CN105602088A - Preparation method of oyster mushroom fresh-keeping film master batches containing rare earth complex - Google Patents
Preparation method of oyster mushroom fresh-keeping film master batches containing rare earth complex Download PDFInfo
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- 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
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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2323/02—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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- 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
- C08L2203/00—Applications
- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to a preparation method of oyster mushroom fresh-keeping film master batches containing a rare earth complex. The method comprises the following steps: dissolving plant polysaccharide into an acetic acid solution, adding methanol and acetic anhydride, and adding a product to ethanol after reaction to obtain an acetylated plant polysaccharide solution; weighing compounds of lanthanum, yttrium, neodymium and cerium for mixing, and adding the mixture to distilled water to obtain a rare-earth compound mixed water solution; dropwise adding the rare-earth compound mixed water solution to the acetylated plant polysaccharide solution; filtering, washing and drying the product, and grinding the product into powder; putting the rare earth complex and diatomite into a stirrer, and adding aluminic acid ester to obtain a raw material I; putting tourmaline powder into a high-speed kneading machine, and adding sodium stearate to form a raw material II; and mixing the raw material II, the raw material I and LLDPE, and extruding and dicing in a twin-screw extruder to form the master patches. By adopting the tourmaline powder, rare earth and natural plant polysaccharide, the cost can be effectively reduced; the master batches are free of harm to a human body and have antibacterial fresh-keeping functions; and the antibacterial fresh-keeping effects can be effectively strengthened in manners of modification, compounding and the like.
Description
Technical field
The present invention relates to the preparation method of functional plastic film master batch, be specifically related to a kind of preparation method of the flat mushroom preservative film master batch containing rare earth compounding.
Background technology
Flat mushroom formal name used at school (Pleurtusostreatus). Flat mushroom is nutritious, is rich in amino acid, and amino acid A wide selection of colours and designs, active polysaccharide, activated protein etc. that flat mushroom is contained, and to strengthening immune function of human body, prevention " three height " has good result. Meanwhile, because fat content in flat mushroom is extremely low, therefore, be cardiovascular and cerebrovascular disease and obesity patient's ultimate food. Flat mushroom tissue water content is higher; the flat mushroom water content of newly gathering generally can reach more than 90%; and tender and crisp owing to organizing, surperficial unprotect tissue, adopts rear respiratory metabolism vigorous; producing a large amount of moisture and heat very easily breeds microorganism; accelerate old and feeble going bad, in storage, in body, part enzyme affects the physiological activities such as brown stain, oxidation, catabolism; these cause shelf life very short, under normal temperature, generally only have 2 ~ 3 days.
China's rare earth resources is abundant, and rare earth develops and has great potential. Rare earth and derivative thereof can be used as antimicrobial antistaling agent, and lanthanum ion or lanthanum complex can enter in cell, with intracellular biomolecule action, the growth metabolism of cell are suppressed; And Ca2+Be the ion that maintains bacterium normal activity, and lanthanum ion have antagonism Ca2+Effect, so lanthanum ion can cause interference to bacterium normal activities, cause bacterium death, in simultaneously Rare Earth Lanthanum coordination antiseptic, part has strengthened anti-microbial property. And cerium ion has hydrolysis, the polypeptide chain that can rupture, and enzyme is protein, so cerium ion makes the polypeptide chain fracture in enzyme; Thereby the displacement of cerium ion on metal ion in enzyme and competition have affected the physiological function of enzyme in addition, therefore can suppress respiration and brown stain by affecting enzyme. Many biological oxidation processes are as mouldy, rotten etc. all closely related with the generation of free radical in food, and rare earth has the ability of stronger removing hydroxyl radical free radical. Tourmaline Ye Shi China is rich in mineral resources, and tourmaline powder anion releasing is killing pathogenic bacteria effectively. After its mechanism is mainly that anion is combined with bacterium, make bacterium produce the change of structure or the transfer of energy, cause bacterium death. Plant polyose is abundant renewable resource, itself has certain antibacterial effect, and acetylizad plant polyose has the ability of stronger removing hydroxyl radical free radical.
When conventional packaging room temperature storage, shelf life is short, has a strong impact on its transport and sale. At present, edible mushroom preservation method research, apply the more preservation technique that relates generally to current edible mushroom and mainly contain cold storing and fresh-keeping, quick-freezing fresh-keeping, ozone (O3) though the physical method such as fresh-keeping, controlled atmosphere, radiation preservation, fresh chemically is nontoxic and more effective, cost is higher, needs specific appointed condition, is not suitable for generally applying; And adopt chemicals to make antistaling agent, relate to again the problem such as residual hazard of some medicine.
In recent years, some research units are devoted to research and develop the packaging material with sterilizing fresh-keeping function both at home and abroad, as shitosan/nanometer titanium dioxide antibiotic preservative film, PE/Ag nano mildew-proof preservative film etc., are obtaining good effect aspect the anti-bacterial refreshing of fresh food. But above-mentioned antibacterial fresh-keeping film high cost, has restricted and has applied.
Three, summary of the invention
The deficiency bad for existing flat mushroom fresh-keeping packaging fresh-keeping effect and cost is high. The invention provides the preparation method of the good lower-cost master batch of a kind of anti-bacterial refreshing, it is characterized in that: taking LLDPE as vector resin, add tourmaline powder, rare earth compounding, diatomite, Aluminate, odium stearate by coated dispersion, interface modification, mixing of materials, extrude pelletizing and process. Master batch prepared by this method, adds in LLDPE resin with 4～8% ratio, and blowing is made after film, for flat mushroom fresh-keeping packaging, can suppress respiratory intensity and surface microorganism growth in storage, and normal temperature condition prolongs storage period 8～12 days.
For the technical scheme that realizes object employing of the present invention is:
1, the preparation of rare earth compounding
(1) plant polyose of 2 weight portions is dissolved in the acetic acid solution of 60 weight portions; after stirring, add the methyl alcohol of 80 weight portions, solution is no longer sticky; add the acetic anhydride of 1 weight portion; at 30 DEG C of temperature, react after 1h, the thick liquid of reaction gained is joined in the ethanol of 150 weight portions, filtering precipitate after precipitation generates; with absolute ethanol washing 3 times; after dissolving with acetic acid solution, elimination insoluble matter, obtains acetylation plant polyose solution again.
(2) ratio that is 2.85～2.95:0.50～0.60:1.05～1.25:0.95～1.05 according to the mol ratio of lanthanum, yttrium, neodymium, cerium ion, take respectively the compound of lanthanum, compound, the compound of neodymium and the compound of cerium of yttrium becomes rare earth compound, and join in distilled water with the weight part ratio of 1 ﹕ 5, after dissolving completely, obtain rare earth compound mixed aqueous solution; According to the weight ratio such as plant polyose and rare earth compound, rare earth compound mixed aqueous solution is slowly dropped in acetylation plant polyose solution, regulate reaction system pH to 7.0, under rotating speed 1000r/min, 25～30 DEG C of conditions of temperature, react 6～7 hours, product is separated out with precipitation form; Filter after sediment, remove unreacted rare earth ion with distilled water washing, dry in vacuum drying chamber, grind into powder, obtains rare earth compounding.
2, the preparation of master batch
(1) by the rare earth compounding of 18～24 weight portions, the diatomite of 2～3 weight portions, composite being placed in mixer, adds 0.8～1.0 weight portion Aluminate, and obtain raw material I after 15min coated dispersion;
(2) 12～15 weight portion tourmaline powders are placed in to high-speed kneading machine and mediate after 10min, then add 1.1～1.3 weight portion odium stearate, carry out becoming raw material II after interface modification 20min;
(3) raw material II and raw material I are placed in to mixer and are mixed into compound, then add the LLDPE mixing 10min of 55.7～64.8 weight portions to obtain mixed material;
(4) mixed material being placed in to double screw extruder extrudes pelletizing and is master batch. Utilize blow molding machine to adopt common process condition, further prepare a kind of flat mushroom preservative film containing rare earth compounding.
On the flat mushroom preservative film containing rare earth compounding that the present invention is prepared and market, under 20 DEG C of conditions of widely used common preservative film, flat mushroom ppo enzymatic activity, soluble protein content and the flat mushroom mda content of storage are compared, result shows, the flat mushroom preservative film of rare earth compounding prepared by employing the present invention is in storage, and ppo enzymatic activity, soluble protein content and flat mushroom mda content are all conducive to the storage of flat mushroom.
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 μ m.
Acetic acid solution mass percent concentration of the present invention is 2%.
Plant polyose of the present invention is the mixture of one or more arbitrary proportions in starch, fructose, cellulose, chitin.
The compound of lanthanum of the present invention is the one in lanthanum hydroxide, lanthanum acetate, lanthanum nitrate, lanthanum chloride.
The compound of yttrium of the present invention is the one in yttrium hydroxide, acetic acid yttrium, yttrium nitrate, yttrium chloride.
The compound of samarium of the present invention is the one in samaric hydroxide, acetic acid samarium, samaric nitrate, samarium trichloride.
The compound of cerium of the present invention is the one in cerium hydroxide, cerous acetate, cerous nitrate, cerium chloride.
In coated dispersion process of the present invention, the rotating speed of mixer is 250r/min, and temperature is 102 ± 1 DEG C.
The rotating speed of interface 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.
Of the present inventionly extrude double screw extruder barrel temperature in pelletizing process and be controlled at 130～140 DEG C, I district, 145～150 DEG C, II district, 150～155 DEG C, III district, 160～165 DEG C, IV district, 155～160 DEG C, V district, 155～160 DEG C of die heads.
The invention has the beneficial effects as follows: the tourmaline powder, rare earth, the natural plant polyose aboundresources that 1. adopt, can effectively reduce costs; 2. the tourmaline powder, rare earth, the natural plant polyose that adopt are harmless, and the material safety making, can relievedly pack for fresh food; 3. the tourmaline powder, rare earth, the natural plant polyose itself that adopt have sterilizing fresh-keeping function, can effectively strengthen anti-bacterial refreshing effect by modification, the mode such as composite.
Brief description of the drawings
Fig. 1 is the impact that the prepared sample of the embodiment of the present invention 1 and common preservative film are packed 10 DEG C of PPO enzymatic activitys on storage flat mushroom.
Fig. 2 is the impact that the prepared sample of the embodiment of the present invention 1 and common preservative film are packed 10 DEG C of content of soluble protein on storage flat mushroom.
Fig. 3 is the impact that the prepared sample of the embodiment of the present invention 1 and common preservative film are packed 10 DEG C of mda contents on storage flat mushroom.
Detailed description of the invention
For the present invention being had to better understanding, be now described further by reference to the accompanying drawings.
In Fig. 1, two curves represent respectively the impact of common preservative film and 15 days process PPO enzymatic activitys of the flat mushroom preservative film containing rare earth compounding of the present invention storage. As can be seen from the figure,, while adopting the storage of the flat mushroom preservative film containing rare earth compounding of the present invention to the 4.5th day, there is comparatively significantly advantage in flat mushroom PPO enzymatic activity, lower than common preservative film; While preserving to the 15th day, the PPO enzymatic activity of flat mushroom is still lower than common preservative film. As shown in Figure 1.
In Fig. 2, two curves represent respectively the soluble protein content of common preservative film and 15 days process flat mushroom fruit grains of the flat mushroom preservative film containing rare earth compounding of the present invention storage. As can be seen from the figure, along with the prolongation of storage time, adopt the flat mushroom fruit grain of the fruit of the flat mushroom preservative film containing rare earth compounding grain hardness of the present invention compared to common preservative film packaging, still keep higher content. As shown in Figure 2.
In Fig. 3, two curves represent respectively common preservative film and 25 days process flat mushroom mda contents of the flat mushroom preservative film containing rare earth compounding of the present invention storage. As can be seen from the figure,, although along with the prolongation of time, mda content is synchronous rising and rise process. As shown in Figure 3.
Embodiment 1
The component of master batch is by linear low density polyethylene (LLDPE) 5.89kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, diatomite 0.30kg, Aluminate 0.10kg, odium stearate 0.11kg composition.
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 methyl alcohol; solution is no longer sticky; add acetic anhydride 1L, at 30 DEG C of temperature, react after 1h, the thick liquid of reaction gained is joined in 150 ethanol; there is precipitation to generate; leach solid, use 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 lanthanum nitrate that 2.90:0.50:1.25:1.00 takes respectively total amount 2kg, yttrium nitrate, neodymium nitrate, cerous nitrate, be dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly dropped to acetylation chitin solution, control rotating speed 1000r/min, 25 DEG C of temperature, react 6 hours, pH value of solution is adjusted to 7.0, product is separated out with flocculent deposit form, filter after sediment, with the unreacted metal ion of distilled water washing removal, dry in vacuum drying chamber, grind, obtain buff powder, be rare earth compounding.
2, the preparation of master batch
(1) by 2.4kg rare earth compounding, 0.30kg diatomite, composite being placed in mixer, adds 0.10kg Aluminate, and at rotating speed 250r/min, temperature is under 102 ± 1 DEG C of conditions, to be coated to disperse to become raw material I after 15min;
(2) 1.2kg tourmaline powder being placed in to high-speed kneading machine, is 500r/min at rotating speed, and temperature is to mediate after 10min under 105 ± 1 DEG C of conditions, is placed in high-speed kneading machine and mediates after 10min, adds 0.11kg odium stearate, after interface modification 20min, becomes raw material II;
(3) raw material II and raw material I are placed in to mixer and are mixed into compound, then add 5.89kg linear low density polyethylene (LLDPE) mixing 10min to obtain mixed material;
(4) mixed material is placed in to double screw extruder, mixed material is placed in to double screw extruder, control extruder barrel temperature: 132 DEG C, I district, 150 DEG C, II district, 155 DEG C, III district, 161 DEG C, IV district, 158 DEG C, V district, 160 DEG C of die heads, extrude pelletizing and be master batch.
Embodiment 2
The component of master batch is by linear low density polyethylene (LLDPE) 6.03kg, tourmaline powder 1.5kg, rare earth compounding 2.0kg, diatomite 0.25kg, Aluminate 0.09kg, odium stearate 0.13kg composition.
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 methyl alcohol; solution is no longer sticky; add acetic anhydride 1L, at 30 DEG C of temperature, react after 1h, the thick liquid of reaction gained is joined in 150 ethanol; there is precipitation to generate; leach solid, use 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 lanthanum nitrate that 2.90:0.50:1.25:1.00 takes respectively total amount 2kg, yttrium nitrate, neodymium nitrate, cerous nitrate, be dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly dropped to acetylation chitin solution, control rotating speed 1000r/min, 25 DEG C of temperature, react 6 hours, pH value of solution is adjusted to 7.0, product is separated out with flocculent deposit form, filter after sediment, with the unreacted metal ion of distilled water washing removal, dry in vacuum drying chamber, grind, obtain buff powder, be rare earth compounding.
2, the preparation of master batch
(1) by 2.0kg rare earth compounding, 0.25kg diatomite, composite being placed in mixer, adds 0.09kg Aluminate, and at rotating speed 250r/min, temperature is under 102 ± 1 DEG C of conditions, to be coated to disperse to become raw material I after 15min;
(2) 1.5kg tourmaline powder being placed in to high-speed kneading machine, is 500r/min at rotating speed, and temperature is to mediate after 10min under 105 ± 1 DEG C of conditions, is placed in high-speed kneading machine and mediates after 10min, adds 0.13kg odium stearate, after interface modification 20min, becomes raw material II;
(3) raw material II and raw material I are placed in to mixer and are mixed into compound, then add 6.03kg linear low density polyethylene (LLDPE) mixing 10min to obtain mixed material;
(4) mixed material is placed in to double screw extruder, mixed material is placed in to double screw extruder, control extruder barrel temperature: 135 DEG C, I district, 150 DEG C, II district, 155 DEG C, III district, 160 DEG C, IV district, 155 DEG C, V district, 155 DEG C of die heads, extrude pelletizing and be master batch.
Embodiment 3
The component of master batch is by linear low density polyethylene (LLDPE) 6.04kg, tourmaline powder 1.3kg, rare earth compounding 2.2kg, diatomite 0.25kg, Aluminate 0.09kg, odium stearate 0.12kg composition.
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 methyl alcohol; solution is no longer sticky; add acetic anhydride 1L, at 30 DEG C of temperature, react after 1h, the thick liquid of reaction gained is joined in 150 ethanol; there is precipitation to generate; leach solid, use 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 lanthanum nitrate that 2.90:0.50:1.25:1.00 takes respectively total amount 2kg, yttrium nitrate, neodymium nitrate, cerous nitrate, be dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly dropped to acetylation chitin solution, control rotating speed 1000r/min, 25 DEG C of temperature, react 6 hours, pH value of solution is adjusted to 7.0, product is separated out with flocculent deposit form, filter after sediment, with the unreacted metal ion of distilled water washing removal, dry in vacuum drying chamber, grind, obtain buff powder, be rare earth compounding.
2, the preparation of master batch
(1) by 2.2kg rare earth compounding, 0.25kg diatomite, composite being placed in mixer, adds 0.09kg Aluminate, and at rotating speed 250r/min, temperature is under 102 ± 1 DEG C of conditions, to be coated to disperse to become raw material I after 15min;
(2) 1.3kg tourmaline powder being placed in to high-speed kneading machine, is 500r/min at rotating speed, and temperature is to mediate after 10min under 105 ± 1 DEG C of conditions, is placed in high-speed kneading machine and mediates after 10min, adds 0.12kg odium stearate, after interface modification 20min, becomes raw material II;
(3) raw material II and raw material I are placed in to mixer and are mixed into compound, then add 6.04kg linear low density polyethylene (LLDPE) mixing 10min to obtain mixed material;
(4) mixed material is placed in to double screw extruder, mixed material is placed in to double screw extruder, control extruder barrel temperature: 130 DEG C, I district, 145 DEG C, II district, 155 DEG C, III district, 160 DEG C, IV district, 160 DEG C, V district, 155 DEG C of die heads, extrude pelletizing and be master batch.
Embodiment 4
The component of master batch is by linear low density polyethylene (LLDPE) 5.89kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, diatomite 0.30kg, Aluminate 0.10kg, odium stearate 0.11kg composition.
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 methyl alcohol; solution is no longer sticky; add acetic anhydride 1L, at 30 DEG C of temperature, react after 1h, the thick liquid of reaction gained is joined in 150 ethanol; there is precipitation to generate; leach solid, use 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 lanthanum nitrate that 2.85:0.55:1.25:0.95 takes respectively total amount 2kg, yttrium nitrate, neodymium nitrate, cerous nitrate, be dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly dropped to acetylation chitin solution, control rotating speed 1000r/min, 25 DEG C of temperature, react 6 hours, pH value of solution is adjusted to 7.0, product is separated out with flocculent deposit form, filter after sediment, with the unreacted metal ion of distilled water washing removal, dry in vacuum drying chamber, grind, obtain buff powder, be rare earth compounding.
2, the preparation of master batch
(1) by 2.4kg rare earth compounding, 0.30kg diatomite, composite being placed in mixer, adds 0.10kg Aluminate, and at rotating speed 250r/min, temperature is under 102 ± 1 DEG C of conditions, to be coated to disperse to become raw material I after 15min;
(2) 1.2kg tourmaline powder being placed in to high-speed kneading machine, is 500r/min at rotating speed, and temperature is to mediate after 10min under 105 ± 1 DEG C of conditions, is placed in high-speed kneading machine and mediates after 10min, adds 0.11kg odium stearate, after interface modification 20min, becomes raw material II;
(3) raw material II and raw material I are placed in to mixer and are mixed into compound, then add 5.89kg linear low density polyethylene (LLDPE) mixing 10min to obtain mixed material;
(4) mixed material is placed in to double screw extruder, mixed material is placed in to double screw extruder, control extruder barrel temperature: 132 DEG C, I district, 150 DEG C, II district, 155 DEG C, III district, 161 DEG C, IV district, 158 DEG C, V district, 160 DEG C of die heads, extrude pelletizing and be master batch.
Embodiment 5
The component of master batch is by linear low density polyethylene (LLDPE) 6.03kg, tourmaline powder 1.5kg, rare earth compounding 2.0kg, diatomite 0.25kg, Aluminate 0.09kg, odium stearate 0.13kg composition.
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 methyl alcohol; solution is no longer sticky; add acetic anhydride 1L, at 30 DEG C of temperature, react after 1h, the thick liquid of reaction gained is joined in 150 ethanol; there is precipitation to generate; leach solid, use 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 lanthanum nitrate that 2.85:0.55:1.25:0.95 takes respectively total amount 2kg, yttrium nitrate, neodymium nitrate, cerous nitrate, be dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly dropped to acetylation chitin solution, control rotating speed 1000r/min, 25 DEG C of temperature, react 6 hours, pH value of solution is adjusted to 7.0, product is separated out with flocculent deposit form, filter after sediment, with the unreacted metal ion of distilled water washing removal, dry in vacuum drying chamber, grind, obtain buff powder, be rare earth compounding.
2, the preparation of master batch
(1) by 2.0kg rare earth compounding, 0.25kg diatomite, composite being placed in mixer, adds 0.09kg Aluminate, and at rotating speed 250r/min, temperature is under 102 ± 1 DEG C of conditions, to be coated to disperse to become raw material I after 15min;
(2) 1.5kg tourmaline powder being placed in to high-speed kneading machine, is 500r/min at rotating speed, and temperature is to mediate after 10min under 105 ± 1 DEG C of conditions, is placed in high-speed kneading machine and mediates after 10min, adds 0.13kg odium stearate, after interface modification 20min, becomes raw material II;
(3) raw material II and raw material I are placed in to mixer and are mixed into compound, then add 6.03kg linear low density polyethylene (LLDPE) mixing 10min to obtain mixed material;
(4) mixed material is placed in to double screw extruder, mixed material is placed in to double screw extruder, control extruder barrel temperature: 135 DEG C, I district, 150 DEG C, II district, 155 DEG C, III district, 160 DEG C, IV district, 155 DEG C, V district, 155 DEG C of die heads, extrude pelletizing and be master batch.
Embodiment 6
The component of master batch is by linear low density polyethylene (LLDPE) 6.04kg, tourmaline powder 1.3kg, rare earth compounding 2.2kg, diatomite 0.25kg, Aluminate 0.09kg, odium stearate 0.12kg composition.
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 methyl alcohol; solution is no longer sticky; add acetic anhydride 1L, at 30 DEG C of temperature, react after 1h, the thick liquid of reaction gained is joined in 150 ethanol; there is precipitation to generate; leach solid, use 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 lanthanum nitrate that 2.85:0.55:1.25:0.95 takes respectively total amount 2kg, yttrium nitrate, neodymium nitrate, cerous nitrate, be dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly dropped to acetylation chitin solution, control rotating speed 1000r/min, 25 DEG C of temperature, react 6 hours, pH value of solution is adjusted to 7.0, product is separated out with flocculent deposit form, filter after sediment, with the unreacted metal ion of distilled water washing removal, dry in vacuum drying chamber, grind, obtain buff powder, be rare earth compounding.
2, the preparation of master batch
(1) by 2.2kg rare earth compounding, 0.25kg diatomite, composite being placed in mixer, adds 0.09kg Aluminate, and at rotating speed 250r/min, temperature is under 102 ± 1 DEG C of conditions, to be coated to disperse to become raw material I after 15min;
(2) 1.3kg tourmaline powder being placed in to high-speed kneading machine, is 500r/min at rotating speed, and temperature is to mediate after 10min under 105 ± 1 DEG C of conditions, is placed in high-speed kneading machine and mediates after 10min, adds 0.12kg odium stearate, after interface modification 20min, becomes raw material II;
(3) raw material II and raw material I are placed in to mixer and are mixed into compound, then add 6.04kg linear low density polyethylene (LLDPE) mixing 10min to obtain mixed material;
(4) mixed material is placed in to double screw extruder, mixed material is placed in to double screw extruder, control extruder barrel temperature: 130 DEG C, I district, 145 DEG C, II district, 155 DEG C, III district, 160 DEG C, IV district, 160 DEG C, V district, 155 DEG C of die heads, extrude pelletizing and be master batch.
Claims (9)
1. a preparation method who contains the flat mushroom preservative film master batch of rare earth compounding, is characterized in that:
The preparation of rare earth compounding:
(1) plant polyose of 2 weight portions is dissolved in the acetic acid solution of 60 weight portions, after stirring, add the methyl alcohol of 80 weight portions, solution is no longer sticky, add the acetic anhydride of 1 weight portion, at 30 DEG C of temperature, react after 1h, the thick liquid of reaction gained is joined in the ethanol of 150 weight portions, filtering precipitate after precipitation generates, with absolute ethanol washing 3 times, after dissolving with acetic acid solution, elimination insoluble matter, obtains acetylation plant polyose solution again;
(2) ratio that is 2.85～2.95:0.50～0.60:1.05～1.25:0.95～1.05 according to the mol ratio of lanthanum, yttrium, neodymium, cerium ion, take respectively the compound of lanthanum, compound, the compound of neodymium and the compound of cerium of yttrium becomes rare earth compound, and join in distilled water with the weight part ratio of 1 ﹕ 5, after dissolving completely, obtain rare earth compound mixed aqueous solution; According to the weight ratio such as plant polyose and rare earth compound, rare earth compound mixed aqueous solution is slowly dropped in acetylation plant polyose solution, regulate reaction system pH to 7.0, under rotating speed 1000r/min, 25～30 DEG C of conditions of temperature, react 6～7 hours, product is separated out with precipitation form; Filter after sediment, remove unreacted rare earth ion with distilled water washing, dry in vacuum drying chamber, grind into powder, obtains rare earth compounding;
The preparation of master batch:
(1) by the rare earth compounding of 18～24 weight portions, the diatomite of 2～3 weight portions, composite being placed in mixer, adds 0.8～1.0 weight portion Aluminate, and obtain raw material I after 15min coated dispersion;
(2) 12～15 weight portion tourmaline powders are placed in to high-speed kneading machine and mediate after 10min, then add 1.1～1.3 weight portion odium stearate, carry out becoming raw material II after interface modification 20min;
(3) raw material II and raw material I are placed in to mixer and are mixed into compound, then add the LLDPE mixing 10min of 55.7～64.8 weight portions to obtain mixed material;
(4) mixed material being placed in to double screw extruder extrudes pelletizing and is master batch.
2. the preparation method of a kind of flat mushroom preservative film master batch containing rare earth compounding according to claim 1, is characterized in that described tourmaline powder 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 μ m.
3. the preparation method of a kind of flat mushroom preservative 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 flat mushroom preservative film master batch containing rare earth compounding according to claim 1, is characterized in that described plant polyose is the mixture of one or more arbitrary proportions in starch, fructose, cellulose, chitin.
5. the preparation method of a kind of flat mushroom preservative film master batch containing rare earth compounding according to claim 1, is characterized in that the compound of described lanthanum is the one in lanthanum hydroxide, lanthanum acetate, lanthanum nitrate, lanthanum chloride; The compound of described yttrium is the one in yttrium hydroxide, acetic acid yttrium, yttrium nitrate, yttrium chloride; The compound of described samarium is the one in samaric hydroxide, acetic acid samarium, samaric nitrate, samarium trichloride; The compound of described cerium is the one in cerium hydroxide, cerous acetate, cerous nitrate, cerium chloride.
6. the preparation method of a kind of flat mushroom preservative film master batch containing rare earth compounding according to claim 1, is characterized in that the rotating speed of mixer in described coated dispersion process is 250r/min, and temperature is 102 ± 1 DEG C.
7. the preparation method of a kind of flat mushroom preservative film master batch containing rare earth compounding according to claim 1, is characterized in that the rotating speed of described interface modification process high speed kneader is 500r/min, and temperature is 105 ± 1 DEG C.
8. the preparation method of a kind of flat mushroom preservative film master batch containing rare earth compounding according to claim 1, is characterized in that the rotating speed of mixer in described mixing of materials process is 120r/min, and temperature is 108 ± 1 DEG C.
9. the preparation method of a kind of flat mushroom preservative film master batch containing rare earth compounding according to claim 1, is characterized in that the described double screw extruder barrel temperature in pelletizing process of extruding is controlled at 130～140 DEG C, I district, 145～150 DEG C, II district, 150～155 DEG C, III district, 160～165 DEG C, IV district, 155～160 DEG C, V district, 155～160 DEG C of die heads.
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