CN112778597B - Polyethylene composition, polyethylene double-layer composite material and preparation method thereof - Google Patents

Polyethylene composition, polyethylene double-layer composite material and preparation method thereof Download PDF

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CN112778597B
CN112778597B CN201911089165.XA CN201911089165A CN112778597B CN 112778597 B CN112778597 B CN 112778597B CN 201911089165 A CN201911089165 A CN 201911089165A CN 112778597 B CN112778597 B CN 112778597B
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polyethylene
composition
weight
density
parts
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CN112778597A (en
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朱鹤翔
孙小杰
梁文斌
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Shenhua Beijing New Material Technology Co ltd
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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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
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • B32B2250/02—2 layers
    • 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
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • 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
    • C08L2207/066—LDPE (radical process)

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Laminated Bodies (AREA)

Abstract

The utility model relates to the field of polyolefin, in particular to a polyethylene composition, a polyethylene double-layer composite material and a preparation method thereof. The polyethylene composition comprises a composition A and a composition B which are independent of each other, wherein the composition A comprises: 100 parts by weight of first polyethylene resin, 0.2-6 parts by weight of peroxide crosslinking agent, 0.05-5 parts by weight of crosslinking assistant and 0.01-0.5 part by weight of first antioxidant; the composition B comprises: 100 parts by weight of a second polyethylene resin and 0.2 to 2 parts by weight of a second antioxidant; the parts by weight of the A composition and the B composition are calculated independently, and the weight ratio of the first polyethylene resin to the second polyethylene resin is 1: (0.2-5). The polyethylene double-layer composite material has good adhesion between double layers, does not need to additionally add an adhesive, and has excellent comprehensive performance.

Description

Polyethylene composition, polyethylene double-layer composite material and preparation method thereof
Technical Field
The utility model relates to the field of polyolefin, in particular to a polyethylene composition, a polyethylene double-layer composite material and a preparation method thereof.
Background
The crosslinkable polyethylene composition has excellent high temperature resistance, chemical corrosion resistance, good impact strength and the like, and has important application value in the aspects of chemical storage and transportation, oil and gas transportation, chemical anticorrosion and the like. However, in some strong oxidation environments, the crosslinked polyethylene can also undergo oxidative corrosion, and an antioxidant auxiliary agent must be added.
The CN104118146A invention relates to a box body and a preparation method thereof, the box body comprises at least one supporting layer and at least one insulating layer, and is characterized in that the supporting layer and the insulating layer are respectively made of polyolefin materials, and the thermal conductivity and/or density of any supporting layer is larger than that of any insulating layer.
CN103937061B provides a polyolefin blend composition comprising a polyolefin component and an elastomer component, and optionally fillers and auxiliaries; also provided is a composite material having a multilayer structure of A, B in which layers of two materials, respectively, alternate, wherein at least one of the two materials A and B is the polyolefin blend composition, and the two materials A and B are the same or different in composition; a method of making a composite material having acoustical insulation properties is also provided.
CN206984792U relates to a flame-retardant and heat-insulating box. The shell of the box body comprises a flame-retardant layer (1) arranged at the outermost part and a heat-insulating layer (2) arranged in the flame-retardant layer (1), wherein (i) a cavity (3) is arranged in the heat-insulating layer (2) and at the interface adjacent to the flame-retardant layer (1); or (ii) a blank layer (4) is sandwiched in the flame retardant layer (1). The cavity is arranged at the heat insulation layer or the blank layer is arranged in the flame retardant layer, so that heat and mass transfer is better prevented, and the obtained flame retardant heat insulation box body is more suitable for storing and transporting inflammable and explosive products.
However, the above patent mainly realizes a double-layer structure through a structural design, mainly a plastic/foamed double-layer structure, and does not relate to a sheet layer of the double-layer structure and a support layer and a functional layer of a cross-linked polyethylene and polyethylene blend.
Disclosure of Invention
The utility model aims to overcome the defects that polyethylene double-layer materials in the prior art generally need to be bonded by adhesives between double layers and the like, and provides a polyethylene composition, a polyethylene double-layer composite material and a preparation method thereof. The two-layer material of the polyethylene double-layer composite material prepared from the polyethylene composition has different functions, is tightly bonded, has a simple preparation method, and realizes the optimization of the storage and transportation use performance of the product in chemicals.
In order to achieve the above object, the first aspect of the present invention provides a polyethylene composition comprising each of the compositions A and B independently,
the composition A comprises: 100 parts by weight of first polyethylene resin, 0.2-6 parts by weight of peroxide crosslinking agent, 0.05-5 parts by weight of crosslinking assistant and 0.01-0.5 part by weight of first antioxidant;
the composition B comprises: 100 parts by weight of a second polyethylene resin and 0.2 to 2 parts by weight of a second antioxidant;
the parts by weight of the A composition and the B composition are calculated independently, and the weight ratio of the first polyethylene resin to the second polyethylene resin is 1: (0.2-5).
In a second aspect, the present invention provides a polyethylene two-layer composite material, which comprises a polyethylene a layer and a polyethylene B layer, wherein the polyethylene a layer is obtained by mixing, melting and crosslinking the composition a in the polyethylene composition of the first aspect, and the polyethylene B layer is obtained by mixing and melting the composition B in the polyethylene composition of the first aspect.
The third aspect of the utility model provides a method for preparing a polyethylene double-layer composite material, which adopts a rotational molding process and sequentially carries out the following two steps of feeding materials, including:
in a first step, the composition A of the polyethylene composition of the first aspect of the utility model is introduced and the melting of the composition A is carried out without crosslinking
In a second step, the composition B of the polyethylene composition of the first aspect of the utility model is dosed.
The technical scheme of the utility model at least has the following advantages:
(1) the two layers of materials of the polyethylene double-layer composite material are matched properly in function, the inner layer (a polyethylene B layer used for contacting articles) provides excellent long-term performance such as oxidation resistance, chemical reagent corrosion resistance and the like, and the outer layer (a polyethylene A layer) provides high strength, deformation resistance, UV long-term performance and durability;
(2) the inner layer and the outer layer have excellent adhesion without additional adhesive;
(3) the rotational molding process is integrally molded by secondary feeding, the manufacturing method is simple, and the product is tight and is not easy to leak.
Additional features and advantages of the utility model will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the utility model provides a polyethylene composition comprising, independently of each other, a composition A and a composition B,
the composition A comprises: 100 parts by weight of first polyethylene resin, 0.2-6 parts by weight of peroxide crosslinking agent, 0.05-5 parts by weight of crosslinking assistant and 0.01-0.5 part by weight of first antioxidant;
the composition B comprises: 100 parts by weight of a second polyethylene resin and 0.2 to 2 parts by weight of a second antioxidant;
the parts by weight of the A composition and the B composition are calculated independently, and the weight ratio of the first polyethylene resin to the second polyethylene resin is 1: (0.2-5).
In the present invention, since the a composition is used to prepare the outer layer material having better mechanical properties and the B composition is used to prepare the inner layer having better chemical properties, the person skilled in the art can adjust the weight ratio of the a composition and the B composition according to the requirements for the mechanical properties and the chemical properties of the resulting polyethylene two-layer composite. In order to obtain a polyethylene bilayer composite with a better combination of mechanical and chemical properties, preferably the weight ratio of the first polyethylene resin to the second polyethylene resin is 1: (0.5-2).
In the present invention, in order to exert a better synergistic effect between the components in the a composition, it is preferable that the a composition comprises: 100 parts by weight of first polyethylene resin, 0.2-2 parts by weight of peroxide crosslinking agent, 1-3 parts by weight of crosslinking assistant and 0.02-0.4 part by weight of first antioxidant; more preferably, the a composition comprises: 100 parts by weight of first polyethylene resin, 0.3-1.2 parts by weight of peroxide crosslinking agent, 2-3 parts by weight of crosslinking assistant and 0.1-0.15 part by weight of first antioxidant.
In order to obtain a polyethylene composition according to the utility model in which composition a, the first polyethylene resin is preferably selected from the group consisting of polyethylene resins having a density of 0.92-0.944g/cm, in order to obtain a polyethylene a layer having better interlayer adhesion and high strength, deformation and UV long term properties and durability properties3The low density polyethylene has a density of 0.945 to 0.965g/cm3High density polyethylene of (A) and ethylene and C4-C8At least one of copolymers of olefins of (a); more preferably, the first polyethylene resin has a density of 0.945 to 0.965g/cm3Or a high density polyethylene having a density of 0.92 to 0.944g/cm3And a density of 0.945 to 0.965g/cm3A combination of high density polyethylenes.
When the density of the first polyethylene resin is 0.92-0.944g/cm3And a density of 0.945 to 0.965g/cm3In the combination of the high-density polyethylenes of (2), the density is from 0.92 to 0.944g/cm based on the total weight of the first polyethylene resin3The low density polyethylene has a content of 10-25 wt%, and the density is 0.945-0.965g/cm3The content of the high-density polyethylene (C) is 75 to 90% by weight.
The type of peroxide crosslinking agent in the a-composition may be a peroxide crosslinking agent conventional in the art, and the inventors of the present invention have found that a specific type of peroxide crosslinking agent can be combined with the other components of the inventive polyethylene composition to provide a polyethylene a-layer having better interlayer adhesion as well as high strength, deformation and UV long term properties and durability. Preferably, the peroxide crosslinking agent is selected from one or more of alkyl peroxides, aryl peroxides, acyl peroxides, and ketone peroxides. More preferably, the peroxide crosslinking agent is selected from the group consisting of 1, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 7-dimethyl-2, 7-bis (tert-butylperoxy) octadiyne-3, 5, 2, 7-dimethyl-2, 7-bis (ethyl peroxycarbonate) octadiyne-3, 5, 3, 6-dimethyl-3, 6-bis (ethyl peroxycarbonate) octyne-4, 3, 6-dimethyl-3, 6-bis (tert-butylperoxy) octyne-4, 2, 5-dimethyl-2, 5-bis (peroxybenzoate) hexyne-3, 2, 5-dimethyl-2, 5-bis (n-propyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-3, 5-bis (n-propyl peroxycarbonate) hexyne-3, Hexyne-3, 2, 5-dimethyl-2, 5-di (isobutyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (ethyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (alpha-cumylperoxy) hexyne-3, 2, 5-dimethyl-2, 5-di (beta-chloroethyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexyne-3, butyl 4, 4-di (tert-butylperoxy) valerate, di (2, 4-dichlorobenzoyl) peroxide, di (4-methylbenzoyl) peroxide, di (tert-butylperoxyisopropyl) benzene, di (tert-butyl peroxyisopropyl) n-butyl-ethyl acetate, di (tert-butyl-peroxy) valerate, di (2, 4-dichlorobenzoyl) peroxide, di (tert-butyl peroxyisopropyl) benzene, di (tert-butyl peroxyethyl-butyl-propyl) hexyne-3, di (tert-butyl-propyl-3, di (tert-butyl-propyl-butyl-peroxy-butyl-propyl-3, di (butyl-propyl-butyl-propyl-butyl-hexyl-3, butyl-peroxy) valerate, di (butyl-benzoyl peroxide, di (butyl-propyl-benzoyl) hexyl-butyl-propyl-butyl-p-butyl-p-butyl-propyl-butyl-3, di (butyl-propyl-butyl-3, butyl-propyl-butyl-3, di (butyl-propyl-butyl-propyl-butyl-propyl) valerate, di (butyl-p-butyl-p-propyl) valerate, di (butyl-benzoyl peroxide, di (butyl-p-butyl-benzoyl peroxide, di (butyl-benzoyl peroxide, di (butyl-benzoyl) valerate, di (butyl-benzoyl) phenyl) valerate, di (butyl-benzoyl peroxide, di-butyl-p-butyl-p-butyl-, One or more of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, t-butylperoxy-3, 5,5 trimethyl hexanoate, t-butylperoxy benzoate, and t-butylperoxy 2-ethylhexyl carbonate and derivatives thereof. According to a preferred embodiment, the peroxide crosslinking agent is selected from one or more of alkyl peroxides and acyl peroxides in order to cooperate with the crosslinking coagent and other ingredients.
In the a composition, the crosslinking assistant may be a conventional crosslinking assistant in the art, and preferably, the crosslinking assistant is selected from one or more of 1,2 polybutadiene, diallyl terephthalate (DATP), Divinylbenzene (DVB), triallyl cyanurate (TAC), triallyl cyanurate (TAP), triallyl isocyanate (TAIC), and derivatives thereof, in order to be better compounded with other components in the inventive polyethylene composition. According to a preferred embodiment, the crosslinking coagent is selected from one or more of triallyl cyanurate (TAC), triallyl cyanurate (TAP) and triallyl isocyanate (TAIC) for the purpose of interworking with the peroxide crosslinker and other ingredients.
In the a composition, the first antioxidant may be an antioxidant conventional in the art, and in order to be better matched with other components in the inventive polyethylene composition, preferably, the first antioxidant is selected from one or more of benzofuranone-type antioxidants, hindered phenol-type antioxidants, amine-type antioxidants, phosphorus-type antioxidants and thioether-type antioxidants; more preferably, the first antioxidant is selected from the group consisting of 5-tert-butyl-7-methyl-3- (4-methoxyphenyl) -3-hydro-benzofuran-2-one, 5-tert-butyl-7-methyl-3- (4-methylphenyl) -3-hydro-benzofuran-2-one, 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) -3-hydro-benzofuran-2-one, 2, 6-di-tert-butyl-4-methylphenol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) pentaerythritol ester, octylated diphenylamine, 4 ' -bis (. alpha.,. alpha. -dimethylbenzyl) diphenylamine, N ' -bis (1, 4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N ' - (p-toluenesulfonyl) -p-phenylenediamine, trioctyl ester, tridecyl ester, tridodecyl ester and trihexadecyl ester, and thiodipropionate distearate. According to a preferred embodiment, the first antioxidant is selected from one or more of the group of antioxidants of the benzofuran-type, more preferably from one or more of the group consisting of 5-tert-butyl-7-methyl-3- (4-methoxyphenyl) -3-hydro-benzofuran-2-one, 5-tert-butyl-7-methyl-3- (4-methylphenyl) -3-hydro-benzofuran-2-one, 5, 7-di-tert-butyl-3- (4-methylphenyl) -3-hydro-benzofuran-2-one and 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) -3-hydro-benzofuran-2-one, for co-operation with the second antioxidant and with further components And (4) seed preparation.
The A composition may further comprise other processing aids conventional in the art, such as UV resistant aids, flame retardants and color concentrates, the selection and amount of which are not particularly limited and may be performed in a manner conventional in the art. The processing aid may be contained in an amount of 0 to 5 parts by weight with respect to 100 parts by weight of the first polyethylene resin.
Preferably, the B composition comprises: 100 parts by weight of the second polyethylene resin and 0.8 to 1.2 parts by weight of the second antioxidant.
The polyethylene composition according to the utility model, in which composition B, in order to obtain a polyethylene B layer having better interlayer adhesion and multiple oxidation and chemical corrosion resistance, is preferably chosen from polyethylene resins having a density of from 0.92 to 0.944g/cm3The low density polyethylene has a density of 0.945 to 0.965g/cm3High density polyethylene of (A) and ethylene and C4-C8At least one of copolymers of olefins of (a); more preferably, the second polyethylene resin has a density of 0.92 to 0.944g/cm3Or a low density polyethylene having a density of 0.92 to 0.944g/cm3And a high density polyethylene having a density of 0.945 to 0.965.
When the second polyethylene resin has a density of 0.92-0.944g/cm3And a density of 0.945 to 0.965g/cm3In combination with the high-density polyethylene of (2), the density is preferably from 0.92 to 0.944g/cm, based on the total weight of the second polyethylene resin3The low density polyethylene has a content of 50-90 wt%, and the density is 0.945-0.965g/cm3The content of the high-density polyethylene is 10 to 50 wt%; further preferably, the density is from 0.92 to 0.944g/cm, based on the total weight of the second polyethylene resin3The low density polyethylene has a content of 60-80 wt%, and the density is 0.945-0.965g/cm3The content of the high-density polyethylene (C) is 20 to 40% by weight.
In the B composition, the second antioxidant may be an antioxidant conventional in the art, and in order to better cooperate with other ingredients in the inventive polyethylene composition, preferably, the second antioxidant is selected from one or more of phosphite antioxidants, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants and thioether antioxidants; more preferably, the second antioxidant is selected from the group consisting of triphenyl phosphite, triphenyl isodecyl phosphite, phenyl-bis (4-octylphenyl) phosphite, tris (4-octylphenyl) phosphite, 2, 6-di-tert-butyl-4-methylphenol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) pentaerythritol ester, octylated diphenylamine, 4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, N, one or more of N '-bis (1, 4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N' - (p-toluenesulfonyl) -p-phenylenediamine, trioctyl ester, tridecyl ester, tridodecyl ester, and trihexadecyl ester, and thiodipropionate distearate.
For the purpose of interworking with the first antioxidant and the other ingredients, preferably the second antioxidant is selected from one or more of triphenyl phosphite, triphenyl isodecyl phosphite, phenyl-bis (4-octylphenyl) phosphite and tris (4-octylphenyl) phosphite, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, dioctadecyl thiodipropionate and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; more preferably, the second antioxidant is a combination of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and dioctadecyl thiodipropionate in a weight ratio of 1:0.8 to 1.2, a combination of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] in a weight ratio of 1:0.8 to 1.2, and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dioctadecyl thiodipropionate in a weight ratio of 1: 0.8-1.2.
The composition B may further comprise other processing aids conventional in the art, and the selection and amount of these processing aids are not particularly limited and may be performed in a manner conventional in the art.
In a second aspect, the present invention provides a polyethylene two-layer composite material, which comprises a polyethylene a layer and a polyethylene B layer, wherein the polyethylene a layer is obtained by mixing, melting and crosslinking the composition a in the polyethylene composition of the first aspect, and the polyethylene B layer is obtained by mixing and melting the composition B in the polyethylene composition of the first aspect.
In a preferred aspect of the present invention, when the polyethylene two-layer composite is used for storing an article, for example, when the polyethylene two-layer composite is formed into a container, the polyethylene B layer serves as an inner layer contacting the article.
According to the polyethylene double-layer composite material, the thickness ratio of the polyethylene A layer to the polyethylene B layer can be set according to needs, and in a preferable case, the thickness ratio of the polyethylene A layer to the polyethylene B layer is 1: 0.2-5.
In the polyethylene double-layer composite material, the polyethylene A layer and the polyethylene B layer have good cohesiveness without adding any additional adhesive, the polyethylene A layer has good high strength, deformation resistance, UV long-term performance and durability, and the polyethylene B layer has good long-term performance such as multiple oxidation resistance, chemical reagent corrosion resistance and the like.
The third aspect of the utility model provides a method for preparing a polyethylene double-layer composite material, which adopts a rotational molding process and sequentially carries out the following two steps of feeding materials, including:
in a first step, the composition A of the polyethylene composition of the first aspect of the utility model is introduced and the melting of the composition A is carried out without crosslinking
In a second step, the composition B of the polyethylene composition of the first aspect of the utility model is dosed.
Preferably, the B composition is administered in an inner layer of the material formed by the a composition.
According to the preparation method of the utility model, the rotational molding process adopts a process conventional in the art, and the composition A undergoes a crosslinking reaction in the rotational molding process, preferably, the rotational molding temperature is 250-290 ℃, and more preferably 260-280 ℃. That is, preferably, the conditions of the two-step charging include: the temperature is 250 ℃ and 290 ℃, more preferably 260 ℃ and 280 ℃.
Preferably, the two-step dosing comprises:
the first step is to feed the composition A and perform rotational molding for 5-15min, and then the process is performed
And a second step of feeding, wherein the composition B is fed into the inner layer of the material formed by the first step of feeding and is subjected to rotational molding for 10-30 min.
Preferably, the composition a is dosed in powder form, the powder of composition a being obtained in a manner comprising: the components of the composition a are mixed and the resulting mixture is subjected to a first extrusion granulation (the resulting material is denoted as polyethylene blend a) and grinding in that order.
Preferably, the temperature of the first extrusion granulation is 130-160 ℃.
Preferably, the grinding is such that the particle size of the polyethylene blend a is 30-60 mesh.
Preferably, the B composition is dosed in powder form, the powder of the B composition being obtained in a manner comprising: the components of the composition B were mixed and the resulting mixture was subjected to a second extrusion granulation (the resulting material was denoted as polyethylene blend B) and grinding in that order.
Preferably, the temperature of the second extrusion granulation is 140-180 ℃.
Preferably, the grinding is such that the particle size of the polyethylene blend b is 30-60 mesh.
The present invention will be described in detail below by way of examples.
The following group a preparations are illustrative of the composition a of the present invention.
Preparation A1
(1) Preparing a composition a of a polyethylene composition comprising the following ingredients:
a-1 a first polyethylene resin comprising:
high density polyethylene (trade name HDPE 8920, manufactured by Mono-mountain Co., Ltd., China petrochemical Co.), melt index of 20g/10min, and density of 0.960g/cm386 parts by weight;
low ethylene polyethylene (LLDPE 5220 by Shenhua company), melt index of 2g/10min, density of 0.924g/cm314 parts by weight;
a-2 peroxide crosslinking agent: 0.45 part by weight of di-tert-butyl peroxide (J & K Scientific manufacturer);
a-3 crosslinking assistant: 2.5 parts by weight of triacrylate isocyanurate (TAIC, J & K Scientific);
a-4 first antioxidant: pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (brand 1010, from Shanghai Ciba Gaobaokou chemical Co., Ltd.), 0.15 parts by weight;
a-5 processing aid: 0.15 part of color master batch.
(2) The above prepared A combination was pelletized by extrusion at 140 ℃ and 120rpm with a twin-screw extruder, and was designated as A1.
Preparation A2
(1) Preparing a composition a of a polyethylene composition comprising the following ingredients:
a-1 a first polyethylene resin comprising:
high density polyethylene (trade name HDPE 8920, manufactured by Mono-mountain Co., Ltd., China petrochemical Co.), melt index of 20g/10min, and density of 0.960g/cm3100 parts by weight;
a-2 peroxide crosslinking agent: 0.8 part by weight of 1, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane (J & K Scientific, manufacturer);
a-3 crosslinking assistant: 3 parts by weight of divinylbenzene (the trade name is DVB, and the manufacturer is J & K Scientific);
a-4 first antioxidant: tris [ 2.4-di-tert-butylphenyl ] phosphite (model 1330, manufactured by sigma aldrich trade ltd), 0.1 part by weight;
a-5 processing aid: 0.15 part of color master batch.
(2) The composition A prepared above was pelletized by extrusion at 140 ℃ and 120rpm using a twin-screw extruder and was designated as A2.
Preparation A3
(1) Preparing a composition a of a polyethylene composition comprising the following ingredients:
a-1 a first polyethylene resin comprising:
high density polyethylene (trade name 8007, from Shenhua company), melt index of 8g/10min, density of 0.965g/cm375 parts by weight;
low ethylenePolyethylene (7042, from Shenhua company), 2g/10min melt index, 0.924g/cm density325 parts by weight;
a-2 peroxide crosslinking agent: dicumyl peroxide (J & K Scientific, manufacturer), 0.6 parts by weight;
a-3 crosslinking assistant: 2 parts by weight of diallyl terephthalate (No. DATP, J & K Scientific from manufacturer);
a-4 first antioxidant tris [2, 4-di-tert-butylphenyl ] phosphite: (product name 1330, product name Sigma Aldrich trade Co., Ltd.), 0.1 part by weight;
a-5 processing aid: 0.15 part of color master batch.
(2) The composition A prepared above was pelletized by extrusion at 140 ℃ and 120rpm using a twin-screw extruder and was designated as A3.
Preparation A4
A composition of polyethylene composition A was prepared as in preparation A2, except that the first polyethylene resin was changed to a low ethylene polyethylene (LLDPE 5220, from Shenhua company) having a melt index of 2g/10min and a density of 0.924g/cm3100 parts by weight.
The composition A was designated A4.
Preparation A5
A composition of polyethylene composition A was prepared in the manner as in preparation A3, except that the low density polyethylene resin was changed to a copolymer of ethylene and octene (POE 8100, Dow chemical Co., Ltd.) having a melt index of 0.5g/10min and a density of 0.865g/cm325 parts by weight.
The composition A was designated A5.
Comparative example AD1
A composition of polyethylene composition A was prepared in the manner of preparation A1, except that no peroxide crosslinking agent and no crosslinking coagent were added.
This composition A was designated as AD 1.
The following group B preparations are illustrative of the composition B of the present invention.
Preparation B1
(1) Preparing a B composition of polyethylene composition comprising the following ingredients:
b-1 a second polyethylene resin comprising:
high density polyethylene (trade name HDPE 8920, manufactured by Mono-mountain Co., Ltd., China petrochemical Co.), melt index of 20g/10min, and density of 0.960g/cm340 parts by weight;
low ethylene polyethylene (LLDPE 5220 by Shenhua company), melt index of 2g/10min, density of 0.924g/cm360 parts by weight;
b-2 a second antioxidant comprising:
0.5 part by weight of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene;
distearyl thiodipropionate (antioxidant DSTP, manufactured by Sigma Aldrich trade company, Ltd.), 0.5 part by weight.
(2) The composition B prepared above was pelletized by extrusion at 150 ℃ and 120rpm using a twin-screw extruder and was designated as B1.
Preparation B2
(1) Preparing a B composition of polyethylene composition comprising the following ingredients:
b-1 second polyethylene resin: low ethylene polyethylene (LLDPE 5220 by Shenhua company), melt index of 2g/10min, density of 0.924g/cm3100 parts by weight;
b-2 a second antioxidant comprising:
0.6 part by weight of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene;
0.6 part by weight of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
(2) The composition B prepared above was pelletized by extrusion at 160 ℃ and 120rpm using a twin-screw extruder and was designated as B2.
Preparation B3
(1) Preparing a B composition of polyethylene composition comprising the following ingredients:
b-1 a second polyethylene resin comprising:
high density polyethylene (trade name 8007, from Shenhua company), melt index of 8g/10min, density of 0.965g/cm320 parts by weight;
low ethylene polyethylene (trade name 7042, from Shenhua company), 2g/10min of melt index and 0.924g/cm of density380 parts by weight;
b-2 a second antioxidant comprising:
0.4 part by weight of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
0.4 part by weight of 2, 6-di-tert-butyl-4-methylphenol.
(2) The composition B prepared above was pelletized by extrusion at 170 ℃ and 120rpm using a twin-screw extruder and was designated as B3.
Preparation B4
A composition B of a polyethylene composition was prepared in the manner of preparation B1, except that the second polyethylene resin was changed to a high density polyethylene (trade name HDPE 8920, manufactured by Mount, petrochemical company), having a melt index of 20g/10min and a density of 0.960g/cm3100 parts by weight.
The composition B was designated as B4.
Preparation B5
A composition B of a polyethylene composition was prepared as in preparation B1, except that a copolymer of ethylene and octene (POE 8100, Dow. RTM.) having a melt index of 0.5g/10min and a density of 0.865g/cm was further added to the second polyethylene resin320 parts by weight.
The composition B was designated as B5.
The following group C examples are presented to illustrate the polyethylene two-layer composites of the present invention and the method of making the same.
Example C1
(1) The A1 and B1 obtained above were ground into 50 mesh powders respectively for use, and the weight ratio of A1 to B1 was 1: 2.
(2) The barrel-shaped container is prepared by adopting a rotational molding process, a secondary feeding mode is adopted, specifically, after the powdery combination A is firstly fed for rotational molding for 10min at a rotational molding temperature of 270 ℃ (the powder is molten but not crosslinked), the powdery combination B is fed into the inner layer of the barrel-shaped container for further rotational molding for 30min (the crosslinking reaction is completed), and then the barrel-shaped container is cooled.
The product obtained is designated C1.
Example C2
(1) The A1 and B1 obtained above were ground into 50 mesh powders respectively for use, and the weight ratio of A1 to B1 was 1: 5.
(2) The barrel-shaped container is prepared by adopting a rotational molding process, a secondary feeding mode is adopted, specifically, after the powdery combination A is firstly fed for rotational molding for 8min at the rotational molding temperature of 260 ℃ (the powder is molten but not crosslinked), the powdery combination B is fed into the inner layer of the barrel-shaped container for further rotational molding for 35min (the crosslinking reaction is completed), and then the barrel-shaped container is cooled.
The product obtained is designated C2.
Example C3
(1) The A1 and B1 obtained above were ground into 50 mesh powders respectively for use, and the weight ratio of A1 to B1 was 5: 1.
(2) The barrel-shaped container is prepared by adopting a rotational molding process, a secondary feeding mode is adopted, specifically, after the powdery combination A is firstly fed for rotational molding for 15min at the rotational molding temperature of 280 ℃ (the powder is molten but not crosslinked), the powdery combination B is fed into the inner layer of the barrel-shaped container for further rotational molding for 30min (the crosslinking reaction is completed), and then the barrel-shaped container is cooled.
The product obtained is designated C3.
Comparative example CD1
(1) Same as in example C1.
(2) The barrel-shaped container is prepared by adopting a rotational molding process, a secondary feeding mode is adopted, specifically, after the powdery combination A is firstly fed for rotational molding for 20min at a rotational molding temperature of 270 ℃ (at the moment, the powder starts to generate a cross-linking reaction), the powdery combination B is fed into the inner layer of the barrel-shaped container for further rotational molding for 30min (the cross-linking reaction is completed), and then the barrel-shaped container is cooled.
The resulting product was designated as CD 1.
Other examples (C4-C9) and comparative example (CD2) were conducted as in example C1, except that the A and B compositions were varied as specifically shown in Table 1.
Test example
The obtained products were subjected to the following tests, respectively, and the obtained results are shown in table 1.
(1) The degree of crosslinking (%) of the outer (layer a) polyethylene composite obtained from composition a was tested according to the method specified in ASTM D2765, which specifically comprises: a plastic block having a mass of W1 (about 0.300. + -. 0.015g) was cut from the cross-linked polyethylene product, cut up and placed into a 100ml stainless steel mesh bag (specification for mesh bags refer to ASTM D2765). After the sample was extracted in xylene solution at 170 ℃ for 20 hours, the sample was taken out and dried in a vacuum oven at 90 ℃ for 6 hours, and then the mass was designated as W2. The degree of crosslinking is (W2/W1) × 100%.
(2) Flexural modulus (MPa) was determined according to the method specified in GB/T9341-2008.
(3) Impact Strength (KJ/m)2) Determined according to the method specified in GB/T1843-2008.
(4) The environmental stress crack resistance (h) was determined according to the method specified in GB/T1842-.
(5) The oxidative induction period (min) is determined according to the method specified in GB/T1466.
TABLE 1
Figure BDA0002266352260000161
Figure BDA0002266352260000171
As can be seen from the table, the polyethylene double-layer composite material prepared from the polyethylene composition provided by the utility model has good comprehensive properties such as impact strength, flexural modulus, environmental stress cracking resistance and oxidation resistance; and the experiment finds that the adhesion between the two layers of materials is excellent and the adhesion is tight without using extra adhesive. The polyethylene two-layer composite material of comparative example CD1 was poor in environmental stress crack resistance and the inner and outer layers were separated. The polyethylene two-layer composite material of comparative example CD2 has lower impact strength, environmental cracking resistance and crosslinking degree, and poorer comprehensive properties.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the utility model, many simple modifications can be made to the technical solution of the utility model, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the utility model, and all fall within the scope of the utility model.

Claims (10)

1. The polyethylene double-layer composite material is characterized by comprising a polyethylene A layer and a polyethylene B layer which are tightly combined, wherein the polyethylene A layer is obtained by mixing, melting and crosslinking a composition A in a polyethylene composition, and the polyethylene B layer is obtained by mixing and melting a composition B in the polyethylene composition;
the polyethylene composition comprises a composition A and a composition B which are independent of each other;
the composition A comprises: 100 parts by weight of first polyethylene resin, 0.2-6 parts by weight of peroxide crosslinking agent, 0.05-5 parts by weight of crosslinking assistant and 0.01-0.5 part by weight of first antioxidant;
the composition B comprises: 100 parts by weight of a second polyethylene resin and 0.2 to 2 parts by weight of a second antioxidant;
the parts by weight of the A composition and the B composition are calculated independently, and the weight ratio of the first polyethylene resin to the second polyethylene resin is 1: (0.2-5);
the preparation method of the polyethylene double-layer composite material adopts a rotational molding process, and sequentially comprises the following two steps of feeding materials:
the first step of feeding the A composition of the polyethylene composition, and the step of feeding the A composition of the polyethylene composition until the A composition is melted and not crosslinked
And a second step of feeding the B composition in the polyethylene composition.
2. The polyethylene bilayer composite of claim 1, wherein the a composition comprises: 100 parts by weight of first polyethylene resin, 0.2-2 parts by weight of peroxide crosslinking agent, 1-3 parts by weight of crosslinking assistant and 0.02-0.4 part by weight of first antioxidant;
and/or, the B composition comprises: 100 parts by weight of a second polyethylene resin and 0.8 to 1.2 parts by weight of a second antioxidant;
and/or the weight ratio of the first polyethylene resin to the second polyethylene resin is 1: (0.5-2).
3. The polyethylene bilayer composite of claim 1 or 2 wherein the first polyethylene resin is of density 0.945 to 0.965g/cm3High density polyethylene of (a);
or the first polyethylene resin has the density of 0.92-0.944g/cm3And a density of 0.945 to 0.965g/cm3And the density is 0.92 to 0.944g/cm, based on the total weight of the first polyethylene resin3The low density polyethylene has a content of 10-25 wt%, and the density is 0.945-0.965g/cm3The content of the high-density polyethylene (C) is 75 to 90% by weight.
4. The polyethylene bilayer composite of claim 1 or 2 wherein the second polyethylene resin is of a density of from 0.92 to 0.944g/cm3Low density polyethylene of (a);
or the second polyethylene resin has the density of 0.92-0.944g/cm3And a high density polyethylene having a density of 0.945 to 0.965, and the density is 0.92 to 0.944g/cm, based on the total weight of the second polyethylene resin3The low density polyethylene has a content of 50-90 wt%, and the density is 0.945-0.965g/cm3The content of the high-density polyethylene (C) is 10 to 50% by weight.
5. The polyethylene bilayer composite of claim 1 or 2 wherein the peroxide crosslinking agent is selected from one or more of an alkyl peroxide, an aryl peroxide, an acyl peroxide and a ketone peroxide;
and/or the crosslinking assistant is selected from triallyl cyanurate and/or triallyl isocyanate;
and/or the second antioxidant is a combination of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and dioctadecyl thiodipropionate in a weight ratio of 1:0.8-1.2, a combination of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] in a weight ratio of 1:0.8-1.2, and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dioctadecyl thiodipropionate in a weight ratio of 1: 0.8-1.2.
6. The polyethylene bilayer composite of claim 1 or 2 wherein the polyethylene B layer acts as an inner layer contacting the article when the polyethylene bilayer composite is used to store the article.
7. The polyethylene bilayer composite of claim 1 or 2 wherein the ratio of the thickness of the polyethylene a layer and the polyethylene B layer is 1: 0.2-5.
8. The polyethylene bilayer composite of claim 1 or 2 wherein the two-stage dosing conditions comprise: the temperature is 250-290 ℃.
9. The polyethylene bilayer composite of claim 1 or 2 wherein the two-step dosing comprises:
the first step is to feed the composition A and perform rotational molding for 5-15min, and then the process is performed
And a second step of feeding, wherein the composition B is fed into the inner layer of the material formed by the first step of feeding and is subjected to rotational molding for 10-30 min.
10. The polyethylene bilayer composite of claim 1 or 2 wherein the a composition is dosed as a powder obtained by: mixing the components of the composition A, and sequentially performing first extrusion granulation and grinding on the obtained mixture, wherein the temperature of the first extrusion granulation is 130-160 ℃;
and/or the B composition is put in a powder mode, and the powder of the B composition is obtained in a mode that: mixing the components of the composition B, and sequentially performing second extrusion granulation and grinding on the obtained mixture, wherein the temperature of the second extrusion granulation is 140-180 ℃.
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