CN107082994A - A kind of self-adhesion is fresh-keeping to use PVDC composition - Google Patents
A kind of self-adhesion is fresh-keeping to use PVDC composition Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L27/08—Homopolymers or copolymers of vinylidene chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- 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
- C08J2327/08—Homopolymers or copolymers of vinylidene chloride
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- 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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a kind of fresh-keeping use PVDC composition of self-adhesion, composition by weight is：26.25~29.75 parts of vinylidene, 5.25~8.75 parts of VCM, 0.001~0.007 part of intercalating agent, 0.01~0.05 part of buffer, 0.01~0.06 part of dispersant, 0.07 0.3 parts of initiator, I 0.3~1.1 parts of plasticiser, II 1~2 parts of plasticiser.Said composition processing characteristics is excellent, has the high grade of transparency and barrier by film made from screw extruder, it is adaptable to which food fresh keeping is packed.
Description
Technical field
The present invention relates to PVDC resins, more particularly, it relates to which a kind of self-adhesion is fresh-keeping to use PVDC composition.
Background technology
Food fresh keeping membrane has appropriate barrier (resistance oxygen, resistance are wet), and regulation is by fresh-keeping product (prepared food, gourd, fruit and vegetable etc.) week
The oxygen and the content of moisture enclosed, extends the freshness date of food.Food fresh keeping membrane is divided into polyethylene (PE), polyvinyl chloride by material
(PVC), the species such as polyvinylidene chloride (PVDC).PE preservative films are the plastics package systems for the class fresh-keeping foodstuff that people commonly use
Product, temperature in use is no more than 110 DEG C.PVC fresh-preserving film contains carcinogen, and harm to the human body is larger.PVDC can be not only used for refrigerator
It is fresh-keeping, it can also be used to micro-wave oven, common preservative film is far superior in terms of heat-resisting, non-toxic.
PVDC not only has high resistant oxygen, the vapour that blocks water, protects taste, the excellent performances such as perfume (or spice) protected, also with self-extinguishment, oil resistant
Property, taste and the excellent performance such as moistureproof, mould proof are protected, while also having excellent printing, heat sealability, plyability and transparent spy
Property.Compared with general barrier plastics, PVDC is that have very high barrier to oxygen and steam simultaneously, in flavor barrier
Aspect has played its impayable superiority.At the same time, PVDC barrier does not change with the increase of ambient humidity, when
When ambient humidity is more than 70%-80%, PVDC barrier is far better than ethylene-vinyl alcohol copolymer (EVOH), biaxial tension
The barrier material such as polypropylene (BOPP) and polyamide (PA).
With PVDC composition made from vinylidene chloride (VDC) and vinyl chloride (VC) monomer copolymerization, make as preservative film
Used time, have the disadvantage poor transparency, tack is poor, and processing heat stability is poor, abjection hydrogen chloride is extremely easy in decomposition at processing temperatures.Cause
This must improve the heat endurance, tack and transparency of PVDC composition to PVDC composition modification.
Such as China Patent Publication No. CN101631664A, a kind of polyvinylidene chloride resin wrap film and its system are disclosed
Method is made, polyvinylidene chloride resin is extruded into tubulose from die melt, forms homogeneous molten being possible to compatible with water
The aqueous solution of the liquid of liquid is stored in the state of the hollow bulb of extrudate, and the outside of extrudate is cooled down with refrigerant,
Then the extrudate of solidification is blow molded, thus makes the polyvinylidene chloride resin wrap film；Wherein, it is described can
Concentration of the liquid that is compatible with water and forming uniform solution in the aqueous solution is mass percent 80~95%, described poly- inclined
Dichloroethylene resin wrap film is coated with the 50~4000ppm liquid.
And for example China Patent Publication No. CN101717541A, discloses a kind of moisture retention, antibacterial preservative film and preparation side
Method.It is composed of the following components and by weight percentage, polyethylene or polyvinylidene chloride 70~90%, chitosan 10~
30%, wherein copper compound accounts for the 0.5~5% of polyethylene or polyvinylidene chloride and chitosan total amount, and surface modifier accounts for poly-
The 0.1~0.5% of ethene or polyvinylidene chloride and chitosan total amount, takes copper compound to be mixed with surface modifier by said ratio
Close, drying is surface-treated, then polyethylene or polyvinylidene chloride, chitosan are added by said ratio, carry out mixing use
Disposable blowing, which is made, has moisture retention, antibacterial preservative film.
And for example China Patent Publication No. CN105273341A, discloses a kind of vinylidene chloride resin preservative film, purpose
It is to provide a kind of food packaging material, it is mixed with epoxidized vegetable oil, wherein, the food packaging material can suppress
Peculiar smell and coloring, feel are more excellent.The resin combination of the invention contains vinylidene chloride resin and epoxidized vegetable oil,
In all fatty acids unit for constituting above-mentioned epoxidized vegetable oil, the ratio of flax acid unit is more than 5mol% and is 60mol%
Below.
Above patent is mainly by adding auxiliary agent, improving PVDC after-processing technologies, the property such as heat endurance to improve PVDC
Can index, but this is the problems such as can not fundamentally solve poor preservative film PVDC resin tacks, poor transparency.
Patent US3762979 discloses a kind of composition of vinylidene chloride polymer, and said composition contains relative to inclined
The weight of vinylidene chloride polymerization thing is from a kind of 2% to 6% 6-caprolactone polymer, and 6-caprolactone polymer is to inclined
Vinylidene chloride polymerization thing has a kind of plasticization.The composition by two kinds by being in powdery or the polymer of silty state
It is simply mixed to prepare.The disadvantage of the method is that the composition that it is formed generally lacks uniformity, and
Lack the reappearance to its characteristic to a certain extent.
The content of the invention
The technical problems to be solved by the invention are to overcome the defect of prior art high there is provided a kind of transparency, tack
Good, the self-adhesion of good heat stability is fresh-keeping to use PVDC composition.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of fresh-keeping use PVDC composition of self-adhesion,
Composition is by weight：
During described intercalating agent is preferably disodium ethylene diamine tetraacetate (EDTA), cyclohexane edetate disodium (DCTA)
One or two kinds of mixtures.
Described buffer is preferably one or more of in sodium pyrophosphate, Sodium Acid Pyrophosphate, disodium hydrogen phosphate
Mixture.
Described dispersant is preferably the mixture of one or both of methylcellulose, hydroxypropyl methyl cellulose.
During described initiator is preferably di-isopropyl peroxydicarbonate, azobisisobutyronitrile, the different eyeball in heptan of azo two
One or more of mixtures.
Described plasticiser I is preferably one in epoxidized soybean oil (ESO), SA dibutyl ester (DBS), epoxidized linseed oil
Plant or several mixtures.
Described plasticiser II is preferably one kind in ATBC (TBC), tributyl 2-acetylcitrate (ATBC)
Or two kinds of mixture.
The self-adhesion of the present invention it is fresh-keeping with PVDC composition by optimizing polymerization formula, change each component in PVDC composition
Ratio improves the processing heat stability of PVDC composition, transparency and tack, high with transparency, and tack is good, and heat is steady
Qualitative excellent advantage.Said composition processing characteristics is excellent, by film made from screw extruder have good transparency,
Barrier and tack, it is adaptable to which food fresh keeping is packed.
VDC content of monomer is higher in the component of copolymer, and heat endurance during processing and forming is poorer, and easier decompose becomes
Color, and other high-temperature fusion resin materials (such as nylon) once-combined difficult forming, therefore the suitable VDC and VC of selection ratio
Example, the lifting to the heat endurance of finished product is most important.In the present invention by weight vinylidene be 26.25~
29.75 parts, VCM is 5.25~8.75 parts.
Citric acid ester type plasticiser is nontoxic, odorless, heat-resisting, fast light, water resistance are excellent.With respect to other several plasticisers,
The citric acid ester type plasticiser of proper proportion is mixed in resin, the transparency and tack of resin, resin knot can be effectively lifted
Lattice structure is more neat after crystalline substance, has been obviously improved the transparency and tack of resin.Therefore, plasticiser II presses weight in the present invention
It is 1~2 part to measure number, and plasticiser II is preferably one kind in ATBC (TBC), tributyl 2-acetylcitrate (ATBC)
Or two kinds of mixture.
Compared with prior art, beneficial effects of the present invention are：
1st, modified effect is good, by optimizing polymerization formula, selects suitable VDC and VC ratio to significantly improve PVDC groups
The processing heat stability of compound, mixes lattice structure after the citric acid ester type plasticiser of proper proportion, Resin crystallization in resin
It is more neat, the transparency and tack of resin are obviously improved, said composition processing characteristics is excellent, passes through Screw Extrusion mechanism
The film obtained has excellent transparency, barrier and tack, it is adaptable to which food fresh keeping is packed；
2nd, properties of product are excellent, and obtained PVDC resin stabilities and processing characteristics are excellent, and extruder machining load is 40
Between~60%；The PVDC films tack being made is good, and shearing peel strength is in 0.2N/cm2More than；Transparency is high, and film forming is saturating
Luminosity is more than 85%；Mist degree is low, and mist degree is below 5%.
Embodiment
The present invention is described in further detail with reference to embodiments, but the present invention is not limited solely to following implementation
Example.
Embodiment 1
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation process is as follows：
(1) in 100L stainless steels polymeric kettle, (draw ratio is 2:1, double-deck two leaf 45 " oblique oar) in, put into 55kg deionizations
Water, 4g disodium ethylene diamine tetraacetates, 22g methylcellulose, 22g hydroxypropyl methyl celluloses, 25g sodium pyrophosphates, 105g peroxides
After changing two diisopropyl carbonates, 28kg vinylidene chlorides, 7kg vinyl chloride cold scattered 30 minutes, risen under 22.5rpm speeds of agitator
Temperature starts polymerization to 37 DEG C；
(2) with 1.5 DEG C/h temperature rate progressively by temperature lifting to 55.5 DEG C, the synchronous stirring speed with 1.3rpm/h
Speed of agitator is progressively promoted to 30rpm by degree；
(3) polymerization is terminated after reaction 36h, discharged, then heating, vacuum abjection residual monomer add epoxidized soybean oil
(ESO) 700g, is then centrifuged for, dries；
(4) into dried material, discontinuity adds ATBC (TBC) 1.75kg, and constant temperature one is mixed at 58 DEG C
Hour, discharging packaging curing 10 days obtains that white powder self-adhesion is fresh-keeping uses PVDC composition.
Embodiment 2
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation method be the same as Example 1, as a result：Obtain white powder composition.
Embodiment 3
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation method be the same as Example 1, as a result：Obtain white powder composition.
Embodiment 4
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation method be the same as Example 1, as a result：Obtain white powder composition.
Embodiment 5
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation method be the same as Example 1, as a result：Obtain white powder composition.
Embodiment 6
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation method be the same as Example 1, as a result：Obtain white powder composition.
Embodiment 7
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation method be the same as Example 1, as a result obtains white powder composition.
Embodiment 8
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation method be the same as Example 1, as a result：Obtain white powder composition.
Embodiment 9
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation method be the same as Example 1, as a result：Obtain white powder composition.
Comparative example 1
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation method be the same as Example 1, as a result：Obtain white powder composition.
Comparative example 2
A kind of fresh-keeping use PVDC composition of self-adhesion, its composition of raw materials is as follows：
Preparation method be the same as Example 1, as a result：Obtain white powder composition.
The self-adhesion of the present invention is fresh-keeping to be made PVDC films with PVDC resins on Φ 45mm melt extruder and is tested,
The performances such as machining load, the transparency of PVDC films, mist degree, shearing peel strength, the storage colour-change of melt extruder are investigated to refer to
Mark.Wherein：Transparency is tested by U.S. Oakland transparency meters RT-6000；Mist degree presses GB2410-80《Transparent plastic
Light transmittance and haze test method》Perform；Shear peel strength and press GB/T8808-1988《Soft composite plastics material peels off examination
Proved recipe method》Perform.
Process of the test is as follows：By the self-adhering plastic wrap PVDC composition obtained by embodiment 1~9, comparative example 1-2 in melting
Extruder (screw slenderness ratio 22:1) extruded, screw speed is 32rpm.Silicon carbide sets such as table 1 on melt extruder,
Draft temperature is arranged on 27 DEG C of scopes, extrudes processing characteristics such as table 2.
Z1 represents extruder screw first paragraph warming-up section temperature, and Z2 represents extruder screw second segment fluxing zone temperature, Z3
Represent the 3rd section of compression section temperature of extruder screw.
Extruder temperature index (the unit of table 1：℃)
Table 2 extrudes processing characteristics result
Claims (7)
1. a kind of fresh-keeping use PVDC composition of self-adhesion, it is characterised in that composition is by weight：
2. the fresh-keeping use PVDC composition of self-adhesion according to claim 1, it is characterised in that described intercalating agent is ethylenediamine
The mixture of one or both of tetraacethyl disodium, cyclohexane edetate disodium.
3. the fresh-keeping use PVDC composition of self-adhesion according to claim 1, it is characterised in that described buffer is pyrophosphoric acid
One or more of mixtures in sodium, Sodium Acid Pyrophosphate, disodium hydrogen phosphate.
4. the fresh-keeping use PVDC composition of self-adhesion according to claim 1, it is characterised in that described dispersant is that methyl is fine
The mixture of one or both of dimension element, hydroxypropyl methyl cellulose.
5. the fresh-keeping use PVDC composition of self-adhesion according to claim 1, it is characterised in that described initiator is peroxidating
One or more of mixtures in the different eyeball in heptan of two diisopropyl carbonates, azobisisobutyronitrile, azo two.
6. the fresh-keeping use PVDC composition of self-adhesion according to claim 1, it is characterised in that described plasticiser I is epoxy
One or more of mixtures in soybean oil, SA dibutyl ester, epoxidized linseed oil.
7. the fresh-keeping use PVDC composition of self-adhesion according to claim 1, it is characterised in that described plasticiser II is lemon
The mixture of one or both of sour tributyl, tributyl 2-acetylcitrate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114987017A (en) * | 2022-04-19 | 2022-09-02 | 毕玛时软包装（苏州）有限公司 | Low-migration and high-barrier flexible packaging film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838000A (en) * | 2016-05-19 | 2016-08-10 | 浙江巨化股份有限公司电化厂 | Preparation method of PVDC resin for inner printed film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838000A (en) * | 2016-05-19 | 2016-08-10 | 浙江巨化股份有限公司电化厂 | Preparation method of PVDC resin for inner printed film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114987017A (en) * | 2022-04-19 | 2022-09-02 | 毕玛时软包装（苏州）有限公司 | Low-migration and high-barrier flexible packaging film and preparation method thereof |
| CN114987017B (en) * | 2022-04-19 | 2023-10-10 | 毕玛时软包装（苏州）有限公司 | Low-migration high-barrier flexible packaging film and preparation method thereof |
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