CN113308013B - High-barrier composite film for packaging sensitive medicinal materials and preparation method thereof - Google Patents
High-barrier composite film for packaging sensitive medicinal materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-barrier composite film for packaging sensitive medicinal materials and a preparation method thereof, wherein a synergistic solution is coated on a polyethylene film, and the high-barrier composite film is obtained by hot air drying and forming; the preparation raw materials of the synergistic liquid comprise inorganic filler and auxiliary filler. The high-barrier composite film has the advantages of high mechanical strength and good barrier capability for gases including oxygen and water vapor.
Description
Technical Field
The invention relates to the technical field of high-barrier composite films, in particular to a high-barrier composite film for packaging sensitive medicinal materials and a preparation method thereof.
Background
Polyethylene (PE) films have excellent water and drought resistance, moisture resistance, and chemical resistance, and are used in a large number of packages for medical products including medicines. However, for those drugs sensitive to oxygen and water vapor, the gas barrier capability of the polyethylene film produced by the prior art still fails to satisfy the requirement of sealed package.
The hexagonal crystal boron nitride with the graphene-like structure has very good barrier capability to gases such as water vapor, oxygen and the like; the silicon dioxide is dispersed in the base material, so that the mechanical strength of the whole material, such as tensile strength and the like, can be improved; however, if the inorganic non-metallic powder particles are directly added into a high molecular material, such as a polyethylene film, the difference between the acting force and the activation energy of the two main raw materials on the molecular layer is large, so that the material is easy to lose effectiveness, such as aging, brittle failure, cracking and the like, in the processes of storage, transportation and service, and thus, the immeasurable loss is caused. The prior art has no report of good combination of the two raw materials and a high polymer film, so that the invention provides a technical scheme for organically and highly combining boron nitride, silicon dioxide and a polyethylene film, and obtains a synergist capable of improving the water vapor and oxygen isolation capability and mechanical strength of high polymer films including but not limited to polyethylene films.
Patent CN207517772U discloses a barrier film, which comprises a first substrate layer, an inorganic barrier layer, and a second substrate layer; the inorganic substance barrier layer is clamped between the first substrate layer and the second substrate layer; the bottom surface of the first substrate layer is also covered with a diffusion layer or a hard coating, but the mechanical strength of the obtained film is poor, and the barrier capability for gas is not satisfactory.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-barrier composite film for packaging sensitive medicinal materials and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
a high-barrier composite film for packaging sensitive medicinal materials is prepared by the following steps:
coating the synergistic solution on two surfaces of the polyethylene film; and drying and forming by hot air to obtain the high-barrier composite film for packaging sensitive medicinal materials.
As a preferred scheme, the high-barrier composite film for packaging sensitive medicinal materials is prepared by the following steps:
coating the synergistic solution on two surfaces of the polyethylene film, wherein the coating thickness is 1.5-2 μm; and (3) drying and forming by hot air at 70-75 ℃ at a wind speed of 1.5-2m/s for 50-60min to obtain the high-barrier composite film for packaging sensitive medicinal materials.
The preparation method of the synergistic solution comprises the following steps: and mixing the synergist and absolute ethyl alcohol, and homogenizing to obtain the synergistic liquid.
As a preferable scheme, the preparation method of the synergistic solution comprises the following steps: mixing the synergist and absolute ethyl alcohol according to the mass ratio of 1 (2-3), and homogenizing at the rotating speed of 12000-14000r/min for 2-5min to obtain the synergistic solution.
The preparation method of the synergist comprises the following steps:
v1, putting the inorganic filler into the zinc citrate solution, homogenizing, filtering, taking filter residue and drying to obtain the pretreated inorganic filler; the inorganic filler is at least one of silicon dioxide and boron nitride;
v2 mixing the auxiliary filler and the solvent, heating and stirring to obtain latex A; the auxiliary filler is at least one of ethylene-vinyl alcohol copolymer and polyethylene terephthalate; the solvent is a mixture of dimethyl carbonate and absolute ethyl alcohol;
v3, mixing the pretreated inorganic filler obtained from V1, the latex A obtained from V2, the coupling agent and the acid anhydride, stirring, simultaneously performing microwave treatment, filtering to obtain filter residue, washing with absolute ethyl alcohol, then performing reduced pressure drying, crushing and sieving to obtain the synergist; the coupling agent is at least one of heptamethyldisilamine and hexaethylcyclotrisiloxane; the acid anhydride is at least one of maleic anhydride and isobutyric anhydride.
The hexagonal crystal boron nitride with the graphene-like structure has very good barrier capability to gases such as water vapor, oxygen and the like; the silicon dioxide is dispersed in the base material, so that the mechanical strength of the whole material, such as tensile strength and the like, can be improved; however, if the inorganic non-metallic powder particles are directly added into a high molecular material, such as a polyethylene film, the difference between the acting force and the activation energy of the two main raw materials on the molecular layer is large, so that the material is easy to lose effectiveness, such as aging, brittle failure, cracking and the like, in the processes of storage, transportation and service, and thus, the immeasurable loss is caused. The prior art has no report of good combination of the two raw materials and a high polymer film, so that the invention provides a technical scheme for organically and highly combining boron nitride, silicon dioxide and a polyethylene film, and obtains a synergist capable of improving the water vapor and oxygen isolation capability and mechanical strength of high polymer films including but not limited to polyethylene films.
Hydroxyl and ester groups in the ethyl lactate can improve the dispersibility and uniformity of the silicon dioxide and the boron nitride. Divalent zinc ions in the zinc citrate and citrate rich in oxygen atoms can generate certain charge attraction effect on the silicon dioxide and the boron nitride to guide the silicon dioxide and the boron nitride to uniformly diffuse in the ethyl lactate aqueous solution; and the doping of a small amount of zinc ions can improve the mutual wettability of the hexagonal boron nitride and the acid anhydride in the subsequent process. The ethylene-vinyl alcohol has good mechanical strength, elasticity, hardness, wear resistance and weather resistance, and the polyethylene terephthalate has good various mechanical properties including creep resistance, fatigue resistance, friction resistance, dimensional stability and the like in a wider temperature range, so that the two raw materials can be used as auxiliary fillers for the synergist to improve the mechanical properties of the high polymer film and the barrier property of various gases including oxygen and water vapor; in addition, the auxiliary filler can be highly combined with the inorganic filler under the promoting action of the anhydride, so that the compatibility of the inorganic filler and a polymer film is greatly improved, and the service life and the reliability of the synergist are also improved.
As a preferred scheme, the preparation method of the synergist comprises the following steps:
v1, putting the inorganic filler into the zinc citrate solution, homogenizing, filtering, taking filter residue and drying to obtain the pretreated inorganic filler; the inorganic filler is a mixture of silicon dioxide and boron nitride according to the mass ratio of (1-3) to (1-3);
v2 mixing the auxiliary filler and the solvent, heating and stirring to obtain latex A; the auxiliary filler is a mixture of ethylene-vinyl alcohol copolymer and polyethylene glycol terephthalate according to the mass ratio of (1-5) to (1-5); the solvent is a mixture of dimethyl carbonate and absolute ethyl alcohol according to a mass ratio of 1 (1-4);
v3, mixing the pretreated inorganic filler obtained from V1, the latex A obtained from V2, the coupling agent and the acid anhydride, stirring, simultaneously performing microwave treatment, filtering to obtain filter residue, washing with absolute ethyl alcohol, performing reduced pressure drying, crushing, and screening with a 1000-mesh 1200-mesh screen to obtain the synergist; the coupling agent is a mixture of heptamethyldisilamine and hexaethylcyclotrisiloxane according to the mass ratio of (1-4) to (1-4); the acid anhydride is a mixture of maleic anhydride and isobutyric anhydride in a mass ratio of (1-3) to (1-3).
The negative charge center formed by three oxygens in the dimethyl carbonate can be cooperated with the oxygen-containing unsaturated bond heterocyclic structure of maleic anhydride and the symmetrical trioxane structure of isobutyric anhydride to enhance the compatibility between the auxiliary filler and the inorganic filler. The nitrogen atoms in the heptamethyldisilamine are positioned at the center of the molecule, the silicon-oxygen interphase heterocyclic ring in the hexaethylcyclotrisiloxane and the short carbon chain extending outside the silicon-oxygen interphase heterocyclic ring generate strong acting force with the surface of the inorganic filler, so that the mutual infiltration capacity and the sufficient bonding strength of the inorganic filler, the auxiliary filler and the high polymer film are improved, and the service life and the reliability of the synergist are also improved. The invention adopts microwave as an auxiliary means, provides necessary energy disturbance, promotes the grafting modification between the coupling agent, the acid anhydride and the two fillers in a dynamics level, and leads the raw materials to be combined in a microscopic level so as to obtain excellent macroscopic performance.
In the step V1: the bath ratio of the inorganic filler to the zinc citrate solution is 1g (10-15) mL; the mass fraction of ethyl lactate in the zinc citrate solution is 58-63%, the mass fraction of zinc citrate is (2-5)%, and the balance is water, and the temperature is 35-45 ℃; the rotation speed of the homogenization treatment is 12000-14000r/min, and the time duration of the homogenization treatment is 2-5 min; the drying temperature is 90-95 ℃, and the drying time is 5-6 h.
In the step V2: the mass ratio of the auxiliary filler to the solvent is 1 (5.5-8); the heating temperature in the step V2 is 68-73 ℃, the heating time is 110-140min, and the stirring speed is 70-85 r/min.
In the step V3: the mass ratio of the inorganic filler, the latex A, the coupling agent and the acid anhydride is (0.5-1.2): 6-8): 1-1.7): 0.1-0.4; the stirring time of the step V3 is 60-80min, and the stirring speed is 80-110 r/min; the power of the microwave treatment is 520-560W, and the frequency is 410-420 MHz; the washing flow rate is 450-600mL/min, the temperature is 40-50 ℃, and the washing time is 12-20 min; the temperature of the reduced pressure drying is 70-75 ℃, the pressure is 1.2-1.5kPa, and the time of the reduced pressure drying is 6-8 h.
The invention has the beneficial effects that:
1. the invention provides a high-barrier composite film for packaging sensitive medicinal materials and a preparation method thereof, and the high-barrier composite film has very good mechanical strength and very good barrier capability to water vapor and oxygen.
2. The invention provides a synergist which can enhance the mechanical strength of high polymer films such as polyethylene films and the like and the barrier capability of gases such as oxygen, water vapor and the like, wherein the synergist is prepared by taking silicon dioxide and boron nitride as inorganic fillers, taking ethylene-vinyl alcohol copolymer and polyethylene glycol terephthalate as auxiliary fillers, taking maleic anhydride and isobutyric anhydride as anhydride accelerators, taking heptamethyldisilamine and hexaethylcyclotrisiloxane as coupling agents and providing energy disturbance through microwave assistance.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
polyethylene film, purchased from kay pigeon plastification ltd, CAS: 9002-88-4, trade mark: 2420H, processing: film blowing, density: 0.924g/cm3Melt flow rate: 1.9g/10min, tensile modulus: 260MPa, tensile strength: 26MPa, Vicat softening temperature: at 94 ℃.
Zinc citrate, available from carbofuran technologies ltd, CAS: 546-46-3.
Ethyl lactate, purchased from my heimairei chemical technologies, inc, CAS: 97-64-3.
Silica, purchased from beijing gagaku new materials science and technology limited, CAS: 7631-86-9, model: GK-SiO2-15, particle size: 15 nm.
Boron nitride, purchased from seiko technologies ltd, CAS: 10043-11-5, particle size: 50nm, crystal form: hexagonal, type: DK-BN-001.
Ethylene-vinyl alcohol copolymer, purchased from hong plastification limited of Dongguan city, degree of polymerization: 2000, particle size: 320 μm, brand: kolepi, brand: FP 201B.
Polyethylene terephthalate, purchased from mairei chemical technologies, inc, CAS: 25038-59-9, particle size: 0.6mm, molecular weight: 6800.
dimethyl carbonate, purchased from my shanghai meiriel chemical technology limited, CAS: 616-38-6.
Heptamethyldisilamine, purchased from maireil chemical technologies, inc: 920-68-3.
Hexaethylcyclotrisiloxane, purchased from carbofuran technologies, inc, CAS: 2031-79-0.
Maleic anhydride, purchased from carbofuran technologies ltd, CAS: 108-31-6.
Isobutyric anhydride, purchased from carbofuran technologies ltd, CAS: 97-72-3.
Example 1
A high-barrier composite film for packaging sensitive medicinal materials is prepared by the following steps:
coating the synergistic solution on two surfaces of the polyethylene film, wherein the coating thickness is 1.5 mu m; and (3) drying and forming by hot air at 70 ℃ at a wind speed of 1.5m/s for 50min to obtain the high-barrier composite film for packaging sensitive medicinal materials.
The preparation method of the synergistic solution comprises the following steps: and mixing the synergist and absolute ethyl alcohol according to the mass ratio of 1:2.2, and homogenizing at the rotating speed of 14000r/min for 2min to obtain the synergistic liquid.
The preparation method of the synergist comprises the following steps:
v1, putting the inorganic filler into the zinc citrate solution, homogenizing, filtering, taking filter residue and drying to obtain the pretreated inorganic filler; the inorganic filler is a mixture of silicon dioxide and boron nitride according to a mass ratio of 1: 2.2;
v2 mixing the auxiliary filler and the solvent, heating and stirring to obtain latex A; the auxiliary filler is a mixture of ethylene-vinyl alcohol copolymer and polyethylene glycol terephthalate according to the mass ratio of 3: 1; the solvent is a mixture of dimethyl carbonate and absolute ethyl alcohol according to a mass ratio of 1: 1.2;
v3, mixing the pretreated inorganic filler obtained from V1, the latex A obtained from V2, the coupling agent and the acid anhydride, stirring, simultaneously performing microwave treatment, filtering to obtain filter residue, washing with absolute ethyl alcohol, performing reduced pressure drying, crushing, and screening with a 1200-mesh screen to obtain the synergist; the coupling agent is a mixture of heptamethyldisilamine and hexaethylcyclotrisiloxane in a mass ratio of 1: 1; the acid anhydride is a mixture of maleic anhydride and isobutyric anhydride according to the mass ratio of 3: 1.2.
In the step V1: the bath ratio of the inorganic filler to the zinc citrate solution is 1g:12 mL; the mass fraction of ethyl lactate in the zinc citrate solution is 62%, the mass fraction of zinc citrate is 4.3%, and the balance is water, and the temperature is 40 ℃; the rotation speed of the homogenization treatment is 14000r/min, and the time duration of the homogenization treatment is 3 min; the drying temperature is 93 ℃, and the drying time is 5 h.
In the step V2: the mass ratio of the auxiliary filler to the solvent is 1: 6; the heating temperature of the step V2 is 70 ℃, the heating time is 130min, and the stirring speed is 80 r/min.
In the step V3: the mass ratio of the inorganic filler to the latex A to the coupling agent to the anhydride is 1:7:1.2: 0.3; the stirring time of the step V3 is 70min, and the stirring speed is 100 r/min; the power of the microwave treatment is 550W, and the frequency is 420 MHz; the flushing flow rate is 600mL/min, the temperature is 50 ℃, and the flushing time is 15 min; the temperature of the reduced pressure drying is 75 ℃, the pressure is 1.5kPa, and the time length of the reduced pressure drying is 6 h.
Example 2
Essentially the same as in example 1, except that:
the preparation method of the synergist comprises the following steps:
v1, putting the inorganic filler into the zinc citrate solution, homogenizing, filtering, taking filter residue and drying to obtain the pretreated inorganic filler; the inorganic filler is a mixture of silicon dioxide and boron nitride according to a mass ratio of 1: 2.2;
v2 mixing the auxiliary filler and the solvent, heating and stirring to obtain latex A; the auxiliary filler is a mixture of ethylene-vinyl alcohol copolymer and polyethylene glycol terephthalate according to the mass ratio of 3: 1; the solvent is a mixture of dimethyl carbonate and absolute ethyl alcohol according to a mass ratio of 1: 1.2;
v3, mixing the pretreated inorganic filler obtained from V1, the latex A obtained from V2, the coupling agent and the acid anhydride, stirring, simultaneously performing microwave treatment, filtering to obtain filter residue, washing with absolute ethyl alcohol, performing reduced pressure drying, crushing, and screening with a 1200-mesh screen to obtain the synergist; the coupling agent is heptamethyl disilylamine; the acid anhydride is a mixture of maleic anhydride and isobutyric anhydride according to the mass ratio of 3: 1.2.
In the step V1: the bath ratio of the inorganic filler to the zinc citrate solution is 1g:12 mL; the mass fraction of ethyl lactate in the zinc citrate solution is 62%, the mass fraction of zinc citrate is 4.3%, and the balance is water, and the temperature is 40 ℃; the rotation speed of the homogenization treatment is 14000r/min, and the time duration of the homogenization treatment is 3 min; the drying temperature is 93 ℃, and the drying time is 5 h.
In the step V2: the mass ratio of the auxiliary filler to the solvent is 1: 6; the heating temperature of the step V2 is 70 ℃, the heating time is 130min, and the stirring speed is 80 r/min.
In the step V3: the mass ratio of the inorganic filler to the latex A to the coupling agent to the anhydride is 1:7:1.2: 0.3; the stirring time of the step V3 is 70min, and the stirring speed is 100 r/min; the power of the microwave treatment is 550W, and the frequency is 420 MHz; the flushing flow rate is 600mL/min, the temperature is 50 ℃, and the flushing time is 15 min; the temperature of the reduced pressure drying is 75 ℃, the pressure is 1.5kPa, and the time length of the reduced pressure drying is 6 h.
Example 3
Essentially the same as in example 1, except that:
the preparation method of the synergist comprises the following steps:
v1, putting the inorganic filler into the zinc citrate solution, homogenizing, filtering, taking filter residue and drying to obtain the pretreated inorganic filler; the inorganic filler is a mixture of silicon dioxide and boron nitride according to a mass ratio of 1: 2.2;
v2 mixing the auxiliary filler and the solvent, heating and stirring to obtain latex A; the auxiliary filler is a mixture of ethylene-vinyl alcohol copolymer and polyethylene glycol terephthalate according to the mass ratio of 3: 1; the solvent is a mixture of dimethyl carbonate and absolute ethyl alcohol according to a mass ratio of 1: 1.2;
v3, mixing the pretreated inorganic filler obtained from V1, the latex A obtained from V2, the coupling agent and the acid anhydride, stirring, simultaneously performing microwave treatment, filtering to obtain filter residue, washing with absolute ethyl alcohol, performing reduced pressure drying, crushing, and screening with a 1200-mesh screen to obtain the synergist; the coupling agent is hexaethylcyclotrisiloxane; the acid anhydride is a mixture of maleic anhydride and isobutyric anhydride according to the mass ratio of 3: 1.2.
In the step V1: the bath ratio of the inorganic filler to the zinc citrate solution is 1g:12 mL; the mass fraction of ethyl lactate in the zinc citrate solution is 62%, the mass fraction of zinc citrate is 4.3%, and the balance is water, and the temperature is 40 ℃; the rotation speed of the homogenization treatment is 14000r/min, and the time duration of the homogenization treatment is 3 min; the drying temperature is 93 ℃, and the drying time is 5 h.
In the step V2: the mass ratio of the auxiliary filler to the solvent is 1: 6; the heating temperature of the step V2 is 70 ℃, the heating time is 130min, and the stirring speed is 80 r/min.
In the step V3: the mass ratio of the inorganic filler to the latex A to the coupling agent to the anhydride is 1:7:1.2: 0.3; the stirring time of the step V3 is 70min, and the stirring speed is 100 r/min; the power of the microwave treatment is 550W, and the frequency is 420 MHz; the flushing flow rate is 600mL/min, the temperature is 50 ℃, and the flushing time is 15 min; the temperature of the reduced pressure drying is 75 ℃, the pressure is 1.5kPa, and the time length of the reduced pressure drying is 6 h.
Example 4
Essentially the same as in example 1, except that:
the preparation method of the synergist comprises the following steps:
v1, putting the inorganic filler into the zinc citrate solution, homogenizing, filtering, taking filter residue and drying to obtain the pretreated inorganic filler; the inorganic filler is a mixture of silicon dioxide and boron nitride according to a mass ratio of 1: 2.2;
v2 mixing the auxiliary filler and the solvent, heating and stirring to obtain latex A; the auxiliary filler is a mixture of ethylene-vinyl alcohol copolymer and polyethylene glycol terephthalate according to the mass ratio of 3: 1; the solvent is a mixture of dimethyl carbonate and absolute ethyl alcohol according to a mass ratio of 1: 1.2;
v3, mixing the pretreated inorganic filler obtained from V1, the latex A obtained from V2, the coupling agent and the acid anhydride, stirring, simultaneously performing microwave treatment, filtering to obtain filter residue, washing with absolute ethyl alcohol, performing reduced pressure drying, crushing, and screening with a 1200-mesh screen to obtain the synergist; the coupling agent is a mixture of heptamethyldisilamine and hexaethylcyclotrisiloxane in a mass ratio of 1: 1; the acid anhydride is isobutyric anhydride.
In the step V1: the bath ratio of the inorganic filler to the zinc citrate solution is 1g:12 mL; the mass fraction of ethyl lactate in the zinc citrate solution is 62%, the mass fraction of zinc citrate is 4.3%, and the balance is water, and the temperature is 40 ℃; the rotation speed of the homogenization treatment is 14000r/min, and the time duration of the homogenization treatment is 3 min; the drying temperature is 93 ℃, and the drying time is 5 h.
In the step V2: the mass ratio of the auxiliary filler to the solvent is 1: 6; the heating temperature of the step V2 is 70 ℃, the heating time is 130min, and the stirring speed is 80 r/min.
In the step V3: the mass ratio of the inorganic filler to the latex A to the coupling agent to the anhydride is 1:7:1.2: 0.3; the stirring time of the step V3 is 70min, and the stirring speed is 100 r/min; the power of the microwave treatment is 550W, and the frequency is 420 MHz; the flushing flow rate is 600mL/min, the temperature is 50 ℃, and the flushing time is 15 min; the temperature of the reduced pressure drying is 75 ℃, the pressure is 1.5kPa, and the time length of the reduced pressure drying is 6 h.
Example 5
Essentially the same as in example 1, except that:
the preparation method of the synergist comprises the following steps:
v1, putting the inorganic filler into the zinc citrate solution, homogenizing, filtering, taking filter residue and drying to obtain the pretreated inorganic filler; the inorganic filler is a mixture of silicon dioxide and boron nitride according to a mass ratio of 1: 2.2;
v2 mixing the auxiliary filler and the solvent, heating and stirring to obtain latex A; the auxiliary filler is a mixture of ethylene-vinyl alcohol copolymer and polyethylene glycol terephthalate according to the mass ratio of 3: 1; the solvent is a mixture of dimethyl carbonate and absolute ethyl alcohol according to a mass ratio of 1: 1.2;
v3, mixing the pretreated inorganic filler obtained from V1, the latex A obtained from V2, the coupling agent and the acid anhydride, stirring, heating in a water bath, filtering to obtain filter residue, washing with absolute ethyl alcohol, drying under reduced pressure, crushing, and screening with a 1200-mesh screen to obtain the synergist; the coupling agent is a mixture of heptamethyldisilamine and hexaethylcyclotrisiloxane in a mass ratio of 1: 1; the acid anhydride is a mixture of maleic anhydride and isobutyric anhydride according to the mass ratio of 3: 1.2.
In the step V1: the bath ratio of the inorganic filler to the zinc citrate solution is 1g:12 mL; the mass fraction of ethyl lactate in the zinc citrate solution is 62%, the mass fraction of zinc citrate is 4.3%, and the balance is water, and the temperature is 40 ℃; the rotation speed of the homogenization treatment is 14000r/min, and the time duration of the homogenization treatment is 3 min; the drying temperature is 93 ℃, and the drying time is 5 h.
In the step V2: the mass ratio of the auxiliary filler to the solvent is 1: 6; the heating temperature of the step V2 is 70 ℃, the heating time is 130min, and the stirring speed is 80 r/min.
In the step V3: the mass ratio of the inorganic filler to the latex A to the coupling agent to the anhydride is 1:7:1.2: 0.3; the stirring time of the step V3 is 70min, and the stirring speed is 100 r/min; the temperature of the water bath heating is 85 ℃; the flushing flow rate is 600mL/min, the temperature is 50 ℃, and the flushing time is 15 min; the temperature of the reduced pressure drying is 75 ℃, the pressure is 1.5kPa, and the time length of the reduced pressure drying is 6 h.
Example 6
Essentially the same as in example 1, except that:
the preparation method of the synergist comprises the following steps:
v1, putting the inorganic filler into the zinc citrate solution, homogenizing, filtering, taking filter residue and drying to obtain the pretreated inorganic filler; the inorganic filler is a mixture of silicon dioxide and boron nitride according to a mass ratio of 1: 2.2;
v2 mixing the auxiliary filler and the solvent, heating and stirring to obtain latex A; the auxiliary filler is polyethylene glycol terephthalate; the solvent is a mixture of dimethyl carbonate and absolute ethyl alcohol according to a mass ratio of 1: 1.2;
v3, mixing the pretreated inorganic filler obtained from V1, the latex A obtained from V2, the coupling agent and the acid anhydride, stirring, simultaneously performing microwave treatment, filtering to obtain filter residue, washing with absolute ethyl alcohol, performing reduced pressure drying, crushing, and screening with a 1200-mesh screen to obtain the synergist; the coupling agent is a mixture of heptamethyldisilamine and hexaethylcyclotrisiloxane in a mass ratio of 1: 1; the acid anhydride is a mixture of maleic anhydride and isobutyric anhydride according to the mass ratio of 3: 1.2.
In the step V1: the bath ratio of the inorganic filler to the zinc citrate solution is 1g:12 mL; the mass fraction of ethyl lactate in the zinc citrate solution is 62%, the mass fraction of zinc citrate is 4.3%, and the balance is water, and the temperature is 40 ℃; the rotation speed of the homogenization treatment is 14000r/min, and the time duration of the homogenization treatment is 3 min; the drying temperature is 93 ℃, and the drying time is 5 h.
In the step V2: the mass ratio of the auxiliary filler to the solvent is 1: 6; the heating temperature of the step V2 is 70 ℃, the heating time is 130min, and the stirring speed is 80 r/min.
In the step V3: the mass ratio of the inorganic filler to the latex A to the coupling agent to the anhydride is 1:7:1.2: 0.3; the stirring time of the step V3 is 70min, and the stirring speed is 100 r/min; the power of the microwave treatment is 550W, and the frequency is 420 MHz; the flushing flow rate is 600mL/min, the temperature is 50 ℃, and the flushing time is 15 min; the temperature of the reduced pressure drying is 75 ℃, the pressure is 1.5kPa, and the time length of the reduced pressure drying is 6 h.
Example 7
Essentially the same as in example 1, except that:
the preparation method of the synergist comprises the following steps:
v1, putting the inorganic filler into the treatment liquid, homogenizing, filtering, taking filter residue and drying to obtain the pretreated inorganic filler; the inorganic filler is a mixture of silicon dioxide and boron nitride according to a mass ratio of 1: 2.2;
v2 mixing the auxiliary filler and the solvent, heating and stirring to obtain latex A; the auxiliary filler is a mixture of ethylene-vinyl alcohol copolymer and polyethylene glycol terephthalate according to the mass ratio of 3: 1; the solvent is a mixture of dimethyl carbonate and absolute ethyl alcohol according to a mass ratio of 1: 1.2;
v3, mixing the pretreated inorganic filler obtained from V1, the latex A obtained from V2, the coupling agent and the acid anhydride, stirring, simultaneously performing microwave treatment, filtering to obtain filter residue, washing with absolute ethyl alcohol, performing reduced pressure drying, crushing, and screening with a 1200-mesh screen to obtain the synergist; the coupling agent is a mixture of heptamethyldisilamine and hexaethylcyclotrisiloxane in a mass ratio of 1: 1; the acid anhydride is a mixture of maleic anhydride and isobutyric anhydride according to the mass ratio of 3: 1.2.
In the step V1: the bath ratio of the inorganic filler to the treatment liquid is 1g:12 mL; the mass fraction of the ethyl lactate in the treatment solution is 62%, the balance is water, and the temperature is 40 ℃; the rotation speed of the homogenization treatment is 14000r/min, and the time duration of the homogenization treatment is 3 min; the drying temperature is 93 ℃, and the drying time is 5 h.
In the step V2: the mass ratio of the auxiliary filler to the solvent is 1: 6; the heating temperature of the step V2 is 70 ℃, the heating time is 130min, and the stirring speed is 80 r/min.
In the step V3: the mass ratio of the inorganic filler to the latex A to the coupling agent to the anhydride is 1:7:1.2: 0.3; the stirring time of the step V3 is 70min, and the stirring speed is 100 r/min; the power of the microwave treatment is 550W, and the frequency is 420 MHz; the flushing flow rate is 600mL/min, the temperature is 50 ℃, and the flushing time is 15 min; the temperature of the reduced pressure drying is 75 ℃, the pressure is 1.5kPa, and the time length of the reduced pressure drying is 6 h.
Test example 1
And (3) testing the breaking force: according to GB/T10004-: general rules and GB/T1040.3-2006 section 3 of determination of tensile Properties of plastics: test conditions for films and sheets the breaking force of the high barrier composite film for sensitive pharmaceutical packaging obtained in each example of the present invention was measured. The sample is 2 type, the length is 150mm, the width is 15mm, and the thickness is 0.003 mm; the width of the blade is 0.05mm, and the cutting angle is 10 degrees; the test tensile speed was 200 mm/min. The test results are shown in table 1.
TABLE 1 breaking force of composite film adhesive
Test example 2
Testing the water vapor transmission rate: the water vapor transmission rate of the high-barrier composite film for packaging sensitive medicines obtained in each example of the present invention was measured according to GB/T10004-. Taking the condition A as a test condition, namely, the temperature is 38 ℃ and the relative humidity is 90 percent; the temperature in the dryer was 23 ℃.5 samples were tested for each case and the sample results averaged. The test results are shown in table 2.
TABLE 2 Water vapor Transmission of composite Membrane Adhesives
Test example 3
Oxygen permeability test: the oxygen permeability of the high-barrier composite film for sensitive medicine packaging obtained in each example of the present invention was measured according to GB/T19789-2005 coulometer detection method for oxygen permeability test of packaging plastic film and sheet. Putting the sample into a dryer filled with anhydrous calcium chloride for sample state adjustment for 50 h; the laboratory ambient temperature was 23 ℃ and the relative humidity was 50%. And opening a helium carrier gas switch of the ventilation chamber, opening a helium carrier gas valve, blowing air in the upper part and the lower part of the ventilation chamber at the flow rate of 50mL/min, reducing the flow rate to 10mL after 3min, and maintaining the flow rate for 30 min. In each case 5 specimens were tested and the results averaged. The test results are shown in table 3.
TABLE 3 oxygen permeability of composite film adhesive
The hexagonal crystal boron nitride with the graphene-like structure has very good barrier capability to gases such as water vapor, oxygen and the like; the silicon dioxide is dispersed in the base material, so that the mechanical strength of the whole material, such as tensile strength and the like, can be improved; however, if the inorganic non-metallic powder particles are directly added into a high molecular material, such as a polyethylene film, the difference between the acting force and the activation energy of the two main raw materials on the molecular layer is large, so that the material is easy to lose effectiveness, such as aging, brittle failure, cracking and the like, in the processes of storage, transportation and service, and thus, the immeasurable loss is caused. Therefore, the invention provides a technical scheme capable of organically and highly combining boron nitride, silicon dioxide and polyethylene films, and obtains a synergist capable of improving the water vapor and oxygen isolation capability and mechanical strength of high polymer films such as but not limited to polyethylene films. Hydroxyl and ester groups in the ethyl lactate can improve the dispersibility and uniformity of the silicon dioxide and the boron nitride. Divalent zinc ions in the zinc citrate and citrate rich in oxygen atoms can generate certain charge attraction effect on the silicon dioxide and the boron nitride to guide the silicon dioxide and the boron nitride to uniformly diffuse in the ethyl lactate aqueous solution; and the doping of a small amount of zinc ions can improve the mutual wettability of the hexagonal boron nitride and the acid anhydride in the subsequent process. The ethylene-vinyl alcohol has good mechanical strength, elasticity, hardness, wear resistance and weather resistance, and the polyethylene terephthalate has good various mechanical properties including creep resistance, fatigue resistance, friction resistance, dimensional stability and the like in a wider temperature range, so that the two raw materials can be used as auxiliary fillers for the synergist to improve the mechanical properties of the high polymer film and the barrier property of various gases including oxygen and water vapor; in addition, the auxiliary filler can be highly combined with the inorganic filler under the promoting action of the anhydride, so that the compatibility of the inorganic filler and a polymer film is greatly improved, and the service life and the reliability of the synergist are also improved. The negative charge center formed by three oxygens in the dimethyl carbonate can be cooperated with the oxygen-containing unsaturated bond heterocyclic structure of maleic anhydride and the symmetrical trioxane structure of isobutyric anhydride to enhance the compatibility between the auxiliary filler and the inorganic filler. The nitrogen atoms in the heptamethyldisilamine are positioned at the center of the molecule, the silicon-oxygen interphase heterocyclic ring in the hexaethylcyclotrisiloxane and the short carbon chain extending outside the silicon-oxygen interphase heterocyclic ring generate strong acting force with the surface of the inorganic filler, so that the mutual infiltration capacity and the sufficient bonding strength of the inorganic filler, the auxiliary filler and the high polymer film are improved, and the service life and the reliability of the synergist are also improved. The invention adopts microwave as an auxiliary means, provides necessary energy disturbance, promotes the grafting modification between the coupling agent, the acid anhydride and the two fillers in a dynamics level, and leads the raw materials to be combined in a microscopic level so as to obtain excellent macroscopic performance.
Claims (6)
1. A preparation method of a high-barrier composite film for packaging sensitive medicinal materials is characterized by comprising the following steps:
coating the synergistic solution on two surfaces of the polyethylene film, wherein the coating thickness is 1.5-2 μm; the high-barrier composite film for packaging sensitive medicinal materials is obtained by hot air drying and forming, wherein the temperature of the hot air drying and forming is 70-75 ℃, the air speed is 1.5-2m/s, and the time duration is 50-60 min;
the preparation method of the synergistic solution comprises the following steps: mixing a synergist and absolute ethyl alcohol, and homogenizing to obtain the synergistic liquid; the preparation method of the synergist comprises the following steps:
v1, putting the inorganic filler into the zinc citrate solution, homogenizing, filtering, taking filter residue and drying to obtain the pretreated inorganic filler;
v2 mixing the auxiliary filler and the solvent, heating and stirring to obtain latex A; the solvent is a mixture of dimethyl carbonate and absolute ethyl alcohol; the auxiliary filler is a mixture of ethylene-vinyl alcohol copolymer and polyethylene terephthalate;
v3 mixing the pretreated inorganic filler obtained from V1, the latex A obtained from V2, the coupling agent and the acid anhydride, stirring while performing microwave treatment, filtering to obtain filter residue, washing with absolute ethyl alcohol, drying under reduced pressure, crushing and sieving to obtain the synergist.
2. The preparation method of the high-barrier composite film for packaging sensitive medicinal materials according to claim 1, which is characterized in that: the inorganic filler is at least one of silicon dioxide and boron nitride.
3. The preparation method of the high-barrier composite film for packaging sensitive medicinal materials according to claim 1, which is characterized in that: the coupling agent is at least one of heptamethyldisilamine and hexaethylcyclotrisiloxane; the acid anhydride is at least one of maleic anhydride and isobutyric anhydride.
4. The method for preparing the high-barrier composite film for packaging sensitive medicinal materials according to claim 1, wherein in the step V1: the bath ratio of the inorganic filler to the zinc citrate solution is 1g (10-15) mL; the mass fraction of ethyl lactate in the zinc citrate solution is 58-63%, the mass fraction of zinc citrate is 2-5%, and the balance is water, and the temperature is 35-45 ℃; the rotation speed of the homogenization treatment is 12000-14000r/min, and the time duration of the homogenization treatment is 2-5 min; the drying temperature is 90-95 ℃, and the drying time is 5-6 h.
5. The method for preparing the high-barrier composite film for packaging sensitive medicinal materials according to claim 1, wherein in the step V2: the mass ratio of the auxiliary filler to the solvent is 1 (5.5-8); the heating temperature in the step V2 is 68-73 ℃, the heating time is 110-140min, and the stirring speed is 70-85 r/min;
in the step V3: the mass ratio of the inorganic filler, the latex A, the coupling agent and the acid anhydride is (0.5-1.2): 6-8): 1-1.7): 0.1-0.4; the stirring time of the step V3 is 60-80min, and the stirring speed is 80-110 r/min; the power of the microwave treatment is 520-560W, and the frequency is 410-420 MHz; the washing flow rate is 450-600mL/min, the temperature is 40-50 ℃, and the washing time is 12-20 min; the temperature of the reduced pressure drying is 70-75 ℃, the pressure is 1.2-1.5kPa, and the time of the reduced pressure drying is 6-8 h.
6. A high resistant separates complex film for sensitive medicinal material packing which characterized in that: obtained by the production method according to any one of claims 1 to 5.
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