CN115141432A - Antibacterial starch and preparation method thereof - Google Patents
Antibacterial starch and preparation method thereof Download PDFInfo
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Abstract
The invention discloses antibacterial starch and a preparation method thereof. According to the invention, the isothiazolinone antibacterial agent is connected to the starch molecule in a chemical bond combination mode, so that the problem of insufficient compatibility between the starch-based material and the antibacterial agent is effectively solved, and the obtained novel starch-based material has excellent antibacterial performance and good comprehensive mechanical performance; in addition, the method has less synthesis steps, avoids the purification step of intermediate products, reduces the workload and improves the efficiency.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to antibacterial starch and a preparation method thereof.
Background
Antibacterial agents are usually added to starch-based plastic products to enhance antibacterial property, but the starch-based plastic products have insufficient compatibility with most antibacterial agents, and the added antibacterial agents are easy to separate out, so that the antibacterial property, safety, durability and comprehensive mechanical property of the products are affected.
In patent CN112679895A, a plasticizer, a release agent and a bactericide are sequentially added into a polyvinyl alcohol aqueous solution at 40 ℃, the mixture is continuously stirred for 1 hour to form a uniform solution, the film solution is stood still, vacuumized to remove bubbles, scraped on a glass plate, dried and uncovered to obtain an antibacterial film, and the antibacterial film can be used for food packaging, freshness protection bags, medicine packaging and the like. The antibacterial agent comprises isothiazole, 2-bromo-2-nitro-1,3-propylene glycol, phenoxyethanol and the like.
Alotaibi (Development of a sweet potato starch-based coating and its effects on quality attributes of dried sweet potato reconstituted stored [ J ]) A Balsamite oil/Tween 80 stabilizing system and a sweet potato starch/glycerin aqueous solution were mixed together and dispersed in a homogenizer to form an emulsion, which was then applied to the surface of fresh shrimp to form a film.
In both of the above processes, the antibacterial agent is added to the product by blending, and there are the following problems: 1. the antibacterial agent is easy to separate out in the using process, so that the antibacterial property of the product is influenced; 2. the compatibility of the antibacterial agent and the base material is poor, the antibacterial agent is difficult to be uniformly mixed, and the comprehensive mechanical performance of the product is influenced.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the technical defects of the background technology and provides antibacterial starch and a preparation method thereof. According to the invention, the isothiazolinone antibacterial agent is connected to the starch molecule in a chemical bond combination manner, so that the problem of insufficient compatibility between the starch-based material and the antibacterial agent is effectively solved, and the obtained novel starch-based material has excellent antibacterial property and good comprehensive mechanical property; in addition, the method has less synthesis steps, avoids the purification step of intermediate products, reduces the workload and improves the efficiency.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in a first aspect, the present invention provides an antibacterial starch comprising a repeat unit having formula I:
in the formula I, at least one group in R1, R2 and R3 is a group structure shown in a formula II; the group structures which are not shown in formula II in R1, R2 and R3 respectively and independently represent any one of carboxyl, ester group, alkyl, hydroxyalkyl, dihydroxyalkyl, carboxyalkyl, aryl, cycloalkyl, aminoalkyl, alkylamine alkyl and hydrogen atom; in the formula I, n is an integer of 200-6000;
in the formula II, R4, R5, R6 and R7 independently represent any one of alkyl, nitro, halogen and hydrogen atoms, R8 represents a benzene ring, and m is a positive integer between 1 and 5.
Preferably, the group structures of R1, R2 and R3 which are not shown in formula II each independently represent any one of a hydrogen atom, an ester group and an alkyl group.
Preferably, R4, R5, R6, and R7 each independently represent any one of a methyl group, an ethyl group, and a hydrogen atom.
More preferably, R4, R5, R6, R7 are hydrogen atoms.
In a second aspect, the present invention provides a method for preparing the antibacterial starch, comprising the following steps:
(1) Soaking 100 parts of starch in 150-300 parts of distilled water for activation for 10-30 h, performing suction filtration, washing with a first reagent, adding the activated starch and 200-400 parts of the first reagent into a reaction vessel, uniformly mixing, dropwise adding 200-400 parts of a second reagent and 0.5-3.5 parts of a catalyst, controlling the reaction temperature at 50-80 ℃ and the reaction time at 1-4 h; filtering at room temperature, washing with distilled water, drying, pulverizing, and sieving to obtain esterified starch;
the first reagent comprises one or more of chloroacetic acid, 3-chloropropionic acid, 4-chlorobutyric acid and 5-chlorovaleric acid; the second reagent comprises one or more of chloroacetic anhydride, 3-chloropropionic anhydride, 4-chlorobutyric anhydride and 5-chlorovaleric anhydride, and the second reagent is the anhydride corresponding to the first reagent; the catalyst is any one or more of concentrated sulfuric acid, p-toluenesulfonic acid and tetrabutylammonium iodide;
(2) Mixing 70-150 parts of antibacterial agent and 160-220 parts of third reagent, adding 55-130 parts of acid-binding agent at room temperature, adding 100 parts of esterified starch prepared in the step (1), heating to 30-80 ℃, reacting for 3-7 hours, cooling to room temperature after the reaction is finished, performing rotary evaporation, washing with water, and performing vacuum drying to obtain antibacterial starch;
the antibacterial agent is any one of 1,2-benzisothiazolin-3-one, 6-chloro-1,2 benzisothiazolin-3-one and 6-nitro-1,2-benzisothiazolin-3-one; the third reagent is any one or more of chloroform, ethyl acetate, acetone, dichloromethane, dimethyl sulfoxide and methanol; the acid-binding agent is any one or more of triethylamine, 4-dimethylamino pyridine and triphenyl tin hydroxide.
Preferably, in the step (1), the starch is any one or more of corn starch, tapioca starch, potato starch, wheat starch and pea starch.
Preferably, in the step (1), the catalyst is p-toluenesulfonic acid.
Preferably, in the step (1), the reaction temperature is 65-75 ℃, and the reaction time is 2-3 h.
Preferably, in the step (2), the antibacterial agent is 1,2-benzisothiazolin-3-one.
Preferably, in the step (2), the third reagent is any one or two of acetone and ethyl acetate.
Preferably, in the step (2), the acid-binding agent is triethylamine.
Preferably, in the step (2), the antibacterial agent is 100 to 130 parts, the third reagent is 190 to 210 parts, and the acid-binding agent is 80 to 100 parts.
Preferably, in the step (2), the temperature is raised to 50-60 ℃ and the reaction is carried out for 4-6 h.
In a third aspect, the present invention provides a method for preparing a starch-based antibacterial material, comprising the following steps:
the starch-based antibacterial material comprises a fully degradable starch-based antibacterial material, partially degradable starch-based antibacterial plastic and partially degradable starch-based antibacterial rubber;
the preparation method of the starch-based antibacterial material comprises the following steps:
(1) Soaking 100 parts of starch in 150-300 parts of distilled water for activation for 10-30 h, performing suction filtration, washing with a first reagent, adding the activated starch and 200-400 parts of the first reagent into a reaction vessel, uniformly mixing, dropwise adding 200-400 parts of a second reagent and 0.5-3.5 parts of a catalyst, controlling the reaction temperature at 50-80 ℃ and the reaction time at 1-4 h; filtering at room temperature, washing with distilled water, drying, pulverizing, and sieving to obtain esterified starch;
the first reagent comprises one or more of chloroacetic acid, 3-chloropropionic acid, 4-chlorobutyric acid and 5-chlorovaleric acid; the second reagent comprises one or more of chloroacetic anhydride, 3-chloropropionic anhydride, 4-chlorobutyric anhydride and 5-chlorovaleric anhydride, and the second reagent is the anhydride corresponding to the first reagent; the catalyst is any one or more of concentrated sulfuric acid, p-toluenesulfonic acid and tetrabutylammonium iodide;
(2) Mixing 70-150 parts of antibacterial agent and 160-220 parts of third reagent, adding 55-130 parts of acid-binding agent at room temperature, adding 100 parts of esterified starch prepared in the step (1), heating to 30-80 ℃, reacting for 3-7 hours, cooling to room temperature after the reaction is finished, performing rotary evaporation, washing with water, and performing vacuum drying to obtain antibacterial starch;
the antibacterial agent is any one of 1,2-benzisothiazolin-3-one, 6-chloro-1,2 benzisothiazolin-3-one and 6-nitro-1,2-benzisothiazolin-3-one; the third reagent is any one or more of chloroform, ethyl acetate, acetone, dichloromethane, dimethyl sulfoxide and methanol; the acid-binding agent is any one or more of triethylamine, 4-dimethylaminopyridine and triphenyltin hydroxide;
(3a) When the antibacterial starch prepared in the step (2) is used for preparing the fully degradable starch-based antibacterial material, the preparation method comprises the following steps:
vacuum drying the antibacterial starch prepared in the step (2) at 30-60 ℃ for 2-5 h, blending 30-100 parts of the antibacterial starch, 0-70 parts of degradable polymer and 9-35 parts of auxiliary agent in an extruder, extruding and granulating, and molding the obtained granules by an injection molding machine or a film making machine to obtain the fully degradable starch-based antibacterial material;
(3b) When the antibacterial starch prepared in the step (2) is used for preparing the partially degradable starch-based antibacterial plastic, the preparation method comprises the following steps:
vacuum drying the antibacterial starch prepared in the step (2) at 30-60 ℃ for 2-5 h, blending 10-50 parts of the antibacterial starch, 50-90 parts of polyolefin material and 5-30 parts of auxiliary agent in an extruder, extruding and granulating, and molding the obtained granules by an injection molding machine or a film making machine to obtain the partially degradable starch-based antibacterial plastic;
(3c) When the antibacterial starch prepared in the step (2) is used for preparing the partially degradable starch-based antibacterial rubber, the preparation method comprises the following steps:
and (3) drying the antibacterial starch prepared in the step (2) at 30-60 ℃ in vacuum for 2-5 h, and putting 5-30 parts of the antibacterial starch, 70-95 parts of rubber material and 20-60 parts of auxiliary agent into a vacuum kneader or internal mixer to obtain the partially degradable starch-based antibacterial rubber.
Preferably, in the step (3 a), the degradable polymer is any one or more of polylactic acid (PLA), polybutylene terephthalate adipate (PBAT), polycaprolactone (PCL) and polyvinyl alcohol (PVA).
Preferably, in the step (3 a), the auxiliary is a plasticizing auxiliary; the plasticizing auxiliary agent is any one or more of glycerol, sucrose, mannitol, sorbitol and propylene glycol.
Preferably, in the step (3 a), the temperature of the cylinder of the extruder is 120-180 ℃, and the rotating speed of the screw is 50-500 rpm.
Preferably, in the step (3 b), the formula of the partially degradable starch-based antibacterial plastic is as follows: 10-30 parts of antibacterial starch, 70-90 parts of polyolefin material and 5-15 parts of auxiliary agent.
Preferably, in the step (3 b), the polyolefin material is any one or more of Linear Low Density Polyethylene (LLDPE), low Density Polyethylene (LDPE), polypropylene (PP), polyolefin elastomer (POE), and Cyclic Olefin Copolymer (COC).
Preferably, in the step (3 b), the auxiliary is a plasticizing auxiliary; the plasticizing auxiliary agent is any one or more of glycerol, sucrose, mannitol, sorbitol and propylene glycol.
Preferably, in the step (3 b), the temperature of the cylinder of the extruder is 120-220 ℃, more preferably 120-190 ℃ and the rotating speed of the screw is 50-500 rpm.
Preferably, in the step (3 c), the rubber is any one or more of Natural Rubber (NR), silicone rubber and Styrene Butadiene Rubber (SBR).
Preferably, in the step (3 c), the auxiliary agent is any one or more of hydroxy silicone oil, 2-mercaptobenzothiazole, 2' -dithiodibenzothiazole, zinc oxide, white carbon black and ethyl orthosilicate.
Preferably, in the step (3 c), when the antibacterial starch prepared in the step (2) is used for preparing the partially degradable starch-based antibacterial rubber, the preparation method comprises the following steps:
vacuum drying the antibacterial starch prepared in the step (2) at 30-60 ℃ for 2-5 h, putting 70 parts of raw methyl vinyl silicone rubber and 0.8 part of hydroxyl silicone oil into a vacuum kneading machine, and kneading for 10 minutes at 70 ℃; adding 30 parts of fumed silica subjected to surface treatment in 5 batches, adding the next batch of fumed silica subjected to surface treatment after each kneading, adding all the fumed silica subjected to surface treatment, kneading into a dough, introducing steam, raising the temperature in a kneader to 150 ℃, simultaneously vacuumizing to-0.05 MPa, keeping the temperature and pressure for 2 hours to prepare a silica gel dough, naturally cooling to 80 ℃ at room temperature, adding 30 parts of the antibacterial starch and 0.5 part of ethyl orthosilicate with silicon dioxide content of 40% in 5 batches, and adding the antibacterial starch and the ethyl orthosilicate in the next batch after each mixing into the dough; after mixing and agglomerating, heating to 100 ℃, and vacuumizing for 1 hour to obtain the partially degradable starch-based antibacterial rubber.
In a fourth aspect, the invention provides a starch-based antibacterial material, which is prepared by the preparation method of the starch-based antibacterial material.
The basic principle of the invention is as follows:
the synthetic route of the antibacterial starch is as follows:
in the formula III, R1 and R2 independently represent any one of carboxyl, ester group, alkyl, hydroxyalkyl, carboxyalkyl, aryl, cycloalkyl, aminoalkyl, alkylamine alkyl and hydrogen atom, and m is a positive integer between 1 and 5; in the above reaction, R1 and R2 are hydrogen atoms.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the acid-binding agent is added, so that the reaction balance between the isothiazolinone antibacterial agent and the esterified starch is moved to the direction of the product, and the conversion rate of the reaction is improved; meanwhile, compared with the prior art, the method reduces the synthesis steps, avoids the purification steps of intermediate products, reduces the workload and improves the efficiency;
(2) The isothiazolinone antibacterial agent is connected to the starch molecule through a chemical bond by using the chloroanhydride, so that the problem of poor compatibility of the antibacterial agent and the starch is solved;
(3) The invention can exert respective advantages through the chemical combination of the isothiazolinone antibacterial agent and the starch: the isothiazolinone antibacterial agent has broad spectrum, high efficiency and environmental friendliness; the starch can be completely degraded and has wide sources; the prepared antibacterial starch and the compound thereof have excellent antibacterial performance and good comprehensive mechanical performance.
Drawings
FIG. 1 is a schematic representation of the dimensions of a specimen in the tensile strength test of the present invention.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It is to be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. In addition, it should be understood that the invention is not limited to the above-described embodiments, but is capable of various modifications and changes within the scope of the invention.
Example 1
(1) Soaking 30g of corn starch in 60mL of distilled water for 24h, carrying out suction filtration, washing with chloroacetic acid, then adding activated starch and 98g of chloroacetic acid into a reaction container, dropwise adding 98g of chloroacetic anhydride and 0.6g of p-toluenesulfonic acid, and carrying out oil bath reaction for 2.5h at the temperature of 70 ℃; filtering at room temperature, washing with distilled water, drying, pulverizing, and sieving to obtain esterified starch;
(2) Mixing 19g 1, 2-benzisothiazolin-3-one and 30mL acetone, adding 13mL triethylamine at room temperature, heating to 50 ℃, slowly adding 15g of the obtained esterified starch while stirring, reacting for 6 hours, after the reaction is finished, carrying out rotary evaporation at 50 ℃, washing with water, and drying to obtain antibacterial starch;
(3) And (3) drying the prepared antibacterial starch for 2 hours in vacuum at 50 ℃, mixing the antibacterial starch with glycerol according to the weight ratio of 100:35, then feeding the mixed materials into a double screw to extrude and granulate, controlling the temperature of a cylinder of a machine to be 135 ℃, the temperature of a nose to be 130 ℃, and the rotating speed of the screw to be 200rpm, and granulating to obtain particles with uniform size and uniform texture, namely the antibacterial starch particles.
The structure of the obtained antibacterial starch is shown as follows:
example 2
(1) Soaking 30g of corn starch in 60mL of distilled water for 24h, carrying out suction filtration, washing with chloroacetic acid, then adding activated starch and 98g of chloroacetic acid into a reaction container, dropwise adding 98g of chloroacetic anhydride and 0.6g of p-toluenesulfonic acid, and carrying out oil bath reaction for 2.5h at the temperature of 70 ℃; filtering at room temperature, washing with distilled water, drying, pulverizing, and sieving to obtain esterified starch;
(2) Mixing 19g of 1, 2-benzisothiazolin-3-one and 30mL of acetone, adding 13mL of triethylamine at room temperature, heating to 50 ℃, slowly adding 15g of the obtained esterified starch while stirring, reacting for 6 hours, after the reaction is finished, carrying out rotary evaporation at 50 ℃, washing with water, and drying to obtain antibacterial starch;
(3) The prepared antibacterial starch is dried for 2 hours in vacuum at 50 ℃, the antibacterial starch, polypropylene (Yanshan petrochemical F1608) and glycerol are uniformly mixed according to the ratio of 30:70:9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a double screw cylinder is 175 ℃, the head temperature is 170 ℃, the rotating speed of the screw is 260rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/polypropylene composite product granules, are obtained through granulation.
Example 3
The rest conditions are the same as example 2, except that in the step c, the antibacterial starch, linear low density polyethylene (LLDPE 620) and glycerol are uniformly mixed according to the ratio of 30:70:9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a cylinder of the double screw is 190 ℃, the temperature of a machine head is 180 ℃, the rotating speed of the screw is 200rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/linear low density polyethylene composite product granules, are obtained through granulation.
Example 4
The rest conditions are the same as the example 2, except that in the step c, the antibacterial starch, the low-density polyethylene (TAISOX 6520G) and the glycerol are uniformly mixed according to the ratio of 30:70:9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a double screw cylinder is 190 ℃, the temperature of a machine head is 180 ℃, the rotating speed of the screw is 200rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/low-density polyethylene composite product granules, are obtained through granulation.
Example 5
The other conditions were the same as in example 2, except that in step c the antimicrobial starch was mixed with a polyolefin elastomer (Vistamaxx) TM 6202 30), glycerol was added at a ratio of 30:70:9, uniformly mixing, feeding the mixed materials into a double screw extruder to extrude and granulate, wherein the temperature of the double screw extruder barrel is 190 ℃, the temperature of a machine head is 180 ℃, and the rotating speed of the screw is 220rpm, and granulating to obtain particles with uniform size and uniform texture, namely the antibacterial starch/polyolefin elastomer composite product particles.
Example 6
The rest conditions are the same as the example 2, except that in the step c, the antibacterial starch, the cycloolefin copolymer (TOPAS 8007) and the glycerol are uniformly mixed according to the ratio of 30:70:9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a double screw cylinder is 190 ℃, the temperature of a machine head is 180 ℃, the rotating speed of the screw is 240rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/cycloolefin copolymer composite product granules, are obtained through granulation.
Example 7
The other conditions were the same as in example 2 except that in step c, the antibacterial starch was mixed with polylactic acid (A)
V554X 51) and glycerol are uniformly mixed according to the ratio of 30:70:9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a cylinder of the double screw is 175 ℃, the temperature of a machine head is 170 ℃, the rotating speed of the screw is 200rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/polylactic acid composite product granules, are obtained through granulation.
Example 8
The rest conditions are the same as the example 2, except that in the step c, the antibacterial starch, the polybutylene terephthalate-adipate (ECO-A05) and the glycerol are uniformly mixed according to the ratio of 30:70:9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a double screw cylinder is 180 ℃, the temperature of a machine head is 175 ℃, the rotating speed of the screw is 220rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/polybutylene terephthalate-adipate composite product granules, are obtained through granulation.
Example 9
The same conditions as in example 2 are followed, except that in step c the antibacterial starch is combined with polycaprolactone (Andur 6 APLM @)
442 Mixing glycerol and the raw materials uniformly according to the ratio of 30:70:9, feeding the mixed materials into a double screw to extrude and granulate, wherein the temperature of a double screw machine barrel is 135 ℃, the temperature of a machine head is 130 ℃, the rotating speed of the screw is 220rpm, and granulating to obtain particles with uniform size and uniform texture, namely the particles of the antibacterial starch/polycaprolactone composite product.
Example 10
The other conditions were the same as in example 2 except that in the step c, 70g of raw methyl vinyl silicone rubber (constant 110-1S) and 0.8g of hydroxy silicone oil were charged into a vacuum kneader and kneaded at 70 ℃ for 10 minutes; adding 30g of surface-treated fumed silica into 5 batches of the mixture, adding the next batch of surface-treated fumed silica after kneading into a cluster each time, adding all the surface-treated fumed silica into the mixture, kneading into a cluster, introducing steam, raising the temperature in a kneader to 150 ℃, simultaneously vacuumizing to-0.05 MPa, keeping the temperature and the pressure for 2 hours to prepare a silica gel cluster, naturally cooling to 80 ℃ at room temperature, adding 30g of antibacterial starch and 0.5g of ethyl orthosilicate with the silicon dioxide content of 40% into the kneader in 5 batches, and adding the next batch of antibacterial starch and ethyl orthosilicate after mixing into a cluster each time; after the mixture is agglomerated, the temperature is raised to 100 ℃ again, and the vacuum pumping is carried out for 1 hour, thus obtaining the antibacterial starch/silicon rubber composite product.
Comparative example 1
Vacuum drying corn starch at 50 deg.C for 2 hr, mixing starch and glycerol at a ratio of 100:35, feeding the mixed material into twin-screw extruder, granulating, and granulating at barrel temperature of 135 deg.C, head temperature of 130 deg.C, screw rotation speed of 200rpm to obtain uniform granules, i.e. starch product granules.
Comparative example 2
Vacuum drying corn starch at 50 ℃ for 2h, uniformly mixing starch, 1,2-benzisothiazolin-3-one and glycerol according to the ratio of 100: 3: 35, feeding the mixed material into a double screw to extrude and granulate, controlling the temperature of a machine barrel at 135 ℃, the temperature of a machine head at 130 ℃, the rotation speed of the screw at 200rpm, and granulating to obtain particles with uniform size, namely the starch/antibacterial agent composite product particles.
Comparative example 3
The rest of the conditions were the same as in example 2, except that no acid-binding agent was added in step b.
Comparative example 4
Vacuum drying corn starch at 50 ℃ for 2h, uniformly mixing starch, glycerol, 1,2-benzisothiazolin-3-one and polypropylene (Yanshan petrochemical F1608) according to a ratio of 30: 9: 3: 70, feeding the mixed material into a double screw to extrude and granulate, controlling the temperature of a machine barrel at 175 ℃, the temperature of a machine head at 170 ℃, the rotating speed of the screw at 260rpm, and granulating to obtain uniform particles, namely the starch/polypropylene/antibacterial agent composite product particles.
Effects of the embodiment
1. Test of bacteriostatic Property
The bacteriostatic performance test is carried out according to GB/T31402-2015. The resulting product pellets were pressed into 40mm by 1mm pieces using a press vulcanizer. Sucking 0.4mL of different inoculation solutions into a disposable culture dish, covering the prepared sheet on the inoculation solution, slightly pressing a film downwards to diffuse the bacteria solution to the periphery to ensure that the bacteria solution does not overflow from the edge of the film, covering a culture dish cover, placing the culture dish cover in an incubator at the temperature of 35 +/-1 ℃ and the relative humidity of not less than 90 percent for culturing for 24 hours, and performing colony recovery counting.
The results of the bacteriostatic performance test of the starch-based antibacterial materials prepared in examples 1 to 10 of the present invention and comparative examples 1 to 4 are shown in table 1.
TABLE 1 results of the bacteriostatic activity test of the starch-based antibacterial materials prepared in examples 1 to 10 of the present invention and comparative examples 1 to 4
As can be seen from Table 1:
(1) The comparison between the example 1 and the comparative example 1 shows that the antibacterial starch obtained by grafting the antibacterial agent on the starch has good antibacterial effect;
(2) Compared with the comparative example 2, the antibacterial starch has better antibacterial performance, and the original starch has poor compatibility with the antibacterial agent, so that the antibacterial agent is poor in dispersion and antibacterial effect;
(3) In the comparison between the example 2 and the comparative example 3, after the acid-binding agent is added in the reaction process, the bacteriostatic effect of the obtained product particles is higher than that of the product particles without the acid-binding agent, because hydrogen halide is generated in the reaction process, and the hydrogen halide generated in the reaction can be effectively removed by adding the acid-binding agent, so that the conversion rate of the reaction is improved;
(4) Compared with the comparative example 4, the product particles prepared by blending the raw starch, the antibacterial agent and the polypropylene have poorer antibacterial effect, which shows that the compatibility of the raw starch, the antibacterial agent and the polypropylene blending system is poor, and the antibacterial effect of the final product is influenced;
(5) Examples 2 to 10 showed good inhibitory effects on escherichia coli and staphylococcus aureus, indicating that the antibacterial starch obtained by grafting the antibacterial agent with the starch has good compatibility with PP, LLDPE, LDPE, POE, COC, PLA, PBAT, PCL, and methyl vinyl silicone rubber.
2. Tensile Strength test
Tensile Strength test part 2 of the determination of tensile Properties of plastics according to GB/T1040.2-2006: test conditions of molded and extruded plastics test conditions of "type 5A" test conditions the test was carried out and the samples were injection molded with the dimensions shown in FIG. 1, the total length being 75mm and the thickness being 2mm.
And (3) performing a tensile test on an electronic universal testing machine, wherein the tensile speed is 50mm/min, the environmental temperature is 23 ℃, the relative humidity is 50 +/-5%, and the test result is the average value of the test data of 5 sample bars.
The results of mechanical property tests of the starch-based antibacterial materials prepared in examples 1 to 9 of the present invention and comparative examples 1 to 4 are shown in table 2.
TABLE 2 mechanical Property test results of starch-based antibacterial materials prepared in examples 1 to 9 of the present invention and comparative examples 1 to 4
The mechanical property test results of the starch-based antibacterial material prepared in example 10 of the present invention are shown in table 3.
TABLE 3 mechanical Property test results of the starch-based antibacterial material obtained in example 10 of the present invention
| Performance test items | Performance test method | Performance test data |
| Hardness of | ASTM D-2240 | 59A |
| Tensile strength | ASTM D-412 | 7.3MPa |
| Elongation at break | ASTM D-412 | 362％ |
| Tear strength | ASTM D-624 | 2.1×10 4 N/m |
| Degree of plasticity | ASTM D-926 | 251 |
As can be seen from Table 2:
(1) Comparing the example 1 with the comparative example 1, the tensile strength and the elongation at break of the antibacterial starch obtained by grafting the antibacterial agent on the starch are obviously improved, which shows that the comprehensive mechanical property of the starch can be improved after the antibacterial agent is grafted on the starch;
(2) Compared with the mixture of the original starch and the antibacterial agent, the antibacterial starch obtained by grafting the antibacterial agent on the original starch has obviously improved tensile strength and elongation at break compared with the mixture of the original starch and the antibacterial agent, which shows that the problem of insufficient compatibility between the starch and the antibacterial agent is effectively solved by connecting the antibacterial agent on starch molecules, and the comprehensive mechanical property of the product is improved;
(3) Compared with the comparative example 4, the tensile strength and the elongation at break of the product obtained by blending the antibacterial starch grafted with the antibacterial agent and the polypropylene are improved compared with the blend of the raw starch and the polypropylene, because the blend system of the raw starch, the antibacterial agent and the polypropylene has poor compatibility and the antibacterial agent has poor dispersion effect, so that the mechanical property of the product is influenced;
(4) Compared with the embodiment 1, the comprehensive mechanical properties of the product particles prepared in the embodiments 2 to 9 are remarkably improved, which shows that the antibacterial starch obtained by grafting the antibacterial agent with the starch has good blending properties with PP, LLDPE, LDPE, POE, COC, PLA, PBAT and PCL, and the product obtained after blending has good comprehensive mechanical properties.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (10)
1. An antibacterial starch comprising a repeat unit having formula I:
in the formula I, at least one group in R1, R2 and R3 is a group structure shown in a formula II; the group structures shown in the non-formula II in R1, R2 and R3 respectively and independently represent any one of carboxyl, ester group, alkyl, hydroxyalkyl, dihydroxyalkyl, carboxyalkyl, aryl, cycloalkyl, aminoalkyl, alkylamine alkyl and hydrogen atom; in the formula I, n is an integer of 200-6000;
in the formula II, R4, R5, R6 and R7 independently represent any one of alkyl, nitro, halogen and hydrogen atoms, R8 represents a benzene ring, and m is a positive integer between 1 and 5.
2. The method for preparing antibacterial starch according to claim 1, comprising the steps of:
(1) Soaking and activating 100 parts of starch in 150-300 parts of distilled water for 10-30 hours, washing with a first reagent after suction filtration, adding the activated starch and 200-400 parts of the first reagent into a reaction vessel, uniformly mixing, dropwise adding 200-400 parts of a second reagent and 0.5-3.5 parts of a catalyst, controlling the reaction temperature to be 50-80 ℃ and the reaction time to be 1-4 hours; filtering at room temperature, washing with distilled water, drying, pulverizing, and sieving to obtain esterified starch;
the first reagent comprises one or more of chloroacetic acid, 3-chloropropionic acid, 4-chlorobutyric acid and 5-chlorovaleric acid; the second reagent comprises any one or more of chloroacetic anhydride, 3-chloropropionic anhydride, 4-chlorobutyric anhydride and 5-chlorovaleric anhydride, and the second reagent is the anhydride corresponding to the first reagent; the catalyst is any one or more of concentrated sulfuric acid, p-toluenesulfonic acid and tetrabutylammonium iodide;
(2) Mixing 70-150 parts of antibacterial agent and 160-220 parts of third reagent, adding 55-130 parts of acid-binding agent at room temperature, adding 100 parts of esterified starch prepared in the step (1), heating to 30-80 ℃, reacting for 3-7 hours, cooling to room temperature after the reaction is finished, performing rotary evaporation, washing with water, and performing vacuum drying to obtain antibacterial starch;
the antibacterial agent is any one of 1,2-benzisothiazolin-3-one, 6-chloro-1,2 benzisothiazolin-3-one and 6-nitro-1,2-benzisothiazolin-3-one; the third reagent is any one or more of chloroform, ethyl acetate, acetone, dichloromethane, dimethyl sulfoxide and methanol; the acid-binding agent is any one or more of triethylamine, 4-dimethylamino pyridine and triphenyl tin hydroxide.
3. The method for preparing the antibacterial starch according to claim 2, wherein in the step (1), the starch is any one or more of corn starch, tapioca starch, potato starch, wheat starch and pea starch.
4. The method for preparing antibacterial starch according to claim 2, wherein in the step (1), the catalyst is p-toluenesulfonic acid.
5. The method for preparing antibacterial starch according to claim 2, wherein in the step (1), the reaction temperature is 65-75 ℃ and the reaction time is 2-3 h.
6. The method for preparing antibacterial starch according to claim 2, wherein in the step (2), the antibacterial agent is 1,2-benzisothiazolin-3-one.
7. The method for preparing antibacterial starch according to claim 2, wherein in the step (2), the third agent is one or two of acetone and ethyl acetate.
8. The method for preparing antibacterial starch according to claim 2, wherein in the step (2), the acid-binding agent is triethylamine.
9. The method for preparing antibacterial starch according to claim 1, wherein in the step (2), the antibacterial agent is 100-130 parts, the third reagent is 190-210 parts, and the acid-binding agent is 80-100 parts.
10. The method for preparing antibacterial starch according to claim 2, wherein in the step (2), the temperature is raised to 50-60 ℃ and the reaction is carried out for 4-6 h.
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| US20080139441A1 (en) * | 2006-10-31 | 2008-06-12 | Huining Xiao | Antimicrobial and bacteriostatic-modified polymers for cellulose fibres |
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| US20080139441A1 (en) * | 2006-10-31 | 2008-06-12 | Huining Xiao | Antimicrobial and bacteriostatic-modified polymers for cellulose fibres |
| CN110129917A (en) * | 2019-05-05 | 2019-08-16 | 苏州回蓝环保科技有限公司 | A kind of antibacterial starch base melt spinning resin and its application |
| US20220073706A1 (en) * | 2020-12-09 | 2022-03-10 | Jiangnan University | Self-reinforced Starch-based Multifunctional Materials and Processing Method thereof |
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