CN109810221A - A kind of preparation method and application of betaines antibacterial agent - Google Patents
A kind of preparation method and application of betaines antibacterial agent Download PDFInfo
- Publication number
- CN109810221A CN109810221A CN201910095741.5A CN201910095741A CN109810221A CN 109810221 A CN109810221 A CN 109810221A CN 201910095741 A CN201910095741 A CN 201910095741A CN 109810221 A CN109810221 A CN 109810221A
- Authority
- CN
- China
- Prior art keywords
- polymer
- antibacterial
- fabric
- antibacterial agent
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of preparation method and applications of betaines antibacterial agent, belong to field of textiles.The present invention obtains a kind of antibacterial polymer using unsaturated tertiary amine monomers, acrylic ester monomer, monomer containing epoxy group and the monomer polymerization containing sulfonic acid group or carboxylic acid group.According to different fabrics, different purpose selective polymerization monomers, openr thinking is provided to the synthesis of antibacterial agent, and the ratio of different polymerized monomers can be regulated and controled according to the performance requirement of fabric after final arrange, the antibiotic rate of fabric is high after arrangement, washing fastness is good, washing still just has preferable antibacterial effect for 50 times, and physical mechanical property, strongly without significantly sacrificing.Antibacterial agent application range of the present invention is wider, non-hazardous to environment；And no cytotoxicity, it is non-stimulated to skin；It has no drug resistance, is suitble to be widely used.
Description
Technical field
The present invention relates to a kind of preparation method and applications of betaines antibacterial agent, belong to field of textiles.
Background technique
With the development of people's modern times environmental protection concept, textile made by natural fiber is comfortable and easy to wear with its, it is renewable,
It is readily biodegradable etc. and to be liked.However, due to containing on natural fiber macromolecular structure chain, there are many amino (- NH2), carboxyl
The hydrophilic radicals such as (- COOH), hydroxyl (- OH), easily absorb human body secretion, thus for microorganism growth and breeding provide it is good
Good environment.The microorganism bred on the fabric can not only reduce textile quality and physical property, and being more likely to can be strong to human body
Health generates harm.Therefore, antibiotic finish is carried out to fabric, with the ability for inhibiting or killing the microorganisms such as bacterium, it appears
It is particularly important.
Currently, the antibacterial finishing agent for fabric can be divided into dissolution type (metal class, antibiotic according to stripping property difference
Deng) and non-dissolving type (quaternary ammonium salt, chitosan, polymerizing cationically, antibacterial peptide etc.) two major classes.Dissolution type (metal class, antibiotic
Deng) antibiotic fabric by its slow release antibacterial agent reach into ambient enviroment it is antibacterial or sterilization purpose.However as using
The increase residual antibacterial agent on the fabric of washing times more comes fewer, and the antibacterial activity of fabric gradually decreases and final funeral completely
It loses, a small amount of remaining antibiotic is not enough to kill bacterium, can cause the formation of drug resistance and biological mocromembrane instead.And nanometer Ag+
There are still larger disputes in terms of cytotoxicity and genetoxic.
Non-dissolving type quaternary ammonium salt antibacterial agent high water solubility, easily elution directly and the combination of fiber and insecure need pair
Fabric is pre-processed, so that fabric feeling is deteriorated and yellowing discoloration, and quaternary ammonium salt antibacterial agent is it is verified that can make bacterium
Drug resistance is generated, antibacterial effect durability is not strong；Antibacterial peptide can interfere with the divalent cation-exchanged on cell membrane, to destroy
Cytoplasma membrane reaches bactericidal effect.CN201510595396.3 handles wool fabric with antibacterial peptide, makes antibacterial peptide using glutaraldehyde
In the surface-crosslinked of wool fabric, to obtain antibacterial wool fabric.But waste water produced during the preparation process is to environment nocuousness, to water
Body generates pollution, and influence of the antibacterial peptide vulnerable to enzymatic hydrolysis, and to salt density value, stability is poor.
For glycine betaine as a kind of zwitterionic compound, hydrophilicity is good, the equally distributed yin with equimolar quantity
Ion and cation group can resist bacterial adhesion, and prevent the formation of biological mycoderm, and bacterium is inhibited to increase breeding.Meanwhile
It also has stronger thermal stability, chemical stability, biocompatibility and no cytotoxicity, is a kind of more satisfactoryization
Antibacterial agent.CN201010116533.8 is prepared for a kind of organosilicon sulfobetaines antibacterial agent, but type siloxane glycine betaine
Poor storage stability is easy to self-solidifying, and reactivity is poor, forms Covalent bonding together at high temperature with fabric, has damaged fabric
Physical mechanical property.CN201580001138.6 develops the azochlorosulfonate propyl lycine antibacterial agent of terminal isocyanate, but it is made
Standby complex process, cost of material are high, it is difficult to industrial application.Meanwhile above-mentioned prepared betaines antibacterial agent is all short chain
The glycine betaine of small molecule, can not penetrate bacterium film layer, and willful murder bacterium is ineffective.CN201711472560.7 by glycine betaine monomer with
Maleic anhydride is polymerize, and obtains the betaine polymer of macromolecular, then the carboxylic acid group generated by maleic anhydride hydrolysis with
Hydroxyl reaction on cellulose fibre molecule is grafted on cotton fabric in a manner of covalent bond.Gained betaine polymer antibacterial agent
The cell membrane of particle-bound bacteria is penetrated, so that cellular content be made to flow out, kills bacterium, good anti-bacterial effect.But due to the glycine betaine
There is extremely more acidic carboxypolymers, the fabric yellowing after arrangement is serious, and the Physical Mechanical energy loss of fabric on polymer macromolecule
Hurt larger, causes fabric strength decline serious, be not able to satisfy and take requirement, practical value is little.So how to overcome anti-at present
The shortcomings that microbial inoculum exists as previously discussed, a new class of curable, long-term effect of developmental research do not damage fabric property, to human body
The antibacterial agent for not generating toxic side effect becomes the urgent need of fabric functionalization development.
Summary of the invention
The shortcomings that in order to overcome current antibacterial agent to exist as previously discussed, the present invention construct a kind of with betaine structure
Macromolecule polyalcohol antibacterial agent.The outer membrane of microbial cell is semi-permeable membrane, is made of fat deposit and protein, is for inside and outside two layers
Protein, middle layer are fat, therefore to permeate microbial cell kill bacterium and need antibacterial agent while having amphipathic property.Cause
This ideal textile antibacterial agent should be that one kind is provided simultaneously with hydrophilic radical and hydrophobic grouping, and can be straight with active group on fabric
Connect the macromolecular antibacterial agent of bonding.The present invention response type functional group in a manner of covalent bond securely with fabric macromolecular chain
Bonding introduces unsaturated tertiary amine monomers, acrylate monomer, crosslinkable monomers and prepares betaines antibacterial agent, and it is lasting to obtain
Antibacterial activity.
The first purpose of this invention is to provide a kind of antibacterial polymer, and the polymer is to utilize unsaturated tertiary amine list
Body A, acrylic ester monomer B, the C of monomer containing epoxy group and the compound E containing sulfonic acid group or carboxylic acid group are raw material preparation
It obtains.
In one embodiment of the invention, the unsaturated tertiary amine monomers and the molar ratio of acrylic ester monomer are
1:9~9:1.
In one embodiment of the invention, the additive amount of the monomer containing epoxy group account for unsaturated tertiary amine monomers,
The 1-20% of acrylic ester monomer and the monomer gross mass containing epoxy group.
In one embodiment of the invention, the unsaturation tertiary amine monomers A includes N, N- Diethyl Allylnime, N,
One of N- dimethylallylamine, allylamine, N- methyl-prop enamine, dimethylaminoethyl acrylate are a variety of.
In one embodiment of the invention, the acrylic ester monomer B includes that butyl acrylate, acrylic acid are different pungent
One of ester, ethyl acrylate or hydroxy-ethyl acrylate are a variety of.
In one embodiment of the invention, the C of monomer containing epoxy group includes glycidyl methacrylate
Or allyl glycidyl ether.
In one embodiment of the invention, the compound E containing sulfonic acid group or carboxylic acid group is containing sulfonic group
The saturated hydrocarbons compound of group or carboxylic acid group.
In one embodiment of the invention, the compound E includes X- (CH2)vCHCO2 -、X-(CH2)wCHSO3 -In
One or two；Wherein v, w are the positive integer more than or equal to 1, X Cl, Br or I.
In one embodiment of the invention, the preparation method of the antibacterial polymer includes:
(1) intermediate polymerization is prepared using unsaturation tertiary amine monomers A and acrylic ester monomer B, the C of monomer containing epoxy group
Object D；
(2) midbody polymer D is reacted to obtain the antibacterial of betaines with the monomer E containing sulfonic acid group or carboxylic acid group
Polymer F.
In one embodiment of the invention, the step (1) specifically includes: by unsaturated tertiary amine monomers A and propylene
Esters of gallic acid monomer B, the C of monomer containing epoxy group mixing, in N2In environment, temperature be 20-80 DEG C under conditions of, in the work of initiator
Under, 4-24h is reacted to get midbody polymer D.
In one embodiment of the invention, the initiator includes peroxide type initiators, azo-initiator
One or both of.
In one embodiment of the invention, the peroxide type initiators include benzoyl peroxide, peroxidating
One of dialkyl group, peroxidating two acyl are a variety of.
In one embodiment of the invention, the azo-initiator includes azo-bis-isobutyl cyanide, azo two different heptan
One or both of nitrile.
In one embodiment of the invention, contain uncle in compound E and midbody polymer D in the step (2)
The molar ratio of amine monomers is 1:(1~2).
In one embodiment of the invention, the step (2) specifically includes: midbody polymer D and monomer E are mixed
Close, under a nitrogen, temperature be 50-80 DEG C at environment in stir 2-10h hours, obtain the antibacterial polymer F of betaines；
In one embodiment of the invention, the synthetic route of the method is as follows:
Wherein, m=1~1000, n=1~1000, q=1~1000；
R1For-H ,-CH3Or CH2CH3；R2For-H ,-CH3Or CH2CH3；R3For-(CH2)p, or-COO- (CH2)k,
Middle p is any one integer in 1-18, and k is any one integer in 0-18；R4For-(CH2)lCH3, or-(CH2)r- OH,
Middle l, r are respectively any one integer in 1-6；R5For-H, or-CH3；R6ForOr-CH2-；R7For-H, or-CH3；R8
For-CH2, or-CH2CH3；R9For-(CH2)t, wherein t is the positive integer more than or equal to 2；
X- is-COO- ,-SO3 -。
A second object of the present invention is to provide a kind of antibacterial polymer, the polymer is polymer shown in formula (I),
Wherein, m=1~1000, n=1~1000, q=1~1000；
R1For-H ,-CH3Or CH2CH3；R2For-H ,-CH3Or CH2CH3；R3For-(CH2)p, or-COO- (CH2)k,
Middle p is any one integer in 1-18, and k is any one integer in 0-18；R4For-(CH2)lCH3, or-(CH2)r- OH,
Middle l, r are respectively any one integer in 1-6；R5For-H, or-CH3；R6ForOr-CH2-；R7For-H, or-CH3；R8
For-CH2, or-CH2CH3；R9For-(CH2)t, wherein t is the positive integer more than or equal to 2；
X- is-COO- ,-SO3 -。
Third object of the present invention is to provide a kind of antibacterial agent, the antibacterial agent includes above-mentioned antibacterial polymer.
Fourth object of the present invention is to provide a kind of antibiotic finish of the fabric method, which comprises
(1) above-mentioned antibacterial polymer is configured to antibiotic finishing solution according to the ratio that solid content is 1%-25%；
(2) fabric is immersed in antibiotic finishing solution, carries out the processing that mangles, then baked to get antibiotic fabric.
In one embodiment of the invention, the bath raio of the fabric and antibiotic finishing solution is 1:(20-40).
In one embodiment of the invention, the temperature to mangle when handling is 10-60 DEG C.
In one embodiment of the invention, the concrete technology of the processing that mangles includes: to soak fabric according to bath raio
Enter in antibiotic finishing solution, temperature is controlled at 10-60 DEG C, keeps the temperature 10-300min；Fabric is taken out, the processing that mangles is carried out.
In one embodiment of the invention, above-mentioned mangle can also be by the way of second dipping and rolling.
The invention has the following advantages:
1, the present invention by the good glycine betaine monomer of hydrophily with have centainly hydrophobic monomer combine obtained polymerization
Object, which is provided simultaneously with hydrophilic radical and hydrophobic grouping, and ratio is adjustable.Compared to original small point of hydrophily glycine betaine
Son, according to the principle of similar compatibility, the introducing of hydrophobic structure easily makes it while permeating the fat deposit and egg of microbial cell outer membrane
Lamina albae (two layers is protein layer inside and outside microbial cell film, and centre is fat deposit), meanwhile, the antibacterial agent of macromolecular chain is to life
The penetration capacity of object film is strong, and bactericidal effect becomes apparent；Epoxy group (reactant C) is introduced in poly- glycine betaine antibacterial agent, this
So that open loop occurs in it under appropriate conditions, and it is bonded with the active group above fabric, so that antibacterial agent is firm
Solid combination on the fabric, enhance its antibacterial washing fastness.
2, the present invention designs the polymer formulae of A-B-C, according to different fabrics, different purpose selective polymerization monomers,
Openr thinking is provided to the synthesis of antibacterial agent, and it is single to regulate and control different polymerizations according to the performance requirement of fabric after final arrange
The ratio of body, application range are wider；The poly- glycine betaine antibacterial agent of the present invention belongs to non-dissolving type antibacterial agent, non-hazardous to environment；And
No cytotoxicity, it is non-stimulated to skin；It has no drug resistance, is suitble to be widely used.
3, the preparation method reaction process of the poly- glycine betaine antibacterial agent of the present invention is easy to control, and yield is high, is highly suitable for industry
Metaplasia produces.
4, the antibiotic rate of the fabric after antibacterial agent of the present invention arranges is high, and washing fastness is good, still just have for washing 30 times compared with
Good antibacterial effect, and physical mechanical property, strongly without significantly sacrificing.
Detailed description of the invention
Fig. 1: the antibacterial effect figure of glycine betaine antibacterial agent；Wherein, 1a is the staphylococcus aureus growth for not adding antibacterial agent
Blank control, 1b are the staphylococcus aureus growth blank control that antibacterial agent prepared by 2.5g/L is added；2a is not add antibacterial
The Escherichia coli Growth blank control of agent, 2b are the Escherichia coli Growth blank control that antibacterial agent prepared by 2.5g/L is added.
Specific embodiment
The present invention is further described below with reference to specific example, the given examples are served only to explain the present invention, not
For limiting the scope of the invention.
The measuring method of antibiotic rate: referring to " the evaluation third portion of GB/T 20944.3-2008-T antibacterial textile performance:
Succusion " anti-microbial property for arranging front and back fabric is tested.To the bacteriostasis rate of staphylococcus aureus and Escherichia coli >=
When 70%, sample has antibacterial effect.AAA grades of products, after washing 50 times, to bacteriostasis rate >=80% of staphylococcus aureus,
To bacteriostasis rate >=70% of Escherichia coli.
Embodiment 1:
Betaines antibacterial agent and finish fabric is prepared according to the following steps:
1) preparation of antibacterial finishing agent:
The dimethylallylamine (being dissolved in acetone) for weighing 8.5g is added to anti-with mechanical stirring and reflux unit
It answers in container, in N2Under environment, after the benzoyl peroxide of 0.21g is added, it is slowly added dropwise in the case where stirring with 20 DEG C with syringe
The butyl acrylate of 12.8g and the glycidyl methacrylate of 1.065g, for 24 hours, room temperature stops reaction, centrifuge separation for reaction
It is purified for several times to get polymer is arrived；Polymer 21.3g is taken to be dissolved in tetrahydrofuran, in N2Under environment, used in the case where stirring with 50 DEG C
12.2g propane sultone is slowly added dropwise in syringe, reacts 10h, obtains white precipitate, extracted, and removes byproduct of reaction, and vacuum is dry
It is dry, obtain the poly- glycine betaine antibacterial agent of final product.
The effect of gained antibacterial agent is as shown in Figure 1,1a, 2a are the Escherichia coli and staphylococcus aureus for not adding antibacterial agent
Growing state, 1b, 2b are Escherichia coli and the staphylococcus aureus growth situation that antibacterial agent prepared by 5g/L is added.It can see
Resulting antibacterial agent has apparent inhibiting effect (to Staphylococcus aureus the growth of staphylococcus aureus and Escherichia coli out
The bacteriostasis rate of bacterium is 99.9999%, 99.9984%) bacteriostasis rate to Escherichia coli is that antibacterial effect is very good.
2) preparation of antibiotic fabric:
The poly- glycine betaine antibacterial agent for weighing 10.5g, is dissolved in 300mL water and antimicrobial is made；Bath raio is 1:30, by 2
Gained fabric immerses in antimicrobial, and 20 DEG C of temperature, soaking time 30min；Fabric is taken out, is mangled, pick-up 100% is sent
To 80 DEG C of preliminary drying, 5min, bake 130 DEG C, 3min to get arrive antibiotic fabric, the antibacterial effect of fabric such as table 1 after processing.
Embodiment 2:
Referring to the condition of embodiment 1, the molar fraction of butyl acrylate and dimethylallylamine is adjusted to 1:9,2:
3,3:2,9:1, other conditions are constant, and poly-sulphonic acid betaine antibacterial agent is prepared.
Referring to 1 fabric treating condition of embodiment, fabric is handled using resulting poly-sulphonic acid betaine antibacterial agent, is located
Fabric relevant parameter after reason is shown in Table 1.
The antibacterial effect of fabric after the processing of table 1
Note: water-fastness test is according to GB/T 20944.3-2008 " the evaluation third portion of antibacterial textile performance: oscillation
Method " in testing standard carry out.
Product antibacterial effect: it as shown in Table 1, is prepared under the molar ratio of different butyl acrylates and dimethylallylamine
Fabric anti-bacterial effect gap after poly-sulphonic acid betaine antibacterial agent arranges is larger.
Product washing fastness: after being equivalent to 50 washings, butyl acrylate and dimethylallylamine mole
When than between 2:3-3:2, antibacterial fabric rate is above 70%, and antibiotic property with higher illustrates prepared by the method
After antibacterial agent finish fabric, preferable wash resistant effect can reach, wherein the slightly more washing-resistant effect of same amount or tertiary amine
Preferably.There is more apparent reduce in excessive butyl acrylate or dimethylallylamine, the resistance to fastness after 50 washings.
Embodiment 3:
Betaines antibacterial agent and finish fabric is prepared according to the following steps:
1) preparation of antibacterial finishing agent:
The dimethylaminoethyl acrylate for weighing 14.3g is added to the reaction vessel with mechanical stirring and reflux unit
In, in N2Under environment, after the azodiisobutyronitrile of 0.27g is added, it is slowly added dropwise 12.8g's with syringe in the case where stirring with 80 DEG C
The allyl glycidyl ether of butyl acrylate and 1.355g reacts 4h, and room temperature stops reaction, and centrifuge separation purifies for several times, i.e.,
Obtain polymer；Polymer 27g is taken, in N2Under environment, 12.2g propane sulfonic acid is slowly added dropwise with syringe in the case where stirring with 80 DEG C
Lactone reacts 2h, obtains white precipitate, extracted, and removes byproduct of reaction, and it is anti-to obtain the poly- glycine betaine of final product for vacuum drying
Microbial inoculum；
2) preparation of antibiotic fabric:
The poly- glycine betaine antibacterial agent for weighing 10.5g, is dissolved in 300mL water and antimicrobial is made；Bath raio is 1:30, by 2
Gained fabric immerses in antimicrobial, and 20 DEG C of temperature, soaking time 30min；Fabric is taken out, is mangled, pick-up 100% is sent
To 80 DEG C of preliminary drying, 5min, bake 130 DEG C, 3min to get arrive antibiotic fabric, the antibacterial effect of fabric such as table 2 after processing.
Embodiment 4:
Referring to the condition of embodiment 3, the mass fraction of allyl glycidyl ether is adjusted to 0.25%, 1%, 10%,
20%, 50%, other conditions are constant, and poly-sulphonic acid betaine antibacterial agent is prepared.
Referring to 3 fabric treating condition of embodiment, fabric is handled using resulting poly-sulphonic acid betaine antibacterial agent, is located
Fabric relevant parameter after reason is shown in Table 2.
The relevant parameter of fabric after the processing of table 2
Note: fabric whiteness value is 73.2 before handling, and through being 795N to breaking strength, broadwise breaking strength is 410N, water-fast
Wash test according to the testing standard in GB/T20944.3-2008 " the evaluation third portion of antibacterial textile performance: succusion " into
Row.
Embodiment 5:
Referring to the condition of embodiment 3, the molar ratio of the monomer containing tertiary amine and propane sultone is adjusted to 1:2, other
Condition is constant, and poly-sulphonic acid betaine antibacterial agent is prepared.
Referring to 3 fabric treating condition of embodiment, fabric is handled using resulting poly-sulphonic acid betaine antibacterial agent, is located
Fabric relevant parameter after reason is shown in Table 3.
Embodiment 6:
Betaines antibacterial agent and finish fabric is prepared according to the following steps:
1) preparation of antibacterial finishing agent:
The N of 11.3g is weighed, N- Diethyl Allylnime is added to the reaction vessel with mechanical stirring and reflux unit
In, in N2Under environment, after the azodiisobutyronitrile of 0.23g is added, it is slowly added dropwise 11.8g's with syringe in the case where stirring with 60 DEG C
The allyl glycidyl ether of Isooctyl acrylate monomer and 1.355g reacts 10h, and room temperature stops reaction, and centrifuge separation purifies for several times,
Obtain polymer；Polymer 23g is taken, in N2Under environment, 8.6gB- fourth is slowly added dropwise with syringe in the case where stirring with 60 DEG C
Lactone reacts 2h, obtains white precipitate, extracted, and removes byproduct of reaction, and it is anti-to obtain the poly- glycine betaine of final product for vacuum drying
Microbial inoculum；
2) preparation of antibiotic fabric:
The poly- glycine betaine antibacterial agent for weighing 10.5g, is dissolved in 300mL water and antimicrobial is made；Bath raio is 1:30, by 2
Gained fabric immerses in antimicrobial, and 20 DEG C of temperature, soaking time 30min；Fabric is taken out, is mangled, pick-up 100% is sent
To 80 DEG C of preliminary drying, 5min, bake 130 DEG C, 3min to get arrive antibiotic fabric, the antibacterial effect of fabric such as table 3 after processing.
Reference examples 1:
Poly-sulphonic acid betaine antibacterial agent is prepared according to the following steps:
It is added without glycidyl methacrylate only when the first step prepares polymer referring to embodiment 1, other
Part is constant, and poly-sulphonic acid betaine antibacterial agent is prepared.
Prepare antibacterial agent finish fabric method:
Fabric finishing method is with embodiment 1, and fabric relevant parameter is shown in Table 3 after processing.
Reference examples 2:
Poly-sulphonic acid betaine antibacterial agent is prepared according to the following steps:
It is added without Isooctyl acrylate monomer only in first step synthetic polymer referring to embodiment 6, other conditions are constant,
Poly-sulphonic acid betaine antibacterial agent is prepared.
Prepare antibacterial agent finish fabric method:
Fabric finishing method is with embodiment 6, and fabric relevant parameter is shown in Table 3 after processing.
Reference examples 3:
Poly-sulphonic acid betaine antibacterial agent is prepared according to the following steps:
Referring to embodiment 6, only in first step synthetic polymer, it is being added without Isooctyl acrylate monomer and allyl glycidyl is sweet
Oily ether, other conditions are constant, and poly-sulphonic acid betaine antibacterial agent is prepared.
Prepare antibacterial agent finish fabric method:
Fabric finishing method is with embodiment 6, and fabric relevant parameter is shown in Table 3 after processing.
Reference examples 4:
Antibacterial agent preparation method: weighing 25.55g dimethyl propylene amine and be added in four-hole boiling flask, in a nitrogen environment, temperature
When being 50 DEG C, syringe is slowly added dropwise propane sultone (36.6g is dissolved in 300mL dehydrated alcohol), is reacted 2h, is purified repeatedly
Obtain glycine betaine monomer.The 62.1g glycine betaine monomer, 29.4g maleic anhydride and a certain amount of ammonium persulfate are weighed, deionization is dissolved in
Water, polymerization reaction 2h at 90 DEG C purify dry glycine betaine antibacterial finishing agent.
Antibacterial agent finish fabric preparation method:
Fabric finishing method is with embodiment 6, and fabric relevant parameter is shown in Table 3 after processing.
Fabric relevant parameter after the processing of table 3
Note: fabric whiteness value is 73.2 before handling, and through being 795N to breaking strength, broadwise breaking strength is 410N, water-fast
Wash test according to the testing standard in GB/T20944.3-2008 " the evaluation third portion of antibacterial textile performance: succusion " into
Row.
Product antibacterial effect: antibacterial agent processing after fabric anti-microbial property data as shown in table 1-3, comparative example 1-6
With reference examples 1-3 it is found that the fabric for the polysulfobetaine antibacterial agent processing that the present invention designs only contains tertiary amine than polymerized monomer
Only have more containing tertiary amine and acrylate with the only antibacterial agent containing tertiary amine monomers with the antibacterial agent of cross-linking monomer, polymerized monomer
Good antibacterial effect.
Water-wash resistance: it is marked referring to GB/T 20944.3-2008 " the evaluation third portion of antibacterial textile performance: succusion "
Standard carries out washing fastness test to the fabric after antibacterial agent arranges.After washing, the antibacterial effect of fabric is measured.
The fabric and comparative example 1-4 that embodiment 1-6 is arranged compare it is found that the fabric that the antibacterial agent that designs of the present invention is handled still have it is higher
Anti-microbial property illustrates that the antibacterial agent has preferable wash durability.
Other performance: referring to 3923-2013 " measurement strip of fabric tension performance ultimate strength and elongation at break of GB/T
Sample method ", the fabric for arranging front and back to poly-sulphonic acid betaine antibacterial agent carries out ultimate strength test.It can be seen from the data in Table 3 that
The ultimate strength of the fabric arranged by poly-sulphonic acid betaine loses smaller.Especially compared with reference examples 4, strength retention is remote
Higher than by antibacterial cotton fabric prepared by reference examples 4.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of antibacterial polymer, which is characterized in that the polymer is to utilize unsaturated tertiary amine monomers, esters of acrylic acid list
Body, monomer containing epoxy group, the compound containing sulfonic acid group or carboxylic acid group are what raw material was prepared.
2. polymer according to claim 1, which is characterized in that the unsaturation tertiary amine monomers and acrylic ester monomer
Molar ratio be 1:9~9:1.
3. polymer according to claim 1 or 2, which is characterized in that the additive amount of the monomer containing epoxy group accounts for not
It is saturated the 1-20% of tertiary amine monomers, acrylic ester monomer and the monomer gross mass containing epoxy group.
4. polymer according to claim 1, which is characterized in that the unsaturation tertiary amine monomers include N, N- diethyl alkene
Propyl amine, N, one of N- dimethylallylamine, allylamine, N- methyl-prop enamine, dimethylaminoethyl acrylate or more
Kind.
5. polymer according to claim 1 to 4, which is characterized in that the acrylic ester monomer includes acrylic acid
One of butyl ester, Isooctyl acrylate monomer, ethyl acrylate or hydroxy-ethyl acrylate are a variety of.
6. polymer according to claim 1, which is characterized in that the monomer containing epoxy group includes methacrylic acid contracting
Water glyceride or allyl glycidyl ether.
7. -6 any polymer according to claim 1, which is characterized in that the preparation method packet of the antibacterial polymer
It includes:
(1) midbody polymer is prepared using unsaturated tertiary amine monomers and acrylic ester monomer, monomer containing epoxy group；
(2) step (1) resulting midbody polymer is reacted to obtain beet with the compound containing sulfonic acid group or carboxylic acid group
The antibacterial polymer of bases.
8. a kind of antibacterial polymer, which is characterized in that the polymer is polymer shown in formula (I),
Wherein, m=1~1000, n=1~1000, q=1~1000；
R1For-H ,-CH3Or CH2CH3；R2For-H ,-CH3Or CH2CH3；R3For-(CH2)p, or-COO- (CH2)k, wherein p be
Any one integer in 1-18, k are any one integer in 0-18；R4For-(CH2)lCH3, or-(CH2)r- OH, wherein l, r
Any one integer in respectively 1-6；R5For-H, or-CH3；R6ForOr-CH2-；R7For-H, or-CH3；R8For-
CH2, or-CH2CH3；R9For-(CH2)t, wherein t is the positive integer more than or equal to 2；
X-For-COO- ,-SO3 -。
9. a kind of antibacterial agent, which is characterized in that the antibacterial agent includes any antibacterial polymer of claim 1-8.
10. a kind of antibiotic finish of the fabric method, which is characterized in that the described method includes:
(1) any antibacterial polymer of claim 1-8 is configured to antibacterial according to the ratio that solid content is 1%-25%
Finishing fluid；
(2) fabric is immersed in antibiotic finishing solution, carries out the processing that mangles, then baked to get antibiotic fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910095741.5A CN109810221B (en) | 2019-01-31 | 2019-01-31 | Preparation method and application of betaine antibacterial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910095741.5A CN109810221B (en) | 2019-01-31 | 2019-01-31 | Preparation method and application of betaine antibacterial agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109810221A true CN109810221A (en) | 2019-05-28 |
| CN109810221B CN109810221B (en) | 2020-07-03 |
Family
ID=66606143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910095741.5A Active CN109810221B (en) | 2019-01-31 | 2019-01-31 | Preparation method and application of betaine antibacterial agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109810221B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683536A (en) * | 2021-08-19 | 2021-11-23 | 浙江三元纺织有限公司 | Preparation of betaine type quaternary ammonium salt antibacterial agent and method for applying same to fabric finishing |
| CN114225723A (en) * | 2021-12-02 | 2022-03-25 | 深圳市君信达环境科技股份有限公司 | Piezoelectric antibacterial nano-film air filtering membrane and preparation method thereof |
| CN114685714A (en) * | 2020-12-29 | 2022-07-01 | 上海朗亿功能材料有限公司 | Modified polymer, antibacterial composition, preparation method, fabric finishing and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524652A (en) * | 2013-09-30 | 2014-01-22 | 江南大学 | Quaternary ammonium salt group-containing halide amine polymer antibacterial agent, and preparation method and application thereof |
| CN107383283A (en) * | 2017-08-23 | 2017-11-24 | 广州科迩博新材料科技有限公司 | A kind of structural type antimicrobial acrylic emulsion and its preparation method and application |
| CN108219065A (en) * | 2017-12-29 | 2018-06-29 | 江南大学 | A kind of betaine type antibacterial finishing agent and preparation method thereof |
-
2019
- 2019-01-31 CN CN201910095741.5A patent/CN109810221B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524652A (en) * | 2013-09-30 | 2014-01-22 | 江南大学 | Quaternary ammonium salt group-containing halide amine polymer antibacterial agent, and preparation method and application thereof |
| CN107383283A (en) * | 2017-08-23 | 2017-11-24 | 广州科迩博新材料科技有限公司 | A kind of structural type antimicrobial acrylic emulsion and its preparation method and application |
| CN108219065A (en) * | 2017-12-29 | 2018-06-29 | 江南大学 | A kind of betaine type antibacterial finishing agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JACQUELINE S. DE VERA等: "Self-Cleaning Interfaces of Polydimethylsiloxane Grafted with pH Responsive Zwitterionic Copolymers", 《LANGMUIR》 * |
| 李亮等: "含内盐丙烯酸酯防污涂料的制备和性能研究", 《中国涂料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685714A (en) * | 2020-12-29 | 2022-07-01 | 上海朗亿功能材料有限公司 | Modified polymer, antibacterial composition, preparation method, fabric finishing and application |
| CN114685714B (en) * | 2020-12-29 | 2023-09-22 | 上海朗亿功能材料有限公司 | Modified polymer, antibacterial composition, preparation method, textile finishing and application |
| CN113683536A (en) * | 2021-08-19 | 2021-11-23 | 浙江三元纺织有限公司 | Preparation of betaine type quaternary ammonium salt antibacterial agent and method for applying same to fabric finishing |
| CN113683536B (en) * | 2021-08-19 | 2023-01-13 | 浙江三元纺织有限公司 | Preparation of betaine type quaternary ammonium salt antibacterial agent and method for applying same to fabric finishing |
| CN114225723A (en) * | 2021-12-02 | 2022-03-25 | 深圳市君信达环境科技股份有限公司 | Piezoelectric antibacterial nano-film air filtering membrane and preparation method thereof |
| CN114225723B (en) * | 2021-12-02 | 2023-05-09 | 深圳市君信达环境科技股份有限公司 | Piezoelectric antibacterial nano-film air filtering membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109810221B (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8486428B2 (en) | Compositions and methods for making and using acyclic N-halamine-based biocidal polymeric materials and articles | |
| CN109810221A (en) | A kind of preparation method and application of betaines antibacterial agent | |
| US7781498B2 (en) | Cationic latex as a carrier for bioactive ingredients and methods for making and using the same | |
| US20120202912A1 (en) | Surface treatment by photopolymerisation to obtain biocidal properties | |
| US9220725B2 (en) | Cationic latex as a carrier for bioactive ingredients and methods for making and using the same | |
| CN100554296C (en) | Reactable polymer antibacterial agent and its production and application | |
| US20070086976A1 (en) | Acyclic N-halamines in antibacterial materials | |
| US20090324536A1 (en) | Antimicrobial polymers and coatings | |
| CN104968655A (en) | Biocidal compounds and methods for using same | |
| CN101967351A (en) | Heterocyclic halamine-substituted siloxanes for use in biocidal coatings and materials | |
| CN107383283A (en) | A kind of structural type antimicrobial acrylic emulsion and its preparation method and application | |
| JP2003528860A (en) | N-halamine vinyl compounds and their polymeric biocides | |
| AU2012273010A1 (en) | Alkylaminoalkyl oligomers as broad-spectrum antimicrobial agent | |
| CN108299667A (en) | Antibacterial and anti-protein adhesion coating and preparation method thereof | |
| AU672996B2 (en) | Antiseptic polymer | |
| JPH06239941A (en) | Antimicrobial polymer | |
| WO2023003839A1 (en) | Antimicrobial finish for textiles | |
| JP3165235B2 (en) | Antibacterial processed fiber product and its processing method | |
| CN103608008A (en) | Non-leaching antimicrobial wound dressing | |
| JP7161856B2 (en) | Fiber treatment agent | |
| AU747790B2 (en) | Acrylamide and trialkylammonium salt copolymer, method for obtaining same and coated textile | |
| CN108003740A (en) | A kind of antibacterial polymer of blood compatibility and its preparation method and application | |
| JPWO2013146782A1 (en) | Influenza virus infection inhibitor for textile processing, textile product using the same, and method for producing the same | |
| JPH05331235A (en) | Antimicrobial resin, its production and antimicrobial fiber structure | |
| JPH04342504A (en) | Antimicrobial composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |