CN105778259A - Preparation method of rare earth complex-containing strawberry fresh-keeping film master batch - Google Patents
Preparation method of rare earth complex-containing strawberry fresh-keeping film master batch Download PDFInfo
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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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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- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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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
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Abstract
The invention relates to a preparation method of a rare earth complex containing strawberry fresh-keeping film master batch. According to the preparation method, LLDPE serves as carrier resin, and tourmaline powder, rare earth complexes, diatomite, oleamide and sodium stearate are added to prepare the strawberry fresh-keeping film master batch through coating dispersion, interfacial modification, material mixing and extrusion pelletizing processing. The strawberry fresh-keeping film master batch prepared by the method is applied to linear low density polyethylene (LLPDE) resin with a proportion of 5-8% and forms a film through blow molding; the film is used for fresh-keeping packing of strawberries, can restrain the respiration intensity and growth of surface microorganisms, and prolongs the fresh period by 5-7 days at room temperature. The preparation method of the rare earth complex containing strawberry fresh-keeping film master batch has the beneficial effects that the resources of the tourmaline powder, rare earth and natural plant polysaccharide used by this method are abundant, can effectively reduce cost and do no harm to human bodies, and the prepared material is safe and can be applied to packages of fresh food safely; furthermore, the tourmaline powder, the rare earth and the natural plant polysaccharide have antibacterial and fresh-keeping functions, and the antibacterial and fresh-keeping effect can be effectively reinforced through modes such as modification and compounding.
Description
Technical field
The preparation method that the present invention relates to functional plastic film master batch, the preparation method being specifically related to a kind of strawberry preservation film master batch containing rare earth compounding.
Background technology
Fructus Fragariae Ananssae (FragariaananassaDuchesne) belongs to Rosaceae Fragaria herbaceos perennial.Fructus Fragariae Ananssae is berries fruit, has clearing away summer-heat antipyretic, promoting the production of body fluid to quench thirst, effect of diuresis antidiarrheal, has significantly high nutritive value and dietary function.Have the good reputation of " fruit queen ".But Fructus Fragariae Ananssae is moisture up to 90%～95%, organizes tender and lovely, and peel is very thin, crust unprotect effect, thus subject to damage and microbial infection rot in gathering and storing and transporting, pole is storage tolerance not.In storage, respiratory increase is a kind of reaction of Fructus Fragariae Ananssae ripening and senescence, is the not long keeping one of the main reasons of Fructus Fragariae Ananssae.And the effect of the softening of strawberry fruit mainly cellulase.Free radical is the initiator of tissue film's lipid peroxidation.Generally, Fructus Fragariae Ananssae is placed 1～2d after gathering and namely tarnishes, and fruit face is shunk, and Quality Down, thus losing commercial value.In recent years, the yield of Fructus Fragariae Ananssae presents the gesture of swift and violent risings, but solves its preservation and freshness problem owing to failing, and causes substantial amounts of Fructus Fragariae Ananssae rotten, causes very big loss.Therefore, how to extend storage period or the shelf life of strawberry fruit, be problem demanding prompt solution in producing.
China's rare earth resources enriches, and rare earth develops exists great potential.Rare earth and derivant thereof can as antimicrobial antistaling agents, Ca2+It is the ion maintaining antibacterial normal activity, and lanthanum ion has antagonism Ca2+Effect, so antibacterial normal activities can be interfered by lanthanum ion, cause bacterial death, in Rare Earth Lanthanum coordination antibacterial, part enhances anti-microbial property simultaneously.Cerium ion has hydrolysis, it is possible to fracture polypeptide chain, and enzyme is protein, so cerium ion makes the polypeptide chain in enzyme rupture；In addition cerium ion is to the displacement of metal ion and competition in enzyme thus have impact on the physiological function of enzyme, therefore can slow down softening process by suppression cellulase activity, it is suppressed that respiratory intensity.Rare earth has the stronger ability removing hydroxyl radical free radical, by reducing respiration of fruits, reducing free radical and occurs, weaken active oxygen injury, thus producing to suppress the peroxidation of membrane lipids of tissue, delayed fruit ripening and senescence, extending Fructus Fragariae Ananssae shelf life.Tourmaline Ye Shi China is rich in mineral resources, and tourmaline powder anion releasing can effective killing pathogenic bacteria.Its mechanism essentially consists in after anion is combined with antibacterial, makes antibacterial produce the change of structure or the transfer of energy, causes bacterial death.Vegetable polysaccharides is abundant Renewable resource, itself has certain antibacterial effect, and acetylizad vegetable polysaccharides has the stronger ability removing hydroxyl radical free radical.
During conventional packaging room temperature storage, shelf life is short, has a strong impact on its transport and sells.At present, strawberry preservation technology mainly has cryopreservation, air conditioned storage, high oxygen treatment, coating preservation method, irradiated targets, fresh chemically etc..Though physical method is nontoxic and compares effectively, but relatively costly, needs specific appointed condition, be not suitable for commonly used；And adopt chemical drugs to make antistaling agent, the problem such as residual hazard further relating to some medicine.Some other novel antistaling film poor effect or relatively costly, constrains popularization and application.
Summary of the invention
For the deficiency that existing strawberry preservation fresh-keeping effect is bad and cost is high.The preparation method that the invention provides the good lower-cost master batch of a kind of anti-bacterial refreshing, it is characterized in that: with LLDPE for vector resin, interpolation tourmaline powder, rare earth compounding, kieselguhr, oleamide, sodium stearate are processed by cladding dispersion, interface modification, mixing of materials, extrusion pelletizing.Master batch prepared by this method, add in linear low density polyethylene (LLDPE) (LLDPE) resin with the ratio of 5～8%, after thin film is made in blowing, pack for strawberry preservation, can suppressing respiratory intensity and surface microorganism growth in storage, normal temperature condition prolongs storage period 5～7 days.
The technical scheme is that for realizing the purpose of the present invention
1, the preparation of rare earth compounding
(1) vegetable polysaccharides of 2 weight portions is dissolved in the acetic acid solution of 60 weight portions; after stirring, adding the methanol of 80 weight portions, solution is no longer sticky; add the acetic anhydride of 1 weight portion; after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in the ethanol of 150 weight portions, filtering precipitate after precipitation generation; with absolute ethanol washing 3 times; after dissolving with acetic acid solution again, elimination insoluble matter, obtain acetylation vegetable polysaccharides solution.
(2) according to lanthanum, yttrium, neodymium, cerium ion mol ratio be 2.90～3.0:0.55～0.65:1.00～1.05:1.25～1.35, weigh the compound of lanthanum, the compound of yttrium, the compound of neodymium and the compound of cerium respectively and be mixed into rare earth compound, and join in distilled water with the weight part ratio of 15, obtain rare earth compound mixed aqueous solution after being entirely capable of dissolving；According to weight ratios such as vegetable polysaccharides and rare earth compounds; rare earth compound mixed aqueous solution is slowly added dropwise to acetylation vegetable polysaccharides solution; regulating reaction system pH to 7.0, react 6～7 hours under rotating speed 1000r/min, 25～30 DEG C of conditions of temperature, product precipitates out with precipitation form；Filter after precipitate, remove unreacted rare earth ion with distilled water wash, dry in vacuum drying oven, grind, obtain pulverous rare earth compounding.
2, the preparation of master batch
(1) by 22～25 weight portion rare earth compoundings, 2.5～3.5 weight portion kieselguhr, composite it is placed in blender, adds 0.9～1.2 weight portion oleamide, be 250r/min at rotating speed, temperature is cladding dispersion under 102 ± 1 DEG C of conditions, becomes raw material I after 15min；
(2) being placed in high-speed kneading machine by 12～15 parts of tourmaline powders, be rotating speed at rotating speed be 500r/min, temperature is kneading 10min under 105 ± 1 DEG C of conditions, adds 1.0～1.2 weight portion sodium stearates, becomes raw material II after carrying out interface modification 20min；
(3) raw material II and raw material I being placed in mixer and be mixed into compound, the LLDPE mixing 10min adding 54.1～61.6 weight portions obtains mixed material；
(4) mixed material is placed in double screw extruder extrude pelletizing be master batch.Utilize blow molding machine to adopt common process condition, prepare a kind of strawberry preservation film containing rare earth compounding further.
The impact of the Fructus Fragariae Ananssae titratable acid content of storage and the Content of Soluble Solid Substance of Strawberry of storage is contrasted at widely used common preservative film 15 DEG C by the strawberry preservation film containing rare earth compounding that the present invention is prepared and market by the Fructus Fragariae Ananssae respiratory intensity of storage, room temperature, result shows, the strawberry preservation film of rare earth compounding prepared by the present invention is after 5 days, and Fructus Fragariae Ananssae respiratory intensity is 68.8CO2Mg/(kg.h), the 102CO of common preservative film lower than under equal conditions2Mg/(kg.h)；Utilizing under the strawberry preservation film room temperature of rare earth compounding prepared by the present invention the storage Fructus Fragariae Ananssae titratable acid content of 5 days is 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 the mixture of one or more arbitrary proportions in dravite powder, schorl powder, elbaite powder, tsilaisite powder；Described tourmaline powder particle diameter is 1.3～6.5 μm.
Acetic acid solution mass percent concentration of the present invention is 2%.
Vegetable polysaccharides of the present invention is one or more arbitrary proportions in starch, fructose, cellulose, chitin.
The compound of lanthanum of the present invention is the one of lanthanum hydroxide, lanthanum acetate, Lanthanum (III) nitrate or lanthanum chloride.
The compound of yttrium of the present invention is the one of Yttrium trihydroxide, acetic acid yttrium, Yttrium trinitrate or Yttrium chloride(Y2Cl6).
The compound of samarium of the present invention is the one of Samarium trihydroxide., acetic acid samarium, samaric nitrate or samarium trichloride.
The compound of cerium of the present invention is the one of cerium hydroxide, cerous acetate, cerous nitrate or cerium chloride.
Rare earth compounding reaction condition of the present invention is rotating speed 1000r/min, temperature 25～30 DEG C.
In cladding dispersive process of the present invention, the rotating speed of blender is 250r/min, 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.
In mixing of materials process of the present invention, the rotating speed of mixer is 120r/min, and temperature is 108 ± 1 DEG C.
In extrusion pelletizing process of the present invention twin-screw extruder barrel temperature control in 130～140 DEG C of I district, 145～150 DEG C of II district, 150～155 DEG C of III district, 160～165 DEG C of IV district, 155～160 DEG C of V district, die head 155～160 DEG C.
The invention has the beneficial effects as follows: the tourmaline powder that 1. adopts, rare earth, natural plant polyose aboundresources, can effectively reduce cost；2. the tourmaline powder that adopts, rare earth, natural plant polyose are harmless, the material safety prepared, and can relieved pack for fresh food；3. the tourmaline powder that adopts, rare earth, natural plant polyose itself have sterilizing fresh-keeping function, can effectively strengthen anti-bacterial refreshing effect by the mode such as modified, composite.
Accompanying drawing explanation
The sample that Fig. 1 is prepared by the embodiment of the present invention 1 packs the room temperature impact on the Fructus Fragariae Ananssae respiratory intensity of storage with common preservative film.
Detailed description of the invention
Embodiment 1
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.89kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, kieselguhr 0.3kg, oleamide 0.11kg, sodium stearate 0.10kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150L ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 3.00:0.60:1.05:1.25 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.4kg rare earth compounding, 0.3kg kieselguhr, composite being placed in blender, add 0.11kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.2kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.10kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.89kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 132 DEG C of I district, 150 DEG C of II district, 155 DEG C of III district, 161 DEG C of IV district, 158 DEG C of V district, die head 160 DEG C, extrusion pelletizing is master batch.
(5) utilize blow molding machine to adopt common process condition, prepare a kind of strawberry preservation film containing rare earth compounding further.
The impact of the Fructus Fragariae Ananssae titratable acid content of storage and the Content of Soluble Solid Substance of Strawberry of storage is contrasted at widely used common preservative film 15 DEG C by the strawberry preservation film containing rare earth compounding that the present embodiment is prepared and market by the Fructus Fragariae Ananssae respiratory intensity of storage, room temperature, result shows, the strawberry preservation film respiratory intensity of rare earth compounding prepared by the present embodiment is common preservative film lower than under equal conditions, as shown in Figure 1.
Embodiment 2
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.83kg, tourmaline powder 1.5kg, rare earth compounding 2.2kg, kieselguhr 0.25kg, oleamide 0.10kg, sodium stearate 0.12kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150L ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 3.00:0.60:1.05:1.25 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.2kg rare earth compounding, 0.25kg kieselguhr, composite being placed in blender, add 0.10kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.5kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.12kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.83.kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 135 DEG C of I district, 150 DEG C of II district, 155 DEG C of III district, 160 DEG C of IV district, 155 DEG C of V district, die head 155 DEG C, extrusion pelletizing is master batch.
(5) utilize blow molding machine to adopt common process condition, prepare a kind of strawberry preservation film containing rare earth compounding further.
Embodiment 3
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.62kg, tourmaline powder 1.3kg, rare earth compounding 2.5kg, kieselguhr 0.35kg, oleamide 0.12kg, sodium stearate 0.11kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150L ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 3.00:0.60:1.05:1.25 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.5kg rare earth compounding, 0.35kg kieselguhr, composite being placed in blender, add 0.12kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.3kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.11kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.62.kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 130 DEG C of I district, 145 DEG C of II district, 155 DEG C of III district, 160 DEG C of IV district, 160 DEG C of V district, die head 155 DEG C, extrusion pelletizing is master batch.
(5) utilize blow molding machine to adopt common process condition, prepare a kind of strawberry preservation film containing rare earth compounding further.
Embodiment 4
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.89kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, kieselguhr 0.3kg, oleamide 0.11kg, sodium stearate 0.10kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150L ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 2.95:0.65:1.05:1.35 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.4kg rare earth compounding, 0.3kg kieselguhr, composite being placed in blender, add 0.11kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.2kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.10kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.89kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 132 DEG C of I district, 150 DEG C of II district, 155 DEG C of III district, 161 DEG C of IV district, 158 DEG C of V district, die head 160 DEG C, extrusion pelletizing is master batch.
(5) utilize blow molding machine to adopt common process condition, prepare a kind of strawberry preservation film containing rare earth compounding further.
Embodiment 5
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.83kg, tourmaline powder 1.5kg, rare earth compounding 2.2kg, kieselguhr 0.25kg, oleamide 0.10kg, sodium stearate 0.12kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150L ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 2.95:0.65:1.05:1.35 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.2kg rare earth compounding, 0.25kg kieselguhr, composite being placed in blender, add 0.10kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.5kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.12kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.83.kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 135 DEG C of I district, 150 DEG C of II district, 155 DEG C of III district, 160 DEG C of IV district, 155 DEG C of V district, die head 155 DEG C, extrusion pelletizing is master batch.
(5) utilize blow molding machine to adopt common process condition, prepare a kind of strawberry preservation film containing rare earth compounding further.
Embodiment 6
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.62kg, tourmaline powder 1.3kg, rare earth compounding 2.5kg, kieselguhr 0.35kg, oleamide 0.12kg, sodium stearate 0.11kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150L ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 2.95:0.65:1.05:1.35 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.5kg rare earth compounding, 0.35kg kieselguhr, composite being placed in blender, add 0.12kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.3kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.11kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.62.kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 130 DEG C of I district, 145 DEG C of II district, 155 DEG C of III district, 160 DEG C of IV district, 160 DEG C of V district, die head 155 DEG C, extrusion pelletizing is master batch.
(5) utilize blow molding machine to adopt common process condition, prepare a kind of strawberry preservation film containing rare earth compounding further.
Claims (9)
1. a preparation method for the strawberry preservation film master batch containing rare earth compounding, is characterized in that:
The preparation of rare earth compounding
(1) vegetable polysaccharides of 2 weight portions is dissolved in the acetic acid solution of 60 weight portions; after stirring, adding the methanol of 80 weight portions, solution is no longer sticky; add the acetic anhydride of 1 weight portion; after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in the ethanol of 150 weight portions, filtering precipitate after precipitation generation; with absolute ethanol washing 3 times; after dissolving with acetic acid solution again, elimination insoluble matter, obtain acetylation vegetable polysaccharides solution；
(2) according to lanthanum, yttrium, neodymium, cerium ion mol ratio be 2.90～3.0:0.55～0.65:1.00～1.05:1.25～1.35, weigh the compound of lanthanum, the compound of yttrium, the compound of neodymium and the compound of cerium respectively and be mixed into rare earth compound, and join in distilled water with the weight part ratio of 15, obtain rare earth compound mixed aqueous solution after being entirely capable of dissolving；According to weight ratios such as vegetable polysaccharides and rare earth compounds; rare earth compound mixed aqueous solution is slowly added dropwise to acetylation vegetable polysaccharides solution; regulating reaction system pH to 7.0, react 6～7 hours under rotating speed 1000r/min, 25～30 DEG C of conditions of temperature, product precipitates out with precipitation form；Filter after precipitate, remove unreacted rare earth ion with distilled water wash, dry in vacuum drying oven, grind, obtain pulverous rare earth compounding；
The preparation of master batch
(1) by 22～25 weight portion rare earth compoundings, 2.5～3.5 weight portion kieselguhr, composite it is placed in blender, adds 0.9～1.2 weight portion oleamide, be 250r/min at rotating speed, temperature is cladding dispersion under 102 ± 1 DEG C of conditions, becomes raw material I after 15min；
(2) being placed in high-speed kneading machine by 12～15 parts of tourmaline powders, be rotating speed at rotating speed be 500r/min, temperature is kneading 10min under 105 ± 1 DEG C of conditions, adds 1.0～1.2 weight portion sodium stearates, becomes raw material II after carrying out interface modification 20min；
(3) raw material II and raw material I being placed in mixer and be mixed into compound, the LLDPE mixing 10min adding 54.1～61.6 weight portions obtains mixed material；
(4) mixed material is placed in double screw extruder extrude pelletizing be master batch.
2. the preparation method of a kind of strawberry preservation film master batch containing rare earth compounding according to claim 1, is characterized in that the mixture that described tourmaline powder is one or more arbitrary proportions in dravite powder, schorl powder, elbaite powder, tsilaisite powder；Described tourmaline powder particle diameter is 1.3～6.5 μm.
3. the preparation method of a kind of strawberry preservation film master batch containing rare earth compounding according to claim 1, is characterized in that described acetic acid solution mass percent concentration is 2%.
4. the preparation method of a kind of strawberry preservation film master batch containing rare earth compounding according to claim 1, is characterized in that described vegetable polysaccharides is one or more arbitrary proportions in starch, fructose, cellulose, chitin.
5. the preparation method of a kind of strawberry preservation film master batch containing rare earth compounding according to claim 1, is characterized in that the one that the compound of described lanthanum is lanthanum hydroxide, lanthanum acetate, Lanthanum (III) nitrate or lanthanum chloride；The compound of described yttrium is the one of Yttrium trihydroxide, acetic acid yttrium, Yttrium trinitrate or Yttrium chloride(Y2Cl6)；The compound of described samarium is the one of Samarium trihydroxide., acetic acid samarium, samaric nitrate or samarium trichloride；The compound of described cerium is the one of cerium hydroxide, cerous acetate, cerous nitrate or cerium chloride.
6. the preparation method of a kind of strawberry preservation film master batch containing rare earth compounding according to claim 1, is characterized in that in this described cladding dispersive process, the rotating speed of blender is 250r/min, and temperature is 102 ± 1 DEG C.
7. the preparation method of a kind of strawberry preservation film master batch containing rare earth compounding according to claim 1, 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. the preparation method of a kind of strawberry preservation film master batch containing rare earth compounding according to claim 1, is characterized in that in described mixing of materials process, the rotating speed of mixer is 120r/min, and temperature is 108 ± 1 DEG C.
9. the preparation method of a kind of strawberry preservation film master batch containing rare earth compounding according to claim 1, it is characterized in that in described extrusion pelletizing process, twin-screw extruder barrel temperature controls in 130～140 DEG C of I district, 145～150 DEG C of II district, 150～155 DEG C of III district, 160～165 DEG C of IV district, 155～160 DEG C of V district, die head 155～160 DEG C.
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| CN109135559A (en) * | 2018-08-30 | 2019-01-04 | 江苏京展能源科技有限公司 | A kind of solar energy vacuum tube spectral selection absorbing coating and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09510484A (en) * | 1994-03-15 | 1997-10-21 | エクソン・ケミカル・パテンツ・インク | Polymer blends, films and articles thereof |
| US20020016381A1 (en) * | 2000-01-31 | 2002-02-07 | Kroll Mark S. | 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 |
| CN1467245A (en) * | 2002-07-08 | 2004-01-14 | 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 |
| 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 |
| 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 |
| 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 |
-
2016
- 2016-03-24 CN CN201610177180.XA patent/CN105778259B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09510484A (en) * | 1994-03-15 | 1997-10-21 | エクソン・ケミカル・パテンツ・インク | Polymer blends, films and articles thereof |
| US20020016381A1 (en) * | 2000-01-31 | 2002-02-07 | Kroll Mark S. | 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 |
| CN1467245A (en) * | 2002-07-08 | 2004-01-14 | 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 |
| 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 |
| 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 |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135559A (en) * | 2018-08-30 | 2019-01-04 | 江苏京展能源科技有限公司 | A kind of solar energy vacuum tube spectral selection absorbing coating and preparation method thereof |
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