CN109796655B - 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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- CN109796655B CN109796655B CN201811580183.3A CN201811580183A CN109796655B CN 109796655 B CN109796655 B CN 109796655B CN 201811580183 A CN201811580183 A CN 201811580183A CN 109796655 B CN109796655 B CN 109796655B
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Abstract
The invention relates to an irradiation crosslinking polyethylene foam material and a preparation method thereof, and particularly relates to a preparation method of the irradiation crosslinking polyethylene foam material, wherein thermosetting phenolic resin is added into low-density polyethylene, a thermoplastic elastomer, a foaming agent, a sensitizing agent and an antioxidant to serve as a reinforcing agent, and the high-rigidity polyethylene foam material is prepared by adjusting the molecular structure and the dosage of the thermosetting phenolic resin. The product prepared by the method has high rigidity and elastic modulus of more than 5.5MPa, and is widely applied to the fields of ground mats, floor mats, electronic equipment and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an irradiation crosslinking polyethylene foam material and a preparation method thereof.
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 toughness, 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-rigidity polyethylene foamed product is widely applied to the fields of ground mats, automotive interiors, electronic equipment and the like, and higher requirements are put forward on the product rigidity along with the improvement of the product quality requirements.
The traditional method for improving the rigidity 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 and calcium carbonate are poor in intersolubility with polyethylene, the improvement on the rigidity of the product is limited, and a large amount of inorganic fillers seriously affect the foaming process and other physical properties of the product. Too large a degree of crosslinking causes difficulty in foaming and fails to achieve a suitable expansion ratio.
Therefore, how to improve the rigidity of the polyethylene foam material is still a difficult problem to be solved urgently.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a radiation crosslinking polyethylene foam material and a preparation method thereof, and thermosetting phenolic resin is used as a reinforcing agent to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a radiation cross-linked polyethylene foam material is provided, and comprises the following steps:
firstly, mixing the following components, adding the mixture into a screw extruder, and carrying out mixing extrusion to obtain a master slice;
then, carrying out electron irradiation crosslinking on the master slice obtained in the step; after the electron irradiation crosslinking is finished, the obtained material is subjected to foaming treatment, so that the thermosetting phenolic resin reinforced polyethylene foam material is obtained.
Preferably, the thickness of the master is 0.2-1 mm; preferably 0.7 mm.
Preferably, the thermoplastic elastomer is one or a combination of more than one 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.
Preferably, the antioxidant is selected from one or more of the group consisting of: 2, 6-tert-butyl-4-methylphenol, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, and pentaerythritol tetrakis [ beta- (3, 5-tert-butyl-4-hydroxyphenyl) propionate ].
Preferably, the foaming agent is selected from one or more of the following group: including azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, toluenesulfonyl hydrazide, 4' -oxybis-benzenesulfonyl hydrazide.
Preferably, the sensitizer is selected from one or more of the following group: zinc acetate, zinc stearate, cobalt stearate, zinc oxide and barium stearate.
Preferably, the thermosetting phenolic resin is prepared by condensation reaction of alkyl phenol and formaldehyde.
Preferably, the thermosetting phenolic resin is prepared by a method comprising the following steps: in sodium hydroxide water solution, carrying out condensation reaction on alkylphenol and formaldehyde; after the reaction is finished, adjusting the pH of the reaction solution to 6.5-7.5 by using acid; and then distilling under reduced pressure to remove unreacted raw materials to obtain the thermosetting phenolic resin.
Preferably, the alkylphenol is selected from the group consisting of: tert-butylphenol, nonylphenol, methylphenol.
Preferably, the alkylphenol is p-cresol, o-tert-butylphenol, p-nonylphenol, m-nonylphenol or o-cresol.
Preferably, the sodium hydroxide aqueous solution is a 30% sodium hydroxide aqueous solution in percentage by mass.
Preferably, the molar ratio of alkylphenol to formaldehyde is 1: (1-10).
Preferably, the sodium hydroxide aqueous solution is a catalyst, and the catalyst accounts for 0.5-2% of the total mass of the reactants.
Preferably, the condensation reaction is carried out at 50-110 ℃.
Preferably, the condensation reaction is carried out for 0.5-12 h.
Preferably, the acid is hydrochloric acid.
Preferably, the pH is adjusted to 7.
Preferably, the distillation under reduced pressure is carried out at 80 ℃.
Preferably, the contents of the respective components are as follows:
preferably, the contents of the respective components are as follows:
preferably, the extrusion temperature of the screw extruder is 95-130 ℃.
Preferably, the screw rotating speed of the screw extruder is 60-120 rpm.
Preferably, the temperature of a die head of the screw extruder is 90-130 ℃.
Preferably, the irradiation dose of the electron irradiation crosslinking is 5-50 kGy.
Preferably, the foaming is carried out in a foaming machine; the temperature of the foaming furnace is 170-310 ℃, and the foaming time is 0.5-7 min.
Provides a radiation crosslinking polyethylene foam material, which is prepared by the preparation method.
The application of the irradiation crosslinking polyethylene foam material is provided, and the irradiation crosslinking polyethylene foam material is used for ground mats, automobile interiors and electronic equipment.
Compared with the prior art, the technical scheme of the invention has the advantages that:
(1) the product prepared by the preparation method has high rigidity and the elastic modulus is more than 5.5 MPa;
(2) the preparation method of the invention adopts phenol formaldehyde resin synthesized by alkylphenol such as tert-butyl phenol and the like to have good intersolubility with polyethylene, and can account for more than 30 percent of the total weight of reaction raw materials;
(3) the preparation method has rich raw material sources and low price;
(4) the preparation method can effectively adjust the rigidity of the material by adjusting the structure and the dosage of the thermosetting phenolic resin;
(5) the material prepared by the preparation method disclosed by the invention is widely applied to the fields of ground mats, automotive interiors, electronic equipment and the like.
Detailed Description
According to the invention, thermosetting phenolic resin is introduced into a low-density polyethylene formula as a reinforcing agent, and a rigid crosslinking network is formed in the processes of irradiation crosslinking and high-temperature foaming by adjusting the molecular structure and the dosage of the thermosetting phenolic resin, so that the high-rigidity polyethylene foam material is prepared.
The thermosetting phenolic resin can be cured into a cross-linked network with rigid aromatic rings at high temperature, so that the thermosetting phenolic resin has good rigidity. However, the traditional phenolic resin has poor intersolubility with polyethylene due to the strong polarity of phenol.
The invention adopts thermosetting alkyl phenolic resin as a reinforcing agent, and improves the mutual solubility of the phenolic resin and polyethylene by utilizing the good affinity of alkyl and polyethylene. The invention utilizes the characteristics of abundant aromatic ring structures and thermal curing crosslinking in the resin, further performs curing reaction in the processes of irradiation crosslinking and high-temperature foaming to form a high-rigidity polymer network, and improves the rigidity of the product.
The following detailed description of the preferred embodiments of the present invention is provided to provide a more clear understanding of the objects, features and advantages of the present invention.
In the description herein, for the purposes of illustrating the various disclosed embodiments, certain specific details are set forth in order to provide a thorough understanding of the various disclosed embodiments. One skilled in the relevant art will recognize, however, that the embodiments may be practiced without one or more of the specific details. In other instances, well-known devices, structures and techniques associated with this application may not be shown or described in detail to avoid unnecessarily obscuring the description of the embodiments.
Throughout the specification and claims, the word "comprise" and variations thereof, such as "comprises" and "comprising," are to be understood as an open, inclusive meaning, i.e., as being interpreted to mean "including, but not limited to," unless the context requires otherwise.
Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. It should be noted that the term "or" is generally employed in its sense including "and/or" unless the context clearly dictates otherwise.
The elastic modulus is tested by measuring the bending property of GB/T9341-.
Example 1
Step 1 Synthesis of thermosetting phenol resin
P-tert-butylphenol (corresponding to alkylphenol indicated in table 1) was mixed with a 37% aqueous formaldehyde solution in a molar ratio of p-tert-butylphenol to formaldehyde of 1: 2, adding 30% NaOH sodium hydroxide solution as a catalyst, wherein the catalyst accounts for 1% of the total mass of the reactants. The reaction mixture was warmed to 80 ℃ (corresponding to the phenolic resin reaction temperature indicated in table 3) and reacted for 4 h. Then, hydrochloric acid was added to adjust the pH of the solution to 7, and finally, rotary evaporation was carried out at 80 ℃ under reduced pressure to remove unreacted raw materials, and the residue was collected to obtain a thermosetting phenol resin.
Step 2 polyethylene foam preparation
Mixing the thermosetting phenolic resin prepared in the above steps, low-density polyethylene, ethylene propylene diene monomer, tetra [ beta- (3, 5-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, azodicarbonamide and zinc acetate according to a mass ratio of 10: 80: 10: 2: 10: 1, 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 80rpm and the die head temperature to be 120 ℃ to obtain a master slice with the thickness of 0.7 mm;
then, carrying out irradiation crosslinking on the master slice by an electron accelerator, and controlling the irradiation dose to be 30kGy 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 290 ℃, and keeping the residence time of the crosslinked master slice to be 1min to obtain the high-rigidity polyethylene foam material with the elastic modulus of 6.9 MPa.
Examples 2 to 6
The conditions were the same as in example 1, except that different kinds of alkylphenols were selected.
TABLE 1
Examples 7 to 10
The same conditions as in example 1 were followed, except that the weight ratio of phenolic resin to polyethylene was chosen differently.
TABLE 2
Examples 11 to 14
The conditions were the same as in example 1, except that the reaction temperature of the phenolic resin was chosen differently.
TABLE 3
Comparative example 1
According to the embodiment 1, without heating the thermosetting phenolic resin, low-density polyethylene, ethylene propylene diene monomer, pentaerythritol tetrakis [ beta- (3, 5-tert-butyl-4-hydroxyphenyl) propionate ], azodicarbonamide and zinc acetate are mixed according to the mass ratio of 80: 10: 2: 10: 1, 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 80rpm and the die head temperature to be 120 ℃ to obtain a master slice with the thickness of 0.7 mm;
then, carrying out irradiation crosslinking on the master slice by an electron accelerator, and controlling the irradiation dose to be 30kGy 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 290 ℃, and keeping the residence time of the crosslinked master slice to be 1min to obtain the irradiation crosslinked polyethylene foam material with the elastic modulus of 3.3 MPa.
The products prepared by the preparation method have good elastic modulus.
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 (9)
1. A preparation method of irradiation cross-linked polyethylene foam material is characterized by comprising the following steps: the preparation method comprises the following steps:
firstly, mixing the following components, adding the mixture into a screw extruder, and carrying out mixing extrusion to obtain a master slice;
then, carrying out electron irradiation crosslinking on the master slice obtained in the step; after the electron irradiation crosslinking is finished, the obtained material is subjected to foaming treatment, so that the thermosetting phenolic resin reinforced polyethylene foam material is obtained;
the thermosetting phenolic resin is prepared by condensation reaction of alkylphenol and formaldehyde;
the alkylphenol is selected from p-cresol, o-tert-butylphenol or o-cresol.
2. The method of claim 1, wherein: the contents of the components are as follows:
3. the method of claim 1, wherein: the extrusion temperature of the screw extruder is 95-130 ℃.
4. The method of claim 1, wherein: the screw rotating speed of the screw extruder is 60-120 rpm.
5. The method of claim 1, wherein: the die head temperature of the screw extruder is 90-130 ℃.
6. The method of claim 1, wherein: the irradiation dose of electron irradiation crosslinking is 5-50 kGy.
7. The method of claim 1, wherein: the foaming is carried out in a foaming machine; the temperature of the foaming furnace is 170-310 ℃, and the foaming time is 0.5-7 min.
8. A radiation cross-linked polyethylene foam material, which is prepared by the preparation method of any one of claims 1 to 7.
9. Use of the radiation crosslinked polyethylene foam material according to claim 8, wherein the radiation crosslinked polyethylene foam material is used for floor mats, automotive interiors, electronic devices.
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| WO2004016678A3 (en) * | 2002-08-15 | 2004-04-29 | Advanced Elastomer Systems | Process for preparing foamed thermoplastic vulcanisates |
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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: 20211130 Pledgee: Industrial and Commercial Bank of China Limited Pan'an sub branch Pledgor: ZHEJIANG WANLI NEW MATERIALS TECHNOLOGY Co.,Ltd. Registration number: Y2023330001094 |
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