CN114349906A - Super cross-linked polystyrene and preparation method thereof - Google Patents
Super cross-linked polystyrene and preparation method thereof Download PDFInfo
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- CN114349906A CN114349906A CN202210034642.8A CN202210034642A CN114349906A CN 114349906 A CN114349906 A CN 114349906A CN 202210034642 A CN202210034642 A CN 202210034642A CN 114349906 A CN114349906 A CN 114349906A
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 98
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000003999 initiator Substances 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 31
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 10
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 2
- -1 4-tert-butylcyclohexyl ester Chemical class 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920005669 high impact polystyrene Polymers 0.000 claims 1
- 239000004797 high-impact polystyrene Substances 0.000 claims 1
- 238000004891 communication Methods 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 5
- 239000012212 insulator Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000005452 bending Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 5
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000010943 off-gassing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
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- 239000000126 substance Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- 229920006113 non-polar polymer Polymers 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The super-crosslinked polystyrene comprises styrene, polystyrene, a crosslinking agent, an initiator and an auxiliary agent, wherein the mass ratio of the styrene to the polystyrene is 10: 0-5; the content of the cross-linking agent accounts for 0.05-10% of the mass sum of the styrene and the polystyrene; the content of the initiator accounts for 0.001-3% of the mass sum of the styrene and the polystyrene; the content of the auxiliary agent accounts for 0-10% of the mass sum of the styrene and the polystyrene. The super-crosslinked polystyrene product prepared by the method has excellent comprehensive performance, and can be applied to radar antennas, military communication satellite antenna windows, missile radomes, guidance system room sonar converters, high-frequency coaxial connectors, high-frequency circuit board substrates, single-mode fiber plugs, high-power pulse vacuum insulators and the like.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a super-crosslinked polystyrene and a preparation method thereof.
Background
Polystyrene is a product of addition polymerization of styrene monomer, and belongs to a non-polar polymer. Conventional methods for synthesizing polystyrene include bulk polymerization, suspension polymerization, and the like. The polystyrene has excellent electrical and optical properties, and has high volume resistivity and surface resistivity which are respectively 1016～1018Omega cm and 1015～1018Omega cm; the dielectric loss tangent value of the polystyrene is extremely low and is not influenced by frequency and ambient temperature; the light transmittance is more than 88-92%, and the product has excellent optical performance and transmittanceThe nature is clear. But the polystyrene has obvious performance defects, the heat resistance is poor, the Tg is 80-105 ℃, the continuous use temperature is about 60 ℃, and the maximum temperature is not more than 80 ℃; in addition, the coating is easy to age under the conditions of heat, oxygen, impurities and atmosphere for a long time, and the coating has low surface hardness and limited application. Therefore, the performance is improved and the application range is enlarged by methods such as crosslinking, copolymerization or blending.
The invention aims to further optimize the raw material formula and the production process on the basis of not changing the excellent dielectric property and optical property of the polystyrene, so that the obtained product has better performance, thereby better meeting the market and actual needs.
Disclosure of Invention
The invention aims to provide a super cross-linked polystyrene and a preparation method thereof so as to obtain a super cross-linked polystyrene product with better performance.
The technical problem solved by the invention is realized by adopting the following technical scheme:
the super-crosslinked polystyrene comprises styrene, polystyrene, a crosslinking agent, an initiator and an auxiliary agent, wherein the mass ratio of the styrene to the polystyrene is 10: 0-5; the content of the cross-linking agent accounts for 0.05-10% of the mass sum of the styrene and the polystyrene; the content of the initiator accounts for 0.001-3% of the mass sum of the styrene and the polystyrene; the content of the auxiliary agent accounts for 0-10% of the mass sum of the styrene and the polystyrene.
Further, the polystyrene comprises one or two of general purpose polystyrene and impact resistant polystyrene; the polystyrene comprises one or two of granular polystyrene or powdery polystyrene.
Further, the crosslinking agent comprises divinyl benzene, N-methylol acrylamide, N-methylene bisacrylamide, allyl methacrylate, diisocyanate and at least two of triallyl isocyanurate.
Further, the initiator includes at least two of azobisisoheptonitrile, azobisisobutyronitrile, t-butyl peroxybenzoate, dilauroyl peroxide, peroxydicarbonate, 4-t-butylcyclohexyl ester, t-butylperoxy-2-ethylhexanoate.
Further, the initiator consists of azobisisoheptonitrile, azobisisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate, and the mass ratio of the azobisisoheptonitrile, the azobisisobutyronitrile, the tert-butyl peroxybenzoate and the tert-butyl peroxy-2-ethylhexanoate is 1:1:1: 1.
Further, the auxiliary agent comprises one or two of alpha-methyl styrene oligomer and butadiene oligomer.
A method for preparing the hypercrosslinked polystyrene comprises the following steps:
1) fully dissolving the styrene, the polystyrene, the cross-linking agent and the auxiliary agent, adding an initiator, uniformly stirring, carrying out polymerization reaction in a reaction container, and obtaining a prepolymer after the polymerization reaction is finished;
2) and injecting the prepolymer into a mold, carrying out curing treatment on the mold and the prepolymer together, wherein the curing treatment adopts a water bath heating mode, taking the blank out of the mold when the prepolymer in the mold is cured and molded to form a blank, and then transferring the blank into an oven for curing treatment, wherein the temperature of the curing treatment is 60-130 ℃.
Further, in the step 1), the stirring treatment is carried out in a vacuum environment with the vacuum degree of more than-0.08 MPa. Under the condition, air bubbles in the prepolymer can be eliminated, bubbles generated in the later curing process are avoided, and the blank body performance is more stable.
Further, in the step 2), the temperature of water bath heating is 15-50 ℃ during curing treatment. And controlling the temperature by adopting a program in the water bath heating process until the prepolymer is completely cured.
Further, in the step 2), during curing treatment, the blank is primarily baked in an oven at the temperature of 60 ℃ for 8-12 hours, then is baked again at 80 ℃ for 12-24 hours, and is continuously baked at 100 ℃ for 24-48 hours after the baking is finished, and then is baked at 130 ℃ for 24-48 hours, and is taken out after the baking is finished, and then is cooled to room temperature.The polymerization reaction in the aging stage is slower toward the later stage, and the low molecular weight substances in the green body can be further sufficiently reacted by an aging method of raising the temperature in a stepwise gradient manner, thereby further improving the heat resistance, surface hardness and aging resistance of the product. Has the advantages that: the super-crosslinked polystyrene has extremely low dielectric loss and excellent insulativity, the dielectric loss tangent value is less than 0.0008, and the surface resistivity is more than 1015Omega cm, volume resistivity > 1016Omega cm; tg is more than 120 ℃, the electrical strength reaches 60MV/m, and the surface hardness and the aging resistance are better; the mechanical strength is excellent, the tensile strength and the bending strength are excellent, the mechanical processing is good, the processing such as milling, planing and drilling of a vehicle can be carried out, the chemical stability is good, the heat resistance is good, the water absorption rate is less than 0.05 percent, and the comprehensive performance is excellent.
The super-crosslinked polystyrene disclosed by the invention adopts a compound crosslinking system, so that the crosslinking density is further improved, and particularly, the crosslinking agent participates in the polymerization reaction in the early prepolymerization stage, the early reaction system is low in viscosity, the crosslinking agent is more easily dispersed and uniform, and the crosslinking efficiency is higher. Meanwhile, an auxiliary agent with reaction activity is added, so that the brittleness and the ageing resistance of the glass are improved.
The super-crosslinked polystyrene has convenient operation, controllable and easily-controlled key nodes, stable quality of the produced super-crosslinked polystyrene product, strong practicability and suitability for industrial production and popularization,
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
The super cross-linked polystyrene described in this embodiment includes styrene, polystyrene, a cross-linking agent, an initiator, and an auxiliary agent, where a mass ratio of styrene to polystyrene is 10: 2; the content of the cross-linking agent accounts for 3 percent of the total mass of the styrene and the polystyrene; the content of the auxiliary agent accounts for 0.5 percent of the mass sum of the styrene and the polystyrene, and the content of the initiator accounts for 0.2 percent of the mass sum of the styrene and the polystyrene. The initiator consists of azobisisoheptonitrile, azobisisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in a mass ratio of 1:1:1: 1. The cross-linking agent is composed of divinylbenzene and N, N-methylene bisacrylamide according to the mass ratio of 1: 1. The auxiliary agent is a butadiene oligomer.
The preparation method of the hypercrosslinked polystyrene described in this example includes the following steps:
1) fully dissolving the styrene, the polystyrene, the cross-linking agent and the auxiliary agent, then adding the initiator, and uniformly stirring, wherein the stirring is carried out in a vacuum environment with the vacuum degree of more than-0.08 MPa; after being uniformly stirred, the mixture is subjected to polymerization reaction in a reaction container, and a prepolymer is obtained after the polymerization reaction is finished;
2) injecting the prepolymer into a die, carrying out curing treatment on the die and the prepolymer together, wherein the curing treatment adopts a water bath heating mode, the initial temperature of the water bath heating is 33 ℃, when the mixed liquid is separated from the edge of the die and forms a blank, the water bath temperature is raised to 50 ℃, the blank is taken out of the die after the temperature is kept for 48 hours, then the blank is transferred into an oven for curing treatment, when the curing treatment is carried out, the blank is baked for 12 hours at 60 ℃ in the oven, baked for 24 hours at 80 ℃, baked for 24 hours at 100 ℃, baked for 48 hours at 120 ℃, and then taken out and naturally cooled to the room temperature after the baking is finished.
The product obtained in this example was a transparent solid in appearance and had a density of 1.05g/cm3Dielectric constant of 2.49, loss tangent of less than 0.0008, wave-transparent rate of 99%, electric strength of more than 60MV/m, and surface resistivity of more than 1015Omega cm, volume resistivity > 1016Omega cm, tensile strength more than 45MPa, bending strength more than 70MPa, Vicat heat-resistant temperature of 120 ℃, Rockwell hardness of 84HRM, water absorption rate less than 0.05%, vacuum outgassing rate less than 0.002%, and service temperature range of-60-105 ℃. The product can be used in the field of manufacturing high-end devices such as radar antennas, military communication satellite antenna windows, missile radomes, guidance system room sonar converters, high-frequency coaxial connectors, high-frequency circuit board substrates, single-mode fiber plugs, high-power pulse vacuum insulators and the like.
Example 2
The super cross-linked polystyrene described in this embodiment includes styrene, polystyrene, a cross-linking agent, an initiator, and an auxiliary agent, where a mass ratio of styrene to polystyrene is 10: 2; the content of the cross-linking agent accounts for 3 percent of the total mass of the styrene and the polystyrene; the content of the auxiliary agent accounts for 0.5 percent of the mass sum of the styrene and the polystyrene, and the content of the initiator accounts for 0.2 percent of the mass sum of the styrene and the polystyrene. The initiator consists of azobisisoheptonitrile, azobisisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in a mass ratio of 1:1:1: 1. The cross-linking agent is composed of divinylbenzene and N, N-methylene bisacrylamide according to the mass ratio of 1: 1. The auxiliary agent is composed of butadiene oligomer and alpha-methyl styrene oligomer according to the mass ratio of 1: 1.
The preparation conditions were the same as in example 1.
The product obtained in this example was a transparent solid in appearance and had a density of 1.05g/cm3Dielectric constant of 2.58, loss tangent of less than 0.0008, wave-transparent rate of 99%, electric strength of more than 60MV/m, and surface resistivity of more than 1015Omega cm, volume resistivity > 1016Omega cm, tensile strength more than 48MPa, bending strength more than 73MPa, Vicat heat-resistant temperature of 120 ℃, Rockwell hardness of 84HRM, water absorption rate less than 0.05, vacuum outgassing rate less than 0.002 percent, and use temperature range of-60-108 ℃. The product can be used in the field of manufacturing high-end devices such as radar antennas, military communication satellite antenna windows, missile radomes, guidance system room sonar converters, high-frequency coaxial connectors, high-frequency circuit board substrates, single-mode fiber plugs, high-power pulse vacuum insulators and the like.
Example 3
The super cross-linked polystyrene described in this embodiment includes styrene, polystyrene, a cross-linking agent, an auxiliary agent, and an initiator, wherein the mass ratio of styrene to polystyrene is 10: 2; the content of the cross-linking agent accounts for 5 percent of the total mass of the styrene and the polystyrene; the content of the auxiliary agent accounts for 0.5 percent of the mass sum of the styrene and the polystyrene, and the content of the initiator accounts for 0.2 percent of the mass sum of the styrene and the polystyrene. The initiator consists of azobisisoheptonitrile, azobisisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in a mass ratio of 1:1:1: 1. The cross-linking agent is composed of divinylbenzene and N, N-methylene bisacrylamide according to the mass ratio of 1: 1. The auxiliary agent is composed of butadiene oligomer and alpha-methyl styrene oligomer according to the mass ratio of 1: 1.
The preparation conditions were the same as in example 1.
The product obtained in this example was a transparent solid in appearance and had a density of 1.06g/cm3Dielectric constant of 2.56, loss tangent of less than 0.0008, wave-transparent rate of 99%, electric strength of more than 60MV/m, and surface resistivity of more than 1015Omega cm, volume resistivity > 1016Omega cm, tensile strength more than 53MPa, bending strength more than 79MPa, Vicat heat-resistant temperature of 125 ℃, Rockwell hardness of 90HRM, water absorption rate less than 0.05, vacuum outgassing rate less than 0.002 percent, and use temperature range of-60-119 ℃. The product can be used in the field of manufacturing high-end devices such as radar antennas, military communication satellite antenna windows, missile radomes, guidance system room sonar converters, high-frequency coaxial connectors, high-frequency circuit board substrates, single-mode fiber plugs, high-power pulse vacuum insulators and the like.
Example 4
The hypercrosslinked polystyrene described in this embodiment includes styrene, polystyrene, a crosslinking agent, an initiator and an auxiliary agent, wherein the mass ratio of styrene to polystyrene is 10: 2; the content of the cross-linking agent accounts for 5 percent of the total mass of the styrene and the polystyrene; the content of the auxiliary agent accounts for 3% of the mass sum of the styrene and the polystyrene, and the content of the initiator accounts for 0.2% of the mass sum of the styrene and the polystyrene. The initiator consists of azobisisoheptonitrile, azobisisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in a mass ratio of 1:1:1: 1. The cross-linking agent is composed of divinylbenzene and N, N-methylene bisacrylamide according to the mass ratio of 1: 1. The auxiliary agent is composed of butadiene oligomer and alpha-methyl styrene oligomer according to the mass ratio of 1: 1.
The preparation conditions were the same as in example 1.
The product obtained in this example had a clear appearanceBright solid, density 1.06g/cm3Dielectric constant of 2.51, loss tangent of less than 0.0008, wave-transparent rate of 99%, electric strength of more than 60MV/m, and surface resistivity of more than 1015Ohm cm, volume resistivity > 1016Ohm cm, tensile strength more than 55MPa, bending strength more than 80MPa, Vicat heat-resistant temperature 120 ℃, Rockwell hardness 88HRM, water absorption less than 0.05, vacuum outgassing rate less than 0.002 percent, and use temperature range of-60-105 ℃. The product can be used in the field of manufacturing high-end devices such as radar antennas, military communication satellite antenna windows, missile radomes, guidance system room sonar converters, high-frequency coaxial connectors, high-frequency circuit board substrates, single-mode fiber plugs, high-power pulse vacuum insulators and the like.
Comparative example 1
The super cross-linked polystyrene raw material does not comprise an auxiliary agent, and only comprises styrene, polystyrene, a cross-linking agent and an initiator, wherein the mass ratio of the styrene to the polystyrene is 10: 2; the content of the cross-linking agent accounts for 3 percent of the total mass of the styrene and the polystyrene; the content of the initiator accounts for 0.2 percent of the total mass of the styrene and the polystyrene. The initiator consists of azobisisoheptonitrile, azobisisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in a mass ratio of 1:1:1: 1.
In addition, the crosslinking agent consists of divinylbenzene and triallyl isocyanurate in a mass ratio of 1: 1.
The preparation method of the hypercrosslinked polystyrene described in this example includes the following steps:
1) fully dissolving the styrene, the polystyrene and the cross-linking agent, adding an initiator, and uniformly stirring, wherein the stirring is carried out in a vacuum environment with the vacuum degree of more than-0.08 MPa; after being uniformly stirred, the mixture is subjected to polymerization reaction in a reaction container, and a prepolymer is obtained after the polymerization reaction is finished;
2) injecting the prepolymer into a die, carrying out curing treatment on the die and the prepolymer together, wherein the curing treatment adopts a water bath heating mode, the initial temperature of the water bath heating is 33 ℃, when the mixed liquid is separated from the edge of the die and forms a blank, the water bath temperature is raised to 50 ℃, the blank is taken out of the die after the temperature is kept for 48 hours, then the blank is transferred into an oven for curing treatment, when the curing treatment is carried out, the blank is baked for 12 hours at 60 ℃ in the oven, baked for 12 hours at 80 ℃, baked for 12 hours at 100 ℃, baked for 12 hours at 130 ℃, and then taken out and naturally cooled to the room temperature after the baking is finished.
The density of the product obtained in this example was 1.05g/cm3The Vicat temperature is 110 ℃ and the Rockwell hardness is 72 HRM. The product does not reach the standard.
Comparative example 2
The super cross-linked polystyrene raw material does not include a cross-linking agent, and only includes styrene, polystyrene, an initiator and an auxiliary agent, wherein the mass ratio of the styrene to the polystyrene is 10: 2; the content of the initiator accounts for 0.2 percent of the total mass of the styrene and the polystyrene. The initiator consists of azobisisoheptonitrile, azobisisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in a mass ratio of 1:1:1: 1.
The preparation method of the hypercrosslinked polystyrene described in this example includes the following steps:
1) fully dissolving the styrene, the polystyrene and the auxiliary agent, then adding the initiator, and uniformly stirring, wherein the stirring is carried out in a vacuum environment with the vacuum degree of more than-0.08 MPa; after being uniformly stirred, the mixture is subjected to polymerization reaction in a reaction container, and a prepolymer is obtained after the polymerization reaction is finished;
2) injecting the prepolymer into a die, carrying out curing treatment on the die and the prepolymer together, wherein the curing treatment adopts a water bath heating mode, the initial temperature of the water bath heating is 33 ℃, when the mixed liquid is separated from the edge of the die and forms a blank, the water bath temperature is raised to 50 ℃, the blank is taken out of the die after the temperature is kept for 48 hours, then the blank is transferred into an oven for curing treatment, when the curing treatment is carried out, the blank is baked for 12 hours at 60 ℃ in the oven, baked for 12 hours at 80 ℃, baked for 12 hours at 100 ℃, and then taken out and naturally cooled to room temperature after the baking is finished. Product obtained in this example the product obtained in this example had a density of 1.04g/cm3Tensile strength greater than 42MPa, bending strength greater than 65MPa, and Vicat heat-resistant temperatureThe degree is 110 ℃ and the Rockwell hardness is 70 HRM. The product does not reach the standard.
Comparative example 3
The formulation described in this example is the same as in example 1.
The preparation method of the hypercrosslinked polystyrene described in this example includes the following steps:
1) fully dissolving the styrene, the polystyrene, the auxiliary agent and the cross-linking agent, then adding the initiator, and uniformly stirring, wherein the stirring is carried out in a vacuum environment with the vacuum degree of more than-0.08 MPa; and after the mixture is uniformly stirred, carrying out polymerization reaction in a reaction container to obtain a prepolymer after the polymerization reaction is finished.
2) And injecting the prepolymer into a mold, carrying out curing treatment on the mold and the prepolymer together, wherein the curing treatment adopts a constant-temperature water bath heating mode, the water bath temperature is 30 ℃, taking out the blank from the mold after heat preservation is carried out for 48 hours, further transferring the blank into an oven for curing treatment, baking the blank in the oven for 12 hours at the temperature of 60 ℃, baking for 24 hours at the temperature of 80 ℃, and taking out the blank after the baking is finished and naturally cooling to room temperature.
The density of the product obtained in this example was 1.05g/cm3The tensile strength is less than 45MPa, the bending strength is less than 60MPa, the Vicat heat-resisting temperature is 105 ℃, and the Rockwell hardness is 62 HRM. The product does not reach the standard.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The super-crosslinked polystyrene is characterized by comprising styrene, polystyrene, a crosslinking agent, an initiator and an auxiliary agent, wherein the mass ratio of the styrene to the polystyrene is 10: 0-5; the content of the cross-linking agent accounts for 0.05-10% of the mass sum of the styrene and the polystyrene; the content of the initiator accounts for 0.001-3% of the mass sum of the styrene and the polystyrene; the content of the auxiliary agent accounts for 0-10% of the mass sum of the styrene and the polystyrene.
2. The hypercrosslinked polystyrene as claimed in claim 1, wherein the polystyrene comprises one or both of general purpose polystyrene and high impact polystyrene; the polystyrene comprises one or two of granular polystyrene or powdery polystyrene.
3. The hypercrosslinked polystyrene as claimed in claim 1, wherein the crosslinking agent comprises at least two of divinylbenzene, N-methylolacrylamide, N-methylenebisacrylamide, allyl methacrylate, diisocyanate, and triallyl isocyanurate.
4. The hypercrosslinked polystyrene as claimed in claim 1, wherein said initiator comprises at least two of azobisisoheptonitrile, azobisisobutyronitrile, tert-butylperoxybenzoate, dilauroyl peroxide, peroxydicarbonate, 4-tert-butylcyclohexyl ester, tert-butylperoxy-2-ethylhexanoate.
5. The hypercrosslinked polystyrene as claimed in claim 4, wherein said initiator is composed of azobisisoheptonitrile, azobisisobutyronitrile, tert-butylperoxybenzoate and tert-butylperoxy-2-ethylhexanoate at a mass ratio of 1:1:1: 1.
6. The hypercrosslinked polystyrene as claimed in claim 1, wherein said coagent comprises one or both of alpha-methylstyrene oligomer and butadiene oligomer.
7. A method for preparing a hypercrosslinked polystyrene as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
1) fully dissolving the styrene, the polystyrene, the cross-linking agent and the auxiliary agent, adding an initiator, uniformly stirring, carrying out polymerization reaction in a reaction container, and obtaining a prepolymer after the polymerization reaction is finished;
2) and injecting the prepolymer into a mold, carrying out curing treatment on the mold and the prepolymer together, wherein the curing treatment adopts a water bath heating mode, taking the blank out of the mold when the prepolymer in the mold is cured and molded to form a blank, and then transferring the blank into an oven for curing treatment, wherein the temperature of the curing treatment is 60-130 ℃.
8. The method for preparing hypercrosslinked polystyrene as claimed in claim 7, wherein the stirring treatment in step 1) is performed in a vacuum atmosphere having a vacuum degree of more than 0.08 MPa.
9. The method for preparing hypercrosslinked polystyrene as claimed in claim 7, wherein the temperature of water bath heating is 15-50 ℃ during the curing treatment in step 2).
10. The preparation method of the super-crosslinked polystyrene as claimed in claim 7, wherein in the step 2), during curing treatment, the blank is primarily baked in an oven at a temperature of 60 ℃ for 8-12 h, then is baked again at 80 ℃ for 12-24 h, and is continuously baked at 100 ℃ for 24-48 h after the baking is finished, and then is baked at 130 ℃ for 24-48 h, and is taken out after the baking is finished, and then is cooled to room temperature.
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| CN102336872A (en) * | 2011-07-04 | 2012-02-01 | 武汉理工大学 | Method of preparing cross-linking type polystyrene material with low dielectric properties assisted by ultraviolet light |
| CN103012646A (en) * | 2013-01-07 | 2013-04-03 | 四川久信科技集团有限公司 | Crosslinked polystyrene, high-power pulse vacuum insulator and preparation method |
| CN103804811A (en) * | 2014-02-19 | 2014-05-21 | 北京化工大学 | Preparation method of high-melt strength polystyrene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102336872A (en) * | 2011-07-04 | 2012-02-01 | 武汉理工大学 | Method of preparing cross-linking type polystyrene material with low dielectric properties assisted by ultraviolet light |
| CN103012646A (en) * | 2013-01-07 | 2013-04-03 | 四川久信科技集团有限公司 | Crosslinked polystyrene, high-power pulse vacuum insulator and preparation method |
| CN103804811A (en) * | 2014-02-19 | 2014-05-21 | 北京化工大学 | Preparation method of high-melt strength polystyrene |
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