CN112172076B - Halogen-free flame-retardant polyolefin foam material with sandwich structure and preparation method thereof - Google Patents

Halogen-free flame-retardant polyolefin foam material with sandwich structure and preparation method thereof Download PDF

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Publication number
CN112172076B
CN112172076B CN202010987034.XA CN202010987034A CN112172076B CN 112172076 B CN112172076 B CN 112172076B CN 202010987034 A CN202010987034 A CN 202010987034A CN 112172076 B CN112172076 B CN 112172076B
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polyethylene
flame retardant
parts
antioxidant
halogen
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CN112172076A (en
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方凯
魏琼
魏志祥
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Guangde Xiangyuan New Material Technology Co ltd
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Guangde Xiangyuan New Material Technology Co ltd
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  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract

The invention discloses a halogen-free flame-retardant polyolefin foam material with a sandwich structure, which mainly comprises two polyethylene resin layers and a polyethylene foam layer, wherein each polyethylene resin layer comprises the following raw materials in parts by weight: 76-93 parts of polyethylene resin, 0.3-0.6 part of antioxidant and 8-25 parts of flame retardant; the polyethylene foaming layer comprises the following raw materials in parts by weight: 56-83 parts of polyethylene resin, 5-10 parts of polyethylene-acrylic resin, 8-15 parts of foaming agent master batch, 0.08-0.6 part of antioxidant and 5-20 parts of flame retardant. The polyolefin foam material prepared by the invention has higher buffer performance, hardness and strength, and is not easy to be damaged by external force; in addition, the flame retardant has the advantages of good flame retardant property, excellent environmental protection property, no generation of toxic and dense smoke during combustion and low cost.

Description

Halogen-free flame-retardant polyolefin foam material with sandwich structure and preparation method thereof
Technical Field
The invention belongs to the field of foaming materials, and particularly relates to a halogen-free flame-retardant polyolefin foaming material and a preparation method thereof.
Background
The radiation cross-linked polyethylene foam is prepared through extruding polyethylene or modified polyethylene and various stuffing, radiation cross-linking with electron accelerator without chemical bridging agent and high temperature foaming. The radiation crosslinking foaming process can avoid harmful gas generated after the decomposition of a chemical crosslinking agent, and the foaming process is easy to control and the foaming speed is high, so that the radiation crosslinking polyethylene foam plays an important role in the field of foaming materials with excellent performance at present.
The radiation crosslinking polyethylene foam on the market at present has soft hardness and low strength while showing excellent buffering performance, and cannot be directly used for surface materials requiring high hardness and strength and good buffering performance, such as automotive interiors and the like; moreover, most of the commercially available flame-retardant grade irradiation crosslinked polyethylene foam is basically halogen flame-retardant, the material is not environment-friendly and harmful to human health, and a large amount of black toxic dense smoke is generated during combustion, so that the escape of personnel in case of fire is not facilitated; almost all the commercially available halogen-free flame-retardant irradiation crosslinked polyethylene foam is high in cost, and the flame retardant property of the halogen-free flame-retardant irradiation crosslinked polyethylene foam is poorer than that of the traditional halogen-free flame-retardant irradiation crosslinked polyethylene foam, so that the halogen-free flame-retardant irradiation crosslinked polyethylene foam cannot be used in large quantities.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a halogen-free flame-retardant polyolefin foam material with a sandwich structure and a preparation method thereof, wherein the halogen-free flame-retardant polyolefin foam material has relatively high hardness and strength while maintaining excellent buffer performance, and can be directly used for surface materials such as automotive interiors and the like requiring high hardness and strength and good buffer performance; meanwhile, compared with the traditional halogen flame-retardant irradiation cross-linked polyethylene foam, the halogen-free flame-retardant polyethylene foam with the sandwich structure also has the advantages of excellent flame-retardant performance, outstanding environment friendliness, lower cost compared with the existing halogen-free flame-retardant irradiation cross-linked polyethylene foam on the market and the like.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a halogen-free flame retardant polyolefin foam material of a sandwich structure, which is mainly composed of two polyethylene resin layers sandwiching a polyethylene foam layer,
each polyethylene resin layer comprises the following raw materials in parts by weight: 76-93 parts of polyethylene resin, 0.3-0.6 part of antioxidant and 8-25 parts of flame retardant;
the polyethylene foaming layer comprises the following raw materials in parts by weight: 56-83 parts of polyethylene resin, 5-10 parts of polyethylene-acrylic resin, 8-15 parts of foaming agent master batch, 0.08-0.6 part of antioxidant and 5-20 parts of flame retardant;
the thickness of each polyethylene resin layer is 0.05 mm-0.2 mm, and the thickness of the polyethylene foaming layer is 0.6 mm-3.6 mm;
the melt index of the polyethylene resin layer is 11g/10 min-27 g/10min, and the melt index of the polyethylene resin of the polyethylene foaming layer is 0.8g/10 min-3 g/10 min.
Preferably, the antioxidant of the polyethylene resin layer is selected from one or more of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants.
Preferably, the antioxidant of the polyethylene foaming layer is selected from one or more of hindered phenol antioxidant, phosphite antioxidant and thioester antioxidant.
Preferably, the antioxidant of the polyethylene resin layer is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 618, antioxidant DLTDP and antioxidant 412S.
Preferably, the antioxidant of the polyethylene foam layer is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 618, antioxidant DLTDP and antioxidant 412S.
Preferably, the flame retardant of the polyethylene resin layer is selected from one or more of melamine pyrophosphate, ammonium polyphosphate, magnesium hydroxide, a compound flame retardant and red phosphorus, wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant;
the flame retardant of the polyethylene foaming layer is selected from one or more of melamine pyrophosphate, ammonium polyphosphate, magnesium hydroxide, a compound flame retardant and red phosphorus, wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant.
Preferably, the magnesium hydroxide is obtained by treating the surface with a coupling agent to improve the compatibility with the polyethylene resin, wherein the coupling agent is silane or a silane derivative;
the red phosphorus is coated by a melamine resin microcapsule to improve the compatibility with the polyethylene resin;
the compound flame retardant is an intumescent flame retardant obtained by compounding.
Preferably, the foaming agent master batch is a master batch manufactured by azodicarbonamide foaming agent and polyethylene resin, the melt index of the polyethylene resin in the foaming agent master batch is 0.8g/10 min-3 g/10min, and the proportion of the azodicarbonamide foaming agent in the foaming agent master batch is 45 wt% -65 wt%. This is because if the concentration of the foaming agent masterbatch is too low, the foaming agent masterbatch is added too much in the formula when the required foaming ratio is satisfied, so that the formula design space is too small (other components cannot be added); the concentration is too high, the processing is difficult, the azodicarbonamide foaming agent is powder, and the limit problem of the resin 'eating in' powder and the corresponding difficulty exist when the azodicarbonamide foaming agent is granulated with polyethylene resin.
Preferably, in the polyethylene-acrylic resin, the acrylic acid segment accounts for 4 wt% to 12 wt%. The polyethylene-acrylic resin in the proportion can effectively promote the compatibility of powder, particularly flame retardant powder and matrix polyethylene resin, and has low cost and outstanding cost performance; if the proportion of the acrylic acid chain segment is too small, the effect of promoting compatibility is poor, and the product performance is influenced by too many addition parts; if the proportion of the acrylic segment is too large, the effect of promoting compatibility is improved to some extent, but the cost is increased too much and the cost performance is poor.
According to another aspect of the present invention, there is provided a method for preparing the halogen-free flame retardant polyolefin foam material with a sandwich structure, comprising the following steps:
1) uniformly mixing raw materials used by a polyethylene resin layer according to the weight part of claim 1, and dividing the mixture into A, B parts;
2) uniformly mixing the raw materials for the polyethylene foaming layer according to the parts by weight in the claim 1;
3) respectively putting the A part and the B part of the polyethylene resin layer and the raw materials used by the polyethylene foaming layer into three extruders of a three-layer co-extrusion film blowing machine, and forming a composite coiled material by a three-layer co-extrusion process;
4) and (3) irradiating and crosslinking the composite coiled material by using an electron accelerator, and foaming the composite coiled material by using a high-temperature foaming furnace to obtain the halogen-free flame-retardant polyolefin foaming material with the sandwich structure.
Tests prove that the halogen-free flame-retardant polyethylene foam with the sandwich structure prepared by the method provided by the invention has excellent flame-retardant performance, higher strength and hardness; through analysis and comparison, the halogen-free flame-retardant polyethylene foam with the sandwich structure prepared by the method provided by the invention has the advantage of extremely high cost compared with the existing commercially available halogen-free flame-retardant irradiation cross-linked polyethylene foam, and the cost of the halogen-free flame-retardant irradiation cross-linked polyethylene foam is equivalent to or even lower than that of the halogen-free flame-retardant irradiation cross-linked polyethylene foam.
The halogen-free flame-retardant polyethylene foam with the sandwich structure has the thickness of 0.7-4.0 mm, the multiplying power (absolute value is equal to the reciprocal of the density, the unit is multiple) of 5-30 times, the hardness (Shore hardness C) of 32-64, the tensile strength (test standard: GB/T528-, compared with the same-magnification irradiation crosslinking polyethylene halogen-free flame-retardant foam, the halogen-free flame-retardant foam is reduced by about 17000-23000 yuan/ton.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) compared with the irradiation cross-linked polyethylene halogen flame-retardant foam with the same multiplying power, the halogen-free flame-retardant polyethylene foam with the sandwich structure provided by the invention has the advantages of equivalent buffer performance, higher hardness and strength, difficulty in being damaged by external force, and capability of being directly used in the field of surface materials requiring higher hardness and strength and better buffer performance, such as automobile interior trim and the like;
(2) compared with the halogen-free flame-retardant polyethylene foam with the same multiplying power, the halogen-free flame-retardant polyethylene foam with the sandwich structure has quite even better flame retardant property;
(3) compared with irradiation crosslinking polyethylene halogen flame-retardant foam, the halogen-free flame-retardant polyethylene foam with the sandwich structure provided by the invention has excellent environmental protection performance, does not generate toxic dense smoke during combustion, and is more favorable for escape of people in case of fire.
(4) Compared with the irradiation crosslinking polyethylene halogen flame-retardant foam with the same multiplying power, the halogen-free flame-retardant polyethylene foam with the sandwich structure provided by the invention has the cost which is approximately equivalent to or even lower than that of the irradiation crosslinking polyethylene halogen flame-retardant foam with the same multiplying power, and compared with the irradiation crosslinking polyethylene halogen-free flame-retardant foam with the same multiplying power, the halogen-free flame-retardant polyethylene foam with the sandwich structure has great cost advantage.
Drawings
FIG. 1 is a flow chart of a method for preparing a halogen-free flame-retardant polyethylene foam with a sandwich structure according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a specification of a flame retardant strip adopted by a halogen-free flame retardant polyethylene foam with a sandwich structure according to an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
According to the preparation method of the halogen-free flame-retardant polyethylene foam with the sandwich structure, the raw materials required by the polyethylene resin layer are uniformly mixed according to the proportion and are divided into A, B parts for later use; uniformly mixing the raw materials used by the polyethylene foaming layer according to the proportion for later use; the three materials are respectively put into a three-layer co-extrusion film blowing machine to be continuously extruded into an upper, a middle and a lower three-layer composite coiled material substrate (the two outer layers are polyethylene resin layers, the middle layer is a polyethylene foaming layer, namely the three layers are formed at one time by a three-layer co-extrusion process); carrying out irradiation crosslinking on the composite coiled material substrate in an electron accelerator to prepare a master slice; and (3) foaming the master slice in a high-temperature foaming furnace at high temperature to obtain the finished sandwich structure halogen-free flame-retardant polyethylene foam.
In the polyethylene resin layer, 76-93 parts of Polyethylene (PE) resin, 0.3-0.6 part of antioxidant and 8-25 parts of flame retardant by weight;
the polyethylene foaming layer comprises, by weight, 56-83 parts of polyethylene resin, 5-10 parts of polyethylene-acrylic acid resin (EAA) resin, 8-15 parts of foaming agent master batch, 0.08-0.6 part of antioxidant and 5-20 parts of flame retardant.
The preparation method specifically comprises the following steps:
s1: stirring and mixing the antioxidant and the flame retardant in the raw materials of the polyethylene resin layer for 3-4 min in a high-speed stirrer at the stirring speed of 500-700 rpm, and obtaining uniformly mixed powder for later use in the form of an auxiliary agent bag;
s2: stirring and mixing the auxiliary agent package in the S1 and polyethylene resin at the speed of 800-1000 rpm for 3-4 min, and dividing the obtained uniformly mixed material into A, B parts for later use;
s3: stirring and mixing the antioxidant and the flame retardant in the polyethylene foaming layer raw material in a high-speed stirrer at a stirring speed of 500-700 rpm for 3-4 min to obtain uniformly mixed powder for later use in an auxiliary agent bag mode;
s4: stirring and mixing the auxiliary agent package in the S3 with polyethylene resin, polyethylene-acrylic acid resin (EAA) resin and foaming agent master batch at the speed of 800-1000 rpm for 3-4 min to obtain a mixed material for later use;
s5: respectively putting A, B parts of mixed materials in S2 and mixed materials in S4 into three extruders of a three-layer co-extrusion film blowing machine for melt blending, and continuously extruding the materials into an upper, middle and lower three-layer composite coiled material substrate (the two outer layers are polyethylene resin layers, and the middle layer is a polyethylene foaming layer) through a three-layer runner structure die of the three-layer co-extrusion film blowing machine;
s6: carrying out irradiation crosslinking on the obtained composite coiled material substrate in an electron accelerator to prepare a master slice;
s7: and (3) carrying out high-temperature foaming on the obtained master slice in a high-temperature foaming furnace to obtain the finished product of the halogen-free flame-retardant polyethylene foam with the sandwich structure.
In the halogen-free flame-retardant polyethylene foam with the sandwich structure, the thickness of the polyethylene resin layer is smaller than that of the polyethylene foam layer (the thickness of each polyethylene resin layer is 0.05-0.2 mm, and the thickness of the polyethylene foam layer is 0.6-3.6 mm), the polyethylene resin layer mainly endows the halogen-free flame-retardant polyethylene foam with higher hardness and strength, and the polyethylene foam layer mainly endows the halogen-free flame-retardant polyethylene foam with excellent buffering performance.
The polyethylene resin layer cannot be too thick relative to the polyethylene foaming layer (the thickness ratio of the two layers is 1/72-1/3), otherwise the composite material has excellent hardness and strength and loses the most key buffering property and flexibility of the foaming material.
If the polyethylene resin layer is too thick, problems may also result in the foaming process. The polyethylene resin layer is too thick, and when the composite material master slice is foamed, the composite material master slice is restrained by the upper and lower resin layers, the foaming expansion in the thickness direction is easy when the foaming layer is foamed, and the foaming expansion in the width direction (transverse direction) and the rolling direction (longitudinal direction) is difficult to realize.
Meanwhile, in order to further solve the problem and also in order to achieve process matching between the polyethylene resin layer and the polyethylene foaming layer during extrusion molding of the substrate in the extrusion process, the melt index of the polyethylene resin layer is 11g/10 min-27 g/10min, the melt index of the polyethylene resin of the polyethylene foaming layer is 0.8g/10 min-3 g/10min, and the polyethylene used in the formula of the polyethylene resin layer is low-viscosity high-fluidity polyethylene, so that the transverse and longitudinal internal stress between the polyethylene resin layer and the polyethylene foaming layer in the substrate can be greatly reduced; when foaming, the restriction of the polyethylene resin layer to the transverse and longitudinal expansion of the polyethylene foam layer is greatly reduced. In the formula of the polyethylene foaming layer, the polyethylene adopts high-viscosity high-melt-strength polyethylene, so that gas can be better locked to form bubbles during foaming, and the defects that the wall of the bubble melt is broken and the bubbles form large cells and the like are overcome.
The halogen-free flame retardant polyethylene foam with the sandwich structure is endowed with excellent environmental protection characteristic by adding the halogen-free flame retardant into the polyethylene resin layer and the polyethylene foaming layer; the existence of the polyethylene resin layer added with the halogen-free flame retardant further endows the halogen-free flame-retardant polyethylene foam with the sandwich structure with the flame retardant property which is equivalent to or even better than that of common irradiation crosslinking polyethylene halogen flame-retardant foam, and the flame retardant property which is better than that of common irradiation crosslinking polyethylene halogen-free flame-retardant foam and lower cost. The advantages are that the non-foaming material (polyethylene resin layer) has better flame retardant property than the foaming material (polyethylene foaming layer), even though the flame retardant effect of the halogen-free flame retardant system is poorer than that of the halogen flame retardant system.
The polyethylene-acrylic acid resin (EAA) resin is added into the polyethylene foaming layer to enhance the wettability of the high-viscosity low-fluidity polyethylene resin melt of the polyethylene foaming layer to the halogen-free flame retardant powder and improve the compatibility and the dispersibility.
The polyethylene resin, polyethylene-acrylic resin, antioxidant, flame retardant and foaming agent masterbatch used in the following examples are all commercially available products.
Example 1
The invention provides a sandwich structure halogen-free flame-retardant polyethylene foam, wherein a polyethylene resin layer comprises the following components in parts by weight:
polyethylene (PE) resin 91.7 parts
0.3 part of antioxidant
8 portions of flame retardant
The polyethylene foaming layer comprises the following components in parts by weight:
Figure BDA0002689609160000081
the polyethylene resin in the polyethylene resin layer is high-fluidity polyethylene resin with the melt index of 20/10min, and the antioxidant comprises 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168; the flame retardant is 3 parts of magnesium hydroxide and 5 parts of red phosphorus;
in the polyethylene foaming layer, the polyethylene resin is high-viscosity high-melt-strength polyethylene resin with a melt index of 1.5/10min, the polyethylene-acrylic resin is polyethylene-acrylic resin with an acrylic acid chain segment accounting for 8 wt%, the foaming agent master batch is master batch prepared from azodicarbonamide foaming agent and high-viscosity high-melt-strength polyethylene resin with a melt index of 1.5g/10min according to the concentration of 50% by weight, the antioxidant comprises 0.3 part of antioxidant 1010 and 0.2 part of antioxidant 168, and the flame retardant is a compound flame retardant prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant.
The preparation method comprises the following specific steps:
1) stirring and mixing the antioxidant and the flame retardant in the formula of the polyethylene resin layer in a high-speed stirrer at a stirring speed of 650pm for 3.5min to obtain uniformly mixed powder for later use in the form of an auxiliary agent bag;
2) stirring and mixing the mixed powder to be used in the S1 and polyethylene resin at the speed of 1000rpm for 4min, and dividing the obtained uniformly mixed material into A, B parts for use;
3) stirring and mixing the antioxidant and the flame retardant in the formula of the polyethylene foaming layer in a high-speed stirrer at a stirring speed of 650rpm for 3min to obtain uniformly mixed powder for later use in the form of an auxiliary agent bag;
4) stirring and mixing the mixed powder to be used in the S3 with polyethylene resin, polyethylene-acrylic resin (EAA) resin and foaming agent master batch at the speed of 1000rpm for 4min to obtain a mixed material for later use;
5) respectively putting the A, B two parts of materials in the step 2) and the three parts of materials to be used in the step 4) into three extruders of a T-shaped combination of a three-layer co-extrusion film blowing machine for melting and blending, and continuously extruding the materials into an upper, middle and lower three-layer composite coiled material substrate (the two outer layers are polyethylene resin layers, and the middle layer is a polyethylene foaming layer) through a die with a three-layer runner structure (the three runners of the die are adjusted to be set thicknesses);
6) carrying out irradiation crosslinking on the obtained substrate in an electron accelerator to prepare a master slice;
7) and (3) carrying out high-temperature foaming on the obtained master slice in a high-temperature foaming furnace to obtain the finished sandwich-structure halogen-free flame-retardant polyethylene foam (the multiplying power is 11 times, and the total thickness is 2mm), wherein the thickness of each polyethylene resin layer is 0.2mm, and the thickness of each polyethylene foam layer is 1.6 mm.
Example 2
This example differs from example 1 in that:
in the polyethylene resin layer, 84.7 parts of polyethylene resin and a flame retardant comprise 5.5 parts of magnesium hydroxide flame retardant and 9.5 parts of red phosphorus flame retardant;
in the polyethylene foaming layer, 70.5 parts of polyethylene resin and 15 parts of compound flame retardant; wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant;
in the prepared halogen-free flame-retardant polyethylene foam with a sandwich structure (the multiplying power is 11 times, and the total thickness is 2mm), the thickness of each layer of polyethylene resin layer is 0.1mm, and the thickness of the polyethylene foam layer is 1.8 mm.
The rest of this embodiment is basically the same as embodiment 1, and is not described in detail here.
Example 3
This example differs from example 1 in that:
in the polyethylene resin layer, 79.7 parts of polyethylene resin is adopted, and the used flame retardant comprises 7.5 parts of magnesium hydroxide flame retardant and 12.5 parts of red phosphorus flame retardant;
in the prepared halogen-free flame-retardant polyethylene foam with a sandwich structure (the multiplying power is 11 times, and the total thickness is 2mm), the thickness of each layer of polyethylene resin layer is 0.05mm, and the thickness of the polyethylene foam layer is 1.9 mm.
The rest of this embodiment is basically the same as embodiment 1, and the description thereof is omitted.
Example 4
This example differs from example 1 in that:
in the polyethylene resin layer, 79.7 parts of polyethylene resin is adopted, and the used flame retardant comprises 7.5 parts of magnesium hydroxide flame retardant and 12.5 parts of red phosphorus flame retardant;
in the polyethylene foaming layer, 68 parts of polyethylene resin and 8.5 parts of foaming agent master batch are adopted, and the used flame retardant comprises 5 parts of magnesium hydroxide flame retardant and 10 parts of red phosphorus flame retardant;
in the prepared halogen-free flame-retardant polyethylene foam with a sandwich structure (the multiplying power is 15 times, and the total thickness is 2mm), the thickness of each layer of polyethylene resin layer is 0.1mm, and the thickness of the polyethylene foam layer is 1.8 mm.
The rest of this embodiment is basically the same as embodiment 1, and is not described in detail here.
Example 5
This example differs from example 1 in that:
in the polyethylene resin layer, 79.7 parts of polyethylene resin is adopted, and the used flame retardant comprises 7.5 parts of magnesium hydroxide flame retardant and 12.5 parts of red phosphorus flame retardant;
in the polyethylene foaming layer, 62.8 parts of polyethylene resin and 8.7 parts of foaming agent master batch are adopted, and the used flame retardant comprises 6.5 parts of magnesium hydroxide flame retardant and 13.5 parts of red phosphorus flame retardant;
in the prepared halogen-free flame-retardant polyethylene foam with a sandwich structure (the multiplying power is 15 times, and the total thickness is 2mm), the thickness of each layer of polyethylene resin layer is 0.05mm, and the thickness of the polyethylene foam layer is 1.9 mm.
The rest of this embodiment is basically the same as embodiment 1, and is not described in detail here.
Example 6
This example differs from example 1 in that:
in the polyethylene resin layer, 79.7 parts of polyethylene resin and 20 parts of compound flame retardant; wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant;
in the polyethylene foaming layer, 68 parts of polyethylene resin and 8.5 parts of foaming agent master batch are adopted, and the used flame retardant comprises 5 parts of melamine pyrophosphate (MPP) flame retardant and 10 parts of red phosphorus flame retardant;
in the prepared halogen-free flame-retardant polyethylene foam with a sandwich structure (the multiplying power is 15 times, and the total thickness is 2mm), the thickness of each layer of polyethylene resin layer is 0.1mm, and the thickness of the polyethylene foam layer is 1.8 mm.
The rest of this embodiment is basically the same as embodiment 1, and is not described in detail here.
Example 7
This example differs from example 1 in that:
in the polyethylene resin layer, 79.7 parts of polyethylene resin and 20 parts of compound flame retardant; wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant;
in the polyethylene foaming layer, 61.2 parts of polyethylene resin and 15 parts of foaming agent master batch are adopted, and the used flame retardant comprises 5 parts of melamine pyrophosphate (MPP) flame retardant and 10 parts of red phosphorus flame retardant;
in the prepared halogen-free flame-retardant polyethylene foam with a sandwich structure (the multiplying power is 30 times, and the total thickness is 2mm), the thickness of each layer of polyethylene resin layer is 0.1mm, and the thickness of the polyethylene foam layer is 1.8 mm.
The rest of this embodiment is basically the same as embodiment 1, and is not described in detail here.
Example 8
The present example differs from example 1 in that:
in the polyethylene resin layer, 79.7 parts of polyethylene resin, 5 parts of melamine pyrophosphate (MPP) flame retardant and 15 parts of compound flame retardant are used as flame retardants; wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant;
in the polyethylene foaming layer, 55.9 parts of polyethylene resin and 15 parts of foaming agent master batch are adopted, and the used flame retardant comprises 10 parts of ammonium polyphosphate (APP) flame retardant and 10 parts of magnesium hydroxide flame retardant;
in the prepared halogen-free flame-retardant polyethylene foam with a sandwich structure (the multiplying power is 30 times, and the total thickness is 2mm), the thickness of each layer of polyethylene resin layer is 0.05mm, and the thickness of the polyethylene foam layer is 1.9 mm.
The rest of this embodiment is basically the same as embodiment 1, and is not described in detail here.
Example 9
This example differs from example 1 in that:
in the polyethylene resin layer, 79.7 parts of polyethylene resin is adopted, and the used flame retardant comprises 7.5 parts of magnesium hydroxide flame retardant and 12.5 parts of red phosphorus flame retardant;
in the polyethylene foaming layer, 55.9 parts of polyethylene resin and 15 parts of foaming agent master batch, wherein the used flame retardant comprises 10 parts of ammonium polyphosphate (APP) flame retardant and 10 parts of magnesium hydroxide flame retardant;
in the prepared halogen-free flame-retardant polyethylene foam with a sandwich structure (the multiplying power is 30 times, and the total thickness is 2mm), the thickness of each layer of polyethylene resin layer is 0.05mm, and the thickness of the polyethylene foam layer is 1.9 mm.
The rest of this embodiment is basically the same as embodiment 1, and the description thereof is omitted.
Example 10
This example differs from example 1 in that:
in the polyethylene resin layer, 76 parts of polyethylene resin, 11g/10min of polyethylene resin melt index, 0.4 part of antioxidant DLTDP and 0.2 part of antioxidant 168 are used as flame retardants, 10 parts of melamine pyrophosphate (MPP) flame retardant, 5 parts of magnesium hydroxide and 10 parts of compound flame retardant are used as flame retardants; wherein the compound flame retardant is compounded by melamine pyrophosphate, hexaphenoxycyclotriphosphazene and organosilicon synergistic flame retardant;
in the polyethylene foaming layer, 56 parts of polyethylene resin, 0.8g/10min of polyethylene resin melt index and 5 parts of polyethylene-propylene resin, wherein 4% of acrylic acid chain segment and 10 parts of foaming agent master batch are adopted, wherein 45% of azodicarbonamide foaming agent is adopted in the foaming agent master batch, 0.8g/10min of polyethylene melt index is adopted in the foaming agent master batch, the used flame retardant comprises 2 parts of ammonium polyphosphate (APP) flame retardant and 3 parts of magnesium hydroxide flame retardant, and the antioxidant comprises 0.6 part of antioxidant DLTDP and 0.2 part of antioxidant 412S.
In the prepared halogen-free flame-retardant polyethylene foam with a sandwich structure (the multiplying power is 20 times, and the total thickness is 0.8mm), the thickness of each layer of polyethylene resin layer is 0.1mm, and the thickness of the polyethylene foam layer is 0.6 mm.
The rest of this embodiment is basically the same as embodiment 1, and is not described in detail here.
Example 11
This example differs from example 1 in that:
in the polyethylene resin layer, 93 parts of polyethylene resin, wherein the melt index of the polyethylene resin is 18g/10min, the antioxidant comprises 0.1 part of antioxidant 1076 and 0.4 part of antioxidant DLTDP, and the used flame retardant comprises 5 parts of ammonium polyphosphate and 13 parts of red phosphorus;
in the polyethylene foaming layer, 83 parts of polyethylene resin, 3g/10min of polyethylene resin melt index and 10 parts of polyethylene-propylene resin, wherein 12% of acrylic acid chain segments and 9 parts of foaming agent master batches, wherein 52% of azodicarbonamide foaming agent in the foaming agent master batches and 3g/10min of polyethylene melt index in the foaming agent master batches are adopted, the used flame retardant comprises 10 parts of ammonium polyphosphate (APP), and the antioxidant comprises 0.6 part of antioxidant DLTDP.
The preparation method comprises the following specific steps:
1) stirring and mixing the antioxidant and the flame retardant in the formula of the polyethylene resin layer in a high-speed stirrer at the stirring speed of 700pm for 4min to obtain uniformly mixed powder for later use in the form of an auxiliary agent bag;
2) stirring and mixing the mixed powder to be used in the S1 and polyethylene resin at the speed of 800rpm for 3min, and dividing the obtained uniformly mixed material into A, B parts for later use;
3) stirring and mixing the antioxidant and the flame retardant in the formula of the polyethylene foaming layer in a high-speed stirrer at the stirring speed of 700rpm for 4min to obtain uniformly mixed powder for later use in the form of an auxiliary agent bag;
4) stirring and mixing the mixed powder to be used in the S3 with polyethylene resin, polyethylene-acrylic acid resin (EAA) resin and foaming agent master batch at the speed of 800rpm for 3min to obtain a mixed material for later use;
5) respectively putting the A, B two parts of materials in the step 2) and the three parts of materials to be used in the step 4) into three extruders of a T-shaped combination of a three-layer co-extrusion film blowing machine for melting and blending, and continuously extruding the materials into an upper, middle and lower three-layer composite coiled material substrate (the two outer layers are polyethylene resin layers, and the middle layer is a polyethylene foaming layer) through a die with a three-layer runner structure (the three runners of the die are adjusted to be set thicknesses);
6) carrying out irradiation crosslinking on the obtained substrate in an electron accelerator to prepare a master slice;
7) and (3) carrying out high-temperature foaming on the obtained master slice in a high-temperature foaming furnace to obtain the finished sandwich-structure halogen-free flame-retardant polyethylene foam (the multiplying power is 20 times, and the total thickness is 3.75mm), wherein the thickness of each layer of polyethylene resin layer is 0.075mm, and the thickness of the polyethylene foam layer is 3.6 mm.
The rest of this embodiment is basically the same as embodiment 1, and is not described in detail here.
Example 12
This example differs from example 1 in that:
in the polyethylene resin layer, 93 parts of polyethylene resin, the melt index of the polyethylene resin is 27g/10min, the antioxidant comprises 0.4 part of antioxidant 1076, and the used flame retardant is 8 parts of red phosphorus;
in the polyethylene foaming layer, 75 parts of polyethylene resin, 2.2g/10min of polyethylene resin melt index and 7 parts of polyethylene-propylene resin, wherein 6 percent of acrylic acid chain segment and 12 parts of foaming agent master batches are adopted, wherein 65 percent of azodicarbonamide foaming agent is adopted in the foaming agent master batches, 2.2g/10min of polyethylene melt index is adopted in the foaming agent master batches, the used flame retardant comprises 6 parts of magnesium hydroxide and 8 parts of red phosphorus, and the antioxidant comprises 0.3 part of antioxidant 168.
The preparation method comprises the following specific steps:
1) stirring and mixing the antioxidant and the flame retardant in the formula of the polyethylene resin layer in a high-speed stirrer at a stirring speed of 500pm for 3min to obtain uniformly mixed powder for later use in the form of an auxiliary agent bag;
2) stirring and mixing the mixed powder to be used in the S1 and polyethylene resin at the speed of 900rpm for 3.5min, and dividing the obtained uniformly mixed material into A, B parts for later use;
3) stirring and mixing the antioxidant and the flame retardant in the formula of the polyethylene foaming layer in a high-speed stirrer at the stirring speed of 500rpm for 3.5min to obtain uniformly mixed powder for later use in the form of an auxiliary agent bag;
4) stirring and mixing the mixed powder to be used in the S3 with polyethylene resin, polyethylene-acrylic acid resin (EAA) resin and foaming agent master batch at the speed of 900rpm for 3.5min to obtain a mixed material for later use;
5) respectively putting the A, B two parts of materials in the step 2) and the three parts of materials to be used in the step 4) into three extruders of a T-shaped combination of a three-layer co-extrusion film blowing machine for melting and blending, and continuously extruding the materials into an upper, middle and lower three-layer composite coiled material substrate (the two outer layers are polyethylene resin layers, and the middle layer is a polyethylene foaming layer) through a die with a three-layer runner structure (the three runners of the die are adjusted to be set thicknesses);
6) carrying out irradiation crosslinking on the obtained substrate in an electron accelerator to prepare a master slice;
7) and (3) carrying out high-temperature foaming on the obtained master slice in a high-temperature foaming furnace to obtain the finished sandwich-structure halogen-free flame-retardant polyethylene foam (the multiplying power is 22 times, and the thickness is 3.8mm), wherein the thickness of each polyethylene resin layer is 0.1mm, and the thickness of the polyethylene foam layer is 3.6 mm.
The rest of this embodiment is basically the same as embodiment 1, and is not described in detail here.
Comparative example 1
The foam (halogen flame-retardant specification, multiplying power of 11 times and thickness of 2mm) obtained in the comparative example is halogen flame-retardant irradiation cross-linked polyethylene foam, which specifically comprises the following components in parts by weight:
Figure BDA0002689609160000141
the polyethylene resin is high-viscosity high-melt-strength polyethylene resin with a melt index of 0.8-3 g/10min, the polyethylene-vinyl acetate resin is polyethylene-vinyl acetate resin with a Vinyl Acetate (VA) content of 12% -18%, the foaming agent master batch is master batch prepared from azodicarbonamide foaming agent and the polyethylene resin according to a concentration of 45% -65% by weight, the antioxidant comprises 0.3 part of antioxidant 1010 and 0.2 part of antioxidant 168, and the halogen flame retardant comprises 6 parts of decabromodiphenylethane and 2 parts of antimony trioxide.
The preparation method comprises the following specific steps:
1) stirring and mixing the antioxidant and the halogen flame retardant in a high-speed stirrer at the stirring speed of 800rpm for 4min, and obtaining uniformly mixed powder for later use in the form of an auxiliary agent bag;
2) stirring and mixing Polyethylene (PE) resin, polyethylene-vinyl acetate (EVA) resin and foaming agent master batch in a high-speed stirrer at the speed of 1000rpm for 3min to obtain uniformly mixed granules for later use;
3) stirring and mixing the auxiliary agent package and the mixed granules in a high-speed stirrer at the speed of 1000rpm for 3 min;
4) putting the obtained mixed material into an extruder to be melted and extruded to form a continuous sheet (substrate for short) for standby;
5) carrying out irradiation crosslinking on the obtained substrate in an electron accelerator, and obtaining a sheet material called a master slice;
6) and (3) carrying out high-temperature foaming on the obtained master slice in a high-temperature foaming furnace to obtain a sheet material, namely the finished product foam.
Comparative example 2
The foam obtained in the comparative example (halogen flame-retardant specification, multiplying power of 15 times and thickness of 2mm) is halogen flame-retardant irradiation cross-linked polyethylene foam, and the difference between the comparative example and the comparative example 1 is that 8.4 parts of foaming agent master batch and 78.1 parts of Polyethylene (PE) resin.
The rest of the comparative example is substantially the same as comparative example 1, and the description thereof is omitted.
Comparative example 3
The foam obtained in the comparative example is halogen flame-retardant irradiation crosslinked polyethylene foam with the specification of (halogen flame-retardant specification, multiplying power of 30 times and thickness of 2mm), and the difference between the comparative example and the comparative example 1 is that 14.7 parts of foaming agent master batch and 71.8 parts of Polyethylene (PE) resin.
The rest of the comparative example is substantially the same as comparative example 1, and the description thereof is omitted.
Comparative example 4
The foam (halogen-free flame retardant specification, multiplying power of 11 times and thickness of 2mm) specification halogen-free flame retardant irradiation crosslinked polyethylene foam obtained by the comparative example is different from that of the comparative example 1 in that 20 parts of compound flame retardant, 6.2 parts of foaming agent master batch and 68.3 parts of Polyethylene (PE) resin are adopted; wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant;
the rest of the comparative example is substantially the same as comparative example 1, and the description thereof is omitted.
Comparative example 5
The foam (halogen-free flame retardant specification, multiplying power of 15 times and thickness of 2mm) specification halogen-free flame retardant irradiation crosslinked polyethylene foam obtained by the comparative example is different from that of the comparative example 1 in that 20 parts of compound flame retardant, 8.7 parts of foaming agent master batch and 65.8 parts of Polyethylene (PE) resin are adopted; wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant;
the rest of the comparative example is substantially the same as comparative example 1, and the description thereof is omitted.
Comparative example 6
The foam (halogen-free flame retardant specification, multiplying power of 30 times and thickness of 2mm) specification halogen-free flame retardant irradiation crosslinked polyethylene foam obtained by the comparative example is different from that of the comparative example 1 in that 20 parts of compound flame retardant, 15.6 parts of foaming agent master batch and 58.9 parts of Polyethylene (PE) resin are adopted; wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant;
the rest of the comparative example is substantially the same as comparative example 1, and the description thereof is omitted.
Test example
The foam prepared in the typical examples 1-9 and the comparative examples 1-6 is subjected to flame retardant property, tensile strength, elongation at break and hardness tests, and the specific test processes are as follows:
1) the foam obtained in examples 1-9 and comparative examples 1-6 was cut into 10 flame retardant sample strips with length of 356mm and width of 100mm according to GB8410 test standard, and marked at 38mm and 292mm from one end, as shown in FIG. 2:
and (4) carrying out combustion test on the flame-retardant sample strips corresponding to the formulas according to the GB8410 test standard, and recording the test results.
2) And (4) testing the tensile strength and the elongation at break of the foam obtained by each formula according to the GB/T528-2009 test standard, and recording the test result.
3) And (3) testing the hardness (Shore hardness C) of the foam obtained by each formula, and recording the test result.
Test results
The foam prepared in examples 1 to 9 and comparative examples 1 to 6 were subjected to the tests of flame retardancy, tensile strength, elongation at break and hardness, and the test results are shown in table 1 below:
TABLE 1 Performance test results of IXPE foams prepared in examples 1-9 and comparative examples 1-6
Figure BDA0002689609160000171
From comparative examples 1 and 4 (magnification of 11 times, thickness of 2mm, halogen flame retardant versus halogen-free flame retardant), comparative examples 2 and 5 (magnification of 15 times, thickness of 2mm, halogen flame retardant versus halogen-free flame retardant), and comparative examples 3 and 6 (magnification of 30 times, thickness of 2mm, halogen flame retardant versus halogen-free flame retardant): under the condition of the same multiplying power and thickness, the halogen flame-retardant foam has better tensile strength, elongation at break, hardness and flame retardant property than halogen-free flame-retardant foam, has much lower cost than halogen-free flame-retardant foam, and has outstanding advantages, but the halogen flame-retardant foam is not environment-friendly compared with halogen-free flame-retardant foam. Therefore, how to greatly reduce the cost without obviously damaging the mechanical property of the foam on the basis of ensuring the excellent environmental protection performance is the key point of the development of the invention.
Comparing examples 1-3 (halogen-free flame retardant polyethylene foam with a sandwich structure, halogen-free flame retardant specification, multiplying power 11 times, thickness 2mm) with comparative example 1 (halogen flame retardant specification, multiplying power 11 times, thickness 2mm), it can be seen that the halogen-free flame retardant polyethylene foam with a sandwich structure, multiplying power 11 times, thickness 2mm, of the invention has outstanding mechanical property advantages compared with the polyethylene foam with a halogen flame retardant specification, multiplying power 11 times, thickness 2 mm. The halogen-free flame-retardant polyethylene foam with the sandwich structure is characterized in that two outer layers are polyethylene resin layers, and compared with a polyethylene foamed layer, the polyethylene resin layer has higher tensile strength, elongation at break and hardness due to non-foaming. Compared with a comparative example 4 (halogen-free flame retardant specification, multiplying power of 11 times and thickness of 2mm), the foam obtained in the examples 1-3 has more obvious mechanical property advantages; and the flame retardant property is greatly improved compared with that of the comparative example 4. Except that the flame retardant performance of the foam obtained in the example 1 is only slightly better than that of the foam obtained in the comparative example 4 (the flame retardant performance is C-grade, the combustion speed is reduced by 9.5mm/min), the flame retardant performance of the foam obtained in the example 2 and the foam obtained in the example 3 is remarkably improved compared with that of the foam obtained in the comparative example 4, the foam reaches B-grade, the flame retardant performance of the foam obtained in the comparative example 1 is at the same grade, the combustion speed is lower than that of the foam obtained in the comparative example 1, and the flame retardant performance of the foam is better than that of the foam obtained in the comparative example 1. The foam obtained in example 2 has the best flame retardant property, and the flame retardant property is B-16.6 mm/min. Compared with the comparative example 1, the foam obtained in the examples 1-3 is halogen-free flame retardant foam, and the environmental protection performance is excellent; the cost of the foam obtained in the embodiments 1 to 3 is higher than that of the foam obtained in the comparative example 1 by a limit (the cost is floated between-0.1 ten thousand yuan/ton and 0.3 ten thousand yuan/ton); the cost of the foam obtained in the embodiments 1 to 3 is greatly reduced compared with that of the foam obtained in the comparative example 4, and the reduction range reaches 1.2 to 1.4 ten thousand yuan/ton. Meanwhile, the foam with the flame retardant specification of 11 times and the thickness of 2mm has the advantages that compared with the traditional halogen (comparative example 1) and halogen-free (comparative example 4) flame retardant foam, the foam obtained in the embodiments 1-3 of the invention has more excellent mechanical properties (tensile strength, elongation at break and hardness), outstanding environmental protection performance compared with the traditional halogen flame retardant foam, and obvious cost advantage compared with the traditional halogen-free flame retardant foam.
The above can also be concluded by comparing examples 4-6 with comparative examples 2 and 5, and comparing examples 7-9 with comparative examples 3 and 6. Wherein, compared with the comparative example 2, the cost of the examples 4 to 6 is 0.2 to 0.7 ten thousand yuan/ton higher, and compared with the comparative example 5, the cost is reduced by 1.0 to 1.5 ten thousand yuan/ton; the cost of examples 7 to 9 is 1.0 to 1.5 ten thousand yuan/ton higher than that of comparative example 3, and the cost of the comparative example 6 is 0.7 to 1.2 ten thousand yuan/ton lower than that of comparative example.
In conclusion, compared with the traditional foam, the halogen-free flame-retardant polyethylene foam with the sandwich structure prepared by the invention has a unique structure; by combining the unique structural design, the specific polyethylene matrix resin selection and the specific halogen-free flame retardant selection and matching, the halogen-free flame-retardant polyethylene foam with the sandwich structure has more excellent mechanical properties (tensile strength, elongation at break and hardness) compared with the traditional halogen and halogen-free flame-retardant foam, outstanding environmental protection performance compared with the traditional halogen flame-retardant foam and obvious cost advantage compared with the traditional halogen-free flame-retardant foam on the premise of the same multiplying power and thickness.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. A halogen-free flame-retardant polyolefin foam material with a sandwich structure is mainly composed of two polyethylene resin layers and a polyethylene foam layer, and is characterized in that,
each polyethylene resin layer comprises the following raw materials in parts by weight: 76-93 parts of polyethylene resin, 0.3-0.6 part of antioxidant and 8-25 parts of flame retardant;
the polyethylene foaming layer comprises the following raw materials in parts by weight: 56-83 parts of polyethylene resin, 5-10 parts of polyethylene-acrylic resin, 8-15 parts of foaming agent master batch, 0.08-0.6 part of antioxidant and 5-20 parts of flame retardant;
the flame retardant of the polyethylene resin layer is selected from one or more of melamine pyrophosphate, ammonium polyphosphate, magnesium hydroxide, a compound flame retardant and red phosphorus, wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant;
the flame retardant of the polyethylene foaming layer is selected from one or more of melamine pyrophosphate, ammonium polyphosphate, magnesium hydroxide, a compound flame retardant and red phosphorus, wherein the compound flame retardant is prepared by compounding melamine pyrophosphate, hexaphenoxycyclotriphosphazene and an organic silicon synergistic flame retardant;
the magnesium hydroxide is obtained by treating the surface with a coupling agent to improve the compatibility with polyethylene resin, wherein the coupling agent is silane and a silane derivative;
the red phosphorus is coated by a melamine resin microcapsule to improve the compatibility with the polyethylene resin;
the thickness of each polyethylene resin layer is 0.05 mm-0.2 mm, and the thickness of the polyethylene foaming layer is 0.6 mm-3.6 mm;
the melt index of the polyethylene resin layer is 11g/10 min-27 g/10min, and the melt index of the polyethylene resin of the polyethylene foaming layer is 0.8g/10 min-3 g/10 min;
in the polyethylene-acrylic resin, the acrylic acid chain segment accounts for 4-12 wt%.
2. The sandwich structure halogen-free flame retardant polyolefin foam material of claim 1, wherein the antioxidant of the polyethylene resin layer is selected from one or more of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants.
3. The halogen-free flame retardant polyolefin foam material with a sandwich structure as claimed in claim 1, wherein the antioxidant of the polyethylene foam layer is selected from one or more of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants.
4. The sandwich structure halogen-free flame retardant polyolefin foam material of claim 1, wherein the antioxidant of the polyethylene resin layer is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 618, antioxidant DLTDP and antioxidant 412S.
5. The sandwich structure halogen-free flame retardant polyolefin foam material of claim 1, wherein the antioxidant of the polyethylene foam layer is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 618, antioxidant DLTDP and antioxidant 412S.
6. The sandwich structure halogen-free flame retardant polyolefin foam material of claim 1, wherein the compounded flame retardant is an intumescent flame retardant obtained by compounding.
7. The halogen-free flame retardant polyolefin foaming material with a sandwich structure according to claim 1, wherein the foaming agent master batch is a master batch made of azodicarbonamide type foaming agent and polyethylene resin, the polyethylene resin melt index in the foaming agent master batch is 0.8g/10 min-3 g/10min, and the azodicarbonamide type foaming agent accounts for 45 wt% -65 wt% of the foaming agent master batch.
8. The preparation method of the halogen-free flame retardant polyolefin foam material with the sandwich structure as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
1) uniformly mixing raw materials used by a polyethylene resin layer according to the weight part of claim 1, and dividing the mixture into A, B parts;
2) uniformly mixing the raw materials used by the polyethylene foaming layer according to the weight part of claim 1;
3) respectively putting the A part and the B part of the polyethylene resin layer and the raw materials used by the polyethylene foaming layer into three extruders of a three-layer co-extrusion film blowing machine, and forming a composite coiled material by a three-layer co-extrusion process;
4) and (3) irradiating and crosslinking the composite coiled material by using an electron accelerator, and foaming the composite coiled material by using a high-temperature foaming furnace to obtain the halogen-free flame-retardant polyolefin foaming material with the sandwich structure.
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