CN105542177B - A kind of guanidine radicals high-molecular anti-bacteria nanosphere and preparation method thereof - Google Patents
A kind of guanidine radicals high-molecular anti-bacteria nanosphere and preparation method thereof Download PDFInfo
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- CN105542177B CN105542177B CN201610111798.6A CN201610111798A CN105542177B CN 105542177 B CN105542177 B CN 105542177B CN 201610111798 A CN201610111798 A CN 201610111798A CN 105542177 B CN105542177 B CN 105542177B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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Abstract
The present invention discloses a kind of guanidine radicals high-molecular anti-bacteria nanosphere and preparation method thereof, and preparation step includes：Vinyl monomer and glycidyl methacrylate (GMA) are obtained into P-GMA copolymer by emulsifier-free emulsion polymerization, then the copolymer emulsion is reacted under triethylamine catalytic action with polyhexamethylene list guanidine salt or cosmocil stearate, is finally dried to obtain guanidine radicals high-molecular anti-bacteria nanosphere by centrifuge separation, washing.For antimicrobial nano microballoon prepared by the present invention using water-soluble polyhexamethylene list guanidine salt/cosmocil stearate as shell, hydrophobic copolymer is core, and dispersion easily dispersion, bactericidal effect is good in water.This method is by the way of emulsifier-free emulsion polymerization, using water as solvent, environmental-friendly, economical and effective, simple process.
Description
Technical field
The present invention relates to functional polymer material fields.More particularly, to a kind of guanidine radicals high-molecular anti-bacteria nanosphere
And preparation method thereof.
Background technique
Polyguanidine salt is usually used in antimicrobial treatment, especially in aqueous solution, since bio-toxicity is low, very to biological cell injury
It is small, have been widely used for the antibacterials of crops, mould proof, the disinfection of pharmaceutical sanitary field, anti-corrosion, anti-corrosion in cosmetics and
In the antibiotic finish of textile, also it is widely used in aquaculture field.Since the water solubility of polyguanidine salt is preferable, hygroscopicity
By force, cause it in plastics, fiber, rubber and coating application be restricted.Polyguanidine in the plastic application in recent years by
Extensive concern, but phenomena such as wall built-up adheres to screw rod (patent CN is easy to appear during polyguanidine salt melt-processed
201010519982), cause antibacterial matrices that should not squeeze out, and be easy it from material matrix due to its is water-soluble
It is slowly precipitated, material property is caused to decline.It improves its molecular weight, active group is introduced into polyguanidine salt by the method for graft modification
Group, or with other inorganic antiseptics are compound prepares complex antimicrobials, so that the compatibility for improving itself and material matrix is to open up
Open up the main method of polyguanidine salt application.2009/0182118 A1 of patent US describes a kind of synthetic method of polyguanidine salt, this
The polyguanidine salt molecular weight with higher and preferable antibacterial effect that method obtains, can be applied to water treatment system, and disinfection produces
Product, in preservative and cosmetics.Such as patent ZL00125721.8 describes a kind of polyamine and guanidine salt polymer and its preparation
Method introduces the C of 1-5 active unsaturated double-bond in polyguanidine salt1-20Acyl class or ester type compound, work with higher
Property, it can be firmly combined with polyolefin.ZL00125768.4 describes the mixing system of modified polyguanidine salt and polyolefin based materials
It the method for standby Functional Polyolefine master batch and is applied in plastic product.For another example patent ZL1569923 describes a kind of polyguanidine
Antibacterial functionalized master batch is obtained after salt and polyester, polyamide reaction.
The modification of polyguanidine has the modification to itself, can also by the modification to material matrix, reach increase polyguanidine with
The purpose of material compatibility.
Summary of the invention
The object of the present invention is to provide a kind of guanidine radicals high-molecular anti-bacteria nanospheres.The guanidine radicals high-molecular anti-bacteria nanosphere
Using water-soluble polyhexamethylene list guanidine salt/cosmocil stearate as shell, hydrophobic copolymer is core, and partial size is small,
Easily disperse in water, also there is good dispersibility and antibiotic property, sterilization effect other than having good compatibility with high molecular material
Fruit is good.
It is a further object to provide a kind of preparation methods of guanidine radicals high-molecular anti-bacteria nanosphere.This method makes
A kind of polymer with functional groups and the polyguanidine salt containing amido carry out chemical bonds, obtain the antibacterial of graft copolymerization
Macromolecule, this method take water as a solvent, and simple process is economic and environment-friendly.
In order to solve the first technical problem mentioned above, the present invention adopts the following technical scheme that：
A kind of guanidine radicals high-molecular anti-bacteria nanosphere, the guanidine radicals high-molecular anti-bacteria nanosphere is with water-soluble poly- six methylene
Base list guanidine salt/cosmocil stearate is shell, and hydrophobic copolymer is core, the knot of the guanidine radicals high-molecular anti-bacteria nanosphere
Structure feature is as follows：
Wherein：
X is H or CH3One kind；Y is phenyl ring or phenyl compound or ester group compound；
Z is polyhexamethylene list guanidine group or poly hexamethylene biguanide group, specific structure are：
Polyhexamethylene list guanidine group：
Poly hexamethylene biguanide group：
Wherein M is Cl-、NO3 -、H2PO4 -One of.
Preferably, in the average grain diameter of the guanidine radicals high-molecular anti-bacteria nanosphere in lotion between 100nm-250nm；
Preferably, the phenyl compound is to methylbenzene, to one of ethylo benzene, sulfonic benzo.
Preferably, the ester group compound is-COOCH3、-COOCH2CH3、-COOCH2CH2CH2CH3One of；
To solve above-mentioned second technical problem, the present invention provides a kind of side for preparing guanidine radicals high-molecular anti-bacteria nanosphere
Method, this method comprises the following steps：
(1) vinyl monomer being added to containing in deionized water reactor, stirring, logical nitrogen are heated to 60-85 DEG C,
The aqueous solution of the initiator of the 1-2% of monomer gross mass is added, obtains mixed liquor, reacts two hours backward mixed liquor and first is added
Base glycidyl acrylate is (hereinafter referred to as：GMA), keep stopping after temperature and constant the reaction was continued the 18-24h of mixing speed anti-
It answers, it is neutrality that sodium bicarbonate aqueous solution is added into above-mentioned mixed liquor and adjusts pH, milky white liquid a is obtained, to the milky liquid
Body a is centrifuged and washs drying, obtains white powdery solids A, as copolymer p-GMA nanosphere；
(2) white powdery solids A step (1) being prepared is soluble in water, its dispersion is made to obtain P-GMA lotion,
40-80 DEG C is heated to it under agitation, be then added with the antibacterial agent polyhexamethylene list guanidine salt of quality such as P-GMA or
Then cosmocil stearate adds catalyst of triethylamine (Et3N), milky white liquid b is obtained after reacting 10-60h, is passed through
Centrifuge separation, washing, drying are crossed, white powdery solids B, as guanidine radicals high-molecular anti-bacteria nanosphere are obtained.
Preferably, in step (1), the vinyl monomer is vinyl benzene class, esters of acrylic acid or methacrylate
One of class monomer is a variety of, wherein the vinyl benzene class such as styrene, p-methylstyrene, p -ethyl-styrene, institute
State esters of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl acrylic ester such as methyl methacrylate
Ester, ethyl methacrylate, butyl methacrylate.
Preferably, in step (1), the mass ratio of the vinyl monomer and GMA are 1:0.5-1.0.
Preferably, in step (1), the initiator is one of potassium peroxydisulfate or ammonium persulfate.
Preferably, in step (1), agitating mode is mechanical stirring.
Wherein, in step (1), being passed through nitrogen is to protect the mixed liquor of reaction to exclude oxygen.
Preferably, in step (2), the concentration of the P-GMA lotion is 10wt%-18wt%.
Preferably, in step (2), the reaction temperature is 50-70 DEG C, reaction time 24-48h.Higher reaction temperature
The reaction time for spending needs is shorter, and the reaction time that lower reaction temperature needs is long, can be only achieved certain grafting efficiency, comprehensive
Saving in time costs is closed, reaction temperature and reaction time are selected.
Preferably, in step (2), the adding manner of catalyst of triethylamine is to be added dropwise.
Preferably, in step (2), dispersing mode is ultrasonic disperse.
Preferably, in step (2), the mode of washing is at least to be washed 5 times with deionized water.
The specific reaction equation of preparation method of the present invention is as follows：
Vinyl monomer (such as vinyl benzene class, esters of acrylic acid or methacrylate-based monomer) and GMA without soap cream
Liquid polymerization reaction equation：
P-GMA and the reaction equation of cosmocil stearate in aqueous solution：
P-GMA and the reaction equation of polyhexamethylene list guanidine salt in aqueous solution：
Wherein M is Cl-、NO3 -、H2PO4 -One of；X is H or CH3One kind；Y is phenyl ring or phenyl compound, or
Ester group compound such as-COOCH3、-COOCH2CH3、-COOCH2CH2CH2CH3One of.
The present invention uses following test method：
Structural characterization：Polymer architecture is surveyed using fourier infrared characterization method.
Morphology characterization：Using the pattern and size of nanosphere prepared by scanning electron microscope and transmission electron microscope observing.
Emulsion particle diameter analysis：Dynamic light scattering method surveys the partial size and particle diameter distribution of nanosphere in lotion.
Anti-microbial property detection：With broth dilution method determination minimal inhibitory concentration, with Escherichia coli and staphylococcus aureus
Bacterium is used as experiment；As a control group using polyhexamethylene list guanidine salt or cosmocil stearate.
Beneficial effects of the present invention are as follows：
1) guanidine radicals high-molecular anti-bacteria nanosphere provided by the invention has guanidine salt wider by the modification of guanidine radicals antibacterial agent
The antibacterial effect of spectrum, bactericidal effect are good；It is well dispersed in water, there is good application prospect in fields such as coating, adhesives；
And guanidine salt is grafted on macromolecule by the present invention, as non-releasing micro antimicrobial macromolecule, performance is stablized, is also had extensively in plastic applications
Wealthy application prospect.
2) method that the present invention prepares guanidine radicals high-molecular anti-bacteria nanosphere, by the way of emulsifier-free emulsion polymerization, with water
Make solvent, environmental-friendly, economical and effective, simple process, safe preparation process environmental protection, all very to the harm of human body and environment
It is small.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
The Fourier infrared spectrum figure for the PHGC-PSGMA that Fig. 1 shows the PSGMA of the preparation of embodiment 1 and prepared by embodiment 3.
Fig. 2 shows the scanning electron microscope (a) and transmission electron microscope (c) photo and reality of PSGMA nanosphere prepared by embodiment 1
Apply the scanning electron microscope (b) and transmission electron microscope (d) photo of the PHGC-PSGMA nanosphere of the preparation of example 3.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.It will be appreciated by those skilled in the art that specifically described content is illustrative and be not restrictive below, it should not be with this
It limits the scope of the invention.
Embodiment 1
1. preparing PSGMA polymer nano granules, include the following steps：
4.0g styrene is added in 130mL deionized water, stirring leads to nitrogen deoxygenation, is heated to 75 DEG C, is then added and contains
The 10mL aqueous solution of potassium peroxydisulfate 0.1g.After reacting two hours, GMA3.0g is added, stops reaction after the reaction was continued 21h.Drop
Sodium bicarbonate aqueous solution is added to adjust pH as neutrality.By being centrifugated, washing, 50 DEG C of baking oven are dried to obtain white powder and consolidate
Body, as PSGMA polymer nano granules.
2. a pair PSGMA polymer nano granules characterize
It 1) is 113.2nm using the average grain diameter that dynamic light scattering method measures nanosphere in PSGMA lotion.
2) Fourier infrared spectrum characterization is carried out to PSGMA polymer nano granules obtained, it is as a result as follows：Due to epoxy
The characteristic peak of key is in 1258cm-1And 910cm-1Place, the characteristic absorption peak of guanidine radicals is in 1630-1659cm-1Locate, N-H is flexible in amido
Vibration is in 3176cm-1Place.It can be seen from figure 1 that PSGMA polymer nano granules prepared by embodiment 1 are in 1258cm-1With
910cm-1There is the presence that epoxy characteristic peak illustrates epoxy bond in place.
Embodiment 2
PEMAGMA polymer nano granules are prepared, are included the following steps：
4.0g ethyl methacrylate is added in 130mL deionized water, stirring leads to nitrogen deoxygenation, is heated to 80 DEG C, adds
Enter the 10mL aqueous solution of the 0.1g containing potassium peroxydisulfate.After reacting two hours, GMA3.0g is added, is stopped after the reaction was continued 18h anti-
It answers.It is neutrality that sodium bicarbonate aqueous solution, which is added dropwise, and adjusts pH.By being centrifugated, washing, 50 DEG C of baking oven are dried to obtain white powder
Shape solid, as PEMAGMA polymer nano granules.
Embodiment 3
1. preparing PHGC-PSGMA nano-antibacterial particle, include the following steps：
The PSGMA polymer 1.0g that embodiment 1 is prepared is added in the deionized water of 5.0g, ultrasonic disperse, so
The polyhexamethylene list guanidine hydrochloride (PHGC) of 1.0g is added afterwards, stirring is heated to 60 DEG C, and Triethylamine catalyst is added
0.002g stops after reacting 48h.By centrifuge separation washing 5 times, 50 DEG C of baking oven are dried to obtain white powdery solids, as
PHGC-PSGMA nano-antibacterial particle.
2. a pair PHGC-PSGMA nano-antibacterial particle carries out characterization and anti-microbial property detection
PHGC is prepared into solution, PHGC-PSGMA obtains lotion after ultrasonic disperse in water.
It 1) is 172.9nm using the average grain diameter that dynamic light scattering method measures nanosphere in PHGC-PSGMA lotion, and
The average grain diameter of nanosphere is 113.2nm in PSGMA lotion in embodiment 1, this illustrates that increased partial size is polyguanidine salt packet
The result wrapped up in.
2) anti-microbial property detects
The minimal inhibitory concentration such as table 1 of PHGC and PHGC-PSGMA is measured by the method for constant meat soup：
The minimal inhibitory concentration (MIC) of 1 PHGC and PHGC-PSGMA lotion of table
Table 1 statistics indicate that due to non-antibiotic property segment PSGMA presence so that the antimicrobial nano microballoon by graft copolymerization
Minimal inhibitory concentration with respect to polyguanidine salt increase.
3) Fourier infrared spectrum characterization is carried out to PHGC-PSGMA nano-antibacterial particle obtained, it is as a result as follows：Due to
The characteristic peak of epoxy bond is in 1258cm-1And 910cm-1Place, the characteristic absorption peak of guanidine radicals is in 1630-1659cm-1Locate, N-H in amido
Stretching vibration is in 3176cm-1Place.It can be seen from figure 1 that PHGC-PSGMA nano-antibacterial particle prepared by embodiment 3 exists
1645cm-1There is the characteristic absorption peak of polyguanidine salt in place, illustrates that there are guanidine radicals in copolymerization product；In 910cm-1The epoxy bond at place
Characteristic absorption peak weakens or disappears, this illustrates that epoxy bond is opened substantially, and ring-opening reaction has occurred in PHGC and epoxy bond.
Embodiment 4
1. preparing PHMB-PSGMA nano-antibacterial particle, include the following steps：
The PSGMA polymer 1.0g that embodiment 1 is prepared is added in the deionized water of 5.0g, ultrasonic disperse, so
The hexamethylene (PHMB) of 1.0g is added afterwards, stirring is heated to 60 DEG C, and Triethylamine catalyst is added
0.002g stops after reacting 48h.By centrifuge separation washing 5 times, 50 DEG C of baking oven are dried to obtain white powdery solids, as
PHMB-PSGMA nano-antibacterial particle.
The anti-microbial property of 2.PHMB-PSGMA nano-antibacterial particle detects
PHMB is prepared into solution, PHMB-PSGMA obtains lotion after ultrasonic disperse in water, passes through the side of constant meat soup
Method measures the minimal inhibitory concentration such as table 2 of PHMB and PHMB-PSGMA：
The minimal inhibitory concentration (MIC) of 2 PHMB and PHMB-PSGMA lotion of table
Table 2 statistics indicate that into cross graft copolymerization after, since the presence of non-antibiotic property PSGMA segment makes antimicrobial nano microballoon
Minimal inhibitory concentration poly bis guanidine salt relatively increase.
Embodiment 5
1. preparing PHGC-PEMAGMA nano-antibacterial particle, include the following steps：
The PEMAGMA polymer 1.0g that embodiment 2 is prepared is added in the deionized water of 5.0g, ultrasonic disperse, so
The PHGC of 1.0g is added afterwards, stirring is heated to 60 DEG C, and Triethylamine catalyst 0.002g is added, and stops after reacting 48h.By from
Heart separation, washing 6 times, 50 DEG C of baking oven are dried to obtain white powdery solids, as PHGC-PEMAGMA nano-antibacterial particle.
The anti-microbial property of 2.PHGC-PEMAGMA nano-antibacterial particle detects
PHGC is prepared into solution, PHGC-EMAGMA obtains lotion after ultrasonic disperse in water, passes through the side of constant meat soup
Method measures the minimal inhibitory concentration such as table 3 of PHGC and PHGC-PEMAGMA：
The minimal inhibitory concentration (MIC) of 3 PHGC and PHGC-PEMAMA lotion of table
Table 3 statistics indicate that into cross graft copolymerization after, since the presence of non-antibiotic property PSGMA segment makes antimicrobial nano microballoon
Minimal inhibitory concentration with respect to polyguanidine salt increase.
Embodiment 6
1. preparing PHMB-PEMAGMA nano-antibacterial particle, include the following steps：
The PEMAGMA polymer 1.0g that embodiment 2 is prepared is added in the deionized water of 5.0g, ultrasonic disperse, so
The PHMB of 1.0g is added afterwards, stirring is heated to 70 DEG C, and Triethylamine catalyst 0.002g is added, and stops after reacting 30h.By from
Heart separating, washing 6 times, 50 DEG C of baking oven are dried to obtain white powdery solids, as PHMB-PEMAGMA nano-antibacterial particle.
The anti-microbial property of 2.PHMB-PEMAGMA nano-antibacterial particle detects
PHMB is prepared into solution, PHMB-PEMAGMA obtains lotion after ultrasonic disperse in water, passes through constant meat soup
Method measures the minimal inhibitory concentration such as table 4 of PHMB and PHMB-PEMAGMA：
The minimal inhibitory concentration (MIC) of 4 PHMB and PHMB-PEMAMA lotion of table
Table 4 statistics indicate that into cross graft copolymerization after, since the presence of non-antibiotic property PSGMA segment makes antimicrobial nano microballoon
Minimal inhibitory concentration poly bis guanidine salt relatively increase.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (8)
1. a kind of method for preparing guanidine radicals high-molecular anti-bacteria nanosphere, which is characterized in that this method comprises the following steps：
(1) vinyl monomer is added to containing in deionized water reactor, stirring, logical nitrogen are heated to 60-85 DEG C, are added
The aqueous solution of the initiator of the 1-2% of monomer gross mass, obtains mixed liquor, reacts two hours backward mixed liquor and methyl-prop is added
Olefin(e) acid ethylene oxidic ester stops reaction after keeping temperature and constant the reaction was continued the 18-24h of mixing speed, into above-mentioned mixed liquor
It is neutrality that sodium bicarbonate aqueous solution, which is added, and adjusts pH, obtains milky white liquid a, is centrifuged, washes to milky white liquid a
Drying is washed, white powdery solids A, as copolymer p-GMA nanosphere are obtained；
(2) white powdery solids A step (1) being prepared is soluble in water, so that its dispersion is obtained P-GMA lotion, is stirring
40-80 DEG C is heated under the conditions of mixing to it, polyhexamethylene list guanidine salt or polyhexamethylene with quality such as P-GMA is then added
Guanoctine, then adds catalyst of triethylamine, obtains milky white liquid b after reacting 10-60h, by centrifuge separation, washing,
Drying, obtains white powdery solids B, as guanidine radicals high-molecular anti-bacteria nanosphere.
2. the method according to claim 1 for preparing guanidine radicals high-molecular anti-bacteria nanosphere, it is characterised in that：In step
(1) in, the mass ratio of the vinyl monomer and GMA are 1:0.5-1.0.
3. the method according to claim 1 or 2 for preparing guanidine radicals high-molecular anti-bacteria nanosphere, it is characterised in that：In step
Suddenly in (1), the vinyl monomer is one of vinyl benzene class, esters of acrylic acid or methacrylate-based monomer or more
Kind, wherein the vinyl benzene class is styrene, p-methylstyrene, p -ethyl-styrene, the esters of acrylic acid is propylene
Sour methyl esters, ethyl acrylate, butyl acrylate, the methyl acrylic ester are methyl methacrylate, methacrylic acid second
Ester, butyl methacrylate.
4. the method according to claim 1 for preparing guanidine radicals high-molecular anti-bacteria nanosphere, it is characterised in that：In step
(1) in, the initiator is one of potassium peroxydisulfate or ammonium persulfate.
5. the method according to claim 1 for preparing guanidine radicals high-molecular anti-bacteria nanosphere, it is characterised in that：In step
(1) in, agitating mode is mechanical stirring.
6. the method according to claim 1 for preparing guanidine radicals high-molecular anti-bacteria nanosphere, it is characterised in that：In step
(2) in, the concentration of the P-GMA lotion is 10wt%-18wt%.
7. the method according to claim 1 for preparing guanidine radicals high-molecular anti-bacteria nanosphere, it is characterised in that：In step
(2) in, the reaction temperature is 50-70 DEG C, reaction time 24-48h.
8. the method according to claim 1 for preparing guanidine radicals high-molecular anti-bacteria nanosphere, it is characterised in that：In step
(2) in, the adding manner of the catalyst of triethylamine is to be added dropwise, and the dispersing mode is ultrasonic disperse, the washing side
Formula is at least to be washed 5 times with deionized water.
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| CN111944232B (en) * | 2019-05-17 | 2022-07-12 | 中国石油化工股份有限公司 | Antibacterial plastic composition and preparation method and application thereof |
| CN114426737B (en) * | 2020-10-29 | 2023-07-21 | 中国石油化工股份有限公司 | Flame-retardant antibacterial long glass fiber reinforced polypropylene composite material and preparation method and application thereof |
| CN113789015B (en) * | 2021-08-02 | 2023-12-22 | 海信容声(广东)冰箱有限公司 | High-transparency antibacterial GPPS material and preparation method and application thereof |
| CN115594786B (en) * | 2022-11-10 | 2024-06-11 | 安徽工程大学 | Structural color fabric based on P (St-co-GMA) and macro rapid preparation method thereof |
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| CN103897199A (en) * | 2014-03-25 | 2014-07-02 | 曲阜师范大学 | Cellulose-based guanidine salt bacteriostatic functional material and preparation method thereof |
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| CN103628306A (en) * | 2013-12-09 | 2014-03-12 | 科凯精细化工（上海）有限公司 | Chitosan single guanidine hydrochloride loaded nanometer titanium dioxide compound and preparation method thereof |
| CN103897199A (en) * | 2014-03-25 | 2014-07-02 | 曲阜师范大学 | Cellulose-based guanidine salt bacteriostatic functional material and preparation method thereof |
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