CN114437381B - Modified crosslinked polyethylene, preparation method and application thereof, and formed polyethylene - Google Patents
Modified crosslinked polyethylene, preparation method and application thereof, and formed polyethylene Download PDFInfo
- Publication number
- CN114437381B CN114437381B CN202210166002.2A CN202210166002A CN114437381B CN 114437381 B CN114437381 B CN 114437381B CN 202210166002 A CN202210166002 A CN 202210166002A CN 114437381 B CN114437381 B CN 114437381B
- Authority
- CN
- China
- Prior art keywords
- polyethylene
- irradiation
- ultraviolet light
- kgy
- energy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 76
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 74
- -1 polyethylene Polymers 0.000 title claims abstract description 73
- 229920003020 cross-linked polyethylene Polymers 0.000 title claims abstract description 31
- 239000004703 cross-linked polyethylene Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 71
- 238000010521 absorption reaction Methods 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- 239000012298 atmosphere Substances 0.000 claims description 21
- 229920001903 high density polyethylene Polymers 0.000 claims description 21
- 239000004700 high-density polyethylene Substances 0.000 claims description 21
- 229920001684 low density polyethylene Polymers 0.000 claims description 21
- 239000004702 low-density polyethylene Substances 0.000 claims description 21
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 19
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 19
- 230000005251 gamma ray Effects 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010894 electron beam technology Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 3
- 238000000462 isostatic pressing Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 210000002381 plasma Anatomy 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 230000002285 radioactive effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a modified crosslinked polyethylene, a preparation method and application thereof, and a formed polyethylene. The preparation method of the modified crosslinked polyethylene comprises the following steps: the polyethylene is subjected to irradiation crosslinking by adopting high-energy rays and ultraviolet light; the absorption dose of the high-energy ray irradiation crosslinking is 5-3000 kGy, and the total irradiation energy of ultraviolet light is 1-200 kWh/m 2. The preparation method of the invention has low energy consumption and no pollution, and the prepared modified crosslinked polyethylene has improved mechanical properties and good comprehensive use performance on the basis of ensuring the crosslinking density.
Description
Technical Field
The invention relates to a modified crosslinked polyethylene, a preparation method and application thereof, and a formed polyethylene.
Background
Polyethylene (polyethene, PE for short) is a thermoplastic resin material prepared by ethylene through polymerization reaction, has excellent low-temperature resistance, good chemical stability, low water absorption and excellent electrical insulation, and is insoluble in common solvents at normal temperature. Polyethylenes can be classified into Ultra High Molecular Weight Polyethylene (UHMWPE), high Density Polyethylene (HDPE), low Density Polyethylene (LDPE) and Linear Low Density Polyethylene (LLDPE) according to the polymerization method, the difference between the molecular weight and the chain structure. Polyethylene can be widely applied to the fields of pipes, film products, engineering plastics, wires, cables and the like.
Some of the disadvantages of polyethylene also limit its scope of application. Such as: the mechanical properties are generally poor in creep resistance, poor in heat resistance, low in PE tensile strength except UHMWPE, and the like. In order to improve the properties of polyethylene, researchers have resorted to various modification methods such as blending, grafting, crosslinking, etc. Wherein the irradiation modification is to make the linear polyethylene into a net-shaped or body-shaped crosslinked polyethylene by high-energy ray irradiation (gamma rays, X rays, electron rays, etc.). The irradiation treatment can provide heat resistance, environmental stress cracking resistance and mechanical properties, and is suitable for large pipes, cable wires, rotational molding products and the like.
The irradiation modification also has uncontrollable factors, and after the PE is modified by adopting an electron beam or gamma ray irradiation crosslinking technology, molecular chain breakage can be caused, so that performances such as impact strength, elongation at break and the like are reduced. For part of materials, the performance of the irradiation modified material is slowly reduced during subsequent storage or use, or referred to as a post-irradiation effect, which is an important factor affecting the long-term stability performance of the material. In order to reduce the effect after irradiation, the prior art often adopts methods of adding an antioxidant, high-temperature annealing and the like. However, these methods either affect the properties of the material or add complexity to the process.
The prior art also proposes the use of ultraviolet light and the addition of photoinitiators for crosslinking polyethylene, but after crosslinking the photoinitiators are present in the form of impurities, which impair the properties of the polyethylene and whose efficiency is far lower than that of electron beam irradiation and gamma (gamma) radiation.
Therefore, research on how to reduce the radiation modified effect of the crosslinked polyethylene, avoid structural damage, reduce the process difficulty and improve the comprehensive usability is necessary.
Disclosure of Invention
The invention aims to overcome the defect that the mechanical property of polyethylene is reduced after irradiation crosslinking is carried out on the polyethylene in the prior art, and provides modified crosslinked polyethylene, a preparation method and application thereof, and formed polyethylene. The method adopts the mode of high-energy rays cooperated with ultraviolet radiation treatment, is simple and easy to implement, and the prepared modified crosslinked polyethylene improves the mechanical property and has good comprehensive use performance on the basis of ensuring the crosslinking density.
The invention solves the technical problems through the following technical proposal.
The invention provides a preparation method of modified crosslinked polyethylene, which comprises the following steps: the polyethylene is subjected to irradiation crosslinking by adopting high-energy rays and ultraviolet light; the absorption dose of the high-energy ray irradiation crosslinking is 5-3000 kGy, and the total irradiation energy of the ultraviolet light is 1-200 kWh/m 2.
In the present invention, the absorption dose of the high-energy ray irradiation crosslinking is preferably 15 to 150kGy, more preferably 25 to 60kGy, for example 25kGy or 50kGy.
In the present invention, the dose rate of the high-energy ray irradiation crosslinking may be 1 to 3kGy/h, for example, 2kGy/h.
In the present invention, the total energy of the ultraviolet light irradiation is preferably 20kWh/m 2、40kWh/m2、60kWh/m2 or 120kWh/m 2, more preferably 40 to 100kWh/m 2, and still more preferably 20 to 60kWh/m 2. If the total energy of ultraviolet radiation is too low, the modification effect is not obvious; if too high, the polyethylene will be aged, causing damage.
In the present invention, the irradiation time of the ultraviolet light may be 0.5 to 2 hours, preferably 0.5 to 1 hour, for example, 0.5 hours or 1 hour.
Preferably, when the absorption dose of the high-energy ray irradiation crosslinking is 15-150 kGy, the dose rate is 1-3 kGy/h, the irradiation is carried out by ultraviolet light, the total energy of the ultraviolet light irradiation is 1-120 kWh/m 2, and the irradiation time of the ultraviolet light is 0.5-2 h.
More preferably, when the absorption dose of the high-energy ray irradiation crosslinking is 25-50 kGy, the dose rate is 2kGy/h, the irradiation is carried out after the irradiation, the total energy of the ultraviolet light irradiation is 20-120 kWh/m 2, and the irradiation time of the ultraviolet light is 0.5-1 h.
In a preferred implementation, when the absorption dose of the high-energy ray irradiation crosslinking is 25kGy, the dose rate is 2kGy/h, the irradiation is carried out by ultraviolet light, the total energy of the ultraviolet light irradiation is 20kWh/m 2, and the irradiation time of the ultraviolet light is 1h.
In a preferred implementation, when the absorption dose of the high-energy ray irradiation crosslinking is 50kGy, the dose rate is 2kGy/h, the irradiation is carried out by ultraviolet light, the total energy of the ultraviolet light irradiation is 20kWh/m 2, and the irradiation time of the ultraviolet light is 1h.
In a preferred implementation, when the absorption dose of the high-energy ray irradiation crosslinking is 25kGy, the dose rate is 2kGy/h, the irradiation is carried out by ultraviolet light, the total energy of the ultraviolet light irradiation is 60kWh/m 2, and the irradiation time of the ultraviolet light is 0.5h.
In a preferred implementation, when the absorption dose of the high-energy ray irradiation crosslinking is 50kGy, the dose rate is 2kGy/h, the irradiation is carried out by ultraviolet light, the total energy of the ultraviolet light irradiation is 60kWh/m 2, and the irradiation time of the ultraviolet light is 0.5h.
In a preferred implementation, when the absorption dose of the high-energy ray irradiation crosslinking is 25kGy, the dose rate is 2kGy/h, the irradiation is carried out by ultraviolet light, the total energy of the ultraviolet light irradiation is 120kWh/m 2, and the irradiation time of the ultraviolet light is 1h.
In a preferred implementation, when the absorption dose of the high-energy ray irradiation crosslinking is 50kGy, the dose rate is 2kGy/h, the irradiation is carried out by ultraviolet light, the total energy of the ultraviolet light irradiation is 120kWh/m 2, and the irradiation time of the ultraviolet light is 1h.
In the present invention, the high energy rays may be electron beams, gamma rays, X rays or plasmas, preferably electron beams, gamma rays or X rays, for example gamma rays. Those skilled in the art know that electron beam dose rate is high, penetrability is poor, and the method is suitable for rapidly irradiating and processing thin samples; the gamma rays and the X rays have low dosage rate and strong penetrability, and are suitable for irradiation processing of irregular or thick samples.
In the present invention, the ultraviolet light may be provided by a metal halogen lamp.
In the present invention, the polyethylene may be of a type conventional in the art, preferably low density polyethylene and/or high density polyethylene; the low-density polyethylene is preferably polyethylene with the density of 0.91-0.93 g/cm 3; the high-density polyethylene is preferably polyethylene with a density of 0.941-0.960 g/cm 3.
In the present invention, the polyethylene may be of a type conventional in the art, preferably ultra-high molecular weight polyethylene; the ultra-high molecular weight polyethylene is preferably unbranched linear polyethylene having a molecular weight of 150 ten thousand or more.
In the present invention, the polyethylene may have a density of 0.90 to 0.97g/cm 3, preferably 0.91 to 0.96g/cm 3.
In the present invention, the polyethylene may be an unshaped polyethylene or a molded polyethylene.
Wherein the unshaped polyethylene may be in powder or granular form.
Wherein the shaped polyethylene may be a powder, a granule, a film, a fiber or a sheet.
The molding method of the molded polyethylene can be extrusion molding, compression molding or isostatic pressing.
In the present invention, the synergy may occur during or after the irradiation crosslinking, and preferably, the irradiation crosslinking treatment is performed on the polyethylene by using the ultraviolet light during or after the irradiation crosslinking is performed on the polyethylene by using the high-energy rays.
In the present invention, the irradiation crosslinking may be generally performed in an air atmosphere, an inert atmosphere or vacuum, for example, in an air atmosphere or an inert atmosphere.
The inert atmosphere may be an atmosphere which is not involved in the system reaction and is conventional in the art, and is not limited to inert gas, but may be nitrogen, such as nitrogen, argon or helium.
In a preferred embodiment, polyethylene is placed in a gamma-ray irradiation chamber, irradiation crosslinking treatment is performed under a nitrogen atmosphere, and the irradiated sample is placed in an ultraviolet lamp box filled with nitrogen for treatment.
The invention also provides modified crosslinked polyethylene, which is prepared by the preparation method.
The invention also provides application of the modified crosslinked polyethylene in preparing formed polyethylene.
In the invention, the formed polyethylene can be a polyethylene plate, polyethylene micropowder, polyethylene fiber or polyethylene film.
In the present invention, the molding method of the molded polyethylene may be extrusion molding, compression molding or isostatic molding.
The invention also provides a formed polyethylene which is prepared from the modified crosslinked polyethylene.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
(1) The modified crosslinked polyethylene is prepared by adopting the high-energy rays to cooperate with ultraviolet light, so that the advantage of high irradiation efficiency of the high-energy rays is maintained, and meanwhile, the ultraviolet light converts polyene free radicals into alkyl free radicals, so that the free radicals are eliminated, the aging phenomenon caused by the polyene free radicals is avoided, the formation of a crosslinked network is promoted, and the damage to the oriented structure of the material caused by the traditional high-temperature annealing treatment is avoided. Meanwhile, compared with the traditional high-temperature annealing treatment, the time required by ultraviolet light treatment can be reduced by 60-90%, and the energy consumption is greatly reduced. The preparation process of the invention can be carried out without introducing other materials, and has high product purity and environment-friendly and pollution-free preparation process.
(2) The modified crosslinked polyethylene prepared by the invention has the advantages of improved mechanical property, improved wear resistance by 8-10%, improved oxidation resistance by 5-10% and good comprehensive use performance on the basis of ensuring the crosslinking density.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples and comparative examples, experiments were conducted using low-density polyethylene (density: 0.91 to 0.92g/cm 3) having a number average molecular weight of about 2 ten thousand, high-density polyethylene (density: 0.94 to 0.96g/cm 3) having a number average molecular weight of about 3 ten thousand, and ultra-high-molecular-weight polyethylene (density: 0.92 to 0.94g/cm 3) having a number average molecular weight of about 150 ten thousand.
In the following examples and comparative examples:
(1) The mechanical properties are judged by tensile strength and elongation at break, and are measured according to national standard GB/T1040.1-2018.
(2) The crosslinking degree of the polyethylene is judged by a trans-vinylidene index (TVI), and the TVI of the polyethylene is defined by measuring the ratio of the area of a trans-vinylidene absorption peak between 950 cm -1 and 980cm -1 to the area of a C-H absorption peak between 1330 cm -1 and 1396cm -1 by using an FT-IR method according to a method prescribed in a Standard test method for evaluating the trans-vinylidene content of a polyethylene product after irradiation for surgical implants by an infrared spectrometry of the pharmaceutical industry standard YY/T0814-2010.
(3) The crystallinity of the polyethylene is calculated according to the following formula:
wherein θ is crystallinity (in%); Δhf represents the heat of fusion of the pattern; delta Hj represents the heat of fusion at which the crystallinity of the polyethylene reaches 100%, and the Delta Hj assumes a value of 289.3J/g.
(4) The degree of swelling is determined according to American society for testing and materials standard ASTM-D2765.
Example 1
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) And (3) placing the three plates in a gamma-ray irradiation chamber, and performing irradiation crosslinking treatment under the atmosphere of nitrogen, wherein the irradiation crosslinking absorption dose is 25kGy, and the dose rate is 2kGy/h.
(3) And (3) placing the irradiated sample into an ultraviolet lamp box filled with nitrogen for treatment, wherein the total energy of ultraviolet light irradiation is 20kWh/m 2 respectively, and the treatment time is 1h.
Example 2
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) And (3) placing the three plates in a gamma-ray irradiation chamber, and performing irradiation crosslinking treatment under the atmosphere of argon, wherein the irradiation crosslinking absorption dose is 50kGy, and the dose rate is 2kGy/h.
(3) And (3) placing the irradiated sample into an ultraviolet lamp box filled with argon for treatment, wherein the total energy of ultraviolet light irradiation is 20kWh/m 2 respectively, and the treatment time is 1h.
Example 3
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) The three plates are placed in a gamma ray irradiation room, irradiation crosslinking treatment is carried out under the atmosphere of helium, the absorption dose of irradiation crosslinking is 25kGy, and the dose rate is 2kGy/h.
(3) And (3) placing the irradiated sample into an ultraviolet lamp box filled with helium for treatment, wherein the total energy of ultraviolet light irradiation is 60kWh/m 2 respectively, and the treatment time is 0.5h.
Example 4
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) The three plates are placed in a gamma ray irradiation room (vacuum) for irradiation crosslinking treatment, the absorption dose of irradiation crosslinking is 50kGy, and the dose rate is 2kGy/h.
(3) And (3) placing the irradiated sample into an ultraviolet lamp box (vacuum) for treatment, wherein the total energy of ultraviolet light irradiation is 60kWh/m 2 respectively, and the treatment time is 0.5h.
Example 5
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) The three plates are placed in a gamma ray irradiation room (air) for irradiation crosslinking treatment, the absorption dose of irradiation crosslinking is 25kGy, and the dose rate is 2kGy/h.
(3) And (3) placing the irradiated sample into an ultraviolet lamp box (air) for treatment, wherein the total energy of ultraviolet light irradiation is 120kWh/m 2 respectively, and the treatment time is 1h.
Example 6
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) And (3) placing the three plates in a gamma-ray irradiation chamber, and performing irradiation crosslinking treatment under the atmosphere of nitrogen, wherein the irradiation crosslinking absorption dose is 50kGy, and the dose rate is 2kGy/h.
(3) And (3) placing the irradiated sample into an ultraviolet lamp box filled with nitrogen for treatment, wherein the total energy of ultraviolet light irradiation is 120kWh/m 2 respectively, and the treatment time is 1h.
Comparative example 1
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) And (3) placing the three plates in a gamma-ray irradiation chamber, and performing irradiation crosslinking treatment under the atmosphere of nitrogen, wherein the irradiation crosslinking absorption dose is 25kGy, and the dose rate is 2kGy/h.
(3) Untreated, and stored in air.
Comparative example 2
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) And (3) placing the three plates in a gamma-ray irradiation chamber, and performing irradiation crosslinking treatment under the atmosphere of nitrogen, wherein the irradiation crosslinking absorption dose is 50kGy, and the dose rate is 2kGy/h.
(3) Untreated, and stored in air.
Comparative example 3
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) And (3) placing the three plates in a gamma-ray irradiation chamber, and performing irradiation crosslinking treatment under the atmosphere of nitrogen, wherein the irradiation crosslinking absorption dose is 25kGy, and the dose rate is 2kGy/h.
(3) The irradiated sample was placed in a forced air oven and heated to 120 ℃ for 5 hours of annealing.
Comparative example 4
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) And (3) placing the three plates in a gamma-ray irradiation chamber, and performing irradiation crosslinking treatment under the atmosphere of nitrogen, wherein the irradiation crosslinking absorption dose is 50kGy, and the dose rate is 2kGy/h.
(3) The irradiated sample was placed in a forced air oven and heated to 120 ℃ for 5 hours of annealing.
Comparative example 5
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) And (3) placing the three plates in a gamma-ray irradiation chamber, and performing irradiation crosslinking treatment under the atmosphere of nitrogen, wherein the irradiation crosslinking absorption dose is 25kGy, and the dose rate is 2kGy/h.
(3) And (3) placing the irradiated sample into an ultraviolet lamp box filled with nitrogen for treatment, wherein the total energy of ultraviolet light irradiation is 0.5kWh/m 2 respectively, and the treatment time is 1h.
Comparative example 6
(1) A low-density polyethylene film having a thickness of 3 μm, a high-density polyethylene plate having a thickness of about 1mm, and an ultra-high molecular weight polyethylene plate were selected as test samples. Gamma rays are used as radioactive sources.
(2) And (3) placing the three plates in a gamma-ray irradiation chamber, and performing irradiation crosslinking treatment under the atmosphere of nitrogen, wherein the irradiation crosslinking absorption dose is 25kGy, and the dose rate is 2kGy/h.
(3) And (3) placing the irradiated sample into an ultraviolet lamp box filled with nitrogen for treatment, wherein the total energy of ultraviolet light irradiation is 250kWh/m 2 respectively, and the treatment time is 1h.
Effect example 1
Tables 1 to 3 show the performance parameters of the low density polyethylene, the high density polyethylene and the ultra high molecular weight polyethylene in examples 1 to 6 and comparative examples 1 to 4, respectively.
Table 1 test data for each of the examples and comparative examples of low density polyethylene
Table 2 test data for each of the examples and comparative examples of high density polyethylene
Table 3 test data for each of the examples and comparative examples of ultra high polyethylene
As is clear from tables 1 to 3, the modified polyethylenes of examples 1 to 6 have a high crosslinking density, good mechanical properties and good comprehensive utilization properties, as compared with comparative examples 1 to 6. The gamma-ray irradiation dose of the embodiment 3 is low, the irradiation intensity of the ultraviolet lamp is moderate, and the comprehensive performance of the ultraviolet lamp is optimal.
Claims (14)
1. The preparation method of the modified crosslinked polyethylene is characterized by comprising the following steps of: the polyethylene is subjected to irradiation crosslinking by adopting high-energy rays and ultraviolet light; the absorption dose of the high-energy ray irradiation crosslinking is 5-150 kGy, the dose rate of the high-energy ray irradiation crosslinking is 1-3 kGy/h, the total irradiation energy of ultraviolet light is 20-200 kWh/m 2, and the irradiation time of the ultraviolet light is 0.5-2 h;
The high-energy rays are electron beams, gamma rays, X rays or plasmas; after the irradiation crosslinking process of the polyethylene by adopting the high-energy rays is finished, carrying out the irradiation crosslinking treatment on the polyethylene by adopting the ultraviolet light; the irradiation crosslinking is performed in an air atmosphere, an inert atmosphere or vacuum.
2. The method for producing a modified crosslinked polyethylene according to claim 1, wherein the absorption dose of the high-energy ray irradiation crosslinking is 25 to 60 kGy;
and/or the dosage rate of the high-energy ray irradiation crosslinking is 2 kGy/h;
and/or the total energy of the ultraviolet light irradiation is 20 kWh/m 2、40 kWh/m2、60 kWh/m2 or 120 kWh/m 2;
And/or the irradiation time of the ultraviolet light is 0.5-1 h.
3. The method for producing a modified crosslinked polyethylene according to claim 1, wherein the absorption dose of the high-energy ray irradiation crosslinking is 25 kGy or 50 kGy;
And/or the total irradiation energy of the ultraviolet light is 40-100 kWh/m 2;
and/or the irradiation time of the ultraviolet light is 0.5h or 1 h.
4. The method for producing a modified crosslinked polyethylene according to claim 1, wherein the total energy of irradiation with ultraviolet light is 20 to 60 kWh/m 2.
5. The method for preparing the modified crosslinked polyethylene according to claim 1, wherein when the absorption dose of the high-energy ray irradiation crosslinking is 15-150 kGy, the dose rate is 1-3 kGy/h, the irradiation is carried out again by ultraviolet light, the total energy of the ultraviolet light irradiation is 20-120 kWh/m 2, and the irradiation time of the ultraviolet light is 0.5-2 h.
6. The method for producing a modified crosslinked polyethylene according to claim 5, wherein when the absorption dose of the high-energy radiation is 25 to 50 kGy, the dose rate is 2 kGy/h, the irradiation is followed by the irradiation with ultraviolet light, the total energy of the ultraviolet light irradiation is 20 to 120 kWh/m 2, and the irradiation time of the ultraviolet light is 0.5 to 1 h.
7. The method for producing a modified crosslinked polyethylene according to claim 1, wherein when the absorption dose of the high-energy ray irradiation crosslinking is 25 kGy, the dose rate is 2 kGy/h, the irradiation is followed by ultraviolet irradiation, the total energy of the ultraviolet irradiation is 20 kWh/m 2, and the irradiation time of the ultraviolet light is 1 h;
Or when the absorption dose of the high-energy ray irradiation crosslinking is 50 kGy, the dose rate is 2 kGy/h, the ultraviolet light is irradiated after the irradiation, the total energy of the ultraviolet light irradiation is 20 kWh/m 2, and the irradiation time of the ultraviolet light is 1 h;
Or when the absorption dose of the high-energy ray irradiation crosslinking is 25 kGy, the dose rate is 2 kGy/h, the ultraviolet light is irradiated after the irradiation, the total energy of the ultraviolet light irradiation is 60 kWh/m 2, and the irradiation time of the ultraviolet light is 0.5 h;
Or when the absorption dose of the high-energy ray irradiation crosslinking is 50 kGy, the dose rate is 2 kGy/h, the ultraviolet light is irradiated after the irradiation, the total energy of the ultraviolet light irradiation is 60 kWh/m 2, and the irradiation time of the ultraviolet light is 0.5 h;
Or when the absorption dose of the high-energy ray irradiation crosslinking is 25 kGy, the dose rate is 2 kGy/h, the ultraviolet light is irradiated after the irradiation, the total energy of the ultraviolet light irradiation is 120 kWh/m 2, and the irradiation time of the ultraviolet light is 1 h;
or when the absorption dose of the high-energy ray irradiation crosslinking is 50 kGy, the dose rate is 2 kGy/h, the ultraviolet light is irradiated after the irradiation, the total energy of the ultraviolet light irradiation is 120 kWh/m 2, and the irradiation time of the ultraviolet light is 1 h.
8. The method for producing a modified crosslinked polyethylene according to claim 1, wherein the high-energy ray is an electron beam, a gamma ray or an X ray;
and/or, the ultraviolet light is provided by a metal halogen lamp;
And/or the polyethylene is low-density polyethylene and/or high-density polyethylene;
and/or the polyethylene is ultra-high molecular weight polyethylene;
and/or the density of the polyethylene is 0.90-0.97 g/cm 3;
and/or the polyethylene is an unshaped polyethylene or a molded polyethylene;
And/or, the irradiation crosslinking is performed in an air atmosphere or an inert atmosphere.
9. The method for producing a modified crosslinked polyethylene according to claim 8, wherein the high-energy ray is a gamma ray;
And/or the low-density polyethylene is polyethylene with the density of 0.91-0.93 g/cm;
and/or the high-density polyethylene is polyethylene with the density of 0.941-0.960 g/cm;
and/or the ultra-high molecular weight polyethylene is unbranched linear polyethylene with a molecular weight of 150 ten thousand or more;
And/or the unshaped polyethylene is in the form of powder or granules;
and/or the formed polyethylene is a powder, a granule, a film, a fiber or a plate;
And/or the molding method of the molded polyethylene is extrusion molding, compression molding or isostatic pressing;
And/or the inert atmosphere is nitrogen, argon or helium.
10. The method for producing a modified crosslinked polyethylene according to claim 1, wherein the polyethylene is placed in a gamma-ray irradiation chamber, irradiation crosslinking treatment is performed under a nitrogen atmosphere, and the irradiated sample is then placed in an ultraviolet lamp box filled with nitrogen for treatment.
11. A modified crosslinked polyethylene produced by the method for producing a modified crosslinked polyethylene according to any one of claims 1 to 10.
12. Use of the modified cross-linked polyethylene of claim 11 for the preparation of a shaped polyethylene.
13. Use of a modified cross-linked polyethylene according to claim 12 for the preparation of a shaped polyethylene, wherein the shaped polyethylene is a polyethylene sheet, polyethylene micropowder, polyethylene fiber or polyethylene film;
and/or the molding method of the molded polyethylene is extrusion molding, compression molding or isostatic pressing.
14. A molded polyethylene made using the modified crosslinked polyethylene of claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210166002.2A CN114437381B (en) | 2022-02-21 | 2022-02-21 | Modified crosslinked polyethylene, preparation method and application thereof, and formed polyethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210166002.2A CN114437381B (en) | 2022-02-21 | 2022-02-21 | Modified crosslinked polyethylene, preparation method and application thereof, and formed polyethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114437381A CN114437381A (en) | 2022-05-06 |
| CN114437381B true CN114437381B (en) | 2024-04-26 |
Family
ID=81373026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210166002.2A Active CN114437381B (en) | 2022-02-21 | 2022-02-21 | Modified crosslinked polyethylene, preparation method and application thereof, and formed polyethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114437381B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958893A (en) * | 2005-10-31 | 2007-05-09 | 香港理工大学 | Polythene cross-linking fibers with shape memory, and preparation method |
| CN102276864A (en) * | 2010-05-07 | 2011-12-14 | 好梅迪卡整形器械公司 | Surface crosslinked polyethylene |
| CN109251389A (en) * | 2018-07-20 | 2019-01-22 | 上海化工研究院有限公司 | The preparation method of light cross-linking radiation ultra-high molecular weight polyethylene injection molding composite material |
| CN113024922A (en) * | 2021-03-01 | 2021-06-25 | 赵志勇 | Ultraviolet irradiation crosslinked polyethylene pipe and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007091521A1 (en) * | 2006-02-06 | 2007-08-16 | Japan Medical Materials Corporation | Low-wear sliding member and artificial joint making use of the same |
| EP2486948B1 (en) * | 2007-04-10 | 2018-02-21 | Zimmer, Inc. | An antioxidant stabilized crosslinked ultra-high molecular weight polyethylene for medical device applications |
-
2022
- 2022-02-21 CN CN202210166002.2A patent/CN114437381B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958893A (en) * | 2005-10-31 | 2007-05-09 | 香港理工大学 | Polythene cross-linking fibers with shape memory, and preparation method |
| CN102276864A (en) * | 2010-05-07 | 2011-12-14 | 好梅迪卡整形器械公司 | Surface crosslinked polyethylene |
| CN109251389A (en) * | 2018-07-20 | 2019-01-22 | 上海化工研究院有限公司 | The preparation method of light cross-linking radiation ultra-high molecular weight polyethylene injection molding composite material |
| CN113024922A (en) * | 2021-03-01 | 2021-06-25 | 赵志勇 | Ultraviolet irradiation crosslinked polyethylene pipe and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114437381A (en) | 2022-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9449761B2 (en) | Polypropylene for film capacitor, polypropylene sheet for film capacitor, method for producing the same, and uses of the same | |
| JP5454726B2 (en) | Modified fluorine-containing copolymer, fluororesin molded product, and method for producing fluororesin molded product | |
| US3852177A (en) | Method of radiation cross-linking olefin polymers containing acrylate cross-linking promoters | |
| CN110372962B (en) | Cross-linked POSS/PP composite diaphragm, preparation method and application | |
| WO2014007350A1 (en) | Modified fluorine resin mixture, fluorine resin molded article, and method for manufacturing fluorine resin molded article | |
| EP1311564B1 (en) | Production of polypropylene having improved properties | |
| WO2014007348A1 (en) | Modified fluorine-containing copolymer, fluorine resin molded article, and method for manufacturing fluorine resin molded article | |
| CN114437381B (en) | Modified crosslinked polyethylene, preparation method and application thereof, and formed polyethylene | |
| CN107337801B (en) | Method for preparing high melt strength polypropylene by electron irradiation crosslinking | |
| JP4846496B2 (en) | Cross-linked polytetrafluoroethylene resin and method for producing the same | |
| RU2657089C1 (en) | Method for producing polymeric nanocomposites | |
| CN105713223A (en) | Surface modifying method of PET thin film | |
| US3816284A (en) | Radiation grafting of vinyl monomers onto cellular polymeric substrates | |
| EP0047171A2 (en) | Process for irradiation of polyethylene | |
| CN113956528A (en) | High-crosslinking ultrahigh molecular weight polyethylene and preparation method and application thereof | |
| Maziad et al. | Polyethylene film modification using polylactic acid‐Starch additives and study ionizing radiation effect onto aging properties | |
| US5977203A (en) | Process for producing crosslinked polycaprolactone | |
| WO2002002658A1 (en) | Production of propylene copolymers having improved properties | |
| Barlow et al. | Radiation processing of polyolefins and compounds | |
| CN111100371A (en) | Homo-polypropylene material for power cable and preparation method thereof | |
| Tokuda et al. | Electron beam irradiation conditions and foam seat properties in polypropylene-polyethylene blends | |
| CN111378260A (en) | Modified polylactic acid and preparation method thereof | |
| US20040113323A1 (en) | Moulding polyolefins | |
| Wu et al. | Effect of light intensity on ultraviolet irradiated polypropylene and its compatibilization with CaCO3 | |
| CN113512211B (en) | Preparation method of ultraviolet light crosslinked polyolefin master batch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Wenli Inventor after: Hu Zhijie Inventor after: Tian Jili Inventor after: Wang Mouhua Inventor after: Lu Manli Inventor after: Li Panpan Inventor before: Zhang Wenli Inventor before: Li Panpan Inventor before: Tian Jili Inventor before: Wang Mouhua Inventor before: Lu Manli |