CN105778258B - A kind of preparation method of the banana fresh-keeping material film master batch containing rare earth compounding - Google Patents
A kind of preparation method of the banana fresh-keeping material film master batch containing rare earth compounding Download PDFInfo
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- CN105778258B CN105778258B CN201610177091.5A CN201610177091A CN105778258B CN 105778258 B CN105778258 B CN 105778258B CN 201610177091 A CN201610177091 A CN 201610177091A CN 105778258 B CN105778258 B CN 105778258B
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- rare earth
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 235000018290 Musa x paradisiaca Nutrition 0.000 title claims abstract description 26
- 240000005561 Musa balbisiana Species 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 38
- -1 cerium ion Chemical class 0.000 claims abstract description 37
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 14
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- 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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- 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
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- 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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- 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
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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
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- 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
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of the banana fresh-keeping film master batch containing rare earth compounding, it is using LLDPE as vector resin, and addition tourmaline powder, rare earth compounding, diatomite, oleamide, odium stearate are mixed by coating scattered, interface modification, material, extrusion pelletizing is process.Lanthanum, yttrium, samarium, the molar ratio of cerium ion are (3.00≤w≤3.15) in rare earth compounding feature:(0.30≤x≤0.40):(1.20≤y≤1.25):(0.90≤z≤1.00).Master batch prepared by this method, is added in LLDPE resins with 6~8% ratio, after film is made in blowing, packed for banana fresh-keeping, respiratory intensity and surface microorganism growth in storage are can inhibit, slows down softening process, normal temperature condition can prolong storage period 9~12 days.
Description
Technical field
The present invention relates to the preparation method of functional plastic film master batch, and in particular to a kind of banana containing rare earth compounding
The preparation method of fresh-keeping film master batch.
Background technology
Banana category Musaceae (Musaceae) Musa (Musa) plant, banana are one of the torrid zone, subtropical zone name fruit, it is produced
Amount is high, and sweet tea cunning is aromatic, very popular containing abundant nutriment.New fresh bananas has active oxygen radical clear
Except effect, human plasma oxidation resistance can be strengthened by often eating banana, the positive work for playing prevention of cardiovascular disease and slowing down aging
With.After banana is adopted, pectinase activity increases, and participates in pulp softening, and polyphenol oxidase participates in producing melanocyte.Under room temperature
There is climacteric rapidly.Ethene can be discharged during after ripening by adopting, and respiratory climacteric occur, and fruit interior tissue occurs
A series of ripe physiological changes with aging.Pericarp is embodied in turn yellow, produce volatile flavor substance and various physiology
The generation of disease.So suppressing the arrival that respiratory intensity delays respiratory climacteric, be just conducive to fresh-keeping.Pathogen and mechanical wounding meeting
Promote physiology after-ripening, shorten the fruit storage service life；Banana is very sensitive to low temperature at the same time, is very easy to that freezing evil occurs, causes
It is difficult to storage and long-distance transportation and sales after Banana.
China's rare earth resources enrich, and there are great potential for rare earth utilization.Rare earth and its derivative can be used as antibacterial to protect
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 interfere, and cause bacterial death, while ligand 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 displacement of the cerium ion to metal ion in enzyme is with competing so as to have impact on the physiological function of enzyme, therefore can pass through suppression
Pectase processed, polyphenol oxidase activity slow down softening process, suppress Tissue Browning；Used relevant enzyme can also be influenced to suppress
Respiratory intensity.Rare earth has the ability of stronger removing hydroxyl radical free radical, reduces free radical, weakens active oxygen injury, prolongs
Slow Fruit anatomy aging, extends banana shelf life.Tourmaline is also China rich in mineral resources, tourmaline powder release anion energy
Effectively kill germ.Its mechanism is essentially consisted in after anion combined with bacterium, bacterium is produced the change of structure or turning for energy
Move, cause bacterial death.Plant polyose is abundant renewable resource, itself has certain antibacterial effect, the plant of acetylation
Polysaccharide has the ability of stronger removing hydroxyl radical free radical.
At present, the main air conditioned storage of banana fresh-keeping technology, variable temperature storage, cold haze, coating-film fresh-keeping, fresh chemically etc..
Though physical method is nontoxic and relatively more effective, cost is higher, needs specific appointed condition, is not suitable for commonly used；And useization
Learn the problems such as medicine makees antistaling agent, further relates to the residual hazard of some medicines.Banana fresh-keeping technology is subject to industry to pay close attention to for a long time, expert,
Scholar has carried out many research, but the problem is not solved at all yet at present.
The content of the invention
For the deficiency of existing banana fresh-keeping packaging.The present invention provides a kind of good lower-cost master batch of anti-bacterial refreshing
Preparation method, it is characterized in that：Using LLDPE as vector resin, addition tourmaline powder, rare earth compounding, diatomite, oleamide,
Odium stearate is mixed by coating scattered, interface modification, material, extrusion pelletizing is process.Master batch prepared by this method, with 6
~8% ratio is added in LLDPE resins, after film is made in blowing, packs, is can inhibit in storage for banana fresh-keeping
Respiratory intensity and surface microorganism growth, normal temperature condition prolong storage period 9~12 days.
It is to achieve the object of the present invention the technical solution of use：
1st, the preparation of rare earth compounding
Master batch is prepared according to the following steps：
（1）The plant polyose of 2 parts by weight is dissolved in the acetic acid solution of 60 parts by weight, after stirring evenly, adds 80 weight
Part methanol, solution is no longer sticky, adds the acetic anhydride of 1 parts by weight, after reacting 1 h at 30 DEG C of temperature, will react gained
Thick liquid is added in the ethanol of 150 parts by weight, and filtering precipitate after precipitation generation, is washed 3 times, then use second with absolute ethyl alcohol
After acid solution dissolving, insoluble matter is filtered off, obtains acetylation plant polyose solution.
（2）Molar ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.00~3.15:0.30~0.40:1.20~1.25:0.90
~1.00, the compound for weighing the compound of lanthanum, the compound of yttrium, the compound of neodymium and cerium respectively is mixed into rare earth compound,
And be added to the weight part ratio of 1 ﹕ 5 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 reaction 6~7 it is small when, product with
Precipitation form separates out；Filter after sediment, be washed with distilled water and remove unreacted rare earth ion, in vacuum drying chamber
Middle drying, grinding, obtains powdered rare earth compounding.
2nd, the preparation of master batch
（1）By 18~21 parts by weight rare earth compoundings, 2.5~3.0 parts by weight diatomite, compounding is placed in mixer,
1.0~1.2 parts by weight oleamides are added, are 250r/min in rotating speed, temperature coats under the conditions of being 102 ± 1 DEG C disperses,
It is placed in after 15min into raw material I in mixer；
（2）12~14 parts of tourmaline powders are placed in high-speed kneading machine, are that rotating speed is 500r/min in rotating speed, temperature is
After mediating 10min under the conditions of 105 ± 1 DEG C, add 0.8~1.0 parts by weight odium stearate, carry out after interface modification 20min into
Raw material II；
（3）Raw material II and raw material I are placed in mixer and are mixed into mixture, adds 59.8~65.7 parts by weight
LLDPE mixing 10min obtains mixed material；
（4）It is master batch that mixed material, which is placed in double screw extruder, and extrudes pelletizing.
It is placed in mixer mixing with raw material I, adds 54.1~61.6 parts of linear low density polyethylene (LLDPE) mixing
10min；It is master batch that mixed material, which is placed in double screw extruder, and extrudes pelletizing.The present invention
The tourmaline powder is dravite powder, one kind in schorl powder, elbaite powder, tsilaisite powder
Or the mixture of several arbitrary proportions；The 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 starch, one or more of arbitrary proportions in 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 samarium of the present invention is one kind of samaric hydroxide, acetic acid samarium, samaric nitrate or samarium trichloride.
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.
During extrusion pelletizing of the present invention 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.
The beneficial effects of the invention are as follows：1. the tourmaline powder used, rare earth, natural plant polyose aboundresources, can be effective
Reduce cost；2. the tourmaline powder used, rare earth, natural plant polyose are harmless, obtained material safety, can trust use
Packed in fresh food；3. the tourmaline powder used, rare earth, natural plant polyose have 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 packs 25 DEG C of banana appearances to storage 8 days with common preservative film
Influence figure.
Fig. 2 is that the sample prepared by the embodiment of the present invention 1 packs 25 DEG C of banana fruit hardness to storage with common preservative film
Influence.
Fig. 3 is that sample prepared by the embodiment of the present invention 1 is packed with common preservative film the banana of storage is reduced at 25 DEG C
The influence of sugared content.
Embodiment
Embodiment 1
The component of master batch is by linear low density polyethylene (LLDPE) 6.08kg, 1.3 kg of tourmaline powder, 2.1 kg of rare earth compounding, silicon
Diatomaceous earth 0.3 kg, oleamide 0.12kg, 0.10 kg of odium stearate composition.
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 evenly, add 80L methanol, solution is no longer sticky,
Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell
Sugar juice.
（2）Molar ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.05:0.40:1.25:1.00 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 1000 r/min of rotating speed, 25 DEG C of temperature, when reaction 6 is small, pH value of solution is adjusted to 7.0, product is with cotton-shaped
Precipitation form separates out, filter after sediment, be washed with distilled water and remove unreacted metal ion, done in vacuum drying chamber
Dry, grinding, obtains buff powder, is rare earth compounding.
2nd, the preparation of master batch
（1）By 2.1kg rare earth compoundings, 0.3kg diatomite, compounding is placed in mixer, adds 0.12kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I；
（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
After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 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 mixture, adds the poly- second of 6.08kg linear, low densities
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.
Embodiment 2
The component of master batch by 6.36 kg of linear low density polyethylene (LLDPE), 1.2 kg of tourmaline powder, 2.0 kg of rare earth compounding,
0.25 kg of diatomite, 0.10 kg of oleamide, 0.09 kg of odium stearate compositions.
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 evenly, add 80L methanol, solution is no longer sticky,
Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell
Sugar juice.
（2）Molar ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.05:0.40:1.25:1.00 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 1000 r/min of rotating speed, 25 DEG C of temperature, when reaction 6 is small, pH value of solution is adjusted to 7.0, product is with cotton-shaped
Precipitation form separates out, filter after sediment, be washed with distilled water and remove unreacted metal ion, done in vacuum drying chamber
Dry, grinding, obtains buff powder, is rare earth compounding.
2nd, the preparation of master batch
（1）By 2.0kg rare earth compoundings, 0.25kg diatomite, compounding is placed in mixer, adds 0.10kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I；
（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
After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 0.09kg 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 mixture, 6.36.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.
Embodiment 3
The component of master batch by 6.33 kg of linear low density polyethylene (LLDPE), 1.4 kg of tourmaline powder, 1.8 kg of rare earth compounding,
0.25 kg of diatomite, 0.12 kg of oleamide, 0.10 kg of odium stearate compositions.
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 evenly, add 80L methanol, solution is no longer sticky,
Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell
Sugar juice.
（2）Molar ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.05:0.40:1.25:1.00 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 1000 r/min of rotating speed, 25 DEG C of temperature, when reaction 6 is small, pH value of solution is adjusted to 7.0, product is with cotton-shaped
Precipitation form separates out, filter after sediment, be washed with distilled water and remove unreacted metal ion, done in vacuum drying chamber
Dry, grinding, obtains buff powder, is rare earth compounding.
2nd, the preparation of master batch
（1）By 1.8kg rare earth compoundings, 0.25kg diatomite, compounding is placed in mixer, adds 0.12kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I；
（2）1.4kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars
After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 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 mixture, 6.33.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.
Embodiment 4
The component of master batch is by linear low density polyethylene (LLDPE) 6.08kg, 1.3 kg of tourmaline powder, 2.1 kg of rare earth compounding, silicon
Diatomaceous earth 0.3 kg, oleamide 0.12kg, 0.10 kg of odium stearate composition.
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 evenly, add 80L methanol, solution is no longer sticky,
Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell
Sugar juice.
（2）Molar ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.10:0.35:1.20:0.95 weighs 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 1000 r/min of rotating speed, 25 DEG C of temperature, when reaction 6 is small, pH value of solution is adjusted to 7.0, product is with cotton-shaped
Precipitation form separates out, filter after sediment, be washed with distilled water and remove unreacted metal ion, done in vacuum drying chamber
Dry, grinding, obtains buff powder, is rare earth compounding.
2nd, the preparation of master batch
（1）By 2.1kg rare earth compoundings, 0.3kg diatomite, compounding is placed in mixer, adds 0.12kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I；
（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
After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 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 mixture, adds the poly- second of 6.08kg linear, low densities
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.
Embodiment 5
The component of master batch by 6.36 kg of linear low density polyethylene (LLDPE), 1.2 kg of tourmaline powder, 2.0 kg of rare earth compounding,
0.25 kg of diatomite, 0.10 kg of oleamide, 0.09 kg of odium stearate compositions.
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 evenly, add 80L methanol, solution is no longer sticky,
Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell
Sugar juice.
（2）Molar ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.10:0.35:1.20:0.95 weighs 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 1000 r/min of rotating speed, 25 DEG C of temperature, when reaction 6 is small, pH value of solution is adjusted to 7.0, product is with cotton-shaped
Precipitation form separates out, filter after sediment, be washed with distilled water and remove unreacted metal ion, done in vacuum drying chamber
Dry, grinding, obtains buff powder, is rare earth compounding.
2nd, the preparation of master batch
（1）By 2.0kg rare earth compoundings, 0.25kg diatomite, compounding is placed in mixer, adds 0.10kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I；
（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
After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 0.09kg 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 mixture, 6.36.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.
Embodiment 6
The component of master batch by 6.33 kg of linear low density polyethylene (LLDPE), 1.4 kg of tourmaline powder, 1.8 kg of rare earth compounding,
0.25 kg of diatomite, 0.12 kg of oleamide, 0.10 kg of odium stearate compositions.
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 evenly, add 80L methanol, solution is no longer sticky,
Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150L ethanol, there is precipitation
Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell
Sugar juice.
（2）Molar ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.10:0.35:1.20:0.95 weighs 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 1000 r/min of rotating speed, 25 DEG C of temperature, when reaction 6 is small, pH value of solution is adjusted to 7.0, product is with cotton-shaped
Precipitation form separates out, filter after sediment, be washed with distilled water and remove unreacted metal ion, done in vacuum drying chamber
Dry, grinding, obtains buff powder, is rare earth compounding.
2nd, the preparation of master batch
（1）By 1.8kg rare earth compoundings, 0.25kg diatomite, compounding is placed in mixer, adds 0.12kg oleic acid acyls
Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I；
（2）1.4kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars
After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 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 mixture, 6.33.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.
Claims (7)
1. a kind of preparation method of the banana fresh-keeping material film master batch containing rare earth compounding, it is characterized in that：
The preparation of rare earth compounding
（1）The plant polyose of 2 parts by weight is dissolved in the acetic acid solution of 60 parts by weight, after stirring evenly, adds 80 parts by weight
Methanol, solution is no longer sticky, adds the acetic anhydride of 1 parts by weight, after reacting 1 h at 30 DEG C of temperature, will react the sticky of gained
Liquid is added in the ethanol of 150 parts by weight, and filtering precipitate after precipitation generation, is washed 3 times with absolute ethyl alcohol, then molten with acetic acid
After liquid dissolving, insoluble matter is filtered off, obtains acetylation plant polyose solution；
（2）Molar ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.00~3.15:0.30~0.40:1.20~1.25:0.90~
1.00, the compound for weighing the compound of lanthanum, the compound of yttrium, the compound of neodymium and cerium respectively is mixed into rare earth compound, and
It is added to the weight part ratio of 1 ﹕ 5 in distilled water, rare earth compound mixed aqueous solution is obtained after being entirely capable of dissolving；It is more 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, when reaction 6~7 is small under the conditions of rotating speed 1000r/min, 25~30 DEG C of temperature, product is to precipitate
Form separates out；Filter after sediment, be washed with distilled water and remove unreacted rare earth ion, done in vacuum drying chamber
Dry, grinding, obtains powdered rare earth compounding；
The preparation of master batch
（1）By 18~21 parts by weight rare earth compoundings, 2.5~3.0 parts by weight diatomite, compounding is placed in mixer, is added
1.0~1.2 parts by weight oleamides, are 250r/min in rotating speed, temperature coats under the conditions of being 102 ± 1 DEG C disperses, after 15min
It is placed in into raw material I in mixer；
（2）12~14 parts of tourmaline powders are placed in high-speed kneading machine, are that rotating speed is 500r/min in rotating speed, temperature is 105 ± 1
After mediating 10min under the conditions of DEG C, 0.8~1.0 parts by weight odium stearate is added, carry out after interface modification 20min into raw material II；
（3）Raw material II and raw material I are placed in mixer and are mixed into mixture, adds the LLDPE of 59.8~65.7 parts by weight
Mixing 10min obtains mixed material；
（4）It is master batch that mixed material, which is placed in double screw extruder, and extrudes pelletizing.
2. a kind of preparation method of banana fresh-keeping material film master batch containing rare earth compounding according to claim 1, it is special
Levy be dravite powder in the tourmaline powder, schorl powder, elbaite powder, one kind in tsilaisite powder or
Several mixtures；The tourmaline powder particle diameter is 1.3~6.5 μm.
3. a kind of preparation method of banana fresh-keeping material film master batch containing rare earth compounding according to claim 1, it is special
Sign is that the acetic acid solution mass percent concentration is 2%.
4. a kind of preparation method of banana fresh-keeping material film master batch containing rare earth compounding according to claim 1, it is special
Sign is the mixture that the plant polyose includes starch, fructose, cellulose, one or several kinds of arbitrary proportions in chitin.
5. a kind of preparation method of banana fresh-keeping material film master batch containing rare earth compounding according to claim 1, it is special
Sign is that the compound of the lanthanum is lanthanum hydroxide, lanthanum acetate, lanthanum nitrate, one kind of lanthanum chloride；The compound of the yttrium is
Yttrium hydroxide, acetic acid yttrium, yttrium nitrate, one kind of yttrium chloride；The compound of the cerium for cerium hydroxide, cerous acetate, cerous nitrate,
One kind of cerium chloride.
6. a kind of preparation method of banana fresh-keeping material film master batch containing rare earth compounding according to claim 1, it is special
Sign is the mixed material, and the rotating speed of mixer is 120r/min in mixed process, and temperature is 108 ± 1 DEG C.
7. a kind of preparation method of banana fresh-keeping material film master batch containing rare earth compounding according to claim 1, it is special
Sign be during the extrusion pelletizing twin-screw extruder barrel temperature control in 130~140 DEG C of I areas, II areas 145~150
DEG C, 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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| CN201610177091.5A CN105778258B (en) | 2016-03-24 | 2016-03-24 | A kind of preparation method of the banana fresh-keeping material film master batch containing rare earth compounding |
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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 |
| CN1775843A (en) * | 2005-11-29 | 2006-05-24 | 上海弘康科技发展有限公司 | Tourmaline multifunctional fresh-retaining material and its preparing method |
| CN101250299B (en) * | 2008-04-02 | 2011-04-20 | 福建师范大学 | Method for preparing antibiotic fresh-keeping linear low density polyethylene film master batch |
| CN103319621B (en) * | 2013-07-02 | 2016-06-15 | 青岛农业大学 | There is the synthetic method of the rare earth polysaccharide complex of bacteriostatic activity |
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