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CN-116693734-B - Preparation method and application of trans-1, 2-poly-ocimene

CN116693734BCN 116693734 BCN116693734 BCN 116693734BCN-116693734-B

Abstract

The invention discloses a preparation method and application of trans-1, 2-poly-ocimene, which comprises the steps of dissolving rare earth compounds, organoboron compounds and alkylaluminum compounds in an organic solvent according to a certain proportion under the protection of inert gas to prepare a catalyst composition solution, directly adding (E) -beta-ocimene into the catalyst composition solution, or dissolving (E) -beta-ocimene into the organic solvent to prepare Cheng Luole ene solution, adding the catalyst composition solution into the ocimene solution, reacting the (E) -beta-ocimene or the ocimene solution with the catalyst composition solution for a period of time at a preset temperature, adding a terminator, terminating a polymerization reaction, settling and drying to obtain trans-1, 2-poly-ocimene, wherein the catalyst composition used in the method can catalyze the polymerization of (E) -beta-ocimene with high activity and high selectivity to prepare the trans-1, 2-poly-ocimene.

Inventors

  • SANG LIPENG
  • HUANG CHEN
  • WANG YANWEI
  • YAN JING
  • LI WEI
  • FU XIAOMENG
  • SHI KE
  • SHI YU
  • HUANG PU
  • LUO CONG
  • LI CHUNTAO

Assignees

  • 湖北航天化学技术研究所

Dates

Publication Date
20260505
Application Date
20230613

Claims (8)

  1. 1. A method for preparing trans-1, 2-poly ocimene, which is characterized by comprising the following steps: S1, under the protection of inert gas, dissolving a rare earth compound, an organoboron compound and an alkyl aluminum compound in an organic solvent according to a certain proportion to prepare a catalyst composition solution, wherein the rare earth compound has a structure shown as a formula I: Wherein Ln in formula I is Sc, Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb or Lu, X 1 and X 2 are alkyl, silyl, aryl, silamino, alkylamino, allyl, borohydride, chlorine or bromine, L w is tetrahydrofuran, pyridine or ethylene glycol dimethyl ether, and w=0, 1 or 2;Q is a monoanionic ligand; The monoanionic ligand has a structure as shown in formula III, IV or V: Wherein R 1 and R 2 in formula III are each independently phenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, p-tert-butylphenyl, m-methylphenyl, m-ethylphenyl, m-isopropylphenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, o-phenylphenyl, mesitylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diethyl-4-methylphenyl, mesitylphenyl, 2, 6-diethyl-4-tert-butylphenyl, 2, 6-diisopropylphenyl, 2, 6-diisopropyl-4-methylphenyl, mesityl, 2, 6-di-tert-butylphenyl, 2, 6-di-tert-butyl-4-methylphenyl, 2, 6-diphenylphenyl, 2, 6-bistrifluoromethylphenyl, 2-fluorophenyl, 3-trifluoromethylphenyl, p-fluorophenyl or 1-naphthyl; R 4 in the general formula III is trimethylsilylmethyl, ditolylmethyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, p-tert-butylphenyl, p-phenylphenyl, pentafluorophenyl, p-methoxyphenyl, o-methoxyphenyl, p-N, N-dimethylphenyl, o-N, N-dimethylbenzyl, 2-pyridylmethylene or o-methylthiophenyl; r 5 in the general formulae IV and V is 2-methylpyridine, 2, 6-dimethylpyridine or 8-methylquinoline; R 6 in the general formulae IV and V is hydrogen, methyl, ethyl or tert-butyl; S2, directly adding (E) -beta-ocimene into the catalyst composition solution, or dissolving (E) -beta-ocimene into an organic solvent to prepare Cheng Luole ene solution, adding the catalyst composition solution into the ocimene solution, mixing the (E) -beta-ocimene or the ocimene solution with the catalyst composition solution, reacting for a period of time at a preset temperature, adding a terminator, and terminating the polymerization reaction; s3, settling and drying to obtain trans-1, 2-poly-ocimene.
  2. 2. The method for preparing trans-1, 2-poly-ocimene according to claim 1, wherein the molar ratio of the rare earth compound to the organoboron compound is 1:0.5-2 and the molar ratio of the rare earth compound to the alkylaluminum compound is 1:0-1000.
  3. 3. The method for preparing trans-1, 2-poly-ocimene according to claim 1, wherein the molar ratio of (E) - β -ocimene to rare earth compound is 250 to 10000:1.
  4. 4. The process for preparing trans-1, 2-poly-ocimene according to claim 1, wherein said organoboron compound is an organoboron reagent comprising [ B (C 6 F 5 ) 4 ] anions or B (C 6 F 5 ) 3 ).
  5. 5. The method for preparing trans-1, 2-poly-ocimene according to claim 4, wherein said organoboron compound is [Ph 3 C][B(C 6 F 5 ) 4 ]、[NEt 3 H][B(C 6 F 5 ) 4 ]、B(C 6 F 5 ) 3 or [ PhNMe 2 H][B(C 6 F 5 ) 4 ].
  6. 6. The method for preparing trans-1, 2-poly ocimene according to claim 1, wherein said alkylaluminum compound is one or more of alkylaluminum, alkylaluminum hydride, alkylaluminum chloride and aluminoxane.
  7. 7. The method for preparing trans-1, 2-poly-ocimene according to claim 1, wherein the preset temperature in step S3 is 0-120 ℃, the reaction period is 10 minutes to 48 hours, and the terminator is ethanol acidified by hydrochloric acid.
  8. 8. Use of trans 1, 2-poly ocimene produced according to the method of any one of claims 1 to 7 in the manufacture of adhesives and rubber articles.

Description

Preparation method and application of trans-1, 2-poly-ocimene Technical Field The invention relates to the technical field of vinyl monomer polymerization, in particular to a preparation method and application of trans-1, 2-poly-ocimene. Background The ocimene is used as a terpene derivative and is present in plant essential oil such as ocimum basilicum oil and lavender oil, the molecule of the ocimum basilicum is provided with conjugated diene structural units, and the ocimum basilicum is a bio-based monomer with a large potential application prospect, but researches on high-selectivity and high-activity polymerization of Guan Luole ene are few so far. Currently, li Xiaofang of Beijing university et al used a cyclopentadienyl scandium, lutetium, yttrium and dysprosium catalyst system to catalyze homo-polymerization of trans 1, 4-beta-ocimene to produce syndiotactic cis 1, 4-poly beta-ocimene and isotactic trans 1, 2-poly beta-ocimene (macromol. Rapid Commun.2016,37, 987-992), but the catalyst system had the disadvantage of relatively complex synthesis and high cost, italy Capacchione et al reported that the polymerization of ocimene was catalyzed by [ OSSO ] type titanium complexes, isotactic 1, 2-ocimene was synthesized at low temperature (below 25 ℃) and trans 1, 4-structure-based ocimene (> 70%) (Polymer 2017,131,151-159) was synthesized at high temperature, but the activity of the catalyst system was very low, and recently Valencia et al studied using Ziegler-Natta neodymium catalyst to catalyze the polymerization of ocimene to produce cis 1,4 structure-ocimene (about 32+79) and the catalyst system was not high in both the catalytic activity and the catalytic activity of cis 34-ocimene (3482). Thus, while ocimene contains conjugated diene structural units, its unique structural units impart unique polymerization behavior that is different from other conjugated diene monomers, many of the conjugated diene high selectivity catalytic systems that have been reported to date have not been effective in catalyzing the high selectivity, high activity polymerization of ocimene. Disclosure of Invention In view of the above problems, a first object of the present invention is to provide a process for preparing trans-1, 2-poly (ocimene) using a catalyst composition comprising a rare earth compound, an organoboron reagent and an alkylaluminum compound, which can catalyze the polymerization of (E) - β -ocimene with high activity and high selectivity to prepare trans-1, 2-poly ((E) - β -ocimene). A second object of the present invention is to provide the use of a trans 1, 2-poly ocimene as defined above. The first technical scheme adopted by the invention is that the preparation method of trans-1, 2-poly-ocimene comprises the following steps: S1, under the protection of inert gas, dissolving a rare earth compound, an organoboron compound and an alkylaluminum compound in an organic solvent according to a certain proportion to prepare a catalyst composition solution; S2, directly adding (E) -beta-ocimene into the catalyst composition solution, or dissolving (E) -beta-ocimene into an organic solvent to prepare Cheng Luole ene solution, adding the catalyst composition solution into the ocimene solution, mixing the (E) -beta-ocimene or the ocimene solution with the catalyst composition solution, reacting for a period of time at a preset temperature, adding a terminator, and terminating the polymerization reaction; s3, settling and drying to obtain trans-1, 2-poly-ocimene. Preferably, the molar ratio of the rare earth compound to the organoboron compound is 1:0.5-2, and the molar ratio of the rare earth compound to the aluminum alkyl compound is 1:0-1000. Preferably, the molar ratio of the (E) -beta-ocimene to the rare earth compound is 250-10000:1. Preferably, the rare earth compound has a structure as shown in formula I: Wherein Ln in formula I is Sc, Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb or Lu, X 1 and X 2 are alkyl, silyl, aryl, silamino, alkylamino, allyl, borohydride, chlorine or bromine, L w is tetrahydrofuran, pyridine or ethylene glycol dimethyl ether, and w=0, 1 or 2;Q is a monoanionic ligand. Preferably, the monoanionic ligand has a structure as shown in formula II, III, IV or V: Wherein R 1 and R 2 in formulas II and III are each independently phenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, p-tert-butylphenyl, m-methylphenyl, m-ethylphenyl, m-isopropylphenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, o-phenylphenyl, mesitylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diethyl-4-methylphenyl, mesitylphenyl, 2, 6-diethyl-4-tert-butylphenyl, 2, 6-diisopropylphenyl, 2, 6-diisopropyl-4-methylphenyl, mesityl, 2, 6-di-tert-butylphenyl, 2, 6-di-tert-butyl-4-methylphenyl, 2, 6-diphenylphenyl, 2, 6-di-trifluoromethylphenyl, 2-fluorophenyl, 3-trifluoromethylphenyl, p-fluorophenyl or 1-naphthyl; R 3 in the general formula II is isopropyl, cyclopentyl, cyclohexyl, methylcyclohexyl,