CN109701066A - A kind of ventilative casein complex microsphere and its preparation method and application - Google Patents
A kind of ventilative casein complex microsphere and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of ventilative casein complex microsphere, raw material includes: casein 31-60%, acrylic acid 4-7.2% by weight percentage, epoxy resin 8-20%, carboxymethyl cellulose 7.9-23.8%, methyl methacrylate 8-20%, catalyst 0.1-0.2%, initiator 0.4-1.6%.The invention discloses the preparation methods of above-mentioned ventilative casein complex microsphere, comprising: is uniformly mixed catalyst, solvent, casein, acrylic acid are sequentially added under stirring, heat preservation obtains pretreatment casein；Epoxy resin, carboxymethyl cellulose, methyl methacrylate, stirring solvent are obtained into emulsion；Pretreatment casein is stirred, initiator is added under stirring thereto, heating stirs evenly, then heats up, and emulsion is added and continues to stir, cooling obtains core-shell particles lotion；It is uniform that stirring solvent is added into core-shell particles lotion, sodium hydroxide solution swelling, cooling, filtering is added, washing obtains ventilative casein complex microsphere.
Description
Technical field
It is above-mentioned ventilative the present invention relates to technical field of protein modification more particularly to a kind of ventilative casein complex microsphere
The application of the preparation method of casein complex microsphere and above-mentioned ventilative casein complex microsphere.
Background technique
In human body wound healing process, the use of wound dressing is conducive to protective tissue from extraneous physical damage
Evil, avoids bacterium etc. from causing the superinfection of the surface of a wound, promotes the normal reparation of the surface of a wound, excellent wound dressing will guarantee that the surface of a wound is exempted from
The secondary damage caused by the surface of a wound by external microbe or other substances has good mechanical performance, guarantees user's
Comfort；It is nontoxic, it is non-stimulated, it is ensured that the safety of user；Guarantee that the surface of a wound has sufficient gas exchange.
Pursuit now with people to the safety and comfort of Wound dressing, blueness of the natural macromolecular material by researchers
It looks at, since protein has the advantages such as natural safety and environmental protection, has been more and more widely used.Wherein casein is as in milk
Most important protein, the 8 kinds of amino acid needed in structure containing human body, is closer to, by junket egg with human skin property
It is white be used as prepare adhesive bandage, not only safety and sanitation, but also comfort level is high.
But since casein is large biological molecule polymer, there is aggregation is close, molecular cavities are small, molecular binding affinities are big etc.
Feature causes gas permeability poor, limits it and further applies.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of ventilative casein complex microsphere and its preparations
Methods and applications, the ventilative casein complex microsphere of gained have hollow core-shell structure, and elongation at break and anti-tensile are strong after film forming
Degree is high, and water-permeable and air permeable effect is good, and contact angle is suitable for, and for protecting wound, had both been conducive to wound healing initial stage height and has oozed out tissue
The exclusion of liquid, and be conducive to the drying of the surface of a wound caused by avoiding the exclusion of wound healing later period low leaching tissue fluid, it is conducive to thin
The formation of the proliferation of born of the same parents, attaching and the synthesis of collagen and granulation tissue, and then promote wound healing, while irritation is small, resistance
Bacterium, bacteriostasis property are good, and comprehensive performance is better than liquid/solid bandage on the market, wide market.
A kind of ventilative casein complex microsphere proposed by the present invention, raw material includes: casein 31- by weight percentage
60%, acrylic acid 4-7.2%, epoxy resin 8-20%, carboxymethyl cellulose 7.9-23.8%, methyl methacrylate 8-
20%, catalyst 0.1-0.2%, initiator 0.4-1.6%.
Containing hydroxyl (- OH), ether (- O-) and extremely active epoxy group in the structure of epoxy resin, due to hydroxyl with
Ether has the polarity of height, so that epoxy molecule and adjacent interfaces is generated stronger intermolecular force, forms chemical bond；The present invention
Middle epoxy resin is preferably epoxy resin E-44, and epoxide number (eq/100g) is 0.44-0.46, softening point 14-17, flowing
Property is fabulous, and is the smallest resin of thermosetting resin shrinking percentage, thermal expansion coefficient 6-10.5%, in the whipping process of S2
It is more convenient for and other stock dispersions, keeps system stability good.
Carboxymethyl cellulose, abbreviation CMC, molecular formula are [C6H7O2(OH)2OCH2COONa]n, structural formula are as follows:
Carboxymethyl cellulose has the effects that thickening, the protection of film forming, gluing, water tariff collection, colloid, emulsification and suspension, extensively
It is general to be applied to the industries such as petroleum, food, medicine, textile and paper, while it is as anionic cellulose ethers, is most important
One of cellulose ethers.Carboxymethyl cellulose after alkali process, uses sodium monochloracetate as ether by natural fiber (cotton etc.)
Agent handles by series reaction and anionic cellulose ether is made, and degree of substitution is generally 0.4-1.4, performance by
Degree of substitution is affected.
Since the structure feature of carboxymethyl cellulose determines that its hygroscopicity is larger, general condition storage can be containing compared with flood
Point, while carboxymethyl cellulose aqueous solution will not generate gel, increase and viscosity decline with temperature, when temperature is more than 50 DEG C, glue
It spends irreversible.It is water-soluble better since degree of substitution is higher；Degree of substitution is lower, water-soluble poorer, carboxymethyl cellulose in the present invention
Degree of substitution be preferably 0.52-0.68, in S2 of the invention, by control whipping temp be 56-65 DEG C, carboxymethyl cellulose
Reach irreversible state in water solution system medium viscosity, gained emulsion fully dispersed with epoxy resin, methyl methacrylate
System it is extremely stable.
Preferably, catalyst is aliphatic amines catalyst, alicyclic amines catalyst, alcohol compound catalyst, virtue
At least one of fragrant race's amines catalyst.
Preferably, aliphatic amines catalyst be N, N- dimethyl cyclohexyl amine, bis- (2- dimethylaminoethyl) ethers, N, N,
N', N'- tetramethyl Alkylenediamine, triethylamine, ethylenediamine tetra-acetic acid, polymethylene diamines, diethylaminopropylamine, N, N- diformazan
At least one of base benzylamine.
Preferably, alcohol compound catalyst is triethanolamine and/or dimethylethanolamine.
Preferably, aromatic amine is m-xylene diamine and/or N, N'- lutidines.
Preferably, catalyst is alcohol compound catalyst, preferably triethanolamine.
Wherein, triethanolamine can regard the trihydroxy substituent of aliphatic amine catalyst of triethylamine, triethanolamine as
Since, there are lone pair electrons, triethanolamine has alkalescent on nitrogen-atoms.Alkaline (pKa7.82) weaker than ammonia of triethanolamine, tool
There is the property of tertiary amine and alcohol, when triethanolamine and organic acid reaction low temperature generates salt, and when high temperature generates ester.
It is lonely as present on the substitution of the trihydroxy of amino with nitrogen-atoms using triethanolamine as catalyst in the present invention
Effect to electronics not only with the property of tertiary amine and alcohol, but also is in alkalescent (pKa7.82), therefore at high temperature (80-90 DEG C)
Under the conditions of its can promote cause pretreatment casein and emulsion esterification and crosslinking, be not easy to cause not adding polymerization inhibitor
The thermal polymerization of double bond, and the side reactions such as etherification reaction are few.
Preferably, initiator is hydroperoxides, acyl class peroxide, dialkyl peroxide, two carbonic ester peroxidating
At least one of object, persulfate.
Preferably, initiator is persulfate, preferably sodium peroxydisulfate.
Sodium peroxydisulfate is also high sodium sulphate, soluble easily in water, can effectively be dropped using sodium peroxydisulfate as initiator in the present invention
Low reaction activation energy, free radical generated can promote system esterification and crosslinking at 80-90 DEG C, esterification and crosslinking temperature be reduced, into one
Walk the generation for avoiding high temperature from leading to side reaction.
The preparation method of above-mentioned ventilative casein complex microsphere proposed by the present invention, includes the following steps:
S1, catalyst, solvent are uniformly mixed, casein, acrylic acid is sequentially added under stirring, heat preservation obtains pre- place
Manage casein；
S2, epoxy resin, carboxymethyl cellulose, methyl methacrylate, stirring solvent are obtained into emulsion；
S3, pretreatment casein is stirred, initiator is added under stirring thereto, is warming up to 60-70 DEG C and stirs
It mixes uniformly, then is warming up to 80-88 DEG C, emulsion is added and continues to stir, cooling obtains core-shell particles lotion；
S4, into core-shell particles lotion, addition stirring solvent is uniform, and sodium hydroxide solution swelling is added, and cooling, filtering is washed
It washs to obtain ventilative casein complex microsphere.
Preferably, in S1, whipping temp is 80-90 DEG C, soaking time 20-100min.
Preferably, in S2, mixing time 2-10min, whipping temp is 56-65 DEG C, mixing speed 500-600r/
min。
Preferably, in S4, the concentration of sodium hydroxide solution is 16-18wt%, swelling time 2-4h, and swelling temperature is
80-90℃。
Preferably, above-mentioned solvent is water, ethyl alcohol, propylene glycol, dimethyl sulfoxide, tetrahydrofuran, isopropyl acetate, dimethyl
At least one of formamide, pyridine, preferably water.
Above-mentioned ventilative casein complex microsphere proposed by the present invention is used for the application of Wound protection.
Due to containing α-H, and hydroxyl, carboxyl and amino isopolarity base rich in structure on the main chain of casein
Group makes the structure of casein have stronger activity, graft reaction easily occurs with other monomers molecule.The present invention uses acrylic acid
The active group of α-H and side chain on attack casein main chain, and be grafted on the strand of casein；And epoxy resin and carboxylic
Methylcellulose, the degree of scatter of methyl methacrylate are good, and gained emulsion uniform level is high, and thermal stability is high, with pre- place
It manages casein compounding and carries out esterification and crosslinking, for esterification process by thermostabilization, forming core after polymerization crosslinking reaction is unsaturated carboxylic acid
Nuclear emulsion grain, then being formed has some strength without leading to the shell collapsed, is the existing carboxylic core of richness, and has complete
The polarity of the core-shell particles of core-shell structure, stratum nucleare and shell is small, and by the variation of pH, alkaline solution infiltrates through shell, is being swollen
Deprotonation carboxylic acids macromolecule in the process forms hollow structure, on the one hand so that the inside of emulsion particle be made gradually to be swollen outward
, can be as deformation occurs for draw direction since hollow microsphere has plastic deformation, elongation at break and tensile strength are high, another party
Face is due to the cavity of core-shell particles, and gas molecule is obvious by the resistance reduction of product, and permeability is good, while having on surface
Carboxyl abundant, facilitates the absorption and transmitting of vapour molecule, and the porous structure formed can as deformation occurs for draw direction,
Elongation at break and tensile strength all further get a promotion.
Detailed description of the invention
Fig. 1 is that the steam penetrating capacity of each group sample in test example 3 changes with time figure.
Fig. 2 is that the erythema of each group sample different phase in test example 6 is scored distribution map.
The oedema that Fig. 3 is 1h after the test of each group sample stimulus in test example 6 is scored figure.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Epoxy resin can be disposable type epoxy resin in the present invention, and following embodiments are carried out using epoxy resin E-44
Illustrate and tests.
Embodiment 1
A kind of ventilative casein complex microsphere, raw material include: casein 52.5g, acrylic acid 7.2g, epoxy resin E-44
8g, carboxymethyl cellulose 8g, methyl methacrylate 8g, triethylamine 8g, m-xylene diamine 8g, (the 2- second of dicetyl peroxydicarbonate two
Base hexyl) ester 0.1g, dibenzoyl peroxide 0.2g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, triethylamine, m-xylene diamine, ethyl alcohol are uniformly mixed, casein, acrylic acid are sequentially added under stirring,
Whipping temp is 90 DEG C, keeps the temperature 20min, obtains pretreatment casein；
S2, epoxy resin E-44, carboxymethyl cellulose, methyl methacrylate, ethyl alcohol are stirred into 10min, whipping temp
It is 56 DEG C, mixing speed 600r/min obtains emulsion；
S3, pretreatment casein is stirred, (the 2- ethyl hexyl of dicetyl peroxydicarbonate two is added under stirring thereto
Base) ester, dibenzoyl peroxide, continue to stir 1h, whipping temp is 70 DEG C, then is warming up to 80 DEG C, and emulsion is added and continues to stir
40min is mixed, cooling obtains core-shell particles lotion；
S4, into core-shell particles lotion, addition water is stirred evenly, and the sodium hydroxide solution that concentration is 16wt% is added and is swollen
4h, swelling temperature is 80 DEG C, cooling, filtering, and washing obtains ventilative casein complex microsphere.
Embodiment 2
A kind of ventilative casein complex microsphere, raw material include: casein 33.26g, acrylic acid 4g, epoxy resin E-44
20g, carboxymethyl cellulose 21g, methyl methacrylate 20g, N, N- dimethyl benzylamine 0.14g, potassium peroxydisulfate 1.6g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, by N, N- dimethyl benzylamine, mixed with propylene glycol are uniform, and casein, acrylic acid are sequentially added under stirring, is stirred
Mixing temperature is 80 DEG C, keeps the temperature 100min, obtains pretreatment casein；
S2, epoxy resin E-44, carboxymethyl cellulose, methyl methacrylate, isopropyl acetate are stirred into 2min, stirring
Temperature is 65 DEG C, and mixing speed 500r/min obtains emulsion；
S3, pretreatment casein is stirred, potassium peroxydisulfate is added under stirring thereto, continued to stir 2h, stir
Mixing temperature is 60 DEG C, then is warming up to 88 DEG C, and emulsion is added and continues to stir 20min, cooling obtains core-shell particles lotion；
S4, into core-shell particles lotion, addition ethyl alcohol is stirred evenly, and it is molten that the sodium hydroxide solution that concentration is 18wt% is added
Swollen 2h, swelling temperature is 90 DEG C, cooling, filtering, and washing obtains ventilative casein complex microsphere.
Embodiment 3
A kind of ventilative casein complex microsphere, raw material include: casein 56.66g, acrylic acid 4.4g, epoxy resin E-
44 10g, carboxymethyl cellulose 17.9g, methyl methacrylate 10g, N, N, N', N'- tetramethyl Alkylenediamine 0.16g, uncle
Butylhydroperoxide 0.48g, lauroyl peroxide 0.4g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, by N, N, N', N'- tetramethyl Alkylenediamine, dimethyl sulfoxide are uniformly mixed, and are sequentially added under stirring
Casein, acrylic acid, whipping temp are 83 DEG C, keep the temperature 30min, obtain pretreatment casein；
S2, epoxy resin E-44, carboxymethyl cellulose, methyl methacrylate, dimethyl sulfoxide are stirred into 5min, stirring
Temperature is 59 DEG C, and mixing speed 520r/min obtains emulsion；
S3, pretreatment casein is stirred, tert-butyl hydroperoxide, the peroxidating moon is added under stirring thereto
Osmanthus acyl continues to stir 1.2h, and whipping temp is 62 DEG C, then is warming up to 83 DEG C, and emulsion is added and continues to stir 22min, cooling
To core-shell particles lotion；
S4, into core-shell particles lotion, addition dimethyl sulfoxide is stirred evenly, and the hydroxide that concentration is 16.8wt% is added
Sodium solution is swollen 2.8h, and swelling temperature is 84 DEG C, and cooling, filtering, washing obtains ventilative casein complex microsphere.
Embodiment 4
A kind of ventilative casein complex microsphere, raw material include: casein 31.78g, acrylic acid 6.8g, epoxy resin E-
44 18g, carboxymethyl cellulose 23.7g, methyl methacrylate 18g, ethylenediamine tetra-acetic acid 0.2g, two ring of dicetyl peroxydicarbonate
Own ester 1.52g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, ethylenediamine tetra-acetic acid, tetrahydrofuran are uniformly mixed, casein, acrylic acid is sequentially added under stirring, is stirred
Mixing temperature is 87 DEG C, keeps the temperature 90min, obtains pretreatment casein；
S2, epoxy resin E-44, carboxymethyl cellulose, methyl methacrylate, pyridine are stirred into 7min, whipping temp is
63 DEG C, mixing speed 580r/min obtains emulsion；
S3, pretreatment casein is stirred, di-cyclohexylperoxy di-carbonate is added under stirring thereto, after
Continue stirring 1.8h, whipping temp is 68 DEG C, then is warming up to 85 DEG C, and emulsion is added and continues to stir 38min, it is micro- that cooling obtains nucleocapsid
Ball lotion；
S4, into core-shell particles lotion, addition ethyl alcohol is stirred evenly, and the sodium hydroxide solution that concentration is 17.2wt% is added
It is swollen 3.2h, swelling temperature is 86 DEG C, and cooling, filtering, washing obtains ventilative casein complex microsphere.
Embodiment 5
A kind of ventilative casein complex microsphere, raw material include: casein 52.02g, acrylic acid 5.2g, epoxy resin E-
44 13.2g, carboxymethyl cellulose 15.6g, methyl methacrylate 12.8g,
Polymethylene diamines 0.11g, N, N'- lutidines 0.03g,
Cumyl peroxide 0.24g, sodium peroxydisulfate 0.8g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, by polymethylene diamines, N, N'- lutidines, dimethylformamide are uniformly mixed, under stirring successively
Casein, acrylic acid is added, whipping temp is 86 DEG C, keeps the temperature 70min, obtains pretreatment casein；
S2, epoxy resin E-44, carboxymethyl cellulose, methyl methacrylate, dimethylformamide are stirred into 9min, stirred
Mixing temperature is 61 DEG C, and mixing speed 560r/min obtains emulsion；
S3, pretreatment casein is stirred, cumyl peroxide, persulfuric acid is added under stirring thereto
Sodium continues to stir 1.6h, and whipping temp is 67 DEG C, then is warming up to 87 DEG C, and emulsion is added and continues to stir 32min, cooling obtains
Core-shell particles lotion；
S4, into core-shell particles lotion, addition dimethylformamide is stirred evenly, and the hydrogen-oxygen that concentration is 17.8wt% is added
Change sodium solution and be swollen 3.4h, swelling temperature is 87 DEG C, and cooling, filtering, washing obtains ventilative casein complex microsphere.
Embodiment 6
A kind of ventilative casein complex microsphere, raw material include: casein 53.325g, acrylic acid 6g, epoxy resin E-44
14.8g, carboxymethyl cellulose 9.2g, methyl methacrylate 15.2g,
Bis- (2- dimethylaminoethyl) ether 0.08g, N, N'- diethyl piperazine 0.035g,
Benzoyl peroxide 0.72g, potassium peroxydisulfate 0.64g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, will be bis- (2- dimethylaminoethyl) ether, N, N'- diethyl piperazine, isopropyl acetate be uniformly mixed, stirring
Under sequentially add casein, acrylic acid, whipping temp is 84 DEG C, keeps the temperature 50min, obtains pretreatment casein；
S2, epoxy resin E-44, carboxymethyl cellulose, methyl methacrylate, water are stirred into 3-9min, whipping temp is
60 DEG C, mixing speed 540r/min obtains emulsion；
S3, pretreatment casein is stirred, benzoyl peroxide, potassium peroxydisulfate is added under stirring thereto,
Continue to stir 1.4h, whipping temp is 63 DEG C, then is warming up to 81 DEG C, and emulsion is added and continues to stir 26min, cooling obtains nucleocapsid
Microballoon lotion；
S4, into core-shell particles lotion, addition dimethylformamide is stirred evenly, and the hydrogen-oxygen that concentration is 16.2wt% is added
Change sodium solution and be swollen 2.6h, swelling temperature is 83 DEG C, and cooling, filtering, washing obtains ventilative casein complex microsphere.
Embodiment 7
A kind of ventilative casein complex microsphere, raw material include: casein 45.877g, acrylic acid 6.4g, epoxy resin E-
44 12g, carboxymethyl cellulose 22.6g, methyl methacrylate 12g, triethanolamine 0.123g, sodium peroxydisulfate 1g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, triethanolamine, water are uniformly mixed, casein, acrylic acid, whipping temp 88 is sequentially added under stirring
DEG C, 40min is kept the temperature, pretreatment casein is obtained；
S2, epoxy resin E-44, carboxymethyl cellulose, methyl methacrylate, water are stirred into 8min, whipping temp 58
DEG C, mixing speed 570r/min obtains emulsion；
S3, pretreatment casein is stirred, sodium peroxydisulfate is added under stirring thereto, continue to stir 1.3h,
Whipping temp is 66 DEG C, then is warming up to 82 DEG C, and emulsion is added and continues to stir 35min, cooling obtains core-shell particles lotion；
S4, into core-shell particles lotion, addition water is stirred evenly, and it is molten that the sodium hydroxide solution that concentration is 16.5wt% is added
Swollen 3.5h, swelling temperature is 82 DEG C, cooling, filtering, and washing obtains ventilative casein complex microsphere.
Embodiment 8
A kind of ventilative casein complex microsphere, raw material include: casein 46.82g, acrylic acid 4.8g, epoxy resin E-
44 16g, carboxymethyl cellulose 14.8g, methyl methacrylate 16g, triethanolamine 0.18g, sodium peroxydisulfate 1.4g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, triethanolamine, water are uniformly mixed, casein, acrylic acid, whipping temp 82 is sequentially added under stirring
DEG C, 80min is kept the temperature, pretreatment casein is obtained；
S2, epoxy resin E-44, carboxymethyl cellulose, methyl methacrylate, water are stirred into 4min, whipping temp 62
DEG C, mixing speed 530r/min obtains emulsion；
S3, pretreatment casein is stirred, sodium peroxydisulfate is added under stirring thereto, continue to stir 1.7h,
Whipping temp is 64 DEG C, then is warming up to 86 DEG C, and emulsion is added and continues to stir 25min, cooling obtains core-shell particles lotion；
S4, into core-shell particles lotion, addition water is stirred evenly, and it is molten that the sodium hydroxide solution that concentration is 17.5wt% is added
Swollen 2.5h, swelling temperature is 88 DEG C, cooling, filtering, and washing obtains ventilative casein complex microsphere.
Embodiment 9
A kind of ventilative casein complex microsphere, raw material include: casein 46.84g, acrylic acid 5.6g, epoxy resin E-
44 14g, carboxymethyl cellulose 18.2g, methyl methacrylate 14g, triethanolamine 0.16g, sodium peroxydisulfate 1.2g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, triethanolamine, water are uniformly mixed, casein, acrylic acid, whipping temp 85 is sequentially added under stirring
DEG C, 60min is kept the temperature, pretreatment casein is obtained；
S2, epoxy resin E-44, carboxymethyl cellulose, methyl methacrylate, water are stirred into 6min, whipping temp 60
DEG C, mixing speed 550r/min obtains emulsion；
S3, pretreatment casein is stirred, sodium peroxydisulfate is added under stirring thereto, continue to stir 1.5h,
Whipping temp is 65 DEG C, then is warming up to 84 DEG C, and emulsion is added and continues to stir 30min, cooling obtains core-shell particles lotion；
S4, into core-shell particles lotion, addition water is stirred evenly, and the sodium hydroxide solution that concentration is 17wt% is added and is swollen
3h, swelling temperature is 85 DEG C, cooling, filtering, and washing obtains ventilative casein complex microsphere.
Comparative example 1
A kind of complex casein microballoon, raw material include: casein 46.84g, acrylic acid 5.6g, epoxy resin E-44
14g, carboxymethyl cellulose 18.2g, methyl methacrylate 14g, triethanolamine 0.16g, ammonium persulfate 1.2g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, ethylenediamine, water are uniformly mixed, casein, acrylic acid, whipping temp 85 is sequentially added under stirring
DEG C, 60min is kept the temperature, pretreatment casein is obtained；
S2, epoxy resin E-44, carboxymethyl cellulose, methyl methacrylate, water are stirred into 6min, whipping temp 60
DEG C, mixing speed 550r/min obtains emulsion；
S3, pretreatment casein is stirred, ammonium persulfate is added under stirring thereto, continue to stir 1.5h,
Whipping temp is 65 DEG C, then is warming up to 84 DEG C, and emulsion is added and continues to stir 30min, cooling obtains core-shell particles lotion；
S4, into core-shell particles lotion, addition water is stirred evenly, and the sodium hydroxide solution that concentration is 17wt% is added and is swollen
3h, swelling temperature is 85 DEG C, cooling, and filtering, washing obtains complex casein microballoon.
Comparative example 2
A kind of complex casein microballoon, raw material include: casein 46.84g, methacrylic acid 5.6g, styrene 14g,
Carboxymethyl cellulose 18.2g, methyl methacrylate 14g, triethanolamine 0.16g, sodium peroxydisulfate 1.2g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, triethanolamine, water are uniformly mixed, casein, methacrylic acid, whipping temp is sequentially added under stirring
It is 85 DEG C, keeps the temperature 60min, obtains pretreatment casein；
S2, styrene, carboxymethyl cellulose, methyl methacrylate, water are stirred to 6min, whipping temp is 60 DEG C, is stirred
Mixing speed is 550r/min, obtains emulsion；
S3, pretreatment casein is stirred, sodium peroxydisulfate is added under stirring thereto, continue to stir 1.5h,
Whipping temp is 65 DEG C, then is warming up to 84 DEG C, and emulsion is added and continues to stir 30min, cooling obtains core-shell particles lotion；
S4, into core-shell particles lotion, addition water is stirred evenly, and the sodium hydroxide solution that concentration is 17wt% is added and is swollen
3h, swelling temperature is 85 DEG C, cooling, and filtering, washing obtains complex casein microballoon.
Comparative example 3
A kind of complex casein, raw material include: casein 46.84g, acrylic acid 5.6g, triethanolamine 0.16g.
The preparation method of above-mentioned ventilative casein complex microsphere, includes the following steps:
S1, triethanolamine, water are uniformly mixed, casein, acrylic acid, whipping temp 85 is sequentially added under stirring
DEG C, 60min is kept the temperature, first material is obtained；
S2, first material is stirred, whipping temp is 65 DEG C, then is warming up to 84 DEG C, and cooling obtains second material；
S3, into second material, addition water is stirred evenly, and the sodium hydroxide solution that concentration is 17wt% is added and is swollen 3h, molten
Swollen temperature is 85 DEG C, cooling, and filtering, washing obtains complex casein.
Comparative example 4
Using commercially available casein.
Casein manufacturer used is Zhejiang Hua Tian Fine Chemical Co., Ltd in above-mentioned experimentation, and specification is single-minded
It is pure.
Test example 1
By casein complex microsphere and the 1 gained complex casein microballoon of comparative example, 2 institute of comparative example of breathing freely obtained by embodiment 9
Complex casein microballoon, 3 gained complex casein of comparative example, commercially available casein used in comparative example 4 carry out partial size test: spend
It is 0.05wt% that ionized water, which is diluted to concentration to sample, is subsequently placed in Malvern company, Britain Nano-ZS dynamic light scattering particle size
In the sample cell of instrument, result is as follows:
| Average grain diameter, nm | |
| Embodiment 9 | 156 |
| Comparative example 1 | 138 |
| Comparative example 2 | 117 |
| Comparative example 3 | 103 |
| Comparative example 4 | 200 |
Due to newborn source casein have surface-active, but be different from other Small molecular surfactants have polar head and
Non-polar tail, it by based on different hydrophobic amino acids not charged region and the leading charging zone of hydrophilic amino acid
Composition.As other surfaces bioactive molecule, when concentration is higher than its critical concentration condition, casein self-assemble is at hydrophobic
Region is core, and hydrophilic segment and other hydrophily lactalbumins are wrapped in the particle on surface.In golgiosome, the junket of monomer
Albumen by and phosphorus and calcium combination, shielding casein itself possessed by charge simultaneously be allowed to aggregation become larger particle state.
Therefore comparative example 3 is relative to comparative example 4, using the active group of α-H and side chain on acrylic acid attack casein main chain
Group, and be grafted on the strand of casein, it is allowed to be difficult to reunite, to reduce average grain diameter；But shown according to document: junket egg
White partial size is 80-500nm, also illustrates the reason of average grain diameter of comparative example 3 is greater than casein minimum grain size instead.
And embodiment 9, comparative example 1, comparative example 2, relative to comparative example 3 and comparative example 4, the particle diameter distribution of hollow microsphere is bright
It is aobvious to narrow, illustrate that emulsion has apparent influence to the breathe freely stability of casein complex microsphere of gained, makes to be distributed in nucleocapsid
Carboxyl amount on microsphere surface and sour core increases, after being swollen progress, hollow microsphere surface electronegativity enhancing, so as to cause hollow
Electrostatic repulsion between microballoon increases, and partial size reduces.
Comparative example 5
The liquid adhesive bandage of Japanese certain drugmaker production.
Comparative example 6
The common adhesive bandage of Chinese yunnan medicine enterprise production.
Test example 2
By casein complex microsphere and the 1 gained complex casein microballoon of comparative example, 2 institute of comparative example of breathing freely obtained by embodiment 9
Complex casein microballoon, 3 gained complex casein of comparative example, liquid used in commercially available casein, comparative example 5 used in comparative example 4
Common adhesive bandage used in adhesive bandage, comparative example 6 carries out mechanical test.
Take obtained by the embodiment 9 of phase homogenous quantities breathe freely casein complex microsphere, 1 gained complex casein microballoon of comparative example,
2 gained complex casein microballoon of comparative example, 3 gained complex casein of comparative example, commercially available casein, comparative example 5 used in comparative example 4
Liquid adhesive bandage used, is poured into mold slots, is stood 5min, is allowed to form uniform bubble-free film, cross-sectional area is respectively
25mm × (0.034 ± 0.002mm) removes film and is allowed to the smooth of the edge non-notch.
The both ends of common adhesive bandage used in above-mentioned sample and comparative example 6 are successively sandwiched in Tensile Tester and are tested,
Access time result average value, result are as follows:
| Tensile strength, N/mm2 | Elongation at break, % | |
| Embodiment 9 | 6.25 | 148.9 |
| Comparative example 1 | 5.16 | 122.7 |
| Comparative example 2 | 4.32 | 116.3 |
| Comparative example 3 | 3.04 | 77.3 |
| Comparative example 4 | 1.53 | 68.4 |
| Comparative example 5 | 6.13 | 124.3 |
| Comparative example 6 | 11.68 | 151.6 |
Ventilative casein complex microsphere and 1 gained complex casein microballoon of comparative example, comparative example 2 as obtained by embodiment 9
Gained complex casein microballoon, 3 gained complex casein of comparative example, commercially available casein compares used in comparative example 4, can see
Out: the ventilative 1 gained complex casein microballoon of casein complex microsphere and comparative example of present invention gained, the 2 compound junket of gained of comparative example
Protein microsphere have can deformation behavior, the film with porous structure is formed after film forming, porous structure can be sent out with draw direction
Injury of the external force to film bulk is offset in raw deformation, therefore tensile strength and elongation at break all get a promotion；But gained of the invention
Ventilative casein complex microsphere has relative to 1 gained complex casein microballoon of comparative example, 2 gained complex casein microballoon of comparative example
There is bigger cavity, is formed by film porous structure as bigger deformation quantity, therefore the present invention can occur for draw direction
Gained breathes freely casein complex microsphere with higher tensile strength and elongation at break.
After human skin forms wound, since human motion causes skin to be pullled, but as adhesive bandage can not fix wound,
Then will lead to wound to be torn, wound caused to rupture again, but as adhesive bandage can not in time with skin movements alternatively, it will cause
Body movement is limited, therefore adhesive bandage is required to answer tensile strength with higher and elongation at break.It is breathed freely as obtained by embodiment 9
Casein complex microsphere is compared with common adhesive bandage used in liquid adhesive bandage, comparative example 6 used in comparative example 5, it will thus be seen that
Embodiment 9 is close with the tensile strength of comparative example 5, and the elongation at break of embodiment 9 is better than comparative example 5；Embodiment 9 and comparative example
6 elongation at break is close, but the tensile strength of embodiment 9 is inferior to comparative example 6.
Test example 3
By casein complex microsphere and the 1 gained complex casein microballoon of comparative example, 2 institute of comparative example of breathing freely obtained by embodiment 9
Complex casein microballoon, 3 gained complex casein of comparative example, liquid used in commercially available casein, comparative example 5 used in comparative example 4
Common adhesive bandage used in adhesive bandage, comparative example 6 carries out vapor pervious test.
Take obtained by the embodiment 9 of phase homogenous quantities breathe freely casein complex microsphere, 1 gained complex casein microballoon of comparative example,
2 gained complex casein microballoon of comparative example, 3 gained complex casein of comparative example, commercially available casein, comparative example 5 used in comparative example 4
Liquid adhesive bandage used, is poured into mold slots, is stood 5min, is allowed to form uniform bubble-free film, cross-sectional area is respectively
25mm × (0.034 ± 0.002mm) removes film and is allowed to the smooth of the edge non-notch.
Common adhesive bandage used in above-mentioned sample and comparative example 6 is pressed into " GB/T 1037-88 plastic film and the permeable steaming of sheet material
The cup type method of gas test method " in regulation carry out steam penetrating capacity detection, result is as shown in Figure 1.Referring to Fig.1, embodiment 9
The ventilative casein complex microsphere of gained is formed by film as time goes by, and steam penetrating capacity is in downward trend.
By casein complex microsphere and the 1 gained complex casein microballoon of comparative example, 2 institute of comparative example of breathing freely obtained by the present invention
Obtaining complex casein microballoon has hollow structure, while having carboxyl abundant on surface, facilitates the suction of vapour molecule early period
Echo transmitting, though and commercially available casein used in 3 gained complex casein of comparative example, comparative example 4 be macro-molecular protein, without in
Hollow structure and surface carboxyl groups cause steam penetrating capacity low, are unfavorable for the exclusion of wound healing initial stage height exudation tissue fluid.
Filling, blocking of the later period due to tissue fluid, penetrate the vapor of ventilative casein complex microsphere obtained by the present invention
Amount decline, is conducive to the drying of the surface of a wound caused by avoiding the exclusion of wound healing later period low leaching tissue fluid instead, and compares
The steam penetrating capacity of liquid adhesive bandage used in example 5 is in downward trend as time goes by, but effect is outstanding not as good as the present invention,
Common adhesive bandage used in comparative example 6 maintains always similar steam penetrating capacity, has both been unfavorable for that wound is kept early period to keep dry
It is dry, also it is unfavorable for later period wound and keeps wetting.
But gained of the invention breathes freely casein complex microsphere relative to 1 gained complex casein microballoon of comparative example, comparative example 2
Gained complex casein microballoon has higher steam penetrating capacity, and, explanation lower in later period steam penetrating capacity in early period
The ventilative casein complex microsphere of gained of the invention is more suitable for Wound protection.
Test example 4
By casein complex microsphere and the 1 gained complex casein microballoon of comparative example, 2 institute of comparative example of breathing freely obtained by embodiment 9
Complex casein microballoon, 3 gained complex casein of comparative example, liquid used in commercially available casein, comparative example 5 used in comparative example 4
Common adhesive bandage used in adhesive bandage, comparative example 6 carries out permeability test.
Take obtained by the embodiment 9 of phase homogenous quantities breathe freely casein complex microsphere, 1 gained complex casein microballoon of comparative example,
2 gained complex casein microballoon of comparative example, 3 gained complex casein of comparative example, commercially available casein, comparative example 5 used in comparative example 4
Liquid adhesive bandage used, is poured into mold slots, is stood 5min, is allowed to form uniform bubble-free film, cross-sectional area is respectively
25mm × (0.034 ± 0.002mm) removes film and is allowed to the smooth of the edge non-notch.
Common adhesive bandage used in above-mentioned sample and comparative example 6 is pressed into " GB/T 1038-2000 plastic film and thin slice gas
Permeability test method pressure differential method " in regulation carry out the detection of gas transit dose, result is as follows:
As seen from the above table: present invention gained is breathed freely 1 gained complex casein microballoon of casein complex microsphere and comparative example, right
2 gained complex casein microballoon of ratio has hollow structure, can reduce the circulating resistance of gas molecule, and in remaining comparative example
Macromolecule be solid construction, hinder air circulation, gas transit dose is low, often will cause the skin hair of wound and wound circumference
White, softening, easily leads to the secondary infection of bacterium.
Gained of the invention breathes freely casein complex microsphere relative to 1 gained complex casein microballoon of comparative example, 2 institute of comparative example
Obtaining complex casein microballoon has bigger cavity, therefore its permeability is more preferable.
Test example 5
By casein complex microsphere and the 1 gained complex casein microballoon of comparative example, 2 institute of comparative example of breathing freely obtained by embodiment 9
Complex casein microballoon, 3 gained complex casein of comparative example, liquid used in commercially available casein, comparative example 5 used in comparative example 4
Common adhesive bandage used in adhesive bandage, comparative example 6 carries out contact angle test.
Take obtained by the embodiment 9 of phase homogenous quantities breathe freely casein complex microsphere, 1 gained complex casein microballoon of comparative example,
2 gained complex casein microballoon of comparative example, 3 gained complex casein of comparative example, commercially available casein, comparative example 5 used in comparative example 4
Liquid adhesive bandage used, is poured into mold slots, is stood 5min, is allowed to form uniform bubble-free film, cross-sectional area is respectively
25mm × (0.034 ± 0.002mm) removes film and is allowed to the smooth of the edge non-notch.
Above-mentioned sample is dried overnight under the conditions of 37 DEG C, by after drying sample and comparative example 6 used in common adhesive bandage
It is measured using the size of the contact angle on the surface optical video contact angle instrument (KRUSS DSA100), the following institute of result
Show:
| Contact angle, ° | |
| Embodiment 9 | 72 |
| Comparative example 1 | 63 |
| Comparative example 2 | 60 |
| Comparative example 3 | 58 |
| Comparative example 4 | 33 |
| Comparative example 5 | 65 |
| Comparative example 6 | 46 |
The size of contact angle reflects the hydrophilic/hydrophobic performance on wound dressing surface, and hydrophobic scope is belonged to greater than 90 °, small
Belong to hydrophilic scope in 90 °.Reported according to existing literature, contact angle 60-80 ° of range wound dressing most beneficial for cell
Growth, when material surface becomes excessively hydrophilic or excessively hydrophobic, the proliferation of cell shows decline.
Due to cell proliferation and attach linear correlation to a certain extent, the patch of the proliferative effect of cell to cell
Attached, contact angle is equally beneficial for the attaching of cell in the wound dressing of 60-80 ° of range.Simultaneously because cell has preferable increase
Rate and attaching ability are grown, contact angle is conducive to the synthesis of collagen in wound healing process in the wound dressing of 60-80 ° of range, into
And promote the formation of granulation tissue.
As seen from the above table: the contact angle of the ventilative casein complex microsphere of present invention gained is 72 °, and 1 gained of comparative example is compound
The contact angle of casein micelles is 63 °, and the contact angle of 2 gained complex casein microballoon of comparative example is 60 °, liquid used in comparative example 5
The contact angle of body adhesive bandage is 65 °, all has good hydrophily/hydrophobic domains, guarantees that the surface of a wound is in moist environment, is conducive to
The formation of the proliferation of cell, attaching and the synthesis of collagen and granulation tissue, and then promote wound healing, and remaining comparative example
Contact angle is respectively less than 60 °, excessively hydrophilic, causes the surface of a wound easily dry, is unfavorable for the proliferation of cell, and granulation tissue is easy to be bonded
Adhesive bandage is unfavorable for taking off, easily causes secondary wound dehiscence.
Test example 6
By casein complex microsphere and the 1 gained complex casein microballoon of comparative example, 2 institute of comparative example of breathing freely obtained by embodiment 9
Complex casein microballoon, 3 gained complex casein of comparative example, liquid used in commercially available casein, comparative example 5 used in comparative example 4
Common adhesive bandage used in adhesive bandage, comparative example 6 carries out irritation test, the specific steps are as follows:
Rabbit to be measured is taken, the coat at its back is removed using the operating scissors after disinfection, remaining coat is taken off with suitable
Hair cream removal, with the remaining depilatory cream of warm water cleaning and the coat that falls off；By the feeding of unhairing treated rabbit is placed in dried and clean
It supports in environment, raising is for 24 hours；Taking out treated rabbit, auricular vein injects 1% yellow Jackets, dosage 30mg/kg, to
When rabbit goes into a coma, by its back, two sides are divided into 6 symmetrical regions of left and right, labeled as test portion, positive control portion and
Negative control portion；
By obtained by 150 μ L embodiments 9 breathe freely 1 gained complex casein microballoon of casein complex microsphere and 150 μ L comparative example,
150 μ L comparative example, 2 gained complex casein microballoon, 150 μ L comparative example, 3 gained complex casein, city used in 150 μ L comparative examples 4
It sells liquid adhesive bandage used in casein, 150 μ L comparative examples 5 and is uniformly coated on test portion, by common adhesive bandage used in comparative example 6
It is pasted on test portion；It is that 20wt% lauryl sodium sulfate aqueous solution immerses in sizeable gauze by 150 μ L mass fractions,
It is pasted on positive control portion；150 μ 1 × PBS solutions of L are immersed in sizeable gauze, negative control portion is pasted on；
Sizeable breathable gauze is selected to wrap the tested region of rabbit, blend compounds band is fixed, clean in drying
It is residual that 4h is raised under net culture environment, then extracts gauze and experiment sample, carefully cleaned with warm water and removes a rabbit back
Stay substance；
Respectively at extract experiment with sample 0h, 1h, for 24 hours, that each period man rabbit back is recorded after 48h, 72h and 96h is tested
The case where position erythema and oedema.
Evaluation criterion is as follows:
Its erythema is scored as shown in Fig. 2, its oedema is scored as shown in Figure 3 (since only 1h each group occurs after the end of the test
Oedema, later edema extinction, the figure therefore oedema that Fig. 3 is only 1h after each group sampling test is scored).
From Fig. 2 and Fig. 3: in when detecting, positive control shows the stimulate the reaction of severe, and from the positive
The experimental result of control and negative control is it is found that the foundation of experimental model and condition meets stimulus standard.Gained of the invention is ventilative
Casein complex microsphere occurs extremely slight oedema in 1h, it is preceding for 24 hours in there is erythema, it is compound to be superior to the gained of comparative example 1
Casein micelles, 2 gained complex casein microballoon of comparative example, 5 gained liquid-liquid adhesive bandage of comparative example, but it is inferior to comparative example 6
Common adhesive bandage used, and as time goes by, it stimulates and constantly weakens.It is confirmed that: the ventilative casein of present invention gained is multiple
Conjunction microballoon irritation is extremely weak, and use is safe, meets the requirement of wound dressing.
Test example 7
By casein complex microsphere and the 1 gained complex casein microballoon of comparative example, 2 institute of comparative example of breathing freely obtained by embodiment 9
Complex casein microballoon, 3 gained complex casein of comparative example, liquid used in commercially available casein, comparative example 5 used in comparative example 4
Common adhesive bandage used in adhesive bandage, comparative example 6 carries out resistance bacterium property test, the specific steps are as follows:
(1) take breathe freely obtained by the embodiment 9 of phase homogenous quantities casein complex microsphere, 1 gained complex casein of comparative example micro-
Ball, 2 gained complex casein microballoon of comparative example, 3 gained complex casein of comparative example, commercially available casein, comparison used in comparative example 4
Liquid adhesive bandage, is poured into mold slots used in example 5, is stood 5min, is allowed to form uniform bubble-free film, cross-sectional area is respectively
25mm × (0.034 ± 0.002mm) removes film and is allowed to the smooth of the edge non-notch；
(2) nutrient broth agar culture solution is poured into while hot in sterilized culture dish, completely after solidification, by step
(1) ordinary filter paper and 0.22 μm of miillpore filter after common adhesive bandage, aseptic process used in each film sample, comparative example 6 obtained by
(aseptic process after ordinary filter paper and 0.22 μm of miillpore filter as control) is uniformly laid on solid medium；
(3) microorganism (Escherichia coli, golden yellow grape are cultivated in biochemical cultivation case using nutrient broth agar culture medium
Coccus, Pseudomonas aeruginosa, serratia marcescens, Candida albicans), obtaining concentration is 109The bacterium solution of a/mL；
(4) each 10 μ L of bacterium solution obtained by aspiration step (3), is being added dropwise to step (2) obtained solid agar plates just respectively
Center is subsequently placed in the biochemical cultivation case of preference temperature and cultivates (wherein, Escherichia coli, staphylococcus aureus, green pus for 24 hours
The preference temperature of bacillus be 37 DEG C, serratia marcescens, Candida albicans preference temperature be 22 DEG C)；
(5) sterile pipette is used, absorbs the bacterium solution in culture medium, then use aseptic nipper by each film sample, comparison
Ordinary filter paper and 0.22 μm of miillpore filter are removed from solid medium after common adhesive bandage, aseptic process used in example 6, then
Be placed in the biochemical cultivation case of preference temperature cultivate for 24 hours (wherein, Escherichia coli, staphylococcus aureus, Pseudomonas aeruginosa be suitable for
Temperature be 37 DEG C, serratia marcescens, Candida albicans preference temperature be 22 DEG C)；
Its result is as follows:
As seen from the above table: each group except striping continue culture for 24 hours after, obtained by embodiment 9 breathe freely casein complex microsphere with it is right
1 gained complex casein microballoon of ratio, 2 gained complex casein microballoon of comparative example, liquid adhesive bandage is sterile used in comparative example 5
It is born length, and finds the growth of Escherichia coli, staphylococcus aureus, Pseudomonas aeruginosa in miillpore filter group, therefore 9 institute of embodiment
Must breathe freely casein complex microsphere and 1 gained complex casein microballoon of comparative example, 2 gained complex casein microballoon of comparative example, right
Liquid adhesive bandage used in ratio 5 is formed by the aperture of film less than 0.22 μm, illustrates that present invention resistance bacterium property is good.
Test example 8
By casein complex microsphere and the 1 gained complex casein microballoon of comparative example, 2 institute of comparative example of breathing freely obtained by embodiment 9
Complex casein microballoon, 3 gained complex casein of comparative example, liquid used in commercially available casein, comparative example 5 used in comparative example 4
Common adhesive bandage used in adhesive bandage, comparative example 6 carries out biocidal property test, the specific steps are as follows:
(1) by Escherichia coli, staphylococcus aureus and Pseudomonas aeruginosa respectively according to the ratio of 1:100000 with sterile 1
× PBS is diluted；By serratia marcescens and Candida albicans respectively according to the ratio of 1:10000 with 1 sterile × PBS into
Row dilution；
(2) it takes the 10 above-mentioned bacterium solutions of μ L to be uniformly applied in nutrient broth agar culture medium respectively, is then respectively placed in suitable
(wherein, the preference temperature of Escherichia coli, staphylococcus aureus, Pseudomonas aeruginosa is cultivated in the bio-incubator of suitable temperature
Be 37 DEG C, serratia marcescens, Candida albicans preference temperature be 28 DEG C), so that above-mentioned strain is uniformly grown on solid
Body culture medium, and bacterium number is less than 100cfu in unit area；
(3) it in the culture dish after solid medium to be poured into sterilizing while hot, completely after solidification, takes obtained by 10 μ L steps (2)
Bacterium solution is uniformly applied in culture medium with sterilized spreader；
(4) breathe freely casein complex microsphere, 10 μ L comparative example 1 gained compound junket egg are added dropwise obtained by 10 μ L embodiments 9 respectively
Bai Weiqiu, 10 μ L comparative example, 2 gained complex casein microballoon, 10 μ L comparative example, 3 gained complex casein, 10 μ L comparative example, 4 institute
The liquid adhesive bandage used in commercially available casein, 10 μ L comparative examples 5, then will be general used in comparative example 6 on the culture medium for being inoculated with bacterium
Logical adhesive bandage is affixed on the culture medium for being inoculated with bacterium, sticks 0.45 μm of ordinary filter paper in every piece of culture medium again as control；
(5) each group is respectively placed in the bio-incubator of preference temperature and is cultivated (wherein, Escherichia coli, golden yellow for 24 hours
Color staphylococcus, Pseudomonas aeruginosa preference temperature be 37 DEG C, serratia marcescens, Candida albicans preference temperature be 28 DEG C),
The size for detecting inhibition zone, calculates the diameter of inhibition zone；
Its result is (unit mm) as follows:
As seen from the above table: present invention gained is breathed freely bacteriostasis property liquid used in the comparative example 5 of casein complex microsphere
Between common adhesive bandage used in adhesive bandage and comparative example 6, the demand of the wound protection formed in daily life can be met.
Compbined test example 1-8's as a result, it can be found that: due to casein complex microsphere of breathing freely obtained by the present invention have it is hollow
Core-shell structure, therefore elongation at break and tensile strength are high, and water-permeable and air permeable effect is good, and contact angle is suitable for both being conducive to wound healing
Initial stage height oozes out the exclusion of tissue fluid, and is conducive to the surface of a wound caused by avoiding the exclusion of wound healing later period low leaching tissue fluid
Drying, be conducive to the formation of the proliferation of cell, attaching and the synthesis of collagen and granulation tissue, and then promote wound healing,
Irritation is small simultaneously, and resistance bacterium, bacteriostasis property are good, and comprehensive performance is better than liquid/solid bandage on the market, wide market.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of ventilative casein complex microsphere, which is characterized in that its raw material includes: casein 31-60% by weight percentage,
Acrylic acid 4-7.2%, epoxy resin 8-20%, carboxymethyl cellulose 7.9-23.8%, methyl methacrylate 8-20%, catalysis
Agent 0.1-0.2%, initiator 0.4-1.6%.
2. casein complex microsphere of breathing freely according to claim 1, which is characterized in that catalyst is aliphatic amines catalysis
Agent, alicyclic amines catalyst, alcohol compound catalyst, aromatic amine catalyst at least one.
3. casein complex microsphere of breathing freely according to claim 2, which is characterized in that aliphatic amines catalyst is N, N- bis-
Methyl cyclohexylamine, bis- (2- dimethylaminoethyl) ethers, N, N, N', N'- tetramethyl Alkylenediamine, triethylamine, ethylenediamine tetrem
Acid, polymethylene diamines, diethylaminopropylamine, N, at least one of N- dimethyl benzylamine；
Preferably, alcohol compound catalyst is triethanolamine and/or dimethylethanolamine；
Preferably, aromatic amine is m-xylene diamine and/or N, N'- lutidines.
4. any one of -3 ventilative casein complex microsphere according to claim 1, which is characterized in that catalyst is alcohols chemical combination
Object catalyst, preferably triethanolamine.
5. any one of -4 ventilative casein complex microsphere according to claim 1, which is characterized in that initiator is hydroperoxidation
At least one of object, acyl class peroxide, dialkyl peroxide, two carbonic ester peroxide, persulfate.
6. any one of -5 ventilative casein complex microsphere according to claim 1, which is characterized in that initiator is persulfuric acid
Salt, preferably sodium peroxydisulfate.
7. a kind of preparation method for casein complex microsphere of breathing freely as described in claim any one of 1-6, which is characterized in that including
Following steps:
S1, catalyst, solvent are uniformly mixed, casein, acrylic acid is sequentially added under stirring, heat preservation obtains pretreatment junket
Albumen；
S2, epoxy resin, carboxymethyl cellulose, methyl methacrylate, stirring solvent are obtained into emulsion；
S3, pretreatment casein is stirred, initiator is added under stirring thereto, it is equal to be warming up to 60-70 DEG C of stirring
It is even, then it is warming up to 80-88 DEG C, emulsion is added and continues to stir, cooling obtains core-shell particles lotion；
S4, into core-shell particles lotion, addition stirring solvent is uniform, and sodium hydroxide solution swelling is added, and cooling, filtering is washed
To ventilative casein complex microsphere.
8. the preparation method for casein complex microsphere of breathing freely according to claim 3, which is characterized in that in S1, whipping temp
It is 80-90 DEG C, soaking time 20-100min；Preferably, in S2, mixing time 2-10min, whipping temp 56-65
DEG C, mixing speed 500-600r/min.
9. according to the preparation method of the ventilative casein complex microsphere of claim 7 or 8, which is characterized in that in S4, hydroxide
The concentration of sodium solution is 16-18wt%, and swelling time 2-4h, swelling temperature is 80-90 DEG C.
10. the application that a kind of casein complex microsphere of breathing freely as described in claim any one of 1-5 is used for Wound protection.
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| CN108034029A (en) * | 2018-01-16 | 2018-05-15 | 青岛科技大学 | A kind of epoxy emulsion and its green synthesis method with core shell structure |
| WO2018124445A1 (en) * | 2016-12-28 | 2018-07-05 | 롯데정밀화학 주식회사 | Briquette binder composition, briquette including same, and method for producing briquette |
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| CN101648022A (en) * | 2009-08-21 | 2010-02-17 | 南京大学 | Nanometer microsphere or hollow sphere of casein or casein-polyacrylic acid compound and preparation method and application thereof |
| CN103709989A (en) * | 2013-12-02 | 2014-04-09 | 张成栋 | Protein adhesive, preparation method and application thereof |
| WO2018124445A1 (en) * | 2016-12-28 | 2018-07-05 | 롯데정밀화학 주식회사 | Briquette binder composition, briquette including same, and method for producing briquette |
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