CN109280366A - A kind of preparation method of antibiotic property waterproof moisture-penetrating urethane film - Google Patents
A kind of preparation method of antibiotic property waterproof moisture-penetrating urethane film Download PDFInfo
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- CN109280366A CN109280366A CN201810924509.3A CN201810924509A CN109280366A CN 109280366 A CN109280366 A CN 109280366A CN 201810924509 A CN201810924509 A CN 201810924509A CN 109280366 A CN109280366 A CN 109280366A
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
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- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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Abstract
The invention discloses a kind of preparation method of antibiotic property waterproof moisture-penetrating urethane film, include the following steps: that (1) prepares modified composite；(2) antibacterial compounded mix surface modification treatment；(3) preparation antibacterial enhances modified polyurethane resin；(4) polyurethane laminated film is prepared.The present invention is by carrying out surface modification treatment to molybdic tailing, bamboo charcoal powder and nano-titanium dioxide, and it is added in the synthesis process of waterborne polyurethane resin, it is prepared for the enhancing polyurethane resin with essential anti-microbial attributes, film is prepared by carrying out physical blending in the case where nanometer silver antimicrobial liquid participates in beta-cyclodextrin/tetrahydrofuran compound again, make prepared laminated film that there is excellent broad spectrum antibacterial, mechanical property and water resistance, there is excellent breathable and waterproof simultaneously, excellent combination property, wide market.
Description
Technical field
The present invention relates to polyurethane film preparation technical fields, thin more particularly to a kind of antibiotic property waterproof moisture-penetrating urethane
The preparation method of film.
Background technique
Since the 60's of 20th century, polyvinyl chloride, neoprene and various synthetic rubber are widely used in particular surroundings
With collar domain, the clothing made of these materials has many advantages, such as waterproof, liquidproof leakage, but at the same time, human body itself
The sweat that metabolism generates cannot but excrete in time, make one to generate sultry, the cold discomfort such as wet, and this be mainly because
Thus caused by quasi polymer material shortage " can respiratory ".
Waterproof and moisture-inhibiting the two functions can dexterously be had both by the film of raw material and coating of polyurethane, at the same do not lose from
The original excellent physicochemical property of body can be achieved on the choosing of the ideal of above-mentioned " can respiratory " material.Therefore, polyurethane film exists
The fabrics such as diving suit, swimsuit, rhythm clothing and air Landing clothes, Aerated water bed, ball liner, boat, lifebuoy and lining material
What material etc. obtained is widely applied.
But existing polyurethane film in use there is a problem in that, influence using effect and service life: 1,
Microorganisms, the existing waterproof moisture-penetrating urethanes such as the convenient bacterium of organic principle contained by sweat secreted as human skin are thin
Directly and skin contact, the persistence without anti-microbial property or anti-microbial property is shorter, and fastness is poor, and antibacterial effect is paid no attention to for film
Think；2, the water resistance of film, mechanical strength and thermal stability are undesirable, and service life is short.
Summary of the invention
The invention mainly solves the technical problem of providing a kind of preparation method of antibiotic property waterproof moisture-penetrating urethane film,
It is able to solve disadvantages mentioned above existing for existing waterproof moisture-penetrating urethane film.
In order to solve the above technical problems, one technical scheme adopted by the invention is that: a kind of antibiotic property Waterproof Breathable is provided
The preparation method of polyurethane film, includes the following steps:
(1) it prepares modified composite: beta-cyclodextrin is dissolved in the β-ring for being made into certain mass concentration in n,N-dimethylacetamide
Then a certain amount of tetrahydrofuran is added in dextrin solution thereto, after being stirred to react, it is not anti-that enough ethyl alcohol dissolutions are then added
The tetrahydrofuran answered, filtering, obtains beta-cyclodextrin/tetrahydrofuran compound；
(2) antibacterial compounded mix surface modification treatment: molybdic tailing, bamboo charcoal powder and nano-titanium dioxide are mixed in certain mass ratio
It after conjunction, is added in polyoxyethylene sorbitan monooleate, stirs and evenly mixs, thus to molybdic tailing, bamboo charcoal powder and nanometer two
The mixture of titanium oxide is surface-treated；
(3) preparation antibacterial enhances modified polyurethane resin: by formula meter, by dimethylolpropionic acid, isophorone diisocyanate
Ester and polycaprolactone glycol are added in reaction vessel, water bath with thermostatic control reaction, and the antibacterial then prepared in addition step (2) is compound to fill out
Expect, pentaerythritol triacrylate and triethylamine is successively added under the stirring condition of 100~200r/min, is eventually adding and goes in right amount
Ionized water, high-speed stirred reaction obtain the antibacterial enhancing modified polyurethane resin emulsion；
(4) it prepares polyurethane laminated film: stream is added into the antibacterial enhancing modified polyurethane resin emulsion prepared in step (3)
Flat agent, defoaming agent, delustering agent and nanometer silver antimicrobial liquid, are uniformly mixed, then preparation in a certain amount of step (1) is added thereto
Beta-cyclodextrin/tetrahydrofuran compound, after stirring, dripped on glass plate, and formed a film with glass bar striking,
Drying obtains the antibiotic property waterproof moisture-penetrating urethane film.
In a preferred embodiment of the present invention, in the step (1), the mass concentration of the beta-cyclodextrin solution is 25
~30%；The additional amount of the tetrahydrofuran is identical as the dosage of the beta-cyclodextrin.
In a preferred embodiment of the present invention, in the step (1), the condition being stirred to react are as follows: temperature 40~
50 DEG C, 1~1.5h of time, 100~200r/min of stirring rate.
In a preferred embodiment of the present invention, in the step (2), the molybdic tailing, bamboo charcoal powder and nanometer titanium dioxide
The mass ratio of titanium is 1~2:0.5~1:0.5~1；The molybdic tailing, the gross mass of bamboo charcoal powder and nano-titanium dioxide and institute
The mass ratio for stating polyoxyethylene sorbitan monooleate is 1:10~15.
In a preferred embodiment of the present invention, in the step (3), the formula ratio by weight, each component
Dosage are as follows: 15~20 parts of dimethylolpropionic acid, 5~10 parts of polycaprolactone glycol, resists 10~15 parts of isophorone diisocyanate
5~8 parts of bacterium compounded mix, 5~10 parts of pentaerythritol triacrylate, 3~5 parts of triethylamine.
In a preferred embodiment of the present invention, in the step (3), the condition of the water bath with thermostatic control reaction are as follows: temperature
85~90 DEG C, 1~1.5h of time；The condition of the high-speed stirred reaction are as follows: 500~800r/min of stirring rate, temperature 40~
50 DEG C, 15~30min of time.
In a preferred embodiment of the present invention, in the step (3), the pentaerythritol triacrylate and triethylamine
Addition time interval be 3~3.5h, the addition time interval of the deionized water and triethylamine is 0.5~1h.
In a preferred embodiment of the present invention, in the step (4), the levelling agent, defoaming agent, delustering agent and nanometer
The additional amount of silver-colored antimicrobial fluid account for respectively antibacterial enhancing modified polyurethane resin emulsion mass fraction 0.5~0.8%, 2~
3%, 1~2% and 5~10%；The beta-cyclodextrin/tetrahydrofuran compound additional amount accounts for the modified polyurethane resin quality
The 2~8% of score.
In a preferred embodiment of the present invention, the mass concentration of nano silver is 50~70% in the nanometer silver antimicrobial liquid.
The beneficial effects of the present invention are: a kind of preparation method of antibiotic property waterproof moisture-penetrating urethane film of the present invention, technique
Setting is reasonable, it is easy to accomplish, by carrying out surface modification treatment to molybdic tailing, bamboo charcoal powder and nano-titanium dioxide, and it is added
Into the synthesis process of waterborne polyurethane resin, be prepared for the enhancing polyurethane resin with essential anti-microbial attributes, then by with
Beta-cyclodextrin/tetrahydrofuran compound carries out physical blending in the case where nanometer silver antimicrobial liquid participates in and prepares film, makes made
Standby laminated film has excellent broad spectrum antibacterial, mechanical property and water resistance, while having excellent air permeable waterproof
Property, excellent combination property, wide market.
Specific embodiment
The preferred embodiments of the present invention will be described in detail below so that advantages and features of the invention can be easier to by
It will be appreciated by those skilled in the art that so as to make a clearer definition of the protection scope of the present invention.
The embodiment of the present invention includes:
Embodiment 1
Present invention discloses a kind of preparation methods of antibiotic property waterproof moisture-penetrating urethane film, first with the modified molybdenum tail in surface
The mixture of mine, bamboo charcoal powder and nano-titanium dioxide enhances modified aqueous polyurethane resin emulsion to prepare antibacterial, makes poly- ammonia
Ester resin has essential anti-microbial property, and beta-cyclodextrin/tetrahydrofuran compound and antibacterial is recycled to enhance modified polyurethane tree
Rouge carries out physical blending under conditions of nanometer silver antimicrobial liquid participates in, and it is ventilative to obtain anti-microbial property, mechanical property and water resistance
The polyurethane laminated film that performance is all effectively improved.Specific preparation method includes the following steps:
(1) it prepares modified composite: beta-cyclodextrin is dissolved in the mass concentration for being made into beta-cyclodextrin in n,N-dimethylacetamide
For 25% solution, tetrahydrofuran identical with the dosage of the beta-cyclodextrin is then added thereto, at 40~50 DEG C with
After the rate of 100~200r/min is stirred to react 1~1.5h, after dry at 90 DEG C, enough ethyl alcohol dissolution unreacteds are added
Tetrahydrofuran, vacuum filter removal is dissolved with the ethanol solution of tetrahydrofuran, and it is multiple to obtain beta-cyclodextrin/tetrahydrofuran after dry
Close object；
(2) molybdic tailing, bamboo charcoal powder and nano-titanium dioxide antibacterial compounded mix surface modification treatment: are pressed to the matter of 1:0.5:0.5
After the mixing of amount ratio, then said mixture is added in polyoxyethylene sorbitan monooleate, makes the molybdic tailing, bamboo
The mass ratio of the gross mass of powdered carbon and nano-titanium dioxide and the polyoxyethylene sorbitan monooleate is 1:10, is stirred
Mixing is mixed, is surface-treated with the mixture to molybdic tailing, bamboo charcoal powder and nano-titanium dioxide, it is spare；
(3) preparation antibacterial enhances modified polyurethane resin: by weight, by 15 parts of dimethylolpropionic acids, 10 parts of isophorones
Diisocyanate and 5 parts of polycaprolactone glycols are added in reaction vessel, and 1.5h is reacted in 85 DEG C of water bath with thermostatic control, is then added
5 parts of pentaerythrites three are first added under conditions of 30 DEG C in the antibacterial compounded mix prepared in 5 parts of steps (2), the stirring of 100r/min
Acrylate is added 3 parts of triethylamines after stirring 3h, appropriate amount of deionized water is added after 15min, with 500r/ under conditions of 40 DEG C
The rate high-speed stirred of min reacts 30min, obtains the antibacterial enhancing modified polyurethane resin emulsion；
(4) polyurethane laminated film is prepared: by accounting for based on the antibacterial enhancing modified polyurethane resin mass fraction, to step (3)
Middle preparation antibacterial enhancing modified polyurethane resin emulsion in be added 0.5% levelling agent, 1% defoaming agent, 2% delustering agent and
5% nanometer silver antimicrobial liquid (mass concentration of nano silver is 50% in nanometer silver antimicrobial liquid), is uniformly mixed, then add thereto
2% beta-cyclodextrin/tetrahydrofuran the compound for entering to account for the modified polyurethane resin mass fraction will after stirring
It is dripped on glass plate, and is formed a film with glass bar striking, is dried and is obtained the antibiotic property waterproof moisture-penetrating urethane film.
Embodiment 2
Present invention discloses a kind of preparation methods of antibiotic property waterproof moisture-penetrating urethane film, first with the modified molybdenum tail in surface
The mixture of mine, bamboo charcoal powder and nano-titanium dioxide enhances modified aqueous polyurethane resin emulsion to prepare antibacterial, makes poly- ammonia
Ester resin has essential anti-microbial property, and beta-cyclodextrin/tetrahydrofuran compound and antibacterial is recycled to enhance modified polyurethane tree
Rouge carries out physical blending under conditions of nanometer silver antimicrobial liquid participates in, and it is ventilative to obtain anti-microbial property, mechanical property and water resistance
The polyurethane laminated film that performance is all effectively improved.Specific preparation method includes the following steps:
(1) it prepares modified composite: beta-cyclodextrin is dissolved in the mass concentration for being made into beta-cyclodextrin in n,N-dimethylacetamide
For 30% solution, tetrahydrofuran identical with the dosage of the beta-cyclodextrin is then added thereto, at 40~50 DEG C with
After the rate of 100~200r/min is stirred to react 1~1.5h, after dry at 90 DEG C, enough ethyl alcohol dissolution unreacteds are added
Tetrahydrofuran, vacuum filter removal is dissolved with the ethanol solution of tetrahydrofuran, and it is multiple to obtain beta-cyclodextrin/tetrahydrofuran after dry
Close object；
(2) molybdic tailing, bamboo charcoal powder and nano-titanium dioxide antibacterial compounded mix surface modification treatment: are pressed to the mass ratio of 2:1:1
After example mixing, then said mixture is added in polyoxyethylene sorbitan monooleate, makes the molybdic tailing, bamboo charcoal powder
It is 1:15 with the gross mass of nano-titanium dioxide and the mass ratio of the polyoxyethylene sorbitan monooleate, stirring is mixed
It is even, it is surface-treated with the mixture to molybdic tailing, bamboo charcoal powder and nano-titanium dioxide, it is spare；
(3) preparation antibacterial enhances modified polyurethane resin: by weight, by 20 parts of dimethylolpropionic acids, 15 parts of isophorones
Diisocyanate and 10 parts of polycaprolactone glycols are added in reaction vessel, and 1h is reacted in 90 DEG C of water bath with thermostatic control, is then added 8
10 parts of pentaerythrites are first added under conditions of 50 DEG C in the antibacterial compounded mix prepared in part step (2), the stirring of 200r/min
Triacrylate is added 3~5 parts of triethylamines after stirring 3.5h, appropriate amount of deionized water is added after 30min, under conditions of 50 DEG C
20min is reacted with the rate high-speed stirred of 800r/min, obtains the antibacterial enhancing modified polyurethane resin emulsion；
(4) polyurethane laminated film is prepared: by accounting for based on the antibacterial enhancing modified polyurethane resin mass fraction, to step (3)
Middle preparation antibacterial enhancing modified polyurethane resin emulsion in be added 0.8% levelling agent, 2% defoaming agent, 3% delustering agent and
10% nanometer silver antimicrobial liquid (mass concentration of nano silver is 70% in nanometer silver antimicrobial liquid), is uniformly mixed, then thereto
8% beta-cyclodextrin/tetrahydrofuran the compound for accounting for the modified polyurethane resin mass fraction is added, after stirring,
It is dripped on glass plate, and is formed a film with glass bar striking, drying obtains the antibiotic property waterproof moisture-penetrating urethane film.
Polyurethane laminated film obtained by the above method, after tested, vapor transfer rate for 24 hours are 6000g/m2More than, it is resistance to quiet
Hydraulic pressure 0.049MPa, longitudinal tensile strength are 32.2MPa or more, and transverse tensile strength is 29.8MPa or more, and broad spectrum antibacterial reaches
To 97% or more, water-fastness 50 anti-microbial properties are constant.
A kind of preparation method of antibiotic property waterproof moisture-penetrating urethane film of the present invention, technique setting are reasonable, it is easy to accomplish,
By carrying out surface modification treatment to molybdic tailing, bamboo charcoal powder and nano-titanium dioxide, and it is added to the conjunction of waterborne polyurethane resin
At the enhancing polyurethane resin in the process, being prepared for that there are essential anti-microbial attributes, then by compound with beta-cyclodextrin/tetrahydrofuran
Object carries out physical blending in the case where nanometer silver antimicrobial liquid participates in and prepares film, has prepared laminated film excellent
Broad spectrum antibacterial, mechanical property and water resistance, while there are excellent breathable and waterproof, excellent combination property, market prospects
It is wide.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of antibiotic property waterproof moisture-penetrating urethane film, which comprises the steps of:
(1) it prepares modified composite: beta-cyclodextrin is dissolved in the β-ring for being made into certain mass concentration in n,N-dimethylacetamide
Then a certain amount of tetrahydrofuran is added in dextrin solution thereto, after being stirred to react, it is not anti-that enough ethyl alcohol dissolutions are then added
The tetrahydrofuran answered, filtering, obtains beta-cyclodextrin/tetrahydrofuran compound；
(2) antibacterial compounded mix surface modification treatment: molybdic tailing, bamboo charcoal powder and nano-titanium dioxide are mixed in certain mass ratio
It after conjunction, is added in polyoxyethylene sorbitan monooleate, stirs and evenly mixs, thus to molybdic tailing, bamboo charcoal powder and nanometer two
The mixture of titanium oxide is surface-treated；
(3) preparation antibacterial enhances modified polyurethane resin: by formula meter, by dimethylolpropionic acid, isophorone diisocyanate
Ester and polycaprolactone glycol are added in reaction vessel, water bath with thermostatic control reaction, and the antibacterial then prepared in addition step (2) is compound to fill out
Expect, pentaerythritol triacrylate and triethylamine is successively added under the stirring condition of 100~200r/min, is eventually adding and goes in right amount
Ionized water, high-speed stirred reaction obtain the antibacterial enhancing modified polyurethane resin emulsion；
(4) it prepares polyurethane laminated film: stream is added into the antibacterial enhancing modified polyurethane resin emulsion prepared in step (3)
Flat agent, defoaming agent, delustering agent and nanometer silver antimicrobial liquid, are uniformly mixed, then preparation in a certain amount of step (1) is added thereto
Beta-cyclodextrin/tetrahydrofuran compound, after stirring, dripped on glass plate, and formed a film with glass bar striking,
Drying obtains the antibiotic property waterproof moisture-penetrating urethane film.
2. the preparation method of antibiotic property waterproof moisture-penetrating urethane film according to claim 1, which is characterized in that the step
Suddenly in (1), the mass concentration of the beta-cyclodextrin solution is 25~30%；The additional amount of the tetrahydrofuran and the β-ring are pasted
The dosage of essence is identical.
3. the preparation method of antibiotic property waterproof moisture-penetrating urethane film according to claim 1, which is characterized in that the step
Suddenly in (1), the condition being stirred to react are as follows: 40~50 DEG C of temperature, 1~1.5h of time, 100~200r/min of stirring rate.
4. the preparation method of antibiotic property waterproof moisture-penetrating urethane film according to claim 1, which is characterized in that the step
Suddenly in (2), the mass ratio of the molybdic tailing, bamboo charcoal powder and nano-titanium dioxide is 1~2:0.5~1:0.5~1；The molybdenum
The gross mass of tailing, bamboo charcoal powder and nano-titanium dioxide and the mass ratio of the polyoxyethylene sorbitan monooleate are
1:10~15.
5. the preparation method of antibiotic property waterproof moisture-penetrating urethane film according to claim 1, which is characterized in that the step
Suddenly in (3), the formula ratio by weight, the dosage of each component are as follows: 15~20 parts of dimethylolpropionic acid, isophorone two are different
10~15 parts of cyanate, 5~10 parts of polycaprolactone glycol, 5~8 parts of antibacterial compounded mix, pentaerythritol triacrylate 5~10
Part, 3~5 parts of triethylamine.
6. the preparation method of antibiotic property waterproof moisture-penetrating urethane film according to claim 1, which is characterized in that the step
Suddenly in (3), the condition of the water bath with thermostatic control reaction are as follows: 85~90 DEG C of temperature, 1~1.5h of time；The high-speed stirred reaction
Condition are as follows: 500~800r/min of stirring rate, 40~50 DEG C of temperature, 15~30min of time.
7. the preparation method of antibiotic property waterproof moisture-penetrating urethane film according to claim 1, which is characterized in that the step
Suddenly in (3), the addition time interval of the pentaerythritol triacrylate and triethylamine is 3~3.5h, the deionized water with
The addition time interval of triethylamine is 0.5~1h.
8. the preparation method of antibiotic property waterproof moisture-penetrating urethane film according to claim 1, which is characterized in that the step
Suddenly in (4), the levelling agent, defoaming agent, delustering agent and nanometer silver antimicrobial liquid additional amount account for the antibacterial enhancing respectively and be modified
0.5~0.8%, 2~3%, 1~2% and the 5~10% of ester-polyurethane resin emulsion mass fraction；Beta-cyclodextrin/the tetrahydrofuran is multiple
The additional amount for closing object accounts for the 2~8% of the modified polyurethane resin mass fraction.
9. the preparation method of antibiotic property waterproof moisture-penetrating urethane film according to claim 8, which is characterized in that described to receive
The mass concentration of nano silver is 50~70% in the silver-colored antimicrobial fluid of rice.
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Application publication date: 20190129 |