# US 10,246,536 B2 · Functionalized highly syndiotactic polystyrene and preparation method thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,246,536 B2 - Document ID: US10246536B2 - Status: Granted - Kind: B2 - Application number: 15/501,737 - Filed: 2015-08-13 - Published: 2017-11-23 - Granted: 2019-04-02 - Earliest claimed: 2014-08-14 - Assignees: Changchun Institute of Applied Chemistry Chinese Academy of Sciences - Applicants: Changchun Institute of Applied Chemistry Chinese Academy of Sciences - Inventors: Dongmei Cui; Dongtao Liu; Zichuan Wang - Web page: https://patentgrep.com/patent/US10246536B2 ## CPC - C08F 212/08: Styrene - C08F 2/02: Polymerisation in bulk - C08F 2/06: Organic solvent - C08F 4/12: of boron, aluminium, gallium, indium, thallium or rare earths - C08F 4/545: {rare earths being present, e.g. triethylaluminium + neodymium octanoate} - C08F 12/22: Oxygen - C08F 12/30: Sulfur - C08F 112/22: {Oxygen} - C08F 212/22: {Oxygen} - C08L 25/06: Polystyrene - C08L 25/16: Homopolymers or copolymers of alkyl-substituted styrenes - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Compared to the prior art, this invention provides a functionalized highly syndiotactic polystyrene, comprising a repeating unit having a structure represented by formula (I), or comprising a repeating unit having a structure represented by formula (I) and a repeating unit having a structure represented by formula (II). It is indicated by the experimental results that the syndiotacticity selectivity of the highly syndiotactic polymer provided by this invention is no less than 90%, and the proportion of the repeating unit having a structure represented by formula (I) in the polymer may be arbitrarily adjusted and may be up to 100%. Meanwhile, the oxygen- or sulfur-containing groups in the polymer may increase the polarity of the highly syndiotactic polystyrene so as to increase the blendability of the highly syndiotactic polystyrene with other polymers. ## Claims ### Claim 1 A preparation method of a functionalized syndiotactic polystyrene, comprising: performing a polymerization of a functionalized styrene or a polymerization of styrene and a functionalized styrene in the presence of a catalyst to obtain the functionalized syndiotactic polystyrene, wherein the functionalized syndiotactic polystyrene comprises a repeating unit having a structure represented by formula (I), or comprises a repeating unit having a structure represented by formula (I) and a repeating unit having a structure represented formula (II): wherein the functionalized styrene has a structure represented by formula (III): wherein in formula (I) and formula (III), R is independently selected from a C1-20 alkoxy group, a C6-20 aryloxy group, a C1-20 alkylthio group, a C6-20 arylthio group, or a C6-20 aryl group; m is the number of substituent R and is independently selected from an integer from 1 to 5; and the catalyst comprises a rare earth complex, an organoboron compound, and an organoaluminum compound. ### Claim 2 (depends on 1) The preparation method according to claim 1, wherein the rare earth complex has a structure represented by formula (IV) or formula (V): wherein, R1 is selected from any one of a cyclopentadienyl group and derivatives thereof, an indenyl group and derivatives thereof, or a fluorene group and derivatives thereof; R2 is selected from a C1-10 alkyl group, a C1-10 silyl group, a C6-10 aminoaryl group, a C1-10 silylamino group, a C1-10 alkylamino group, a C3-10 allyl group, or a borohydride group; L1 is a ligand selected from tetrahydrofuran, ethyl ether, ethylene glycol dimethyl ether, or toluene; p is the number of L1, wherein 0≤p≤2; R3 is selected from any one of a cyclopentadienyl group and derivatives thereof, an indenyl group and derivatives thereof, or a fluorene group and derivatives thereof; R4 is selected from a methylene group, an ethylene group, or a dimethylsilyl group; R5, R6, and R7 are independently selected from hydrogen, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group; R8 is selected from hydrogen, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a 2,6-dimethylphenyl group, a 4-methylphenyl group, a s-trimethylphenyl group, a 2,6-diisopropyl phenyl group, a 2,4,6-triisopropyl phenyl group, or a 2,6-di-tert-butyl phenyl group; R9 is selected from a C1-10 alkyl group, a C1-10 silyl group, a C6-10 aminoaryl group, a C1-10 silylamino group, a C1-10 alkylamino group, a C3-10 allyl group, or a borohydride group; L2 is a ligand selected from tetrahydrofuran, ethyl ether, ethylene glycol dimethyl ether, or toluene; q is the number of L2, wherein 0≤q≤2; and Ln is independently selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu. ### Claim 3 (depends on 1) The preparation method according to claim 1, wherein the organoboron compound is selected from [Ph3C][B(C6F5)4], [PhNMe2H][BPh4], [NEt3H][BPh4], [PhNMe2H][B(C6F5)4], or B(C6F5)3; and the organoaluminum compound is selected from an alkyl aluminum, a hydrogenated alkyl aluminum, a halogenated alkyl aluminum, or an alumoxane. ### Claim 4 (depends on 3) The preparation method according to claim 3, wherein the organoaluminum compound is one or more selected from trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, tribenzyl aluminum, ethyldibenzyl aluminum, ethyl di-p-tolyl aluminum, diethylbenzyl aluminum, dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminum hydride, dipentyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, ethylbenzyl aluminum hydride, ethyl p-tolyl aluminum hydride, dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dipentyl aluminum chloride, dihexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, diphenyl aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, ethylbenzyl aluminum chloride, ethyl p-tolyl aluminum chloride, methyl alumoxane, ethyl alumoxane, n-propyl alumoxane, and n-butyl alumoxane. ### Claim 5 (depends on 1) The preparation method according to claim 1, wherein the molar ratio of the rare earth complex to the organoboron compound to the organo aluminum compound is 1:(0.5-2.0):(0.5-3000). ### Claim 6 (depends on 1) The preparation method according to claim 1, wherein the molar ratio of the functionalized styrene to the rare earth complex is (50-10000):1, and the molar ratio of the styrene to the rare earth complex is (50-10000): 1. ### Claim 7 (depends on 1) The method according to claim 1, wherein the temperature for the reaction is −60° C. to 80° C., and the time for the reaction is 0.1 hours to 48 hours. ### Claim 8 (depends on 1) The method according to claim 1, wherein the functionalized syndiotactic polystyrene has a syndiotacticity of no less than 90% and the repeating unit represented by formula (I) has a mole fraction w wherein 0%