CN108892900A - A kind of PVDC composition and preparation method thereof for cooked product packaging - Google Patents
A kind of PVDC composition and preparation method thereof for cooked product packaging Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08J2423/22—Copolymers of isobutene; butyl rubber
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- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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Abstract
The invention discloses a kind of PVDC compositions for cooked product packaging, are made of the raw material of following mass fraction：3-5 parts of 100 parts of PVDC resin, isobutene and isoprene copolymer, 3-6 parts of naphthenic oil, 2-4 parts of epoxidized soybean oil, 1-2 parts of stearic acid, 0.2-1 parts of sodium alginate, 2-3 parts of magnesia, 5-8 parts of modified montmorillonoid, 1-2 parts of talcum powder, 0.1-0.3 parts of parabenzoquinone dioxime, 0.2-0.5 parts of 2,2'- dithio-bis-benzothiazole；And provide preparation method.Beneficial effects of the present invention are：The present invention is modified to PVDC by adding polymer-modified and auxiliary agent, and is aided with special preparation method and PVDC composition is made；Packaging film as made from it is compared with traditional PVDC film, its barrier property is also significantly improved while mechanical performance has and improves to a certain degree；It is significantly improved using the cooked product shelf lives that packaging film made from PVDC composition of the invention is packed.
Description
Technical field
The present invention relates to packaging material for food field more particularly to it is a kind of for cooked product packaging PVDC composition and
Preparation method.
Background technique
Prepared food is to pass through that thick gravy, the red oil prepared is cold and dressed with sauce, fire-cure, frying etc. by processing or blanching treated raw material
The dish being made.The yield of China's cooked product and consumption figure are very huge at present, but the based article is being stored and sold
There are some problems for mid-sales:The shelf life of product is short, and sale radius is small, largely smoulders barbecue meat products almost without packaging, only
It is suitble to be produced in situ in and market goods locally, sale has region, lacks the market competitiveness;Cooked product packaging specific aim is not strong,
It is raw ripe regardless of specific aim and science be not strong, or even has damaged product original local flavor, and special when package selection mode packaging material
Door is also fewer and fewer for smouldering the packaging material of baked goods.Cooked product is than barrier property of the ordinary food to packaging material
Ask higher.
The barrier property of packaging material refers to that packaging material or container prevent micro-molecular gas such as O2, CO2, N2, vapor, perfume (or spice)
The ability of the transmissions such as taste and other organic solvent vapors.Article is packed using high barrier plastic package material, can be had
The infiltration of oxygen, vapor etc. in barrier package environment is imitated, and keeps the specific gas ingredient in packaging, is significantly improved all kinds of
The shelf life of commodity, shelf-life.Especially food, pharmaceuticals packaging in, even more increasingly emphasize high barrier.Therefore,
In order to meet market demands, various countries are developed in succession with multi-functional Trend of High Obstructive Materials Ordnance Engineering College.
In packaging industry there are four types of common oxygen-barrier property films:1. polyvinylidene chloride film (single layer, co-extrusion PVDC
Film and coating);2. polyvinyl alcohol film (single layer, co-extrusion PVA or EVOH film);3. polyacrylonitrile film (single layer PAN
Film);4. evaporated film (aluminium paper, glassine paper).Wherein PVDC film has high barrier to oxygen and water vapour and has fragrance protectiveness
And anti-drug, thus it is most widely used.PVDC is the general term of the copolymer of VDC (vinylidene chloride) monomer and second comonomer.
PVDC homopolymer has good crystallinity, that is, contains the crystalline solid of 50%-80%, and high-crystallinity and high density all determine
High barrier of the PVDC copolymer to water vapour and air.As social development and living standard are continuously improved, to food packet
More stringent requirements are proposed for the barrier property of package material, to meet the food longer shelf-life；And in identical storage life, use
The food mouthfeel of the packaging material packaging of more high barrier is more preferable, can more retain original taste.Cooked product is especially ripe
The fat content of meat products is higher, and mechanical ductility of the existing PVDC material in low temperature is slightly worse, cooked product storage
Time is more long, and the barrier property of packaging material can be gradually reduced, and causes cooked product rotten very fast.
Summary of the invention
In order to meet the needs of cooked product further increases packaging material, the present invention provides one kind to be used for prepared food system
The PVDC composition of product packaging.The packaging film being made from it has higher barrier property to gas and vapor, final by it
Packaging bag obtained effectively extends the shelf life of cooked product.
In order to achieve the above-mentioned object of the invention, the present invention provides it is a kind of for cooked product packaging PVDC composition, by
The raw material of following mass fraction is made：3-5 parts of 100 parts of PVDC resin, isobutene and isoprene copolymer, 3-6 parts of naphthenic oil,
2-4 parts of epoxidized soybean oil, 1-2 parts of stearic acid, 0.2-1 parts of sodium alginate, 2-3 parts of magnesia, 5-8 parts of modified montmorillonoid, talcum
1-2 parts of powder, 0.1-0.3 parts of parabenzoquinone dioxime, 0.2-0.5 parts of 2,2'- dithio-bis-benzothiazole.
Preferably, the PVDC composition for cooked product packaging, is made of the raw material of following mass fraction：PVDC
3 parts of 100 parts of resin, isobutene and isoprene copolymer, 3 parts of naphthenic oil, 4 parts of epoxidized soybean oil, 1 part of stearic acid, alginic acid
0.2 part of sodium, 3 parts of magnesia, 5 parts of modified montmorillonoid, 2 parts of talcum powder, 0.1 part of parabenzoquinone dioxime, the thio dibenzo thiophene of 2,2'- bis-
0.2 part of azoles.
Preferably, the PVDC composition for cooked product packaging, is made of the raw material of following mass fraction：PVDC
4 parts of 100 parts of resin, isobutene and isoprene copolymer, 5 parts of naphthenic oil, 3 parts of epoxidized soybean oil, 1.5 parts of stearic acid, seaweed
0.6 part of sour sodium, 2.5 parts of magnesia, 7 parts of modified montmorillonoid, 1.2 parts of talcum powder, 0.2 part of parabenzoquinone dioxime, 2,2'- bis- thio two
0.4 part of benzothiazole.
Preferably, the PVDC composition for cooked product packaging, is made of the raw material of following mass fraction：PVDC
5 parts of 100 parts of resin, isobutene and isoprene copolymer, 6 parts of naphthenic oil, 2 parts of epoxidized soybean oil, 2 parts of stearic acid, alginic acid
1 part of sodium, 2 parts of magnesia, 8 parts of modified montmorillonoid, 1 part of talcum powder, 0.3 part of parabenzoquinone dioxime, 2,2'- dithio-bis-benzothiazole
0.5 part.
Wherein, the PVDC resin is the copolymer of vinylidene chloride monomer and second comonomer, and the second comonomer is chloroethene
One of alkene, acrylonitrile, acrylate, the mass content of the vinylidene chloride monomer are 75-85%.
In the isobutene and isoprene copolymer, the mass content of isobutene is 97-99.5%.
The preparation method of the modified montmorillonoid is：By montmorillonite and the tetrapropyl hydrogen-oxygen relative to montmorillonite quality 2-5%
Change and stirred 1-1.5 hours at 50-60 DEG C of ammonium mixing, the polyethylene glycol relative to montmorillonite quality 4-7% is then added in 95-105
Continue stirring 20-40 minutes at DEG C, obtains modified montmorillonoid after cooling.
In order to which foregoing invention purpose is better achieved, the present invention also provides a kind of as above-mentioned is packed for cooked product
PVDC composition preparation method, include the following steps：
Step（1）Screw rod batch mixer temperature setting sequentially adds PVDC resin, isobutene at 150-160 DEG C, according to quality proportioning
It is kneaded 2-3 minutes with isoprene copolymer, epoxidized soybean oil, stearic acid, sodium alginate, magnesia；
Step（2）Naphthenic oil, modified montmorillonoid, talcum powder, 2,2- dithio-bis-benzothiazole is added according to quality proportioning, continues
It is kneaded 1-2 minutes；
Step（3）Extruding pelletization after parabenzoquinone dioxime is kneaded 0.5-1 minutes is added according to quality proportioning.
A kind of packaging film as made from the above-mentioned PVDC composition packed for cooked product.
It is a kind of to be used for packaging composite film made from the PVDC composition that cooked product is packed using above-mentioned, it is total by multilayer
Extrude to obtain multilayer packaging composite film.
A kind of such as application of above-mentioned packaging film or composite membrane in cooked product packaging field, can be used in prepared food system
The vacuum packaging of product or controlled atmospheric packing.
The beneficial effects of the invention are as follows：The present invention is modified and auxiliary to PVDC by adding polymer-modified and auxiliary agent
PVDC composition is made with special preparation method；Packaging film as made from it is compared with traditional PVDC film, in mechanical performance
There is its barrier property while raising to be to a certain degree also significantly improved；It is wrapped using made from PVDC composition of the invention
The cooked product shelf lives of dress film packaging are significantly improved.
Specific embodiment
In order to clarify the technical characteristics of the invention, being illustrated below by specific embodiment to this programme.
Embodiment 1
The embodiment of the invention provides a kind of PVDC compositions for cooked product packaging, by the raw material system of following mass fraction
At：3 parts of 100 parts of PVDC resin, isobutene and isoprene copolymer, 3 parts of naphthenic oil, 4 parts of epoxidized soybean oil, 1 part of stearic acid,
0.2 part of sodium alginate, 3 parts of magnesia, 5 parts of modified montmorillonoid, 2 parts of talcum powder, 0.1 part of parabenzoquinone dioxime, 2,2'- bis- thio two
0.2 part of benzothiazole.
The PVDC resin is the copolymer of vinylidene chloride monomer and second comonomer, and the second comonomer is vinyl chloride, third
One of alkene nitrile, acrylate, the mass content of the vinylidene chloride monomer are 75%.
In the isobutene and isoprene copolymer, the mass content of isobutene is 97%.
The preparation method of the modified montmorillonoid is：By montmorillonite and relative to the tetrapropyl hydroxide of montmorillonite quality 2%
It is stirred 1-1.5 hours at 50-60 DEG C of ammonium mixing, the polyethylene glycol relative to montmorillonite quality 7% is then added at 95-105 DEG C
Continue stirring 20-40 minutes, obtains modified montmorillonoid after cooling.
In order to which foregoing invention purpose is better achieved, the present invention also provides a kind of as above-mentioned is packed for cooked product
PVDC composition preparation method, include the following steps：
Step（1）Screw rod batch mixer temperature setting sequentially adds PVDC resin, isobutene and different at 160 DEG C, according to quality proportioning
Pentadiene copolymer, epoxidized soybean oil, stearic acid, sodium alginate, magnesia are kneaded 2-3 minutes；
Step（2）Naphthenic oil, modified montmorillonoid, talcum powder, 2,2- dithio-bis-benzothiazole is added according to quality proportioning, continues
It is kneaded 1-2 minutes；
Step（3）Extruding pelletization after parabenzoquinone dioxime is kneaded 0.5-1 minutes is added according to quality proportioning.
A kind of packaging film as made from the above-mentioned PVDC composition packed for cooked product.
It is a kind of to be used for packaging composite film made from the PVDC composition that cooked product is packed using above-mentioned, it is total by multilayer
Extrude to obtain multilayer packaging composite film.
A kind of such as application of above-mentioned packaging film or composite membrane in cooked product packaging field, can be used in prepared food system
The vacuum packaging of product or controlled atmospheric packing.
Embodiment 2
The embodiment of the invention provides a kind of PVDC compositions for cooked product packaging, by the raw material system of following mass fraction
At：4 parts of 100 parts of PVDC resin, isobutene and isoprene copolymer, 5 parts of naphthenic oil, 3 parts of epoxidized soybean oil, stearic acid 1.5
Part, 0.6 part of sodium alginate, 2.5 parts of magnesia, 7 parts of modified montmorillonoid, 1.2 parts of talcum powder, 0.2 part of parabenzoquinone dioxime, 2,2'-
0.4 part of dithio-bis-benzothiazole.
The PVDC resin is the copolymer of vinylidene chloride monomer and second comonomer, and the second comonomer is vinyl chloride, third
One of alkene nitrile, acrylate, the mass content of the vinylidene chloride monomer are 80%.
In the isobutene and isoprene copolymer, the mass content of isobutene is 98%.
The preparation method of the modified montmorillonoid is：By montmorillonite and relative to the tetrapropyl hydroxide of montmorillonite quality 4%
It is stirred 1-1.5 hours at 50-60 DEG C of ammonium mixing, the polyethylene glycol relative to montmorillonite quality 5% is then added at 95-105 DEG C
Continue stirring 20-40 minutes, obtains modified montmorillonoid after cooling.
In order to which foregoing invention purpose is better achieved, the present invention also provides a kind of as above-mentioned is packed for cooked product
PVDC composition preparation method, include the following steps：
Step（1）Screw rod batch mixer temperature setting sequentially adds PVDC resin, isobutene and different at 150 DEG C, according to quality proportioning
Pentadiene copolymer, epoxidized soybean oil, stearic acid, sodium alginate, magnesia are kneaded 2-3 minutes；
Step（2）Naphthenic oil, modified montmorillonoid, talcum powder, 2,2- dithio-bis-benzothiazole is added according to quality proportioning, continues
It is kneaded 1-2 minutes；
Step（3）Extruding pelletization after parabenzoquinone dioxime is kneaded 0.5-1 minutes is added according to quality proportioning.
A kind of packaging film as made from the above-mentioned PVDC composition packed for cooked product.
It is a kind of to be used for packaging composite film made from the PVDC composition that cooked product is packed using above-mentioned, it is total by multilayer
Extrude to obtain multilayer packaging composite film.
A kind of such as application of above-mentioned packaging film or composite membrane in cooked product packaging field, can be used in prepared food system
The vacuum packaging of product or controlled atmospheric packing.
Embodiment 3
The embodiment of the invention provides a kind of PVDC compositions for cooked product packaging, by the raw material system of following mass fraction
At：5 parts of 100 parts of PVDC resin, isobutene and isoprene copolymer, 6 parts of naphthenic oil, 2 parts of epoxidized soybean oil, 2 parts of stearic acid,
1 part of sodium alginate, 2 parts of magnesia, 8 parts of modified montmorillonoid, 1 part of talcum powder, 0.3 part of parabenzoquinone dioxime, the thio hexichol of 2,2'- bis-
And 0.5 part of thiazole.
The PVDC resin is the copolymer of vinylidene chloride monomer and second comonomer, and the second comonomer is vinyl chloride, third
One of alkene nitrile, acrylate, the mass content of the vinylidene chloride monomer are 85%.
In the isobutene and isoprene copolymer, the mass content of isobutene is 99.5%.
The preparation method of the modified montmorillonoid is：By montmorillonite and relative to the tetrapropyl hydroxide of montmorillonite quality 5%
It is stirred 1-1.5 hours at 50-60 DEG C of ammonium mixing, the polyethylene glycol relative to montmorillonite quality 4% is then added at 95-105 DEG C
Continue stirring 20-40 minutes, obtains modified montmorillonoid after cooling.
In order to which foregoing invention purpose is better achieved, the present invention also provides a kind of as above-mentioned is packed for cooked product
PVDC composition preparation method, include the following steps：
Step（1）Screw rod batch mixer temperature setting sequentially adds PVDC resin, isobutene and different at 155 DEG C, according to quality proportioning
Pentadiene copolymer, epoxidized soybean oil, stearic acid, sodium alginate, magnesia are kneaded 2-3 minutes；
Step（2）Naphthenic oil, modified montmorillonoid, talcum powder, 2,2- dithio-bis-benzothiazole is added according to quality proportioning, continues
It is kneaded 1-2 minutes；
Step（3）Extruding pelletization after parabenzoquinone dioxime is kneaded 0.5-1 minutes is added according to quality proportioning.
A kind of packaging film as made from the above-mentioned PVDC composition packed for cooked product.
It is a kind of to be used for packaging composite film made from the PVDC composition that cooked product is packed using above-mentioned, it is total by multilayer
Extrude to obtain multilayer packaging composite film.
A kind of such as application of above-mentioned packaging film or composite membrane in cooked product packaging field, can be used in prepared food system
The vacuum packaging of product or controlled atmospheric packing.
Experimental example
（1）As a comparison case by film made from PVDC film made from embodiment 1-3 and traditional PVDC composition, according to GB/T
The method of 1038-2000 tests the gas of its oxygen, nitrogen, carbon dioxide respectively under 23 DEG C and 50% relative humidity conditions
Transit dose, sample with a thickness of 25.1-25.5 μm, test result such as table 1；According to the method for GB/T 30412-2013 at 38 DEG C
And 100% test its vapor under relative humidities respectively transmitance, test result is as shown in table 1.Analytical table 1 it is found that
Compared with PVDC film produced by the present invention film made from traditional PVDC composition, have to the barrier property of gas and vapor
Apparent raising, especially to the raising highly significant of the barrier property of oxygen.
1 gas of table and steam penetrating capacity
| Transit dose | Unit | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Oxygen | cm3/m2.d.MPa | 67 | 18 | 7 | 13 |
| Nitrogen | cm3/m2.d.MPa | 5.7 | 1.2 | 0.7 | 0.5 |
| Carbon dioxide | cm3/m2.d.MPa | 4.9 | 3.2 | 1.7 | 2.3 |
| Vapor | g/m2.d | 0.7 | 0.4 | 0.3 | 0.3 |
（2）Using multilayer complex films made from PVDC multilayer complex films made from embodiment 1-3 and traditional PVDC composition as
Comparative example is used as the vacuum packaging bag of roast duck, respectively after 60 days, 90 days and 120 days storage lives carry out color,
The sensory evaluation of smell and mouthfeel, as shown in table 2.Analytical table 2 it is found that using PVDC multilayer complex films produced by the present invention with
Multilayer complex films made from traditional PVDC composition are compared, and manufactured packaging bag is when vacuum saves roast duck, the preservation of roast duck
Phase is longer, effectively extends the shelf life of roast duck.
Sensory evaluation of the vacuum-packed roast duck of table 2 in different storage lives
Technical characteristic of the present invention without description can realize that details are not described herein, certainly, above-mentioned by or using the prior art
Illustrate to be not limitation of the present invention, the present invention is also not limited to the example above, those skilled in the art
The variations, modifications, additions or substitutions made within the essential scope of the present invention, also should belong to protection scope of the present invention.
Claims (8)
1. a kind of PVDC composition for cooked product packaging, which is characterized in that be made of the raw material of following mass fraction：
3-5 parts of 100 parts of PVDC resin, isobutene and isoprene copolymer, 3-6 parts of naphthenic oil, 2-4 parts of epoxidized soybean oil, stearic acid
1-2 parts, 0.2-1 parts of sodium alginate, 2-3 parts of magnesia, 5-8 parts of modified montmorillonoid, 1-2 parts of talcum powder, parabenzoquinone dioxime 0.1-
0.3 part, 0.2-0.5 parts of 2,2'- dithio-bis-benzothiazole.
2. the PVDC composition according to claim 1 for cooked product packaging, which is characterized in that the PVDC resin
For the copolymer of vinylidene chloride monomer and second comonomer, two monomer is one of vinyl chloride, acrylonitrile, acrylate,
The mass content of the vinylidene chloride monomer is 75-85%.
3. -2 described in any item PVDC compositions for cooked product packaging according to claim 1, which is characterized in that described
In isobutene and isoprene copolymer, the mass content of isobutene is 97-99.5%.
4. the PVDC composition according to claim 1-3 for cooked product packaging, which is characterized in that described
The preparation method of modified montmorillonoid is：Montmorillonite is mixed into 50- with the tetrapropylammonium hydroxide relative to montmorillonite quality 2-5%
It is stirred 1-1.5 hours at 60 DEG C, is then added and continues to stir at 95-105 DEG C relative to the polyethylene glycol of montmorillonite quality 4-7%
It mixes 20-40 minutes, obtains modified montmorillonoid after cooling.
5. a kind of preparation method of the PVDC composition according to any one of claims 1-4 for cooked product packaging,
It is characterized in that, the preparation method of the PVDC composition includes the following steps：
Step（1）Screw rod batch mixer temperature setting sequentially adds PVDC resin, isobutene at 150-160 DEG C, according to quality proportioning
It is kneaded 2-3 minutes with isoprene copolymer, epoxidized soybean oil, stearic acid, sodium alginate, magnesia；
Step（2）Naphthenic oil, modified de- soil, talcum powder, 2,2- dithio-bis-benzothiazole is added according to quality proportioning, continues to mix
Refining 1-2 minutes；
Step（3）Extruding pelletization after parabenzoquinone dioxime is kneaded 0.5-1 minutes is added according to quality proportioning.
6. a kind of packaging film as made from claim 1-5 described in any item PVDC compositions packed for cooked product.
7. a kind of pack using made from the PVDC composition as claimed in any one of claims 1 to 6 for cooked product packaging
Composite membrane.
8. a kind of packaging film as claimed in claim 6, or composite membrane as claimed in claim 7 is in cooked product packaging field
In application.
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| CN111410804A (en) * | 2020-03-04 | 2020-07-14 | 华南理工大学 | High-barrier vinylidene chloride-methyl acrylate copolymer resin film and manufacturing method thereof |
| CN112143152A (en) * | 2020-09-29 | 2020-12-29 | 上海春宜药品包装材料有限公司 | PVDC (polyvinyl dichloride) degradable high-barrier composite material and preparation method thereof |
| CN112795117A (en) * | 2020-12-31 | 2021-05-14 | 江苏福多美生物科技有限公司 | Food packaging bag with fresh-keeping function and preparation method thereof |
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