Styrene resin synthesis catalyst and application

Abstract

The application provides a styrene resin synthesis catalyst and application. The styrene resin synthesis catalyst comprises a metallocene catalyst; a cocatalyst selected from an oxygen-containing compound A and / or a compound B capable of reacting with a transition metal compound to form an ionic complex; and an oxygen-containing gas as shown in a general formula X w O y wherein X is selected from at least one of carbon, nitrogen and sulfur, and w and y are each an integer of 1-4. By adding the oxygen-containing gas in the catalyst system, the polymerization activity of the catalyst system is significantly improved in cooperation with the metallocene catalyst and the cocatalyst, and the content of residual metal elements in the styrene resin can be significantly reduced.

Description

Technical Field

[0001] This invention relates to the field of styrene-based resin preparation technology, and in particular to a styrene-based resin synthesis catalyst and its application. Background Technology

[0002] Styrene homopolymers can be classified into three types based on their stereoregularity: atactic, isotactic, and syndiotactic. Atactic polystyrene is an amorphous polymer with excellent electrical insulation, transparency, and chemical resistance, and a certain degree of mechanical strength. However, its biggest drawback is its brittleness, low impact resistance, and poor heat resistance. Isotactic polystyrene is a crystalline polymer with a melting point of around 240°C, but its slow crystallization rate makes it difficult to apply industrially. Syndiotactic polystyrene (sPS) is also a crystalline polymer with a melting point as high as 270°C, similar to the engineering plastic Nylon-66. It is a rare non-polar engineering plastic with characteristics such as fast crystallization rate, high crystallinity, and high mechanical strength, resulting in excellent dimensional stability, electrical insulation, heat resistance, chemical resistance, and moisture resistance. Since the successful synthesis of syndiotactic polystyrene using a metallocene catalytic system (metallocene catalyst + co-catalyst alkylaluminoxane MAO) in 1986, its preparation method has been a subject of great interest.

[0003] However, the production of sPS still faces a series of challenges, especially how to improve the polymerization activity, which is a very critical issue. Only by improving the polymerization activity to a certain level can the polymerization product be obtained in high yield and low cost, making industrialization possible. The polymerization activity is closely related to the choice of catalyst.

[0004] Currently, various modifications are made to monotitanium catalysts to improve their polymerization activity or alter their structure. However, there is no clear theoretical guidance on the relationship between catalyst structure and polymerization activity. Much of the research focuses on low-efficiency structural attempts, rather than developing highly active catalysts. Furthermore, many new catalyst structures have complex and costly synthetic routes, and the resulting catalysts do not guarantee high activity. This makes the development of new catalysts a high-risk and high-cost endeavor.

[0005] Therefore, if the polymerization activity of sPS can be improved by adding other components without changing the catalyst structure, this would be a very important and promising endeavor. Summary of the Invention

[0006] This invention aims to at least partially solve one of the technical problems in the prior art. Therefore, one object of this invention is to provide a styrene-based resin synthesis catalyst and its application.

[0007] In a first aspect, the present invention provides a styrene-based resin synthesis catalyst, the catalyst comprising: a metallocene catalyst; The cocatalyst is selected from oxygen-containing compound A and / or compound B, which can react with transition metal compounds to form ionic complexes; For example, the general formula X w O y The oxygen-containing gas shown is wherein X is selected from at least one of carbon, nitrogen, and sulfur, and w and y are integers from 1 to 4.

[0008] According to the above-described styrene-based resin synthesis catalyst of the present invention, by adding an oxygen-containing gas to the catalyst system, the polymerization activity of the catalyst system is significantly improved in synergy with the metallocene catalyst and the co-catalyst. Furthermore, without altering the structure of the metallocene catalyst, production costs can be effectively reduced simply by adding an inexpensive oxygen-containing gas, demonstrating significant economic value. The metal elements in the synthesized styrene-based resin mainly originate from the metal elements in the catalyst; adding an oxygen-containing gas can also significantly reduce the residual metal element content in the styrene-based resin.

[0009] Preferably, the oxygen-containing gas includes at least one of CO and CO2, more preferably CO2.

[0010] According to the above-described styrene-based resin synthesis catalyst of the present invention, the metallocene catalyst is of general formula R. 1 MU a-1 L b As shown, R 1 M is a π-ligand, selected from at least one metal from Groups 3 to 5 of the periodic table and lanthanide transition metals, U is a monoanion ligand, multiple Us may be the same or different, L is a Lewis base, a is the valence of M, b is 0, 1 or 2, and when there are multiple Ls, Ls may be the same or different.

[0011] In some embodiments of the present invention, R 1 The fused polycyclic cyclopentadienyl group is selected from substituted or unsubstituted cyclopentadienyl, (substituted) indenyl, or a polycyclic ring fused with a cyclopentadienyl group, at least one of which is a saturated ring.

[0012] In some embodiments of the present invention, the (substituted) indene group includes 4,5,6,7-tetrahydroindene, octahydrofluorenyl, 1,2,3,4-tetrahydrofluorenyl, 9-methyl-1,2,3,4-tetrahydrofluorenyl, 9-methyloctahydrofluorenyl, etc., preferably 4,5,6,7-tetrahydroindene.

[0013] As examples, 4,5,6,7-tetrahydroindene includes 1-methyl-4,5,6,7-tetrahydroindene; 2-methyl-4,5,6,7-tetrahydroindene; 1,2-dimethyl-4,5,6,7-tetrahydroindene; 1,3-dimethyl-4,5,6,7-tetrahydroindene; 1,2,3-trimethyl-4,5,6,7-tetrahydroindene; 1,2,3,4,5,6,7-heptamethyl-4,5,6,7-tetrahydroindene; 1,2,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindene; 1,3,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindene, etc.

[0014] In some embodiments of the present invention, the fused polycyclic cyclopentadienyl group, in which at least one of the polycyclic rings fused with the cyclopentadienyl group is a saturated ring, is selected from the groups shown in general formulas (i) to (iii). In the above formula, R 12 R 13 and R 14 Each R is selected from hydrogen atoms, halogen atoms, aliphatic hydrocarbon groups with 1 to 20 carbon atoms, aromatic hydrocarbon groups with 6 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, aryloxy groups with 6 to 20 carbon atoms, thioalkoxy groups with 1 to 20 carbon atoms, thioaryloxy groups with 6 to 20 carbon atoms, amino groups, amide groups, carboxyl groups, or alkylsilyl groups. 12 Each R 13 and each R 14 Each can be the same or different from the others. c, d, e, and f represent integers greater than 1.

[0015] Preferably, the fused polycyclic cyclopentadienyl group, in which at least one of the polycyclic rings with a cyclopentadienyl group is a saturated ring, is selected from the groups shown in general formulas (iv) to (vi). In the above formula, R 15 R 16 and R 17 Each is selected from hydrogen atoms or methyl groups, and each R 15 Each R 16 and each R 17 They can be the same or different.

[0016] In some embodiments of the present invention, M includes Group 3 metals such as scandium and yttrium, Group 4 metals such as titanium, zirconium, and hafnium, lanthanide transition metals, and Group 5 metals such as niobium and tantalum. Group 3 or Group 4 metals are preferred, scandium, yttrium, and titanium are more preferred, and titanium is even more preferred.

[0017] In some embodiments of the present invention, U is selected from hydrogen atoms, halogen atoms, aliphatic hydrocarbon groups with 1 to 20 carbon atoms, aromatic hydrocarbon groups with 6 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, aryloxy groups with 6 to 20 carbon atoms, thioalkoxy groups with 1 to 20 carbon atoms, thioaryloxy groups with 6 to 20 carbon atoms, amino groups, amide groups, carboxyl groups, and alkylsilyl groups, etc. Multiple U groups can be the same or different from each other, and can be bonded to each other via optional groups.

[0018] As an example, U can be selected from hydrogen atom, chlorine atom, bromine atom, iodine atom, methyl, benzyl, phenyl, trimethylsilylmethyl, methoxy, ethoxy, phenoxy, thiomethoxy, (phenylthio) group, dimethylamino, diisopropylamino, etc.

[0019] As a metallocene catalyst, R with the characteristics illustrated above can be preferably used. 1 Compounds of groups arbitrarily chosen from M and U.

[0020] As examples, metallocene catalysts include pentamethylcyclopentadienyl titanium trichloride, 1,2,3-trimethylindene titanium trichloride, 4,5,6,7-tetrahydroindene titanium trichloride, 4,5,6,7-tetrahydroindene trimethyl titanium, 4,5,6,7-tetrahydroindene tribenzyl titanium, 4,5,6,7-tetrahydroindene trimethoxy titanium, 1-methyl-4,5,6,7-tetrahydroindene titanium trichloride, 1-methyl-4,5,6,7-tetrahydroindene trimethyl titanium, 1-methyl-4,5,6,7-tetrahydroindene tribenzyl titanium, 1-methyl-4,5,6,7-tetrahydroindene trimethoxy titanium, 2-methyl-4,5,6,7-tetrahydroindene titanium trichloride, 2-methyl-4,5,6,7-tetrahydroindene trimethyl titanium, 2-methyl -4,5,6,7-Tetrahydroindenyltribenzyltitanium, 2-methyl-4,5,6,7-tetrahydroindenyltrimethoxytitanium, 1,2-dimethyl-4,5,6,7-tetrahydroindenyltrichloridetitanium, 1,2-dimethyl-4,5,6,7-tetrahydroindenyltrimethyltitanium, 1,2-dimethyl-4,5,6,7-tetrahydroindenyltribenzyltitanium, 1,2-dimethyl- 4,5,6,7-Tetrahydroindenetrimethoxytitanium, 1,3-dimethyl-4,5,6,7-tetrahydroindenetrichloridetitanium, 1,3-dimethyl-4,5,6,7-tetrahydroindenetrimethyltitanium, 1,3-dimethyl-4,5,6,7-tetrahydroindenetribenzyltitanium, 1,3-dimethyl-4,5,6,7-tetrahydroindenetrimethoxytitanium, 1,2,3- Trimethyl-4,5,6,7-tetrahydroindenyltitanium trichloride, 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltrimethyltitanium, 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltribenzyltitanium, 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltrimethoxytitanium, 1,2,3,4,5,6,7-heptamethyl-4,5 6,7-Tetrahydroindenetrichloride titanium, 1,2,3,4,5,6,7-heptamethyl-4,5,6,7-tetrahydroindenetrimethyltitanium, 1,2,3,4,5,6,7-heptamethyl-4,5,6,7-tetrahydroindenetribenzyltitanium, 1,2,3,4,5,6,7-heptamethyl-4,5,6,7-tetrahydroindenetrimethoxytitanium, 1,2,4 5,6,7-Hexamethyl-4,5,6,7-Tetrahydroindenetrichloride titanium, 1,2,4,5,6,7-Hexamethyl-4,5,6,7-Tetrahydroindenetrimethyltitanium, 1,2,4,5,6,7-Hexamethyl-4,5,6,7-Tetrahydroindenetribenzyltitanium, 1,2,4,5,6,7-Hexamethyl-4,5,6,7-Tetrahydroindenetrimethyltitanium Oxygenated titanium, 1,3,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyltitanium chloride, 1,3,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyltrimethyltitanium, 1,3,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyltribenzyltitanium, 1,3,4,5,6,7-hexamethyl-4,5,6...7-Tetrahydroindenyltrimethoxytitanium, octahydrofluorenyltrichloride titanium, octahydrofluorenyltrimethyltitanium, octahydrofluorenyltribenzyltitanium, octahydrofluorenyltrimethoxytitanium, 1,2,3,4-tetrahydrofluorenyltrichloride titanium, 1,2,3,4-tetrahydrofluorenyltrimethyltitanium, 1,2,3,4-tetrahydrofluorenyltribenzyltitanium, 1,2,3,4-tetrahydrofluorenyltrimethoxytitanium, 9-methyl-1,2,3,4-tetrahydrofluorenyltrichloride titanium, 9-methyl-1,2,3,4-tetrahydrofluorenyltrichloride titanium Methyltitanium, 9-methyl-1,2,3,4-tetrahydrofluorenyltribenzyltitanium, 9-methyl-1,2,3,4-tetrahydrofluorenyltrimethoxytitanium, 9-methyloctahydrofluorenyltrichloridetitanium, 9-methyloctahydrofluorenyltrimethyltitanium, 9-methyloctahydrofluorenyltribenzyltitanium, 9-methyloctahydrofluorenyltrimethoxytitanium, etc., and compounds in which titanium is replaced by zirconium or hafnium, or similar compounds of other group or lanthanide transition metal elements, but not limited thereto.

[0021] According to the above-described styrene-based resin synthesis catalyst of the present invention, compound A includes alkylaluminoxane compounds; and compound B includes boron compounds.

[0022] In some embodiments of the present invention, compound A is selected from compounds represented by general formula (c11) and / or general formula (c12). In the above general formulas (c11) and (c12), R 18 ~R 24 Each represents an alkyl group having 1 to 8 carbon atoms. Specifically, these can be: methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. R 18 ~R 22 They can be the same or different, R 23 and R 24 They can be the same or different. Z 1 ~Z 5 Each of these represents an element in group 13 of the periodic table. Specifically, examples include B, Al, Ga, In, and Tl. Among these, B and Al are suitable, with Al being more suitable. 1 ~Z 3 They can be the same or different, Z 4 and Z 5 They can be the same or different from each other. g, h, s, and t are each numbers from 0 to 50, and (g+h) and (s+t) are each greater than 1. As for g, h, s, and t, each is preferably in the range of 1 to 20, and particularly preferably in the range of 1 to 5.

[0023] In some embodiments of the present invention, compound A includes alkylaluminoxane compounds. As examples, alkylaluminoxane compounds include, but are not limited to, methylaluminoxane, methylisobutylaluminoxane, and isobutylaluminoxane.

[0024] In some embodiments of the present invention, compound B comprises a coordination complex or Lewis acid formed by multiple groups bonded to an anion and a cation of a metal. Various complexes exist as coordination complexes formed by multiple groups bonded to an anion and a cation of a metal.

[0025] In some embodiments of the present invention, compound B may include compounds of general formula (c21) or (c22), ([L 2 ] 1+ ) y ([M 3 X 3 u ] (u-v)- ) z (c21); ([L) 3 -H] 1+ )y([M 4 X 3 u ] (u-v)- )z(c22); In formula (c21) or (c22), L 2 M, as will be discussed later 5 R 25 R 26 M 6 Or R 27 3C, L 3 M is a Lewis base. 3 and M 4 Each is a metal selected from groups 5 through 15 of the periodic table. M 5 M represents metals selected from Groups 1 and 8 through 12 of the periodic table. 6 Metals selected from groups 8 to 10 of the periodic table. X 3 Each represents a hydrogen atom, dialkylamino, alkoxy, aryloxy, alkyl group with 1 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms, alkylaryl, aralkyl, substituted alkyl, organometallic group, or halogen atom. Multiple X's are included. 3 They can be the same or different. R 25 and R 26 Each represents cyclopentadienyl, substituted cyclopentadienyl, indenyl, or fluorenyl, R 27 Indicates alkyl or aryl. v indicates M. 3 M 4 The atomic valence is an integer from 1 to 7, u is an integer from 2 to 8, and i represents [L]. 2 ] and [L 3The valence of the -H ions is an integer from 1 to 7, y is an integer greater than or equal to 1, and z = y × i / (uv).

[0026] As M 3 and M 4 Specific examples could include B, Al, Si, P, As, or Sb, as M. 5 Specific examples could include Ag, Cu, Na, and Li, as M. 6 Specific examples could include Fe, Co, Ni, etc. As X 3 Specific examples include: dimethylamino, diethylamino, etc., as dialkylamino groups; methoxy, ethoxy, n-butoxy, etc., as alkoxy groups; phenoxy, 2,6-dimethylphenoxy, naphthoxy, etc., as aryloxy groups; methyl, ethyl, n-propyl, isopropyl, n-butyl, n-octyl, 2-ethylhexyl, etc., as alkyl groups having 1 to 20 carbon atoms; phenyl, p-tolyl, benzyl, pentafluorophenyl, 3,5-di(trifluoromethyl)phenyl, 4-tert-butylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4-dimethylphenyl, 1,2-dimethylphenyl, etc., as aryl, alkylaryl, or aralkyl groups having 6 to 20 carbon atoms; F, Cl, Br, I, as halogens; pentamethylantimonyl, trimethylsilyl, trimethylgermanyl, diphenylarsyl, dicyclohexylantimonyl, diphenylboryl, etc., as organometallic groups. As R 25 and R 26 Specific examples of substituted cyclopentadienyl groups include methylcyclopentadienyl, butylcyclopentadienyl, and pentamethylcyclopentadienyl.

[0027] As an example, B(C6F5)4 is a metal anion with multiple groups bonded to it. - B(C6HF4)4 - B(C6H2F3)4 - B(C6H3F2)4 - B(C6H4F)4 - B[C6(CF3)F4]4 - B(C6H5)4 - PF6 - P(C6F5)6 - Al(C6HF4)4 - Examples of metal cations include Cp₂Fe. + (MeCp)2Fe + 、( t BuCp)2Fe + (Me2Cp)2Fe + (Me3Cp)2Fe+ (Me4Cp)2Fe + (Me5Cp)2Fe + Ag + Na + Li + In the above formulas, Cp represents cyclopentadienyl, and Me represents methyl. t Bu represents tert-butyl. Other cations include: pyridinium, 2,4-dinitro-N,N-diethylphenylamine, diphenylamine, p-nitrophenylamine, 2,5-dichlorophenylamine, p-nitro-N,N-dimethylphenylamine, quinolineium, N,N-dimethylphenylamine, N,N-diethylphenylamine and other nitrogen-containing compounds, triphenylcarbium, tri(4-methylphenyl)carbium, tri(4-methoxyphenyl)carbium and other carbium compounds, CH3PH3 + C2H5PH3 + C3H7PH3 + (CH3)2PH2 + (C2H5)2PH2 + (C3H7)2PH2 + (CH3)3PH + (C2H5)3PH + (C3H7)3PH + (CF3)3PH + (CH3)4P + (C2H5)4P + (C3H7)4P + Alkylphosphonium ions and C6H5PH3 + (C6H5)2PH2 + (C6H5)3PH + (C6H5)4P + (C2H5)2(C6H5)PH + (CH3)(C6H5)PH2 + (CH3)2(C6H5)PH + (C2H5)2(C6H5)2P + Arylphosphonium ions, etc.

[0028] As examples, compounds of general formula (c21) include, but are not limited to, tetraphenylferrocene, tetra(pentafluorophenyl)borate dimethylferrocene, tetra(pentafluorophenyl)borate dimethylferrocene, tetra(pentafluorophenyl)borate decamethylferrocene, tetra(pentafluorophenyl)borate acetylferrocene, tetra(pentafluorophenyl)borate formylferrocene, tetra(pentafluorophenyl)borate cyanoferrocene, tetraphenylborate silver, tetra(pentafluorophenyl)borate silver, triphenylmethyltetraphenylborate, triphenylmethyltetra(pentafluorophenyl)borate, silver hexafluoroarsenate, silver hexafluoroantimonate, silver tetrafluoroborate, etc.

[0029] As examples, compounds of general formula (c22) include, but are not limited to, triethylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetra(pentafluorophenyl)borate, tri(n-butyl)ammonium tetra(pentafluorophenyl)borate, triethylammonium hexafluoroarsenate, pyridinium tetra(pentafluorophenyl)borate, pyrrolinium tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, methyldiphenylammonium tetra(pentafluorophenyl)borate, etc.

[0030] As examples, Lewis acids include, but are not limited to, B(C6F5)3, B(C6HF4)3, B(C6H2F3)3, B(C6H3F2)3, B(C6H4F)3, B(C6H5)3, BF3, B[C6(CF3)F4]3, PF5, P(C6F5)5, Al(C6HF4)3, etc.

[0031] In some embodiments of the present invention, the metallocene catalyst is considered as 1 mole, and the compound A is considered as 1-10000 moles of aluminum atoms, preferably 10-1000.

[0032] In some embodiments of the present invention, the compound B is calculated as 0.5-10 moles of boron atoms, preferably 0.8-5, based on 1 mole of the metallocene catalyst.

[0033] According to the above-described styrene-based resin synthesis catalyst of the present invention, it further includes compound C, said compound C being of general formula R. 2 p Al(OR 3 ) q X 1 2-p-q As shown in H, where R 2 and R 3 Each is selected from alkyl groups having 1-8 carbon atoms, X 1 For halogen atoms, 0 < p ≤ 2, 0 ≤ q < 2, and p + q ≤ 2.

[0034] Preferably, compound C is selected from dialkyl aluminum hydride compounds and monoalkyl aluminum hydride compounds.

[0035] As examples, compound C includes, but is not limited to, dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, and diisobutyl aluminum hydride; alkyl halide aluminum hydrides such as methyl aluminum chlorohydride, ethyl aluminum chlorohydride, n-propyl aluminum chlorohydride, isopropyl aluminum chlorohydride, n-butyl aluminum chlorohydride, and isobutyl aluminum chlorohydride; and alkylalkoxy aluminum hydrides such as ethyl methoxy aluminum hydride and ethyl ethoxy aluminum hydride. From the viewpoint of catalytic activity, diisobutyl aluminum hydride is preferred.

[0036] According to the above-described styrene-based resin synthesis catalyst of the present invention, it further includes compound D, said compound D being of general formula R. 4 m Al(OR 5 ) n X 2 3-m-n As shown, R 4 and R 5 Each is selected from alkyl groups having 1-8 carbon atoms, X 2 For halogen atoms, 0 < m ≤ 3, 0 ≤ n < 3, and m + n ≤ 3.

[0037] Preferably, compound D is selected from trialkylaluminum and dialkylaluminum compounds.

[0038] As an example, compound D includes, but is not limited to, trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, and triisobutylaluminum; dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, and diisobutylaluminum chloride; and dialkylaluminum alkoxides such as diethylaluminum methanol and diethylaluminum ethanol, wherein triisobutylaluminum is preferred.

[0039] In some embodiments of the present invention, the amount of compound C and / or compound D, relative to 1 mole of metallocene catalyst, is selected in the range of 0.5 to 1000, preferably 1 to 100, in terms of the molar ratio of aluminum atoms when compound C and / or compound D is an aluminum compound.

[0040] According to the above-described styrene-based resin synthesis catalyst of the present invention, the molar ratio of the metallocene catalyst to the oxygen-containing gas is 10:(2-8). For example, the molar ratio is 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:8, etc., or any range between any two of the above values. By controlling the molar ratio of the metallocene catalyst to the oxygen-containing gas within the above range, the polymerization activity of the catalyst can be improved, while the residual amount of metal elements in the resin can be reduced.

[0041] In a second aspect, the present invention provides a method for preparing a styrene-based resin, wherein the method uses the above-mentioned catalyst to perform homopolymerization of styrene or copolymerization of styrene with other styrene species (copolymerization of different types of styrene) to obtain a styrene-based resin.

[0042] This invention does not specifically limit the types of styrene, but may include: styrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, and other alkylstyrene types; p-methoxystyrene, o-methoxystyrene, m-methoxystyrene, and other alkoxystyrene types; p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methylp-fluorostyrene, and other halostyrene types; and styrene, trimethylsilylstyrene, vinyl benzoate, divinylbenzene, etc. Among these, styrene, alkylstyrene types, and divinylbenzene are preferred, and styrene, p-methylstyrene, and divinylbenzene are more preferred. In this invention, the above-mentioned styrene compounds can be used alone or in combination of two or more.

[0043] In some embodiments of the present invention, the polymerization conditions for styrene-based polymers include prepolymerization and formal polymerization.

[0044] In the method for manufacturing the styrene-based polymer of the present invention, the above-described catalyst can be used for prepolymerization. Prepolymerization can be carried out by, for example, contacting a small amount of styrene with the catalyst; the method is not particularly limited and can be carried out using known methods.

[0045] There are no particular limitations on the styrene used in prepolymerization; the aforementioned styrene types can be used. The prepolymerization temperature is typically -20 to 200°C, preferably -1°C to 130°C. In the prepolymerization process, inert hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons, monomers, etc., can be used as solvents.

[0046] There are no particular restrictions on the polymerization method used in the formal polymerization process; any continuous polymerization method can be employed, such as slurry polymerization, powder bed polymerization, solution polymerization, gas-phase polymerization, bulk polymerization, or suspension polymerization. However, from the viewpoint of manufacturing on an industrial scale, continuous powder bed polymerization is preferred.

[0047] There are no restrictions on the contact order between the catalyst components and the monomers. That is, as mentioned above, the catalyst can be prepared by pre-mixing the catalyst components and then added to the monomer. Alternatively, instead of pre-mixing the catalyst components to prepare the catalyst, the catalyst components and monomers can be added to the polymerization site in any order.

[0048] In this invention, it is more preferable to use a powder bed continuous polymerization apparatus to polymerize styrene monomers in the presence of the aforementioned catalyst. Here, hydrogen can be added to the polymerization site to improve catalyst activity. Based on the metallocene catalyst, hydrogen can be added to the reaction system in molar ratios, for example, 0 to 20 times, preferably 0 to 15 times, more preferably 0 to 10 times, and even more preferably 0.1 to 10 times. By supplying hydrogen to the reaction system during polymerization, the catalyst activity can be improved while the amount used is suppressed. Therefore, the residual metal content, such as residual aluminum content and residual titanium content, in the manufactured styrene-based resin can be reduced to a range preferred from the viewpoint of long-term heat resistance when producing injection molded articles. However, if the amount of hydrogen added exceeds 20 times based on the central metal of the metallocene catalyst, the reflow heat resistance is poor, and therefore it is not preferred.

[0049] When solvents are used in polymerization, examples include hydrocarbons and halogenated hydrocarbons such as benzene, toluene, ethylbenzene, n-hexane, n-heptane, cyclohexane, dichloromethane, chloroform, 1,2-dichloroethane, and chlorobenzene. These can be used alone or in combination of two or more. Additionally, depending on the type of monomer used in the polymerization, it may sometimes be used as the polymerization solvent itself.

[0050] In some embodiments of the present invention, the amount of catalyst used in the polymerization reaction is typically selected in the range of 0.1 to 500 micromoles, preferably 0.5 to 100 micromoles, of metallocene catalyst relative to 1 mole of monomer. The polymerization pressure is typically selected in the range of 0.5 MPa to 1.0 MPa using an apparent pressure gauge. The reaction temperature is typically in the range of -50 to 150°C.

[0051] From the viewpoint of resin flowability during molding and the strength of the resulting molded article, the weight-average molecular weight of the SPS resin obtained by the manufacturing method of the present invention is preferably 1 × 10⁻⁶. 4 Above and 1×10 6 The following is more preferably 50,000 or more and 500,000 or less. If the weight-average molecular weight is 1×10⁻⁶... 4 The above methods can yield molded articles with sufficient strength. On the other hand, if the weight-average molecular weight is 1×10⁻⁶... 6 In the following cases, the flowability of the resin during molding is also not a problem.

[0052] In this invention, a styrene-based resin obtained by the above-described manufacturing method can be injection molded to obtain a molded article. The molded article obtained by injection molding the styrene-based resin of this invention may have the following characteristics based on the properties of the styrene-based resin obtained by the manufacturing method of this invention.

[0053] In some embodiments of the present invention, the injection-molded SPS resin of the present invention, as described above, may contain a metal component derived from a compound used as a catalyst. Specifically, in the injection-molded SPS resin of the present invention, the transition metal component serving as a metallocene catalyst includes 1.0 to 40 ppm by mass of titanium. The upper limit of the above-mentioned titanium component is preferably 20 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 8 ppm by mass or less.

[0054] In some embodiments of the present invention, the injection-molded SPS resin of the present invention further comprises aluminum. Specifically, the SPS resin molded article of the present invention may contain an aluminum content of 10 to 600 ppm by mass or less. This aluminum content is less than 600 ppm by mass, more preferably less than 500 ppm by mass, and even more preferably less than 400 ppm by mass.

[0055] In the SPS resin obtained by the manufacturing method of the present invention, commonly used thermoplastic resins, rubbery elastomers, antioxidants, inorganic fillers, crosslinking agents, crosslinking aids, nucleating agents, plasticizers, compatibilizers, colorants and / or antistatic agents may be added without prejudice to the purpose of the present invention to form an injection molded body containing SPS resin.

[0056] Examples of thermoplastic resins mentioned above include: polyesters such as polyethylene terephthalate, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyamide, polyphenylene sulfide (PPS), polyoxymethylene, and other condensation polymers; acrylic polymers such as polyacrylic acid, polyacrylate, and polymethyl methacrylate; polyolefins such as polyethylene, polypropylene, polybutene, poly4-methyl-1-pentene, and ethylene-propylene copolymer; or halogenated vinyl compound polymers such as polyvinyl chloride, polyvinylidene chloride, and polyvinylidene fluoride; or mixtures thereof.

[0057] A wide variety of rubber-like elastomers can be used as rubber-like elastomers. Examples include: natural rubber, polybutadiene, polyisoprene, polyisobutylene, chloroprene rubber, polysulfide rubber, Thiokol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, and hydrogenated styrene- Butadiene random copolymers, styrene-ethylene-propylene random copolymers, styrene-ethylene-butene random copolymers, ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), or acrylonitrile-butadiene-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core-shell rubber (MAS), octyl acrylate-butadiene-styrene-core-shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene-core-shell rubber (AABS), butadiene-styrene-core-shell rubber (SBR), and core-shell type particulate elastomers such as methyl methacrylate-butyl acrylate siloxane-containing core-shell rubbers, or rubbers modified from them.

[0058] Among them, SBR, SBS, SEB, SEBS, SIR, SEP, SIS, SEPS, core-shell rubber, or rubbers modified from these are particularly preferred.

[0059] Examples of modified rubber-like elastomers include rubbers modified with modifiers having polar groups, such as styrene-butyl acrylate copolymer rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butene random copolymer, ethylene propylene rubber (EPR), and ethylene propylene diene rubber (EPDM).

[0060] Among these, rubbers modified with SEB, SEBS, SEP, SEPS, EPR, and EPDM are particularly preferred. Specifically, examples include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, maleic anhydride-modified EPR, maleic anhydride-modified EPDM, epoxy-modified SEBS, and epoxy-modified SEPS. One or two of these rubber-like elastomers can be used.

[0061] When the above-mentioned thermoplastic resin and / or (modified) rubber-like elastomer are added to the SPS resin obtained by the manufacturing method of the present invention, it is preferable that the total amount of SPS resin, thermoplastic resin and / or (modified) rubber-like elastomer is set to 100% by mass, and preferably, the thermoplastic resin and / or (modified) rubber-like elastomer are added within the range of SPS resin preferably 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0062] There are various antioxidants, with phosphorus-based antioxidants such as tris(2,4-di-tert-butylphenyl) phosphite and tris(mono- or dinonylphenyl) phosphite, and phenolic antioxidants being particularly preferred.

[0063] As a diphosphite, a phosphorus-based compound represented by the following general formula is preferred. In the above formula, R 30 and R 31 Each can be independently represented as an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0064] As examples, the aforementioned phosphorus compounds include distearyl pentaerythritol diphosphite; dioctyl pentaerythritol diphosphite; diphenyl pentaerythritol diphosphite; bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite; bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite; dicyclohexyl pentaerythritol diphosphite, etc.

[0065] Phenolic antioxidants can be known phenolic antioxidants, and specific examples include: 2,6-di-tert-butyl-4-methylphenol; 2,6-diphenyl-4-methoxyphenol; 2,2′-methylenebis(6-tert-butyl-4-methylphenol); 2,2′-methylenebis(6-tert-butyl-4-methylphenol); 2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol]; 1,1-bis(5-tert-butyl)phenol. 4-Hydroxy-2-methylphenyl)butane; 2,2′-methylenebis(4-methyl-6-cyclohexylphenol); 2,2′-methylenebis(4-methyl-6-nonylphenol); 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-dodecylmercaptobutane; ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butane] [Ester Acid Esters]; 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-3-(n-dodecylthio)-butane; 4,4′-thiobis(6-tert-butyl-3-methylphenol); 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene; 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate di(octadecyl) ester; 3-(4-hydroxy-3,5-di-tert-butylphenyl)propane Octadecyl ester of acid; tetra[methylene(3,5-di-tert-butyl-4-hydroxycinnamate)]methane, pentaerythritol tetra(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, etc. A wide variety of sulfur-based antioxidants can be used as sulfur-based antioxidants, such as bis[3-(dodecylthio)propionic acid]2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propanediyl, etc.

[0066] In addition to the aforementioned phosphorus-based and phenolic antioxidants, amine-based and sulfur-based antioxidants can also be used alone or in combination. Particularly in the injection-molded articles of the present invention, the antioxidant preferably includes at least one selected from phosphorus-based, phenolic, amine, and sulfur-based antioxidants, and more preferably, a combination of three types of phosphorus-based, phenolic, and sulfur-based antioxidants.

[0067] The antioxidant mentioned above is typically 0.005 to 5 parts by weight relative to the SPS100. If the antioxidant proportion is less than 0.005 parts by weight, the molecular weight decreases significantly; conversely, if it is greater than 5 parts by weight, antioxidant leakage or negative impacts on mechanical strength and appearance may occur, both of which are undesirable. When two or more antioxidants are included in the composition, it is preferable to adjust the total amount to the range described above. The amount of antioxidant relative to the SPS100 is more preferably 0.01 to 4 parts by weight, and even more preferably 0.02 to 3 parts by weight.

[0068] Inorganic fillers can be fibrous, granular, or powdered.

[0069] Examples of fibrous inorganic fillers include glass fiber, carbon fiber, and alumina fiber. Examples of granular and powdered inorganic fillers include talc, carbon black, graphite, titanium dioxide, silicon dioxide, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfates, tin oxide, alumina, kaolin, silicon carbide, and metal powders.

[0070] As compatibilizers, examples include polymers with polar groups that are compatible or compatible with SPS and the aforementioned thermoplastic resins and rubber-like elastomers. Specifically, examples include rubbers modified with acid anhydrides, such as maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, maleic anhydride-modified SEB, maleic anhydride-modified SEP, maleic anhydride-modified EPR, styrene-maleic anhydride copolymer (SMA), styrene-glycidyl methacrylate copolymer, terminal carboxylic acid-modified polystyrene, terminal epoxy-modified polystyrene, terminal oxazoline-modified polystyrene, terminal amine-modified polystyrene, sulfonated polystyrene, styrene-based ionomers, styrene-methyl methacrylate graft polymers, and (styrene-glycidyl methacrylate)-methyl methacrylate graft polymers. Polymers, acid-modified acrylic-styrene-grafted polymers, (styrene-glycidyl methacrylate)-styrene grafted polymers, polybutylene terephthalate-polystyrene grafted polymers, and modified styrene polymers such as maleic anhydride-modified syndiotactic polystyrene, fumaric acid-modified syndiotactic polystyrene, glycidyl methacrylate-modified syndiotactic polystyrene, and amine-modified syndiotactic polystyrene; (styrene-maleic anhydride)-polyphenylene ether grafted polymers, maleic anhydride-modified polyphenylene ether (PPE), fumaric acid-modified polyphenylene ether, glycidyl methacrylate-modified polyphenylene ether, and amine-modified polyphenylene ether; etc. These compatibilizers can be used alone or in combination of two or more. The amount of compatibilizer added is not particularly limited, but is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, relative to 100 parts by weight of SPS resin.

[0071] As nucleating agents, any known nucleating agents can be selected from those such as metal salts of carboxylic acids, represented by aluminum bis(p-tert-butylbenzoic acid), metal salts of phosphoric acids, represented by sodium methylene bis(2,4-di-tert-butylphenol) phosphate, talc, and phthalocyanine derivatives. It should be noted that these nucleating agents can be used alone or in combination of two or more. The amount of nucleating agent is not particularly limited, but is preferably 0.01 to 5 parts by weight, more preferably 0.04 to 2 parts by weight, relative to 100 parts by weight of SPS resin.

[0072] As a release agent, any known release agent can be selected from polyethylene wax, silicone oil, long-chain carboxylic acids, and metal salts of long-chain carboxylic acids. It should be noted that one of these release agents can be used alone, or two or more can be used in combination. The amount of release agent is not particularly limited, but is preferably 0.1 to 3 parts by weight, more preferably 0.2 to 1 part by weight, relative to 100 parts by weight of SPS resin.

[0073] As a method for manufacturing the styrene-based resin molded article of the present invention, any method among injection molding methods can be applied. For example, a composition containing the above-described SPS resin and the various components described above as needed is first obtained. Injection molding can be used to form the above-described composition using a mold of a predetermined shape.

[0074] The styrene-based resin molded articles of the present invention have excellent long-term heat resistance, and therefore can be ideally used for applications requiring this property, such as automotive sensors, housings, connectors, solenoid valves for large automotive exhaust brake devices, LED display components that generate heat, vehicle lighting, signal lights, emergency lights, terminal blocks, fuse components, high-voltage components, etc.

[0075] The present invention has at least the following technical effects (1) This invention significantly improves the polymerization activity of the catalyst system by adding oxygen-containing gas to the catalyst system in conjunction with the metallocene catalyst and the co-catalyst. Moreover, without changing the structure of the metallocene catalyst, the production cost can be effectively reduced by simply adding inexpensive oxygen-containing gas, which has significant economic value.

[0076] (2) The metal elements in the synthesized styrene resin mainly come from the metal elements in the catalyst. By adding oxygen-containing gas, the present invention can significantly reduce the content of residual metal elements in the styrene resin. Detailed Implementation

[0077] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention are described clearly and completely. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0078] Example 1 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this embodiment are shown in Table 1.

[0079] (2) The preparation process of styrene resin is as follows: A clean 250ml vertical reactor equipped with a single spiral stirrer is heated to 90℃ and dried under vacuum for 3 hours. Then, the temperature is lowered to 70℃, a predetermined amount of oxygen-containing gas is introduced, and the pressure is replenished to atmospheric pressure with nitrogen. Stirring is then started, and 200ml of styrene monomer and 6µl of catalyst are added. After polymerization for 2 hours, the reaction product is washed out in ethanol and dried to obtain the polymer product.

[0080] Example 2 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this embodiment are shown in Table 1.

[0081] (2) The preparation process of the styrene resin in this embodiment is the same as that in Example 1.

[0082] Example 3 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this embodiment are shown in Table 1.

[0083] (2) The preparation process of the styrene resin in this embodiment is the same as that in Example 1.

[0084] Example 4 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this embodiment are shown in Table 1.

[0085] (2) The preparation process of the styrene resin in this embodiment is the same as that in Example 1.

[0086] Example 5 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this embodiment are shown in Table 1.

[0087] (2) The preparation process of the styrene resin in this embodiment is the same as that in Example 1.

[0088] Example 6 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this embodiment are shown in Table 1.

[0089] (2) The preparation process of the styrene resin in this embodiment is the same as that in Example 1.

[0090] Example 7 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this embodiment are shown in Table 1.

[0091] (2) The preparation process of the styrene resin in this embodiment is the same as that in Example 1.

[0092] Example 9 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this embodiment are shown in Table 1.

[0093] (2) The preparation process of the styrene resin in this embodiment is the same as that in Example 1.

[0094] Comparative Example 1 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this comparative example are shown in Table 1.

[0095] (2) The preparation process of the styrene resin in this comparative example differs from that in Example 1 in that the catalyst in this comparative example does not use oxygen-containing gas.

[0096] Comparative Example 2 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this comparative example are shown in Table 1.

[0097] (2) The preparation process of the styrene resin in this comparative example differs from that in Example 1 in that the catalyst in this comparative example does not use oxygen-containing gas.

[0098] Comparative Example 3 (1) The catalyst raw materials, ratios, and added monomers of the styrene resin in this comparative example are shown in Table 1.

[0099] (2) The preparation process of the styrene resin in this comparative example is the same as that in Example 1.

[0100] The polymerization activity of the catalysts in the examples and comparative examples, as well as the residual metal content in the prepared resins, were determined as follows: (1) Polymerization activity: The amount of polymer that can be produced per mole of catalyst.

[0101] (2) Methods for determining residual aluminum and residual titanium content ICP-OES, OPTIMA8000, manufactured by Platinum Elmer, USA. Operating conditions: High-frequency generator incident power, 1300W; Auxiliary gas flow rate: 0.3L / min; Plasma gas flow rate: 15L / min; Nebulizing gas flow rate: 0.8L / min; Observation height: 15mm; Peristaltic pump speed: 1.5ml / min.

[0102] Sample pretreatment: Accurately weigh approximately 15g of PPR sample into a quartz crucible, place it on an electric furnace and heat until fumes are generated. Ignite the fumes with qualitative filter paper and burn until ash. Then transfer the crucible to a muffle furnace (box-type resistance furnace) and calcine at 550℃ for 3 hours. After cooling, remove the crucible and add 10mL of hydrochloric acid diluted 1:1 (volume ratio). Heat on a 140℃ hot plate until 1-2mL remains. Finally, bring the volume to 10mL with double-distilled water. Prepare a blank sample simultaneously.

[0103] Test: Enable ICP-OES, establish a standard working curve, and input the information of the samples to be tested into its working software. Under the same working conditions as when the standard curve was established, test the samples and blank samples sequentially. The computer will automatically calculate the content of the measured metal elements in the samples.

[0104] The polymerization activity of the catalysts in the examples and comparative examples, as well as the determination results of the metal residue in the prepared resins, are shown in Table 1.

[0105] In Table 1: A1: Pentamethylcyclopentadienyltrimethoxytitanium (metallocene catalyst), purchased from Grace; A2: Pentamethylcyclopentadienyl titanium trichloride (metallocene catalyst), purchased from Grace Company; MAO: Methylaluminoxane (co-catalyst), purchased from Grace Company; MMAO: Triisobutylaluminum modified methylaluminoxane (co-catalyst), purchased from Grace Company; TIBA: Triisobutylaluminum (compound D), purchased from Grace Company; TEA: Triethylaluminum (compound D), purchased from Aldrich.

[0106] As shown in Table 1, neither Comparative Example 1 nor Comparative Example 2 used oxygen-containing gas. Compared with Examples 1-9, the polymerization activity of Comparative Examples 1 and 2 was significantly lower, indicating that the present invention, by combining oxygen-containing gas with existing metallocene catalysts, can effectively improve the polymerization activity of the catalyst and significantly reduce production costs. Meanwhile, the residual metal content in the resins of Comparative Examples 1 and 2 was also significantly higher than that of Examples 1-9, indicating that the catalyst of this application can also significantly reduce the residual metal content in the resin. In Comparative Example 3, the excessive CO2 content led to reduced polymerization activity and excessive residual metal element content.

[0107] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A styrene-based resin synthesis catalyst, characterized in that, include: Metallocene catalysts; The cocatalyst is selected from oxygen-containing compound A and / or compound B, which can react with transition metal compounds to form ionic complexes; For example, the general formula X w O y The oxygen-containing gas shown is wherein X is selected from at least one of carbon, nitrogen, and sulfur, and w and y are integers from 1 to 4.

2. The styrene-based resin synthesis catalyst according to claim 1, characterized in that, The oxygen-containing gas includes at least one of CO and CO2, preferably CO2.

3. The styrene-based resin synthesis catalyst according to claim 1, characterized in that, The metallocene catalyst is of general formula R 1 MU a-1 L b As shown, R 1 M is a π-ligand, selected from at least one metal from Groups 3 to 5 of the periodic table and lanthanide transition metals, U is a monoanion ligand, multiple Us may be the same or different, L is a Lewis base, a is the valence of M, b is 0, 1 or 2, and when there are multiple Ls, Ls may be the same or different.

4. The styrene-based resin synthesis catalyst according to claim 1, characterized in that, Compound A includes alkylaluminoxane compounds; Compound B includes boron compounds.

5. The styrene-based resin synthesis catalyst according to claim 4, characterized in that, Based on 1 mole of the metallocene catalyst, the compound A is calculated in moles of aluminum atoms, with the number of aluminum atoms ranging from 1 to 10,000, preferably 10 to 1,000. With the metallocene catalyst as 1 mole, the compound B, in terms of boron atoms, has 0.5-10 moles of boron atoms, preferably 0.8-5 moles.

6. The styrene-based resin synthesis catalyst according to claim 1, characterized in that, It also includes compound C, which is of general formula R. 2 p Al(OR 3 ) q X 1 2-p-q As shown in H, where R 2 and R 3 Each is selected from alkyl groups having 1-8 carbon atoms, X 1 For halogen atoms, 0 < p ≤ 2, 0 ≤ q < 2, and p + q ≤ 2.

7. The styrene-based resin synthesis catalyst according to claim 1, characterized in that, It also includes compound D, which is of general formula R. 4 m Al(OR 5 ) n X 2 3-m-n As shown, R 4 and R 5 Each is selected from alkyl groups having 1-8 carbon atoms, X 2 For halogen atoms, 0 < m ≤ 3, 0 ≤ n < 3, and m + n ≤ 3.

8. The styrene-based resin synthesis catalyst according to any one of claims 1-7, characterized in that, The molar ratio of the metallocene catalyst to the oxygen-containing gas is 10:(2-8).

9. A method for preparing a styrene-based resin, characterized in that, Styrene-based resins are obtained by homopolymerization of styrene or copolymerization of styrene with other styrene species using the catalyst described in any one of claims 1-8.

10. The method according to claim 9, characterized in that, The styrene-based resin is a syndiotactic polystyrene resin; And / or, the residual titanium element in the styrene-based resin is suppressed to 1.0 to 40 ppm by mass; or, the residual aluminum element in the styrene-based resin is suppressed to 10 to 600 ppm by mass.

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