CN108395724A - A kind of preparation method of tea grounds/cellulose preservative film - Google Patents
A kind of preparation method of tea grounds/cellulose preservative film Download PDFInfo
- Publication number
- CN108395724A CN108395724A CN201810201944.3A CN201810201944A CN108395724A CN 108395724 A CN108395724 A CN 108395724A CN 201810201944 A CN201810201944 A CN 201810201944A CN 108395724 A CN108395724 A CN 108395724A
- Authority
- CN
- China
- Prior art keywords
- tea grounds
- cellulose
- film
- preparation
- tea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- 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
- C08J2399/00—Characterised by the use of natural macromolecular compounds or of derivatives thereof not provided for in groups C08J2301/00 - C08J2307/00 or C08J2389/00 - C08J2397/00
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- 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
- C08J2499/00—Characterised by the use of natural macromolecular compounds or of derivatives thereof not provided for in groups C08J2401/00 - C08J2407/00 or C08J2489/00 - C08J2497/00
-
- 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
Abstract
The invention discloses a kind of preparation methods of tea grounds/cellulose preservative film, it is to dissolve tea grounds and alkali swollen cellulose altogether using ionic liquid using discarded tea grounds as primary raw material, adds edibility plasticizer and obtain mixing film liquid, curing molding after coating obtains tea grounds/cellulose preservative film.Tea grounds prepared by the present invention/cellulose Wrap film safety is nontoxic, biological degradability is good, has preferable mechanical strength and antioxygenic property, can extend shelf life storage.Present invention process method is simple and practicable, at low cost, and application easy to spread has the potentiality of large-scale commercial production.
Description
Technical field
The present invention relates to a kind of preparation methods of tea grounds/cellulose preservative film, belong to packaging material and food preservative technology
Field.
Background technology
The whole world every year due to food spoilage caused by waste be surprising, according to statistics, rotted the food abandoned every year
It is therefore, fresh-keeping for the purpose of food fresh keeping to extend the food fresh keeping phase more than the food summation that the United Nations succours disadvantaged country
Technology and packaging material are by people's pay attention to day by day.Preservative film is the packing timber of common one kind fresh-keeping foodstuff in human lives
Material has the oxygen permeability and moisture permeability of appropriateness, can adjust the oxygen content and moisture around food, obstructs in air
Microorganism, dust etc., to extend freshness date (Shih C M, Shieh Y T, the Twu Y K.Preparation and of food
characterization of cellulose/chitosan blend films.Carbohydrate Polymers,
2009,78(2):169-174)。
The Perserving materials largely used currently on the market are mainly polyethylene (PE), polyvinyl chloride (PVC), gather inclined two chloroethene
The macromolecule plastic films such as alkene (PVDC), the raw material sources of these plastic fresh-keeping membranes are in non-renewable petroleum resources, material sheet
Body is difficult to degrade, and serious " white pollution " is generated to environment.In addition, under the ambient conditions such as microwave, refrigerator, baking, plastics
Film has chemical change, in harmful substance permeated into food, enter human body with food, to be detrimental to health
(Liu C X,Bai R B.Preparation of chitosan/cellulose acetate blend hollow
fibers for adsorptive performance.Journal of Membrane Science,2005,267:68-
77).Efficiently use reproducible biomass class resource be solve petroleum resources increasingly depleted and environmental problem effective way it
One.The biological materials such as cellulose, hemicellulose, protein, polysaccharide and aliphatic acid can pass through itself group or foreign aid point
Interaction between son and form the membrane material for having certain structure and function, therefore, use that biomass exploitation is persistently fresh-keeping, peace
Full health, high-efficiency antimicrobial, anti-corrosion deodorization, the novel green packaging membrane material that property is stable and biological degradability is good have become the modern times
The important directions of packing technique development.
China is the native place of tea and the world's largest Chan Cha states, and the tea place cultivated area of China in 2012 reaches 235.3 ten thousand
Hectare, 178.9 ten thousand tons of tea yield, cultivated area and the 1st, the worlds tea yield Jun Ju.China is in instant tea, tea beverage, tea
A large amount of tea grounds waste is generated during the thick old leaf trimming of the deep processings such as polyphenol production and tea place, the tea grounds generated every year reaches
1.6 hundred million kilograms.Tea grounds offal treatment becomes the environmental problem of a getting worse, and the random discarding of a large amount of tea grounds not only causes
Environmental pollution, and the huge waste of living resources is caused, in recent years, tea grounds resource how is developed and used, it is made to turn waste into wealth,
Have become popular research field.At the same time, more active ingredient is remained in discarded tea grounds, mainly there is protein, fiber
Element, hemicellulose, tea polyphenols, amino acid, tea polysaccharide, caffeine and lipid material etc., tea grounds have reducing blood lipid, anti-oxidant, suppression
Bacterium, antiviral and antitumor and other effects (medicinal ingredient, pharmacological action and the processing of progress Chinese teas of Zou Sheng duty tealeaves,
2004,3:35-37；Ustundag O G,Ersan S,Ozcan E,et al.Black tea processing waste as
a source of antioxidant and antimicrobial phenolic compounds.European Food
Research and Technology,2016,242(9):1523-1532), still there is very high utility value, be to obtain green
Pack the desirable feedstock of membrane material.
Since the independent film forming of tea grounds is poor, membrane material cannot be directly formed, CN104059239A, which is disclosed, a kind of using tea
The method that slag makes preservative film obtains low molecular weight half using tea grounds as raw material by lye extraction, laccase hydrolysis and ultrafiltration purification
Then it is fresh-keeping to add the higher and degradable hemicellulose of plastic agent processing machinery strength in hemicellulose solution for cellulose
Film, however face the problems such as laccase price is high, and tea grounds hemicellulose recovery rate and purity are relatively low, and plasticizer consumption is big, the invention
Purpose is only that the hemicellulose that lower molecular weight is prepared from tea grounds and hemicellulose preservative film.Therefore, how by external
Interaction between molecule and tea grounds and prepare novel tea grounds preservative film material, to reach, to efficiently use biomass discarded
Object can extend the food fresh keeping phase again, be those skilled in the art's technical problem urgently to be resolved hurrily.
Invention content
The present invention is intended to provide a kind of preparation method of tea grounds/cellulose preservative film, tea grounds/cellulose made from this method
Preservative film can be widely used for the preservation and freshness of food, have inexpensive, simple for process, of good preservation effect, degradable, pollution-free etc.
Advantage.
Ionic liquid is a kind of novel green solvent system, stable, nontoxic and pollution-free with physics and chemical property,
Non-volatile, dissolubility is strong, the features such as easily detaching with product, easily recycling and can be recycled, high polymer dissolving, chemical synthesis,
The fields such as living things catalysis and extraction and separation are cellulose, protein, polysaccharide by the ideal substitute as traditional volatile solvent
Etc. biomass dissolving with application opened up a new way.
The preparation method of tea grounds of the present invention/cellulose preservative film is using discarded tea grounds as primary raw material, using ionic liquid
Tea grounds and alkali swollen cellulose are dissolved altogether, are added edibility plasticizer and are obtained mixing film liquid, curing molding after coating obtains tea
Slag/cellulose preservative film.
The preparation method of tea grounds of the present invention/cellulose preservative film, includes the following steps：
Step 1：Tea grounds is placed in 70~80 DEG C of deionized waters 3~4h of immersion, removes soluble pigment, then 80~
Dry 3~5h, smashes it through 150 mesh and sieves to obtain tea grounds powder at 100 DEG C；
Step 2：Step 1 gained tea grounds powder is added according to the concentration of 0.5~1.5wt% in ionic liquid, 90~120 DEG C
Then alkali swollen cellulose is added in 2~4h of lower stirring and dissolving, 30min~120min is stirred at 80~100 DEG C, obtain tea grounds and
Cellulose mixes film liquid；
In step 2, the alkali swollen cellulose is to be prepared via a method which to obtain：
Cellulose is first smashed it through into 80 mesh sieve, be subsequently placed in the sodium hydroxide solution of 2.2~4.8mol/L in 25~
20~60min is impregnated at 45 DEG C, is then washed with deionized and squeezes removing lye, obtains alkali swollen cellulose.
In step 2, the mass ratio of alkali swollen cellulose and tea grounds powder is 2: 8~8: 2.
In step 2, the ionic liquid is 1- ethyl-3-methylimidazoles acetate, 1- methylimidazoles acetate, 1,3- bis-
Methylimidazole acetate, 1- butyl -3- methylimidazoles acetate, glycine hydrochloride/1- butyl -3- methylimidazole villaumites or 1-
Ethyl-3-methylimidazole bromide.
Step 3：Edibility plasticizer is added to tea grounds and fiber by the additive amount for being 0.2~0.6% according to mass concentration
It in element mixing film liquid, is heated to 40~50 DEG C and is uniformly mixed, gained mixing film liquid is poured over surface and is covered with by evacuation and centrifugal degassing
On the glass plate of tenon sheet, thickness is made with automatic coating device and is the uniform film of 0.7~1.8mm, then immerses solid
Coagulation forming and ionic liquid is precipitated completely after impregnating 8~10h in 20~30 DEG C in agent, 6~8 are cleaned with deionized water
It is secondary, then in 30~45 DEG C of dry 4~6h, obtain tea grounds/cellulose preservative film.
In step 3, the edibility plasticizer is one or more of glycerine, polyethylene glycol, sorbierite, xylitol.
In step 3, centrifugation rate when evacuation and centrifugal degassing is 3500~5000r/min, and centrifugation time is 10~25min.
In step 3, the curing agent is made of absolute ethyl alcohol or methanol with deionized water at 5: 5~7: 3 by volume.
Compared with prior art, beneficial effects of the present invention are embodied in：
1, the present invention is that primary raw material prepares tea grounds/cellulose preservative film using tea grounds is discarded, and tea grounds derives from a wealth of sources and can
Regeneration, the comprehensive utilization for waste in tea comprehensive processing production provide new way, and the environment for eliminating tea grounds waste is dirty
Dye solves the problems, such as the recycling of tea grounds biomass.
2, the present invention used in tea grounds and cellulose be environment-friendly degradable natural biomass materials, manufactured tea grounds/
Cellulose preservative film biological degradability is good, safety and sanitation, in moist natural environment 6 months can natural degradation, generate two
Carbonoxide and water.Meanwhile the plurality of active ingredients contained in tea grounds makes natural complex fresh-keeping film have anti-oxidant, antibacterial, mould proof, absorption
The effects that peculiar smell, can significantly extend shelf life storage and freshness.In addition, the glycerine of addition, polyethylene glycol, sorbierite, xylose
The edibilities plasticizer such as alcohol is nontoxic, it is nuisanceless be largely used in food industry, can increase tea grounds/cellulose mixing film liquid at
Film property and uniformity improve the flexibility and mechanical strength of composite membrane, and the plasticizer such as glycerine are alternatively arranged as antistatic agent, make guarantor
Fresh film has antistatic effect, and the food with packaging is avoided to stick together.
3, the present invention carries out swelling treatment using sodium hydrate aqueous solution to cellulose, increases cellulose in ionic liquid
In rate of dissolution and meltage, and alkali swollen cellulose it is quick dissolving can avoid mixing film liquid in cellulosic molecule and tea
Slag adheres to each other, and promotes dissolving of the tea grounds in ionic liquid and evenly dispersed, while alkali swollen fiber in ionic liquid
The meltage of element increases the film forming for also enhancing tea grounds.The good swollen cellulose of sodium hydroxide hydrated ion energy, weakens fine
The intermolecular Hydrogen bonding forces of dimension element, reduce the crystallinity of cellulose, to improve accessibility of the cellulose to solvent, promote it
Dissolving, and the sodium hydroxide swelling treatment under 25~45 DEG C of lower temperature and 20~60min of short period divides cellulose
Son amount influence is smaller, will not cause being decreased obviously for cellulose average molecular mass, maintains the excellent machinery strength of cellulose
With filming performance.
4, the preparation process of this tea grounds/cellulose preservative film is simple and practicable, at low cost, pollution-free, application easy to spread, tool
There is prodigious practical value.This tea grounds/cellulose composite membrane thickness is uniform, has preferable mechanical property, inoxidizability and suppression
Bacterium effect can be widely applied to the fresh-keeping packaging of food.
5, the present invention dissolves tea grounds and cellulose altogether using ionic liquid as solvent, ionic liquid stable in physicochemical property,
It is nontoxic and pollution-free, non-volatile without vapor pres- sure, easily detach with product.The mixing that tea grounds and cellulose dissolution are formed in ionic liquid
Film is made through automatic coating device in film liquid, and tea grounds/cellulose composite membrane can be made by immersing in the curing agent such as absolute ethyl alcohol/deionized water
Moment coagulation forming, while being separated with ionic liquid, to which ionic liquid is easily isolated precipitation from composite membrane, and it is molten
For solution in curing agent, filtered ionic liquid can remove absolute ethyl alcohol and water through flint dry, then can be used as again molten
The good solvent of tea grounds and cellulose is solved, there are the advantages such as recycling reuse, non-environmental-pollution.
Description of the drawings
Fig. 1 is that the SEM of pure cellulose film and tea grounds/cellulose composite membrane schemes in test item 1 of the present invention.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are better understood from, below in conjunction with attached drawing and specifically
The invention will be further described for embodiment, but the present invention is not restricted to the present embodiment.
(1) preparation of tea grounds/cellulose preservative film
Embodiment 1：
The preparation method of tea grounds/cellulose preservative film is as follows in the present embodiment：
1, tea grounds is placed in 70 DEG C of deionized waters and impregnates 4h, remove soluble pigment, then dry 4h, powder at 80 DEG C
150 mesh are crossed after broken to sieve to obtain tea grounds powder；
2,25g ionic liquid 1-butyl-3-methyl imidazoliums are added according to the concentration of 0.8wt% in step 1 gained tea grounds powder
In acetate, then alkali swollen cellulose is added in stirring and dissolving 4h at 90 DEG C, alkali swollen cellulose and the mass ratio of tea grounds powder are
45min is stirred at 7: 3,95 DEG C, obtains tea grounds and cellulose mixing film liquid；
In step 2, the alkali swollen cellulose is to be prepared via a method which to obtain：
Cellulose is first smashed it through into 80 mesh sieve, is subsequently placed in the sodium hydroxide solution of 2.5mol/L and is impregnated at 40 DEG C
Then 45min is washed with deionized and squeezes removing lye, obtain alkali swollen cellulose.
3, edibility plasticizer glycerine is added to tea grounds by the additive amount for being 0.2% according to mass concentration and cellulose mixes
It in film liquid, is heated to 40 DEG C and is uniformly mixed, gained is mixed film liquid and is poured over by the evacuation and centrifugal degassing 20min at 3800r/min
Surface is covered on the glass plate of tenon sheet, the uniform film that thickness is 1.2mm is made with automatic coating device, then immerse
Coagulation forming is impregnated in 25 DEG C after 8h in curing agent (absolute ethyl alcohol and deionized water by volume 6: 4 composition) and by ionic liquid
It is precipitated completely, is cleaned 6 times with deionized water, then in 40 DEG C of dry 4h, obtain tea grounds/cellulose preservative film.
Embodiment 2：
The preparation method of tea grounds/cellulose preservative film is as follows in the present embodiment：
1, tea grounds is placed in 75 DEG C of deionized waters and impregnates 4h, remove soluble pigment, then dry 5h, powder at 90 DEG C
150 mesh are crossed after broken to sieve to obtain tea grounds powder；
2,25g ionic liquid 1-butyl-3-methyl imidazolium vinegar is added according to the concentration of 1wt% in step 1 gained tea grounds powder
In hydrochlorate, then alkali swollen cellulose is added in stirring and dissolving 3h at 100 DEG C, the mass ratio of alkali swollen cellulose and tea grounds powder is 5
: 90min is stirred at 5,90 DEG C, obtains tea grounds and cellulose mixing film liquid；
In step 2, the alkali swollen cellulose is to be prepared via a method which to obtain：
Gossypin is first smashed it through into 80 mesh sieve, is subsequently placed in the sodium hydroxide solution of 2.8mol/L and is soaked at 35 DEG C
40min is steeped, removing lye is then washed with deionized and squeezes, obtains alkali swollen cellulose.
3, edibility plasticizer glycerine is added to tea grounds by the additive amount for being 0.3% according to mass concentration and cellulose mixes
It in film liquid, is heated to 40 DEG C and is uniformly mixed, gained is mixed film liquid and is poured over by the evacuation and centrifugal degassing 15min at 4000r/min
Surface is covered on the glass plate of tenon sheet, the uniform film that thickness is 1.2mm is made with automatic coating device, then immerse
Coagulation forming is impregnated in 20 DEG C after 8h in curing agent (absolute ethyl alcohol and deionized water by volume 5: 5 composition) and by ionic liquid
It is precipitated completely, is cleaned 8 times with deionized water, then in 30 DEG C of dry 5h, obtain tea grounds/cellulose preservative film.
Embodiment 3：
The preparation method of tea grounds/cellulose preservative film is as follows in the present embodiment：
1, tea grounds is placed in 80 DEG C of deionized waters and impregnates 3h, remove soluble pigment, then dry 4h, powder at 95 DEG C
150 mesh are crossed after broken to sieve to obtain tea grounds powder；
2,30g ionic liquid 1- ethyl-3-methylimidazoles are added according to the concentration of 1.2wt% in step 1 gained tea grounds powder
In acetate, then alkali swollen cellulose, the mass ratio of alkali swollen cellulose and tea grounds powder is added in stirring and dissolving 3.5h at 95 DEG C
It is to stir 60min at 4: 6,95 DEG C, obtains tea grounds and cellulose mixing film liquid；
In step 2, the alkali swollen cellulose is to be prepared via a method which to obtain：
Gossypin is first smashed it through into 80 mesh sieve, is subsequently placed in the sodium hydroxide solution of 3.4mol/L and is soaked at 45 DEG C
30min is steeped, removing lye is then washed with deionized and squeezes, obtains alkali swollen cellulose.
3, edibility plasticizer polyethylene glycol is added to tea grounds and cellulose by the additive amount for being 0.4% according to mass concentration
It mixes in film liquid, is heated to 45 DEG C and is uniformly mixed, gained is mixed film liquid and inclined by the evacuation and centrifugal degassing 18min at 4200r/min
It is poured on surface to be covered on the glass plate of tenon sheet, the uniform film that thickness is 1.0mm is made with automatic coating device, then
It immerses in curing agent (methanol and deionized water by volume 5: 5 composition) and to impregnate after 9h coagulation forming in 22 DEG C and by ionic liquid
It is precipitated completely, is cleaned 7 times with deionized water, then in 35 DEG C of dry 4.5h, obtain tea grounds/cellulose preservative film.
Embodiment 4：
The preparation method of tea grounds/cellulose preservative film is as follows in the present embodiment：
1, tea grounds is placed in 72 DEG C of deionized waters and impregnates 3.5h, remove soluble pigment, then the dry 4h at 92 DEG C,
150 mesh are smashed it through to sieve to obtain tea grounds powder；
2,30g ionic liquid 1,3- methylimidazole acetic acid is added according to the concentration of 1.2wt% in step 1 gained tea grounds powder
In salt, then alkali swollen cellulose is added in stirring and dissolving 2.5h at 110 DEG C, the mass ratio of alkali swollen cellulose and tea grounds powder is 2
: 50min is stirred at 8,98 DEG C, obtains tea grounds and cellulose mixing film liquid；
In step 2, the alkali swollen cellulose is to be prepared via a method which to obtain：
Gossypin is first smashed it through into 80 mesh sieve, is subsequently placed in the sodium hydroxide solution of 4.4mol/L and is soaked at 40 DEG C
35min is steeped, removing lye is then washed with deionized and squeezes, obtains alkali swollen cellulose.
3, edibility plasticizer polyethylene glycol is added to tea grounds and cellulose by the additive amount for being 0.5% according to mass concentration
It mixes in film liquid, is heated to 45 DEG C and is uniformly mixed, gained is mixed film liquid and inclined by the evacuation and centrifugal degassing 12min at 4500r/min
It is poured on surface to be covered on the glass plate of tenon sheet, the uniform film that thickness is 1.0mm is made with automatic coating device, then
It immerses in curing agent (methanol and deionized water by volume 6: 4 composition) and to impregnate after 10h coagulation forming in 20 DEG C and by ionic liquid
Body is precipitated completely, is cleaned 8 times with deionized water, then in 30 DEG C of dry 5h, obtains tea grounds/cellulose preservative film.
Comparative example：
The preparation (not adding tea grounds and plasticizer) of pure cellulose film：
Cotton linter is smashed it through into 80 mesh sieve and obtains gossypin powder, to 25g ionic liquid 1- ethyl-3-methylimidazoles
The gossypin powder that mass concentration is 1% is added in acetate, then molten to 100min is persistently stirred at 95 DEG C with oil bath heating
Solution obtains gossypin film liquid, then carries out evacuation and centrifugal degassing (centrifugation rate 4000r/min, centrifugation time to cellulose film liquid
For 20min), gained film liquid is poured over surface and is covered on the glass plate of tenon sheet, thickness is made with automatic coating device
Degree is the uniform film of 1.0mm, then immerses in curing agent (methanol forms at 5: 5 by volume with deionized water) after 25 DEG C of immersion 8h
Simultaneously ionic liquid 1- ethyl-3-methylimidazoles acetate is precipitated completely for coagulation forming, by wet gossypin film deionization
Water cleans 6 times, then in 40 DEG C of dry 4h, obtains pure cellulose film.
(2) performance detection
Test item 1：The sem analysis of pure cellulose film and tea grounds/cellulose composite membrane
Using the surface topography situation of field emission microscopy observation pure cellulose film and tea grounds/cellulose composite membrane.It takes
4 parts of membrane sample, the 1st part of pure cellulose membrane sample to be obtained by the method ion liquid dissolving cellulose of comparative example, the 2nd
Part it is 3 to dissolve tea grounds that tea grounds and cellulose are obtained and cellulose mass ratio altogether with ionic liquid as described in Example 1:
7 composite membrane, the 3rd part for dissolved altogether with ionic liquid as described in Example 2 tea grounds that tea grounds and cellulose are obtained with it is fine
The composite membrane that the plain mass ratio of dimension is 5: 5, the 4th part is dissolves tea grounds and cellulose institute altogether with ionic liquid as described in Example 3
The composite membrane that the tea grounds of acquisition is 6: 4 with cellulose mass ratio, test result successively referring to Fig. 1 (A)~(D) be surface topography,
(a)~(d) is Cross Section Morphology.
It is shown by Fig. 1, pure cellulose film surface (A) and section (a) very flat smooth and densification, there is no particle knots
Structure and cavernous structure.In addition, smaller tea grounds/cellulose composite membrane surface (B) of tea grounds additive amount, (C) also more uniform smooth,
Only there is a small amount of constitution, composite membrane section (b), (c) are also that compare homogeneous close.The side of this and compound film preparation
Method is related, and the cellulose solution and tea grounds/cellulose mixed solution one that ion liquid dissolving is formed enter absolute ethyl alcohol/water etc.
In coagulating bath, phase transfer just has occurred in moment, and so as to form fine and close rather than loose membrane structure, it is existing not generate phase separation
As the biocompatibility in tea grounds/cellulose composite membrane between two components is preferable.Compare the microscopic pattern of pure cellulose film, tea grounds
Tea grounds of the addition mass ratio more than 6: 4/cellulose composite membrane surface (D) there are obvious grain structure, cross-section morphologies (d)
Also there is more hole, mixture of the tea grounds as many kinds of substance, since strand is insufficient to grow, film forming is poor, when
When the tea grounds quality added in composite membrane is excessive, it will influence the aggregated structure of cellulose molecular chain, change tea grounds/cellulose
The network structure of cellulose molecular chain in composite membrane causes the compatibility in tea grounds/cellulose composite membrane between two components to decline.
Test item 2：The Performance Analysis of pure cellulose film and tea grounds/cellulose composite membrane
The system of pure cellulose film and tea grounds/cellulose composite membrane is carried out according to the method for comparative example and Examples 1 to 4 respectively
It is standby, to the thickness of pure cellulose film and tea grounds/cellulose composite membrane, mechanical strength, elongation at break, moisture content and inoxidizability
(DPPH free radical scavenging activities) is tested, and experiment is parallel three times, and test result is referring to table 1.
It is found that the tensile strength of pure cellulose film is higher after test data analysis as shown in Table 1, but elongation at break and
Moisture content is all relatively low, and the DPPH free radical scavenging activities of especially pure cellulose film are very low, and only 1.92%, show pure cellulose film
Oxidation resistance it is very poor.And tea grounds made from the embodiment of the present invention/cellulose composite membrane mechanical strength is answered in 14MPa or more
The elongation at break for closing film improves 58.15% or more, and moisture content increases 28.98% or more, and especially tea grounds/cellulose is multiple
The DPPH free radical scavenging activities for closing film improve 4.97~23.24 times than pure cellulose film, and the antioxygenic property of composite membrane is significantly
Enhancing.
1 pure cellulose film of table and tea grounds/cellulose composite membrane performance evaluation
Test item 3：Fresh beef appetizer total plate count test analysis
The system of pure cellulose film and tea grounds/cellulose composite membrane is carried out according to the method for comparative example and Examples 1 to 4 respectively
It is standby, after pure cellulose film and tea grounds/cellulose composite membrane package fresh beef appetizer, it is placed in refrigerate in 0~4 DEG C of refrigerator and protects
It deposits, then according to GB 4789.2-2003《Food hygiene microbiologic inhibition tests total plate count measures》To different refrigeration number of days
The total plate count of fresh beef appetizer is tested, and experiment is parallel three times, and measurement result is referring to table 2.Meat Freshness evaluation standard pair
According to meat quality sanitary index total plate count general recommendations standard, (green meat is 1~104Cfu/g, secondary fresh meat are 104~106cfu/
G, the meat that goes bad are 106Cfu/g or more) it executes.
As can be seen from Table 2, tea grounds/cellulose composite membrane made from the method for the present invention is in packaging fresh beef appetizer refrigeration
During preservation, the 6th day total plate count still substantially conforms to the quality health standard of green meat, total plate count at the 12nd day according to
The old sanitary standard for meeting time fresh meat, and occur without any peculiar smell.By fresh packaged by pure cellulose film made from comparative example
Total plate count of beef when the 6th day goes bad having shown that beef, a small amount of spot occurs, and with peculiar smell, and arrives
Fresh beef appetizer packaged by 9th day has started corruption and stink occur.It can be seen that tea grounds/cellulose prepared by the present invention is protected
Fresh film is used for the preservation and freshness of fresh beef appetizer, can effectively inhibit the growth of microbe colony, effective period of food quality is made to extend 6 days left sides
It is right.
Total plate count (lg cfu/g) analysis of 2 pure cellulose film of table and tea grounds/cellulose composite membrane packaging fresh beef appetizer
In conclusion dissolving tea grounds and alkali swollen cellulose altogether using ionic liquid, adds edibility plasticiser and obtain
Mix film liquid, film in homogeneous thickness then be made with spreader, then immerse in curing agent impregnate after coagulation forming and separate out
Ionic liquid, prepares that thickness is uniform, and adhesion food, safety and sanitation, biological degradability is good after low temperature drying, has preferably
Mechanical property, inoxidizability and fungistatic effect tea grounds/cellulose preservative film.The present invention is based on discarded tea grounds biomass
Raw material is wanted, the environmental pollution of tea grounds waste is eliminated, effectively increases the higher value application of tea grounds, and the technique side of the present invention
Method is simple and practicable, at low cost, pollution-free, and application easy to spread has great practical value.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
All any modification, equivalent and improvement made by within principle etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of tea grounds/cellulose preservative film, it is characterised in that：It is to be used using discarded tea grounds as primary raw material
Ionic liquid dissolves tea grounds and alkali swollen cellulose altogether, adds edibility plasticizer and obtains mixing film liquid, is solidified into after coating
Type obtains tea grounds/cellulose preservative film.
2. preparation method according to claim 1, it is characterised in that include the following steps：
Step 1：Tea grounds is placed in 3~4h of immersion in 70~80 DEG C of deionized waters, soluble pigment is removed, then 80~100
Dry 3~5h, smashes it through 150 mesh and sieves to obtain tea grounds powder at DEG C；
Step 2：Step 1 gained tea grounds powder is added according to the concentration of 0.5~1.5wt% in ionic liquid, is stirred at 90~120 DEG C
2~4h of dissolving is mixed, alkali swollen cellulose is then added, stirs 30min~120min at 80~100 DEG C, obtains tea grounds and fiber
Element mixing film liquid；
Step 3：Edibility plasticizer is added to tea grounds to the additive amount for being 0.2~0.6% according to mass concentration and cellulose mixes
It closes in film liquid, is heated to 40~50 DEG C and is uniformly mixed, gained mixing film liquid is poured over surface and is covered with poly- four by evacuation and centrifugal degassing
On the glass plate of vinyl fluoride thin plate, thickness is made with automatic coating device and is the uniform film of 0.7~1.8mm, then immerses curing agent
In impregnate 8~10h in 20~30 DEG C after coagulation forming and ionic liquid is precipitated completely, clean 6~8 times with deionized water, so
Afterwards in 30~45 DEG C of dry 4~6h, tea grounds/cellulose preservative film is obtained.
3. preparation method according to claim 2, it is characterised in that：
In step 2, the alkali swollen cellulose is to be prepared via a method which to obtain：
Cellulose is first smashed it through into 80 mesh sieve, is subsequently placed in the sodium hydroxide solution of 2.2~4.8mol/L in 25~45 DEG C
Then 20~60min of lower immersion is washed with deionized and squeezes removing lye, obtain alkali swollen cellulose.
4. preparation method according to claim 2 or 3, it is characterised in that：
In step 2, the mass ratio of alkali swollen cellulose and tea grounds powder is 2: 8~8: 2.
5. preparation method according to claim 2, it is characterised in that：
In step 2, the ionic liquid is 1- ethyl-3-methylimidazoles acetate, 1- methylimidazoles acetate, 1,3- dimethyl
Imidazoles acetate, 1- butyl -3- methylimidazoles acetate, glycine hydrochloride/1- butyl -3- methylimidazole villaumites or 1- second
Base -3- methylimidazole bromides.
6. preparation method according to claim 2, it is characterised in that：
In step 3, the edibility plasticizer is one or more of glycerine, polyethylene glycol, sorbierite, xylitol.
7. preparation method according to claim 2, it is characterised in that：
In step 3, centrifugation rate when evacuation and centrifugal degassing is 3500~5000r/min, and centrifugation time is 10~25min.
8. preparation method according to claim 2, it is characterised in that：
In step 3, the curing agent is made of absolute ethyl alcohol or methanol with deionized water at 5: 5~7: 3 by volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810201944.3A CN108395724A (en) | 2018-03-12 | 2018-03-12 | A kind of preparation method of tea grounds/cellulose preservative film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810201944.3A CN108395724A (en) | 2018-03-12 | 2018-03-12 | A kind of preparation method of tea grounds/cellulose preservative film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108395724A true CN108395724A (en) | 2018-08-14 |
Family
ID=63092268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810201944.3A Pending CN108395724A (en) | 2018-03-12 | 2018-03-12 | A kind of preparation method of tea grounds/cellulose preservative film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108395724A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293959A (en) * | 2018-09-30 | 2019-02-01 | 安徽农业大学 | Tea grounds modified oxidized cellulose composite membrane and the preparation method and application thereof |
| CN110344236A (en) * | 2019-07-31 | 2019-10-18 | 安徽农业大学 | A kind of tea grounds modified function quilted stockings of antibacterial and deodouring and preparation method thereof |
| CN113794396A (en) * | 2021-07-20 | 2021-12-14 | 浙江大学 | Friction nanometer generator with slit effect for efficiently collecting wind energy |
| CN113785753A (en) * | 2021-09-03 | 2021-12-14 | 浙江传化生物技术有限公司 | Cymbidium hybridum cultivation medium and preparation method thereof |
| CN115232339A (en) * | 2022-07-20 | 2022-10-25 | 华南理工大学 | Method for preparing regenerated composite membrane by using coffee grounds |
| CN115710365A (en) * | 2022-11-03 | 2023-02-24 | 安徽农业大学 | Preparation method based on tea residue/cellulose composite membrane |
| CN116249614A (en) * | 2020-06-01 | 2023-06-09 | 得克萨斯技术大学联合体 | Method for producing cellulose bioplastic |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284913A (en) * | 2008-05-22 | 2008-10-15 | 高小山 | Preparation method of cellulose membrane by using ion liquid as solvent |
| CN102936353A (en) * | 2012-10-15 | 2013-02-20 | 武汉纺织大学 | Method for preparing high air tightness antibacterial reinforced membrane by using straws |
| CN104059239A (en) * | 2014-07-09 | 2014-09-24 | 杭州艺福堂茶业有限公司 | Method for producing preservative film by using used tea leaves |
| CN106188774A (en) * | 2016-08-11 | 2016-12-07 | 马鞍山杰创塑胶科技有限公司 | Polyethylene coating materials that a kind of nanocrystal is cellulose modified and preparation method thereof |
| CN107400249A (en) * | 2017-07-26 | 2017-11-28 | 中国热带农业科学院海口实验站 | A kind of preparation method and applications of banana cellulose film |
-
2018
- 2018-03-12 CN CN201810201944.3A patent/CN108395724A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284913A (en) * | 2008-05-22 | 2008-10-15 | 高小山 | Preparation method of cellulose membrane by using ion liquid as solvent |
| CN102936353A (en) * | 2012-10-15 | 2013-02-20 | 武汉纺织大学 | Method for preparing high air tightness antibacterial reinforced membrane by using straws |
| CN104059239A (en) * | 2014-07-09 | 2014-09-24 | 杭州艺福堂茶业有限公司 | Method for producing preservative film by using used tea leaves |
| CN106188774A (en) * | 2016-08-11 | 2016-12-07 | 马鞍山杰创塑胶科技有限公司 | Polyethylene coating materials that a kind of nanocrystal is cellulose modified and preparation method thereof |
| CN107400249A (en) * | 2017-07-26 | 2017-11-28 | 中国热带农业科学院海口实验站 | A kind of preparation method and applications of banana cellulose film |
Non-Patent Citations (3)
| Title |
|---|
| J. DUANA等: "Effects of spent tea leaf powder on the properties and functions of ellulose green composite films", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》 * |
| 关志宇: "《药物制剂辅料与包装材料》", 31 January 2017, 中国医药科技出版社 * |
| 段久芳: "《天然高分子材料》", 30 September 2015, 华中科技大学出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293959A (en) * | 2018-09-30 | 2019-02-01 | 安徽农业大学 | Tea grounds modified oxidized cellulose composite membrane and the preparation method and application thereof |
| CN109293959B (en) * | 2018-09-30 | 2021-07-30 | 安徽农业大学 | Tea-residue-modified oxidized cellulose composite membrane and preparation method and application thereof |
| CN110344236A (en) * | 2019-07-31 | 2019-10-18 | 安徽农业大学 | A kind of tea grounds modified function quilted stockings of antibacterial and deodouring and preparation method thereof |
| CN110344236B (en) * | 2019-07-31 | 2021-08-20 | 安徽农业大学 | Antibacterial and deodorant tea residue modified functional cotton sock and preparation method thereof |
| CN116249614A (en) * | 2020-06-01 | 2023-06-09 | 得克萨斯技术大学联合体 | Method for producing cellulose bioplastic |
| CN113794396A (en) * | 2021-07-20 | 2021-12-14 | 浙江大学 | Friction nanometer generator with slit effect for efficiently collecting wind energy |
| CN113785753A (en) * | 2021-09-03 | 2021-12-14 | 浙江传化生物技术有限公司 | Cymbidium hybridum cultivation medium and preparation method thereof |
| CN115232339A (en) * | 2022-07-20 | 2022-10-25 | 华南理工大学 | Method for preparing regenerated composite membrane by using coffee grounds |
| CN115232339B (en) * | 2022-07-20 | 2023-08-22 | 华南理工大学 | Method for preparing regenerated composite membrane by using coffee grounds |
| CN115710365A (en) * | 2022-11-03 | 2023-02-24 | 安徽农业大学 | Preparation method based on tea residue/cellulose composite membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108395724A (en) | A kind of preparation method of tea grounds/cellulose preservative film | |
| CN101811596B (en) | Edible polysaccharide-protein composite packaging film and preparation method thereof | |
| CN102733001B (en) | Feather protein fiber and method for preparing same | |
| CN107840981A (en) | A kind of sodium alginate chitosan bilayer edible film, its preparation method and its application | |
| CN110863354B (en) | Multifunctional preservative film for meat products and application | |
| WO2021088515A1 (en) | Chitosan, kojic acid and chlorokojic acid composite bacteriostatic preservative film and preparation method therefor | |
| CN104277249A (en) | Antibacterial packaging film and preparation method thereof | |
| CN106220876A (en) | A kind of preparation method of chitosan protocatechuic acid graft copolymer membrane | |
| CN108841049A (en) | A kind of stalk cellulose antimicrobial preservative film and preparation method thereof | |
| CN113292753B (en) | Preparation method and application of controlled-release antibacterial chitosan-based composite membrane | |
| CN103819799A (en) | Polymer/potassium permanganate composite film and preparation method thereof | |
| CN106966047A (en) | A kind of preparation method of edible nanofiber preservative film | |
| CN109293959A (en) | Tea grounds modified oxidized cellulose composite membrane and the preparation method and application thereof | |
| CN108484988A (en) | A kind of preparation method of the amine-modified modified by nano particles chitosan bacteriostatic film of DOPA | |
| CN111471307A (en) | Preparation method of degradable collagen packaging material | |
| Liu et al. | Fabricating κ-carrageenan/carboxymethyl cellulose films encapsulating bromothymol blue fixed rice straw fiber for monitoring meat freshness | |
| CN107474501B (en) | A kind of degradable food fresh keeping membrane and preparation method thereof | |
| CN104725648A (en) | Preparation method for degradable feather protein/sodium carboxymethylcellulose composite membrane | |
| CN108928559A (en) | A kind of preparation method of high tensile elasticity cellulose membrane | |
| Lin et al. | Characterization of anglerfish gelatin/polyvinyl alcohol film and its application in preservation of small yellow croaker (Larimichthys polyactis) | |
| CN114044996A (en) | Preparation and use methods of pH-sensitive intelligent active packaging film for chilled fresh multi-wave mutton | |
| CN113080251A (en) | Edible composite coating material and preparation method thereof | |
| CN113402734B (en) | Preparation method and application of hydrogel for indicating freshness of chilled meat | |
| CN112280315A (en) | Soybean protein nano antibacterial film and preparation method thereof | |
| CN116043603B (en) | Preparation method and application of multifunctional cellulose-based visual intelligent tag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180814 |