CN108822347A - A kind of preparation method of carragheen-sodium alginate blend film - Google Patents
A kind of preparation method of carragheen-sodium alginate blend film Download PDFInfo
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- CN108822347A CN108822347A CN201810827614.5A CN201810827614A CN108822347A CN 108822347 A CN108822347 A CN 108822347A CN 201810827614 A CN201810827614 A CN 201810827614A CN 108822347 A CN108822347 A CN 108822347A
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- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
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Abstract
The invention discloses a kind of carragheen-sodium alginate blend film preparation methods, belong to bioabsorbable polymer material technical field.The present invention first reacts sodium alginate dispersion liquid and sodium periodate solution heating stirring, modified sodium alginate dispersion liquid is made, after carragheen dispersion liquid, modified sodium alginate dispersion liquid and Enzymatic Hydrolysis of Chitosan liquid are uniformly mixed again, sequentially add epoxidized vegetable oil, emulsifier, defoaming agent, calcium salt soln and terephthalaldehyde, continue to be stirred, obtains into film liquid；It will then form a film after liquid casting film-forming, film is taken off in drying, then through hot pressing, cooling to get carragheen-sodium alginate blend film.Gained carragheen-sodium alginate blend film of the invention has excellent mechanical property, waterproof performance and flame retardant property.
Description
Technical field
The invention discloses a kind of carragheen-sodium alginate blend film preparation methods, belong to bioabsorbable polymer material
Technical field.
Background technique
With advances in technology with people to the raising of product storage phase and product quality requirement, the increasing of environmental consciousness
By force, the edible film using natural biologic material as raw material is having been to be concerned by more and more people.Current edible film is no longer
It is confined to the form membrane as prepared by single component, gradually development is by be combineding with each other between a variety of large biological molecule substances
Multicomponent, multi-functional property composite membrane, have more superior membrane property.Edible polysaccharide film has been widely used in
The packaging of food is mainly used for the fresh-keeping of fruits and vegetables, and fruits and vegetables are many kinds of, and requirement of the different fruits and vegetables to preservation condition is also different,
The characteristic for only knowing about film and fruits and vegetables selects suitable film that could obtain good fresh-keeping effect.
Carragheen is a kind of phycocolloid extracted from marine red alga, is a kind of natural poly- polysaccharide.Carragheen has excellent
Heat-convertible gel, nontoxic, hydrophilic, stable dispersion and preferable film forming etc., in food, drug, daily-use chemical industry and packet
The fields such as dress are widely used.In recent years using carragheen as edible packaging membrane material, replaces traditional plastics, become food
The new trend of packaging field.Since carragheen film strength is low, water resistance, thermal stability are poor, therefore usually require carragheen
With other edible materials（Such as konjaku glucomannan）The method of blending prepares carragheen packaging film.Sodium alginate is from brown alga
A kind of natural high molecular substance extracted in the kelp or sargassum of class, the sodium alginate that is otherwise known as, algin, mosanom, sea
Band glue etc..Sodium alginate is white or pale yellow powder, almost odorless, tasteless, does not dissolve in ethyl alcohol, ether, chloroform and acid, is parent
Aqueous high molecular, gelatinization is functional, and hydratability is very strong, there is hygroscopicity, is dissolved in hot water and cold water, is dissolved in water and forms vigorous thick shape
Colloidal gel.
After carragheen has good thermal stability and sodium alginate mixing, the thermal degradation of sodium alginate can be improved,
Sodium alginate has good fibre forming property simultaneously, helps to improve the intensity of pure carrageenin fibre.It is both water-soluble more
Saccharide compound is dissolved in water if they mixed, then is prepared into fiber with wet spinning process, can improve the one of their own
A little disadvantages.Carragheen blend film traditional at present during the preparation process, relies solely between carragheen and other macromolecular substances
Hydrogenbond, products obtained therefrom mechanical property and flame retardant property can not promote further, and due to that can form hydrogen with water in product
The radical amount of key is instructed, and causes product hygroscopicity stronger, is unfavorable for product preservation, therefore also need to study it.
Summary of the invention
The present invention solves the technical problem of：During the preparation process for traditional carragheen blend film, it relies solely on
Hydrogenbond between carragheen and other macromolecular substances, products obtained therefrom mechanical property and flame retardant property can not be mentioned further
It rises, and since the radical amount that can form hydrogen bond in product with water is instructed, causes product hygroscopicity stronger, be unfavorable for product preservation
The drawbacks of, provide a kind of preparation method of carragheen-sodium alginate blend film.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that：
（1）It is in mass ratio 5 by sodium alginate dispersion liquid and sodium periodate solution：1~10：The reaction of 1 heating stirring, must be modified sea
Mosanom dispersion liquid；
（2）According to parts by weight, 40~60 parts of carragheen dispersion liquids are successively taken, 30~40 parts of modified sodium alginate dispersion liquids, 10
~20 parts of Enzymatic Hydrolysis of Chitosan liquid, 6~8 parts of epoxidized vegetable oils, 3~5 parts of emulsifiers, 4~6 parts of defoaming agents, 8~10 parts of calcium salts are molten
Carragheen dispersion liquid, modified sodium alginate dispersion liquid and Enzymatic Hydrolysis of Chitosan liquid are first stirred by liquid, 4~8 parts of terephthalaldehydes
After uniformly, epoxidized vegetable oil, emulsifier, defoaming agent, calcium salt soln and terephthalaldehyde are sequentially added, continues to be stirred,
It obtains into film liquid；
（3）It will form a film after liquid casting film-forming, film is taken off in drying, then through hot pressing, cooling thin to get carragheen-sodium alginate blending
Film.
Step（1）It is 1 that the sodium alginate dispersion liquid is by sodium alginate and water in mass ratio：8~1：10 are formulated.
Step（1）The sodium periodate solution is the sodium periodate solution that mass fraction is 5~10%.
Step（2）It is 1 that the carragheen dispersion liquid is by carragheen and water in mass ratio：8~1：10 are formulated.
Step（2）The Enzymatic Hydrolysis of Chitosan liquid enzymolysis process is：It is in mass ratio 1 by chitosan and water：10~1：12 stir
After mixing mixing, the chitosan enzyme of chitosan mass 5~10% is added, after constant temperature stirring digests 45~60min, heat up enzyme deactivation, cold
But, Enzymatic Hydrolysis of Chitosan liquid is obtained.
Step（2）The epoxidized vegetable oil is any one in epoxidized soybean oil, epoxy castor oil or epoxidized linseed oil.
Step（2）The emulsifier is appointing in Tea Saponin, lecithin, emulsifier op-10 or neopelex
It anticipates one kind.
Step（2）The defoaming agent is silicone emulsion, polyoxyethylene polyoxypropylene pentaerythrite ether or polydimethylsiloxanes
Any one in alkane.
Step（2）The calcium salt soln is any one in calcium chloride solution or calcium nitrate solution；The calcium salt soln
The calcium salt soln for being 4~6% for mass fraction.
The beneficial effects of the invention are as follows：
（1）Technical solution of the present invention carries out oxidation modification to sodium alginate using sodium metaperiodate, makes in sodium alginate molecular structure
Hydroxyl be oxidized to aldehyde radical, during following process, especially under hot pressing condition, in modified sodium alginate molecular structure
Aldehyde radical can react with the hydroxyl in carrageenan molecule structure, to form new chemical bonding, the reaction of the two not only has
Conducive to the binding force improved in film between macromolecular substances, so that the mechanical property of product is improved, in addition, can also effectively shield
It reduces the hydroxyl quantity for easily forming hydrogen bond with water in film and is conducive to the preservation of product so that the hygroscopicity of product be effectively reduced；
And under the effect of subsequent calcium salt, calcium ion may replace the sodium ion on sodium alginate, and form chelate structure, increase alginic acid chain
Between binding force, greatly improve the stability of molecular structure, improve product mechanical property while, in combustion, need
Consuming more energy just can be such that the structure destroys, to change the cracking mode of macromolecular script in product, raising is split
Temperature is solved, and calcium ion can generate calcium carbonate after being heated, with the further raising of temperature, Decomposition of Calcium Carbonate produces calcium oxide
And carbon dioxide, carbon dioxide can play the role of oxygen and imflammable gas in diluent air, calcium oxide then can be with residual carbon
Sour calcium is covered in film surface, forms heat-insulated oxygen-impermeable barrier together, and the reaction is the endothermic reaction, film week can be effectively reduced
Environment temperature is enclosed, furthermore, after sodium alginate and carragheen reaction, covalent structure increases in system, and pyrolysis needs to consume more
Heat improves the thermal stability and carbon yield of film, and after the processing of calcium ion, calcium ion can catalyst system activity in
The dehydration of the heart cracks carragheen in lower temperature to make the reduction of blend film incipient degradation temperature, and cracking produces
Raw imflammable gas is directly overflowed since ignition point is not achieved, and reduces its combustion feedback to the heat of film, thus favorably
Remaining film is prevented to continue to crack in further, and at a lower temperature, carragheen and sealer（Calcium alginate）It generates
The reaction of coke occupies leading position, and the coke of generation can be covered in film surface with calcium oxide, calcium carbonate etc., prevents oxygen
Into the diffusion with heat, play the role of good fire retardant barriers；
（2）Technical solution of the present invention makes in system organic big point by being aided with chitosan, and using terephthalaldehyde as crosslinking agent
Occur appropriately crosslinked between son, glue film is blended compared to tradition, the connection between macromolecular is only connected by hydrogen bond, cross-linked network
The formation of network cooperates the generation of above-mentioned chemical bonding, promotes the mechanical performance of product further, and the use of terephthalaldehyde,
Rigid benzene ring structure is introduced, in the cross-linked network structure of product effectively so as to adjust rigidly tying in macromolecular network structure
The ratio of structure and flexible structure, in addition, the use of terephthalaldehyde, for the small molecule crosslinking agents such as glutaraldehyde, molecule
Structure is bigger, so that macromolecular chain inside cross-linked network be made to keep fairly good sub-chain motion ability（That is the fortune of small molecule segment
Kinetic force）, thus assigning the good elasticity of product and flexibility, to effectively realize product rigidity and unification flexible；
（3）On the one hand the present invention can be used as plasticizer, play good increasing by adding a small amount of epoxidized vegetable oil, epoxidized vegetable oil
Effect is moulded, in addition, part function in remaining macromolecular film forming matter molecular structure can be occupied in film after epoxidized vegetable oil is added
The position of group, the radical amount that hydrogen bond can be formed with water in film by reducing are conducive to product so that the hygroscopicity of product be effectively reduced
Preservation.
Specific embodiment
By deacetylation be 90~95% chitosan and water be in mass ratio 1：10~1：12 mixing are poured into beaker, are used
After glass bar is stirred 10~20min, in standing 4~6h of swelling under room temperature, add after being swollen, then into beaker
Enter the chitosan enzyme of chitosan mass 5~10%, and beaker moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 35~
38 DEG C, under the conditions of revolving speed is 300~500r/min, after 45~60min of constant temperature stirring enzymatic hydrolysis, 85~95 DEG C is heated to, is protected
It is cooling after warm 10~20min of enzyme deactivation, obtain Enzymatic Hydrolysis of Chitosan liquid；The height for being 5~10% by sodium alginate dispersion liquid and mass fraction
Sodium iodide solution is 5 in mass ratio：1~10：1 mixing is poured into three-necked flask, and three-necked flask is moved to digital display and is tested the speed constant temperature
Magnetic stirring apparatus, in temperature be 75~80 DEG C, revolving speed be 400~800r/min under the conditions of, after constant temperature is stirred to react 1~3h, out
Material, obtains modified sodium alginate dispersion liquid；According to parts by weight, 40~60 parts of carragheen dispersion liquids, 30~40 parts of modifications are successively taken
Sodium alginate dispersion liquid, 10~20 parts of Enzymatic Hydrolysis of Chitosan liquid, 6~8 parts of epoxidized vegetable oils, 3~5 parts of emulsifiers, 4~6 parts of defoamings
Agent, 8~10 parts of calcium salt solns, 4~8 parts of terephthalaldehydes first gather carragheen dispersion liquid, modified sodium alginate dispersion liquid and shell
Sugared enzymolysis liquid mixing is poured into reaction kettle, after being stirred 45~60min with blender with 600~800r/min revolving speed, then according to
Secondary addition epoxidized vegetable oil, emulsifier, defoaming agent, calcium salt soln and terephthalaldehyde continue with blender with 400~600r/
After min revolving speed is stirred 1~3h, standing and defoaming obtains into film liquid；Gained is added in casting machine hopper at film liquid again, adjustment
Scraper knife is away to 0.8~1.2mm, and after casting film-forming, under the conditions of temperature is 75~80 DEG C, dry 30~45min takes off film, obtains
Dry film, then gained dry film is moved in hot press, it is 120~130 DEG C in temperature, pressure is 5~10MPa condition
Under, 20~30min of hot pressing, then through cooled to room temperature to get carragheen-sodium alginate blend film.The sodium alginate
It is 1 that dispersion liquid is by sodium alginate and water in mass ratio：8~1：10 are formulated.The carragheen dispersion liquid is by carragheen
It is in mass ratio 1 with water：8~1：10 are formulated.The epoxidized vegetable oil is that epoxidized soybean oil, epoxy castor oil or epoxy are sub-
Any one in sesame oil.The emulsifier is in Tea Saponin, lecithin, emulsifier op-10 or neopelex
Any one.The defoaming agent is silicone emulsion, in polyoxyethylene polyoxypropylene pentaerythrite ether or dimethyl silicone polymer
Any one.The calcium salt soln is any one in calcium chloride solution or calcium nitrate solution；The calcium salt soln is quality
The calcium salt soln that score is 4~6%.
Example 1
By deacetylation be 95% chitosan and water be in mass ratio 1：12 mixing are poured into beaker, are stirred with glass bar
After 20min, in standing swelling 6h under room temperature, the shell of addition chitosan mass 10% is poly- after being swollen, then into beaker
Carbohydrase, and beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 38 DEG C, it is permanent under the conditions of revolving speed is 500r/min
After temperature stirring enzymatic hydrolysis 60min, 95 DEG C are heated to, it is cooling after keeping the temperature enzyme deactivation 20min, obtain Enzymatic Hydrolysis of Chitosan liquid；By alginic acid
The sodium periodate solution that sodium dispersion liquid and mass fraction are 10% is 10 in mass ratio：1 mixing is poured into three-necked flask, and by three
Mouthful flask moves to digital display and tests the speed constant temperature blender with magnetic force, is 80 DEG C in temperature, under the conditions of revolving speed is 800r/min, constant temperature stirring is anti-
After answering 3h, discharging obtains modified sodium alginate dispersion liquid；According to parts by weight, 60 parts of carragheen dispersion liquids, 40 parts of modifications are successively taken
Sodium alginate dispersion liquid, 20 parts of Enzymatic Hydrolysis of Chitosan liquid, 8 parts of epoxidized vegetable oils, 5 parts of emulsifiers, 6 parts of defoaming agents, 10 parts of calcium salts are molten
Carragheen dispersion liquid, modified sodium alginate dispersion liquid and Enzymatic Hydrolysis of Chitosan liquid are first mixed and are poured into instead by liquid, 8 parts of terephthalaldehydes
It answers in kettle, after being stirred 60min with blender with 800r/min revolving speed, sequentially adds epoxidized vegetable oil, emulsifier, defoaming
Agent, calcium salt soln and terephthalaldehyde continue after being stirred 3h with blender with 600r/min revolving speed, and standing and defoaming is obtained into
Film liquid；Gained is added in casting machine hopper at film liquid again, adjustment scraper knife is away to 1.2mm, after casting film-forming, in temperature be 80
Under the conditions of DEG C, dry 45min takes off film, obtains dry film, then gained dry film is moved in hot press, in temperature be 130
DEG C, under the conditions of pressure is 10MPa, hot pressing 30min, then it is thin to get carragheen-sodium alginate blending through cooled to room temperature
Film.It is 1 that the sodium alginate dispersion liquid is by sodium alginate and water in mass ratio：10 are formulated.The carragheen dispersion liquid
It is by carragheen and water is in mass ratio 1：10 are formulated.The epoxidized vegetable oil is epoxidized soybean oil.The emulsifier is
Tea Saponin.The defoaming agent is silicone emulsion.The calcium salt soln is calcium chloride solution；The calcium salt soln is that mass fraction is
6% calcium salt soln.
Example 2
By deacetylation be 95% chitosan and water be in mass ratio 1：12 mixing are poured into beaker, are stirred with glass bar
After 20min, in standing swelling 6h under room temperature, the shell of addition chitosan mass 10% is poly- after being swollen, then into beaker
Carbohydrase, and beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 38 DEG C, it is permanent under the conditions of revolving speed is 500r/min
After temperature stirring enzymatic hydrolysis 60min, 95 DEG C are heated to, it is cooling after keeping the temperature enzyme deactivation 20min, obtain Enzymatic Hydrolysis of Chitosan liquid；By weight
Number meter, successively takes 60 parts of carragheen dispersion liquids, 40 parts of sodium alginate dispersion liquids, 20 parts of Enzymatic Hydrolysis of Chitosan liquid, 8 parts of epoxy plants
Oil, 5 parts of emulsifiers, 6 parts of defoaming agents, 10 parts of calcium salt solns, 8 parts of terephthalaldehydes, first by carragheen dispersion liquid, sodium alginate point
Dispersion liquid and the mixing of Enzymatic Hydrolysis of Chitosan liquid are poured into reaction kettle, after being stirred 60min with blender with 800r/min revolving speed, then according to
Secondary addition epoxidized vegetable oil, emulsifier, defoaming agent, calcium salt soln and terephthalaldehyde continue to be turned with blender with 600r/min
After speed is stirred 3h, standing and defoaming obtains into film liquid；Again by gained at film liquid be added casting machine hopper in, adjustment scraper knife away from
To 1.2mm, after casting film-forming, under the conditions of temperature is 80 DEG C, dry 45min takes off film, obtains dry film, then gained is dry
Film moves in hot press, in temperature be 130 DEG C, under the conditions of pressure is 10MPa, hot pressing 30min, then through naturally cooling to room
Temperature is to get carragheen-sodium alginate blend film.It is 1 that the sodium alginate dispersion liquid is by sodium alginate and water in mass ratio：
10 are formulated.It is 1 that the carragheen dispersion liquid is by carragheen and water in mass ratio：10 are formulated.The epoxy plant
Oil is epoxidized soybean oil.The emulsifier is Tea Saponin.The defoaming agent is silicone emulsion.The calcium salt soln is that calcium chloride is molten
Liquid；The calcium salt soln is the calcium salt soln that mass fraction is 6%.
Example 3
By deacetylation be 95% chitosan and water be in mass ratio 1：12 mixing are poured into beaker, are stirred with glass bar
After 20min, in standing swelling 6h under room temperature, the shell of addition chitosan mass 10% is poly- after being swollen, then into beaker
Carbohydrase, and beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 38 DEG C, it is permanent under the conditions of revolving speed is 500r/min
After temperature stirring enzymatic hydrolysis 60min, 95 DEG C are heated to, it is cooling after keeping the temperature enzyme deactivation 20min, obtain Enzymatic Hydrolysis of Chitosan liquid；By weight
Number meter successively takes 60 parts of carragheen dispersion liquids, 20 parts of Enzymatic Hydrolysis of Chitosan liquid, 8 parts of epoxidized vegetable oils, 5 parts of emulsifiers, 6 parts of defoamings
Carragheen dispersion liquid and Enzymatic Hydrolysis of Chitosan liquid are first mixed and are poured into reaction kettle by agent, 10 parts of calcium salt solns, 8 parts of terephthalaldehydes,
After being stirred 60min with blender with 800r/min revolving speed, epoxidized vegetable oil, emulsifier, defoaming agent, calcium salt are sequentially added
Solution and terephthalaldehyde continue after being stirred 3h with blender with 600r/min revolving speed, and standing and defoaming obtains into film liquid；Again
Gained is added in casting machine hopper at film liquid, adjustment scraper knife is away to 1.2mm, after casting film-forming, in temperature be 80 DEG C of conditions
Under, dry 45min takes off film, obtains dry film, then gained dry film is moved in hot press, in temperature be 130 DEG C, pressure
Under the conditions of 10MPa, hot pressing 30min, then through cooled to room temperature to get carragheen film.The carragheen dispersion liquid is
It is in mass ratio 1 by carragheen and water：10 are formulated.The epoxidized vegetable oil is epoxidized soybean oil.The emulsifier is tea
Saponin.The defoaming agent is silicone emulsion.The calcium salt soln is calcium chloride solution；The calcium salt soln is that mass fraction is 6%
Calcium salt soln.
Example 4
By deacetylation be 95% chitosan and water be in mass ratio 1：12 mixing are poured into beaker, are stirred with glass bar
After 20min, in standing swelling 6h under room temperature, the shell of addition chitosan mass 10% is poly- after being swollen, then into beaker
Carbohydrase, and beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 38 DEG C, it is permanent under the conditions of revolving speed is 500r/min
After temperature stirring enzymatic hydrolysis 60min, 95 DEG C are heated to, it is cooling after keeping the temperature enzyme deactivation 20min, obtain Enzymatic Hydrolysis of Chitosan liquid；By alginic acid
The sodium periodate solution that sodium dispersion liquid and mass fraction are 10% is 10 in mass ratio：1 mixing is poured into three-necked flask, and by three
Mouthful flask moves to digital display and tests the speed constant temperature blender with magnetic force, is 80 DEG C in temperature, under the conditions of revolving speed is 800r/min, constant temperature stirring is anti-
After answering 3h, discharging obtains modified sodium alginate dispersion liquid；According to parts by weight, 60 parts of carragheen dispersion liquids, 40 parts of modifications are successively taken
Sodium alginate dispersion liquid, 20 parts of Enzymatic Hydrolysis of Chitosan liquid, 5 parts of emulsifiers, 6 parts of defoaming agents, 10 parts of calcium salt solns, 8 parts of terephthaldehydes
Carragheen dispersion liquid, modified sodium alginate dispersion liquid and Enzymatic Hydrolysis of Chitosan liquid are first mixed and are poured into reaction kettle, uses blender by aldehyde
After being stirred 60min with 800r/min revolving speed, emulsifier, defoaming agent, calcium salt soln and terephthalaldehyde are sequentially added, after
Continue after being stirred 3h with blender with 600r/min revolving speed, standing and defoaming obtains into film liquid；Gained is added at film liquid again and is cast
In machine hopper, adjustment scraper knife is away to 1.2mm, and after casting film-forming, under the conditions of temperature is 80 DEG C, dry 45min takes off film, obtains
Dry film, then gained dry film is moved in hot press, in temperature be 130 DEG C, under the conditions of pressure is 10MPa, hot pressing
30min, then through cooled to room temperature to get carragheen-sodium alginate blend film.The sodium alginate dispersion liquid is by sea
Mosanom and water are 1 in mass ratio：10 are formulated.It is 1 that the carragheen dispersion liquid is by carragheen and water in mass ratio：10
It is formulated.The emulsifier is Tea Saponin.The defoaming agent is silicone emulsion.The calcium salt soln is calcium chloride solution；Institute
Stating calcium salt soln is the calcium salt soln that mass fraction is 6%.
Example 5
By deacetylation be 95% chitosan and water be in mass ratio 1：12 mixing are poured into beaker, are stirred with glass bar
After 20min, in standing swelling 6h under room temperature, the shell of addition chitosan mass 10% is poly- after being swollen, then into beaker
Carbohydrase, and beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 38 DEG C, it is permanent under the conditions of revolving speed is 500r/min
After temperature stirring enzymatic hydrolysis 60min, 95 DEG C are heated to, it is cooling after keeping the temperature enzyme deactivation 20min, obtain Enzymatic Hydrolysis of Chitosan liquid；By alginic acid
The sodium periodate solution that sodium dispersion liquid and mass fraction are 10% is 10 in mass ratio：1 mixing is poured into three-necked flask, and by three
Mouthful flask moves to digital display and tests the speed constant temperature blender with magnetic force, is 80 DEG C in temperature, under the conditions of revolving speed is 800r/min, constant temperature stirring is anti-
After answering 3h, discharging obtains modified sodium alginate dispersion liquid；According to parts by weight, 60 parts of carragheen dispersion liquids, 40 parts of modifications are successively taken
Sodium alginate dispersion liquid, 20 parts of Enzymatic Hydrolysis of Chitosan liquid, 8 parts of epoxidized vegetable oils, 5 parts of emulsifiers, 6 parts of defoaming agents, 8 parts of terephthaldehydes
Carragheen dispersion liquid, modified sodium alginate dispersion liquid and Enzymatic Hydrolysis of Chitosan liquid are first mixed and are poured into reaction kettle, uses blender by aldehyde
After being stirred 60min with 800r/min revolving speed, epoxidized vegetable oil, emulsifier, defoaming agent and terephthalaldehyde are sequentially added,
Continue after being stirred 3h with blender with 600r/min revolving speed, standing and defoaming obtains into film liquid；Gained is added at film liquid again and is flowed
Prolonging in machine hopper, adjustment scraper knife is away to 1.2mm, and after casting film-forming, under the conditions of temperature is 80 DEG C, dry 45min takes off film,
Dry film, then gained dry film is moved in hot press, in temperature be 130 DEG C, under the conditions of pressure is 10MPa, hot pressing
30min, then through cooled to room temperature to get carragheen-sodium alginate blend film.The sodium alginate dispersion liquid is by sea
Mosanom and water are 1 in mass ratio：10 are formulated.It is 1 that the carragheen dispersion liquid is by carragheen and water in mass ratio：10
It is formulated.The epoxidized vegetable oil is epoxidized soybean oil.The emulsifier is Tea Saponin.The defoaming agent is silicone emulsion.
Example 6
By deacetylation be 95% chitosan and water be in mass ratio 1：12 mixing are poured into beaker, are stirred with glass bar
After 20min, in standing swelling 6h under room temperature, the shell of addition chitosan mass 10% is poly- after being swollen, then into beaker
Carbohydrase, and beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 38 DEG C, it is permanent under the conditions of revolving speed is 500r/min
After temperature stirring enzymatic hydrolysis 60min, 95 DEG C are heated to, it is cooling after keeping the temperature enzyme deactivation 20min, obtain Enzymatic Hydrolysis of Chitosan liquid；By alginic acid
The sodium periodate solution that sodium dispersion liquid and mass fraction are 10% is 10 in mass ratio：1 mixing is poured into three-necked flask, and by three
Mouthful flask moves to digital display and tests the speed constant temperature blender with magnetic force, is 80 DEG C in temperature, under the conditions of revolving speed is 800r/min, constant temperature stirring is anti-
After answering 3h, discharging obtains modified sodium alginate dispersion liquid；According to parts by weight, 60 parts of carragheen dispersion liquids, 40 parts of modifications are successively taken
Sodium alginate dispersion liquid, 20 parts of Enzymatic Hydrolysis of Chitosan liquid, 8 parts of epoxidized vegetable oils, 5 parts of emulsifiers, 6 parts of defoaming agents, 10 parts of calcium salts are molten
Carragheen dispersion liquid, modified sodium alginate dispersion liquid and Enzymatic Hydrolysis of Chitosan liquid are first mixed and pour into reaction kettle by liquid, 8 parts of glutaraldehydes
In, after being stirred 60min with blender with 800r/min revolving speed, sequentially add epoxidized vegetable oil, emulsifier, defoaming agent,
Calcium salt soln and glutaraldehyde continue after being stirred 3h with blender with 600r/min revolving speed, and standing and defoaming obtains into film liquid；Again
Gained is added in casting machine hopper at film liquid, adjustment scraper knife is away to 1.2mm, after casting film-forming, in temperature be 80 DEG C of conditions
Under, dry 45min takes off film, obtains dry film, then gained dry film is moved in hot press, in temperature be 130 DEG C, pressure
Under the conditions of 10MPa, hot pressing 30min, then through cooled to room temperature to get carragheen-sodium alginate blend film.The sea
It is 1 that mosanom dispersion liquid is by sodium alginate and water in mass ratio：10 are formulated.The carragheen dispersion liquid is by carragheen
It is in mass ratio 1 with water：10 are formulated.The epoxidized vegetable oil is epoxidized soybean oil.The emulsifier is Tea Saponin.It is described
Defoaming agent is silicone emulsion.The calcium salt soln is calcium chloride solution；The calcium salt soln is that the calcium salt that mass fraction is 6% is molten
Liquid.
Comparative example：The OK a karaoke club glue film of Guangdong Science and Technology Ltd. production.
1 to 6 gained carragheen film of example and comparative example product are subjected to performance detection, the specific detection method is as follows：
Detect tensile strength, elongation at break, contact angle and the limit oxygen index of above-mentioned carragheen blend film.Film surface is being blended
A droplet deionized water is dripped, the contact angle on water droplet both sides is measured and is averaged；Dry carragheen blend film is cut into 8cm
The strip of × 1.5cm tests its tensile strength and elongation at break.
Specific testing result is as shown in table 1：
Table 1：Performance detection table
By 1 testing result of table it is found that present invention gained carragheen-sodium alginate blend film has excellent mechanical property, prevents
Aqueous energy and flame retardant property.
Claims (9)
1. a kind of carragheen-sodium alginate blend film preparation method, it is characterised in that specifically preparation step is：
（1）It is in mass ratio 5 by sodium alginate dispersion liquid and sodium periodate solution：1~10：The reaction of 1 heating stirring, must be modified sea
Mosanom dispersion liquid；
（2）According to parts by weight, 40~60 parts of carragheen dispersion liquids are successively taken, 30~40 parts of modified sodium alginate dispersion liquids, 10
~20 parts of Enzymatic Hydrolysis of Chitosan liquid, 6~8 parts of epoxidized vegetable oils, 3~5 parts of emulsifiers, 4~6 parts of defoaming agents, 8~10 parts of calcium salts are molten
Carragheen dispersion liquid, modified sodium alginate dispersion liquid and Enzymatic Hydrolysis of Chitosan liquid are first stirred by liquid, 4~8 parts of terephthalaldehydes
After uniformly, epoxidized vegetable oil, emulsifier, defoaming agent, calcium salt soln and terephthalaldehyde are sequentially added, continues to be stirred,
It obtains into film liquid；
（3）It will form a film after liquid casting film-forming, film is taken off in drying, then through hot pressing, cooling thin to get carragheen-sodium alginate blending
Film.
2. a kind of preparation method of carragheen-sodium alginate blend film according to claim 1, which is characterized in that step
Suddenly（1）It is 1 that the sodium alginate dispersion liquid is by sodium alginate and water in mass ratio：8~1：10 are formulated.
3. a kind of preparation method of carragheen-sodium alginate blend film according to claim 1, which is characterized in that step
Suddenly（1）The sodium periodate solution is the sodium periodate solution that mass fraction is 5~10%.
4. a kind of preparation method of carragheen-sodium alginate blend film according to claim 1, which is characterized in that step
Suddenly（2）It is 1 that the carragheen dispersion liquid is by carragheen and water in mass ratio：8~1：10 are formulated.
5. a kind of preparation method of carragheen-sodium alginate blend film according to claim 1, which is characterized in that step
Suddenly（2）The Enzymatic Hydrolysis of Chitosan liquid enzymolysis process is：It is in mass ratio 1 by chitosan and water：10~1：After 12 are stirred, then
The chitosan enzyme of chitosan mass 5~10% is added, after constant temperature stirring digests 45~60min, heat up enzyme deactivation, and it is cooling, obtain chitosan
Enzymolysis liquid.
6. a kind of preparation method of carragheen-sodium alginate blend film according to claim 1, which is characterized in that step
Suddenly（2）The epoxidized vegetable oil is any one in epoxidized soybean oil, epoxy castor oil or epoxidized linseed oil.
7. a kind of preparation method of carragheen-sodium alginate blend film according to claim 1, which is characterized in that step
Suddenly（2）The emulsifier is any one in Tea Saponin, lecithin, emulsifier op-10 or neopelex.
8. a kind of preparation method of carragheen-sodium alginate blend film according to claim 1, which is characterized in that step
Suddenly（2）The defoaming agent is silicone emulsion, any in polyoxyethylene polyoxypropylene pentaerythrite ether or dimethyl silicone polymer
It is a kind of.
9. a kind of preparation method of carragheen-sodium alginate blend film according to claim 1, which is characterized in that step
Suddenly（2）The calcium salt soln is any one in calcium chloride solution or calcium nitrate solution；The calcium salt soln is mass fraction
For 4~6% calcium salt soln.
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| CN109464987A (en) * | 2018-11-20 | 2019-03-15 | 上海海洋大学 | Carragheen-sodium alginate plural gel ball preparation of antibiotic in water can be enriched with |
| CN109925531A (en) * | 2019-03-31 | 2019-06-25 | 吴碧玉 | The medical antibacterial combine dressing and its processing technology of carbon nano-tube modification |
| CN110180019A (en) * | 2019-07-11 | 2019-08-30 | 周玉芳 | A kind of complex enzyme and preparation method thereof improving skin repair function |
| CN111048235A (en) * | 2019-11-25 | 2020-04-21 | 陈开兵 | Flexible transparent conductive thin film based on graphene/silver nanowire/chitosan |
| CN114164240A (en) * | 2021-09-08 | 2022-03-11 | 新洋丰农业科技股份有限公司 | Preparation method of seaweed extract by segmented enzymolysis |
| CN114409968A (en) * | 2022-02-23 | 2022-04-29 | 山东大学 | Enteromorpha extract-based biodegradable film material and preparation method and application thereof |
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Application publication date: 20181116 |