CN116198183A - Composite hose with high-temperature-resistant steaming performance and preparation method thereof - Google Patents

Composite hose with high-temperature-resistant steaming performance and preparation method thereof Download PDF

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Publication number
CN116198183A
CN116198183A CN202310041037.8A CN202310041037A CN116198183A CN 116198183 A CN116198183 A CN 116198183A CN 202310041037 A CN202310041037 A CN 202310041037A CN 116198183 A CN116198183 A CN 116198183A
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CN
China
Prior art keywords
layer
composite hose
adhesive layer
hose
pressure
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Pending
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CN202310041037.8A
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Chinese (zh)
Inventor
徐运龙
王明生
刘健
容龙平
李征
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Rego Packing Gz Industry Co ltd
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Rego Packing Gz Industry Co ltd
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Priority to CN202310041037.8A priority Critical patent/CN116198183A/en
Publication of CN116198183A publication Critical patent/CN116198183A/en
Pending legal-status Critical Current

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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
    • B32B1/00—Layered products having a general shape other than plane
    • B32B1/08—Tubular products
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/08—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 of synthetic resin
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment

Abstract

The invention discloses a composite hose with high-temperature steaming resistance and a preparation method thereof, and belongs to the technical field of foods. The composite hose comprises a first PE layer, a first adhesive layer, a first PET layer, a printing ink layer, a second adhesive layer, a second PET layer, a third adhesive layer, an aluminum foil layer, a fourth adhesive layer and a second PE layer from outside to inside in sequence, wherein the first adhesive layer, the second adhesive layer, the third adhesive layer and the fourth adhesive layer are all ethylene acrylic acid copolymers. The composite hose with high-temperature steaming resistance has good composite strength and heat sealing strength.

Description

Composite hose with high-temperature-resistant steaming performance and preparation method thereof
Technical Field
The invention belongs to the technical field of foods, and particularly relates to a composite hose with high-temperature steaming resistance and a preparation method thereof.
Background
When the hose is used for food packaging, high-temperature cooking is needed, however, the existing hose packaging material is often poor in high-temperature resistance and strength, and is easy to melt even when being cooked at high temperature, so that the composite material is layered or severely deformed, and the hose packaging material is not beneficial to popularization in the food packaging industry of high-temperature damp-heat sterilization.
The applicant's prior patent CN114379157a discloses a composite hose for food packaging capable of high temperature retorting, which, in subsequent studies, was found to be prone to delamination of the layers after repeated use.
Disclosure of Invention
The invention aims to provide a composite hose with good composite strength and heat sealing strength performance and high-temperature steaming resistance.
The first aspect of the invention discloses a composite hose with high-temperature steaming resistance, which comprises a first PE layer, a first adhesive layer, a first PET layer, a printing ink layer, a second adhesive layer, a second PET layer, a third adhesive layer, an aluminum foil layer, a fourth adhesive layer and a second PE layer from outside to inside, wherein the first adhesive layer, the second adhesive layer, the third adhesive layer and the fourth adhesive layer are all ethylene acrylic acid copolymers.
In some embodiments of the invention, the ethylene acrylic acid copolymer is polymerized from ethylene monomers and acrylic acid monomers in a preparation system comprising ammonium octoate, n-hexadecane, and deionized water.
In some embodiments of the invention, the ethylene acrylic acid copolymer is prepared in a system that does not include a thickener component.
In some embodiments of the present invention, the method of preparing an ethylene acrylic acid copolymer comprises the steps of:
s01, mixing deionized water, ammonium octoate, n-hexadecane and ammonium persulfate, and introducing nitrogen;
s02, heating, introducing ethylene monomer, polymerizing, cooling to normal temperature and ending the polymerization;
s03, adding an acrylic acid monomer, mixing, heating for polymerization, separating and drying;
s04, dissolving the mixture in a mixed solution of methanol and hydrochloric acid, and adding a sodium hydroxide aqueous solution for hydrolysis to obtain the ethylene-acrylic acid copolymer.
In some embodiments of the invention, in S01, the weight ratio of deionized water, ammonium octoate, n-hexadecane, and ammonium persulfate is 1000: (1-10): (1-10): (1-10), preferably 1000: (3-6): (4-7): (4-6).
In some embodiments of the invention, in S02, after the temperature is raised to 80-90 ℃, ethylene monomer is started to be introduced to the set pressure of 2.5-3.5MPa, polymerization is started, after the pressure in the kettle is reduced by 0.1MPa, ethylene monomer is supplemented to 2.5-3.5MPa, after 2-4 times of supplementation, polymerization is continued until the pressure is reduced to 1.5MPa, and the polymerization is completed after cooling to normal temperature.
In some embodiments of the invention, in S03, the polymerization is continued for 10-14 hours with an elevated temperature of 80-90 ℃.
In some embodiments of the invention, the first PE layer and the second PE layer are each composed of the following components: 50% of high-density polyethylene, 30% of metallocene linear medium-density polyethylene and 20% of linear low-density polyethylene;
the linear low density polyethylene is a copolymer of ethylene and a-olefin and has a density of 0.85-0.95g/cm 3 The melt index is 0.8-1.2g/10min;
the first PET layer and the second PET layer are respectively composed of the following components: 65% of high-density PET resin, 15% of medium-density PET resin, 20% of plasticizer and 10% of other auxiliary agents;
the plasticizer is glycol and glycerol with the weight ratio of 1:1;
the other auxiliary agent is microcrystalline paraffin;
the printing ink layer is high-temperature steaming-resistant ink.
The composite hose with high-temperature steaming resistance can be used for food split charging and can also be used for non-food packaging, such as conveying non-edible paste, liquid, flowing powder and other materials.
A second aspect of the present invention is to disclose the method for manufacturing a composite hose having high temperature steam resistant performance according to the first aspect, wherein the composite hose is detected by a specific leak detection device, the leak detection device comprising: the device comprises an air cylinder, a shunt tube, a hose joint and a water tank; the air cylinder is arranged above the water tank through a bracket, a guide rod perpendicular to the water tank is arranged on the bracket, the air cylinder is arranged on the guide rod, and the air cylinder moves up and down along the axial direction of the guide rod; the output end of the cylinder is connected with the shunt pipe; the shunt tube comprises an air inlet, a tube body, a first air outlet and a second air outlet, the air outlet is arranged above the middle part of the tube body, and the first air outlet and the second air outlet are arranged below the two ends of the tube body; the output end of the air cylinder is communicated with the air inlet, and hose connectors are respectively arranged at the first air outlet and the second air outlet; the two ends of the composite hose are respectively communicated with the first air outlet and the second air outlet through the hose connectors, the air cylinder is started to introduce compressed air into the composite hose through the shunt pipes, and the air cylinder is lowered to drive the composite hose simultaneously, so that the composite hose is immersed into a water tank under the air cylinder, whether air bubbles are generated around the composite hose or not is observed, and whether the composite hose leaks air or not is judged.
In some embodiments of the present invention, the leakage detection device is connected to a pressure strength detection system, where the pressure strength detection system includes a pressure detection unit and a data processing unit, where the pressure detection unit is connected to the pipe body and is used to detect a pressure value in the composite hose after the air cylinder introduces compressed air into the composite hose, the air cylinder continuously introduces compressed air into the composite hose, and the data processing unit determines, according to a pressure change condition of the pressure detection unit in a certain time, a leakage amount of the composite hose and a pressure strength grade of the composite hose.
The invention has the beneficial effects that:
1. the composite hose with high-temperature steaming resistance comprises a first PE layer, a first adhesive layer, a first PET layer, a printing ink layer, a second adhesive layer, a second PET layer, a third adhesive layer, an aluminum foil layer, a fourth adhesive layer and a second PE layer from outside to inside, wherein the adhesive layer is ethylene acrylic acid copolymer, and the composite hose has good composite strength and heat sealing strength.
2. The adhesive layer of the composite hose is ethylene acrylic acid copolymer, in the preparation method, the monomer dissolution condition in a reaction system is regulated by two substances of ammonium octoate and n-hexadecane, a thickener is not needed, and the obtained ethylene acrylic acid copolymer has good viscosity, thorough reaction and less residual monomers.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The examples and comparative examples are parallel runs of the same components, component contents, preparation steps, preparation parameters, unless otherwise specified.
The thickness of the first PE layer is 115 mu m, the thickness of the second PE layer is 100 mu m, the thicknesses of the first PET layer and the second PET layer are 12 mu m, the thickness of the printing ink layer is 1 mu m, the thickness of the aluminum foil layer is 20 mu m, and the thicknesses of the first adhesive layer, the second adhesive layer, the third adhesive layer and the fourth adhesive layer are all 4 mu m. The weight parts are in kilograms.
Example 1
A composite hose with high-temperature steaming resistance performance comprises a first PE layer, a first adhesive layer, a first PET layer, a printing ink layer, a second adhesive layer, a second PET layer, a third adhesive layer, an aluminum foil layer, a fourth adhesive layer and a second PE layer from outside to inside.
The first PE layer and the second PE layer are respectively composed of the following components: 50% of high-density polyethylene, 30% of metallocene linear medium-density polyethylene and 20% of linear low-density polyethylene.
The linear low density polyethylene is a copolymer of ethylene and a-olefin and has a density of 0.90g/cm 3 The melt index was 1g/10min.
The first PET layer and the second PET layer are respectively composed of the following components (weight): 65% of high-density PET resin, 15% of medium-density PET resin, 20% of plasticizer and 10% of other auxiliary agents.
The plasticizer is glycol and glycerol with the weight ratio of 1:1.
The other auxiliary agent is microcrystalline paraffin.
The printing ink layer is high-temperature steaming-resistant ink.
The first adhesive layer, the second adhesive layer, the third adhesive layer and the fourth adhesive layer are all ethylene acrylic acid copolymers.
The preparation method of the ethylene acrylic acid copolymer comprises the following steps:
(1) 1000 parts by weight of deionized water, 5 parts by weight of ammonium octoate, 5 parts by weight of n-hexadecane and 5 parts by weight of ammonium persulfate are taken and added into a reaction kettle, and are stirred and mixed, and nitrogen is introduced for 30min;
(2) After the temperature is raised to 85 ℃, starting to introduce ethylene monomers to the set pressure of 3.0MPa, starting to polymerize, supplementing ethylene monomers to 3.0MPa after the pressure in the kettle is reduced by 0.1MPa, continuing to polymerize until the pressure is reduced to 1.5MPa after supplementing for 3 times, and cooling to normal temperature to finish polymerization;
(3) Adding 100 parts by weight of acrylic acid monomer, stirring and mixing for 6 hours, heating to 85 ℃ and continuing to polymerize for 12 hours, centrifuging and drying;
(4) And (3) dissolving the solid obtained in the step (3) in a mixed solution of 6 times of methanol and 10% hydrochloric acid (volume ratio is 1:1), then adding a 10% sodium hydroxide aqueous solution with 3 times of the solid obtained in the step (3), and hydrolyzing at 70 ℃ for 4 hours to obtain the ethylene-acrylic acid copolymer.
Example 2
A composite hose with high-temperature steaming resistance performance comprises a first PE layer, a first adhesive layer, a first PET layer, a printing ink layer, a second adhesive layer, a second PET layer, a third adhesive layer, an aluminum foil layer, a fourth adhesive layer and a second PE layer from outside to inside.
The first PE layer and the second PE layer are respectively composed of the following components: 50% of high-density polyethylene, 30% of metallocene linear medium-density polyethylene and 20% of linear low-density polyethylene.
The linear low density polyethylene is a copolymer of ethylene and a-olefin and has a density of 0.90g/cm 3 The melt index was 1g/10min.
The first PET layer and the second PET layer are respectively composed of the following components (weight): 65% of high-density PET resin, 15% of medium-density PET resin, 20% of plasticizer and 10% of other auxiliary agents.
The plasticizer is glycol and glycerol with the weight ratio of 1:1.
The other auxiliary agent is microcrystalline paraffin.
The printing ink layer is high-temperature steaming-resistant ink.
The first adhesive layer, the second adhesive layer, the third adhesive layer and the fourth adhesive layer are all ethylene acrylic acid copolymers.
The preparation method of the ethylene acrylic acid copolymer comprises the following steps:
(1) 1000 parts by weight of deionized water, 4 parts by weight of ammonium octoate, 6 parts by weight of n-hexadecane and 5 parts by weight of ammonium persulfate are taken and added into a reaction kettle, and are stirred and mixed, and nitrogen is introduced for 30min;
(2) After the temperature is raised to 85 ℃, starting to introduce ethylene monomers to the set pressure of 3.0MPa, starting to polymerize, supplementing ethylene monomers to 3.0MPa after the pressure in the kettle is reduced by 0.1MPa, continuing to polymerize until the pressure is reduced to 1.5MPa after supplementing for 3 times, and cooling to normal temperature to finish polymerization;
(3) Adding 100 parts by weight of acrylic acid monomer, stirring and mixing for 8 hours, heating to 85 ℃ and continuing to polymerize for 12 hours, centrifuging and drying;
(4) And (3) dissolving the solid obtained in the step (3) in a mixed solution of 6 times of methanol and 10% hydrochloric acid (volume ratio is 1:1), then adding a 10% sodium hydroxide aqueous solution with 3 times of the solid obtained in the step (3), and hydrolyzing at 70 ℃ for 6 hours to obtain the ethylene-acrylic acid copolymer.
Example 3
A composite hose with high-temperature steaming resistance performance comprises a first PE layer, a first adhesive layer, a first PET layer, a printing ink layer, a second adhesive layer, a second PET layer, a third adhesive layer, an aluminum foil layer, a fourth adhesive layer and a second PE layer from outside to inside.
The first PE layer and the second PE layer are respectively composed of the following components: 50% of high-density polyethylene, 30% of metallocene linear medium-density polyethylene and 20% of linear low-density polyethylene.
The linear low density polyethylene is a copolymer of ethylene and a-olefin and has a density of 0.90g/cm 3 The melt index was 1g/10min.
The first PET layer and the second PET layer are respectively composed of the following components (weight): 65% of high-density PET resin, 15% of medium-density PET resin, 20% of plasticizer and 10% of other auxiliary agents.
The plasticizer is glycol and glycerol with the weight ratio of 1:1.
The other auxiliary agent is microcrystalline paraffin.
The printing ink layer is high-temperature steaming-resistant ink.
The first adhesive layer, the second adhesive layer, the third adhesive layer and the fourth adhesive layer are all ethylene acrylic acid copolymers.
The preparation method of the ethylene acrylic acid copolymer comprises the following steps:
(1) 1000 parts by weight of deionized water, 6 parts by weight of ammonium octoate, 4 parts by weight of n-hexadecane and 5 parts by weight of ammonium persulfate are taken and added into a reaction kettle, and are stirred and mixed, and nitrogen is introduced for 30min;
(2) After the temperature is raised to 85 ℃, starting to introduce ethylene monomers to the set pressure of 3.0MPa, starting to polymerize, supplementing ethylene monomers to 3.0MPa after the pressure in the kettle is reduced by 0.1MPa, continuing to polymerize until the pressure is reduced to 1.5MPa after supplementing for 3 times, and cooling to normal temperature to finish polymerization;
(3) Adding 100 parts by weight of acrylic acid monomer, stirring and mixing for 6 hours, heating to 90 ℃ and continuing to polymerize for 10 hours, centrifuging and drying;
(4) And (3) dissolving the solid obtained in the step (3) in a mixed solution of 6 times of methanol and 10% hydrochloric acid (volume ratio is 1:1), then adding a 10% sodium hydroxide aqueous solution with 3 times of the solid obtained in the step (3), and hydrolyzing at 70 ℃ for 4 hours to obtain the ethylene-acrylic acid copolymer.
Example 4
A composite hose with high-temperature steaming resistance performance comprises a first PE layer, a first adhesive layer, a first PET layer, a printing ink layer, a second adhesive layer, a second PET layer, a third adhesive layer, an aluminum foil layer, a fourth adhesive layer and a second PE layer from outside to inside.
The first PE layer and the second PE layer are respectively composed of the following components: 50% of high-density polyethylene, 30% of metallocene linear medium-density polyethylene and 20% of linear low-density polyethylene.
The linear low density polyethylene is a copolymer of ethylene and a-olefin and has a density of 0.90g/cm 3 The melt index was 1g/10min.
The first PET layer and the second PET layer are respectively composed of the following components (weight): 65% of high-density PET resin, 15% of medium-density PET resin, 20% of plasticizer and 10% of other auxiliary agents.
The plasticizer is glycol and glycerol with the weight ratio of 1:1.
The other auxiliary agent is microcrystalline paraffin.
The printing ink layer is high-temperature steaming-resistant ink.
The first adhesive layer, the second adhesive layer, the third adhesive layer and the fourth adhesive layer are all ethylene acrylic acid copolymers.
The preparation method of the ethylene acrylic acid copolymer comprises the following steps:
(1) 1000 parts by weight of deionized water, 3 parts by weight of ammonium octoate, 7 parts by weight of n-hexadecane and 5 parts by weight of ammonium persulfate are taken and added into a reaction kettle, and are stirred and mixed, and nitrogen is introduced for 40min;
(2) After the temperature is raised to 85 ℃, starting to introduce ethylene monomers to the set pressure of 3.0MPa, starting to polymerize, supplementing ethylene monomers to 3.0MPa after the pressure in the kettle is reduced by 0.1MPa, continuing to polymerize until the pressure is reduced to 1.5MPa after supplementing for 3 times, and cooling to normal temperature to finish polymerization;
(3) Adding 100 parts by weight of acrylic acid monomer, stirring and mixing for 6 hours, heating to 85 ℃ and continuing to polymerize for 12 hours, centrifuging and drying;
(4) And (3) dissolving the solid obtained in the step (3) in a mixed solution of 6 times of methanol and 10% hydrochloric acid (volume ratio is 1:1), then adding a 10% sodium hydroxide aqueous solution with 3 times of the solid obtained in the step (3), and hydrolyzing at 70 ℃ for 4 hours to obtain the ethylene-acrylic acid copolymer.
Example 5
A composite hose with high-temperature steaming resistance performance comprises a first PE layer, a first adhesive layer, a first PET layer, a printing ink layer, a second adhesive layer, a second PET layer, a third adhesive layer, an aluminum foil layer, a fourth adhesive layer and a second PE layer from outside to inside.
The first PE layer and the second PE layer are respectively composed of the following components: 50% of high-density polyethylene, 30% of metallocene linear medium-density polyethylene and 20% of linear low-density polyethylene.
The linear low density polyethylene is a copolymer of ethylene and a-olefin and has a density of 0.90g/cm 3 The melt index was 1g/10min.
The first PET layer and the second PET layer are respectively composed of the following components (weight): 65% of high-density PET resin, 15% of medium-density PET resin, 20% of plasticizer and 10% of other auxiliary agents.
The plasticizer is glycol and glycerol with the weight ratio of 1:1.
The other auxiliary agent is microcrystalline paraffin.
The printing ink layer is high-temperature steaming-resistant ink.
The first adhesive layer, the second adhesive layer, the third adhesive layer and the fourth adhesive layer are all ethylene acrylic acid copolymers.
The preparation method of the ethylene acrylic acid copolymer comprises the following steps:
(1) 1000 parts by weight of deionized water, 1 part by weight of ammonium octoate, 9 parts by weight of n-hexadecane and 5 parts by weight of ammonium persulfate are taken and added into a reaction kettle, and are stirred and mixed, and nitrogen is introduced for 30min;
(2) After the temperature is raised to 85 ℃, starting to introduce ethylene monomers to the set pressure of 3.0MPa, starting to polymerize, supplementing ethylene monomers to 3.0MPa after the pressure in the kettle is reduced by 0.1MPa, continuing to polymerize until the pressure is reduced to 1.5MPa after supplementing for 3 times, and cooling to normal temperature to finish polymerization;
(3) Adding 150 parts by weight of acrylic acid monomer, stirring and mixing for 6 hours, heating to 85 ℃ and continuing to polymerize for 12 hours, centrifuging and drying;
(4) And (3) dissolving the solid obtained in the step (3) in a mixed solution of 6 times of methanol and 10% hydrochloric acid (volume ratio is 1:1), then adding a 10% sodium hydroxide aqueous solution with 3 times of the solid obtained in the step (3), and hydrolyzing at 70 ℃ for 4 hours to obtain the ethylene-acrylic acid copolymer.
Example 6
A composite hose with high-temperature steaming resistance performance comprises a first PE layer, a first adhesive layer, a first PET layer, a printing ink layer, a second adhesive layer, a second PET layer, a third adhesive layer, an aluminum foil layer, a fourth adhesive layer and a second PE layer from outside to inside.
The first PE layer and the second PE layer are respectively composed of the following components: 50% of high-density polyethylene, 30% of metallocene linear medium-density polyethylene and 20% of linear low-density polyethylene.
The linear low density polyethylene is a copolymer of ethylene and a-olefin and has a density of 0.90g/cm 3 The melt index was 1g/10min.
The first PET layer and the second PET layer are respectively composed of the following components (weight): 65% of high-density PET resin, 15% of medium-density PET resin, 20% of plasticizer and 10% of other auxiliary agents.
The plasticizer is glycol and glycerol with the weight ratio of 1:1.
The other auxiliary agent is microcrystalline paraffin.
The printing ink layer is high-temperature steaming-resistant ink.
The first adhesive layer, the second adhesive layer, the third adhesive layer and the fourth adhesive layer are all ethylene acrylic acid copolymers.
The preparation method of the ethylene acrylic acid copolymer comprises the following steps:
(1) 1000 parts by weight of deionized water, 9 parts by weight of ammonium octoate, 1 part by weight of n-hexadecane and 5 parts by weight of ammonium persulfate are taken and added into a reaction kettle, and are stirred and mixed, and nitrogen is introduced for 30min;
(2) After the temperature is raised to 85 ℃, starting to introduce ethylene monomers to the set pressure of 3.0MPa, starting to polymerize, supplementing ethylene monomers to 3.0MPa after the pressure in the kettle is reduced by 0.1MPa, continuing to polymerize until the pressure is reduced to 1.5MPa after supplementing for 3 times, and cooling to normal temperature to finish polymerization;
(3) Adding 50 parts by weight of acrylic acid monomer, stirring and mixing for 6 hours, heating to 85 ℃ and continuing to polymerize for 12 hours, centrifuging and drying;
(4) And (3) dissolving the solid obtained in the step (3) in a mixed solution of 6 times of methanol and 10% hydrochloric acid (volume ratio is 1:1), then adding a 10% sodium hydroxide aqueous solution with 3 times of the solid obtained in the step (3), and hydrolyzing at 70 ℃ for 4 hours to obtain the ethylene-acrylic acid copolymer.
Example 7
A composite hose with high-temperature steaming resistance performance comprises a first PE layer, a first adhesive layer, a first PET layer, a printing ink layer, a second adhesive layer, a second PET layer, a third adhesive layer, an aluminum foil layer, a fourth adhesive layer and a second PE layer from outside to inside.
The composite hose is detected by a leak detection device comprising: the device comprises an air cylinder, a shunt tube, a hose joint and a water tank; the air cylinder is arranged above the water tank through a bracket, a guide rod perpendicular to the water tank is arranged on the bracket, the air cylinder is arranged on the guide rod, and the air cylinder moves up and down along the axial direction of the guide rod; the output end of the cylinder is connected with the shunt pipe; the shunt tube comprises an air inlet, a tube body, a first air outlet and a second air outlet, the air outlet is arranged above the middle part of the tube body, and the first air outlet and the second air outlet are arranged below the two ends of the tube body; the output end of the air cylinder is communicated with the air inlet, and hose connectors are respectively arranged at the first air outlet and the second air outlet; the two ends of the composite hose are respectively communicated with the first air outlet and the second air outlet through the hose connectors, the air cylinder is started to introduce compressed air into the composite hose through the shunt pipes, and the air cylinder is lowered to drive the composite hose at the same time, so that the composite hose is immersed into a water tank under the air cylinder, whether air bubbles are generated around the composite hose is observed, and whether the composite hose leaks air or not is judged;
the leakage detection device is connected with a pressure-resistant strength detection system, the pressure-resistant strength detection system comprises a pressure detection unit and a data processing unit, the pressure detection unit is connected with the pipe body and is used for detecting the pressure value in the composite hose after the air cylinder is filled with compressed air into the composite hose, the air cylinder is continuously filled with compressed air into the composite hose, and the data processing unit judges the leakage amount of the composite hose and the pressure-resistant strength grade of the composite hose according to the pressure change condition of the pressure detection unit in a certain time;
by the calculation formula:
Figure BDA0004050711800000141
wherein: sigma represents stress within the composite hose; p represents the pressure within the composite hose; r is R 1 Representing the inner radius of the composite hose; r is R 2 Represents the outer radius of the composite hose; according to the calculation formula, the larger the stress value is, the larger the compressive strength is, the composite hose is deformed entirely until the damage is caused after the stress exceeds a certain limit, the threshold stress is preset through the formula during detection, the composite hose meets the threshold stress, the compressive strength is judged to be qualified, when the composite hose is pressurized to a certain pressure value, if the composite hose can bear the pressure value, the compressive strength of the composite hose is qualified, the pressure change condition in the composite hose is detected in real time through the pressure detection unit, when the pressure value reaches the pressure value corresponding to the threshold stress, whether the composite hose is deformed or damaged is observed, and the compressive strength of the composite hose is judged to be qualified if the deformation or damage does not occur.
Comparative example 1
The difference from example 1 is that the first adhesive layer, the second adhesive layer, the third adhesive layer and the fourth adhesive layer are each composed of japanese triple well chemical EV 310 (vinyl acetate).
Experimental example performance test
The composite hoses of examples and comparative example 1 were taken for performance testing. Wherein, the peel strength and the heat sealing strength are referenced to YBB 00252005-2015 polyethylene/aluminum/polyethylene composite medicinal ointment tube; high temperature resistant cooking performance test is referred to GB/T10004-2008: pressurizing in a high temperature digester at 121deg.C for 30min, cooling under the condition of constant pressure, and observing appearance, breaking force, elongation, stripping force and heat sealing strength.
Tests show that the composite strength of the composite hose can reach more than 8N/15mm, and the heat sealing strength can reach more than 80N/15mm, which is obviously better than 6N/15mm and 75N/15mm of the comparative example 1. Wherein, the composite strength of the examples 1-4 can reach 10N/15mm, and the heat sealing strength can reach 90N/15mm, which is obviously superior to the examples 5 and 6.
All examples are applicable to 121 ℃ x 30min wet heat sterilization requirements for retort-like foods and maintain all performance requirements of the composite tube after high temperature wet heat sterilization.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the above-described embodiments and examples, and various changes may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (10)

1. The utility model provides a compound hose that possesses high temperature resistant steaming and boiling performance, its characterized in that includes from outside to inside in proper order first PE layer, first adhesive layer, first PET layer, printing ink layer, second adhesive layer, second PET layer, third adhesive layer, aluminium foil layer, fourth adhesive layer and second PE layer, first adhesive layer, second adhesive layer, third adhesive layer and fourth adhesive layer are ethylene acrylic acid copolymer.
2. The composite hose of claim 1, wherein the ethylene acrylic acid copolymer is polymerized from ethylene monomers and acrylic acid monomers in a preparation system comprising ammonium octoate, n-hexadecane, and deionized water.
3. The composite hose having high temperature retort resistance according to claim 1 or 2, wherein the ethylene acrylic acid copolymer is prepared in a system that does not include a thickener component.
4. A composite hose having high temperature retort resistance according to any one of claims 1 to 3, wherein the ethylene acrylic acid copolymer is prepared by a process comprising the steps of:
s01, mixing deionized water, ammonium octoate, n-hexadecane and ammonium persulfate, and introducing nitrogen;
s02, heating, introducing ethylene monomer, polymerizing, cooling to normal temperature and ending the polymerization;
s03, adding an acrylic acid monomer, mixing, heating for polymerization, separating and drying;
s04, dissolving the mixture in a mixed solution of methanol and hydrochloric acid, and adding a sodium hydroxide aqueous solution for hydrolysis to obtain the ethylene-acrylic acid copolymer.
5. The composite hose with high temperature resistant steaming performance according to any one of claims 1 to 4, wherein in S01, the weight ratio of deionized water, ammonium octoate, n-hexadecane and ammonium persulfate is 1000: (1-10): (1-10): (1-10), preferably 1000: (3-6): (4-7): (4-6).
6. The composite hose with high temperature resistant property according to any one of claims 1 to 5, wherein in S02, after the temperature is raised to 80 to 90 ℃, ethylene monomer is introduced to a set pressure of 2.5 to 3.5MPa, polymerization is started, after the pressure in the kettle is reduced by 0.1MPa, ethylene monomer is supplemented to 2.5 to 3.5MPa, after 2 to 4 times supplementation, polymerization is continued until the pressure is reduced to 1.5MPa, and the polymerization is completed after cooling to normal temperature.
7. The composite hose having high temperature resistant property according to any one of claims 1 to 6, wherein in S03, the polymerization is continued by heating to 80 to 90 ℃ for 10 to 14 hours.
8. The composite hose having high temperature resistant steaming performance according to any one of claims 1 to 7, wherein the first PE layer and the second PE layer are each composed of: 50% of high-density polyethylene, 30% of metallocene linear medium-density polyethylene and 20% of linear low-density polyethylene;
the linear low density polyethylene is a copolymer of ethylene and a-olefin and has a density of 0.85-0.95g/cm 3 The melt index is 0.8-1.2g/10min;
the first PET layer and the second PET layer are respectively composed of the following components: 65% of high-density PET resin, 15% of medium-density PET resin, 20% of plasticizer and 10% of other auxiliary agents;
the plasticizer is glycol and glycerol with the weight ratio of 1:1;
the other auxiliary agent is microcrystalline paraffin;
the printing ink layer is high-temperature steaming-resistant ink.
9. A method of manufacturing a composite hose having high temperature resistant digestion properties according to any one of claims 1-8, wherein the composite hose is tested by a dedicated leak testing device comprising: the device comprises an air cylinder, a shunt tube, a hose joint and a water tank; the air cylinder is arranged above the water tank through a bracket, a guide rod perpendicular to the water tank is arranged on the bracket, the air cylinder is arranged on the guide rod, and the air cylinder moves up and down along the axial direction of the guide rod; the output end of the cylinder is connected with the shunt pipe; the shunt tube comprises an air inlet, a tube body, a first air outlet and a second air outlet, the air outlet is arranged above the middle part of the tube body, and the first air outlet and the second air outlet are arranged below the two ends of the tube body; the output end of the air cylinder is communicated with the air inlet, and hose connectors are respectively arranged at the first air outlet and the second air outlet; the two ends of the composite hose are respectively communicated with the first air outlet and the second air outlet through the hose connectors, the air cylinder is started to introduce compressed air into the composite hose through the shunt pipes, and the air cylinder is lowered to drive the composite hose simultaneously, so that the composite hose is immersed into a water tank under the air cylinder, whether air bubbles are generated around the composite hose or not is observed, and whether the composite hose leaks air or not is judged.
10. The manufacturing method according to claim 9, wherein the leakage detection device is connected to a pressure-resistant strength detection system, the pressure-resistant strength detection system comprises a pressure detection unit and a data processing unit, the pressure detection unit is connected to the pipe body and is used for detecting the pressure value of the air cylinder in the composite hose after compressed air is introduced into the composite hose, the air cylinder continuously introduces compressed air into the composite hose, and the data processing unit judges the leakage amount of the composite hose and the pressure-resistant strength grade of the composite hose according to the pressure change condition of the pressure detection unit in a certain time.
CN202310041037.8A 2023-01-12 2023-01-12 Composite hose with high-temperature-resistant steaming performance and preparation method thereof Pending CN116198183A (en)

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