CN115230271A - High-barrier anti-bonding composite film and preparation method and application thereof - Google Patents

High-barrier anti-bonding composite film and preparation method and application thereof Download PDF

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CN115230271A
CN115230271A CN202110443333.1A CN202110443333A CN115230271A CN 115230271 A CN115230271 A CN 115230271A CN 202110443333 A CN202110443333 A CN 202110443333A CN 115230271 A CN115230271 A CN 115230271A
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guanidine
microspheres
composite film
salt
zinc
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CN115230271B (en
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胡晨曦
王宇韬
初立秋
茹越
张晓红
乔金樑
戚桂村
董穆
蔡传伦
赖金梅
蒋海斌
李�杰
高达利
张师军
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
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    • C08J2435/00—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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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    • C08J2435/00—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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
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Abstract

The invention relates to a high-barrier anti-bonding composite film and a preparation method and application thereof, belonging to the technical field of high polymer materials. The high-barrier anti-bonding composite film comprises an outer layer film and an inner layer film; the outer film comprises an anti-adhesive composition; the anti-adhesion composition comprises a polyolefin resin and a multifunctional additive; the multifunctional additive is selected from at least one of a zinc salt microsphere composition and a guanidine salt microsphere composition; the inner film comprises a high-resistance heat-insulating plastic resin. The high-barrier anti-bonding composite film has excellent barrier property and opening property, higher product added value, low cost of related raw materials, simple preparation process and easy industrial popularization.

Description

High-barrier anti-bonding composite film and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-barrier anti-bonding composite film and a preparation method and application thereof.
Background
Compared with the traditional packaging materials (such as paper, aluminum foil, ceramics, glass and the like), the plastic package has the advantages of low price, light weight, easy forming and transportation and the like. With the rapid development of the plastic packaging industry and the improvement of living standard, the requirements of people on packaging materials are continuously improved, and the functional film gradually becomes a field with the most development prospect of the packaging technology. Plastic packaging films with high barrier properties and easy opening have become one of the hot spots in the market development.
Food and medicine usually need to keep apart oxygen, vapor in transportation and the preservation, and current plastic packaging material uses PVDC coating, EVOH, PVA, nylon class etc. as the barrier layer mostly, but PVDC environmental protection nature is relatively poor, and EVOH, PVA, nylon class material are water-fast. Generally, the above water-proof barrier materials need to be compounded with other materials, such as PP, PE, PET, etc., which have good moisture-proof performance. In the patent (publication number: CN 204506031U), a PE film is used as an outer layer, and an EVOH film is used as a barrier layer, so that a tear-resistant high-barrier composite film is prepared; liang Xiaogong (research on mechanical, thermal and barrier properties of ethylene-vinyl alcohol copolymer composite films, plastics science, 2015,43 (06), 21-24) multilayer composite films prepared from EVOH, PA6 and PE have been found to have gradually increased oxygen barrier properties but decreased water vapor barrier properties in high humidity environments, and to have improved ductility after compounding EVOH with PA6 and PE, indicating that the three can be compounded to form tough composite films.
Plastic film materials have a high surface friction coefficient, which makes them stick when heated and pressed (air pressure, extrusion, press rolls, winding), and also during processing, use and storage of films (especially PE, PP-based materials). To solve such problems, an opening agent is often added to the film to facilitate subsequent use. The current commonly used opening agents can be divided into organic and inorganic opening agents, and the organic opening agents such as amide compounds and stearate can migrate to the surface of the film to serve as a barrier to achieve an opening effect; the inorganic opening agent has low price and rich varieties, and comprises silicon dioxide, calcium carbonate, calcium hydrophosphate, diatomite, talcum powder, molecular sieves and the like.
Multifunctional plastic packaging films have a wide development prospect, but the modification research of the current composite film is more complex. Therefore, the development of the high-performance composite membrane with the integration of barrier property and opening property, the preparation method and the application thereof have important market value and economic significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a high-barrier anti-adhesion composite film. In particular to a high-barrier anti-bonding composite film and a preparation method and application thereof. The high-performance composite membrane has high barrier and adhesion prevention functions, and is low in cost of related raw materials, simple in preparation process and easy to industrially popularize.
One of the purposes of the invention is to provide a high-barrier anti-adhesion composite film which can comprise an outer layer film and an inner layer film which are overlapped;
the outer film may comprise an anti-adhesive composition;
the release composition may comprise a polyolefin resin, a multifunctional additive;
the multifunctional additive can be selected from at least one of zinc salt microsphere composition and guanidine salt microsphere composition;
the inner film may comprise a high-resistance thermal insulation plastic resin.
Preferably, the first and second electrodes are formed of a metal,
the total thickness of the high-barrier anti-bonding composite film can be 10-250 mu m;
the thickness ratio of the outer layer film to the inner layer film may be (10 to 0.1): 1, preferably (10 to 0.5): 1.
specifically, the anti-bonding composition may comprise the following components in parts by weight:
the multifunctional additive is used in an amount of 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the polyolefin resin.
The polyolefin resin can be selected from at least one of various polypropylene resins and polyethylene resins in the prior art; wherein, the polypropylene resin can be selected from at least one of homo polypropylene and co polypropylene; the polyethylene resin may be at least one selected from high density polyethylene and low density polyethylene, and is preferably linear low density polyethylene.
The zinc salt microsphere composition comprises a mixture of zinc salt microspheres and a release agent; wherein the weight ratio range of the zinc salt microspheres to the release agent can be 1: (0.1 to 1), preferably 1: (0.1 to 0.5);
the guanidine salt microsphere composition comprises a mixture of guanidine salt microspheres and a release agent; wherein the weight ratio of the guanidine salt microspheres to the release agent can be in the range of 1: (0.1 to 1), preferably 1: (0.1-0.5).
The zinc salt microspheres and/or guanidine salt microspheres can be maleic anhydride cross-linked alternating copolymer zinc salt and/or guanidine salt derivatives.
The zinc salt microspheres and/or guanidine salt microspheres can be microspheres or sphere-like, and the average particle size can be in the conventional particle size range of conventional polymer microspheres, such as 150-3000 nm.
The zinc salt microspheres and/or guanidine salt microspheres are polymer microspheres with surfaces subjected to grafting or complexing reaction with zinc ions and/or guanidine salt polymers;
in the zinc salt microsphere, the weight fraction of zinc element can be 10-70%, preferably 20-60%. The content in the concrete use can be adjusted according to the actual situation.
The guanidine salt polymer can be selected from at least one of polyhexamethylene (bis) guanidine inorganic salt, polyhexamethylene (bis) guanidine organic salt, polyoxyethylene guanidine inorganic salt and polyoxyethylene guanidine organic salt; the guanidine salt polymer is preferably at least one selected from the group consisting of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine sulfonate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate, polyoxyethylene guanidine hydrochloride, polyoxyethylene guanidine phosphate, polyoxyethylene guanidine sulfonate, polyoxyethylene guanidine acetate, polyoxyethylene guanidine propionate, polyoxyethylene guanidine stearate, polyoxyethylene guanidine laurate, polyoxyethylene guanidine benzoate; more preferably at least one of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate, and polyoxyethylene guanidine hydrochloride.
The polymer microspheres are maleic anhydride alternating copolymer microspheres, preferably maleic anhydride cross-linked alternating copolymer microspheres.
Specifically, the polymer microspheres in the zinc salt microspheres and/or guanidine salt microspheres can be maleic anhydride cross-linked alternating copolymers obtained by combining a structural unit A provided by maleic anhydride, a structural unit B provided by a monomer M and a structural unit C provided by a cross-linking agent. Wherein said monomer M is selected from monomers containing isolated carbon-carbon double bonds; the crosslinking agent may be selected from vinyl-containing monomers having two or more functionalities capable of free radical polymerization.
The structural characteristics of the zinc salt microspheres and/or guanidine salt microspheres are as follows: in the microsphere, maleic anhydride and a zinc ion and/or guanidinium polymer generate a grafting or complexing reaction, and one zinc ion and/or guanidinium polymer can be connected with one or more maleic anhydride cross-linked alternating copolymer molecular chains.
Wherein said monomer M is selected from monomers containing isolated carbon-carbon double bonds; preferably at least one olefin selected from the group consisting of vinyl acetate, styrene, alpha-methylstyrene, C4, C5, C8 and C9 mixed olefins; preferably at least one of vinyl acetate, styrene, alpha-methyl styrene, C4 and C5 mixed olefins; wherein the C4, C5 mixed olefins are selected from the C four and/or C five fractions of the oil refinery or ethylene industry, preferably from the C four and/or C five fractions of the petrochemical industry for ethylene cracking.
The crosslinking agent may be any of various conventional vinyl-containing monomers having two or more functionalities capable of free radical polymerization. Preferably, the crosslinking agent may beDivinylbenzene and/or an acrylate crosslinking agent containing at least two acrylate groups; the acrylate group may have the formula: -O-C (O) -C (R') = CH 2 R' is H or C1-C4 alkyl (such as methyl); more preferably, the crosslinking agent may be selected from at least one of divinylbenzene, propylene glycol-based di (meth) acrylate, ethylene glycol-based di (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, phthalic acid ethylene glycol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylate;
the propylene glycol-based di (meth) acrylate is preferably at least one selected from the group consisting of 1,3-propylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol diacrylate, 1,2-propylene glycol diacrylate and the like; the ethylene glycol-based di (meth) acrylate is preferably at least one selected from the group consisting of ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate and the like.
In particular embodiments, the anti-adhesion composition may further comprise other adjuvants;
based on 100 parts by weight of the polyolefin resin, 0.1-5 parts by weight of other auxiliary agents. The other auxiliary agent can be selected from at least one of an antioxidant (such as hindered phenols, phosphite antioxidants and the like), an antistatic agent (such as quaternary ammonium salts, sulfonic acid type and carboxylate type antistatic agents and the like), a lubricant (such as erucamide, stearic acid, ethylene bis stearamide and the like), an ultraviolet absorbent (such as salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazine type ultraviolet absorbents and the like), a plasticizer and other common processing aids in the field, and the types and the adding amounts of the auxiliary agents are well known to those skilled in the art.
In the high-barrier adhesion-preventing composite film of the present invention, the high-barrier heat-insulating plastic resin forming the inner layer film may be selected from the group consisting of common high-barrier heat-insulating plastic resins, and preferably at least one of ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyethylene naphthalate (PEN), nitrile resin, polyamide, and the like.
The invention also aims to provide a preparation method of the high-barrier anti-bonding composite film, which comprises the following steps:
and carrying out multilayer coextrusion on the components comprising the anti-adhesion composition and the high-resistance heat-insulation plastic resin to obtain the high-resistance anti-adhesion composite film.
Specifically, the preparation method of the high-barrier anti-adhesion composite film can comprise the following steps:
(1) Fully mixing the components including the polyolefin resin and the multifunctional additive, and performing melt granulation by an extruder to obtain an anti-adhesion composition;
(2) And (2) preparing the material obtained in the step (1) and the high-resistance heat-insulation plastic resin into a film by multilayer coextrusion casting, for example, the procedures of coextrusion die casting, cooling, thickness measurement, traction, coiling, slitting and the like are included, so that the high-resistance heat-insulation anti-adhesion composite film with different thicknesses and width specifications is obtained.
Preferably, in steps (1), (2), the temperature of the extruder depends on the resin used, and specifically, the co-extrusion die temperature in step (2) may be 190 to 250 ℃. The cooling temperature of the co-extrusion die flow delay in the step (2) is 30-65 ℃.
In the step (1), the multifunctional additive is at least one of a zinc salt microsphere composition and a guanidine salt microsphere composition. The mixing method can adopt the mixing method and mixing equipment commonly used in the prior art for resin, and preferably adopts high-speed stirrer equipment; the addition amount of the other auxiliary agents is conventional amount, or is properly adjusted according to actual conditions.
Specifically, the polymer microsphere can be a maleic anhydride cross-linked alternating copolymer obtained by combining a structural unit A provided by maleic anhydride, a structural unit B provided by a monomer M and a structural unit C provided by a cross-linking agent.
The guanidine salt microspheres or the polymer microspheres in the zinc salt microspheres can be prepared by adopting a self-stabilizing precipitation polymerization method. Specifically, the microspheres may be prepared from raw materials including maleic anhydride, monomer M, a crosslinking agent, an initiator, and an organic solvent by a self-stabilizing precipitation polymerization method which is conventional in the art.
Wherein the ratio of the amount of the maleic anhydride to the amount of the monomer M may be selected conventionally, for example, in a specific embodiment, the amount of the monomer M may be 50 to 150mol, more preferably 75 to 100mol, relative to 100mol of the maleic anhydride; the amount of cross-linking agent may be from 1% to 20% by weight of the polymerized monomers (sum of the amounts of maleic anhydride and monomer M). In specific implementation, the dosage can be adjusted according to actual conditions.
The polymerization of the polymeric microspheres can be self-made by methods known in the art, for example according to the literature: polymer compositions with high haze and high transmission. Polymer. Chem.,2015,6,6632-6636; liu Zhenjie, research on self-stabilizing precipitation polymerization to prepare monodisperse copolymer microspheres [ D ]. University of beijing chemical industry, 2008; and a microsphere preparation method proposed in patent CN101338008A, CN109705269B, CN111793167A, CN111944155A, CN111944156A, CN111944232A, CN111944233A and the like.
In a specific implementation, the preparation method of the zinc salt microsphere composition can comprise the following steps:
adding the polymer microspheres into an alkali metal hydroxide aqueous solution for full reaction, and then adding a zinc salt aqueous solution for full reaction; or adding an alkali metal hydroxide aqueous solution into a polymerization system of the polymer microsphere, and then adding a zinc salt aqueous solution for full reaction; then separating and drying, and mixing the obtained zinc salt microspheres and a separant in a high-speed stirrer to obtain the zinc salt microsphere composition;
preferably, the preparation method of the zinc salt microsphere composition can comprise the following steps:
a. taking alkali metal hydroxide, adding the alkali metal hydroxide into water for dissolving to obtain an alkali metal hydroxide aqueous solution; preferably, the weight ratio of the alkali metal hydroxide to water is in the range of (0.1 to 100): 100, more preferably (0.5 to 50): 100, respectively;
b. b, adding the polymer microspheres into the alkali metal hydroxide aqueous solution prepared in the step a, and fully mixing for reaction; or adding the alkali metal hydroxide aqueous solution prepared in the step a into a polymerization system of the polymer microspheres (after the polymerization of the polymer microspheres is finished), and fully mixing for reaction; wherein, the weight ratio range of the polymer microspheres to the alkali metal hydroxide is preferably (0.1-20): 1, more preferably (0.1 to 10): 1; the reaction is acid-base neutralization reaction of carboxylic acid groups of the microspheres and alkali metal hydroxide;
c. taking zinc salt solid, adding the zinc salt solid into water for dissolving to obtain a zinc salt water solution, then adding the zinc salt water solution into the mixed solution obtained in the step b, fully mixing and reacting, separating suspended matters, and drying to obtain the zinc salt microspheres; ion replacement is carried out in the reaction process of the step c, and the alkali metal ions on the reaction product of the alkali metal hydroxide and the microspheres obtained in the step b are replaced by high-valence zinc ions; preferably, the weight ratio of the zinc salt (solids) to the microspheres is in the range (0.1 to 20): 1, more preferably (0.1 to 10): 1;
the concentration of the aqueous solution of zinc salt is not required as long as the amount of zinc salt in water is within the solubility range of zinc salt.
d. C, mixing the zinc salt microspheres obtained in the step c and a separant in a high-speed stirrer to obtain the zinc salt microsphere composition;
wherein, preferably, the weight ratio of the zinc salt microspheres to the release agent is in the range of 1: (0.1 to 1), more preferably 1: (0.1-0.5); the separant is selected from particles with the particle size of 150-5000 nm, preferably at least one of silicon dioxide, calcium carbonate, talcum powder, diatomite, kaolin, calcium hydrophosphate and silicone resin.
Wherein the content of the first and second substances,
in the step a, the alkali metal hydroxide may be at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, preferably at least one selected from lithium hydroxide, sodium hydroxide and potassium hydroxide; and/or the presence of a gas in the gas,
in the step c, the zinc salt can be selected from various zinc salts in the prior art, preferably at least one of water-soluble zinc salts, more preferably at least one of zinc acetate, zinc lactate, zinc chloride, zinc bromide, zinc nitrate, zinc sulfate, zinc gluconate and the like;
in a specific implementation, the preparation method of the guanidinium microsphere composition in the multifunctional additive may include the steps of:
adding the polymer microspheres into a guanidine salt polymer aqueous solution for grafting reaction, or adding a guanidine salt polymer or a guanidine salt polymer aqueous solution into a polymerization system of the polymer microspheres (after the polymerization of the polymer microspheres is finished) and rapidly stirring for grafting reaction; further separating, and mixing the separated guanidine salt microsphere solid with a separant in a high-speed stirrer to obtain the guanidine salt microsphere composition.
Preferably, the first and second electrodes are formed of a metal,
the amount of the guanidinium polymer or the aqueous guanidinium polymer solution may be conventionally selected, for example, the amount of the guanidinium polymer solution may be 500 to 10000g, preferably 1000 to 8000g, and more preferably 1000 to 5000g, based on 1000g of the maleic anhydride (i.e., the amount of the maleic anhydride raw material used for preparing the polymeric microspheres) in the structural units of the polymeric microspheres; the concentration of the guanidine salt polymer aqueous solution is 0.5 to 50wt%, preferably 1 to 30wt%, more preferably 1 to 20wt%;
and/or, the grafting reaction may be carried out under conventional conditions, for example, the conditions of the grafting reaction include: the temperature is 0-100 ℃, preferably 2.5-90 ℃, and more preferably 5-80 ℃; the reaction time is 0.5 to 10 hours, preferably 0.5 to 8 hours, and more preferably 0.5 to 6 hours; the stirring speed is 50 to 1000rpm, preferably 50 to 500rpm, and more preferably 100 to 500rpm.
The separant can be selected from particles with the particle size of 150-5000 nm, and preferably at least one of silicon dioxide, calcium carbonate, talcum powder, diatomite, kaolin, calcium hydrophosphate, silicone resin and the like; the weight ratio of the guanidine salt microspheres to the release agent can range from 1: (0.1 to 1), preferably 1: (0.1-0.5).
The guanidine salt microspheres obtained through the grafting reaction are further separated to obtain guanidine salt microsphere solid products, for example, the separation can be performed in the following manner: centrifuging, washing with water, washing with organic solvent (such as at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, propanol, isopropanol, diethyl ether, isopropyl ether and methyl tert-butyl ether), centrifuging, and drying (such as vacuum drying).
In the process of preparing the high-barrier anti-bonding composite film, after the zinc salt and/or guanidinium microsphere composition used as the outer layer component is blended with polyolefin resin to form a film, the microspheres can form a rugged structure on the surface of the film so as to increase the interval of the polyolefin film and further solve the problem of poor opening performance of the film. After the microspheres are modified by zinc salt and/or guanidine salt, the microspheres are easy to adhere to each other because the introduced zinc or guanidine group can react with one or more maleic anhydride copolymer molecular chains, and the microspheres are easy to aggregate by the interaction of ionic bonds, hydrogen bonds, coordination bonds and the like, and the aggregation can influence the dispersion effect of the microspheres in the polyolefin resin. The introduction of the release agent in the microspheres can greatly reduce the agglomeration of the microspheres, and the synergistic effect of the release agent and the release agent can ensure that the microspheres are more uniformly dispersed in the resin, thereby further improving the opening property of the film. In addition, because the microsphere matrix is maleic anhydride copolymer and the microspheres contain a large number of polar groups, when the high-barrier adhesion-preventing composite film is subjected to multilayer coextrusion, the microspheres in the outer polyolefin resin can be bonded with the inner high-barrier plastic resin through interaction, so that the use of a binder can be omitted, the production flow is simplified, and the production cost is reduced.
The third purpose of the invention is to provide the application of the high-barrier and anti-adhesion composite film or the composite film prepared by the preparation method, especially the application in food and medicine packaging.
The applicant of the invention finds in research that a single-component and multifunctional product can be obtained by modifying microspheres, the single-component and multifunctional product is blended with polyolefin resin in an additive form and then is subjected to multilayer compounding with high-resistance heat-insulation plastic resin, and a composite film with high barrier property and adhesion resistance can be obtained, and the composite film can be used in the fields of food, medicine packaging and the like with high requirements on safety. The main advantages of the invention are:
(1) the high-performance composite membrane has excellent barrier property and opening property, and has higher added value of products;
(2) the microsphere composition used in the outer layer of the high-performance composite membrane has a multifunctional effect, can be used as a compatilizer of an opening agent and an inner-layer membrane and an outer-layer membrane, and has the advantages of mature industrial production process of microspheres, easily obtained raw materials, cheap and conventional materials used in the preparation process, and equipment which is also common equipment for industrial production;
(3) the inner layer resin and the outer layer resin used by the high-performance composite membrane are commercial products, and the equipment related to the preparation of the membrane is common equipment in industrial production.
Drawings
Fig. 1 is an element energy spectrum diagram of zinc salt microsphere 1# prepared in example 1, wherein the ordinate is intensity and the abscissa is energy value of the element, and the corresponding element can be found in a handbook according to the energy value.
Detailed Description
While the present invention will be described in conjunction with specific embodiments thereof, it is to be understood that the following embodiments are presented by way of illustration only and not by way of limitation, and that numerous insubstantial modifications and adaptations of the invention may be made by those skilled in the art in light of the teachings herein.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
1. The raw materials and the equipment used in the examples and comparative examples included:
linear Low Density Polyethylene (LLDPE): zhongtian adhesive bandage, EGF-34;
EVOH (3) in the following ratio: jequiry, japan, F171B;
polypropylene (PP): shanghai petrochemical, F800E;
maleic anhydride grafted polyethylene: mitsui ADMER, NF529;
PVA: sichuan vitamin chemical industry, SM-A2;
nitrile resin: british oil company, barex;
calcium carbonate: inokay, particle size 0.5 μm;
silicone resin: sanhe chemical industry, microbead T, particle size 2.5 μm;
silicon dioxide: inokay, particle size 1.5 μm;
antioxidant 168: basf, germany, irgafos168;
antioxidant 1010: ciba, germany, irganox1010;
polyhexamethylene guanidine hydrochloride: shanghai high polymer practice Co., ltd
Polyhexamethylene guanidine propionate: shanghai high polymer industries Ltd
Polyhexamethylene biguanide hydrochloride: utility Co Ltd of Shanghai mountain
Maleic anhydride, alpha-methylstyrene, styrene, divinylbenzene, isoamyl acetate, azobisisobutyronitrile, lithium hydroxide, sodium hydroxide, potassium hydroxide, and zinc nitrate were all purchased from inokay and were analytically pure; the mixed carbon 4 comes from the sea-fighting refining.
Other raw materials are all obtained from the market.
2. Raw materials for examples and comparative examples:
maleic anhydride-alpha-methylstyrene crosslinked alternating copolymer Microspheres (MASC) used in example 1 were prepared according to the methods described in the publications Polymer composites with high haze and high transmittance (DOI: 10.1039/c5py01072 a), under the main preparation conditions and parameters: the molar ratio of the reaction monomer maleic anhydride and alpha-methyl styrene is 1:1, the crosslinking agent is divinylbenzene, the dosage of the divinylbenzene is 13.8 percent of the weight of the monomer (the sum of the weight of the maleic anhydride and the weight of the alpha-methyl styrene), the medium is isoamyl acetate, the initiator is azobisisobutyronitrile, the reaction is carried out at 70 ℃ for 6 hours, and the particle size of the prepared polymer microsphere is 2.5 mu m.
Maleic anhydride-styrene crosslinked alternating copolymer Microspheres (MSC) used in example 2, refer to the preparation method described in the patent publication CN101338008a, and the main preparation conditions and parameters are as follows: the molar ratio of the reaction monomer maleic anhydride and styrene is 1:1, the crosslinking agent is divinylbenzene, the dosage of the divinylbenzene is 1.9 percent of the weight of the monomer (the sum of the weight of the maleic anhydride and the weight of the styrene), the medium is isoamyl acetate, the initiator is azobisisobutyronitrile, the reaction is carried out for 6 hours at 70 ℃, and the particle size of the prepared polymer microsphere is 600nm.
The maleic anhydride-carbon tetra-crosslinked alternating copolymer microspheres (MC 4C) used in example 3 refer to the preparation method described in the steps (1) to (2) in example 1 of chinese patent publication No. CN109705269B, and the main preparation conditions and parameters are as follows: the reaction monomers are maleic anhydride (100 g) and mixed carbon-tetra-A (the molar ratio of the maleic anhydride to the active ingredients (terminal olefin) in the mixed olefin is 1:1), the medium is isoamyl acetate (800 mL), the initiator is azobisisobutyronitrile (6 g), and divinylbenzene (25 g) are reacted for 6 hours at 70 ℃ and 0.5MPa, wherein the mixed carbon-tetra-A comprises the following components in percentage by weight: trans-2-butene, 40.83%; cis-2-butene, 18.18%; n-butane, 24.29%; n-butene, 9.52%; isobutene, 2.78%; others, 4.4%. The particle size of the prepared polymer microsphere is 1.5 mu m.
3. The experimental data of the examples and comparative examples were determined using the following methods:
(1) Antibacterial test standard: GB/T31402-2015 test method for antibacterial property of plastic surface; detection bacteria: escherichia coli (ATCC 8739), staphylococcus aureus (ATCC 6538P).
The antibacterial testing step refers to GB/T31402-2015 standard for testing, and comprises the following specific steps: the composite membrane to be tested is cut into 50X 50mm samples, and the bacterial suspension is diluted by 1/500 nutrient broth for standby. 0.4mL of inoculation liquid is dripped on the surface of a sample, a film with the size of 40 multiplied by 40mm is covered, then the sample is covered with a culture dish cover and cultured for 24 hours under the conditions of the temperature of 35 ℃ and the humidity of 90 percent, and finally the viable bacteria on the sample are counted to calculate the antibacterial rate.
(2) Oxygen permeability test standards: GB/T19789-2005 coulometer detection method for oxygen permeability test of plastic films and sheets of packaging materials.
The oxygen permeability testing step refers to the GB/T19789-2005 standard for testing, and comprises the following specific steps: cutting the dried composite membrane into a proper size, placing the composite membrane on grease, fastening and sealing a cover of a gas permeable chamber, blowing air in the gas permeable chamber completely by using nitrogen, setting the flow rate to be 5-15 mL/min for 30 minutes, then introducing the nitrogen into a coulometer, and measuring the zero voltage E 0 Then, the nitrogen is turned off, oxygen is introduced, and a stable test voltage value Ee is measured.
Oxygen permeability = (Ee-E) 0 ) Q/(A.R), wherein A is the area of the composite membrane, Q is the instrument test constant, and R is the load resistance value.
(3) Opening force, peel force test:
collecting and cutting the composite film by two layers (outer layers are mutually contacted), and then testing the opening force of the outer layers of the two layers of composite films according to GB/T8808-1988, a peeling test method for soft composite plastic materials;
the peeling force is carried out according to GB/T8808-1988, peel test method for soft composite plastic materials, the composite film is made into an outer layer/inner layer/outer layer structure, and the peeling force of the outer layer and the inner layer is tested.
Preparation of microsphere composition:
example 1:
dissolving 5g of sodium hydroxide in 100g of water, adding 15g of MASC microspheres into an aqueous solution of sodium hydroxide, stirring for 1 hour, adding a zinc nitrate solution (15 g of zinc nitrate is dissolved in 100g of water), stirring for 30 minutes, separating suspended matters, and drying to obtain zinc salt microspheres No. 1, wherein the energy spectrum data is shown in figure 1, gold elements sprayed on the surface of a sample are at 2.15eV, zinc elements exist in the product, the weight part of the zinc elements is 39%, and no sodium element exists, so that the sodium element is completely replaced by zinc. And mixing 10g of zinc salt microsphere No. 1 and 1g of silicone resin microsphere in a high-speed mixer for 1 minute to obtain the zinc salt microsphere composition A.
Example 2:
dissolving 1g of potassium hydroxide in 200g of water, adding 10g of MSC microspheres into the potassium hydroxide aqueous solution, stirring for 1 hour, adding a zinc nitrate solution (1 g of zinc nitrate is dissolved in 100g of water), stirring for 30 minutes, separating suspended matters, and drying to obtain zinc salt microspheres No. 2, wherein the weight fraction of zinc element is 20% as measured by element energy spectrum analysis. And mixing 10g of zinc salt microsphere No. 2 and 2g of calcium carbonate in a high-speed stirrer for 1 minute to obtain the zinc salt microsphere composition B.
Example 3:
dissolving 50g of lithium hydroxide in 100g of water, adding 5g of MC4C microspheres into a lithium hydroxide aqueous solution, stirring for 1 hour, adding a zinc nitrate solution (50 g of zinc nitrate is dissolved in 150g of water), stirring for 30 minutes, separating suspended matters, and drying to obtain zinc salt microspheres No. 3, wherein the weight fraction of zinc element is 60% as measured by element energy spectrum analysis. And mixing 10g of zinc salt microsphere No. 3 and 5g of silicon dioxide in a high-speed stirrer for 1 minute to obtain the zinc salt microsphere composition C.
Example 4:
according to the preparation method described in the publications of Polymer compositions with high haze and high transmittince, maleic anhydride, alpha-methylstyrene, azobisisobutyronitrile and divinylbenzene were added in an amount of 100g, 120.52g, 1.97g and 15.20g, respectively, and reacted at 70 ℃ for 6 hours. Then, 200g (20 wt%) of aqueous polyhexamethylene biguanide hydrochloride was added thereto, and the reaction was carried out at 80 ℃ for 3 hours. And standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge at 5000rad/min, adding 2L of water into the solid, stirring and washing, centrifuging and separating for 20 minutes by the centrifuge at 5000rad/min, and drying the solid in vacuum to obtain the guanidinium microsphere 4# with the guanidinium polymer grafted on the surface. And mixing 10g of guanidine salt microsphere No. 4 and 1g of silicone resin microsphere in a high-speed mixer for 1 minute to obtain a guanidine salt microsphere composition D.
Example 5:
the solid MASC polymer microspheres polymerized according to example 4 were isolated and added to 100g (10 wt%) of aqueous polyhexamethyleneguanidine hydrochloride and reacted at 80 ℃ for 3 hours. Standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge at 5000rad/min, adding 2L of water into the solid, stirring and washing, centrifuging and separating for 20 minutes by a centrifuge at 5000rad/min, and drying the solid in vacuum to obtain the guanidinium microspheres with the guanidinium polymers grafted on the surface # 6. And mixing 10g of guanidine salt microspheres 6# and 2g of calcium carbonate in a high-speed mixer for 1 minute to obtain a guanidine salt microsphere composition E.
Example 6:
the maleic anhydride-carbon tetra-crosslinked alternating copolymer (MC 4C) is prepared by referring to the preparation method of the steps (1) to (2) described in the chinese patent publication No. CN109705269B, and the main preparation conditions and parameters are as follows: the reaction monomers are maleic anhydride (100 g) and mixed carbon-tetra-A (the molar ratio of the maleic anhydride to the active ingredients (terminal olefin) in the mixed olefin is 1:1), the medium is isoamyl acetate (800 mL), an initiator is azobisisobutyronitrile (6 g), and divinylbenzene (25 g), wherein the mixed carbon-tetra-A comprises the following components in percentage by weight: trans-2-butene, 40.83%; cis-2-butene, 18.18%; n-butane, 24.29%; n-butene, 9.52%; isobutene, 2.78%; others, 4.4%. After 6 hours at 70 ℃ and 0.5MPa, 500g (1 wt%) of an aqueous solution of polyhexamethylene guanidine propionate was added and the reaction was carried out at 80 ℃ for 3 hours. And standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge at 5000rad/min, adding 1L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge at 5000rad/min, and drying the solid in vacuum to obtain the guanidinium microspheres 7# with the guanidinium polymers grafted on the surface. And mixing 10g of guanidine salt microsphere No. 7 and 1g of silicon dioxide in a high-speed stirrer for 1 minute to obtain a guanidine salt microsphere composition F.
Preparing a high-performance composite membrane:
example 7:
this example illustrates the preparation of the high performance composite film provided by the present invention, wherein the mass of each 100 parts of the material is 2kg;
the outer layer formula comprises: 100 parts of LLDPE resin (EGF-34, zhongtian Hemsang, the same below), 1 part of zinc salt microsphere composition A and 0.1 part of antioxidant 168;
an extrusion molding process: (a) drying of raw materials: weighing raw materials according to a formula, and drying LLDPE and EVOH resin (F171B, nippon Coli, the same below) to a moisture content of 0.3%; (b) mixing raw materials: and respectively carrying out two stages of mixing processes of high rotating speed and low rotating speed on the outer layer material by adopting a high-speed mixer. The material temperature of the high-speed mixing section is 50 ℃, the rotating speed of a main shaft is 1500rpm, and the mixing time is 2min; a low-speed mixing section: the material temperature is 35 ℃, the main shaft rotation speed is 80rpm, and the mixing time is 1min; (c) melting and plasticizing materials: the screw processing temperature of the LLDPE composition at the outer layer is as follows in sequence: 150. 190, 205 and 205 ℃ and the screw rotation speed is 60rpm; the screw processing temperature of the inner EVOH layer is 180, 200, 220 and 220 ℃ in sequence, and the screw rotating speed is 55rpm; (d) die temperature: the temperature of a co-extrusion die head is 220 ℃; (e) Cooling (at 30 deg.C), drawing, curling and cutting to obtain the high-performance composite film-1. The thickness of the composite film-1 is 50 μm, and the thickness ratio of the outer layer to the inner layer is 2:1.
Comparative example 1:
the zinc salt microsphere composition A was removed from the outer layer formulation in example 7, and the other formulation and processing technique were not changed to obtain composite film-2. The thickness of the composite film-2 is 50 μm, and the thickness ratio of the outer layer to the inner layer is 2:1.
Comparative example 2:
in example 7, the zinc salt microsphere composition a of the outer layer formulation was changed to zinc salt microsphere # 1, and the composite film-3 was prepared without changing other formulations and processing techniques. The thickness of the composite film-3 is 50 μm, and the thickness ratio of the outer layer to the inner layer is 2:1.
Comparative example 3:
in example 7, the zinc salt microsphere composition a of the outer layer formulation was changed to silicone microspheres, and the other formulations and processing techniques were unchanged to produce composite film-4. The thickness of the composite film-4 is 50 μm, and the thickness ratio of the outer layer to the inner layer is 2:1.
Comparative example 4:
the zinc salt microsphere composition A in the outer layer formula in the example 7 is changed into maleic anhydride grafted polyethylene, and other formulas and processing techniques are not changed, so that the composite film-5 is prepared. The thickness of the composite film 5 is 50 μm, and the thickness ratio of the outer layer to the inner layer is 2:1.
Comparative example 5:
the zinc salt microsphere composition A in the outer layer formula in example 7 was changed to MASC microspheres, and the other formula and processing technique were not changed to obtain composite film-6. The thickness of the composite film-6 is 50 μm, and the thickness ratio of the outer layer to the inner layer is 2:1.
Example 8:
this example illustrates the preparation of the high performance composite film provided by the present invention, wherein the mass of each 100 parts of the material is 2kg;
the outer layer formula is as follows: 100 parts of PP resin (F800E, shanghai petrochemical), 0.2 part of zinc salt microsphere composition B,0.5 part of antioxidant 168,0.5 parts of lubricant PEG;
the extrusion molding process comprises the following steps: (a) drying raw materials: weighing raw materials according to a formula, and drying PP and EVOH resin until the moisture content is 0.3%; (b) mixing raw materials: and respectively carrying out two stages of mixing processes of high rotating speed and low rotating speed on the outer layer material by adopting a high-speed mixer. The material temperature of the high-speed mixing section is 50 ℃, the rotating speed of a main shaft is 1500rpm, and the mixing time is 2min; a low-speed mixing section: the material temperature is 35 ℃, the main shaft rotation speed is 80rpm, and the mixing time is 1min; (c) melting and plasticizing materials: the screw processing temperature of the outer PP composition is as follows in sequence: 150. 190, 205 and 205 ℃ and the screw rotation speed is 60rpm; the screw processing temperature of the inner EVOH layer is 180, 200, 220 and 220 ℃ in sequence, and the screw rotating speed is 55rpm; (d) die temperature: the temperature of a co-extrusion die head is 200 ℃; (e) Cooling (at 45 deg.C), drawing, curling and cutting to obtain the high-performance composite film-7. The thickness of the composite film-7 is 100 μm, and the thickness ratio of the outer layer to the inner layer is 10.
Example 9:
this example illustrates the preparation of the high performance composite film provided by the present invention, wherein the mass of each 100 parts of the material is 2kg;
the outer layer formula is as follows: 100 parts of PP resin (F800E, shanghai petrochemical), 20 parts of zinc salt microsphere composition C,2.5 parts of antioxidant 168,2.5 parts of plasticizer tributyl citrate;
the extrusion molding process comprises the following steps: (a) drying of raw materials: weighing raw materials according to a formula, and drying PP and PVA resin (SM-A2, sichuan vitamin chemical industry) to water content of 0.3%; (b) mixing raw materials: and respectively carrying out two stages of mixing processes of high rotating speed and low rotating speed on the outer layer material by adopting a high-speed mixer. The material temperature of the high-speed mixing section is 50 ℃, the rotating speed of a main shaft is 1500rpm, and the mixing time is 2min; a low-speed mixing section: the material temperature is 35 ℃, the main shaft rotation speed is 80rpm, and the mixing time is 1min; and (c) melting and plasticizing materials: the screw processing temperature of the outer PP composition is as follows in sequence: 150. 190, 205 and 205 ℃ and the screw rotating speed is 60rpm; the processing temperature of the screw of the PVA at the inner layer is 180 ℃,200 ℃, 220 ℃ and 220 ℃ in sequence, and the rotating speed of the screw is 55rpm; (d) die temperature: the temperature of a co-extrusion die head is 190 ℃; (e) Cooling (at 55 deg.C), drawing, curling and cutting to obtain the high-performance composite film-8. The thickness of the composite film-8 is 10 μm, and the thickness ratio of the outer layer to the inner layer is 1:1.
Example 10:
this example illustrates the preparation of a high performance composite film according to the present invention, wherein the mass of each 100 parts of the material is 2kg;
the outer layer formula comprises: 100 parts of LLDPE resin, 5 parts of guanidine salt microsphere composition D and 1 part of antioxidant 168;
the extrusion molding process comprises the following steps: (a) drying of raw materials: weighing raw materials according to a formula, and drying LLDPE and nitrile resin (Barex, british oil company) to a moisture content of 0.3%; (b) mixing raw materials: and respectively carrying out two stages of mixing processes of high rotating speed and low rotating speed on the outer layer material by adopting a high-speed mixer. The material temperature of the high-speed mixing section is 50 ℃, the main shaft rotating speed is 1500rpm, and the mixing time is 2min; a low-speed mixing section: the material temperature is 35 ℃, the main shaft rotation speed is 80rpm, and the mixing time is 1min; and (c) melting and plasticizing materials: the screw processing temperature of the outer layer LLDPE composition is as follows in sequence: 150. 190, 205 and 205 ℃ and the screw rotation speed is 60rpm; the screw processing temperature of the inner EVOH layer is 180, 200, 220, 240 and 240 ℃ in sequence, and the screw rotating speed is 55rpm; (d) die temperature: the temperature of a co-extrusion die head is 230 ℃; (e) Cooling (at 65 deg.C), drawing, curling and cutting to obtain the high-performance composite film-9. The thickness of the composite film-9 is 200 μm, and the thickness ratio of the outer layer to the inner layer is 0.5.
Example 11:
this example illustrates the preparation of the high performance composite film provided by the present invention, wherein the mass of each 100 parts of the material is 2kg;
the outer layer formula is as follows: 100 parts of LLDPE resin, 0.5 part of guanidine salt microsphere composition E and 0.2 part of antioxidant 168;
the extrusion molding process comprises the following steps: (a) drying of raw materials: weighing raw materials according to a formula, and drying LLDPE and EVOH resin until the moisture content is 0.3%; (b) mixing raw materials: and respectively carrying out two stages of mixing processes of high rotating speed and low rotating speed on the outer layer material by adopting a high-speed mixer. The material temperature of the high-speed mixing section is 50 ℃, the main shaft rotating speed is 1500rpm, and the mixing time is 2min; a low-speed mixing section: the material temperature is 35 ℃, the main shaft rotation speed is 80rpm, and the mixing time is 1min; and (c) melting and plasticizing materials: the screw processing temperature of the outer layer LLDPE composition is as follows in sequence: 150. 190, 205 and 205 ℃ and the screw rotation speed is 60rpm; the screw processing temperature of the inner EVOH layer is 180, 200, 220 and 220 ℃ in sequence, and the screw rotating speed is 55rpm; (d) die temperature: the temperature of a co-extrusion die head is 200 ℃; (e) Cooling (at 30 deg.C), drawing, curling and cutting to obtain the high-performance composite film-10. The thickness of the composite film is 50 μm, and the thickness ratio of the outer layer to the inner layer is 2:1.
Example 12:
this example illustrates the preparation of the high performance composite film provided by the present invention, wherein the mass of each 100 parts of the material is 2kg;
the outer layer formula is as follows: 100 parts of LLDPE resin, 0.3 part of guanidine salt microsphere composition F and 0.2 part of antioxidant 168;
the extrusion molding process comprises the following steps: (a) drying of raw materials: weighing raw materials according to a formula, and drying LLDPE and EVOH resin until the moisture content is 0.3%; (b) mixing raw materials: and respectively carrying out two stages of mixing processes of high rotating speed and low rotating speed on the outer layer material by adopting a high-speed mixer. The material temperature of the high-speed mixing section is 50 ℃, the rotating speed of a main shaft is 1500rpm, and the mixing time is 2min; a low-speed mixing section: the material temperature is 35 ℃, the main shaft rotation speed is 80rpm, and the mixing time is 1min; (c) melting and plasticizing materials: the screw processing temperature of the outer layer LLDPE composition is as follows in sequence: 150. 190, 205 and 205 ℃ and the screw rotation speed is 60rpm; the screw processing temperature of the inner EVOH layer is 180 ℃,200 ℃, 230 ℃, 250 ℃ and 250 ℃ in sequence, and the screw rotating speed is 55rpm; (d) die temperature: the temperature of a co-extrusion die head is 250 ℃; (e) Cooling (at 30 deg.C), drawing, curling and cutting to obtain the high-performance composite film-11. The thickness of the composite film-11 is 250 μm, and the thickness ratio of the outer layer to the inner layer is 5:1.
Examples, comparative example composite film data
Figure BDA0003035820220000191
As can be seen from the above table, compared with the composite film 2, the zinc salt microspheres (composite film 3), the microsphere composition (composite film 1) or the silicone resin microspheres (composite film 4) all have an opening effect on the outer layer of the composite film, wherein the opening effect of the zinc salt microspheres is equivalent to that of the commercially available silicone resin microspheres, so that the opening force of the original resin can be reduced by one order of magnitude, and the microsphere composition can further reduce the opening force by about 42%; compared with unmodified microspheres (composite membrane 6), the opening force is reduced after the modification by the zinc salt and/or the guanidine salt, which shows that the microsphere composition provided by the invention has more excellent opening property. In addition, the composite films 2 and 4 are compared to find that the bonding effect between the outer layer and the inner layer of the composite film is reduced after the silicone microspheres are added into the resin, and the peeling force can be improved by about 78% after the modified microspheres are added, which is attributed to that the modified microspheres of the invention are provided with a large number of polar groups, and the high-barrier material of the inner layer is also provided with a large number of polar groups, so that the microspheres and the inner layer directly have hydrogen bond interaction and the like, and the bonding effect is improved; the outer layer of the composite film belongs to nonpolar polyolefin, and the acting force of the microspheres is far lower than that of the microspheres and the inner layer material. Compared with the modified microspheres, the modified microsphere composition has no obvious change in the stripping force. The above data of the examples and comparative examples illustrate that the microsphere composition used in the present invention has both open and cohesive effects, and the inner layer material provides the composite film with excellent barrier properties, so that the composite film of the present invention has high performance such as open and barrier properties.

Claims (17)

1. A high-barrier anti-bonding composite film comprises an outer layer film and an inner layer film;
the outer film comprises an anti-adhesive composition;
the anti-adhesion composition comprises a polyolefin resin and a multifunctional additive;
the multifunctional additive is selected from at least one of a zinc salt microsphere composition and a guanidine salt microsphere composition;
the inner film comprises a high-resistance heat-insulation plastic resin;
preferably, the first and second electrodes are formed of a metal,
the thickness ratio of the outer layer film to the inner layer film is (10-0.1): 1, preferably (10 to 0.5): 1;
more preferably, the total thickness of the high-barrier adhesion-preventing composite film is 10 to 250 μm.
2. The high barrier anti-adhesion composite film according to claim 1, wherein:
the anti-bonding composition comprises the following components in parts by weight:
100 parts by weight of a polyolefin resin,
0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight of the multifunctional additive.
3. The high barrier anti-adhesion composite film according to claim 1, wherein:
the polyolefin resin is at least one selected from polypropylene resin and polyethylene resin;
wherein the polypropylene resin is selected from at least one of homo-polypropylene and co-polypropylene;
the polyethylene resin is at least one selected from high-density polyethylene and low-density polyethylene; linear low density polyethylene is preferred.
4. The high barrier anti-adhesion composite film according to claim 1, wherein:
the zinc salt microsphere composition comprises a mixture of zinc salt microspheres and a release agent; wherein the weight ratio range of the zinc salt microspheres to the release agent is 1: (0.1 to 1), preferably 1: (0.1 to 0.5); and/or the presence of a gas in the gas,
the guanidine salt microsphere composition comprises a mixture of guanidine salt microspheres and a release agent; wherein the weight ratio range of the guanidine salt microspheres to the release agent is 1: (0.1 to 1), preferably 1: (0.1-0.5).
5. The high barrier anti-adhesion composite film according to claim 4, wherein:
the zinc salt microspheres and/or guanidine salt microspheres are polymer microspheres with surfaces subjected to grafting or complexing reaction with zinc ions and/or guanidine salt polymers;
the polymer microspheres are maleic anhydride alternating copolymer microspheres, preferably maleic anhydride cross-linked alternating copolymer microspheres;
preferably, the polymer microspheres are prepared by a self-stabilizing precipitation polymerization method.
6. The high-barrier anti-adhesion composite film according to claim 4, wherein:
in the zinc salt microsphere, the weight percentage of zinc element is 10-70%, preferably 20-60%.
7. The high-barrier anti-adhesion composite film according to claim 5, wherein:
the guanidine salt polymer is selected from at least one of polyhexamethylene (bis) guanidine inorganic salt, polyhexamethylene (bis) guanidine organic salt, polyoxyethylene guanidine inorganic salt and polyoxyethylene guanidine organic salt; the guanidine salt polymer is preferably at least one selected from the group consisting of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine sulfonate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate, polyoxyethylene guanidine hydrochloride, polyoxyethylene guanidine phosphate, polyoxyethylene guanidine sulfonate, polyoxyethylene guanidine acetate, polyoxyethylene guanidine propionate, polyoxyethylene guanidine stearate, polyoxyethylene guanidine laurate, and polyoxyethylene guanidine benzoate; more preferably at least one of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate, and polyoxyethylene guanidine hydrochloride.
8. The high-barrier anti-adhesion composite film according to claim 5, wherein:
the polymer microspheres in the zinc salt microspheres and/or guanidine salt microspheres are maleic anhydride cross-linked alternating copolymers obtained by a structural unit A provided by maleic anhydride, a structural unit B provided by a monomer M and a structural unit C provided by a cross-linking agent; wherein, the monomer M is selected from monomers containing isolated carbon-carbon double bonds; the crosslinking agent is selected from vinyl-containing monomers with two or more functionalities capable of free radical polymerization.
9. The high barrier adhesion-preventing composite film according to claim 8, wherein:
the monomer M is selected from monomers containing isolated carbon-carbon double bonds; preferably, the monomer M is selected from at least one of vinyl acetate, styrene, alpha-methyl styrene, C4, C5, C8 and C9 mixed olefin; more preferably at least one of vinyl acetate, styrene, alpha-methylstyrene, C4-C5 mixed olefins; and/or the presence of a gas in the gas,
the crosslinking agent is divinylbenzene and/or an acrylate crosslinking agent containing at least two acrylate groups; the structural formula of the acrylate group is as follows: -O-C (O) -C (R') = CH 2 R' is H or C1-C4 alkyl; preferably, the crosslinking agent is selected from at least one of divinylbenzene, propylene glycol-based di (meth) acrylate, ethylene glycol-based di (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, phthalic acid ethylene glycol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylate;
the propylene glycol-based di (meth) acrylate is preferably at least one selected from the group consisting of 1,3-propylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol diacrylate and 1,2-propylene glycol diacrylate; the ethylene glycol-based di (meth) acrylate is preferably at least one selected from the group consisting of ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate and tetraethylene glycol diacrylate.
10. The high barrier anti-adhesion composite film according to claim 1, wherein:
the anti-adhesion composition comprises other auxiliary agents;
based on 100 parts by weight of the polyolefin resin, 0.1-5 parts by weight of other additives;
the other auxiliary agent is at least one selected from antioxidant, antistatic agent, lubricant, ultraviolet absorbent and plasticizer.
11. The high barrier anti-adhesion composite film according to claim 1, wherein:
the high-resistance heat-insulation plastic resin is selected from at least one of ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyethylene naphthalate (PEN), nitrile resin and polyamide.
12. The method for preparing the high-barrier anti-adhesion composite film according to any one of claims 1 to 11, characterized by comprising the following steps:
and carrying out multilayer coextrusion on the components comprising the anti-adhesion composition and the high-resistance heat-insulation plastic resin to obtain the high-resistance anti-adhesion composite film.
13. The preparation method of the high-barrier anti-adhesion composite film according to claim 12, characterized by comprising the following steps:
(1) Fully mixing the components including the polyolefin resin and the multifunctional additive, and extruding, melting and granulating to obtain an anti-adhesion composition;
(2) Preparing a film from the anti-adhesion composition obtained in the step (1) and high-resistance heat-insulation plastic resin through multilayer coextrusion casting to obtain the high-resistance anti-adhesion composite film; preferably, the cooling temperature during the co-extrusion die flow in the step (2) is 30 to 65 ℃.
14. The preparation method of the high-barrier anti-adhesion composite film according to claim 13, wherein the method comprises the following steps:
the preparation method of the zinc salt microsphere composition in the multifunctional additive comprises the following steps:
adding the polymer microspheres into an alkali metal hydroxide aqueous solution for full reaction, and then adding a zinc salt aqueous solution for full reaction; or adding an alkali metal hydroxide aqueous solution into a polymerization system of the polymer microsphere, and then adding a zinc salt aqueous solution for full reaction; then separating and drying, and mixing the obtained zinc salt microspheres with a separant to obtain the zinc salt microsphere composition;
preferably, the preparation method of the zinc salt microsphere composition comprises the following steps:
a. taking alkali metal hydroxide, adding the alkali metal hydroxide into water for dissolving to obtain an alkali metal hydroxide aqueous solution; preferably, the weight ratio of the alkali metal hydroxide to water ranges from (0.1 to 100): 100, more preferably (0.5 to 50): 100, respectively;
b. adding the polymer microspheres into the alkali metal hydroxide aqueous solution prepared in the step a, and fully mixing for reaction; or adding the alkali metal hydroxide aqueous solution prepared in the step a into a polymerization system of polymer microspheres, and fully mixing for reaction;
wherein, the weight ratio of the polymer microspheres to the alkali metal hydroxide is preferably (0.1-20): 1, more preferably (0.1 to 10): 1;
c. adding zinc salt into water for dissolving to obtain a zinc salt aqueous solution, then adding the zinc salt aqueous solution into the mixed solution obtained in the step b, fully mixing and reacting, separating suspended matters, and drying to obtain the zinc salt microspheres;
preferably, the weight ratio of the zinc salt to the polymeric microspheres is in the range of (0.1-20): 1, more preferably (0.1 to 10): 1;
d. c, mixing the zinc salt microspheres obtained in the step c with a separant to obtain the zinc salt microsphere composition;
wherein, preferably, the weight ratio of the zinc salt microspheres to the release agent is in the range of 1: (0.1 to 1), more preferably 1: (0.1 to 0.5); the separant is selected from particles with the particle size of 150-5000 nm, preferably at least one of silicon dioxide, calcium carbonate, talcum powder, diatomite, kaolin, calcium hydrophosphate and silicone resin.
15. The preparation method of the high-barrier anti-adhesion composite film according to claim 14, wherein the method comprises the following steps:
in the step a, the alkali metal hydroxide is at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, preferably at least one selected from lithium hydroxide, sodium hydroxide and potassium hydroxide; and/or the presence of a gas in the gas,
in the step c, the zinc salt is selected from at least one water-soluble zinc salt, preferably at least one of zinc acetate, zinc lactate, zinc chloride, zinc bromide, zinc nitrate, zinc sulfate and zinc gluconate.
16. The preparation method of the high-barrier anti-adhesion composite film according to claim 13, wherein the method comprises the following steps:
the preparation method of the guanidine salt microsphere composition in the multifunctional additive comprises the following steps:
adding the polymer microspheres into a guanidine salt polymer aqueous solution for grafting reaction, or adding the guanidine salt polymer aqueous solution into a polymerization system of the polymer microspheres for grafting reaction; then separating and drying, and mixing the obtained guanidine salt microspheres with a separant to obtain the guanidine salt microsphere composition;
preferably, the first and second electrodes are formed of a metal,
the amount of maleic anhydride used to provide the structural units of the polymeric microspheres was 1000g,
the dosage of the guanidine salt polymer aqueous solution is 500-10000 g, preferably 1000-8000 g; the concentration of the aqueous guanidinium polymer solution is from 0.5 to 50% by weight, preferably from 1 to 30% by weight; and/or the presence of a gas in the gas,
the conditions of the grafting reaction include: the temperature is 0-100 ℃, and the optimal temperature is 2.5-90 ℃; the reaction time is 0.5 to 10 hours; and/or the presence of a gas in the gas,
the separant is selected from particles with the particle size of 150-5000 nm, preferably at least one of silicon dioxide, calcium carbonate, talcum powder, diatomite, kaolin, calcium hydrophosphate and silicone resin; the weight ratio of the guanidine salt microspheres to the release agent is in the range of 1: (0.1 to 1), preferably 1: (0.1-0.5).
17. Use of a high barrier adhesion preventing composite film according to any of claims 1 to 11 or a composite film prepared by the preparation method according to any of claims 12 to 16, preferably in food and pharmaceutical packaging.
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