CN114349906B - Super-crosslinked polystyrene and preparation method thereof - Google Patents
Super-crosslinked polystyrene and preparation method thereof Download PDFInfo
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 97
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 98
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 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 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 11
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 11
- 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
- 239000002131 composite material Substances 0.000 claims description 4
- 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
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- -1 dicarbonic acid peroxide Chemical class 0.000 claims description 2
- 229920005669 high impact polystyrene Polymers 0.000 claims description 2
- 239000004797 high-impact polystyrene Substances 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
- 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 claims 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 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
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- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 4
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- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 125000005442 diisocyanate group Chemical group 0.000 description 1
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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 is 0.05-10% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the initiator accounts for 0.001-3% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the auxiliary agent accounts for 0-10% of the sum of the mass of the styrene and the mass of 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 super-crosslinked polystyrene and a preparation method thereof.
Background
Polystyrene is a product obtained by the polyaddition of styrene monomers, and belongs to a nonpolar polymer. The conventional synthetic methods of polystyrene include bulk polymerization, suspension polymerization, and the like. Polystyrene has excellent electric and optical properties, and has high volume resistivity and surface resistivity of 10 16 ～10 18 Omega cm and 10 15 ～10 18 Omega cm; the dielectric loss tangent of polystyrene is extremely low and is not affected by frequency and ambient temperature; the light transmittance is more than 88-92%, and the optical property and the transparency are excellent. However, polystyrene has obvious performance defects, has poor heat resistance, tg of 80-105 ℃, continuous use temperature of about 60 ℃ and maximum inadequacy of 80 ℃; in addition, the product is easy to age under the conditions of heat, oxygen, impurities and atmosphere for a long time, and has lower surface hardness and limited application. For this reason, the properties are often improved by crosslinking, copolymerization or blending, etc., to expand the application range.
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 polystyrene, so that the obtained product has better performance, thereby better meeting the market and actual needs.
Disclosure of Invention
The technical problem solved by the invention is to provide the super-crosslinked polystyrene and the preparation method thereof, so as to obtain a super-crosslinked polystyrene product with better performance.
The technical problems solved by the invention are 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 is 0.05-10% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the initiator accounts for 0.001-3% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the auxiliary agent accounts for 0-10% of the sum of the mass of the styrene and the mass of the polystyrene.
Further, the polystyrene includes one or two of general-purpose polystyrene and high-impact polystyrene; the polystyrene comprises one or both of granular polystyrene or powdered polystyrene.
Further, the crosslinking agent comprises at least two of divinylbenzene, N-methylolacrylamide, N-methylenebisacrylamide, allyl methacrylate, diisocyanate, triallyl isocyanurate.
Further, the initiator comprises at least two of azodiisoheptonitrile, azodiisobutyronitrile, tert-butyl peroxybenzoate, dilauroyl peroxide, peroxydicarbonate, 4-tert-butylcyclohexyl ester and tert-butyl peroxy-2-ethylhexanoate.
Further, the initiator consists of azodiisoheptonitrile, azodiisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate, wherein the mass ratio of the azodiisoheptonitrile to the azodiisobutyronitrile to the tert-butyl peroxybenzoate to 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.
The preparation process of super cross-linked polystyrene includes the following steps:
1) Fully dissolving the styrene, the polystyrene, the cross-linking agent and the auxiliary agent, adding an initiator, uniformly stirring, and then carrying out polymerization reaction in a reaction container to obtain a prepolymer after the polymerization reaction is completed;
2) Injecting the prepolymer into a mold, curing the mold and the prepolymer together, wherein the curing adopts a water bath heating mode, and taking the blank out of the mold when the prepolymer in the mold is cured and molded to form the blank, and then transferring the blank into an oven for curing treatment, wherein the curing treatment temperature is 60-130 ℃.
Further, in the step 1), the stirring treatment is performed in a vacuum environment having a vacuum degree of more than-0.08 MPa. Under the condition, air bubbles in the prepolymer can be eliminated, and bubbles generated in the later curing process are avoided, so that the performance of the blank body is more stable.
Further, in the step 2), the temperature of water bath heating is 15-50 ℃ during curing treatment. The temperature of the water bath is controlled by a program in the heating process, and the prepolymer is completely solidified.
Further, in the step 2), during curing treatment, the blank is firstly baked for 8-12 hours under the temperature of 60 ℃ in an oven, then is baked again for 12-24 hours under the temperature of 80 ℃, is baked for 24-48 hours under the temperature of 100 ℃ after the re-baking is finished, is baked for 24-48 hours under the temperature of 130 ℃, is taken out after the baking is finished, and is cooled to room temperature. The slower the polymerization reaction in the curing stage is, the slower the later reaction is, and the low molecular weight substances in the green body can be fully reacted by a curing mode of gradually and gradiently heating, so that the heat resistance, the surface hardness and the ageing resistance of the product are further improved. The beneficial effects are that: the super-crosslinked polystyrene has extremely low dielectric loss, excellent insulativity, dielectric loss tangent less than 0.0008 and surface resistivity more than 10 15 Omega cm, volume resistivity > 10 16 Omega 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 light and the bending light are excellent, the mechanical processing is good, the processing such as milling and drilling can be performed, meanwhile, the chemical stability is good, the heat resistance is good, the water absorption is less than 0.05%, and the comprehensive performance is excellent.
The super-crosslinked polystyrene adopts a composite crosslinking system, so that the crosslinking density of the super-crosslinked polystyrene is further improved, and particularly, the crosslinking agent is enabled to participate in polymerization reaction in the pre-polymerization stage, the viscosity of the pre-reaction system is low, the crosslinking agent is easier to disperse uniformly, and the crosslinking efficiency is higher. Meanwhile, an auxiliary agent with reactivity is added, so that brittleness and ageing resistance of the composite material are improved.
The super-crosslinked polystyrene of the invention has convenient operation, controllable and easily controlled key nodes, stable quality of the produced super-crosslinked polystyrene product, suitability for industrial production and popularization, strong practicability,
Detailed Description
In order that the manner in which the invention is attained, as well as the features and advantages thereof, will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Example 1
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 10:2; the content of the cross-linking agent is 3% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the auxiliary agent is 0.5% of the sum of the mass of the styrene and the mass of the polystyrene, and the content of the initiator is 0.2% of the sum of the mass of the styrene and the mass of the polystyrene. The initiator consists of azodiisoheptonitrile, azodiisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in the 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 butadiene oligomer.
The preparation method of the super crosslinked polystyrene comprises 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 performed in a vacuum environment with the vacuum degree of more than-0.08 MPa; uniformly stirring, and then carrying out polymerization reaction in a reaction container to obtain a prepolymer after the polymerization reaction is completed;
2) Injecting the prepolymer into a mold, carrying out curing treatment on the mold and the prepolymer together, wherein the initial temperature of the curing treatment is 33 ℃ in a water bath heating mode, when the mixed solution is separated from the edge of the mold and a green body is formed, raising the temperature of the water bath to 50 ℃, preserving heat for 48 hours, taking the green body out of the mold, transferring the green body into a baking oven for curing treatment, baking the green body in the baking oven for 12 hours at 60 ℃, baking for 24 hours at 80 ℃, baking for 24 hours at 100 ℃, baking for 48 hours at 120 ℃, taking out and naturally cooling to room temperature after the baking is finished.
The product obtained in this example was a transparent solid with a density of 1.05g/cm 3 The dielectric constant is 2.49, the loss tangent value is less than 0.0008, the wave transmission rate is 99 percent, the electrical strength is more than 60MV/m, and the surface resistivity is more than 10 15 Omega cm, volume resistivity > 10 16 Omega cm, tensile strength > 45MPa, bending strength > 70MPa, vicat heat-resistant temperature is 120 ℃, rockwell hardness is 84HRM, water absorption rate is less than 0.05%, vacuum deflation rate is less than 0.002%, and using temperature range is-60-105 ℃. The product can be used in the fields 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-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 10:2; the content of the cross-linking agent is 3% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the auxiliary agent is 0.5% of the sum of the mass of the styrene and the mass of the polystyrene, and the content of the initiator is 0.2% of the sum of the mass of the styrene and the mass of the polystyrene. The initiator consists of azodiisoheptonitrile, azodiisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in the 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 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 with a density of 1.05g/cm 3 Dielectric constantThe number is 2.58, the loss tangent value is less than 0.0008, the wave transmission rate is 99%, the electrical strength is more than 60MV/m, and the surface resistivity is more than 10 15 Omega cm, volume resistivity > 10 16 Omega cm, tensile strength > 48MPa, bending strength > 73MPa, vicat heat-resistant temperature is 120 ℃, rockwell hardness is 84HRM, water absorption rate is less than 0.05, vacuum deflation rate is less than 0.002%, and using temperature is-60-108 ℃. The product can be used in the fields 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-crosslinked polystyrene comprises styrene, polystyrene, a crosslinking agent, an auxiliary agent and an initiator, wherein the mass ratio of the styrene to the polystyrene is 10:2; the content of the cross-linking agent is 5% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the auxiliary agent is 0.5% of the sum of the mass of the styrene and the mass of the polystyrene, and the content of the initiator is 0.2% of the sum of the mass of the styrene and the mass of the polystyrene. The initiator consists of azodiisoheptonitrile, azodiisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in the 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 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 with a density of 1.06g/cm 3 Dielectric constant of 2.56, loss tangent less than 0.0008, wave transmission rate of 99%, electric strength of > 60MV/m, and surface resistivity of > 10 15 Omega cm, volume resistivity > 10 16 Omega cm, tensile strength > 53MPa, bending strength > 79MPa, vicat heat-resistant temperature is 125 ℃, rockwell hardness is 90HRM, water absorption rate is less than 0.05, vacuum deflation rate is less than 0.002%, and using temperature range is-60 ℃ to 119 ℃. The product can be used for radar antenna, military communication satellite antenna window, missile antenna housing,The manufacturing fields of high-end devices such as a guidance system room sonar converter, a high-frequency coaxial connector, a high-frequency circuit board substrate, a single-mode fiber plug, a high-power pulse vacuum insulator and the like.
Example 4
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 10:2; the content of the cross-linking agent is 5% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the auxiliary agent is 3% of the sum of the mass of the styrene and the mass of the polystyrene, and the content of the initiator is 0.2% of the sum of the mass of the styrene and the mass of the polystyrene. The initiator consists of azodiisoheptonitrile, azodiisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in the 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 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 with a density of 1.06g/cm 3 The dielectric constant is 2.51, the loss tangent value is less than 0.0008, the wave transmission rate is 99 percent, the electrical strength is more than 60MV/m, and the surface resistivity is more than 10 15 Ohm cm, volume resistivity > 10 16 Ohm cm, tensile strength > 55MPa, bending strength > 80MPa, vicat heat-resistant temperature is 120 ℃, rockwell hardness is 88HRM, water absorption rate is less than 0.05, vacuum air release rate is less than 0.002%, and using temperature is-60-105 ℃. The product can be used in the fields 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 raw material of the super-crosslinked polystyrene in the embodiment does not comprise an auxiliary agent, and only comprises styrene, polystyrene, a crosslinking agent and an initiator, wherein the mass ratio of the styrene to the polystyrene is 10:2; the content of the cross-linking agent is 3% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the initiator is 0.2 percent of the sum of the mass of the styrene and the mass of the polystyrene. The initiator consists of azodiisoheptonitrile, azodiisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in the mass ratio of 1:1:1:1.
Furthermore, the crosslinking agent consists of divinylbenzene and triallyl isocyanurate in a mass ratio of 1:1.
The preparation method of the super crosslinked polystyrene comprises the following steps:
1) Fully dissolving the styrene, the polystyrene and the crosslinking agent, then adding an initiator, and uniformly stirring, wherein the stirring is performed in a vacuum environment with the vacuum degree of more than-0.08 MPa; uniformly stirring, and then carrying out polymerization reaction in a reaction container to obtain a prepolymer after the polymerization reaction is completed;
2) Injecting the prepolymer into a mold, carrying out curing treatment on the mold and the prepolymer together, wherein the initial temperature of the curing treatment is 33 ℃ in a water bath heating mode, when the mixed solution is separated from the edge of the mold and a green body is formed, raising the temperature of the water bath to 50 ℃, preserving heat for 48 hours, taking the green body out of the mold, transferring the green body into a baking oven for curing treatment, baking the green body in the baking oven at 60 ℃ for 12 hours, baking the green body at 80 ℃ for 12 hours, baking the green body at 100 ℃ for 12 hours, baking the green body at 130 ℃ for 12 hours, and taking the green body out after the baking is finished and naturally cooling the green body to room temperature.
The product obtained in this example has a density of 1.05g/cm 3 The Vicat heat-resistant temperature is 110 ℃ and the Rockwell hardness is 72HRM. The product does not reach the standard.
Comparative example 2
The raw material of the super-crosslinked polystyrene in the embodiment does not comprise a crosslinking agent, and only comprises 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 is 0.2 percent of the sum of the mass of the styrene and the mass of the polystyrene. The initiator consists of azodiisoheptonitrile, azodiisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate in the mass ratio of 1:1:1:1.
The preparation method of the super crosslinked polystyrene comprises the following steps:
1) Fully dissolving the styrene, the polystyrene and the auxiliary agent, then adding an initiator, and uniformly stirring, wherein the stirring is performed in a vacuum environment with the vacuum degree of more than-0.08 MPa; uniformly stirring, and then carrying out polymerization reaction in a reaction container to obtain a prepolymer after the polymerization reaction is completed;
2) 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, the initial temperature of water bath heating is 33 ℃, when the mixed solution is separated from the edge of the mold and a green body is formed, the water bath temperature is raised to 50 ℃, the green body is taken out of the mold after heat preservation is carried out for 48 hours, the green body is further transferred into a baking oven for curing treatment, the green body is baked for 12 hours at 60 ℃ in the baking oven and for 12 hours at 80 ℃, baked for 12 hours at 100 ℃, and the green body is taken out and naturally cooled to room temperature after the baking is finished. The product obtained in this example has a density of 1.04g/cm 3 The tensile strength is more than 42MPa, the bending strength is more than 65MPa, the Vicat heat-resistant temperature is 110 ℃, and the Rockwell hardness is 70HRM. 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 super crosslinked polystyrene comprises 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 performed in a vacuum environment with the vacuum degree of more than-0.08 MPa; and (3) uniformly stirring, and then carrying out polymerization reaction in a reaction container, wherein a prepolymer is obtained after the polymerization reaction is completed.
2) Injecting the prepolymer into a mold, curing the mold and the prepolymer together, wherein the curing adopts a constant-temperature water bath heating mode, the water bath temperature is 30 ℃, the blank is taken out of the mold after heat preservation is carried out for 48 hours, then the blank is transferred into a baking oven for curing, and when the curing is carried out, the blank is baked for 12 hours at 60 ℃ in the baking oven and baked for 24 hours at 80 ℃, and then the blank is taken out and naturally cooled to room temperature after the baking is finished.
The product obtained in this example has a density of 1.05g/cm 3 The tensile strength is less than 45MPa, the bending strength is less than 60MPa, the Vicat heat-resistant temperature is 105 ℃, and the Rockwell hardness is 62HRM. The product does not reach the standard.
The foregoing has shown and described the basic principles, principal 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, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The super-crosslinked polystyrene is characterized in that,
the modified styrene-polystyrene composite material comprises styrene, polystyrene, a cross-linking agent, an initiator and an auxiliary agent, wherein the mass ratio of the styrene to the polystyrene is 10:2-5; the content of the cross-linking agent is 0.05-10% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the initiator is 0.001-3% of the sum of the mass of the styrene and the mass of the polystyrene; the content of the auxiliary agent is 0.5-10% of the sum of the mass of the styrene and the mass of the polystyrene;
the auxiliary comprises butadiene oligomer or combination of butadiene oligomer and alpha-methyl styrene oligomer;
the preparation method of the super-crosslinked 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, and then carrying out polymerization reaction in a reaction container to obtain a prepolymer after the polymerization reaction is completed;
2) Injecting the prepolymer into a mold, curing the mold and the prepolymer together, wherein the curing adopts a water bath heating mode, and taking out the blank from the mold when the prepolymer in the mold is cured and molded to form the blank, and then transferring the blank into an oven for curing treatment, wherein the curing treatment temperature is 60-130 ℃;
and (3) during curing treatment, the blank is firstly subjected to primary baking for 8-12 hours at the temperature of 60 ℃ in a baking oven, then subjected to secondary baking for 12-24 hours at the temperature of 80 ℃, continuously subjected to baking for 24-48 hours at the temperature of 100 ℃ after the secondary baking is finished, further subjected to baking for 24-48 hours at the temperature of 130 ℃, taken out after the baking is finished, and cooled to room temperature.
2. The super crosslinked polystyrene according to claim 1, wherein the polystyrene comprises one or both of general purpose polystyrene and high impact polystyrene; the polystyrene comprises one or both of granular polystyrene or powdered polystyrene.
3. The super crosslinked polystyrene according to claim 1, wherein the crosslinking agent comprises at least two of divinylbenzene, N-methylenebisacrylamide, allyl methacrylate, triallyl isocyanurate.
4. The super crosslinked polystyrene according to claim 1, wherein the initiator comprises at least two of azobisisoheptonitrile, azobisisobutyronitrile, t-butyl peroxybenzoate, dilauroyl peroxide, dicarbonic acid peroxide, t-butyl peroxy-2-ethylhexanoate.
5. The super crosslinked polystyrene according to claim 4, wherein the initiator consists of azobisisoheptonitrile, azobisisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate, and the mass ratio of azobisisoheptonitrile, azobisisobutyronitrile, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate is 1:1:1.
6. The super crosslinked polystyrene according to claim 1, wherein in step 1), the stirring treatment is performed in a vacuum atmosphere having a vacuum degree of more than 0.08 MPa.
7. The super crosslinked polystyrene according to claim 1, wherein in the step 2), the temperature of heating in a water bath is 15 to 50 ℃ during the curing treatment.
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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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| 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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