CN103012606A - Modified starch for grafting guazatine oligomer as well as preparation method and application of modified starch - Google Patents
Modified starch for grafting guazatine oligomer as well as preparation method and application of modified starch Download PDFInfo
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Abstract
The invention provides modified starch for grafting guazatine oligomer as well as a preparation method and an application of the modified starch. The modified starch for grafting guazatine oligomer is obtained by grafting the guazatine oligomer to a starch macromolecular chain by a chemical bonding method, and has a chemical structural formula as shown in the specification, wherein x equals to 2-10, m equals to 2-100, Y is one of Cl<-1>, Br<-1>, NO3<-1>, HCO3<-1> or H2PO4<-1>, and R is a molecular structure obtained by reacting coupling agent, starch and the guazatine. Compared with the prior art, the modified starch provided by the invention effectively avoids the problems that other products are polluted due to antibacterial agent loss, and the antibacterial effect is non-resistant, and relieves the potential hazard of the leaked antibacterial agent to the body health. The modified starch provided by the invention is co-blended with the corresponding paper pump, textile fabric, binder and the like in a proportion of (0.5-10.0wt%), can be used for preparing the products which have high-efficiency broad-spectrum antibacterial anti-mold property and are safe and harmless to the body health, such as papers, textiles and binders.
Description
Technical field
The present invention relates to a kind of preparation method and application of treated starch of grafting Guanoctine oligopolymer, belong to starch conversion and processed and applied field.
Background technology
Starch is the macromole that is polymerized take glucose molecule as structural unit, be only second to cellulosic second largest natural high molecular substance as output, starch has the advantages such as aboundresources, wide material sources, cheap, environmental protection, except food industries, also have a wide range of applications in fields such as papermaking, weaving, sizing agent, medicine, coating, plastics.Along with the raising of society, the reach of science and people's living standard, people are more and more higher to the requirement of health and health, and the living environment of environment protection health becomes human pursuing a goal day by day.Give in the daily productive life and the various materials of human close contact and goods thereof the anti-microbial property with high-efficiency broad spectrum, become an important directions of current Materials.
Anti-biotic material is that a class possesses antibacterial and type material sterilizing function, makes by adding one or more specific antiseptic-germicides.US Patent No. 6627785 discloses the antibacterial modified starch of a kind of metal ion (such as silver, copper), is used for wound dressings; Chinese patent CN 102552963, CN 102698313 and CN102132709 disclose respectively the preparation method of the antibacterial modified starch that contains inorganic silver salt; Chinese patent CN102182111 disclose a kind of with succinylation chitosan and Sumstar 190 blend as sizing agent, not only can improve paper strength, and improve the germ resistance of paper.Yet, present starch is antibacterial modified to be to adopt the mode with antiseptic-germicide and starch simple blend to prepare mostly, exist antiseptic-germicide and resin compatible poor, disperse inhomogeneous, thereby use difficulty for the processing of material, other this class antiseptic-germicide, particularly use maximum silver-based inorganic salt, the silver ions that its blend is entered easily oozes out, useful life short, and these shortcomings have limited the development of such material to a great extent.
Polymeric guanidine (comprising single guanidine and Guanoctine) is to have one of bioactive polymkeric substance, guanidine derivative is the widely used environment sterilant such as food factory, pharmaceutical factory, hospital, and application arranged also in makeup, textiles, it has the anti-microbial property of high-efficiency broad spectrum, can suppress, kill the microorganism that comprises bacterium, mould, virus etc., nontoxic to human-body safety simultaneously.
For example, the scavenging agent that Japanese Patent JP 05209197, JP05209196 use as water treatment with the two Guanidinium hydrochlorides of polyhexamethylene, the characteristics of this scavenging agent are good water-soluble and Environmental Safety highly; US Patent No. 5356555, US 5096607 usefulness polyoxyethylene diamine biguanides are used for the sterilization of the scavenging solution of contact lens or skin clean articles for washing etc., and as seen this type of antiseptic-germicide is good to the safety performance of human body.
Domestic also have many about guanidine salt derivative as the patent of antimicrobial material, for example CN 1671439 discloses a kind of toothpaste, is effective ingredient with bis-biguanide antibacterial agent, for antiplaque and gingivitis, and can reduce tooth staining.Similarly relevant report also has a lot.
In sum, we can see that the polymkeric substance that contains the guanidine structure is the effective antiseptic-germicide of a class, have good antimicrobial properties and to the security of human body.But because guanidinesalt and derivative thereof are the compounds of strong polarity, it is good water-solublely to have limited it as the antibacterial modified dose of application at aspects such as plastics, fiber, rubber, coating.Chinese patent ZL 02111048.4, ZL 03141772.8 discloses the guanidinesalt oligopolymer has been bonded on the macromolecular chains such as polyolefine and nylon, polyester, preparation has the method for high-efficiency broad spectrum antimicrobial properties material, thereby has solved the guanidinesalt antiseptic-germicide and the problems such as the polymeric matrix consistency is poor, easily ooze out, the antibacterial effect difficulty is lasting.
Method for adopting chemical bonding is grafted to the guanidinesalt oligopolymer on the starch polymer chain, prepares antibacterial modified starch, and contriver's research formerly had report (Cellulose, 2008,15:609-618; Cellulose, 2008,15:619-629).But above-mentioned research is take single guanidinesalt oligopolymer as the basis, and for the higher Guanoctine oligopolymer of lower, the antibiotic effective component content of relative cost, the application in starch conversion there is no report.
Summary of the invention
Purpose of the present invention, the defective that exists in order to overcome above-mentioned prior art exactly provides treated starch of a kind of Guanoctine oligopolymer and its preparation method and application.
Purpose of the present invention can be achieved through the following technical solutions: a kind of treated starch of grafting Guanoctine oligopolymer, and its chemical structural formula is as follows:
Wherein: x=2～10, m=2～100, Y is Cl
-, Br
-, NO
3 -, HCO
3 -Or H
2PO
4 -In a kind of, R is coupling agent and starch and the reacted molecular structure of Guanoctine oligopolymer.
The preparation method of the treated starch of above-mentioned grafting Guanoctine oligopolymer is that the material that adopts following component and weight percent content is raw material:
The starch of 50%-98%;
The Guanoctine oligopolymer of 2%-50%;
The coupling agent of 0.5%-15%;
The alkali of 0.01%-5.0%;
Above-mentioned coupling agent and the weight percent content of alkali are all take the total amount of starch and Guanoctine oligopolymer as benchmark;
Concrete preparation method is as follows: starch is added to the water, is warming up to 85-95 ℃, gelatinization 10-30 minute, obtain the amidin of 10-20wt%; Then be cooled to 50-70 ℃, add alkali, regulate the pH value to 10-12, add again an amount of coupling agent, stirred 10-60 minute, and added again the Guanoctine oligopolymer, react after 30-240 minute, add coupling agent, reacted again 1-2 hour, finally obtain the solution of the treated starch of grafting Guanoctine oligopolymer; This solution can directly be used, and also can through the dehydration pulverization process, obtain the treated starch of solid grafting Guanoctine oligopolymer.
The preparation method of the treated starch of above-mentioned grafting Guanoctine oligopolymer, wherein, the molecular weight of described Guanoctine oligopolymer is between 500-20000; This Guanoctine oligopolymer is to prepare by melt polycondensation reaction by amine salt and the Dyhard RU 100 that generates behind polyamine and the inorganic acid reaction; Concrete steps are as follows: mineral acid is added dropwise in the liquid polyamine, until the pH value of system reaches 2-3, underpressure distillation; remove the moisture in the system; obtain amine salt, then this amine salt is mixed with the ratio of mol ratio 1: 1-1.5 with Dyhard RU 100, add in the reactor; under nitrogen protection, be heated to 90-150 ℃; reacted 0.5-8 hour, and then be warming up to 160-250 ℃, after 2-10 hour; finish reaction, obtain the Guanoctine oligopolymer.
The preparation method of the treated starch of above-mentioned grafting Guanoctine oligopolymer, wherein, described polyamine is selected from quadrol, Putriscine, 1, a kind of in 6-hexanediamine, 1，10-diaminodecane, hexamethylenetetramine, diethylenetriamine, the triethylene tetramine; Described mineral acid is selected from a kind of in carbonic acid, hydrochloric acid, Hydrogen bromide, nitric acid, the phosphoric acid.
The preparation method of the treated starch of above-mentioned grafting Guanoctine oligopolymer, wherein, described coupling agent is selected from one or more in epoxy chloropropane, ethylene glycol diglycidylether, glutaraldehyde, Glycerin triglycidyl ether or the glycerin triglycidyl ether.
The application of the treated starch of above-mentioned grafting Guanoctine oligopolymer is, as anti-bacterium mildewproof additive.
The application of the treated starch of above-mentioned grafting Guanoctine oligopolymer is, treated starch and paper pulp, synthon or natural fiber or binding agent blend with the grafting Guanoctine oligopolymer of 0.5-10.0%wt, prepare and have high-efficiency broad spectrum antibacterial and mouldproof performance, simultaneously to the safe and harmless paper of HUMAN HEALTH, textiles or binding agent.
Synthesizing of above-mentioned Guanoctine oligopolymer, reaction formula is as follows:
The present invention adopts the Guanoctine oligopolymer as antibacterial group, analyze from molecular structure, guanidine radicals is main antimicrobial group, Guanoctine has the high effective groups density of glue, and is remarkable to comprising the harmful microbe restraining effect such as Gram-negative bacteria (take intestinal bacteria as representative), gram-positive microorganism (take streptococcus aureus as representative), mould.Therefore, using the Guanoctine oligopolymer, is highly significant for improving the goods antimicrobial properties, widening its Application Areas.
The present invention adopts the method for chemical bonding, the Guanoctine oligomer chain is received on the macromolecular chain of starch, with existing with silver be or other organic antibacterial agent and starch blending, the technology of preparation anti-biotic material is compared, not only effectively avoided other goods of pollution, the non-resistant problem of antibacterial effect that run off and to cause because of antiseptic-germicide, the potential hazard that from having eliminated the antiseptic-germicide that oozes out HUMAN HEALTH has been caused especially; Compare with single guanidinesalt oligopolymer, the synthetic route of Guanoctine oligopolymer is simple economy more, and the density of antibiotic effective efficiency group is higher.
Therefore, the antibacterial modified starch of the present invention's preparation has the antibacterial and mouldproof performance of high-efficiency broad spectrum, and is safe and harmless to HUMAN HEALTH simultaneously, can be applicable to the antibacterial modified of the goods such as paper, textiles, binding agent.When antibacterial modified starch was used for antibiotic paper, it can be used as the wet end functional additive, thereby can utilize existing paper making equipment to carry out suitability for industrialized production.When the content of Guanoctine oligopolymer in the goods surpasses 0.3-1.0wt%, material has excellent inhibition killing action to common are harmful microorganism, to the bacteriostasis rate of intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, pneumococcus, Candida albicans etc. greater than 99%, and to comprising the fungi of black-koji mould, rhizopus niger, Aspergillus flavus etc., the mildew-resistant grade reaches the 0-1 level.In papermaking was used, antibacterial modified starch can improve the wet of paper, dry strength simultaneously as the wet end functional additive.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Adopt in embodiments of the present invention following testing method:
Anti-microbial property detects antibiotic plastic, with reference to GB15979-1995
Antibacterial fiber is with reference to FZ/T01021-1992
Fungicidal properties detects with reference to GB/T2423.16-1999
Below be the Preparation Example of several Guanoctine oligopolymers:
Embodiment 1
The preparation of poly-butanediamine carbonic acid Guanoctine:
Get 1，10-diaminodecane 88g, be made into the 40%wt aqueous solution, join in the 1000ml three-necked bottle, pass into carbonic acid gas, reach 3 to the pH value, moisture is removed in then underpressure distillation.Under nitrogen protection, add the 84g Dyhard RU 100, stir and be warming up to 90 ℃, reacted 40 minutes, then be warming up to 125 ℃ of reactions 6 hours, stopped heating; After the cooling, obtain butanediamine carbonic acid Guanoctine oligopolymer.Its molecular weight is about 800, and product has efficient anti-microbial property, and its minimum inhibitory concentration is 5.5ppm.
Embodiment 2
The preparation of poly-triethylene tetramine hydrochloric acid Guanoctine:
Get triethylene tetramine 73g, join in the 250ml three-necked bottle, drip 35.5% hydrochloric acid to pH=2, then moisture is removed in underpressure distillation; In system, add again Dyhard RU 100 43g, under nitrogen protection, stir and be warming up to 110 ℃, reacted 2 hours, then be warming up to 180 ℃ of reactions 8 hours, stopped heating; After the cooling, obtain triethylene tetramine hydrochloric acid Guanoctine oligopolymer.Its molecular weight is about 2500, and product has efficient anti-microbial property, and its minimum inhibitory concentration is 1.5ppm.
Embodiment 3
The preparation of poly-hexanediamine phosphate Guanoctine salt:
Get hexanediamine 116g, join in the 500ml three-necked bottle, drip 20% phosphoric acid to pH=2.5, then moisture is removed in underpressure distillation; In system, add again Dyhard RU 100 85g, under nitrogen protection, stir and be warming up to 150 ℃, reacted 2 hours, then be warming up to 200 ℃ of reactions 6 hours, stopped heating; After the cooling, obtain hexanediamine phosphate Guanoctine salt oligopolymer.Its molecular weight is about 1500, and product has efficient anti-microbial property, and its minimum inhibitory concentration is 9.0ppm.
Below be the Preparation Example of the treated starch of several grafting Guanoctine oligopolymers:
Embodiment 4
20g starch is joined in the 80g water, be warming up to 95 ℃, gelatinization obtained the amidin of 20wt% about 15 minutes.Then be cooled to 50 ℃, add an amount of NaOH, regulate pH value to 12, add the 1.0g glutaraldehyde, stirred about 10 minutes, add again the butanediamine carbonic acid Guanoctine oligopolymer of 8g such as example 1 method preparation, react after 100 minutes, add the 0.5g glutaraldehyde, reacted again 1 hour, solution obtains antibacterial modified starch through the dehydration pulverization process, and its antibiotic effective component content is 26.8wt%.
Embodiment 5
20g starch is joined in the 80g water, be warming up to 90 ℃, gelatinization obtained the amidin of 20wt% about 20 minutes.Then be cooled to 60 ℃, add an amount of NH
4OH, regulate pH value to 10, add 5.5g Glycerin triglycidyl ether, stirred about 20 minutes, add again the triethylene tetramine hydrochloric acid Guanoctine oligopolymer of 20g such as example 2 methods preparation, react after 150 minutes, add 1.5g Glycerin triglycidyl ether, reacted 2 hours again, solution is through the dehydration pulverization process, obtain antibacterial modified starch, its antibiotic effective component content is 42.5wt%.
Embodiment 6
20g starch is joined in the 80g water, be warming up to 85 ℃, gelatinization obtained the amidin of 20wt% about 30 minutes.Then be cooled to 60 ℃, add an amount of KOH, regulate pH value to 11, add the 0.5g epoxy chloropropane, stirred about 10 minutes, the hexanediamine phosphate Guanoctine salt oligopolymer that adds again the preparation of 2g such as example 3 methods, react after 60 minutes, add the 0.5g epoxy chloropropane, reacted again 1 hour, obtain the solution that concentration is 22.3wt%, wherein antibiotic effective component content is 1.9wt%.
Below be the effect embodiment of the treated starch of several grafting Guanoctine oligopolymers:
Embodiment 7
Adopt the Guanoctine treated starch of preparation in the example 4, concentration with 5wt% adds in the dipping stoste of hygenic towelette, and the sanitas in the former liquid formula and antiseptic-germicide (phenoxyethyl alcohol, methyl p-hydroxybenzoate, Tegosept E etc.) just can add stimulation and the harm that can avoid like this this class chemical substance that human body skin is brought.Terylene/the non-woven viscose fabric of the mass ratio 50/50 of then such stoste dipping being produced by the water acupuncture manipulation, obtaining can antibacterial and mouldproof, the permanent preservation and non-irritating hygenic towelette.
Embodiment 8
Adopt the Guanoctine treated starch aqueous solution of preparation in the example 6, have all kinds of paper product of antibacterial and antimildew function by the super paper technique preparation of routine.Detailed process is exemplified below: compound concentration is 0.5% paper making pulp, through paper-making process such as dehydration, dryings, obtains having the sheet paper products of antibacterial and mouldproof performance.
It is as shown in table 1 that above-described embodiment 7 and 8 obtains the antibacterial and mouldproof performance of goods:
Table 1
Annotate: what fungus-proof test was tested is the mixed strains that comprises aspergillus niger, terreus, scopulariopsis brevicaulis, multi-trunk natalensis, Paecilomyces varioti, reddish brown mould, penicillium funiculosum, viride etc.
Claims (7)
1. the treated starch of a grafting Guanoctine oligopolymer, its chemical structural formula is as follows:
Wherein: x=2～10, m=2～100, Y is Cl
-, Br
-, NO
3 -, HCO
3 -Or H
2PO
4 -In a kind of, R is coupling agent and starch and the reacted molecular structure of Guanoctine oligopolymer.
2. the preparation method of the treated starch of a grafting Guanoctine oligopolymer is characterized in that, it is raw material that the method adopts the material of following component and weight percent content:
The starch of 50%-98%;
The Guanoctine oligopolymer of 2%-50%;
The coupling agent of 0.5%-15%;
The alkali of 0.01%-5.0%;
Above-mentioned coupling agent and the weight percent content of alkali are all take the total amount of starch and Guanoctine oligopolymer as benchmark;
Concrete preparation method is as follows: starch is added to the water, is warming up to 85-95 ℃, gelatinization 10-30 minute, obtain the amidin of 10-20wt%; Then be cooled to 50-70 ℃, add alkali, regulate the pH value to 10-12, add again an amount of coupling agent, stirred 10-60 minute, and added again the Guanoctine oligopolymer, react after 30-240 minute, add coupling agent, reacted again 1-2 hour, finally obtain the solution of the treated starch of grafting Guanoctine oligopolymer; This solution can directly be used, and also can through the dehydration pulverization process, obtain the treated starch of solid grafting Guanoctine oligopolymer.
3. the preparation method of the treated starch of grafting Guanoctine oligopolymer according to claim 2 is characterized in that, the molecular weight of described Guanoctine oligopolymer is between 500-20000; This Guanoctine oligopolymer is to prepare by melt polycondensation reaction by amine salt and the Dyhard RU 100 that generates behind polyamine and the inorganic acid reaction; Concrete steps are as follows: mineral acid is added dropwise in the liquid polyamine, until the pH value of system reaches 2-3, underpressure distillation; remove the moisture in the system; obtain amine salt, then this amine salt is mixed with the ratio of mol ratio 1: 1-1.5 with Dyhard RU 100, add in the reactor; under nitrogen protection, be heated to 90-150 ℃; reacted 0.5-8 hour, and then be warming up to 160-250 ℃, after 2-10 hour; finish reaction, obtain the Guanoctine oligopolymer.
4. the preparation method of the treated starch of grafting Guanoctine oligopolymer according to claim 3, it is characterized in that described polyamine is selected from quadrol, Putriscine, 1, a kind of in 6-hexanediamine, 1，10-diaminodecane, hexamethylenetetramine, diethylenetriamine, the triethylene tetramine; Described mineral acid is selected from a kind of in carbonic acid, hydrochloric acid, Hydrogen bromide, nitric acid, the phosphoric acid.
5. the preparation method of the treated starch of grafting Guanoctine oligopolymer according to claim 2, it is characterized in that described coupling agent is selected from one or more in epoxy chloropropane, ethylene glycol diglycidylether, glutaraldehyde, Glycerin triglycidyl ether or the glycerin triglycidyl ether.
6. the application of the treated starch of a grafting Guanoctine oligopolymer as claimed in claim 1 is characterized in that, as anti-bacterium mildewproof additive.
7. the application of the treated starch of grafting Guanoctine oligopolymer as claimed in claim 6, it is characterized in that, treated starch and paper pulp, synthon or natural fiber or binding agent blend with the grafting Guanoctine oligopolymer of 0.5-10.0%wt, prepare and have high-efficiency broad spectrum antibacterial and mouldproof performance, simultaneously to the safe and harmless paper of HUMAN HEALTH, textiles or binding agent.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724441A (en) * | 2014-01-09 | 2014-04-16 | 福建农林大学 | Guanidine salt grafted starch multifunctional papermaking additive and preparation method thereof |
| WO2018011667A1 (en) * | 2016-07-11 | 2018-01-18 | Stora Enso Oyj | Process for creating a foam utilizing an antimicrobial starch within a process for manufacturing a paper or board product |
| CN110670353A (en) * | 2019-11-12 | 2020-01-10 | 安徽大学 | Preparation method of simple long-acting antibacterial fabric coating |
| CN110818870A (en) * | 2018-08-14 | 2020-02-21 | 上海富元塑胶科技有限公司 | Oligomer auxiliary agent and preparation method and application thereof |
| CN111870734A (en) * | 2020-08-19 | 2020-11-03 | 山东东贝医药科技有限公司 | Preparation method of medical antibacterial healing-promoting hydrogel dressing |
| CN113999433A (en) * | 2021-11-24 | 2022-02-01 | 湖北人福药用辅料股份有限公司 | Modified starch and preparation method and application thereof |
| CN114342950A (en) * | 2021-12-31 | 2022-04-15 | 上海明涌新材料有限公司 | Macromolecular guanidine salt disinfectant and preparation method and preparation thereof |
| CN114436380A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Lignin-based flocculant and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724441A (en) * | 2014-01-09 | 2014-04-16 | 福建农林大学 | Guanidine salt grafted starch multifunctional papermaking additive and preparation method thereof |
| WO2018011667A1 (en) * | 2016-07-11 | 2018-01-18 | Stora Enso Oyj | Process for creating a foam utilizing an antimicrobial starch within a process for manufacturing a paper or board product |
| US11001969B2 (en) | 2016-07-11 | 2021-05-11 | Stora Enso Oyj | Process for creating a foam utilizing an antimicrobial starch within a process for manufacturing a paper or board product |
| CN110818870A (en) * | 2018-08-14 | 2020-02-21 | 上海富元塑胶科技有限公司 | Oligomer auxiliary agent and preparation method and application thereof |
| CN110818870B (en) * | 2018-08-14 | 2021-12-07 | 上海富元塑胶科技有限公司 | Oligomer auxiliary agent and preparation method and application thereof |
| CN110670353A (en) * | 2019-11-12 | 2020-01-10 | 安徽大学 | Preparation method of simple long-acting antibacterial fabric coating |
| CN111870734A (en) * | 2020-08-19 | 2020-11-03 | 山东东贝医药科技有限公司 | Preparation method of medical antibacterial healing-promoting hydrogel dressing |
| CN114436380A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Lignin-based flocculant and preparation method thereof |
| CN114436380B (en) * | 2020-10-31 | 2023-07-28 | 中国石油化工股份有限公司 | Lignin-based flocculant and preparation method thereof |
| CN113999433A (en) * | 2021-11-24 | 2022-02-01 | 湖北人福药用辅料股份有限公司 | Modified starch and preparation method and application thereof |
| CN114342950A (en) * | 2021-12-31 | 2022-04-15 | 上海明涌新材料有限公司 | Macromolecular guanidine salt disinfectant and preparation method and preparation thereof |
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Application publication date: 20130403 |