CN105778259B - A kind of preparation method of the strawberry preservation film master batch containing rare earth compounding - Google Patents
A kind of preparation method of the strawberry preservation film master batch containing rare earth compounding Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29B9/00—Making granules
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The present invention relates to a kind of preparation method of the strawberry preservation film master batch containing rare earth compounding.The present invention is using LLDPE as vector resin, and addition tourmaline powder, rare earth compounding, diatomite, oleamide, odium stearate are by the way that cladding is scattered, interface modification, material are mixed, extrusion pelletizing is processed.Master batch prepared by this method, linear low density polyethylene (LLDPE) is added to 5~8% ratio（LLDPE）In resin, blowing is made after film, for strawberry preservation packaging, can suppress respiratory intensity and surface microorganism growth in storage, and normal temperature condition prolongs storage period 5~7 days.The beneficial effects of the invention are as follows：Tourmaline powder, rare earth, the natural plant polyose aboundresources of use, can effectively reduce cost, and harmless, obtained material safety, can trust for fresh food packaging；Tourmaline powder, rare earth, natural plant polyose have sterilizing fresh-keeping function in itself, and anti-bacterial refreshing effect can be effectively strengthened by modes such as modification, compoundings.
Description
Technical field
The present invention relates to the preparation method of functional plastic film master batch, and in particular to a kind of strawberry containing rare earth compounding
The preparation method of fresh-keeping film master batch.
Background technology
Strawberry（Fragaria ananassa Duchesne）Belong to rose family Fragaria herbaceos perennial.Strawberry is slurry
Fruit fruit, it is antipyretic with clear heat, promote the production of body fluid to quench thirst, effect of diuresis antidiarrheal has very high nutritive value and dietary function.Element
There is the good reputation of " fruit queen ".But strawberry aqueous up to 90%~95%, organize tender and lovely, pericarp is very thin, crust unprotect is made
With thus subject to damage and microbial infection rot in harvesting and storing, pole not storage tolerance.In storage, breathing
The increase of effect is a kind of reaction of strawberry ripening and senescence, is the not long keeping one of the main reasons of strawberry.And strawberry fruit
Softening is mainly the effect of cellulase.Free radical is the initiator of tissue Lipid peroxidation metabolism.Generally, after strawberry harvesting
It is to tarnish to place 1~2 d, and fruit face is shunk, Quality Down, so as to lose commercial value.In recent years, the yield of strawberry is presented
The gesture of swift and violent rising, but due to failing to solve the problems, such as its preservation and freshness, cause substantial amounts of strawberry to be rotted, cause very big loss.
Therefore, how to extend storage period or the shelf life of strawberry fruit, be urgent problem to be solved in production.
China's rare earth resources enrich, and rare earth, which is developed, has great potential.Rare earth and its derivative can be protected as antibacterial
Fresh dose, Ca2+It is the ion for maintaining bacterium normal activity, and lanthanum ion has antagonism Ca2+Effect, so lanthanum ion can be to thin
Bacterium normal activities are interfered, and cause bacterial death, while part enhances anti-microbial property in Rare Earth Lanthanum coordination antiseptic.
Cerium ion has hydrolysis, can be broken polypeptide chain, and enzyme is protein, so cerium ion makes the polypeptide chain in enzyme break
Split；In addition cerium ion presses down to the displacement of metal ion in enzyme with competition so as to have impact on the physiological function of enzyme, therefore can pass through
Cellulase activity processed slows down softening process, suppresses respiratory intensity.Rare earth has the ability of stronger removing hydroxyl radical free radical,
By reducing respiration of fruits, free radical is reduced, weakens active oxygen injury, so as to produce the Lipid peroxidation metabolism work for suppressing tissue
With delayed fruit ripening and senescence extends strawberry shelf life.Tourmaline is also China rich in mineral resources, and tourmaline powder release is negative
Ion can effectively kill germ.Its mechanism is essentially consisted in after anion combined with bacterium, bacterium is produced change or the energy of structure
The transfer of amount, causes bacterial death.Plant polyose is abundant renewable resource, and itself has certain antibacterial effect, acetylation
Plant polyose there is the ability of stronger removing hydroxyl radical free radical.
Shelf life is short during conventional packaging room temperature storage, has a strong impact on its transport and sells.At present, strawberry preservation technology is main
There are cryopreservation, air conditioned storage, high oxygen treatment, coating-film fresh-keeping method, irradiated targets, fresh chemically etc..Though physical method it is nontoxic and
Compare effectively, but cost is higher, needs specific appointed condition, is not suitable for commonly used；And antistaling agent is made using chemicals, again
The problems such as being related to the residual hazard of some medicines.Some other new antistaling film effect is not good or cost is higher, and constraining popularization should
With.
The content of the invention
For the existing deficiency that strawberry preservation fresh-keeping effect is bad and cost is high.The invention provides a kind of antibacterial
The preparation method of fresh-keeping good lower-cost master batch, it is characterized in that：Using LLDPE as vector resin, addition tourmaline powder, rare earth are matched somebody with somebody
Compound, diatomite, oleamide, odium stearate are by the way that cladding is scattered, interface modification, material are mixed, extrusion pelletizing is processed.
Master batch prepared by this method, linear low density polyethylene (LLDPE) is added to 5~8% ratio（LLDPE）In resin, blowing is made thin
After film, for strawberry preservation packaging, respiratory intensity and surface microorganism growth in storage can be suppressed, normal temperature condition extension is protected
Fresh 5~7 days phases.
For realize the purpose of the present invention use technical scheme be：
1st, the preparation of rare earth compounding
（1）In the acetic acid solution that the plant polyose of 2 parts by weight is dissolved in 60 parts by weight, after stirring, 80 weight are added
Part methanol, solution is no longer sticky, adds the acetic anhydride of 1 parts by weight, is reacted at 30 DEG C of temperature after 1 h, by obtained by reaction
Thick liquid is added in the ethanol of 150 parts by weight, filtering precipitate after precipitation generation, is washed with absolute ethyl alcohol 3 times, then use second
After acid solution dissolving, insoluble matter is filtered off, acetylation plant polyose solution is obtained.
（2）Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 2.90~3.0:0.55~0.65:1.00~1.05:1.25
~1.35, the compound that compound, the compound of yttrium, the compound of neodymium and the cerium of lanthanum are weighed respectively is mixed into rare earth compound,
And be added to 1 ﹕ 5 weight part ratio in distilled water, obtain rare earth compound mixed aqueous solution after being entirely capable of dissolving；According to plant
The weight ratio such as polysaccharide and rare earth compound, rare earth compound mixed aqueous solution is slowly added dropwise to acetylation plant polyose solution
In, adjust reaction system pH to 7.0, under the conditions of rotating speed 1000r/min, 25~30 DEG C of temperature react 6~7 hours, product with
Precipitation form is separated out；Filter after sediment, unreacted rare earth ion is removed with distillation water washing, in vacuum drying chamber
Middle drying, grinding, obtains powdered rare earth compounding.
2nd, the preparation of master batch
（1）By 22~25 parts by weight rare earth compoundings, 2.5~3.5 parts by weight diatomite are placed in mixer after compounding,
0.9~1.2 parts by weight oleamide is added, is 250r/min in rotating speed, temperature is scattered to be coated under the conditions of 102 ± 1 DEG C,
Into raw material I after 15min；
（2）12~15 parts of tourmaline powders are placed in high-speed kneading machine, are that rotating speed is 500r/min in rotating speed, temperature is
10min is mediated under the conditions of 105 ± 1 DEG C, 1.0~1.2 parts by weight odium stearate are added, carried out after interface modification 20min into original
Expect II；
（3）Raw material II and raw material I are placed in mixer and are mixed into compound, 54.1~61.6 parts by weight are added
LLDPE mixing 10min obtains mixed material；
（4）Mixed material is placed in double screw extruder and extrudes pelletizing as master batch.Using blow molding machine using normal
Process conditions are advised, a kind of strawberry preservation film containing rare earth compounding is further prepared.
The strawberry preservation film containing rare earth compounding that the present invention is prepared is widely used commonly fresh-keeping with the market
It is soluble to the strawberry titratable acid content of storage and the strawberry of storage to the strawberry respiratory intensity of storage, normal temperature at 15 DEG C of film
The influence of solid content is contrasted, and is as a result shown, the strawberry preservation film of rare earth compounding prepared by the present invention passes through 5 days
Afterwards, strawberry respiratory intensity is 68.8 CO2mg/（kg.h）, less than 102 CO of common preservative film under equal conditions2mg/（kg.h）；
It is to the strawberry titratable acid content of storage 5 days under the strawberry preservation film normal temperature of the rare earth compounding prepared using the present invention
1.228%, and common preservative film titratable acid content is 0.745%；The Content of Soluble Solid Substance of Strawberry of storage is
9.756%, and common preservative film is 7.445%, thus the present invention has good market application foreground.
Tourmaline powder of the present invention is in dravite powder, schorl powder, elbaite powder, tsilaisite powder
One or more of arbitrary proportions mixture；Described tourmaline powder particle diameter is 1.3~6.5 μm.
Acetic acid solution mass percent concentration of the present invention is 2%.
Plant polyose of the present invention is one or more of arbitrary proportions in starch, fructose, cellulose, chitin.
The compound of lanthanum of the present invention is one kind of lanthanum hydroxide, lanthanum acetate, lanthanum nitrate or lanthanum chloride.
The compound of yttrium of the present invention is one kind of yttrium hydroxide, acetic acid yttrium, yttrium nitrate or yttrium chloride.
The compound of neodymium of the present invention is one kind of neodymium hydroxide, acetic acid neodymium, neodymium nitrate or neodymium chloride.
The compound of cerium of the present invention is one kind of cerium hydroxide, cerous acetate, cerous nitrate or cerium chloride.
Rare earth compounding reaction condition of the present invention is rotating speed 1000r/min, 25~30 DEG C of temperature.
The rotating speed of mixer is 250r/min in cladding dispersion process of the present invention, and temperature is 102 ± 1 DEG C.
The rotating speed of interfacial modification process high speed kneader of the present invention is 500r/min, and temperature is 105 ± 1 DEG C.
The rotating speed of mixer is 120r/min in material mixed process of the present invention, and temperature is 108 ± 1 DEG C.
Twin-screw extruder barrel temperature control is in 130~140 DEG C of I areas, II during extrusion pelletizing of the present invention
145~150 DEG C of area, 150~155 DEG C of III areas, 160~165 DEG C of IV areas, 155~160 DEG C of V areas, 155~160 DEG C of die head.
The beneficial effects of the invention are as follows：1. tourmaline powder, rare earth, the natural plant polyose aboundresources used, can be effective
Reduce cost；2. tourmaline powder, rare earth, the natural plant polyose used is harmless, obtained material safety, can trust use
In fresh food packaging；3. tourmaline powder, rare earth, the natural plant polyose used has sterilizing fresh-keeping function in itself, by changing
The modes such as property, compounding can effectively strengthen anti-bacterial refreshing effect.
Brief description of the drawings
Fig. 1 is that the sample prepared by the embodiment of the present invention 1 breathes strong with common preservative film packaging normal temperature to the strawberry of storage
The influence of degree.
Embodiment
Embodiment 1
The component of master batch is by linear low density polyethylene (LLDPE) 5.89kg, the kg of tourmaline powder 1.2, the kg of rare earth compounding 2.4, silicon
The kg of diatomaceous earth 0.3, the kg of oleamide 0.11, the kg of odium stearate 0.10 are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
（1）2kg chitins are dissolved in 60L acetic acid solutions, after stirring, 80L methanol are added, solution is no longer sticky,
Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many
Sugar juice.
（2）Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.00:0.60:1.05:1.25 weigh total amount 2kg's respectively
Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation
Chitin solution, controls the r/min of rotating speed 1000, and 25 DEG C of temperature is reacted 6 hours, pH value of solution adjusted to 7.0, product is with cotton-shaped
Precipitation form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber
Dry, grinding obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
（1）By 2.4kg rare earth compoundings, 0.3kg diatomite, it is placed in after compounding in mixer, adds 0.11kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
（2）1.2kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars
Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.10kg odium stearate, interface modification 20min
Afterwards into raw material II；
（3）Raw material II and raw material I are placed in mixer and are mixed into compound, the poly- second of 5.89kg linear, low densities is added
Alkene mixing 10min obtains mixed material；
（4）Mixed material is placed in double screw extruder, mixed material is placed in double screw extruder,
Control extruder barrel temperature：132 DEG C of I areas, 150 DEG C of II areas, 155 DEG C of III areas, 161 DEG C of IV areas, 158 DEG C of V areas, die head 160
DEG C, extrusion pelletizing is master batch.
（5）Common process condition is used using blow molding machine, a kind of grass containing rare earth compounding is further prepared
Certain kind of berries preservative film.
The strawberry preservation film containing rare earth compounding that the present embodiment is prepared and in the market are widely used common to protect
It is solvable to the strawberry titratable acid content of storage and the strawberry of storage to the strawberry respiratory intensity of storage, normal temperature at fresh 15 DEG C of film
Property solid content influence contrasted, as a result show, the breathing of the strawberry preservation film of rare earth compounding manufactured in the present embodiment
Intensity is less than common preservative film under equal conditions, as shown in Figure 1；Protected using the strawberry of rare earth compounding manufactured in the present embodiment
Strawberry titratable acid content is higher than the content of common preservative film titratable acid under fresh film normal temperature；The strawberry soluble solid of storage
Content is higher than and common preservative film.
Embodiment 2
The component of master batch by the kg of linear low density polyethylene (LLDPE) 5.83, the kg of tourmaline powder 1.5, the kg of rare earth compounding 2.2,
The kg of diatomite 0.25, the kg of oleamide 0.10, the kg of odium stearate 0.12 are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
（1）2kg chitins are dissolved in 60L acetic acid solutions, after stirring, 80L methanol are added, solution is no longer sticky,
Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many
Sugar juice.
（2）Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.00:0.60:1.05:1.25 weigh total amount 2kg's respectively
Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation
Chitin solution, controls the r/min of rotating speed 1000, and 25 DEG C of temperature is reacted 6 hours, pH value of solution adjusted to 7.0, product is with cotton-shaped
Precipitation form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber
Dry, grinding obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
（1）By 2.2kg rare earth compoundings, 0.25kg diatomite, it is placed in after compounding in mixer, adds 0.10kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
（2）1.5kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars
Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.12kg odium stearate, interface modification 20min
Afterwards into raw material II；
（3）Raw material II and raw material I are placed in mixer and are mixed into compound, 5.83.kg linear, low densities is added and gathers
Ethene mixing 10min obtains mixed material；
（4）Mixed material is placed in double screw extruder, mixed material is placed in double screw extruder,
Control extruder barrel temperature：135 DEG C of I areas, 150 DEG C of II areas, 155 DEG C of III areas, 160 DEG C of IV areas, 155 DEG C of V areas, die head 155
DEG C, extrusion pelletizing is master batch.
（5）Common process condition is used using blow molding machine, a kind of grass containing rare earth compounding is further prepared
Certain kind of berries preservative film.
Embodiment 3
The component of master batch by the kg of linear low density polyethylene (LLDPE) 5.62, the kg of tourmaline powder 1.3, the kg of rare earth compounding 2.5,
The kg of diatomite 0.35, the kg of oleamide 0.12, the kg of odium stearate 0.11 are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
（1）2kg chitins are dissolved in 60L acetic acid solutions, after stirring, 80L methanol are added, solution is no longer sticky,
Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many
Sugar juice.
（2）Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.00:0.60:1.05:1.25 weigh total amount 2kg's respectively
Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation
Chitin solution, controls the r/min of rotating speed 1000, and 25 DEG C of temperature is reacted 6 hours, pH value of solution adjusted to 7.0, product is with cotton-shaped
Precipitation form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber
Dry, grinding obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
（1）By 2.5kg rare earth compoundings, 0.35kg diatomite, it is placed in after compounding in mixer, adds 0.12kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
（2）1.3kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars
Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.11kg odium stearate, interface modification 20min
Afterwards into raw material II；
（3）Raw material II and raw material I are placed in mixer and are mixed into compound, 5.62.kg linear, low densities is added and gathers
Ethene mixing 10min obtains mixed material；
（4）Mixed material is placed in double screw extruder, mixed material is placed in double screw extruder,
Control extruder barrel temperature：130 DEG C of I areas, 145 DEG C of II areas, 155 DEG C of III areas, 160 DEG C of IV areas, 160 DEG C of V areas, die head 155
DEG C, extrusion pelletizing is master batch.
（5）Common process condition is used using blow molding machine, a kind of grass containing rare earth compounding is further prepared
Certain kind of berries preservative film.
Embodiment 4
The component of master batch is by linear low density polyethylene (LLDPE) 5.89kg, the kg of tourmaline powder 1.2, the kg of rare earth compounding 2.4, silicon
The kg of diatomaceous earth 0.3, the kg of oleamide 0.11, the kg of odium stearate 0.10 are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
（1）2kg chitins are dissolved in 60L acetic acid solutions, after stirring, 80L methanol are added, solution is no longer sticky,
Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many
Sugar juice.
（2）Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 2.95:0.65:1.05:1.35 weigh total amount 2kg's respectively
Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation
Chitin solution, controls the r/min of rotating speed 1000, and 25 DEG C of temperature is reacted 6 hours, pH value of solution adjusted to 7.0, product is with cotton-shaped
Precipitation form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber
Dry, grinding obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
（1）By 2.4kg rare earth compoundings, 0.3kg diatomite, it is placed in after compounding in mixer, adds 0.11kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
（2）1.2kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars
Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.10kg odium stearate, interface modification 20min
Afterwards into raw material II；
（3）Raw material II and raw material I are placed in mixer and are mixed into compound, the poly- second of 5.89kg linear, low densities is added
Alkene mixing 10min obtains mixed material；
（4）Mixed material is placed in double screw extruder, mixed material is placed in double screw extruder,
Control extruder barrel temperature：132 DEG C of I areas, 150 DEG C of II areas, 155 DEG C of III areas, 161 DEG C of IV areas, 158 DEG C of V areas, die head 160
DEG C, extrusion pelletizing is master batch.
（5）Common process condition is used using blow molding machine, a kind of grass containing rare earth compounding is further prepared
Certain kind of berries preservative film.
Embodiment 5
The component of master batch by the kg of linear low density polyethylene (LLDPE) 5.83, the kg of tourmaline powder 1.5, the kg of rare earth compounding 2.2,
The kg of diatomite 0.25, the kg of oleamide 0.10, the kg of odium stearate 0.12 are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
（1）2kg chitins are dissolved in 60L acetic acid solutions, after stirring, 80L methanol are added, solution is no longer sticky,
Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many
Sugar juice.
（2）Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 2.95:0.65:1.05:1.35 weigh total amount 2kg's respectively
Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation
Chitin solution, controls the r/min of rotating speed 1000, and 25 DEG C of temperature is reacted 6 hours, pH value of solution adjusted to 7.0, product is with cotton-shaped
Precipitation form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber
Dry, grinding obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
（1）By 2.2kg rare earth compoundings, 0.25kg diatomite, it is placed in after compounding in mixer, adds 0.10kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
（2）1.5kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars
Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.12kg odium stearate, interface modification 20min
Afterwards into raw material II；
（3）Raw material II and raw material I are placed in mixer and are mixed into compound, 5.83.kg linear, low densities is added and gathers
Ethene mixing 10min obtains mixed material；
（4）Mixed material is placed in double screw extruder, mixed material is placed in double screw extruder,
Control extruder barrel temperature：135 DEG C of I areas, 150 DEG C of II areas, 155 DEG C of III areas, 160 DEG C of IV areas, 155 DEG C of V areas, die head 155
DEG C, extrusion pelletizing is master batch.
（5）Common process condition is used using blow molding machine, a kind of grass containing rare earth compounding is further prepared
Certain kind of berries preservative film.
Embodiment 6
The component of master batch by the kg of linear low density polyethylene (LLDPE) 5.62, the kg of tourmaline powder 1.3, the kg of rare earth compounding 2.5,
The kg of diatomite 0.35, the kg of oleamide 0.12, the kg of odium stearate 0.11 are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
（1）2kg chitins are dissolved in 60L acetic acid solutions, after stirring, 80L methanol are added, solution is no longer sticky,
Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many
Sugar juice.
（2）Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 2.95:0.65:1.05:1.35 weigh total amount 2kg's respectively
Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation
Chitin solution, controls the r/min of rotating speed 1000, and 25 DEG C of temperature is reacted 6 hours, pH value of solution adjusted to 7.0, product is with cotton-shaped
Precipitation form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber
Dry, grinding obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
（1）By 2.5kg rare earth compoundings, 0.35kg diatomite, it is placed in after compounding in mixer, adds 0.12kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
（2）1.3kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars
Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.11kg odium stearate, interface modification 20min
Afterwards into raw material II；
（3）Raw material II and raw material I are placed in mixer and are mixed into compound, 5.62.kg linear, low densities is added and gathers
Ethene mixing 10min obtains mixed material；
（4）Mixed material is placed in double screw extruder, mixed material is placed in double screw extruder,
Control extruder barrel temperature：130 DEG C of I areas, 145 DEG C of II areas, 155 DEG C of III areas, 160 DEG C of IV areas, 160 DEG C of V areas, die head 155
DEG C, extrusion pelletizing is master batch.
（5）Common process condition is used using blow molding machine, a kind of grass containing rare earth compounding is further prepared
Certain kind of berries preservative film.
Claims (9)
1. a kind of preparation method of the strawberry preservation film master batch containing rare earth compounding, it is characterized in that：
The preparation of rare earth compounding
（1）In the acetic acid solution that the plant polyose of 2 parts by weight is dissolved in 60 parts by weight, after stirring, 80 parts by weight are added
Methanol, solution is no longer sticky, adds the acetic anhydride of 1 parts by weight, is reacted at 30 DEG C of temperature after 1 h, will be sticky obtained by reaction
Liquid is added in the ethanol of 150 parts by weight, filtering precipitate after precipitation generation, is washed with absolute ethyl alcohol 3 times, then molten with acetic acid
After liquid dissolving, insoluble matter is filtered off, acetylation plant polyose solution is obtained；
（2）Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 2.90~3.0:0.55~0.65:1.00~1.05:1.25~
1.35, the compound that compound, the compound of yttrium, the compound of neodymium and the cerium of lanthanum are weighed respectively is mixed into rare earth compound, and
It is added to 1 ﹕ 5 weight part ratio in distilled water, rare earth compound mixed aqueous solution is obtained after being entirely capable of dissolving；It is many according to plant
The weight ratio such as sugar and rare earth compound, rare earth compound mixed aqueous solution is slowly added dropwise into acetylation plant polyose solution,
Reaction system pH to 7.0 is adjusted, is reacted 6~7 hours under the conditions of rotating speed 1000r/min, 25~30 DEG C of temperature, product is to precipitate
Form is separated out；Filter after sediment, remove unreacted rare earth ion with distillation water washing, done in vacuum drying chamber
Dry, grinding obtains powdered rare earth compounding；
The preparation of master batch
（1）By 22~25 parts by weight rare earth compoundings, 2.5~3.5 parts by weight diatomite are placed in mixer after compounding, added
0.9~1.2 parts by weight oleamide, is 250r/min in rotating speed, temperature is scattered to be coated under the conditions of 102 ± 1 DEG C, after 15min
Into raw material I；
（2）12~15 parts by weight of tourmaline powder are placed in high-speed kneading machine, are that rotating speed is 500r/min in rotating speed, temperature is
10min is mediated under the conditions of 105 ± 1 DEG C, 1.0~1.2 parts by weight odium stearate are added, carried out after interface modification 20min into original
Expect II；
（3）Raw material II and raw material I are placed in mixer and are mixed into compound, the LLDPE of 54.1~61.6 parts by weight is added
Mixing 10min obtains mixed material；
（4）Mixed material is placed in double screw extruder and extrudes pelletizing as master batch.
2. a kind of preparation method of strawberry preservation film master batch containing rare earth compounding according to claim 1, it is characterized in that
The tourmaline powder is that the one or more in dravite powder, schorl powder, elbaite powder, tsilaisite powder are appointed
The mixture of meaning ratio；Described tourmaline powder particle diameter is 1.3~6.5 μm.
3. a kind of preparation method of strawberry preservation film master batch containing rare earth compounding according to claim 1, it is characterized in that
Described acetic acid solution mass percent concentration is 2%.
4. a kind of preparation method of strawberry preservation film master batch containing rare earth compounding according to claim 1, it is characterized in that
Described plant polyose be starch, fructose, cellulose, chitin in one or more of arbitrary proportions mixture.
5. a kind of preparation method of strawberry preservation film master batch containing rare earth compounding according to claim 1, it is characterized in that
The compound of described lanthanum is one kind of lanthanum hydroxide, lanthanum acetate, lanthanum nitrate or lanthanum chloride；The compound of described yttrium is hydrogen-oxygen
Change one kind of yttrium, acetic acid yttrium, yttrium nitrate or yttrium chloride；The compound of described neodymium is neodymium hydroxide, acetic acid neodymium, neodymium nitrate or chlorine
Change one kind of neodymium；The compound of described cerium is one kind of cerium hydroxide, cerous acetate, cerous nitrate or cerium chloride.
6. a kind of preparation method of strawberry preservation film master batch containing rare earth compounding according to claim 1, it is characterized in that
The rotating speed of mixer is 250r/min in cladding dispersion process described in this, and temperature is 102 ± 1 DEG C.
7. a kind of preparation method of strawberry preservation film master batch containing rare earth compounding according to claim 1, it is characterized in that
The rotating speed of described interfacial modification process high speed kneader is 500r/min, and temperature is 105 ± 1 DEG C.
8. a kind of preparation method of strawberry preservation film master batch containing rare earth compounding according to claim 1, it is characterized in that
Mixed in described mixer, the rotating speed of mixer is 120r/min, and temperature is 108 ± 1 DEG C.
9. a kind of preparation method of strawberry preservation film master batch containing rare earth compounding according to claim 1, it is characterized in that
During described extrusion pelletizing twin-screw extruder barrel temperature control 130~140 DEG C of I areas, 145~150 DEG C of II areas,
150~155 DEG C of III areas, 160~165 DEG C of IV areas, 155~160 DEG C of V areas, 155~160 DEG C of die head.
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| CA2185469A1 (en) * | 1994-03-15 | 1995-09-21 | Prasadarao Meka | Polymers blends, films and articles thereof |
| EP1360258B1 (en) * | 2000-01-31 | 2007-03-14 | H.B. Fuller Licensing & Financing, Inc. | Radiation curable adhesive compositions comprising block copolymers having vinyl functionalized polydiene blocks |
| JP2002264282A (en) * | 2001-03-14 | 2002-09-18 | Sumitomo Chem Co Ltd | Multi-layer film and self-adhesive packaging film |
| CN1262592C (en) * | 2002-07-08 | 2006-07-05 | 北京崇高纳米科技有限公司 | Fruit and vegetable fresh-keeping plastic film and method for making the same |
| US20070089989A1 (en) * | 2005-09-02 | 2007-04-26 | William Hoagland | Conformable hydrogen indicating wrap to detect leaking hydrogen gas |
| CN102079834A (en) * | 2010-11-03 | 2011-06-01 | 国家农产品保鲜工程技术研究中心（天津） | Method for preparing modified atmosphere fresh-keeping film for fruits and vegetables |
| CN102030151A (en) * | 2010-11-03 | 2011-04-27 | 国家农产品保鲜工程技术研究中心（天津） | Device for fresh-keeping packaging of bananas |
| CN104017262A (en) * | 2014-06-13 | 2014-09-03 | 齐齐哈尔大学 | Multifunctional fresh-keeping material capable of releasing anions and preparation method of material |
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