CN105694483A - SPI (soy protein isolate)/TiO2 composite film and preparation method thereof - Google Patents

SPI (soy protein isolate)/TiO2 composite film and preparation method thereof Download PDF

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CN105694483A
CN105694483A CN201610133346.8A CN201610133346A CN105694483A CN 105694483 A CN105694483 A CN 105694483A CN 201610133346 A CN201610133346 A CN 201610133346A CN 105694483 A CN105694483 A CN 105694483A
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film
preparation
liquid
spi
protein isolate
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王喆
叶忱
王怀雨
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/463—Edible packaging materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
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    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention provides a preparation method of a SPI (soy protein isolate)/TiO2 composite film. The preparation method comprises the following steps: SPI is taken and dissolved in water for thermal modification, then a plasticizer is added, and a protein film liquid is obtained; pH of the protein film liquid is regulated to 8-10, after the protein film liquid is cooled to the room temperature, nano-TiO2 is slowly added, and a blended film liquid is obtained; then an ultrasonic wave-microwave joint reaction system is adopted for processing; finally, the SPI/TiO2 composite film is obtained from the processed blended film liquid by degassing, film reversing, drying and film forming as well as film stripping sequentially. The method is simple and easy to operate, nano-TiO2 is added to a modified SPI film forming liquid and joint action of ultrasonic waves and microwaves is introduced, so that the mechanical property, the water resistance, the air permeability and other performance of the pure SPI film are improved, and the film further has antibacterial activity. The invention further provides the SPI/TiO2 composite film.

Description

A kind of soybean protein isolate/titanium dioxide composite film and preparation method thereof
Technical field
The present invention relates to field of packaging material, particularly to a kind of soybean protein isolate/titanium dioxide composite film and preparation method thereof。
Background technology
In various packaging material, plastics are widely used in packaging for foodstuff with its superior performance and relatively low cost, but plastics are not easily decomposed after abandonment, cause environmental pollution。Therefore, packaging material are had higher requirement。At present, edible packing membrane because of have higher safety, the feature of environmental protection and become the trend of research。From the biomacromolecules such as protein, polysaccharide and lipid, develop edible coating and thin film has become as the focus that researcher is studied。
In numerous one-tenth film base materials, soybean protein isolate (SPI) abundance, cheap and easy to get, easily biological-degradable and easy film forming and there is good gas barrier properties, it is used widely at edible film packaging field。But, owing to soybean separation protein tunica albuginea has poor blocking water and mechanical performance, limit it and further apply。
Summary of the invention
In view of this, the invention provides a kind of soybean protein isolate/titanium dioxide (being abbreviated as " ST ") composite membrane and preparation method thereof。The method is simple to operation, adds nano-TiO in SPI film forming liquid after modification2, and introduce the combined effect of ultrasonic-microwave, improve the mechanical performance of simple SPI film, block-water performance, permeability etc., and there is biocidal property, obtain soybean protein isolate/titanium dioxide composite film。
First aspect, the preparation method that the invention provides a kind of soybean protein isolate/titanium dioxide composite film, comprise the following steps:
(1) take soybean protein isolate to be dissolved in the water, and heating 30-50min carries out heat modification in the water bath with thermostatic control of 60-80 DEG C, the solution that then thermotropism is modified adds plasticizer, stirring and evenly mixing, obtains albuminous coat liquid；
(2) regulate the pH to 8-10 of albuminous coat liquid, after being cooled to room temperature, be slowly added to nano titanium oxide when being stirred continuously, obtain blend film liquid；
(3) adopting ultrasonic-microwave association response system that described blend film liquid is processed, the power of described process is 300-500W, and temperature is 30-60 DEG C, and the time is 10-30min；
(4) the blend film liquid after above-mentioned process is sequentially carried out degassed, pour mask, drying and forming-film, takes off film, obtain soybean protein isolate/titanium dioxide composite film。
Soybean protein isolate film forming mainly by protein molecule polymerization and solvent evaporation, when albuminous coat liquid under certain condition, protein molecule generation polymerization crosslinking effect。In film forming procedure, relying primarily on the hydrophobic group between peptide chain, disulfide bond and hydrogen bond, heating destroys soybean protein isolate self structure, disulfide bonds, sulfydryl and hydrophobic group is caused to expose, afterwards along with temperature reduces, form new valence link between peptide chain and peptide chain, eventually form reticular membrane structure。
In the present invention, heat modification is primarily intended to and allows the peptide chain of SPI molecule be fully extended in the solution, thus participating in reaction more up hill and dale, and then improves its film properties。Described thermally-denatured temperature is 60-80 DEG C。When temperature is lower than 60 DEG C, SPI cannot film forming, temperature reaches after 60 DEG C, and SPI can launch its internal structure。Along with the rising of temperature, high temperature can promote the hydrogen bond in protein molecule and disulfide bonds so that it is internal structure is launched, be conducive to the redistribution of disulfide bond, SPI appropriateness degeneration simultaneously can make its dissolubility improve, and makes interactive SPI molecule in solution increase, and SPI network structure is strengthened。Meanwhile, high temperature can promote the effect of being cross-linked with each other of (polar group as on lysine, cystine and peptide chain molecule) between peptide chain molecule。But after temperature is more than 80 DEG C, the deformation of SPI terminates substantially。
It is further preferred that described thermally-denatured temperature is 65-75 DEG C。
In the present invention, regulating albuminous coat liquid to 8-10, alkaline environment can promote more disulfide formation, improves the crosslinked action between peptide chain and then film forming。
Preferably, described plasticizer is one or more in glycerol, sorbitol。
Preferably, the addition of described plasticizer is 2-6mL。
Soybean separation protein tunica albuginea improves its pliability mainly by adding plasticizer and prevents fracture。The soybean separation protein tunica albuginea of interpolation plasticizer is transparent and pliability good, but its water preventing ability is still poor。
Nano titanium oxide (nano-TiO2) it is a kind of stable, nontoxic UV absorbent, good mechanical property, photochemical activity and anti-microbial property etc. is had because of the nano effect of its uniqueness。The present invention adds titanium dioxide in spi protein film liquid, it is possible to increase the antibiotic property of most telolemma product, also can improve the mechanical performance etc. of film。TiO2Addition more big, more many with the molecule of protein bound, during film forming, intermolecular interaction is more strong, and intermolecular cross-linking is more tight, and the tensile strength of the composite membrane therefore finally given is more big, but works as TiO2Addition too big time, there is little granule in most telolemma surface, and film is easily torn, and ductility is bad。
Preferably, the particle diameter of described nano titanium oxide is 200-400nm。
Preferably, in described blend film liquid, the concentration of described nano titanium oxide is 0.5-2.0g/mL。
The present invention adopt ultrasonic-microwave association response system (being abbreviated as UMAT) to containing TiO2SPI film forming liquid process, make full use of hyperacoustic ultrasound cavitation effect, mechanical dispersion effect, and the uniform heating effect of microwave and the synergism that produces between the two, improve the emulsion stability of film liquid, bubble stability, what make that nano titanium oxide is distributed in soybean separation protein tunica albuginea liquid is more uniform, will not assemble, film liquid after process is still, uniformly and compact structure, additionally, UMAT processes also can expose and is hidden in intramolecular methyl, ethyl,-H etc., suitably reduce oxygen transmission rate and the permeability rate of film, improve tensile strength and the elongation at break of film。When reaction stops, energy when ultrasonic-microwave processes film liquid still exists, and passes through interfacial tension so that solution is layered, and forms double-deck membranaceous composite membrane, the surface of composite membrane and section uniform ground, and upper surface is yellow, and lower surface is white。
The surface of described composite membrane and section uniform ground, described composite membrane is double membrane structure, and nano titanium oxide content in described composite membrane increases in gradient at thickness direction。The one side that nanometer titanium dioxide Ti content is high is white, and the one side that nanometer titanium dioxide Ti content is low is white。
Yellow face is mainly by SPI molecular composition, and white face is mainly by nano-TiO2Constitute, nano-TiO2The network structure of soybean protein isolate is uniformly distributed。
Preferably, the thickness of described soybean protein isolate/titanium dioxide composite film is 180-200 μm。
It is further preferred that the time that described UMAT processes is 10-20min, power is 400-500W。Under this condition, it is easier to formed and be layered obvious duplicature。
Preferably, described degassed be carry out under vacuum 0.08～0.09MPa, degassing time 1-5min。Degassed purpose is for removing the gas of parcel in coating liquid, so that obtaining the good thin film of planarization。
It is highly preferred that degasification process repeats 1-3 time, and after degassed completing, stand 1-2h。
Preferably, described drying and forming-film is dry 5～7h at 50-60 DEG C。
Preferably, described take off film after, be additionally included in temperature 25 ± 1 DEG C, in the climatic chamber of humidity 50 ± 1% balance 48h。This is mainly used for the detection of film properties。
The preparation method of soybean protein isolate/titanium dioxide composite film provided by the invention is simply easily operated, and ultrasonic-microwave association response system is applied to SPI, TiO2Film forming procedure in, utilize the synergism of ultrasound wave and microwave, prepare the composite membrane with relatively low water penetration, breathability and light transmittance and better biocidal property, it is achieved that utilize the packaging film just can to the common microbiological generation bacteriostasis in food。
Second aspect, the invention provides soybean protein isolate/titanium dioxide composite film that a kind of method adopted described in first aspect present invention prepares。
Preferably, the thickness of described soybean protein isolate/titanium dioxide composite film is 180-200 μm。
The performance indications of soybean protein isolate/titanium dioxide composite film that the present invention prepares are excellent, it is possible to be applied to the packaging field of medicine, food。
Accompanying drawing explanation
Fig. 1 is the outward appearance photo of soybean protein isolate/titanium dioxide composite film that the embodiment of the present invention 1 prepares, wherein, blend film liquid after the process of (a) ultrasonic-microwave, the front of (b) soybean protein isolate/nano titanium dioxide film, the back side of (c) soybean protein isolate/nano titanium dioxide film, the section of (d) soybean protein isolate/nano titanium dioxide film；
Fig. 2 is the stereoscan photograph of soybean protein isolate/titanium dioxide composite film that the embodiment of the present invention 1 prepares, wherein, a soybean separation protein tunica albuginea that () is simple, the front of (b) soybean protein isolate/nano titanium dioxide film, the back side of (c) soybean protein isolate/nano titanium dioxide film, the section of (d) soybean protein isolate/nano titanium dioxide film。
Detailed description of the invention
The following stated is the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention; can also making some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention。
Below by the present invention the test index that arrives of use:
(1) mechanical performance:
The mechanical performance of edible film includes the tensile strength (TS) and the elongation at break (E) that measure edible film。According to GB " stretched plastic film method for testing performance " (GB/13022-1991), measure tensile strength (TS) and the elongation at break (E) of edible film。Edible film being cut into width to be 15mm, length be the strip sample of 120mm, test speed is 200mm/min, is measured with Intelligent electronic tensil testing machine
(2) steam transmission coefficient:
Steam transmission coefficient (the WaterVaporPermeability of film, WVP) according to GB " plastic sheeting and sheet material water vapor permeability test method-cup type method " (GB1037-1988) and " packaging material test method-rate of perviousness " (GB/T16928-1997), measure with TSY-T1L poisture-penetrability tester, test area 100mm2, unit g cm-1·s-1·Pa-1, record three groups of test datas, calculate meansigma methods。
(3) gas permeation rate (OP):
Gas permeation rate, according to GB " plastic sheeting and thin slice gas-premeable test method-pressure differential method " (GB/T1038-2000), measures the OTR oxygen transmission rate (Po of film with gas-premeable tester2) and carbon dioxide transmission rate (Pco2), test area is 108mm2, unit g cm-1·s-1·Pa-1, record three groups of test datas, calculate meansigma methods。Test gas is purity be 99% oxygen and carbon dioxide。
Embodiment 1
The preparation method of a kind of soybean protein isolate/titanium dioxide composite film, comprises the following steps:
(1) soybean protein isolate (SPI) weighing 5g is dissolved in 95mL distilled water, carries out heat modification, and heat modification condition is: the water bath with thermostatic control heating 40min of 80 DEG C, is then added to the glycerol of 2.5mL, stirring and dissolving, obtains albuminous coat liquid；
(2) preparation 0.1mol/L hydrochloric acid solution and 0.1mol/L sodium hydroxide solution, regulates the pH value of albuminous coat liquid to 10；It is cooled to after room temperature (23 DEG C) until albuminous coat liquid, is slowly added into nano titanium oxide (nano-TiO wherein2), do not stop telluric magnetic force and stir to prevent nano-TiO2Film liquid is reunited, obtains blend film liquid, wherein, nano-TiO2Ultimate density in blend film liquid is 1.5g/100mL；
(3) adopting ultrasonic-microwave association response system (Nanjing following current Instrument Ltd., model SL-SM50) that described blend film liquid is processed, wherein, process power is 500W, and the process time is 20min, and treatment temperature is 30 DEG C；
(4) the blend film liquid after above-mentioned process is carried out vacuum outgas: be placed in by the film liquid of mix homogeneously in vacuum 0.08～0.09MPa, degassed 3min, in triplicate, then stand 1h, to remove the gas of parcel in coating liquid；
(5) casting film-forming: adopting constant volume method, film liquid is 100mL, takes 100mL film liquid, is cast in homemade film forming device, dry 6～7h at 50 DEG C, notice that film forming device keeps level；
(6) take off film to preserve: after dry cooling, take off film, obtain soybean protein isolate/titanium dioxide composite film (ST film), and in the climatic chamber that temperature 25 ± 1 DEG C, humidity are 50 ± 1% balance 48h, in order to carry out the detection of film properties。
In order to highlight beneficial effects of the present invention, the present invention is also provided with the comparative example of embodiment 1, and this comparative example contains only soybean protein isolate and glycerol, and without nano titanium oxide, other conditions are all identical with embodiment 1。
The outward appearance photo of Fig. 1, Fig. 2 respectively soybean protein isolate/titanium dioxide composite film (ST) that embodiment 1 prepares and stereoscan photograph。
It will be seen from figure 1 that described ST film occurs in that lamination (in Fig. 1 d), by color observation, (i.e. upper surface, b) for yellow in Fig. 1, infers that this film upper strata is mainly by SPI molecular composition it can be seen that the front of ST film；(i.e. lower surface c) is white in Fig. 1, infers that this film lower floor is mainly by nano-TiO for the back side of ST film2Constitute。
Blend film liquid after ultrasonic-microwave processes is highly uniform, and without lamination in 24 hours, it follows that the self demixing phenomenon that ST film occurs is to occur in film drying course。This is probably when ultrasonic-microwave processes stopping, and energy when ultrasonic-microwave processes film liquid still exists, and passes through interfacial tension so that solution is layered, the composite membrane that formation is double-deck membranaceous。
From Fig. 2 (4 figure of Fig. 2, scale is 2 μm) it can be seen that the smooth surface of simple SPI film (in Fig. 2 a) and smooth, this shows that SPI is good with the compatibility of glycerol。B from Fig. 2 is it can be seen that there is the material of a lot of needle-like to be distributed in the front of film, and this illustrates, the upper surface of ST film, not only containing SPI molecule, also includes nano-TiO2。By c in Fig. 2 it can be seen that there is a lot of particle agglomeration at the reverse side of ST film, this shows that the lower surface of ST film is only by nano-TiO2Composition, this judges consistent (in Fig. 1 c, d) with the appearance color from ST film。Nano-TiO2Content in described composite membrane increases in gradient at thickness direction, namely from the surface of yellow to the surface of white, nano-TiO2Content be gradually increased。By d in Fig. 2 it can be seen that the section of ST film presents stratiform, this shows that ST film is layered, consistent with the macroscopic view observation of ST film in Fig. 1。
From Fig. 1, Fig. 2 generally, the surface of ST film and section are uniform and smooth, and this illustrates nano-TiO2SPI network structure is evenly distributed, and reaction is fully, defines the structure of densification。
Additionally, in order to study nano-TiO2The addition impact on composite membrane performance, controls nano-TiO2Ultimate density in blend film liquid respectively 0,0.5,1,1.5 and the experimental group of 2g/100mL, test respectively its on the mechanical performance of composite membrane, water vapour permeability, OTR oxygen transmission rate impact, result is as shown in table 1。
Table 1nano-TiO2The addition impact on composite membrane performance
As it can be seen from table 1 add nano-TiO2After, the TS of composite membrane exceeds the notable change of 34%-90%, TS performance than simple SPI film (comparative example), is due to Nano-TiO2Can reacting with SPI molecule, the interaction between them makes nano-TiO2In SPI network structure, reaction fully and is evenly distributed, thus forming the structure of densification, and then improves its TS。But, too much nano-TiO2Reuniting, thus destroying the structure that ST film is fine and close, causing that the TS of film diminishes, so nano-TiO2Addition is the TS of the film of 2.0g/100mL is the film of 0.5g/100mL less than addition。
Along with nano-TiO2Content increases, and the WVP of composite membrane reduces。This is because, compared with SPI, nano-TiO2There are higher retentiveness and water preventing ability, so working as nano-TiO2When being filled in SPI network structure, delay hydrone in the speed of ST film internal delivery。Meanwhile, nano-TiO2Hydrogen bond is formed by intermolecular interaction with SPI, thus stoping hydrone to pass through, and then the WVP of reduction ST film, improve water-resisting ability。
Along with nano-TiO2Content increases, and the OP step-down of ST film, choke ability strengthens gradually。It is primarily due to nano-TiO2By the great amount of hydroxy group on surface, with SPI molecular reaction, formation hydrogen bond, thus hindering oxygen in the diffusion within ST film。
Embodiment 2
The preparation method of a kind of soybean protein isolate/titanium dioxide composite film, comprises the following steps:
(1) soybean protein isolate (SPI) weighing 5g is dissolved in 95mL distilled water, carries out heat modification, and heat modification condition is: the water bath with thermostatic control heating 50min of 65 DEG C, is then added to the glycerol of 4mL, stirring and dissolving, obtains albuminous coat liquid；
(2) preparation 0.1mol/L hydrochloric acid solution and 0.1mol/L sodium hydroxide solution, regulates the pH value of albuminous coat liquid to 9；It is cooled to after room temperature (20 DEG C) until albuminous coat liquid, is slowly added into nano titanium oxide (nano-TiO wherein2), do not stop telluric magnetic force and stir to prevent nano-TiO2Film liquid is reunited, obtains blend film liquid, wherein, nano-TiO2Ultimate density in blend film liquid is 2g/100mL；
(3) adopting ultrasonic-microwave association response system (Nanjing following current Instrument Ltd., model SL-SM50) that described blend film liquid is processed, wherein, process power is 400W, and the process time is 10min, and treatment temperature is 30 DEG C；
(4) the blend film liquid after above-mentioned process is carried out vacuum outgas: be placed in by the film liquid of mix homogeneously in vacuum 0.08～0.09MPa, degassed 3min, in triplicate, then stand 2h, to remove the gas of parcel in coating liquid；
(5) casting film-forming: adopting constant volume method, film liquid is 100mL, takes 100mL film liquid, is cast in homemade film forming device, dry 6h at 60 DEG C, notice that film forming device keeps level；
(6) take off film to preserve: after dry cooling, take off film, obtain soybean protein isolate/titanium dioxide composite film (ST film), and in the climatic chamber that temperature 25 ± 1 DEG C, humidity are 50 ± 1% balance 48h, in order to carry out the detection of film properties。
Embodiment 3
The preparation method of a kind of soybean protein isolate/titanium dioxide composite film, comprises the following steps:
(1) soybean protein isolate (SPI) weighing 5g is dissolved in 95mL distilled water, carries out heat modification, and heat modification condition is: the water bath with thermostatic control heating 30min of 70 DEG C, is then added to the glycerol of 3mL, stirring and dissolving, obtains albuminous coat liquid；
(2) preparation 0.1mol/L hydrochloric acid solution and 0.1mol/L sodium hydroxide solution, regulates the pH value of albuminous coat liquid to 8；It is cooled to after room temperature (25 DEG C) until albuminous coat liquid, is slowly added into nano titanium oxide (nano-TiO wherein2), do not stop telluric magnetic force and stir to prevent nano-TiO2Film liquid is reunited, obtains blend film liquid, wherein, nano-TiO2Ultimate density in blend film liquid is 1.0g/100mL；
(3) adopting ultrasonic-microwave association response system (Nanjing following current Instrument Ltd., model SL-SM50) that described blend film liquid is processed, wherein, process power is 300W, and the process time is 30min, and treatment temperature is 40 DEG C；
(4) the blend film liquid after above-mentioned process is carried out vacuum outgas: be placed in by the film liquid of mix homogeneously in vacuum 0.08～0.09MPa, degassed 3min, in triplicate, then stand 1h, to remove the gas of parcel in coating liquid；
(5) casting film-forming: adopting constant volume method, film liquid is 100mL, takes 100mL film liquid, is cast in homemade film forming device, dry 5h at 70 DEG C, notice that film forming device keeps level；
(6) take off film to preserve: after dry cooling, take off film, obtain soybean protein isolate/titanium dioxide composite film (ST film), and in the climatic chamber that temperature 25 ± 1 DEG C, humidity are 50 ± 1% balance 48h, in order to carry out the detection of film properties。
The ST film that embodiment 2 is prepared carries out performance test, and specific targets are as follows: TS is 7.33MPa, E is 39.65%, WVP2.5622 × 10-11g·cm-1·s-1·Pa-1, OP is 1.4375 × 10-5g·cm-1·s-1·Pa-1。
The ST film that embodiment 3 is prepared carries out performance test, and specific targets are as follows: TS is 8.32MPa, E is 42.33%, and WVP is 3.43 × 10-11g·cm-1·s-1·Pa-1, OP is 2.87 × 10-5g·cm-1·s-1·Pa-1。
Embodiment described above only have expressed the several embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention。It should be pointed out that, for the person of ordinary skill of the art, without departing from the inventive concept of the premise, it is also possible to making some deformation and improvement, these broadly fall into protection scope of the present invention。Therefore, the protection domain of patent of the present invention should be as the criterion with claims。

Claims (10)

1. the preparation method of soybean protein isolate/titanium dioxide composite film, it is characterised in that comprise the following steps:
(1) take soybean protein isolate to be dissolved in the water, and heating 30-50min carries out heat modification in the water bath with thermostatic control of 60-80 DEG C, the solution that then thermotropism is modified adds plasticizer, stirring and evenly mixing, obtains albuminous coat liquid；
(2) regulate the pH to 8-10 of albuminous coat liquid, after being cooled to room temperature, be slowly added to nano titanium oxide when being stirred continuously, obtain blend film liquid；
(3) adopting ultrasonic-microwave association response system that described blend film liquid is processed, the power of described process is 300-500W, and temperature is 30-60 DEG C, and the time is 10-30min；
(4) the blend film liquid after above-mentioned process is sequentially carried out degassed, pour mask, drying and forming-film, takes off film, obtain soybean protein isolate/titanium dioxide composite film。
2. preparation method as claimed in claim 1, it is characterised in that in step (2), in described blend film liquid, the concentration of described nano titanium oxide is 0.5-2.0g/mL。
3. preparation method as claimed in claim 1, it is characterised in that the particle diameter of described nano titanium oxide is 200-400nm。
4. preparation method as claimed in claim 1, it is characterised in that in step (1), described thermally-denatured temperature is 65-75 DEG C。
5. preparation method as claimed in claim 1, it is characterised in that described plasticizer is one or both in glycerol, sorbitol。
6. preparation method as claimed in claim 1, it is characterised in that described degassed be carry out under vacuum 0.08～0.09MPa, degassing time 1-5min。
7. preparation method as claimed in claim 1, it is characterised in that described drying and forming-film is dry 5～7h at 50-70 DEG C。
8. preparation method as claimed in claim 1, it is characterised in that the surface of described composite membrane and section uniform ground, described composite membrane is double membrane structure, and nano titanium oxide content in described composite membrane increases in gradient at thickness direction。
9. preparation method as claimed in claim 1, it is characterised in that in described composite membrane, the one side that nanometer titanium dioxide Ti content is high is white, and the one side that nanometer titanium dioxide Ti content is low is white。
10. soybean protein isolate/titanium dioxide composite film that the method as described in any one of claim 1-9 prepares, it is characterised in that the thickness of described composite membrane is 180-200 μm。
CN201610133346.8A 2016-03-09 2016-03-09 SPI (soy protein isolate)/TiO2 composite film and preparation method thereof Pending CN105694483A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
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CN106912543A (en) * 2017-05-11 2017-07-04 石河子大学 A kind of compound antifreeze for preventing protein oxidation from causing pelyad muscle deterioration and preparation method thereof
CN108546345A (en) * 2018-05-03 2018-09-18 吉林大学 A kind of preparation method of modified nano-titanium dioxide/converted starch/chitosan complex film
CN111423604A (en) * 2020-03-20 2020-07-17 江西师范大学 Preparation method of ultrasonic modified composite gelatin film

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106912543A (en) * 2017-05-11 2017-07-04 石河子大学 A kind of compound antifreeze for preventing protein oxidation from causing pelyad muscle deterioration and preparation method thereof
CN108546345A (en) * 2018-05-03 2018-09-18 吉林大学 A kind of preparation method of modified nano-titanium dioxide/converted starch/chitosan complex film
CN111423604A (en) * 2020-03-20 2020-07-17 江西师范大学 Preparation method of ultrasonic modified composite gelatin film
CN111423604B (en) * 2020-03-20 2022-05-20 江西师范大学 Preparation method of ultrasonic modified composite gelatin film

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Application publication date: 20160622