CN116082553A - Method for preparing crosslinked polystyrene material by high-energy particle irradiation technology - Google Patents
Method for preparing crosslinked polystyrene material by high-energy particle irradiation technology Download PDFInfo
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- CN116082553A CN116082553A CN202211634788.2A CN202211634788A CN116082553A CN 116082553 A CN116082553 A CN 116082553A CN 202211634788 A CN202211634788 A CN 202211634788A CN 116082553 A CN116082553 A CN 116082553A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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Abstract
The invention relates to the technical field of polymer free radical crosslinking polymerization, in particular to a method for preparing a crosslinked polystyrene material by a high-energy particle irradiation technology; firstly, uniformly mixing styrene and a composite initiator to obtain a first mixed material; secondly, uniformly mixing the first mixed material and a molecular weight regulator, and carrying out irradiation polymerization by gamma rays to obtain a linear polystyrene prepolymer after polymerization; thirdly, adding a cross-linking agent and uniformly mixing; fourthly, irradiating with gamma rays, and obtaining a crosslinked polystyrene material after irradiation; the invention combines the gamma-ray irradiation technology and the bulk cross-linking polymerization technology, effectively solves the problems in the preparation process of the low dielectric material, and has short production period and low energy consumption; the polymer produced has the mechanical properties of tensile strength, bending strength and impact toughness material, greatly improved insulating strength, reduced dielectric constant and dielectric loss coefficient, and greatly reduced thickness limitation.
Description
Technical Field
The invention relates to the technical field of polymer free radical crosslinking polymerization, in particular to a method for preparing a crosslinked polystyrene material by a high-energy particle irradiation technology.
Background
Polystyrene is a brittle plastic, is not easy to bend, has luster, smoothness and hardness, has the advantages of easy processing and molding, transparency, low cost, insulation, good printability and the like, and can be widely used in the aspects of light industry market, daily decoration, illumination indication, packaging and the like. It can be used for daily necessities, electric and instrument cases, toys, lamps, household appliances, stationery, cosmetics containers, indoor and outdoor ornaments, fruit trays, optical parts (such as triangular prism and lens) lens window mirrors, molding, car lights and telecommunication accessories, electric frequency capacitor films, high-frequency insulating materials, containers such as televisions, wave guides, chemical containers and the like. The polystyrene cross-linked material can be obtained after the polystyrene is cross-linked, and can be used as a low dielectric material.
The low dielectric material is generally a material with a relative dielectric constant lower than 3.6 and a low dielectric loss in a wide frequency band, and is one of materials widely applied in the industries of microwave communication, semiconductors and the like at present. The dielectric loss in communication equipment, integrated circuits and other systems is reduced, and the loss of electric signals, the leakage current of the integrated circuits, the capacitance effect between wires and the like can be reduced, which is very important for the systems. The polystyrene cross-linked material is a low dielectric material with excellent performance, has stable and extremely low dielectric constant and dielectric loss in the range of 1GHz to 40GHz, and has extremely wide application fields.
However, the existing crosslinked polystyrene material is prepared by free radical bulk polymerization, and the method mainly comprises a stage heating method and an ultraviolet light initiated polymerization method when preparing the crosslinked polystyrene material. The stage heating method controls the polymerization reaction through temperature, and because the initial temperature of the reaction is higher, a large amount of reaction heat is generated in the reaction process, the conduction of the reaction heat is difficult to control, and the heat is not conducted out as the viscosity of the reaction system increases, so that the explosion aggregation is easy to occur, and the crosslinking degree of the system is difficult to control; the ultraviolet light initiated polymerization method not only needs to introduce a thermal initiator, a photoinitiator, a photo accelerator and the like into a reaction system to reduce the performance of a final product, but also limits the thickness of the prepared bulk material due to the limitation of ultraviolet light penetrating capacity.
Disclosure of Invention
The invention provides a method for preparing a crosslinked polystyrene material by a high-energy particle irradiation technology, which overcomes the defects of the prior art, and can effectively solve the problems that the crosslinking degree of a system is not easy to control, the performance of a product is not high and the thickness is limited when a block material is prepared by an ultraviolet light initiated polymerization method in the prior stage.
The technical scheme of the invention is realized by the following measures: the method for preparing the crosslinked polystyrene material by the high-energy particle irradiation technology comprises the following steps: firstly, styrene and a composite initiator are mixed according to the mass ratio of 100:5 to 20, and obtaining a first mixed material, wherein the composite initiator is a mixture of cumene hydroperoxide and azobisisobutyronitrile according to a mass ratio of 1:0.6; secondly, filling inert gas into the reaction kettle, then placing the first mixed material into the reaction kettle, adding a molecular weight regulator, and uniformly mixing, wherein the mass ratio of the styrene to the molecular weight regulator is 100:0.8 to 3, and carrying out irradiation polymerization by using gamma rays with the irradiation dose of 1500Gray, so as to obtain a linear polystyrene prepolymer after polymerization; thirdly, adding a cross-linking agent into the linear polystyrene prepolymer and uniformly mixing to obtain a second mixed material, wherein the adding amount of the cross-linking agent is 5-20% of the mass of the linear polystyrene prepolymer; fourthly, irradiating the second mixed material with gamma rays with the irradiation dose of 1200Gray to 65000Gray, and obtaining a crosslinked polystyrene material after irradiation; and fifthly, heating the crosslinked polystyrene material for 10 to 20 hours at the temperature of 40 to 100 ℃ to obtain the crosslinked polystyrene material of the solidified block after heating.
The following are further optimizations and/or improvements to the above-described inventive solution:
the linear polystyrene prepolymer obtained in the above second step has a molecular weight of 100000 to 150000.
In the fourth step, the gamma irradiation is performed in a sealed mold in which air is removed and inert gas is filled; the gamma-ray irradiation distance is 10cm to 30cm.
In the fifth step, the heating is performed in a sealed mold in which air is removed and inert gas is filled.
The inert gas is nitrogen or argon; the molecular weight regulator is n-dodecyl mercaptan or alpha-methyl styrene linear dimer.
The cross-linking agent is glycidyl methacrylate or divinylbenzene.
The invention combines the gamma-ray irradiation technology and the bulk cross-linking polymerization technology, effectively solves the problems in the preparation process of the low dielectric material, has short production period and low energy consumption, and is beneficial to improving the working environment; the generated polymer is pure and defect-free, and the mechanical properties of the tensile strength, bending strength and impact toughness materials are maintained, so that the insulating strength of the material is greatly improved, the dielectric constant and dielectric loss coefficient of the material are reduced, and the limit of thickness is also greatly reduced.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments can be determined according to the technical scheme and practical situations of the present invention. The various chemical reagents and chemical supplies mentioned in the invention are all commonly known and used in the prior art unless specified otherwise; the percentages in the invention are mass percentages unless specified otherwise; the solutions in the present invention are aqueous solutions in which the solvent is water unless otherwise specified, for example, hydrochloric acid solution is hydrochloric acid aqueous solution.
Example 1, the method for preparing crosslinked polystyrene material by the high energy particle irradiation technique is carried out according to the following steps: firstly, styrene and a composite initiator are mixed according to the mass ratio of 100:5 to 20, and obtaining a first mixed material, wherein the composite initiator is a mixture of cumene hydroperoxide and azobisisobutyronitrile according to a mass ratio of 1:0.6; secondly, filling inert gas into the reaction kettle, then placing the first mixed material into the reaction kettle, adding a molecular weight regulator, and uniformly mixing, wherein the mass ratio of the styrene to the molecular weight regulator is 100:0.8 to 3, and carrying out irradiation polymerization by using gamma rays with the irradiation dose of 1500Gray, so as to obtain a linear polystyrene prepolymer after polymerization; thirdly, adding a cross-linking agent into the linear polystyrene prepolymer and uniformly mixing to obtain a second mixed material, wherein the adding amount of the cross-linking agent is 5-20% of the mass of the linear polystyrene prepolymer; fourthly, irradiating the second mixed material with gamma rays with the irradiation dose of 1200Gray to 65000Gray, and obtaining a crosslinked polystyrene material after irradiation; and fifthly, heating the crosslinked polystyrene material for 10 to 20 hours at the temperature of 40 to 100 ℃ to obtain the crosslinked polystyrene material of the solidified block after heating. The linear polystyrene prepolymer obtained in the second step of the present invention has a molecular weight of 100000 to 150000.
Example 2 the method for preparing crosslinked polystyrene material by high energy particle irradiation technique is carried out as follows: firstly, styrene and a composite initiator are mixed according to the mass ratio of 100:5 or 20, and obtaining a first mixed material, wherein the composite initiator is a mixture of cumene hydroperoxide and azobisisobutyronitrile according to a mass ratio of 1:0.6; secondly, filling inert gas into the reaction kettle, then placing the first mixed material into the reaction kettle, adding a molecular weight regulator, and uniformly mixing, wherein the mass ratio of the styrene to the molecular weight regulator is 100:0.8 or 3, using gamma rays with the irradiation dose of 1500Gray to carry out irradiation polymerization, and obtaining linear polystyrene prepolymer after polymerization; thirdly, adding a cross-linking agent into the linear polystyrene prepolymer and uniformly mixing to obtain a second mixed material, wherein the adding amount of the cross-linking agent is 5-20% of the mass of the linear polystyrene prepolymer; fourthly, irradiating the second mixed material with gamma rays with the irradiation dose of 1200Gray or 65000Gray, and obtaining a crosslinked polystyrene material after irradiation; and fifthly, heating the crosslinked polystyrene material for 10 hours or 20 hours at the temperature of 40 ℃ or 100 ℃ to obtain the crosslinked polystyrene material of the solidified block.
Example 3 the method for preparing crosslinked polystyrene material by high energy particle irradiation technique is carried out as follows: firstly, styrene and a composite initiator are mixed according to the mass ratio of 100:5, uniformly mixing to obtain a first mixed material, wherein the composite initiator is a mixture of cumene hydroperoxide and azobisisobutyronitrile according to a mass ratio of 1:0.6; secondly, filling inert gas into the reaction kettle, then placing the first mixed material into the reaction kettle, adding a molecular weight regulator, and uniformly mixing, wherein the mass ratio of the styrene to the molecular weight regulator is 100:0.8, performing radiation polymerization by using gamma rays with the radiation dose of 1500Gray, and obtaining a linear polystyrene prepolymer after polymerization; thirdly, adding a cross-linking agent into the linear polystyrene prepolymer and uniformly mixing to obtain a second mixed material, wherein the adding amount of the cross-linking agent is 5% of the mass of the linear polystyrene prepolymer; fourthly, irradiating the second mixed material with gamma rays with the irradiation dose of 1200Gray, and obtaining the crosslinked polystyrene material after irradiation; and fifthly, heating the crosslinked polystyrene material for 10 hours at the temperature of 40 ℃ to obtain the crosslinked polystyrene material of the solidified block. In example 3, the linear polystyrene prepolymer obtained in the second step had a molecular weight of 100000.
Example 4 the method for preparing crosslinked polystyrene material by high energy particle irradiation technique is carried out as follows: firstly, styrene and a composite initiator are mixed according to the mass ratio of 100:6, uniformly mixing to obtain a first mixed material, wherein the composite initiator is a mixture of cumene hydroperoxide and azobisisobutyronitrile according to a mass ratio of 1:0.6; secondly, filling inert gas into the reaction kettle, then placing the first mixed material into the reaction kettle, adding a molecular weight regulator, and uniformly mixing, wherein the mass ratio of the styrene to the molecular weight regulator is 100:1, performing radiation polymerization by using gamma rays with the radiation dose of 1500Gray, and obtaining a linear polystyrene prepolymer after polymerization; thirdly, adding a cross-linking agent into the linear polystyrene prepolymer and uniformly mixing to obtain a second mixed material, wherein the adding amount of the cross-linking agent is 8% of the mass of the linear polystyrene prepolymer; fourthly, irradiating the second mixed material with gamma rays with the irradiation dose of 1500Gray, and obtaining a crosslinked polystyrene material after irradiation; and fifthly, heating the crosslinked polystyrene material for 10 hours at the temperature of 60 ℃ to obtain the crosslinked polystyrene material of the solidified block. In example 4, the linear polystyrene prepolymer obtained in the second step had a molecular weight of 120000.
Example 5 the method for preparing crosslinked polystyrene material by high energy particle irradiation technique is carried out as follows: firstly, styrene and a composite initiator are mixed according to the mass ratio of 100:10, uniformly mixing to obtain a first mixed material, wherein the composite initiator is a mixture of cumene hydroperoxide and azobisisobutyronitrile according to a mass ratio of 1:0.6; secondly, filling inert gas into the reaction kettle, then placing the first mixed material into the reaction kettle, adding a molecular weight regulator, and uniformly mixing, wherein the mass ratio of the styrene to the molecular weight regulator is 100:2, performing radiation polymerization by using gamma rays with the radiation dose of 1500Gray, and obtaining a linear polystyrene prepolymer after polymerization; thirdly, adding a cross-linking agent into the linear polystyrene prepolymer and uniformly mixing to obtain a second mixed material, wherein the adding amount of the cross-linking agent is 10% of the mass of the linear polystyrene prepolymer; fourthly, irradiating the second mixed material with gamma rays with the irradiation dose of 50000Gray, and obtaining a crosslinked polystyrene material after irradiation; and fifthly, heating the crosslinked polystyrene material for 20 hours at the temperature of 80 ℃ to obtain the crosslinked polystyrene material of the solidified block. In example 5, the molecular weight of the linear polystyrene prepolymer obtained in the second step was 140000.
Example 6 as an optimization of the above example, the linear polystyrene prepolymer obtained in the second step has a molecular weight of 100000 to 150000.
Example 7, as an optimization of the above example, in the fourth step, gamma irradiation is performed in a sealed mold in which air is removed and inert gas is filled; the gamma-ray irradiation distance is 10cm to 30cm.
Example 8 as an optimization of the above example, in the fifth step, heating was performed in a sealed mold in which air was removed and inert gas was filled.
Example 9, as an optimization of the above example, the inert gas is nitrogen or argon; the molecular weight regulator is n-dodecyl mercaptan or alpha-methyl styrene linear dimer.
Example 10, as an optimization of the above examples, the crosslinking agent is glycidyl methacrylate or divinylbenzene.
The invention has the following beneficial effects:
(1) The crosslinked polystyrene block material prepared by adopting the method of initiating the bulk polymerization by gamma-ray irradiation generated by radioactive nuclide has the advantages that the generated polymer is pure and defect-free, no impurity is introduced, the mechanical properties of the material including tensile strength, bending strength and impact toughness are maintained, the insulating strength of the material is greatly improved, and the dielectric constant and dielectric loss coefficient of the material are reduced.
(2) The radiation crosslinking polymerization method can be carried out at normal temperature or low temperature, and is beneficial to controlling the heat emission; meanwhile, as gamma rays with high penetrability are adopted, the prepared material is not limited by thickness; the whole reaction process is free from stirring and heating, the operation is simple and convenient, and the prepared plate has no defects such as any pore, crack and the like.
(4) The radiation crosslinking polymerization method has simple preparation process, can be molded according to the requirement, and can be used as functional structural members such as high-voltage insulation devices, satellite communication windows, radomes and the like after being slightly processed.
The method has longer period of preparing the product, which is far longer than the half-life period of the initiator, so that the crosslinking degree of the system is not easy to control. The invention adopts the gamma-ray initiated crosslinking polymerization technology, and can well solve the problems.
The method for preparing the low-dielectric polystyrene cross-linked material by gamma-ray irradiation cross-linking polymerization expands the radiation polymerization-cross-linking field and has guiding significance for preparing other similar property materials; the invention aims to provide a method for preparing a crosslinked polystyrene material by a high-energy particle irradiation technology, which is characterized in that the molecular weight of a linear polystyrene prepolymer is controlled to be fully mixed with a crosslinking agent, and the gamma-ray irradiation intensity is controlled, so that the crosslinked polystyrene material with light and transparent quality and excellent performance can be prepared.
Test of dielectric Properties of crosslinked polystyrene Material obtained in example 5: the dielectric property test frequency ranges from 1GHz to 20GHz. The dielectric constant of the crosslinked polystyrene material is between 2.21 and 2.40 in the range of 1GHz and 11GHz and is in an ascending trend; rapidly decreasing to 2.10 in the range of 11GHz to 14 GHz; and thereafter remain in the range of 2.10 to 2.20. The dielectric loss of the crosslinked polystyrene material was reduced from 0.056 to 0.020 before 2 GHz; substantially stable in the range of 0.001 to 0.020 in the range of 2GHz to 9 GHz; thereafter, the dielectric loss fluctuates greatly due to the rise in frequency, reaching a maximum of 0.230 at 13.5 GHz. Experiments show that the material has excellent dielectric property and is a good material with low dielectric property.
Crosslinked polymers are insoluble in solvents due to their internal crosslinked network, but swell in a suitable solvent to some extent, depending on the degree of crosslinking of the internal network. In this example 5, the swelling degree of the prepared bulk material was 95% as measured by an equilibrium swelling method using toluene as a solvent, which indicates that a dense crosslinked network had been formed in the prepared bulk material. The test results of the equilibrium swelling method and the FTIR characteristic peak results are combined to show that the prepared material is a crosslinked polystyrene material.
The technical characteristics form the embodiment of the invention, have stronger adaptability and implementation effect, and can increase or decrease unnecessary technical characteristics according to actual needs so as to meet the requirements of different situations.
Claims (10)
1. A method for preparing a crosslinked polystyrene material by a high-energy particle irradiation technology is characterized by comprising the following steps: firstly, styrene and a composite initiator are mixed according to the mass ratio of 100:5 to 20, and obtaining a first mixed material, wherein the composite initiator is a mixture of cumene hydroperoxide and azobisisobutyronitrile according to a mass ratio of 1:0.6; secondly, filling inert gas into the reaction kettle, then placing the first mixed material into the reaction kettle, adding a molecular weight regulator, and uniformly mixing, wherein the mass ratio of the styrene to the molecular weight regulator is 100:0.8 to 3, and carrying out irradiation polymerization by using gamma rays with the irradiation dose of 1500Gray, so as to obtain a linear polystyrene prepolymer after polymerization; thirdly, adding a cross-linking agent into the linear polystyrene prepolymer and uniformly mixing to obtain a second mixed material, wherein the adding amount of the cross-linking agent is 5-20% of the mass of the linear polystyrene prepolymer; fourthly, irradiating the second mixed material with gamma rays with the irradiation dose of 1200Gray to 65000Gray, and obtaining a crosslinked polystyrene material after irradiation; and fifthly, heating the crosslinked polystyrene material for 10 to 20 hours at the temperature of 40 to 100 ℃ to obtain the crosslinked polystyrene material of the solidified block after heating.
2. The method for preparing a crosslinked polystyrene material according to claim 1, wherein the linear polystyrene prepolymer obtained in the second step has a molecular weight of 100000 to 150000.
3. The method for preparing a crosslinked polystyrene material according to the high-energy particle irradiation technique of claim 1 or 2, characterized in that in the fourth step, gamma irradiation is performed in a sealed mold in which air is removed and inert gas is filled; the gamma-ray irradiation distance is 10cm to 30cm.
4. The method for producing a crosslinked polystyrene material according to claim 1 or 2, characterized in that in the fifth step, heating is performed in a sealed mold in which air is removed and inert gas is filled.
5. A method for producing a crosslinked polystyrene material by high-energy particle irradiation technique according to claim 3, characterized in that in the fifth step, heating is performed in a sealed mold in which air is removed and inert gas is filled.
6. The method for preparing a crosslinked polystyrene material according to claim 1 or 2, characterized in that the inert gas is nitrogen or argon; the molecular weight regulator is n-dodecyl mercaptan or alpha-methyl styrene linear dimer.
7. A method for preparing a crosslinked polystyrene material by high-energy particle irradiation technique according to claim 3, characterized in that the inert gas is nitrogen or argon; the molecular weight regulator is n-dodecyl mercaptan or alpha-methyl styrene linear dimer.
8. The method for preparing a crosslinked polystyrene material by the high-energy particle irradiation technique according to claim 5, wherein the inert gas is nitrogen or argon; the molecular weight regulator is n-dodecyl mercaptan or alpha-methyl styrene linear dimer.
9. The method for preparing a crosslinked polystyrene material by the high-energy particle irradiation technique according to claim 1 or 2, characterized in that the crosslinking agent is glycidyl methacrylate or divinylbenzene.
10. The method for preparing a crosslinked polystyrene material by using the high-energy particle irradiation technology according to claim 8, wherein the crosslinking agent is glycidyl methacrylate or divinylbenzene.
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