CN112851893B - Irradiation crosslinking polyethylene foam material and preparation method thereof - Google Patents
Irradiation crosslinking polyethylene foam material and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/107—Nitroso compounds
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
Abstract
The invention discloses an irradiation crosslinking polyethylene foam material and a preparation method thereof. The preparation method comprises the following steps: (1) extruding 60-90 parts by weight of low-density polyethylene, 5-30 parts by weight of the aromatic condensate sulfonate, 5-25 parts by weight of elastomer, 2-20 parts by weight of foaming agent, 1-2 parts by weight of sensitizer and 0.5-4 parts by weight of antioxidant in an extruder to obtain a master slice; (2) carrying out irradiation crosslinking on the master slice in the step (1) to obtain a crosslinked master slice; (3) and (3) foaming the crosslinked master slice in the step (2). The irradiation crosslinking polyethylene foam material prepared by the preparation method has high strength, the elastic modulus is more than 7MPa, the product cohesiveness is high, the surface tension can reach more than 40mN/m, the surface tension can be maintained for more than 6 months, and the requirement of a gluing process is met.
Description
Technical Field
The invention relates to an irradiation crosslinking polyethylene foam material and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
The radiation cross-linked polyethylene foam plastic is a novel foam plastic with a closed-cell structure between soft (polyurethane) foam plastic and hard (polystyrene) foam plastic, has a series of characteristics of excellent obdurability, elasticity, flexibility, wear resistance, chemical corrosion resistance, low temperature resistance, good insulativity and the like, can be used as a good insulating, heat-insulating, shockproof and buoyancy material, and is widely applied to various fields of industry, agriculture, buildings, transportation and the like. The high-strength polyethylene foamed product is widely applied to the fields of mechanical shock absorption, ground mats, automotive interiors, electronic equipment and the like, and has higher requirements on the strength (such as elastic modulus) of the product along with the updating and upgrading of the product. The traditional method for improving the strength of polyethylene foam mainly comprises adding polypropylene, glass fiber, calcium carbonate and the like and increasing the crosslinking degree. Because the melting point of polypropylene is higher, the processing temperature is high, the foaming agent is easy to decompose, and the process is difficult to implement. Inorganic fillers such as glass fiber, calcium carbonate and the like have poor intersolubility with polyethylene, the improvement on the strength of the product is limited, and a large amount of inorganic fillers seriously affect the foaming process and other physical performance products of the product. Too large a crosslinking degree causes foaming difficulty and fails to satisfy an appropriate foaming ratio.
The high-strength polyethylene foamed product is widely applied to the fields of mechanical shock absorption, ground mats, automotive interiors, electronic equipment and the like, adhesive sticker coating processing is needed in the fields, and due to the fact that the nonpolar surface tension of the polyethylene material is small, the requirement of a gluing process cannot be met, the product needs to be subjected to surface treatment, the surface tension of the product is improved, and the surface adhesion and wettability of the product are improved. Corona treatment is a common method for improving the surface tension of polyethylene foam sheets, but corona equipment is required for corona treatment, certain energy consumption is required, and the surface tension of the foam tapes after corona treatment can only be maintained for about 2 weeks, so that the foam tapes cannot be stored for a long time. The addition of ethylene-vinyl acetate copolymer resin (EVA) with polar ester group is an important method for improving the surface tension of the foaming sheet, but the EVA has weak polarity, needs to be added in a large amount, causes the serious self-adhesion problem of the product due to large addition amount, and greatly increases the cost due to the use of the EVA.
Disclosure of Invention
The invention aims to overcome the defects that the polyethylene product in the prior art has low strength and small surface tension and cannot meet high-end application, and provides an irradiation crosslinking polyethylene foam material and a preparation method thereof. The preparation method of the invention ensures that the aromatic condensation compound structure, the sulfonation degree, the metal cation and different aromatic condensation compound sulfonate and polyethylene proportions are screened to ensure that the aromatic condensation compound structure and the polyethylene alkyl chain keep high compatibility, a specific condensed state structure is formed by a proper extrusion process, and the unsaturated bond in the resin is promoted to be connected into a polyethylene crosslinking network in the irradiation crosslinking process, so that the strength and the gluing performance of the product are improved.
The invention adopts the following technical scheme to solve the technical problems.
The invention provides an aromatic condensate sulfonate which is a product of the following reaction: (a)100 parts by mass of an aromatic compound A and 10-20 parts by mass of an aldehyde compound B in an amount of 0.5-2 parts by mass of acetic acid at 120-150 DEG CCarrying out condensation reaction; (b) carrying out sulfonation reaction on the reaction in the step (a) and 40-50 parts by mass of concentrated sulfuric acid at 120-200 ℃, and neutralizing by adopting metal oxide or metal hydroxide to obtain the product; the aromatic compound A is one or more of naphthalene, 2-methylnaphthalene, 1-methylnaphthalene, anthracene, 2-methylanthracene, 9-butylanthracene, phenanthrene and 9-butylphenanthracene; the aldehyde compound B is
R is C 3 ～C 15 Alkyl or C 1 ～C 4 Alkyl substituted C 2 ～C 10 An alkenyl group;
the metal in the metal oxide or metal hydroxide is calcium, zinc, potassium, magnesium, iron, cobalt, nickel or copper.
Said C 3 ～C 15 The alkyl group may be n-butyl, n-hexyl, n-octyl, n-dodecyl, n-hexadecyl or 2-methyl-2-pentenyl.
Said C 1 ～C 4 The alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or isobutyl;
said C 2 ～C 10 The alkenyl group can be hexenyl.
Said C 1 ～C 4 Alkyl substituted C 2 ～C 10 The alkenyl group can be 2-ethyl-2-hexenyl.
The reaction time of the condensation reaction is preferably 4-20 h.
The reaction time of the sulfonation reaction is preferably 6-12 h.
The sulfonation reaction is preferably carried out after the reaction is completed, and the sulfonation reaction is diluted by water and then neutralized. The amount of the water is preferably (200 to 400) parts by mass.
The metal oxide is preferably calcium oxide and/or magnesium oxide.
The metal hydroxide is preferably one or more of potassium hydroxide, iron hydroxide and lithium hydroxide.
The sulfonation reaction can be directly carried out without post-treatment after the condensation reaction.
The post-treatment of the sulfonation reaction preferably comprises the steps of: and after the neutralization is finished, filtering, washing with an organic solvent, and drying. The organic solvent is preferably ethanol and/or ethyl acetate.
In a preferred embodiment of the invention, 100 parts by mass of naphthalene, 15 parts by mass of n-octanal and 1 part by mass of acetic acid are subjected to condensation reaction at 130 ℃ for 6 hours, 45 parts by mass of concentrated sulfuric acid is added for sulfonation reaction at 150 ℃ for 4 hours, 300 parts by mass of water is added for dilution, 15 parts by mass of calcium oxide is neutralized, filtration is carried out, and washing and drying are carried out on ethanol and ethyl acetate, so that the corresponding aromatic condensation compound calcium sulfonate is obtained.
The aromatic condensate sulfonate comprises a repeating structural unit consisting of aromatic rings and aldehyde alkyl chains, the molecular weight is 12000-50000, the alkyl chain connected with aldehyde groups is not less than three carbon atoms, and the proportion of the sulfonate connected with the aromatic rings is 35-70%.
The invention provides a preparation method of an irradiation crosslinking polyethylene foam material, which comprises the following steps:
(1) extruding 60-90 parts by weight of low-density polyethylene, 5-30 parts by weight of the aromatic condensate sulfonate, 5-25 parts by weight of elastomer, 2-20 parts by weight of foaming agent, 1-2 parts by weight of sensitizer and 0.5-4 parts by weight of antioxidant in an extruder to obtain a master slice;
(2) carrying out irradiation crosslinking on the master slice in the step (1) to obtain a crosslinked master slice;
(3) foaming the crosslinked master slice in the step (2);
in the step (1), the low density polyethylene is preferably low density polyethylene and/or linear low density polyethylene.
In the step (1), the elastomer is preferably one or more of ethylene propylene diene monomer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, natural rubber, isoprene rubber, butadiene rubber, styrene butadiene block copolymer (SBS), pentylene block copolymer (SIS) and chlorinated polyethylene.
In the step (1), the foaming agent is preferably one or more of azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, toluenesulfonyl hydrazide and 4, 4' -oxybis-benzenesulfonyl hydrazide.
In the step (1), the sensitizer is preferably one or more of zinc acetate, zinc stearate, cobalt stearate, zinc oxalate, zinc oxide and barium stearate.
In the step (1), the antioxidant is preferably one or more of 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether and pentaerythritol tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ].
In the step (1), the extruder is preferably a single-screw extruder.
In the step (1), the extrusion temperature is preferably 75-145 ℃, for example, 95-125 ℃.
In the step (1), the screw rotation speed of the extruder is preferably 50-85 rpm, for example, 75 rpm.
In the step (1), the die head temperature of the extruder is preferably 85-145 ℃, for example, 125 ℃.
In the step (1), the thickness of the master is preferably 0.1-0.5 mm, for example, 0.3 mm.
Preferably, in the step (1), the low-density polyethylene, the aromatic condensate sulfonate, the elastomer, the foaming agent, the sensitizer and the antioxidant are uniformly mixed and then added into the extruder for extrusion.
In the step (2), the irradiation crosslinking is preferably performed by an electron accelerator.
In the step (2), the irradiation dose of the irradiation crosslinking is preferably 30-40 kGy, for example, 35 kGy.
In step (2), the radiation crosslinking preferably forms a crosslinked polymeric network.
In the step (3), the foaming is preferably performed in a foaming furnace. The temperature of the foaming furnace is preferably 160-260 ℃.
In the step (3), the residence time of the crosslinked master slice is preferably 0.2-1.0 min, for example, 0.5 min.
In a preferred embodiment of the present invention, 80 parts by weight of low density polyethylene, 10 parts by weight of the aromatic condensate calcium sulfonate prepared in step 1, 10 parts by weight of an ethylene-octene copolymer, 5 parts by weight of azodicarbonamide as a foaming agent, 1.5 parts by weight of zinc stearate, and 1 part by weight of antioxidant 1010 are mixed uniformly and then fed into a single screw extruder for extrusion.
The invention also provides the irradiation crosslinking polyethylene foam material prepared by the preparation method.
The invention also provides application of the irradiation cross-linked polyethylene foam material in the fields of mechanical shock resistance, floor mats, heat-insulating pipes or electronic equipment.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the irradiation crosslinking polyethylene foam material prepared by the preparation method has high strength, the elastic modulus is more than 7MPa, the product cohesiveness is high, the surface tension can reach more than 40mN/m, the surface tension can be maintained for more than 6 months, and the requirement of a gluing process is met.
(2) In the preparation method, the aromatic condensate sulfonate has good compatibility with polyethylene, can form an ionic crosslinking structure and can account for 30 percent of the total weight of the reaction raw materials; the aromatic condensate sulfonate is added into a formula of irradiation crosslinking polyethylene foam, so that a polyethylene foam material with high strength and long-term glueability can be obtained;
(3) the preparation method has rich raw material sources and low price;
(4) the preparation method can effectively adjust the strength and the cohesiveness of the material by adjusting the structure and the dosage of the aromatic condensation compound sulfonate;
(5) the irradiation crosslinking polyethylene foam material prepared by the preparation method has wide application in the fields of mechanical shock resistance, floor mats, heat-insulating pipes, electronic equipment and the like.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Wherein, it is required to be noted that:
(1) the elastic modulus is tested by testing the bending property of GB/T9341-2008 plastic.
(2) The surface tension is tested by the wetting tension of GB/T14216-2008 test samples.
(3) The invention adopts gel chromatography (GPC) to measure the molecular weight of the aromatic condensate, and adopts a 515 type gel permeation chromatograph of Waters company, a chromatographic Column ultra hydrogel 250Column, a Column temperature: 40 ℃, mobile phase: 0.1M NaCl, flow rate: 0.6mL/min, standard: polyethylene glycol.
(4) The invention adopts an element analysis method to measure the sulfonation degree, converts sulfur element into sulfonic group, and takes the ratio of the number of the sulfonic group to the number of condensed rings as the sulfonation degree.
Example 1
Step 1 aromatic condensate sulfonates
100 parts by mass of naphthalene, 15 parts by mass of n-octanal and 1 part by mass of acetic acid are subjected to condensation reaction at 130 ℃ for 6 hours, 45 parts by mass of concentrated sulfuric acid is added for sulfonation reaction at 150 ℃ for 4 hours, 300 parts by mass of water is added for dilution, 15 parts by mass of calcium oxide is neutralized, the mixture is filtered, and washed and dried by ethanol and ethyl acetate to obtain the corresponding aromatic condensate calcium sulfonate with the molecular weight of 15000(GPC) and the sulfonation degree of 53% (elemental analysis method).
Step 2 preparation of polyethylene foam
Uniformly mixing 80 parts by weight of low-density polyethylene, 10 parts by weight of the aromatic condensate calcium sulfonate prepared in the step 1, 10 parts by weight of ethylene-octene copolymer, 5 parts by weight of foaming agent azodicarbonamide, 1.5 parts by weight of zinc stearate and 1 part by weight of antioxidant 1010, adding the mixture into a single-screw extruder for extrusion, and controlling the extrusion temperature to be 95-125 ℃, the screw rotation speed to be 75rpm and the die head temperature to be 125 ℃ to obtain a master slice with the thickness of 0.3 mm; then, carrying out irradiation crosslinking on the master slice by an electron accelerator, and controlling the irradiation dose to be 35kGy to form a crosslinked polymer network; and finally, placing the crosslinked master slice in a foaming furnace for foaming, controlling the temperature of the foaming furnace to be 160-260 ℃, and keeping the residence time of the crosslinked master slice for 0.5min to obtain the high-strength irradiation crosslinked polyethylene foaming material, wherein the elastic modulus is 7.5MPa, the surface tension is 43mN/m, and the surface tension is 42mN/m after the high-strength irradiation crosslinked polyethylene foaming material is placed for 6 months.
Examples 2 to 6
Different metal oxides or metal hydroxides were selected as in example 1, except for the following differences.
TABLE 1
| Examples | Metal salts or hydroxides | Modulus of elasticity/MPa | Surface tension mN/m | Surface tension mN/m after 6 months |
| 2 | Zinc oxide | 7.9 | 42 | 41 |
| 3 | Magnesium oxide | 8.9 | 42 | 42 |
| 4 | Potassium hydroxide | 7.6 | 42 | 41 |
| 5 | Ferric hydroxide | 8.5 | 43 | 42 |
| 6 | Lithium hydroxide | 7.4 | 42 | 41 |
Examples 7 to 10
The reaction was carried out in the same manner as in example 1 except that different long carbon chain aldehydes were selected.
TABLE 2
Examples 11 to 14
The reaction was carried out by selecting different polycyclic aromatic hydrocarbons as in example 1 except for the following differences.
TABLE 2
Examples 15 to 18
The same procedure as in example 1 was followed except that the ratio of calcium sulfonate, an aromatic condensate, to polyethylene was varied.
TABLE 3
Comparative example 1
According to the embodiment 1, 90 parts by weight of low-density polyethylene, 10 parts by weight of ethylene-octene copolymer, 5 parts by weight of foaming agent, 1.5 parts by weight of zinc oxalate and 1 part by weight of antioxidant 1010 are uniformly mixed without adding aromatic condensate sulfonate, and then added into a single-screw extruder for extrusion, and the extrusion temperature is controlled to be 95-125 ℃, the screw rotation speed is 80rpm, and the die head temperature is 125 ℃, so that a master slice with the thickness of 0.5mm is obtained; then, carrying out irradiation crosslinking on the master slice by an electron accelerator, and controlling the irradiation dose to be 35kGy to form a crosslinked polymer network; and finally, placing the crosslinked master slice in a foaming furnace for foaming, controlling the temperature of the foaming furnace to be 160-260 ℃, and keeping the residence time of the crosslinked master slice to be 0.4min to obtain the irradiation crosslinked polyethylene foaming material, wherein the elastic modulus is 4.1MPa, the surface tension is 32mN/m, the cohesiveness is poor, the surface tension can reach 41mN/m after corona treatment, and the surface tension is 32mN/m after the crosslinked polyethylene foaming material is placed for 6 months, so that the cohesiveness is still poor.
Comparative example 2
The octanal is exchanged for formaldehyde as in example 1, giving the corresponding naphthalene formaldehyde condensate calcium sulfonate with a molecular weight of 51000(GPC) and a degree of sulfonation of 56% (elemental analysis).
Uniformly mixing 80 parts by weight of low-density polyethylene, 10 parts by weight of the naphthalene formaldehyde condensate calcium sulfonate, 10 parts by weight of an ethylene-octene copolymer, 5 parts by weight of foaming agent azodicarbonamide, 1.5 parts by weight of zinc stearate and 1 part by weight of antioxidant 1010, adding the mixture into a single-screw extruder for extrusion, and controlling the extrusion temperature to be 95-125 ℃, the screw rotation speed to be 75rpm and the die head temperature to be 125 ℃ to obtain a master slice with the thickness of 0.3 mm; then, carrying out irradiation crosslinking on the master slice by an electron accelerator, and controlling the irradiation dose to be 35kGy to form a crosslinked polymer network; and finally, placing the crosslinked master slice in a foaming furnace for foaming, controlling the temperature of the foaming furnace to be 160-260 ℃, and keeping the residence time of the crosslinked master slice for 0.5min to obtain the high-strength irradiation crosslinked polyethylene foaming material, wherein the elastic modulus is 4.2MPa, the surface tension is 43mN/m, and the surface tension is 34mN/m after the high-strength irradiation crosslinked polyethylene foaming material is placed for 6 months.
Comparative example 3
Step 1 aromatic condensate sulfonates
Sulfonation was carried out and condensation was carried out as in example 1. Performing sulfonation reaction on 100 parts by mass of naphthalene and 45 parts by mass of concentrated sulfuric acid at 150 ℃ for 4 hours, adding 15 parts by mass of octanal and 1 part by mass of acetic acid, performing condensation reaction at 130 ℃ for 6 hours, adding 300 parts by mass of water for dilution, neutralizing 15 parts by mass of calcium oxide, filtering, washing with ethanol and ethyl acetate, and drying to obtain the corresponding aromatic condensate calcium sulfonate with the molecular weight of 9000(GPC) and the sulfonation degree of 55% (element analysis method).
Step 2 preparation of polyethylene foam
Uniformly mixing 80 parts by weight of low-density polyethylene, 10 parts by weight of the aromatic condensate calcium sulfonate prepared in the step 1, 10 parts by weight of ethylene-octene copolymer, 5 parts by weight of foaming agent azodicarbonamide, 1.5 parts by weight of zinc stearate and 1 part by weight of antioxidant 1010, adding the mixture into a single-screw extruder for extrusion, and controlling the extrusion temperature to be 95-125 ℃, the screw rotation speed to be 75rpm and the die head temperature to be 125 ℃ to obtain a master slice with the thickness of 0.3 mm; then, carrying out irradiation crosslinking on the master slice by an electron accelerator, and controlling the irradiation dose to be 35kGy to form a crosslinked polymer network; and finally, placing the crosslinked master slice in a foaming furnace for foaming, controlling the temperature of the foaming furnace to be 160-260 ℃, and keeping the crosslinked master slice for 0.5min to obtain the high-strength irradiation crosslinked polyethylene foaming material, wherein the elastic modulus is 4.7MPa, the surface tension is 40mN/m, and the surface tension is 34mN/m after the high-strength irradiation crosslinked polyethylene foaming material is placed for 6 months.
Therefore, the aromatic condensate sulfonate is added into a radiation crosslinking polyethylene foam formula, and a polyethylene foam material with high strength and long-term glueability can be obtained.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An aromatic condensate sulfonate, characterized in that it is the product of the following reaction: (a) condensation reaction of 100 parts by mass of an aromatic compound A and 10-20 parts by mass of an aldehyde compound B in 0.5-2 parts by mass of acetic acid at 120-150 ℃; (b) carrying out sulfonation reaction on the reaction product obtained in the step (a) and 40-50 parts by mass of concentrated sulfuric acid at 120-200 ℃, and neutralizing by using metal oxide or metal hydroxide to obtain the product; the aromatic compound A is one or more of naphthalene, 2-methylnaphthalene, 1-methylnaphthalene, anthracene, 2-methylanthracene, 9-butylanthracene, phenanthrene and 9-butylphenanthracene; the aldehyde compound B is, R is C 3 ~C 15 Alkyl or C 1 ~C 4 Alkyl substituted C 2 ~C 10 An alkenyl group;
the metal in the metal oxide or metal hydroxide is calcium, zinc, potassium, magnesium, iron, cobalt, nickel or copper.
2. The aromatic condensate sulfonate according to claim 1, wherein,
said C 3 ~C 15 The alkyl is n-butyl, n-hexyl, n-octyl, n-dodecyl, n-hexadecyl or 2-methyl-2-pentenyl;
and/or, said C 1 ~C 4 Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or isobutyl;
and/or, said C 2 ~C 10 The alkenyl group is hexenyl.
3. The aromatic condensate sulfonate of claim 2, wherein C is 1 ~C 4 Alkyl substituted C 2 ~C 10 Alkenyl is 2-ethyl-2-hexenyl.
4. The aromatic condensate sulfonate according to claim 1, wherein the reaction time of the condensation reaction is 4 to 20 hours;
and/or the reaction time of the sulfonation reaction is 6-12 h;
and/or the sulfonation reaction is that after the reaction is finished, the reaction product is firstly diluted by water and then neutralized;
and/or, the metal oxide is calcium oxide and/or magnesium oxide;
and/or the metal hydroxide is one or more of potassium hydroxide, ferric hydroxide and lithium hydroxide.
5. The aromatic condensate sulfonate according to claim 4, wherein the sulfonation is directly performed without a post-treatment after the condensation reaction;
and/or the post-treatment of the sulfonation reaction comprises the following steps: and after the neutralization is finished, filtering, washing with an organic solvent, and drying.
6. A preparation method of a radiation cross-linked polyethylene foam material is characterized by comprising the following steps:
(1) extruding 60 to 90 parts by weight of low density polyethylene, 5 to 30 parts by weight of the aromatic condensate sulfonate of any one of claims 1 to 5, 5 to 25 parts by weight of an elastomer, 2 to 20 parts by weight of a foaming agent, 1 to 2 parts by weight of a sensitizer and 0.5 to 4 parts by weight of an antioxidant in an extruder to obtain a master sheet;
(2) carrying out irradiation crosslinking on the master slice in the step (1) to obtain a crosslinked master slice;
(3) and (3) foaming the crosslinked master slice in the step (2).
7. The method according to claim 6, wherein in the step (1), the elastomer is one or more of ethylene-propylene-diene monomer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and chlorinated polyethylene;
and/or, in the step (1), the foaming agent is one or more of azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, toluenesulfonyl hydrazide and 4, 4' -oxybis benzenesulfonyl hydrazide;
and/or in the step (1), the sensitizer is one or more of zinc acetate, zinc stearate, cobalt stearate, zinc oxalate, zinc oxide and barium stearate;
and/or, in the step (1), the antioxidant is one or more of 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether and tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester;
and/or, in the step (1), the extruder is a single-screw extruder;
and/or, in the step (2), the irradiation crosslinking is carried out by an electron accelerator;
and/or, in the step (3), the foaming is carried out in a foaming furnace.
8. The method according to claim 6,
in the step (1), the extrusion temperature is 75-145 ℃;
and/or in the step (1), the rotating speed of a screw of the extruder is 50-85 rpm;
and/or in the step (1), the die head temperature of the extruder is 85-145 ℃;
and/or in the step (1), the thickness of the master slice is 0.1-0.5 mm;
and/or, the step (1) is that the low-density polyethylene, the aromatic condensate sulfonate, the elastomer, the foaming agent, the sensitizer and the antioxidant are uniformly mixed and then are added into the extruder for extrusion;
and/or in the step (2), the irradiation dose of the irradiation crosslinking is 30-40 kGy;
and/or, in step (2), said radiation crosslinking forms a crosslinked polymeric network;
and/or in the step (3), the residence time of the crosslinked master slice is 0.2-1.0 min.
9. A radiation cross-linked polyethylene foam material prepared by the preparation method of any one of claims 6 to 8.
10. Use of the radiation crosslinked polyethylene foam material according to claim 9 in the fields of mechanical shock resistance, floor mats, thermal insulation pipes or electronic equipment.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147880A (en) * | 2007-08-07 | 2008-03-26 | 华东师范大学 | Method for preparing condensing multi-kernel aromatic resin carbon based solid acid catalyst |
| CN101250422A (en) * | 2008-03-28 | 2008-08-27 | 华东师范大学 | Method for synthesizing bio-diesel by using condensed polynuclear anime carbon-based solid acid as catalyst |
| JP2009079010A (en) * | 2007-09-27 | 2009-04-16 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for producing sodium salt of naphthalenesulfonic acid formalin condensate |
| CN102123969A (en) * | 2008-08-15 | 2011-07-13 | 巴斯夫欧洲公司 | Use of aldehyde condensates as drying aids in preparations based on mineral binders |
| CN102453227A (en) * | 2010-10-26 | 2012-05-16 | 武汉保华石化新材料开发有限公司 | Preparation method for polycyclic aromatic hydrocarbon resin |
| CN107573471A (en) * | 2017-08-31 | 2018-01-12 | 浙江吉盛化学建材有限公司 | A kind of production technology of FDN high efficiency water reducing agents |
| CN109181055A (en) * | 2018-07-24 | 2019-01-11 | 深圳市长园特发科技有限公司 | Radiant crosslinked polyethylene foam and its preparation method and application |
-
2021
- 2021-01-07 CN CN202110017177.2A patent/CN112851893B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147880A (en) * | 2007-08-07 | 2008-03-26 | 华东师范大学 | Method for preparing condensing multi-kernel aromatic resin carbon based solid acid catalyst |
| JP2009079010A (en) * | 2007-09-27 | 2009-04-16 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for producing sodium salt of naphthalenesulfonic acid formalin condensate |
| CN101250422A (en) * | 2008-03-28 | 2008-08-27 | 华东师范大学 | Method for synthesizing bio-diesel by using condensed polynuclear anime carbon-based solid acid as catalyst |
| CN102123969A (en) * | 2008-08-15 | 2011-07-13 | 巴斯夫欧洲公司 | Use of aldehyde condensates as drying aids in preparations based on mineral binders |
| CN102453227A (en) * | 2010-10-26 | 2012-05-16 | 武汉保华石化新材料开发有限公司 | Preparation method for polycyclic aromatic hydrocarbon resin |
| CN107573471A (en) * | 2017-08-31 | 2018-01-12 | 浙江吉盛化学建材有限公司 | A kind of production technology of FDN high efficiency water reducing agents |
| CN109181055A (en) * | 2018-07-24 | 2019-01-11 | 深圳市长园特发科技有限公司 | Radiant crosslinked polyethylene foam and its preparation method and application |
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Denomination of invention: A radiation cross-linked polyethylene foam material and its preparation method Effective date of registration: 20230606 Granted publication date: 20220902 Pledgee: Industrial and Commercial Bank of China Limited Pan'an sub branch Pledgor: ZHEJIANG WANLI NEW MATERIALS TECHNOLOGY Co.,Ltd. Registration number: Y2023330001094 |