CN112898768A - High-performance barrier material and multilayer composite barrier structure - Google Patents

High-performance barrier material and multilayer composite barrier structure Download PDF

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Publication number
CN112898768A
CN112898768A CN201911135590.8A CN201911135590A CN112898768A CN 112898768 A CN112898768 A CN 112898768A CN 201911135590 A CN201911135590 A CN 201911135590A CN 112898768 A CN112898768 A CN 112898768A
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barrier
parts
barrier material
layer
agent
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Inventor
李军
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Shanghai Longcheng Plastic Products Co ltd
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Shanghai Longcheng Plastic Products Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2439/00—Containers; Receptacles
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Wrappers (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)

Abstract

The invention discloses a high-performance barrier material which comprises the following components in parts by mass: 80-100 parts of a barrier agent; 1-10 parts of plastic affinity agent; 2-8 parts of a compatilizer; wherein the blocking agent is nylon 6. The high-performance barrier material disclosed by the invention has a good barrier effect on organic solvents, is good in low-temperature resistance and high-temperature resistance, has excellent acid resistance, is environment-friendly and is low in cost.

Description

High-performance barrier material and multilayer composite barrier structure
Technical Field
The invention relates to the technical field of packaging materials, in particular to a high-performance barrier material and a multilayer composite barrier structure.
Background
In the aspects of storage, packaging and the like of organic solvents or products (such as pesticides, paints and the like) related to the organic solvents, part of manufacturers adopt common polyethylene packaging. Resistance to O of polyethylene2And poor oil-barrier property, which can cause the packaged object to be deteriorated due to chemical reaction caused by oxygen permeation or cause the packaged object to be lost and influence on environment due to the permeation of organic solvent when being used as a packaging material alone.
The following three methods are currently used to improve the barrier properties of high density polyethylene:
the first method is to perform surface treatment such as fluorination, sulfonation or spraying on the inner surface of the molded plastic product, which can significantly improve the barrier property of the plastic product against organic solvents, but the above surface treatment technique causes environmental pollution and is complicated to operate and is not suitable for use.
The second method is to blend polyolefin, barrier resin, compatilizer and the like, and then obtain a container product through a corresponding forming process, wherein the barrier resin with the barrier function is distributed in the continuous phase polyolefin resin in a disperse phase, and the barrier layer and a substrate form a multilayer structure, so that the solvent molecule penetration path in the container becomes roundabout and tortuous, and the length of the path is increased, thereby increasing the barrier property of the container.
For the reasons, a third method, namely a multi-layer co-extrusion technology of a polyethylene layer, a bonding layer, a barrier layer and the like, is adopted at present to enable the container wall to form a multi-layer structure so as to improve the barrier property of the container wall, wherein the barrier material commonly used in the multi-layer co-extrusion technology is EVOH, and although the barrier material using EVOH can meet the barrier property requirement, the third method has the following defects: when the filling material is at high temperature or acidic, the barrier property is obviously reduced, the raw material is imported, the cost is high, the low-temperature brittleness is large, and the product is easy to crack and leak.
The invention relates to a barrier material with good barrier effect on an organic solvent, which is used for producing a high-barrier plastic packaging container by a multilayer co-extrusion blow molding process together with a bonding layer and a high-density polyethylene layer, is used for storing and packaging the organic solvent or products related to the organic solvent, can effectively prevent the organic solvent from leaking, and can be applied to the fields of automobile fuel tanks, pesticide packaging, paint packaging, cosmetic packaging and the like.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide a high-performance barrier material which has a good barrier effect on organic solvents, has good low-temperature resistance and high-temperature resistance, has excellent acid resistance, is environment-friendly and has low cost. In addition, the invention also provides a multilayer composite barrier structure.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, a high-performance barrier material is provided, which comprises the following components in parts by mass:
80-100 parts of a barrier agent;
1-10 parts of plastic affinity agent;
2-8 parts of a compatilizer;
wherein the barrier agent is nylon 6.
Preferably, the barrier material comprises the following components in parts by mass:
85-95 parts of a blocking agent;
3-8 parts of plastic affinity agent;
2-5 parts of a compatilizer.
Preferably, the plastic affinity agent is high density polyethylene.
Preferably, the compatibilizer is an ethylene acrylic acid copolymer.
In a second aspect of the present invention, a method for preparing a high performance barrier material is provided, which is used for preparing the high performance barrier material, and includes the following steps:
s1, adding the blocking agent, the plastic affinity agent and the compatilizer into a stirring container according to the corresponding proportion, and stirring and mixing for 10-15 min;
s2, adding the raw material mixture uniformly mixed in the step S1 into an extruder for plasticizing, extruding and granulating to obtain particles, wherein the temperature of the extruder is set to 200-220 ℃;
s3, drying the particles obtained in the step S2, detecting and packaging into products.
In a third aspect of the invention, there is provided a multilayer composite barrier structure comprising, in order from an inner layer contacting the contents of a package, a barrier layer comprising the above barrier material, a tie layer and a high density polyethylene layer.
Preferably, the barrier layer, the bonding layer and the high-density polyethylene layer are extruded and molded by adopting a multilayer co-extrusion blow molding process.
Compared with the prior art, the invention has the following beneficial effects:
the high-performance barrier material in the invention selects nylon 6 as a main component, the nylon 6 has polarity and stronger intermolecular attraction, and has excellent barrier performance, low temperature resistance and high temperature resistance, high-density polyethylene is added as a plastic affinity agent, so that the phase viscosity of the barrier material and a high-density polyethylene layer in a laminated structure can be enhanced, the barrier layer formed by the barrier material has higher adhesion with an adhesive layer and the high-density polyethylene layer, and the phenomenon of delamination and peeling can not occur in the use process, the high-performance barrier material has good barrier effect on organic solvents and good low temperature resistance and high temperature resistance because the high-density polyethylene is nonpolar and the nylon 6 is polar, and the ethylene acrylic acid copolymer is added as a compatilizer, so that the problem of compatibility between the high-density polyethylene and the nylon 6 can be effectively solved, and the acid-resistant paint also has excellent acid resistance, is environment-friendly and has lower cost.
The high-performance barrier material, the bonding layer and the high-density polyethylene layer are produced into the multilayer composite barrier structure through a multilayer co-extrusion blow molding process, can be used as a high-barrier plastic packaging container, is used for storing and packaging organic solvents or products related to the organic solvents, can effectively prevent the leakage of the organic solvents, and can be applied to the fields of automobile fuel tanks, pesticide packaging, paint packaging, cosmetic packaging and the like.
Detailed Description
Example 1
The high performance barrier material in this example comprises the following components:
800g of a barrier agent (nylon 6);
10g of plastic affinity agent (high-density polyethylene);
20g of compatilizer (ethylene acrylic acid copolymer).
The preparation method of the high-performance barrier material comprises the following steps:
s1, adding the blocking agent, the plastic affinity agent and the compatilizer into a stirring container according to the corresponding proportion, and stirring and mixing for 10-15 min;
s2, adding the raw material mixture uniformly mixed in the step S1 into an extruder for plasticizing, extruding and granulating to obtain particles, wherein the temperature of the extruder is set to 200-220 ℃;
s3, drying the particles obtained in the step S2, detecting and packaging into products.
The multilayer composite barrier structure in the embodiment comprises a barrier layer, a bonding layer and a high-density polyethylene layer which are sequentially and outwards made of the barrier material from an inner layer contacting with package contents, wherein the barrier layer, the bonding layer and the high-density polyethylene layer are extruded and molded by adopting a multilayer co-extrusion blow molding process.
Example 2
The high performance barrier material in this example comprises the following components:
850g of a blocking agent (nylon 6);
30g of plastic affinity agent (high-density polyethylene);
50g of a compatibilizer (ethylene acrylic acid copolymer).
The preparation method of the high-performance barrier material comprises the following steps:
s1, adding the blocking agent, the plastic affinity agent and the compatilizer into a stirring container according to the corresponding proportion, and stirring and mixing for 10-15 min;
s2, adding the raw material mixture uniformly mixed in the step S1 into an extruder for plasticizing, extruding and granulating to obtain particles, wherein the temperature of the extruder is set to 200-220 ℃;
s3, drying the particles obtained in the step S2, detecting and packaging into products.
The multilayer composite barrier structure in the embodiment comprises a barrier layer, a bonding layer and a high-density polyethylene layer which are sequentially and outwards made of the barrier material from an inner layer contacting with package contents, wherein the barrier layer, the bonding layer and the high-density polyethylene layer are extruded and molded by adopting a multilayer co-extrusion blow molding process.
Example 3
The high performance barrier material in this example comprises the following components:
1000g of a barrier agent (nylon 6);
100g of plastic affinity agent (high-density polyethylene);
80g of a compatibilizer (ethylene acrylic acid copolymer).
The preparation method of the high-performance barrier material comprises the following steps:
s1, adding the blocking agent, the plastic affinity agent and the compatilizer into a stirring container according to the corresponding proportion, and stirring and mixing for 10-15 min;
s2, adding the raw material mixture uniformly mixed in the step S1 into an extruder for plasticizing, extruding and granulating to obtain particles, wherein the temperature of the extruder is set to 200-220 ℃;
s3, drying the particles obtained in the step S2, detecting and packaging into products.
The multilayer composite barrier structure in the embodiment comprises a barrier layer, a bonding layer and a high-density polyethylene layer which are sequentially and outwards made of the barrier material from an inner layer contacting with package contents, wherein the barrier layer, the bonding layer and the high-density polyethylene layer are extruded and molded by adopting a multilayer co-extrusion blow molding process.
Example 4
The high performance barrier material in this example comprises the following components:
950g of a blocking agent (nylon 6);
50g of plastic affinity agent (high-density polyethylene);
30g of a compatibilizer (ethylene acrylic acid copolymer).
The preparation method of the high-performance barrier material comprises the following steps:
s1, adding the blocking agent, the plastic affinity agent and the compatilizer into a stirring container according to the corresponding proportion, and stirring and mixing for 10-15 min;
s2, adding the raw material mixture uniformly mixed in the step S1 into an extruder for plasticizing, extruding and granulating to obtain particles, wherein the temperature of the extruder is set to 200-220 ℃;
s3, drying the particles obtained in the step S2, detecting and packaging into products.
The multilayer composite barrier structure in the embodiment comprises a barrier layer, a bonding layer and a high-density polyethylene layer which are sequentially and outwards made of the barrier material from an inner layer contacting with package contents, wherein the barrier layer, the bonding layer and the high-density polyethylene layer are extruded and molded by adopting a multilayer co-extrusion blow molding process.
Test examples
The multi-layer composite barrier structures prepared in examples 1 to 4 were respectively manufactured into pesticide packaging containers with a capacity of 1L, a specification of 100 g/piece, and milky white appearance, which were respectively marked as a group a, a group B, a group C, and a group D, each group having three.
In addition, a control experiment is set, and 3 pesticide packaging bottles prepared by a fluorination process are used as a group E.
Filling 1L of dimethylbenzene into each pesticide packaging bottle of the groups A, B, C, D and E, sealing the upper cover, and weighing the bottles to be M1; then placing the pesticide packaging bottles in an oven at 50 ℃ for 15 days, taking out the pesticide packaging bottles, weighing the pesticide packaging bottles to be M2, calculating the weight loss value of each bottle, wherein the weight loss value of each bottle is M2-M1, then calculating the average weight loss value of the pesticide packaging bottles in each group, wherein the smaller the weight loss is, the better the barrier effect of the pesticide packaging bottles is, and the test results are shown in Table 1.
TABLE 1
Figure BDA0002279508040000051
The test results in table 1 show that when the multilayer composite barrier structure produced by the multilayer co-extrusion blow molding process of the high-performance barrier material, the bonding layer and the high-density polyethylene layer is used as a high-barrier plastic packaging container, the leakage of organic solvents can be effectively blocked, and the multilayer composite barrier structure can be applied to the fields of automobile fuel tanks, pesticide packaging, paint packaging, cosmetic packaging and the like.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.

Claims (7)

1. The high-performance barrier material is characterized by comprising the following components in parts by mass:
80-100 parts of a barrier agent;
1-10 parts of plastic affinity agent;
2-8 parts of a compatilizer;
wherein the barrier agent is nylon 6.
2. The high performance barrier material of claim 1, wherein the barrier material comprises the following components in parts by mass:
85-95 parts of a blocking agent;
3-8 parts of plastic affinity agent;
2-5 parts of a compatilizer.
3. The high performance barrier material of claim 2, wherein the plastic affinity agent is high density polyethylene.
4. The high performance barrier material of claim 3, wherein the compatibilizer is an ethylene acrylic acid copolymer.
5. A method of making a high performance barrier material for use in making a high performance barrier material according to any one of claims 1 to 4, comprising the steps of:
s1, adding the blocking agent, the plastic affinity agent and the compatilizer into a stirring container according to the corresponding proportion, and stirring and mixing for 10-15 min;
s2, adding the raw material mixture uniformly mixed in the step S1 into an extruder for plasticizing, extruding and granulating to obtain granules;
s3, drying the particles obtained in the step S2, detecting and packaging into products.
6. A multilayer composite barrier construction characterized in that the multilayer barrier construction is, in order from the inner layer contacting the contents of a package outwards, a barrier layer consisting of the barrier material according to any one of claims 1 to 4, a tie layer and a layer of high density polyethylene.
7. The multilayer composite barrier construction of claim 6, wherein the barrier layer, the tie layer, and the high density polyethylene layer are extruded using a multilayer co-extrusion blow molding process.
CN201911135590.8A 2019-11-19 2019-11-19 High-performance barrier material and multilayer composite barrier structure Pending CN112898768A (en)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
CN2649315Y (en) * 2003-09-29 2004-10-20 轻工业塑料加工应用研究所 High-separate multi-layer coextruding blow-moulding film
US20040209021A1 (en) * 2003-04-18 2004-10-21 Shih Keith S. Multi-layer laminate structure
US20090304959A1 (en) * 2006-12-18 2009-12-10 Umish Srivastava Polypouch for packaging of superior kerosene oil
CN102532645A (en) * 2010-12-17 2012-07-04 合肥杰事杰新材料股份有限公司 Polyethylene-based composite barrier material and preparing method thereof
CN102585325A (en) * 2011-01-18 2012-07-18 合肥杰事杰新材料股份有限公司 High density polyethylene (HDPE)-PA66 composite barrier material and preparation method thereof
CN103665848A (en) * 2013-11-28 2014-03-26 方万漂 Polyethylene and nylon 6 blending modified barrier material

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Publication number Priority date Publication date Assignee Title
US20040209021A1 (en) * 2003-04-18 2004-10-21 Shih Keith S. Multi-layer laminate structure
CN2649315Y (en) * 2003-09-29 2004-10-20 轻工业塑料加工应用研究所 High-separate multi-layer coextruding blow-moulding film
US20090304959A1 (en) * 2006-12-18 2009-12-10 Umish Srivastava Polypouch for packaging of superior kerosene oil
CN102532645A (en) * 2010-12-17 2012-07-04 合肥杰事杰新材料股份有限公司 Polyethylene-based composite barrier material and preparing method thereof
CN102585325A (en) * 2011-01-18 2012-07-18 合肥杰事杰新材料股份有限公司 High density polyethylene (HDPE)-PA66 composite barrier material and preparation method thereof
CN103665848A (en) * 2013-11-28 2014-03-26 方万漂 Polyethylene and nylon 6 blending modified barrier material

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Title
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