CN115895153A - Polyvinyl alcohol fruit and vegetable fresh-keeping film and preparation method thereof - Google Patents
Polyvinyl alcohol fruit and vegetable fresh-keeping film and preparation method thereof Download PDFInfo
- Publication number
- CN115895153A CN115895153A CN202211431210.7A CN202211431210A CN115895153A CN 115895153 A CN115895153 A CN 115895153A CN 202211431210 A CN202211431210 A CN 202211431210A CN 115895153 A CN115895153 A CN 115895153A
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- film
- antioxidant
- fruit
- vegetable fresh
- 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.)
- Granted
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 105
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 105
- 235000012055 fruits and vegetables Nutrition 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 73
- -1 cardanol epoxide Chemical class 0.000 claims abstract description 29
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 25
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 25
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000003490 calendering Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 18
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000006136 alcoholysis reaction Methods 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 8
- 239000012785 packaging film Substances 0.000 claims description 8
- 229920006280 packaging film Polymers 0.000 claims description 8
- 239000003755 preservative agent Substances 0.000 claims description 7
- 230000002335 preservative effect Effects 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000005022 packaging material Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 239000004014 plasticizer Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 6
- 238000004321 preservation Methods 0.000 abstract description 6
- 244000226021 Anacardium occidentale Species 0.000 abstract description 5
- 235000020226 cashew nut Nutrition 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 235000011187 glycerol Nutrition 0.000 description 22
- 230000005540 biological transmission Effects 0.000 description 9
- 241000234295 Musa Species 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical group C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 235000021015 bananas Nutrition 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010466 nut oil Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000012748 slip agent Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyvinyl alcohol fruit and vegetable fresh-keeping film and a preparation method thereof, wherein cardanol epoxide is used for partially replacing glycerol to plasticize polyvinyl alcohol, the polyvinyl alcohol film is prepared by a process of melting, blending, calendering and film forming, so that a transparent, oxygen-resistant, high-strength and dewless polyvinyl alcohol composite film is obtained, the preservation time of fruits and vegetables can be obviously prolonged, the cardanol epoxide is derived from cashew nut shell oil, belongs to a biomass organic molecular material, and contains a benzene ring with large steric hindrance and a soft fat chain segment, a molecular chain contains an ester group, an active hydroxyl group and an epoxy group, the migration resistance is realized, the polyvinyl alcohol crystallinity is reduced due to good compatibility with polyvinyl alcohol, the water resistance of the film is improved, and the problems of water absorption of the film and dissolution of a plasticizer during plasticizing and melting of polyvinyl alcohol are solved.
Description
The technical field is as follows:
the invention relates to the technical field of food fresh-keeping packaging, in particular to a polyvinyl alcohol fruit and vegetable fresh-keeping film and a preparation method thereof.
Background art:
common fruit and vegetable preservative film materials comprise PE, PVC, PP, PVDC and the like, and the plastic packaging films are difficult to degrade and bring serious environmental damage when being widely used. The most common fresh-keeping packaging material is a polyethylene film, which has high oxygen transmission rate and low water vapor transmission rate, and water vapor is easy to condense into water drops on the surface of the film, namely, the phenomenon of condensation is caused, so that the fester on the surface of fruits and vegetables and the rotten core of the fruits and vegetables are easy to cause; meanwhile, too high oxygen transmission rate leads to the fruit and vegetable to breathe fast and cause premature ripening. The common solution is to prepare microporous polyethylene film or to fill small amount of calcium carbonate, and the film may have its water vapor permeability increased and the gas environment inside the package changed through micropores and stuffing, but the effect is limited.
Polyvinyl alcohol is a water-soluble full-biodegradable polymer, is transparent and has good film-forming property, and has the advantages of high strength, gas barrier property, size stability and the like. Many documents have been reported on the blending of polyvinyl alcohol with other polymers to prepare freshness protection packages. The research on polyvinyl alcohol mainly focuses on solution method film formation, and the film is prepared in a solvent evaporation mode, so that the process is complex, and the energy consumption is high. For example, CN101518282B discloses a carbon dioxide high permeability preservative film, which is prepared by using polyethyleneimine and polyvinyl alcohol, but the solution method requires drying at a specific temperature.
The melting point of the polyvinyl alcohol is higher than the decomposition temperature due to high crystallization and strong intramolecular and intermolecular hydrogen bonding, so that the problem of melt blending is difficult to solve. Due to the special chemical structure of polyvinyl alcohol, water and glycerol are commonly used as main plasticizers in the melt processing of polyvinyl alcohol, ethylene glycol, dimethyl sulfoxide and the like are used as auxiliary plasticizers, but the plasticizers are easy to migrate to the surface of the film and absorb moisture in air, the glycerol cannot plasticize the polyvinyl alcohol at a low content, and the film is difficult to normally use due to the poor moisture absorption and migration performance of the glycerol at a high content. The glycerol substitution or partial substitution needs to be found, and the problems of polyvinyl alcohol plasticizing and melting are solved, and meanwhile, the film absorbs water and the plasticizer is prevented from dissolving out.
The invention content is as follows:
the invention aims to provide a polyvinyl alcohol fruit and vegetable fresh-keeping film and a preparation method thereof, wherein cardanol epoxide is used for partially replacing glycerol to plasticize polyvinyl alcohol, the polyvinyl alcohol film is prepared by a process of fusion, blending, calendering and film forming, so that a transparent, oxygen-resistant, high-strength and dewless polyvinyl alcohol composite film is obtained, the preservation time of fruits and vegetables can be obviously prolonged, the cardanol epoxide is derived from cashew nut shell oil, belongs to a biomass organic molecular material, contains a benzene ring with large steric hindrance and a soft fat chain segment, contains ester groups, active hydroxyl groups and epoxy groups on a molecular chain, is resistant to emigration, has good compatibility with polyvinyl alcohol, reduces the crystallinity of the polyvinyl alcohol, improves the water resistance of the film, and solves the problems of water absorption and plasticizer dissolution of the film when the polyvinyl alcohol is plasticized and melted.
The invention is realized by the following technical scheme:
the polyvinyl alcohol fruit and vegetable fresh-keeping film comprises the following raw materials in percentage by mass of 100 percent: 60-80% of polyvinyl alcohol, 10-30% of cardanol epoxide, 5-10% of glycerol, 0.2-0.7% of antioxidant and 0.3-0.5% of erucamide; the polyvinyl alcohol is a compound material with 88 percent of alcoholysis degree and 99 percent of alcoholysis degree, and the mixture ratio is 1.
Preferably, the polyvinyl alcohol fruit and vegetable fresh-keeping film comprises the following raw materials in percentage by mass of 100 percent: 65-75% of polyvinyl alcohol, 15-25% of cardanol epoxide, 7-9% of glycerol, 0.4-0.7% of antioxidant and 0.4-0.5% of erucamide.
The anacardol epoxide is synthesized by carrying out epoxidation reaction on cashew nut oil and hydrogen peroxide under the action of formic acid and phosphoric acid, wherein the reaction temperature is 80 +/-5 ℃, and the reaction time is 4-6h.
The antioxidant is a common antioxidant, and preferably a compound antioxidant of 1 to 2 weight ratios of the antioxidant 1010 to the antioxidant 168 are as follows.
The erucamide is used as the preferred slip agent, other slip agents such as oleamide, PE wax, EVA wax, zinc stearate, and the like. The addition of the slipping agent is beneficial to uniform mixing and uniform blanking of the premix, reducing the internal friction of the melt and improving the smoothness and the opening performance of the extruded film.
Other adjunct materials, such as plasticized starch fillers, mineral fillers, flame retardants; common small molecule polyols and/or small molecule amides, etc., used to partially replace glycerol, are considered reasonable adjustments in the compositions and preparation processes disclosed herein.
The preparation method of the fruit and vegetable fresh-keeping packaging film comprises the following steps:
A. drying polyvinyl alcohol at 80-100 ℃ for 4-6 hours, and then stirring the polyvinyl alcohol and glycerol at a high speed in a high-speed mixer at 80-90 ℃ for 30-60 minutes to obtain a first-time polyvinyl alcohol premix;
B. mixing the polyvinyl alcohol primary premix, cardanol epoxide, antioxidant and erucamide in a high-speed mixer at high speed for 10-20 minutes to obtain a polyvinyl alcohol secondary premix of granular materials and powder materials;
C. b, adding the second premix of the polyvinyl alcohol obtained in the step B into a double-screw extruder for melting, mixing and granulating, wherein the screw temperature is 160-200 ℃, the die head temperature is 170-180 ℃, and cooling and granulating are carried out;
D. and D, adding the granules obtained in the step C into a single-screw extrusion calender, extruding and calendering to form a film at the screw set temperature of 120-160 ℃, wherein the linear speed rotation speed ratio of a calendering roller to a winding roller is 1.1-1, and finally cutting edges, winding and printing to form a bag to obtain a transparent film bag with the thickness of 0.01-0.1 mm.
The invention adopts glycerin to preplasticize polyvinyl alcohol at high temperature, and further plasticizes the polyvinyl alcohol by cardanol epoxide to obtain a polyvinyl alcohol blend which can be melted and plasticized and has high fluidity, thereby meeting the film forming conditions of calendering and tape casting.
The film material obtained by the invention is mainly used for transparent fruit and vegetable fresh-keeping packaging materials, and can also be used for other packaging films.
The invention has the following beneficial effects:
1) The invention uses polyvinyl alcohol, utilizes the high moisture absorption, moisture permeability and oxygen resistance of the polyvinyl alcohol to regulate and control the gas environment in the film, and realizes the fresh-keeping effect that no water drops are condensed on the surface of the film in a high-humidity environment and oxygen outside a package is difficult to enter.
2) The invention utilizes preplasticizing and plasticizing processes to realize efficient melting plasticization and calendaring molding of polyvinyl alcohol, and obtains a flat, transparent and flexible film material which mainly comprises polyvinyl alcohol and has good tensile strength and elongation at break.
3) The packaging material obtained by the invention is composed of fully biodegradable polyvinyl alcohol and decomposable cardanol epoxide material, and belongs to an environment-friendly packaging material.
4) According to the invention, cardanol epoxide is used for partially replacing glycerol to plasticize polyvinyl alcohol, a polyvinyl alcohol film is prepared through a process of melting, blending, calendering and film forming, so that a transparent, oxygen-resistant and high-strength polyvinyl alcohol composite film without dew formation is obtained, the preservation time of fruits and vegetables can be obviously prolonged, the cardanol epoxide is derived from cashew nut shell oil, the cardanol epoxide belongs to a biomass organic molecular material, the cardanol epoxide contains a benzene ring with large steric hindrance and a soft fat chain segment, a molecular chain contains an ester group, an active hydroxyl group and an epoxy group, the cardanol epoxide is resistant to migration, the good compatibility with polyvinyl alcohol is realized, the crystallinity of polyvinyl alcohol is reduced, the water resistance of the film is improved, and the problems of water absorption of the film and dissolution of a plasticizer during plasticizing and melting of polyvinyl alcohol are solved.
Description of the drawings:
FIG. 1 is a graph showing the change in torque during melt plasticization of PVA;
FIG. 2 is a sample after mixing for the torque rheometer, with sample 1 on the left, sample 3 in the middle, and sample 6 on the right;
FIG. 3 is a graph comparing the freshness of bananas, wherein a is a banana preserved with the film of example 3 and left for 24 days, and b is a banana preserved without the preservative film for 24 days.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
1. Investigation of plasticizing Properties of PVA
PVA: polyvinyl alcohol, 1788, inner Mongolia double-euphorbia pekinensis 088-20;
ECO: the cardanol epoxide is prepared by self;
gly: glycerol, henan Yilong Biotech Ltd, food grade;
PEG: polyethylene glycol, dow Carbowax, molecular weight 200.
The mixing process comprises the following steps: torque rheometer, temperature 180 ℃, rotation speed 60rpm. All materials (see table 1) were proportioned and blended directly in the torque rheometer.
TABLE 1 PVA plasticizing Performance study formulation
| Sample numbering | Sample constituent elements | Composition ratio (parts by mass) |
| 1 | PVA/Gly/ECO | 70/10/20 |
| 2 | PVA | 100 |
| 3 | PVA/ECO | 80/20 |
| 4 | PVA/ |
90/10 |
| 5 | PVA/ |
70/30 |
| 6 | PVA/Gly/ECO/PEG | 70/10/15/5 |
The torque-time curve is shown in fig. 1.
As shown in FIG. 1, the torque of sample 1 is moderate, PVA is slowly plasticized under a certain shearing action, and the torque is slightly increased in 4-6 minutes, which indicates that a certain chemical action exists between ECO and PVA; sample 2 represents pure PVA, sample 3 represents PVA with low Gly content (10%), sample 4 represents PVA with ECO only and no Gly, and the torque values for the formulations of samples 2-4 are large, indicating high energy consumption for screw rotation and easy shear heating, so that PVA of these formulations is difficult to melt process; while sample 5 represents a high Gly content (30%), sample 6 represents a partial substitution of ECO with PEG, the torque values of the formulations of samples 5-6 in the torque rheometer are small, indicating a weak shear, with PVA similarly difficult to melt plasticize under weaker shear (as shown in the right panel of fig. 2), and sample 6 also indicates that other plasticizers such as PEG differ from the plasticization of ECO and cannot be equivalently substituted.
2. Preparation and performance test of fruit and vegetable fresh-keeping packaging film
Polyvinyl alcohol, inner Mongolia double-euphorbia pekinensis 088-20 (alcoholysis degree 88%); polyvinyl alcohol, inner Mongolia double-euphorbia pekinensis 098-05 (alcoholysis degree 99%); the cardanol epoxide ECO is prepared by self-making and the preparation method comprises the following steps: 1000g of cashew nut oil was added to the flask, and the mixture was stirred as 9:1, adding 450mL of formic acid (with the purity of 95%) and 50mL of phosphoric acid (with the purity of 95%) in sequence, adding the mixture into a flask, mixing and stirring the mixture for 5min at room temperature, slowly heating the mixture to 80 +/-5 ℃ within 30min, adding 50mL of hydrogen peroxide, reacting for 6h, and washing and separating the mixture to obtain a cardanol epoxide ECO; low density polyethylene, maofengmatite 2426K; high density polyethylene, medium petrochemical refinery 8008; glycerol, henan Yilong Biotech Ltd, food grade; epoxidized soybean oil, commercially available; primary antioxidant 1010 and secondary antioxidant 168.
Example 1: preparation of fruit and vegetable fresh-keeping packaging film
Raw materials: 60 parts of polyvinyl alcohol, 30 parts of cardanol epoxide, 9 parts of glycerol, 0.4 part of antioxidant 1010, 0.3 part of oxidant 168 and 0.3 part of erucamide; the polyvinyl alcohol is a compound material with 88 percent of alcoholysis degree and 99 percent of alcoholysis degree, and the proportion of the polyvinyl alcohol to the polyvinyl alcohol is 1.
The preparation method of the fruit and vegetable fresh-keeping packaging film comprises the following steps:
A. drying polyvinyl alcohol at 100 ℃ for 4 hours, and then stirring the polyvinyl alcohol and glycerol in a high-speed mixer at 80 ℃ for 30 minutes at a high speed to obtain a first premix of the polyvinyl alcohol;
B. mixing the polyvinyl alcohol primary premix, cardanol epoxide, antioxidant and erucamide in a high-speed mixer at high speed for 10 minutes to obtain a polyvinyl alcohol secondary premix of mixed granules and powder;
C. b, adding the second premix of the polyvinyl alcohol obtained in the step B into a double-screw extruder for melting, mixing and granulating, wherein the screw temperature is 160-200 ℃, the die head temperature is 170-180 ℃, cooling and granulating are carried out, and then drying is carried out for 4 hours at the temperature of 80 ℃;
D. and C, adding the granules obtained in the step C into a single-screw extrusion calender, extruding and calendering to form a film at the screw set temperature of 140-180 ℃, wherein the screw rotation speed is 50rpm, the linear speed rotation speed ratio of a calendering roller to a winding roller is 1.1-1.5, and finally cutting edges, winding and printing to form a bag to obtain a transparent film bag with the thickness of 0.01-0.05 mm.
Example 2
Reference example 1, except that the raw materials were: 70 parts of polyvinyl alcohol, 20 parts of cardanol epoxide, 9 parts of glycerin, 0.4 part of antioxidant 1010, 0.3 part of oxidant 168 and 0.3 part of erucamide.
Example 3
Reference example 1, except that the raw materials were: 80 parts of polyvinyl alcohol, 10 parts of cardanol epoxide, 9 parts of glycerin, 0.4 part of antioxidant 1010, 0.3 part of oxidant 168 and 0.3 part of erucamide.
Comparative example 1
80 parts of low-density polyethylene, 19 parts of high-density polyethylene, 0.4 part of antioxidant 1010, 0.3 part of oxidant 168 and 0.3 part of erucamide. Preparing low-density polyethylene, high-density polyethylene, an antioxidant 1010, an antioxidant 168 and erucamide, mixing and granulating in a double screw at 160-180 ℃, drying the granules at 80 ℃ for 4h, adding the granules into a single screw extrusion calender, extruding and calendering at 160-230 ℃ to form a film, wherein the rotation speed of the screw is 50rpm, and the linear speed rotation speed ratio of a calendering roller to a winding roller is 1.1-1.5, so as to obtain a transparent film with the thickness of 0.015-0.100 mm.
Comparative example 2
70 parts of polyvinyl alcohol, 20 parts of low-density polyethylene, 9 parts of glycerol, 0.4 part of antioxidant 1010, 0.3 part of oxidant 168 and 0.3 part of erucamide. And (3) putting the dried polyvinyl alcohol into a high-speed stirrer at the temperature of 80 ℃, starting the stirrer to stir at a high speed of 500rpm, pouring glycerin into an upper feeding port, and stirring for 0.5h to obtain a first polyvinyl alcohol premix. The first-time premix of polyvinyl alcohol, low-density polyethylene, antioxidant 1010, antioxidant 168 and erucamide are prepared and mixed in a double screw, the temperature of the screw is 160-200 ℃, the temperature of a die head is 170-180 ℃, phase separation is carried out at the die head, and the mixture cannot be pulled into strips for granulation.
Comparative example 3:
reference example 2, except that the raw materials were: 70 parts of polyvinyl alcohol, 20 parts of epoxidized soybean oil, 9 parts of glycerol, 0.4 part of antioxidant 1010, 0.3 part of oxidant 168 and 0.3 part of erucamide.
Comparative example 4:
reference example 2, except that the raw materials were: 70 parts of polyvinyl alcohol, 29 parts of glycerol, 0.4 part of antioxidant 1010, 0.3 part of oxidant 168 and 0.3 part of erucamide.
Analysis of film Properties
The properties of the films obtained in examples 1 to 3 and comparative examples 1 to 4 are shown in tables 2 and 3.
And (3) testing the dissolution rate: taking a film of 10cm multiplied by 10cm, weighing m0 after drying, putting the film into water at 23 ℃ for soaking for 4h, taking out the film for drying and weighing m1, wherein the dissolution rate is the ratio of the mass difference (m 0-m 1) before and after soaking of the film to the initial mass m0 multiplied by 100%.
And (3) testing the moisture absorption rate: taking a film of 10cm multiplied by 10cm, drying, weighing m0, putting the film into a constant temperature and humidity box with the relative humidity of 98 percent and the set temperature of 23 ℃, taking out the film after 24 hours, and weighing m2, wherein the moisture absorption rate is the ratio of the mass difference (m 2-m 0) before and after moisture absorption to the initial mass m0 multiplied by 100 percent.
Testing the water vapor transmission rate: the water vapor transmission rate of the film is tested by adopting an infrared sensor testing method, the set temperature is 23 ℃, and the relative humidity between the cavities at two sides of the film is 50%.
Oxygen transmission rate test: the oxygen transmission rate of the film is tested by a coulometric method sensor test method, the set temperature is 23 ℃, and the relative humidity in the cavity is 0%.
Contact angle testing: the films were tested on a contact angle tester for contact angle at 10s and 30s with 2. Mu.L of water drop on the sheet.
Table 2 results of performance testing 1
Table 3 performance test results 2
The preservative films produced in the embodiments 1 to 3 have transparent, smooth and flat appearance, lower dissolution rate and water absorption rate, excellent water resistance, higher water vapor transmission rate and lower oxygen transmission rate, can create a packaging environment with low oxygen content and moderate humidity through the respiration of fruits and vegetables, and are beneficial to the preservation of fruits and vegetables. The preservative films produced in the examples 1 to 3 have lower contact angles, which shows that the surfaces of the films are hydrophilic and are easy to be water films, so that the films have excellent anti-condensation performance and can prevent fruits and vegetables from rotting and deteriorating.
Comparing example 2 with comparative example 4, it is known that the cardanol epoxide is used to partially replace glycerin to plasticize polyvinyl alcohol, so that a transparent, oxygen-resistant, high-strength and dew-condensation-free polyvinyl alcohol composite film is obtained, the water resistance of the film is improved, and the storage time of fruits and vegetables can be obviously prolonged.
As can be seen from FIG. 3, the green bananas after being sealed and preserved for 24 days by the film produced in example 3 have no obvious change in appearance, while the bananas without preservation treatment have changed into dark yellow color when being preserved normally, the banana peels have black spots, and the banana stalks are severely dehydrated and dried, which shows that the film produced in example 3 has good preservation effect.
Claims (6)
1. The polyvinyl alcohol fruit and vegetable fresh-keeping film is characterized by comprising the following raw materials in percentage by mass of 100 percent: 60-80% of polyvinyl alcohol, 10-30% of cardanol epoxide, 5-10% of glycerol, 0.2-0.7% of antioxidant and 0.3-0.5% of erucamide; the polyvinyl alcohol is a compound with 88 percent of alcoholysis degree and 99 percent of alcoholysis degree, and the mixture ratio is 1.
2. The polyvinyl alcohol fruit and vegetable fresh-keeping film as claimed in claim 1, which is characterized by comprising the following raw materials in percentage by mass of 100 percent: 65-75% of polyvinyl alcohol, 15-25% of cardanol epoxide, 7-9% of glycerol, 0.4-0.7% of antioxidant and 0.4-0.5% of erucamide.
3. The polyvinyl alcohol fruit and vegetable fresh-keeping film as claimed in claim 1 or 2, wherein the antioxidant is a compound antioxidant of antioxidant 1010 and antioxidant 168 according to a weight ratio of 1.
4. The polyvinyl alcohol fruit and vegetable fresh-keeping film as claimed in claim 1 or 2, wherein erucamide is replaced by any one of oleamide, PE wax, EVA wax and zinc stearate.
5. The preparation method of the fruit and vegetable fresh-keeping packaging film according to claim 1, which is characterized by comprising the following steps of:
A. drying polyvinyl alcohol at 80-100 ℃ for 4-6 hours, and then stirring the polyvinyl alcohol and glycerol in a high-speed mixer at 80-90 ℃ for 30-60 minutes at a high speed to obtain a first polyvinyl alcohol premix;
B. mixing the polyvinyl alcohol primary premix, cardanol epoxide, antioxidant and erucamide in a high-speed mixer at high speed for 10-20 minutes to obtain a polyvinyl alcohol secondary premix of granular materials and powder materials;
C. b, adding the second premix of the polyvinyl alcohol obtained in the step B into a double-screw extruder for melting, mixing and granulating, wherein the screw temperature is 160-200 ℃, the die head temperature is 170-180 ℃, and cooling and granulating are carried out;
D. and D, adding the granules obtained in the step C into a single-screw extrusion calender, extruding and calendering to form a film at the screw set temperature of 120-160 ℃, wherein the linear speed rotation speed ratio of a calendering roller to a winding roller is 1.1-1, and finally cutting edges, winding and printing to form a bag to obtain a transparent film bag with the thickness of 0.01-0.1 mm.
6. The use of the polyvinyl alcohol fruit and vegetable preservative film according to claim 1, which is used as a transparent fruit and vegetable preservative packaging material or other packaging films.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211431210.7A CN115895153B (en) | 2022-11-14 | 2022-11-14 | Polyvinyl alcohol fruit and vegetable fresh-keeping film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211431210.7A CN115895153B (en) | 2022-11-14 | 2022-11-14 | Polyvinyl alcohol fruit and vegetable fresh-keeping film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115895153A true CN115895153A (en) | 2023-04-04 |
| CN115895153B CN115895153B (en) | 2024-04-16 |
Family
ID=86478865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211431210.7A Active CN115895153B (en) | 2022-11-14 | 2022-11-14 | Polyvinyl alcohol fruit and vegetable fresh-keeping film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115895153B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026471A (en) * | 2013-03-14 | 2015-11-04 | 三井化学东赛璐株式会社 | Freshness-keeping film |
| CN111647243A (en) * | 2020-06-18 | 2020-09-11 | 浙江锦晔科技有限公司 | Polyvinyl alcohol film and preparation method thereof |
| CN112457535A (en) * | 2020-11-30 | 2021-03-09 | 绍兴兆丽新材料科技有限公司 | Environment-friendly spicy cabbage packaging bag and preparation method thereof |
| CN113087941A (en) * | 2021-03-25 | 2021-07-09 | 广州无塑地球新材料科技有限公司 | Water-soluble polyvinyl alcohol film and preparation method thereof |
-
2022
- 2022-11-14 CN CN202211431210.7A patent/CN115895153B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026471A (en) * | 2013-03-14 | 2015-11-04 | 三井化学东赛璐株式会社 | Freshness-keeping film |
| CN111647243A (en) * | 2020-06-18 | 2020-09-11 | 浙江锦晔科技有限公司 | Polyvinyl alcohol film and preparation method thereof |
| CN112457535A (en) * | 2020-11-30 | 2021-03-09 | 绍兴兆丽新材料科技有限公司 | Environment-friendly spicy cabbage packaging bag and preparation method thereof |
| CN113087941A (en) * | 2021-03-25 | 2021-07-09 | 广州无塑地球新材料科技有限公司 | Water-soluble polyvinyl alcohol film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YAHIA RAMADAN，ETL: "Synthesis and characterization of thermoplastic starch/PVA/cardanol oil composites loaded with in‐situ silver nanoparticles", JOURNAL OF APPLIED POLYMER SCIENCE., vol. 139, no. 3, pages 1 - 17 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115895153B (en) | 2024-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101962719B1 (en) | Carbon-neutral bio-based plastics with enhanced mechanical properties, thermoplastic biomass composite used for preparing the same and methods for preparing them | |
| CN101942118B (en) | Plant fiber starch fully-biodegradable material and preparation method thereof | |
| EP1942140B1 (en) | Method for preparing a hydrophobic biodegradable material | |
| CN105504704B (en) | Monoethanolamine activates sodium-based montmorillonite/polymer composite biodegradable blown film resin and preparation method | |
| JP2003073539A (en) | Highly strong biodegradable resin composition and molded article | |
| CN113185820A (en) | Degradable packaging material, packaging film bag and preparation method | |
| CN112694726A (en) | Modified PGA material with higher processing performance and preparation method thereof | |
| EP3892431A1 (en) | Preparation method of highly transparent self-adhesive pbat cling film | |
| CN114573965B (en) | High-barrier biodegradable material and preparation method and application thereof | |
| JP2006518780A (en) | Completely biodegradable plastic raw material and method for producing the same | |
| CN113646363A (en) | Colorant and additive concentrate carrier systems effective over a wide range of polymer processing temperatures | |
| CN115895153B (en) | Polyvinyl alcohol fruit and vegetable fresh-keeping film and preparation method thereof | |
| CN111592715B (en) | High-fineness extrusion-grade modified polypropylene material and automobile outer water cutter | |
| CN111333984A (en) | Starch-filled low-temperature water-soluble PVA composition, starch-filled low-temperature water-soluble PVA film and preparation method thereof | |
| CN115819876B (en) | Degradable high-toughness antibacterial EVA (ethylene-vinyl acetate) foaming material and preparation method thereof | |
| CN111269465A (en) | Starch master batch composition for PVA thermoplastic processing, starch master batch and preparation method thereof | |
| CN109135252B (en) | Degradable TPU film and preparation process thereof | |
| CN115073821B (en) | Polyvinyl alcohol modified starch film and preparation method and application thereof | |
| CN112442259A (en) | Antibacterial freshness protection package and preparation method thereof | |
| CN109504049A (en) | A kind of paper table ware processing PLA composite material | |
| CN1165156A (en) | PVC fresh-preserving film | |
| CN113388165A (en) | Thermoplastic starch for bioplastic and preparation method thereof | |
| CN113105730A (en) | Degradable environment-friendly film material with high transparency, preparation method and application | |
| CN114736404A (en) | Polyvinyl alcohol product capable of remarkably improving plasticizer migration and preparation method thereof | |
| CN110804214A (en) | Food-grade starch master batch composition, food-grade starch master batch and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |