part by weight of talc powder;

[0028] Material 2: every 100 parts by weight of PPR particles are added with 5 parts by weight of the antibacterial masterbatch of the present application (1.1), 0.2 part by weight of methyl phenyl silicone oil, 0.3 part by weight of polypropylene wax, and 0.7 part by weight of talc powder;

[0029] Material 3: every 100 parts by weight of PPR particles are added with 1 part by weight of the antibacterial masterbatch of the present application (1.2), 0.3 part by weight of methyl phenyl silicone oil, 0.5 part by weight of polypropylene wax, and 1 part by weight of talc powder;

[0030] Material 4: every 100 parts by weight of PPR particles are added with 3 parts by weight of the antibacterial masterbatch of CN1111556C, 0.2 part by weight of methyl phenyl silicone oil, 0.3 part by weight of polypropylene wax, and 1 part by weight of talc powder;

[0031] Material 5: no antibacterial masterbatch is added.

[0032] The specific preparation process is as follows: PPR resin raw material particles are added into a mixer, and then added with methyl phenyl silicone oil at 200 rpm; the resultant is continually mixed for 5 minutes, and then added with talc powder, polypropylene wax and optional antibacterial masterbatch of the present application/CN1111556C; the resultant is continually mixed for 5 minutes and then introduced into the injection molding machine, so as to prepare the antibacterial injection molding material (the operating temperatures of four regions of the injection molding machine are about 200° C., 210° C., 220° C., 210° C.).

TABLE-US-00001 TABLE 1 The main properties of the prepared materials Tensile Flexural Vicat softening Sample Relative strength Elongation strength point (1 kg, No. Density MPa at break % MPa 120° C./h) Material 1 0.905 36.2 430 26.7 153 Material 2 0.899 36.5 430 27.2 151 Material 3 0.907 35.2 410 25.4 153 Material 4 0.908 35.7 400 25.8 152 Material 5 0.905 36.4 410 25.2 150

[0033] In order to test the heat water resistant and detergent resistant performances of the anti-bacterial injection molding material of the present application, the materials 1 to 5 are further processed:

[0034] Material 1-1: a plastic sheet of Material 1 is added to a drum-type washing machine with the recommended amount of laundry detergent (Blue Moon, fragrance-free), washed for 50 times under a normal procedure at 40° C. (about 1 hour each time), rinsed well, and dried;

[0035] Material 2-1: a plastic sheet of Material 2 is added to the drum-type washing machine with a recommended amount of laundry detergent (Blue Moon, fragrance-free), washed for 50 times under a normal procedure at 40° C. (about 1 hour each time), rinsed well, and dried;

[0036] Material 3-1: a plastic sheet of Material 3 is added to the drum-type washing machine with a recommended amount of laundry detergent (Blue Moon, fragrance-free), washed for 50 times under a normal procedure at 40° C. (about 1 hour each time), rinsed well, and dried;

[0037] Material 4-1: a plastic sheet of Material 4 is added to the drum-type washing machine with a recommended amount of laundry detergent (Blue Moon, fragrance-free), washed for 50 times under a normal procedure at 40° C. (about 1 hour each time), rinsed well, and dried.

Example 3 Antibacterial Performance Test of Injection Molding Material

[0038] The antibacterial performance test is carried out by the Antibacterial Material Testing Center of the Technical Institute of Physics and Chemistry of the Chinese Academy of Sciences. The test is basically conducted according to the National Light Industry Standard QB/T2591-2003 of the People's Republic of China. Bacteria and Candida albicans are detected: a sterilized polyethylene thin film is spread to cover a plastic sample, eluted after 24 hours of culture, and counted for viable bacteria after 48 hours of culture (72 hours for Candida albicans) according to the method in GB 4789.2, and the antibacterial rate is calculated. Mildew detection is performed: the plastic sheet is spread on a plate medium, and sprayed with a mildew spore suspension evenly, and the coverage area of the grown mildew was tested after 28 days of culture.

[0039] Bacterial test objects include: Staphylococcus aureus ATCC 6538, and Escherichia coli ATCC 2592, and the fungus Candida Albicans ATCC 10231 is also added. Mildew test objects include: Aspergillus niger ATCC 6275, and Chaetoomium globsum ATCC 6205.

TABLE-US-00002 TABLE 1 Anti-bacterial/Candida albicans performance of injection molding materials Antibacterial rate Antibacterial rate Antibacterial rate of Staphylococcus of Escherichia of Candida Sample No. aureus (%) coli (%) albicans (%) Material 1 99.5 99.7 99.2 Material 2 99.1 99.9 99.2 Material 3 98.2 97.8 99.5 Material 4 99.6 99.0 99.3 Material 5 No antibacterial No antibacterial No antibacterial effect effect effect Material 1-1 99.2 99.5 97.7 Material 2-1 99.2 99.1 98.5 Material 3-1 98.0 96.1 99.0 Material 4-1 91.0 No antibacterial No antibacterial effect effect *Refer to the standard of QB/T2591-2003, 90% or less cannot be referred to as having an antibacterial effect.

TABLE-US-00003 TABLE 2 Anti-mildew performance of injection molding materials Mildew grade of Mildew grade of Sample No. Aspergillus niger Chaetomium globosum Material 1 Grade 0 Grade 0 Material 2 Grade 0 Grade 0 Material 3 Grade 0 Grade 0 Material 4 Grade 0 Grade 0 Material 5 No antibacterial No antibacterial effect effect Material 1-1 Grade 0 Grade 0 Material 2-1 Grade 0 Grade 0 Material 3-1 Grade 0 Grade 0 Material 4-1 Grade 1 No antibacterial effect *Coverage area of the grown mildew greater than 10% (Grade 2) cannot be referred to as having an antibacterial effect.

[0040] The above test data shows that the antibacterial performance of the antibacterial masterbatch of the present application is basically identical to that of the antibacterial masterbatch of CN1111556C (the anti-E. coli performance is slightly worse under individual conditions), but the property of water and detergent resistance is significantly better than that of the antibacterial masterbatch of CN1111556C. The anti-bacterial and anti-mildew performances have little change after high-intensity hot water and washing treatment. However, the anti-bacterial and anti-mildew performances of the antibacterial masterbatch of CN1111556C has been reduced after hot water treatment, and most of the anti-bacterial and anti-mildew performances are lost.

[0041] Other tests show that the mechanical and antibacterial properties of a plastic material containing the antibacterial masterbatch of Example 1 (1.3) are similar to those containing the antibacterial masterbatch of Example 1 (1.1 and 1.2), and meanwhile, the produced materials have similar abilities of resistance to hot water immersion and washing (complete testing is not conducted in order to save the time and cost).

[0042] The above-mentioned properties of the antibacterial masterbatch of the present application make it suitable for preparing injection molding materials, polymer materials, fabrics, non-woven fabrics, films, etc., which can maintain the antibacterial ability well after long-term use/washing.

[0043] The injection-molded material products in the above Examples are only exemplarily listed, and the antibacterial effects of other products using the antibacterial masterbatch of the present application, such as various plastic thin films, non-woven fabrics, fabrics, etc., can be reasonably expected from Examples 2 and 3, and these technical solutions are also within the scope disclosed and claimed by the present application.