CN105602090B - A kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding - Google Patents
A kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding Download PDFInfo
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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
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- 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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Abstract
The present invention relates to the preparation method of functional plastic film master batch, and in particular to a kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding.It is that, using LLDPE as vector resin, 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.Lanthanum, yttrium, samarium, the mol ratio of cerium ion are (3.00≤w≤3.05) in rare earth compounding feature:(0.40≤x≤0.45):(1.15≤y≤1.25):(0.95≤z≤1.05).Master batch prepared by this method, is added in LLDPE resins with 6~8% ratio, and blowing is made after film, for lichee fresh-keeping packaging, can suppress respiratory intensity and surface microorganism growth in storage, and normal temperature condition can prolong storage period 5~7 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 lichee containing rare earth compounding
The preparation method of fresh-keeping film master batch.
Background technology
Lichee (Litchi chinensis Sonn.) also known as separated branch, Sapindaceae lichee platymiscium is subtropical fruit,
For special product of China renowned in the world.It is bright-colored, unique flavor, nutritious, is the top grade in the fruit of the south of the Five Ridges.But lichee
The property of " discoloration on the one, two fragrant to become, and taste became on 3rd " can make its freshness decline quickly, attraction to consumer and edible
Value is also decreased.China is the most country of current cultivation lichee, according to statistics, lichee every year because rot and caused by
Loss accounts for more than the 20% of total output.Lichee is as other fruit, because nutritious, sugariness is high and easily causes microorganism
Infect.During litchi fruits postharvest storage, cell leakage increase, the change of membrane structure is one constantly destroyed
Process, accumulation causes cell membrane system peroxidating relevant with free radical for this.Its vigorous respiration consumes substantial amounts of include
Material, and promote the aging of fruit.PPO and POD are the important enzymes for participating in denaturation process, and take part in phenols and Vitamin C
The oxidation of acid.These reasons make lichee turn into the world most intolerant to one of fruit of Tibetan, after adopting easily brown stain, rot, serious shadow
The storing and sale of this fruit are rung.
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
PPO, POD enzymatic activity processed slows down Tissue Browning and nutrient metabolism;Relevant enzyme can also be influenceed to suppress respiratory intensity.It is dilute
Ability of the soil with stronger removing hydroxyl radical free radical, reduces free radical, weakens active oxygen injury, delayed fruit after-ripening declines
Always, lichee shelf life is extended.Tourmaline is also China rich in mineral resources, and tourmaline powder release anion can effectively kill disease
Bacterium.Its mechanism is essentially consisted in after anion combined with bacterium, bacterium is produced the change of structure or the transfer of energy, is caused bacterium
It is dead.Plant polyose is abundant renewable resource, itself has certain antibacterial effect, the plant polyose of acetylation is with stronger
Removing hydroxyl radical free radical ability.
At present, the main preservation by low temperature of litchi preserving technology, quick-freezing fresh-keeping, controlled atmosphere storage, Edible cornstarch film are fresh-keeping, smelly
Oxygen is fresh-keeping, Irradiation preservation fresh-keeping method, 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 antistaling agent is made using chemicals, the problems such as further relating to the residual hazard of some medicines.State
Inside and outside many R&D institutions and institution of higher learning are all numerous and confused to be carried out to lichee Physiological qualities of post-harvest tomato changing rule and storage technique
Research, and have made some progress, but these researchs focus mostly in terms of low-temperature preservation, quick refrigeration storage and air-conditioned cold store preservation, and it is right
Fund, equipment and soil input require higher.
The content of the invention
It is not enough for existing lichee fresh-keeping.The invention provides a kind of preparation side of the good lower-cost master batch of anti-bacterial refreshing
Method, it is characterized in that:With linear low density polyethylene (LLDPE) (LLDPE) for vector resin, addition tourmaline powder, rare earth compounding, diatom
Soil, oleamide, odium stearate are by the way that cladding is scattered, interface modification, material are mixed, extrusion pelletizing is processed.Our legal system
Standby master batch, is added in LLDPE resins with 6~8% ratio, and blowing is made after film, for lichee fresh-keeping packaging, can be pressed down
Respiratory intensity and surface microorganism growth in storage processed, normal temperature condition prolong storage period 5~7 days.
For realize the purpose of the present invention use technical scheme be:
1st, the preparation of rare earth compounding
(1) plant polyose of 2 parts by weight is dissolved in the acetic acid solution of 60 parts by weight, after stirring, adds 80 weight
Part methanol, solution is no longer sticky, adds the acetic anhydride of 1 parts by weight, in after reaction 1h at 30 DEG C of temperature, will be obtained by reaction it is glutinous
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 acetic acid
After solution dissolving, insoluble matter is filtered off, acetylation plant polyose solution is obtained.
(2) it is 3.00~3.05 according to the mol ratio of lanthanum, yttrium, neodymium, cerium ion:0.40~0.45:1.15~1.25:0.95
~1.05, 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 the rare earth compounding of 18~20 parts by weight, the diatomite of 2~2.5 parts by weight is placed in mixer after compounding
In, 1.0~1.2 parts by weight oleamides are added, are that 250r/min, temperature are to carry out cladding point under the conditions of 102 ± 1 DEG C in rotating speed
Dissipate, raw material I is obtained after 15min;
(2) 12~15 parts by weight of tourmaline powder are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105
Mediated under the conditions of ± 1 DEG C after 10min, add 0.8~1.0 parts by weight odium stearate, carried 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 compound, add 60.3~66.2 parts by weight
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 lichee fresh-keeping film containing rare earth compounding is further prepared.
The lichee fresh-keeping film containing rare earth compounding that the present invention is prepared is widely used commonly fresh-keeping with the market
The lichee ppo enzymatic activitys (unit/g FW) of storage are compared under the conditions of 20 DEG C of film, as a result shown, using present invention preparation
Rare earth compounding lichee fresh-keeping film pass through 20 days when, enzymatic activity only reaches 9.85unit/g FW, and respiratory intensity is also only
0.47mlCO2/ g.h, and 15.02unit/g FW are up to using common preservative film enzymatic activity, respiratory intensity is up to
0.84mlCO2/g.h.Table 1 is the every fresh-keeping index delta data of lichee to storage under the conditions of 20 DEG C.
Table 1:
Tourmaline powder of the present invention is in dravite powder, schorl powder, elbaite powder, tsilaisite powder
The mixture of one or more of arbitrary proportions;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
Mixture.
The compound of lanthanum of the present invention is one kind in lanthanum hydroxide, lanthanum acetate, lanthanum nitrate, lanthanum chloride.
The compound of yttrium of the present invention is one kind in yttrium hydroxide, acetic acid yttrium, yttrium nitrate, yttrium chloride.
The compound of samarium of the present invention is one kind in samaric hydroxide, acetic acid samarium, samaric nitrate, samarium trichloride.
The compound of cerium of the present invention is one kind in cerium hydroxide, cerous acetate, cerous nitrate, 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 packs 20 DEG C of litchi PPO enzymes to storage with common preservative film
The influence of activity.
Fig. 2 is that the sample prepared by the embodiment of the present invention 1 packs 20 DEG C of litchi breathings to storage with common preservative film
The influence of intensity.
Embodiment
In order to which present invention may be better understood, it is described further in conjunction with accompanying drawing.
In Fig. 1, two curves represent common preservative film and the lichee fresh-keeping of the present invention containing rare earth compounding respectively
Film preserves the influence of 25 days process enzymatic activitys.It can be seen that using the lichee of the present invention containing rare earth compounding
Enzymatic activity highest when preservative film is preserved 20 days, compared with the lichee that common preservative film is packed, its enzymatic activity is less than common preservative film
Value, beneficial to the preservation of lichee.
In Fig. 2, two curves represent common preservative film and the lichee fresh-keeping of the present invention containing rare earth compounding respectively
Film preserves 25 days process lichee respiratory intensities.It can be seen that using the lichee of the present invention containing rare earth compounding
Lichee soluble solid is low compared to the lichee that common preservative film is packed when preservative film is preserved 20 days.
Embodiment 1
1st, the preparation of rare earth compounding
The component of master batch is by linear low density polyethylene (LLDPE) 5.96kg, tourmaline powder 1.5kg, rare earth compounding 2.0kg, diatom
Native 0.3kg, oleamide 0.11kg, odium stearate 0.13kg are constituted.
Master batch is prepared according to the following steps:
(1) 2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, 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) it is 2.95 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.5:1.25:1.00 weigh total amount 2kg nitre respectively
Sour lanthanum, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation shell
Polysaccharide solution, controls rotating speed 1000r/min, and 25 DEG C of temperature is reacted 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped heavy
Shallow lake form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, dried in vacuum drying chamber,
Grinding, obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1) by 2.0kg rare earth compoundings, 0.30kg 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) 1.5kg 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 0.13kg 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, add the poly- second of 5.96kg 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.
(5) common process condition is used using blow molding machine, further prepares a kind of litchi containing rare earth compounding
Branch preservative film.
Using the lichee fresh-keeping film of rare earth compounding manufactured in the present embodiment, contain rare earth compounding using of the present invention
Lichee fresh-keeping film enzymatic activity highest when preserving 20 days, beneficial to the preservation of lichee, as shown in Figure 1.Lichee can when preserving 20 days
Dissolubility solid content is low compared to the lichee that common preservative film is packed, as shown in Figure 2.
Embodiment 2
The component of master batch is by linear low density polyethylene (LLDPE) 5.82kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, diatom
Native 0.35kg, oleamide 0.12kg, odium stearate 0.11kg 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, add 80L methanol, 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) it is 2.95 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.5:1.25:1.00 weigh total amount 2kg nitre respectively
Sour lanthanum, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation shell
Polysaccharide solution, controls rotating speed 1000r/min, and 25 DEG C of temperature is reacted 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped heavy
Shallow lake form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, dried in vacuum drying chamber,
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) 1.2kg 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 0.11kg 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, add the poly- second of 5.82kg 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: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 is by linear low density polyethylene (LLDPE) 6.08kg, tourmaline powder 1.2kg, rare earth compounding 2.2kg, diatom
Native 0.3kg, oleamide 0.11kg, odium stearate 0.11kg 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, add 80L methanol, 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) it is 2.95 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.5:1.25:1.00 weigh total amount 2kg nitre respectively
Sour lanthanum, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation shell
Polysaccharide solution, controls rotating speed 1000r/min, and 25 DEG C of temperature is reacted 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped heavy
Shallow lake form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, dried in vacuum drying chamber,
Grinding, obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1) by 2.2kg rare earth compoundings, 0.30kg 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 0.11kg 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, add 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: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) 5.96kg, tourmaline powder 1.5kg, rare earth compounding 2.0kg, diatom
Native 0.3kg, oleamide 0.11kg, odium stearate 0.13kg 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, add 80L methanol, 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) it is 3.05 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.55:1.15:0.95 weighs total amount 2kg's respectively
Lanthanum nitrate, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation
Chitin solution, controls rotating speed 1000r/min, 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 2.0kg rare earth compoundings, 0.30kg 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) 1.5kg 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 0.13kg 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, add the poly- second of 5.96kg 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 is by linear low density polyethylene (LLDPE) 5.82kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, diatom
Native 0.35kg, oleamide 0.12kg, odium stearate 0.11kg 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, add 80L methanol, 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) it is 3.05 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.55:1.15:0.95 weighs total amount 2kg's respectively
Lanthanum nitrate, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation
Chitin solution, controls rotating speed 1000r/min, 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) 1.2kg 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 0.11kg 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, add the poly- second of 5.82kg 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: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 is by linear low density polyethylene (LLDPE) 6.08kg, tourmaline powder 1.2kg, rare earth compounding 2.2kg, diatom
Native 0.3kg, oleamide 0.11kg, odium stearate 0.11kg 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, add 80L methanol, 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) it is 3.05 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.55:1.15:0.95 weighs total amount 2kg's respectively
Lanthanum nitrate, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation
Chitin solution, controls rotating speed 1000r/min, 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, 0.30kg 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 0.11kg 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, add 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: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 (9)
1. a kind of preparation method of the lichee fresh-keeping 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 3.00~3.05:0.40~0.45:1.15~1.25:0.95~
1.05, 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 the rare earth compounding of 18~20 parts by weight, the diatomite of 2~2.5 parts by weight is placed in mixer after compounding, plus
Enter 1.0~1.2 parts by weight oleamides, be that 250r/min, temperature are that to carry out cladding under the conditions of 102 ± 1 DEG C scattered in rotating speed,
Raw material I is obtained after 15min;
(2)12~15 parts by weight of tourmaline powder are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C
Under the conditions of mediate after 10min, 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 compound, the LLDPE of 60.3~66.2 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 lichee fresh-keeping 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 any
The mixture of ratio;Described tourmaline powder particle diameter is 1.3~6.5 μm.
3. a kind of preparation method of lichee fresh-keeping 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 lichee fresh-keeping 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 lichee fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that
The compound of described lanthanum is one kind in lanthanum hydroxide, lanthanum acetate, lanthanum nitrate, lanthanum chloride;The compound of described yttrium is hydrogen
One kind in yittrium oxide, acetic acid yttrium, yttrium nitrate, yttrium chloride;The compound of described cerium be cerium hydroxide, cerous acetate, cerous nitrate,
One kind in cerium chloride.
6. a kind of preparation method of lichee fresh-keeping 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 described cladding dispersion process, and temperature is 102 ± 1 DEG C.
7. a kind of preparation method of lichee fresh-keeping 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 lichee fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that
The rotating speed of mixer is 120r/min in described mixed material mixed process, and temperature is 108 ± 1 DEG C.
9. a kind of preparation method of lichee fresh-keeping 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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