CN105801994B - A kind of preparation method of the grape fresh-keeping film master batch containing rare earth compounding - Google Patents

A kind of preparation method of the grape fresh-keeping film master batch containing rare earth compounding Download PDF

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CN105801994B
CN105801994B CN201610176113.6A CN201610176113A CN105801994B CN 105801994 B CN105801994 B CN 105801994B CN 201610176113 A CN201610176113 A CN 201610176113A CN 105801994 B CN105801994 B CN 105801994B
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rare earth
master batch
preparation
earth compounding
compound
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CN105801994A (en
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游瑞云
杨裕金
卢圣钊
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Quangang Petrochemical Research Institute of Fujian Normal University
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Quangang Petrochemical Research Institute of Fujian Normal University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised 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
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised 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
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films

Abstract

The present invention relates to a kind of preparation method of the grape fresh-keeping film master batch containing rare earth compounding, it is using LLDPE as vector resin, and addition tourmaline powder, rare earth compounding, diatomite, oleamide, odium stearate are mixed by coating scattered, interface modification, material, extrusion pelletizing is process.Lanthanum, yttrium, samarium, the mol ratio of cerium ion are 2.90~3.00 in rare earth compounding feature:0.45~0.50:0.95~1.05:1.15~1.25.Master batch prepared by this method, is added in LLDPE resins with 4~8% ratio, after film is made in blowing, packed for grape fresh-keeping, respiratory intensity and surface microorganism growth in storage can be suppressed, slow down softening process, normal temperature condition can prolong storage period 7~10 days.

Description

A kind of preparation method of the grape fresh-keeping film master batch containing rare earth compounding
Technical field
The present invention relates to the preparation method of functional plastic film master batch, and in particular to a kind of grape containing rare earth compounding The preparation method of fresh-keeping film master batch.
Background technology
Grape(Vitis vinifera L.)Vitaceae Vitis bejuco, grape be four big fruit of China it One, grape is not only delicious and tasty, and nutritive value is very high.Grape sugar content is up to 10%~30% in ripe berry, with Portugal Based on grape sugar.A variety of tartaric acid in grape help to digest, appropriate to eat a little grapes more, can strengthening the spleen and stomach.Contain mineral in grape Matter calcium, potassium, phosphorus, iron and multivitamin B1, vitamin B2, vitamin B6, vitamin C and citrin etc., also containing a variety of The amino acid of needed by human body, often feeding grape are of great advantage to neurasthenia, excessive fatigue.Grape is most intolerant to storage in berries One of fruit of Tibetan, grape harvest easy dehydration, threshing under rearmounted normal temperature, rotted.The respiration consumption nutrition of grape, Cause fruit-vegetable quality decline, failure, weight saving, dehydration and aging.The breathing of grape fruit belongs to non-transition type, and Portugal Grape carpopodium is the most active part of physiological activity in fruit ear, does not only belong to type of respiratory climacteric, and respiratory intensity is fruit 8 ~14 times.This is grape carpopodium in storage main physiological apt to deteriorate.Grape is in storage period moisture loss Predominantly evaporation, dehydration 3%~6% can obviously reduce fruit-vegetable quality, its surface shrinkage, gloss is disappeared, cell spaces Increase, organize to become spongy, normal respiration is affected, promote the activity of enzyme, accelerate tissue aging significantly Weaken fruits and vegetables intrinsic storability and premunition.In addition fungi easily causes grape to rot.Therefore grape fresh-keeping storage It is particularly significant.
China's rare earth resources enrich, and rare earth utilization have great potential.Rare earth and its derivative can be used as antibacterial to protect Fresh dose, Ca2+It is the ion for maintaining bacterium normal activity, and lanthanum ion has antagonism Ca2+Effect, so lanthanum ion can be to thin Bacterium normal activities interfere, and cause bacterial death, while 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 displacement and competition of the cerium ion to metal ion in enzyme are so as to have impact on the physiological function of enzyme, therefore can pass through shadow Enzymatic activity is rung to suppress respiration, delaying senility.Rare earth has the ability of stronger removing hydroxyl radical free radical, reduces free radical Occur, weaken active oxygen injury, delayed fruit ripening and senescence, extend grape shelf life.Tourmaline is also that China provides rich in mineral products Source, tourmaline powder release anion can effectively kill germ.Its mechanism is essentially consisted in after anion combined with bacterium, produces bacterium The change of raw structure or the transfer of energy, cause bacterial death.Plant polyose is abundant renewable resource, itself is had certain Antibacterial effect, the plant polyose of acetylation have the ability of stronger removing hydroxyl radical free radical.
At present, the main controlled atmosphere storage of Grape Fresh Keeping Technology, pressure regulation be fresh-keeping, electronic fresh-keeping technology, biological way of keeping fresh, Cold storing and fresh-keeping, fresh chemically etc..Though physical method is nontoxic and relatively more effective, cost is higher, needs specific appointed condition, uncomfortable Close commonly used;And antistaling agent is made using chemicals, the problems such as further relating to the residual hazard of some medicines.
The content of the invention
For the deficiency of existing grape fresh-keeping packaging.The invention provides a kind of good lower-cost master batch of anti-bacterial refreshing Preparation method, it is characterized in that:Using LLDPE as vector resin, addition tourmaline powder, rare earth compounding, diatomite, oleamide, Odium stearate is mixed by coating scattered, interface modification, material, extrusion pelletizing is process.Master batch prepared by this method, with 4 ~8% ratio is added in LLDPE resins, after film is made in blowing, packs, can suppress in storage for grape fresh-keeping Respiratory intensity and surface microorganism growth, normal temperature condition prolong storage period 7~10 days.
For realize the purpose of the present invention use technical scheme be:
1st, the preparation of rare earth compounding
(1)The plant polyose of 2 parts by weight is dissolved in the acetic acid solution of 60 parts by weight, after stirring, adds 80 weight Part methanol, solution is no longer sticky, adds the acetic anhydride of 1 parts by weight, after reacting 1 h at 30 DEG C of temperature, will react gained Thick liquid is added in the ethanol of 150 parts by weight, filtering precipitate after precipitation generation, is washed 3 times with absolute ethyl alcohol, then use second After acid solution dissolving, insoluble matter is filtered off, obtains acetylation plant polyose solution.
(2)Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 2.90~3.00:0.45~0.50:0.95~1.05: 1.15~1.2 5 ratio, the compound for weighing the compound of lanthanum, the compound of yttrium, the compound of neodymium and cerium respectively are mixed into Rare earth compound, and being added in distilled water with 1 ﹕ 5 weight part ratio, it is entirely capable of obtaining rare earth compound mixing after dissolving water-soluble Liquid;According to the weight ratio such as plant polyose and rare earth compound, rare earth compound mixed aqueous solution is slowly added dropwise to acetylation and planted In thing polysaccharide solution, reaction system pH to 7.0 is adjusted, it is small that 6~7 are reacted under the conditions of rotating speed 1000r/min, 25~30 DEG C of temperature When, product is separated out with precipitation form;Filter after sediment, remove unreacted rare earth ion with distillation water washing, Dried in vacuum drying chamber, grind into powder, obtain rare earth compounding.
2nd, the preparation of master batch
(1)By the rare earth compounding of 21~25 parts by weight, the diatomite of 2~3 parts by weight, it is placed in mixer after compounding, 1.1~1.3 parts by weight oleamides are added, raw material I is obtained after coating scattered 15min;
(2)12~14 parts by weight of tourmaline powder are placed in high-speed kneading machine after mediating 10min, add 1.1~1.3 weights Part odium stearate is measured, is 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, adds 55.7~63.1 parts by weight LLDPE mixing 10min obtains mixed material;
(4)It is master batch that mixed material, which is placed in double screw extruder, and extrudes pelletizing.Using blow molding machine using normal Process conditions are advised, a kind of grape fresh-keeping film containing rare earth compounding is further prepared.
The grape fresh-keeping film containing rare earth compounding that the present invention is prepared is widely used commonly fresh-keeping with the market The grape rotting rate, soluble solid and grape hardness of storage are compared under the conditions of 20 DEG C of film, the results showed that, using this The grape fresh-keeping film of the rare earth compounding prepared is invented in storage, the rotting rate of grape has in difference in first 8 days but is not Clearly, the 10th day when, use common preservative film rotting rate as 91.2%, and use it is of the present invention containing rare earth coordinate The grape fresh-keeping film of thing, the rotting rate of grape is only 28.7%;Soluble solid and grape hardness, it is significantly higher than common fresh-keeping Film.
Tourmaline powder of the present invention is in dravite powder, schorl powder, elbaite powder, tsilaisite powder One or more of arbitrary proportions mixture;Described tourmaline powder particle diameter is 1.3~6.5 μm.
Acetic acid solution mass percent concentration of the present invention is 2%.
Plant polyose of the present invention is starch, fructose, cellulose, one or more of arbitrary proportions in 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.
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. the tourmaline powder used, rare earth, natural plant polyose aboundresources, can be effective Reduce cost;2. the tourmaline powder used, rare earth, natural plant polyose are harmless, obtained material safety, use can be trusted Packed in fresh food;3. the tourmaline powder used, rare earth, natural plant polyose have sterilizing fresh-keeping function in itself, by changing The modes such as property, compounding can effectively strengthen anti-bacterial refreshing effect.
Brief description of the drawings
Fig. 1 is that the sample prepared by the embodiment of the present invention 1 packs 20 DEG C of grape rotting rates to storage with common preservative film Influence.
Fig. 2 is that the sample prepared by the embodiment of the present invention 1 packs 20 DEG C of grapes solubilities to storage with common preservative film The influence of solid content.
Fig. 3 is that the sample prepared by the embodiment of the present invention 1 is packed at 20 DEG C to the grape hardness of storage with common preservative film Influence.
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 grape fresh-keeping of the present invention containing rare earth compounding respectively Film stores the rotting rate of 10 days processes.It can be seen that using the grape fresh-keeping of the present invention containing rare earth compounding When film was stored to the 3rd day, grape rotting rate is only 3.25%, is stored by the 10th day, rotting rate is also only 28.7, and uses common When preservative film was stored to the 3rd day, grape rotting rate is 5.25%, is stored by the 10th day, rotting rate is up to 89.7.As shown in Figure 1.
In Fig. 2, two curves represent common preservative film and the grape fresh-keeping of the present invention containing rare earth compounding respectively The soluble solid content of grape fruit during film is stored 10 days.It can be seen that with the extension of storage time, Using the grape fresh-keeping film fruit hardness of the present invention containing rare earth compounding compared to the uva that common preservative film is packed Grain, remains in that higher content.As shown in Figure 2.
In Fig. 3, two curves represent common preservative film and the grape fresh-keeping of the present invention containing rare earth compounding respectively Film stores 25 days process grape hardness.It can be seen that although with the extension of time, the hardness of grape also progressively drops It is low, but the speed reduced is less than common preservative film.As shown in Figure 3.
Embodiment 1
The component of master batch is by linear low density polyethylene (LLDPE) 5.94kg, tourmaline powder 1.4kg, rare earth compounding 2.2kg, diatom Native 0.25kg, oleamide 0.11kg, odium stearate 0.10kg compositions.
Master batch is prepared according to the following steps:
1st, the preparation of rare earth compounding
(1)2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150 ethanol, there is precipitation Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell Sugar juice.
(2)Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 2.95:0.50:0.95:1.10 weigh total amount 2kg's respectively Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, 10L distilled water is dissolved in, rare earth nitrate aqueous solution is slowly added dropwise to acetylation Chitin solution, the r/min of rotating speed 1000 is controlled, 25 DEG C of temperature, reacts 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped Precipitation form separates out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber It is dry, grinding, obtain buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1)By 2.2kg rare earth compoundings, 0.25kg diatomite, it is placed in after compounding in mixer, adds 0.14kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I;
(2)1.4kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 0.10kg odium stearate, interface modification 20min Afterwards into raw material II;
(3)Raw material II and raw material I are placed in mixer and are mixed into compound, adds the poly- second of 5.94kg linear, low densities Alkene mixing 10min obtains mixed material;
(4)Mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, Control extruder barrel temperature:132 DEG C of I areas, 150 DEG C of II areas, 155 DEG C of III areas, 161 DEG C of IV areas, 158 DEG C of V areas, die head 160 DEG C, extrusion pelletizing is master batch.
Embodiment 2
The component of master batch is by linear low density polyethylene (LLDPE) 5.69kg, tourmaline powder 1.3kg, rare earth compounding 2.5kg, diatom Native 0.30kg, oleamide 0.12kg, odium stearate 0.09kg compositions.
Master batch is prepared according to the following steps:
1st, the preparation of rare earth compounding
(1)2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150 ethanol, there is precipitation Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell Sugar juice.
(2)Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 2.95:0.50:0.95:1.10 weigh total amount 2kg's respectively Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, 10L distilled water is dissolved in, rare earth nitrate aqueous solution is slowly added dropwise to acetylation Chitin solution, the r/min of rotating speed 1000 is controlled, 25 DEG C of temperature, reacts 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped Precipitation form separates out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber It is dry, grinding, obtain buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1)By 2.5kg rare earth compoundings, 0.30kg diatomite, it is placed in after compounding in mixer, adds 0.12kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I;
(2)1.3kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 0.09kg odium stearate, interface modification 20min Afterwards into raw material II;
(3)Raw material II and raw material I are placed in mixer and are mixed into compound, adds the poly- second of 5.69kg 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) 5.89kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, diatom Native 0.30kg, oleamide 0.11kg, odium stearate 0.10kg compositions.
Master batch is prepared according to the following steps:
1st, the preparation of rare earth compounding
(1)2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150 ethanol, there is precipitation Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell Sugar juice.
(2)Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 2.95:0.50:0.95:1.10 weigh total amount 2kg's respectively Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, 10L distilled water is dissolved in, rare earth nitrate aqueous solution is slowly added dropwise to acetylation Chitin solution, the r/min of rotating speed 1000 is controlled, 25 DEG C of temperature, reacts 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped Precipitation form separates out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber It is dry, grinding, obtain buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1)By 2.4kg rare earth compoundings, 0.30kg diatomite, it is placed in after compounding in mixer, adds 0.14kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I;
(2)1.2kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 0.10kg odium stearate, interface modification 20min Afterwards into raw material II;
(3)Raw material II and raw material I are placed in mixer and are mixed into compound, adds the poly- second of 5.89kg 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) 5.94kg, tourmaline powder 1.4kg, rare earth compounding 2.2kg, diatom Native 0.25kg, oleamide 0.11kg, odium stearate 0.10kg compositions.
Master batch is prepared according to the following steps:
1st, the preparation of rare earth compounding
(1)2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150 ethanol, there is precipitation Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell Sugar juice.
(2)Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.00:0.45:1.00:1.25 weigh total amount 2kg's respectively Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, 10L distilled water is dissolved in, rare earth nitrate aqueous solution is slowly added dropwise to acetylation Chitin solution, the r/min of rotating speed 1000 is controlled, 25 DEG C of temperature, reacts 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped Precipitation form separates out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber It is dry, grinding, obtain buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1)By 2.2kg rare earth compoundings, 0.25kg diatomite, it is placed in after compounding in mixer, adds 0.14kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I;
(2)1.4kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 0.10kg odium stearate, interface modification 20min Afterwards into raw material II;
(3)Raw material II and raw material I are placed in mixer and are mixed into compound, adds the poly- second of 5.94kg 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) 5.69kg, tourmaline powder 1.3kg, rare earth compounding 2.5kg, diatom Native 0.30kg, oleamide 0.12kg, odium stearate 0.09kg compositions.
Master batch is prepared according to the following steps:
1st, the preparation of rare earth compounding
(1)2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150 ethanol, there is precipitation Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell Sugar juice.
(2)Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.00:0.45:1.00:1.25 weigh total amount 2kg's respectively Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, 10L distilled water is dissolved in, rare earth nitrate aqueous solution is slowly added dropwise to acetylation Chitin solution, the r/min of rotating speed 1000 is controlled, 25 DEG C of temperature, reacts 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped Precipitation form separates out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber It is dry, grinding, obtain buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1)By 2.5kg rare earth compoundings, 0.30kg diatomite, it is placed in after compounding in mixer, adds 0.12kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I;
(2)1.3kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 0.09kg odium stearate, interface modification 20min Afterwards into raw material II;
(3)Raw material II and raw material I are placed in mixer and are mixed into compound, adds the poly- second of 5.69kg 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) 5.89kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, diatom Native 0.30kg, oleamide 0.11kg, odium stearate 0.10kg compositions.
Master batch is prepared according to the following steps:
1st, the preparation of rare earth compounding
(1)2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, after reacting 1h at 30 DEG C of temperature, the thick liquid that will react gained is added in 150 ethanol, there is precipitation Generation, filters out solid, wash 3 times with absolute ethyl alcohol, then after being dissolved with acetic acid solution, elimination insoluble matter, it is more to obtain acetylation shell Sugar juice.
(2)Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.00:0.45:1.00:1.25 weigh total amount 2kg's respectively Lanthanum nitrate, yttrium nitrate, neodymium nitrate, cerous nitrate, 10L distilled water is dissolved in, rare earth nitrate aqueous solution is slowly added dropwise to acetylation Chitin solution, the r/min of rotating speed 1000 is controlled, 25 DEG C of temperature, reacts 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped Precipitation form separates out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber It is dry, grinding, obtain buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1)By 2.4kg rare earth compoundings, 0.30kg diatomite, it is placed in after compounding in mixer, adds 0.14kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is carried out coating after scattered 15min under the conditions of being 102 ± 1 DEG C into raw material I;
(2)1.2kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars After mediating 10min under part, it is placed in high-speed kneading machine after mediating 10min, adds 0.10kg odium stearate, interface modification 20min Afterwards into raw material II;
(3)Raw material II and raw material I are placed in mixer and are mixed into compound, adds the poly- second of 5.89kg 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 grape fresh-keeping film master batch containing rare earth compounding, it is characterized in that:
The preparation of rare earth compounding:
(1)The plant polyose of 2 parts by weight is dissolved in the acetic acid solution of 60 parts by weight, after stirring, adds 80 parts by weight Methanol, solution is no longer sticky, adds the acetic anhydride of 1 parts by weight, after reacting 1 h at 30 DEG C of temperature, will react the sticky of gained Liquid is added in the ethanol of 150 parts by weight, filtering precipitate after precipitation generation, is washed 3 times with absolute ethyl alcohol, then molten with acetic acid After liquid dissolving, insoluble matter is filtered off, obtains acetylation plant polyose solution;
(2)Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 2.90~3.00:0.45~0.50:0.95~1.05: 1.15 ~1.2 5 ratio, the compound for weighing the compound of lanthanum, the compound of yttrium, the compound of neodymium and cerium respectively are 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 the weight ratio such as plant polyose and rare earth compound, rare earth compound mixed aqueous solution is slowly added dropwise more to acetylation plant In sugar juice, 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 separated out with precipitation form;Filter after sediment, unreacted rare earth ion is removed with distillation water washing, in vacuum Dried in drying box, grind into powder, obtain rare earth compounding;
The preparation of master batch:
(1)By the rare earth compounding of 21~25 parts by weight, the diatomite of 2~3 parts by weight, it is placed in mixer after compounding, adds 1.1~1.3 parts by weight oleamides, raw material I is obtained after coating scattered 15min;
(2)12~14 parts by weight of tourmaline powder are placed in high-speed kneading machine after mediating 10min, add 1.1~1.3 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, adds the LLDPE of 55.7~63.1 parts by weight Mixing 10min obtains mixed material;
(4)It is master batch that mixed material, which is placed in double screw extruder, and extrudes pelletizing.
2. a kind of preparation method of grape 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 appointed The mixture of meaning ratio;Described tourmaline powder particle diameter is 1.3~6.5 μm.
3. a kind of preparation method of grape 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 grape fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that Described plant polyose is the mixture of starch, fructose, cellulose, one or more of arbitrary proportions in chitin.
5. a kind of preparation method of grape 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 grape 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 grape 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 grape fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that Described mixed material, the rotating speed of mixer is 120r/min in mixed process, and temperature is 108 ± 1 DEG C.
9. a kind of preparation method of grape 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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