CN105602090B - A kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding - Google Patents

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

Info

Publication number
CN105602090B
CN105602090B CN201610177150.9A CN201610177150A CN105602090B CN 105602090 B CN105602090 B CN 105602090B CN 201610177150 A CN201610177150 A CN 201610177150A CN 105602090 B CN105602090 B CN 105602090B
Authority
CN
China
Prior art keywords
rare earth
master batch
preparation
earth compounding
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610177150.9A
Other languages
Chinese (zh)
Other versions
CN105602090A (en
Inventor
卢玉栋
苏梁妹
吴长机
余仙珠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Normal University
Original Assignee
Fujian Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujian Normal University filed Critical Fujian Normal University
Priority to CN201610177150.9A priority Critical patent/CN105602090B/en
Publication of CN105602090A publication Critical patent/CN105602090A/en
Application granted granted Critical
Publication of CN105602090B publication Critical patent/CN105602090B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • 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
    • 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
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to the preparation method of functional plastic film master batch, and in particular to a kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding.It is that, using LLDPE as vector resin, addition tourmaline powder, rare earth compounding, diatomite, oleamide, odium stearate are by the way that cladding is scattered, interface modification, material are mixed, extrusion pelletizing is processed.Lanthanum, yttrium, samarium, the mol ratio of cerium ion are (3.00≤w≤3.05) in rare earth compounding feature:(0.40≤x≤0.45):(1.15≤y≤1.25):(0.95≤z≤1.05).Master batch prepared by this method, is added in LLDPE resins with 6~8% ratio, and blowing is made after film, for lichee fresh-keeping packaging, can suppress respiratory intensity and surface microorganism growth in storage, and normal temperature condition can prolong storage period 5~7 days.

Description

A kind of preparation method of the lichee 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 lichee containing rare earth compounding The preparation method of fresh-keeping film master batch.
Background technology
Lichee (Litchi chinensis Sonn.) also known as separated branch, Sapindaceae lichee platymiscium is subtropical fruit, For special product of China renowned in the world.It is bright-colored, unique flavor, nutritious, is the top grade in the fruit of the south of the Five Ridges.But lichee The property of " discoloration on the one, two fragrant to become, and taste became on 3rd " can make its freshness decline quickly, attraction to consumer and edible Value is also decreased.China is the most country of current cultivation lichee, according to statistics, lichee every year because rot and caused by Loss accounts for more than the 20% of total output.Lichee is as other fruit, because nutritious, sugariness is high and easily causes microorganism Infect.During litchi fruits postharvest storage, cell leakage increase, the change of membrane structure is one constantly destroyed Process, accumulation causes cell membrane system peroxidating relevant with free radical for this.Its vigorous respiration consumes substantial amounts of include Material, and promote the aging of fruit.PPO and POD are the important enzymes for participating in denaturation process, and take part in phenols and Vitamin C The oxidation of acid.These reasons make lichee turn into the world most intolerant to one of fruit of Tibetan, after adopting easily brown stain, rot, serious shadow The storing and sale of this fruit are rung.
China's rare earth resources enrich, and rare earth, which is developed, has great potential.Rare earth and its derivative can be protected as antibacterial Fresh dose, Ca2+It is the ion for maintaining bacterium normal activity, and lanthanum ion has antagonism Ca2+Effect, so lanthanum ion can be to thin Bacterium normal activities are interfered, and cause bacterial death, while part enhances anti-microbial property in Rare Earth Lanthanum coordination antiseptic. Cerium ion has hydrolysis, can be broken polypeptide chain, and enzyme is protein, so cerium ion makes the polypeptide chain in enzyme break Split；In addition cerium ion presses down to the displacement of metal ion in enzyme with competition so as to have impact on the physiological function of enzyme, therefore can pass through PPO, POD enzymatic activity processed slows down Tissue Browning and nutrient metabolism；Relevant enzyme can also be influenceed to suppress respiratory intensity.It is dilute Ability of the soil with stronger removing hydroxyl radical free radical, reduces free radical, weakens active oxygen injury, delayed fruit after-ripening declines Always, lichee shelf life is extended.Tourmaline is also China rich in mineral resources, and tourmaline powder release anion can effectively kill disease Bacterium.Its mechanism is essentially consisted in after anion combined with bacterium, bacterium is produced the change of structure or the transfer of energy, is caused bacterium It is dead.Plant polyose is abundant renewable resource, itself has certain antibacterial effect, the plant polyose of acetylation is with stronger Removing hydroxyl radical free radical ability.
At present, the main preservation by low temperature of litchi preserving technology, quick-freezing fresh-keeping, controlled atmosphere storage, Edible cornstarch film are fresh-keeping, smelly Oxygen is fresh-keeping, Irradiation preservation fresh-keeping method, fresh chemically etc..Though physical method is nontoxic and relatively more effective, cost is higher, needs specific Appointed condition, is not suitable for commonly used；And antistaling agent is made using chemicals, the problems such as further relating to the residual hazard of some medicines.State Inside and outside many R＆D institutions and institution of higher learning are all numerous and confused to be carried out to lichee Physiological qualities of post-harvest tomato changing rule and storage technique Research, and have made some progress, but these researchs focus mostly in terms of low-temperature preservation, quick refrigeration storage and air-conditioned cold store preservation, and it is right Fund, equipment and soil input require higher.
The content of the invention
It is not enough for existing lichee fresh-keeping.The invention provides a kind of preparation side of the good lower-cost master batch of anti-bacterial refreshing Method, it is characterized in that：With linear low density polyethylene (LLDPE) (LLDPE) for vector resin, addition tourmaline powder, rare earth compounding, diatom Soil, oleamide, odium stearate are by the way that cladding is scattered, interface modification, material are mixed, extrusion pelletizing is processed.Our legal system Standby master batch, is added in LLDPE resins with 6~8% ratio, and blowing is made after film, for lichee fresh-keeping packaging, can be pressed down Respiratory intensity and surface microorganism growth in storage processed, normal temperature condition prolong storage period 5~7 days.
For realize the purpose of the present invention use technical scheme be：
1st, the preparation of rare earth compounding
(1) plant polyose of 2 parts by weight is dissolved in the acetic acid solution of 60 parts by weight, after stirring, adds 80 weight Part methanol, solution is no longer sticky, adds the acetic anhydride of 1 parts by weight, in after reaction 1h at 30 DEG C of temperature, will be obtained by reaction it is glutinous Thick liquid is added in the ethanol of 150 parts by weight, filtering precipitate after precipitation generation, is washed with absolute ethyl alcohol 3 times, then use acetic acid After solution dissolving, insoluble matter is filtered off, acetylation plant polyose solution is obtained.
(2) it is 3.00~3.05 according to the mol ratio of lanthanum, yttrium, neodymium, cerium ion:0.40~0.45:1.15~1.25:0.95 ~1.05, the compound that compound, the compound of yttrium, the compound of neodymium and the cerium of lanthanum are weighed respectively is mixed into rare earth compound, And be added to 1 ﹕ 5 weight part ratio in distilled water, obtain rare earth compound mixed aqueous solution after being entirely capable of dissolving；According to plant The weight ratio such as polysaccharide and rare earth compound, rare earth compound mixed aqueous solution is slowly added dropwise to acetylation plant polyose solution In, adjust reaction system pH to 7.0, under the conditions of rotating speed 1000r/min, 25~30 DEG C of temperature react 6~7 hours, product with Precipitation form is separated out；Filter after sediment, unreacted rare earth ion is removed with distillation water washing, in vacuum drying chamber Middle drying, grinding, obtains powdered rare earth compounding.
2nd, the preparation of master batch
(1) by the rare earth compounding of 18~20 parts by weight, the diatomite of 2~2.5 parts by weight is placed in mixer after compounding In, 1.0~1.2 parts by weight oleamides are added, are that 250r/min, temperature are to carry out cladding point under the conditions of 102 ± 1 DEG C in rotating speed Dissipate, raw material I is obtained after 15min；
(2) 12~15 parts by weight of tourmaline powder are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 Mediated under the conditions of ± 1 DEG C after 10min, add 0.8~1.0 parts by weight odium stearate, carried out after interface modification 20min into raw material II；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 60.3~66.2 parts by weight LLDPE mixing 10min obtains mixed material；
(4) mixed material is placed in double screw extruder and extrudes pelletizing as master batch.Using blow molding machine using normal Process conditions are advised, a kind of lichee fresh-keeping film containing rare earth compounding is further prepared.
The lichee fresh-keeping film containing rare earth compounding that the present invention is prepared is widely used commonly fresh-keeping with the market The lichee ppo enzymatic activitys (unit/g FW) of storage are compared under the conditions of 20 DEG C of film, as a result shown, using present invention preparation Rare earth compounding lichee fresh-keeping film pass through 20 days when, enzymatic activity only reaches 9.85unit/g FW, and respiratory intensity is also only 0.47mlCO2/ g.h, and 15.02unit/g FW are up to using common preservative film enzymatic activity, respiratory intensity is up to 0.84mlCO2/g.h.Table 1 is the every fresh-keeping index delta data of lichee to storage under the conditions of 20 DEG C.
Table 1：
Tourmaline powder of the present invention is in dravite powder, schorl powder, elbaite powder, tsilaisite powder The mixture of one or more of arbitrary proportions；Described tourmaline powder particle diameter is 1.3~6.5 μm.
Acetic acid solution mass percent concentration of the present invention is 2%.
Plant polyose of the present invention is one or more of arbitrary proportions in starch, fructose, cellulose, chitin Mixture.
The compound of lanthanum of the present invention is one kind in lanthanum hydroxide, lanthanum acetate, lanthanum nitrate, lanthanum chloride.
The compound of yttrium of the present invention is one kind in yttrium hydroxide, acetic acid yttrium, yttrium nitrate, yttrium chloride.
The compound of samarium of the present invention is one kind in samaric hydroxide, acetic acid samarium, samaric nitrate, samarium trichloride.
The compound of cerium of the present invention is one kind in cerium hydroxide, cerous acetate, cerous nitrate, cerium chloride.
Rare earth compounding reaction condition of the present invention is rotating speed 1000r/min, 25~30 DEG C of temperature.
The rotating speed of mixer is 250r/min in cladding dispersion process of the present invention, and temperature is 102 ± 1 DEG C.
The rotating speed of interfacial modification process high speed kneader of the present invention is 500r/min, and temperature is 105 ± 1 DEG C.
The rotating speed of mixer is 120r/min in material mixed process of the present invention, and temperature is 108 ± 1 DEG C.
Twin-screw extruder barrel temperature control is in 130~140 DEG C of I areas, II during extrusion pelletizing of the present invention 145~150 DEG C of area, 150~155 DEG C of III areas, 160~165 DEG C of IV areas, 155~160 DEG C of V areas, 155~160 DEG C of die head.
The beneficial effects of the invention are as follows：1. tourmaline powder, rare earth, the natural plant polyose aboundresources used, can be effective Reduce cost；2. tourmaline powder, rare earth, the natural plant polyose used is harmless, obtained material safety, can trust use In fresh food packaging；3. tourmaline powder, rare earth, the natural plant polyose used has sterilizing fresh-keeping function in itself, by changing The modes such as property, compounding can effectively strengthen anti-bacterial refreshing effect.
Brief description of the drawings
Fig. 1 is that the sample prepared by the embodiment of the present invention 1 packs 20 DEG C of litchi PPO enzymes to storage with common preservative film The influence of activity.
Fig. 2 is that the sample prepared by the embodiment of the present invention 1 packs 20 DEG C of litchi breathings to storage with common preservative film The influence of intensity.
Embodiment
In order to which present invention may be better understood, it is described further in conjunction with accompanying drawing.
In Fig. 1, two curves represent common preservative film and the lichee fresh-keeping of the present invention containing rare earth compounding respectively Film preserves the influence of 25 days process enzymatic activitys.It can be seen that using the lichee of the present invention containing rare earth compounding Enzymatic activity highest when preservative film is preserved 20 days, compared with the lichee that common preservative film is packed, its enzymatic activity is less than common preservative film Value, beneficial to the preservation of lichee.
In Fig. 2, two curves represent common preservative film and the lichee fresh-keeping of the present invention containing rare earth compounding respectively Film preserves 25 days process lichee respiratory intensities.It can be seen that using the lichee of the present invention containing rare earth compounding Lichee soluble solid is low compared to the lichee that common preservative film is packed when preservative film is preserved 20 days.
Embodiment 1
1st, the preparation of rare earth compounding
The component of master batch is by linear low density polyethylene (LLDPE) 5.96kg, tourmaline powder 1.5kg, rare earth compounding 2.0kg, diatom Native 0.3kg, oleamide 0.11kg, odium stearate 0.13kg are constituted.
Master batch is prepared according to the following steps：
(1) 2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many Sugar juice.
(2) it is 2.95 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.5:1.25:1.00 weigh total amount 2kg nitre respectively Sour lanthanum, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation shell Polysaccharide solution, controls rotating speed 1000r/min, and 25 DEG C of temperature is reacted 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped heavy Shallow lake form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, dried in vacuum drying chamber, Grinding, obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1) by 2.0kg rare earth compoundings, 0.30kg diatomite, it is placed in after compounding in mixer, adds 0.11kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
(2) 1.5kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.13kg odium stearate, interface modification 20min Afterwards into raw material II；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add the poly- second of 5.96kg linear, low densities Alkene mixing 10min obtains mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, Control extruder barrel temperature：132 DEG C of I areas, 150 DEG C of II areas, 155 DEG C of III areas, 161 DEG C of IV areas, 158 DEG C of V areas, die head 160 DEG C, extrusion pelletizing is master batch.
(5) common process condition is used using blow molding machine, further prepares a kind of litchi containing rare earth compounding Branch preservative film.
Using the lichee fresh-keeping film of rare earth compounding manufactured in the present embodiment, contain rare earth compounding using of the present invention Lichee fresh-keeping film enzymatic activity highest when preserving 20 days, beneficial to the preservation of lichee, as shown in Figure 1.Lichee can when preserving 20 days Dissolubility solid content is low compared to the lichee that common preservative film is packed, as shown in Figure 2.
Embodiment 2
The component of master batch is by linear low density polyethylene (LLDPE) 5.82kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, diatom Native 0.35kg, oleamide 0.12kg, odium stearate 0.11kg are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
(1) 2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many Sugar juice.
(2) it is 2.95 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.5:1.25:1.00 weigh total amount 2kg nitre respectively Sour lanthanum, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation shell Polysaccharide solution, controls rotating speed 1000r/min, and 25 DEG C of temperature is reacted 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped heavy Shallow lake form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, dried in vacuum drying chamber, Grinding, obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1) by 2.5kg rare earth compoundings, 0.35kg diatomite, it is placed in after compounding in mixer, adds 0.12kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
(2) 1.2kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.11kg odium stearate, interface modification 20min Afterwards into raw material II；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add the poly- second of 5.82kg linear, low densities Alkene mixing 10min obtains mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, Control extruder barrel temperature：135 DEG C of I areas, 150 DEG C of II areas, 155 DEG C of III areas, 160 DEG C of IV areas, 155 DEG C of V areas, die head 155 DEG C, extrusion pelletizing is master batch.
Embodiment 3
The component of master batch is by linear low density polyethylene (LLDPE) 6.08kg, tourmaline powder 1.2kg, rare earth compounding 2.2kg, diatom Native 0.3kg, oleamide 0.11kg, odium stearate 0.11kg are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
(1) 2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many Sugar juice.
(2) it is 2.95 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.5:1.25:1.00 weigh total amount 2kg nitre respectively Sour lanthanum, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation shell Polysaccharide solution, controls rotating speed 1000r/min, and 25 DEG C of temperature is reacted 6 hours, pH value of solution is adjusted to 7.0, product is with cotton-shaped heavy Shallow lake form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, dried in vacuum drying chamber, Grinding, obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1) by 2.2kg rare earth compoundings, 0.30kg diatomite, it is placed in after compounding in mixer, adds 0.11kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
(2) 1.2kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.11kg odium stearate, interface modification 20min Afterwards into raw material II；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add the poly- second of 6.08kg linear, low densities Alkene mixing 10min obtains mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, Control extruder barrel temperature：130 DEG C of I areas, 145 DEG C of II areas, 155 DEG C of III areas, 160 DEG C of IV areas, 160 DEG C of V areas, die head 155 DEG C, extrusion pelletizing is master batch.
Embodiment 4
The component of master batch is by linear low density polyethylene (LLDPE) 5.96kg, tourmaline powder 1.5kg, rare earth compounding 2.0kg, diatom Native 0.3kg, oleamide 0.11kg, odium stearate 0.13kg are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
(1) 2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many Sugar juice.
(2) it is 3.05 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.55:1.15:0.95 weighs total amount 2kg's respectively Lanthanum nitrate, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation Chitin solution, controls rotating speed 1000r/min, and 25 DEG C of temperature is reacted 6 hours, pH value of solution adjusted to 7.0, product is with cotton-shaped Precipitation form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber Dry, grinding obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1) by 2.0kg rare earth compoundings, 0.30kg diatomite, it is placed in after compounding in mixer, adds 0.11kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
(2) 1.5kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.13kg odium stearate, interface modification 20min Afterwards into raw material II；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add the poly- second of 5.96kg linear, low densities Alkene mixing 10min obtains mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, Control extruder barrel temperature：132 DEG C of I areas, 150 DEG C of II areas, 155 DEG C of III areas, 161 DEG C of IV areas, 158 DEG C of V areas, die head 160 DEG C, extrusion pelletizing is master batch.
Embodiment 5
The component of master batch is by linear low density polyethylene (LLDPE) 5.82kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, diatom Native 0.35kg, oleamide 0.12kg, odium stearate 0.11kg are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
(1) 2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many Sugar juice.
(2) it is 3.05 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.55:1.15:0.95 weighs total amount 2kg's respectively Lanthanum nitrate, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation Chitin solution, controls rotating speed 1000r/min, and 25 DEG C of temperature is reacted 6 hours, pH value of solution adjusted to 7.0, product is with cotton-shaped Precipitation form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber Dry, grinding obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1) by 2.5kg rare earth compoundings, 0.35kg diatomite, it is placed in after compounding in mixer, adds 0.12kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
(2) 1.2kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.11kg odium stearate, interface modification 20min Afterwards into raw material II；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add the poly- second of 5.82kg linear, low densities Alkene mixing 10min obtains mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, Control extruder barrel temperature：135 DEG C of I areas, 150 DEG C of II areas, 155 DEG C of III areas, 160 DEG C of IV areas, 155 DEG C of V areas, die head 155 DEG C, extrusion pelletizing is master batch.
Embodiment 6
The component of master batch is by linear low density polyethylene (LLDPE) 6.08kg, tourmaline powder 1.2kg, rare earth compounding 2.2kg, diatom Native 0.3kg, oleamide 0.11kg, odium stearate 0.11kg are constituted.
Master batch is prepared according to the following steps：
1st, the preparation of rare earth compounding
(1) 2kg chitins are dissolved in 60L acetic acid solutions, after stirring, add 80L methanol, solution is no longer sticky, Acetic anhydride 1L is added, in after reaction 1h at 30 DEG C of temperature, the thick liquid obtained by reaction is added in 150L ethanol, there is precipitation Generation, filters out solid, wash with absolute ethyl alcohol 3 times, then after being dissolved with acetic acid solution, elimination insoluble matter obtains acetylation shell many Sugar juice.
(2) it is 3.05 according to the mol ratio of lanthanum, yttrium, samarium, cerium ion:0.55:1.15:0.95 weighs total amount 2kg's respectively Lanthanum nitrate, yttrium nitrate, samaric nitrate, cerous nitrate, are dissolved in 10L distilled water, and rare earth nitrate aqueous solution is slowly added dropwise to acetylation Chitin solution, controls rotating speed 1000r/min, and 25 DEG C of temperature is reacted 6 hours, pH value of solution adjusted to 7.0, product is with cotton-shaped Precipitation form is separated out, filter after sediment, remove unreacted metal ion with distillation water washing, done in vacuum drying chamber Dry, grinding obtains buff powder, as rare earth compounding.
2nd, the preparation of master batch
(1) by 2.2kg rare earth compoundings, 0.30kg diatomite, it is placed in after compounding in mixer, adds 0.11kg oleic acid acyls Amine, in rotating speed 250r/min, temperature is disperseed after 15min into raw material I to carry out cladding under the conditions of 102 ± 1 DEG C；
(2) 1.2kg tourmaline powders are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C of bars Mediated under part after 10min, be placed in high-speed kneading machine and mediate after 10min, add 0.11kg odium stearate, interface modification 20min Afterwards into raw material II；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add the poly- second of 6.08kg linear, low densities Alkene mixing 10min obtains mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, Control extruder barrel temperature：130 DEG C of I areas, 145 DEG C of II areas, 155 DEG C of III areas, 160 DEG C of IV areas, 160 DEG C of V areas, die head 155 DEG C, extrusion pelletizing is master batch.

Claims (9)

1. a kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding, it is characterized in that：
The preparation of rare earth compounding：
（1）In the acetic acid solution that the plant polyose of 2 parts by weight is dissolved in 60 parts by weight, after stirring, 80 parts by weight are added Methanol, solution is no longer sticky, adds the acetic anhydride of 1 parts by weight, is reacted at 30 DEG C of temperature after 1 h, will be sticky obtained by reaction Liquid is added in the ethanol of 150 parts by weight, filtering precipitate after precipitation generation, is washed with absolute ethyl alcohol 3 times, then molten with acetic acid After liquid dissolving, insoluble matter is filtered off, acetylation plant polyose solution is obtained；
（2）Mol ratio according to lanthanum, yttrium, neodymium, cerium ion is 3.00~3.05:0.40~0.45:1.15~1.25:0.95~ 1.05, the compound that compound, the compound of yttrium, the compound of neodymium and the cerium of lanthanum are weighed respectively is mixed into rare earth compound, and It is added to 1 ﹕ 5 weight part ratio in distilled water, rare earth compound mixed aqueous solution is obtained after being entirely capable of dissolving；It is many according to plant The weight ratio such as sugar and rare earth compound, rare earth compound mixed aqueous solution is slowly added dropwise into acetylation plant polyose solution, Reaction system pH to 7.0 is adjusted, is reacted 6~7 hours under the conditions of rotating speed 1000r/min, 25~30 DEG C of temperature, product is to precipitate Form is separated out；Filter after sediment, remove unreacted rare earth ion with distillation water washing, done in vacuum drying chamber Dry, grinding obtains powdered rare earth compounding；
The preparation of master batch：
（1）By the rare earth compounding of 18~20 parts by weight, the diatomite of 2~2.5 parts by weight is placed in mixer after compounding, plus Enter 1.0~1.2 parts by weight oleamides, be that 250r/min, temperature are that to carry out cladding under the conditions of 102 ± 1 DEG C scattered in rotating speed, Raw material I is obtained after 15min；
（2）12~15 parts by weight of tourmaline powder are placed in high-speed kneading machine, are 500r/min in rotating speed, temperature is 105 ± 1 DEG C Under the conditions of mediate after 10min, add 0.8~1.0 parts by weight odium stearate, carry out after interface modification 20min into raw material II；
（3）Raw material II and raw material I are placed in mixer and are mixed into compound, the LLDPE of 60.3~66.2 parts by weight is added Mixing 10min obtains mixed material；
（4）Mixed material is placed in double screw extruder and extrudes pelletizing as master batch.
2. a kind of preparation method of lichee fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that The tourmaline powder is that the one or more in dravite powder, schorl powder, elbaite powder, tsilaisite powder are any The mixture of ratio；Described tourmaline powder particle diameter is 1.3~6.5 μm.
3. a kind of preparation method of lichee fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that Described acetic acid solution mass percent concentration is 2%.
4. a kind of preparation method of lichee fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that Described plant polyose be starch, fructose, cellulose, chitin in one or more of arbitrary proportions mixture.
5. a kind of preparation method of lichee fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that The compound of described lanthanum is one kind in lanthanum hydroxide, lanthanum acetate, lanthanum nitrate, lanthanum chloride；The compound of described yttrium is hydrogen One kind in yittrium oxide, acetic acid yttrium, yttrium nitrate, yttrium chloride；The compound of described cerium be cerium hydroxide, cerous acetate, cerous nitrate, One kind in cerium chloride.
6. a kind of preparation method of lichee fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that The rotating speed of mixer is 250r/min in described cladding dispersion process, and temperature is 102 ± 1 DEG C.
7. a kind of preparation method of lichee fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that The rotating speed of described interfacial modification process high speed kneader is 500r/min, and temperature is 105 ± 1 DEG C.
8. a kind of preparation method of lichee fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that The rotating speed of mixer is 120r/min in described mixed material mixed process, and temperature is 108 ± 1 DEG C.
9. a kind of preparation method of lichee fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that During described extrusion pelletizing twin-screw extruder barrel temperature control 130~140 DEG C of I areas, 145~150 DEG C of II areas, 150~155 DEG C of III areas, 160~165 DEG C of IV areas, 155~160 DEG C of V areas, 155~160 DEG C of die head.
CN201610177150.9A 2016-03-24 2016-03-24 A kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding Expired - Fee Related CN105602090B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610177150.9A CN105602090B (en) 2016-03-24 2016-03-24 A kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610177150.9A CN105602090B (en) 2016-03-24 2016-03-24 A kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding

Publications (2)

Publication Number Publication Date
CN105602090A CN105602090A (en) 2016-05-25
CN105602090B true CN105602090B (en) 2017-08-25

Family

ID=55982477

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610177150.9A Expired - Fee Related CN105602090B (en) 2016-03-24 2016-03-24 A kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding

Country Status (1)

Country Link
CN (1) CN105602090B (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2185469A1 (en) * 1994-03-15 1995-09-21 Prasadarao Meka Polymers blends, films and articles thereof
EP1360258B1 (en) * 2000-01-31 2007-03-14 H.B. Fuller Licensing & Financing, Inc. Radiation curable adhesive compositions comprising block copolymers having vinyl functionalized polydiene blocks
JP2002264282A (en) * 2001-03-14 2002-09-18 Sumitomo Chem Co Ltd Multi-layer film and self-adhesive packaging film
CN1262592C (en) * 2002-07-08 2006-07-05 北京崇高纳米科技有限公司 Fruit and vegetable fresh-keeping plastic film and method for making the same
US20070089989A1 (en) * 2005-09-02 2007-04-26 William Hoagland Conformable hydrogen indicating wrap to detect leaking hydrogen gas
CN102079834A (en) * 2010-11-03 2011-06-01 国家农产品保鲜工程技术研究中心（天津） Method for preparing modified atmosphere fresh-keeping film for fruits and vegetables
CN102030151A (en) * 2010-11-03 2011-04-27 国家农产品保鲜工程技术研究中心（天津） Device for fresh-keeping packaging of bananas
CN104017262A (en) * 2014-06-13 2014-09-03 齐齐哈尔大学 Multifunctional fresh-keeping material capable of releasing anions and preparation method of material

Also Published As

Publication number Publication date
CN105602090A (en) 2016-05-25

Similar Documents

Publication Publication Date Title
Hafdani et al. A review on application of chitosan as a natural antimicrobial
CN102018266A (en) All-natural plant composite preservative and preparation method and preservation method thereof
CN107805335A (en) A kind of Antimicrobial preservative degredation plastic and preparation method thereof
Chien et al. Effects of edible micronized chitosan coating on quality and shelf life of sliced papaya
CN105800103B (en) Active packing material, preparation method and application thereof
CN108402174A (en) A kind of garlic fresh-keeping film-coating agent and preparation method thereof
CN112772714B (en) Composite preservative film and preparation method and application thereof
Duguma et al. Turning agricultural waste into packages for food: A literature review from origin to end-of-life
CN108221473A (en) A kind of paper pulp and preparation method thereof
CN105602090B (en) A kind of preparation method of the lichee fresh-keeping film master batch containing rare earth compounding
CN105778260B (en) A kind of preparation method of the fresh-keeping film master batch of loquat containing rare earth compounding
CN105778259B (en) A kind of preparation method of the strawberry preservation film master batch containing rare earth compounding
Li et al. Gas barrier coating based on cellulose nanocrystals and its preservation effects on mango
CN104904714B (en) Purposes of the sodium butyrate in preparing for preventing and treating the bactericide by the microbial plant disease of pathogenic
CN105778258B (en) A kind of preparation method of the banana fresh-keeping material film master batch containing rare earth compounding
CN105778255B (en) A kind of preparation method of the White mushroom preservative film master batch containing rare earth compounding
CN105801994B (en) A kind of preparation method of the grape fresh-keeping film master batch containing rare earth compounding
CN105694197B (en) A kind of preparation method of the fresh-keeping film master batch of Kiwi berry containing rare earth compounding
CN105602088B (en) A kind of preparation method of the fresh-keeping film master batch of flat mushroom containing rare earth compounding
CN109414042A (en) From the antimicrobial wooden promotor composition of timber biological matter
CN105602089B (en) A kind of preparation method of the juicy peach fresh-keeping film master batch containing rare earth compounding
Han et al. Progress on biodegradable films for antibacterial food packaging
CN105585771B (en) A kind of preparation method of the fresh-keeping film master batch of sweet cherry containing rare earth compounding
CN108967530A (en) A kind of apple fresh-keeping liquid and its preparation method and application
CN113150517B (en) Biodegradable plastic film material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170825