A method for preparing trans-1,2-polyocimene and its application

Abstract

This invention discloses a method for preparing trans-1,2-polyocimene and its application. The method includes dissolving a rare earth compound, an organoboron compound, and an alkylaluminum compound in an organic solvent in a certain proportion under inert gas protection to obtain a catalyst composition solution; directly adding (E)-β-ocimene to the catalyst composition solution; or dissolving (E)-β-ocimene in an organic solvent to prepare an ocimene solution, and adding the catalyst composition solution to the ocimene solution; mixing the (E)-β-ocimene or the ocimene solution with the catalyst composition solution and reacting at a preset temperature for a period of time, then adding a terminator to terminate the polymerization reaction; after sedimentation and drying, trans-1,2-polyocimene is obtained. The catalyst composition used in this method can catalyze the polymerization of (E)-β-ocimene with high activity and high selectivity to obtain trans-1,2-polyocimene.

Description

Technical Field

[0001] This invention relates to the field of olefin monomer polymerization technology, specifically to a method for preparing trans-1,2-polyocimene and its application. Background Technology

[0002] Ocimene, a terpene derivative, is found in plant essential oils such as basil oil and lavender oil. Its molecule contains conjugated diene structural units, making it a bio-based monomer with great potential applications. However, to date, there are very few research reports on the highly selective and highly active polymerization of ocimene.

[0003] Currently, Li Xiaofang et al. from Beijing Institute of Technology have used a scandium-luene oxide, lutetium oxide, yttrium oxide, and dysprosium catalytic system to catalyze the homopolymerization of trans-1,4-β-ocimene, obtaining syndiotactic cis-1,4-poly-β-ocimene and isotrans-1,2-poly-β-ocimene (Macromol. Rapid Commun. 2016, 37, 987-992). However, this catalytic system suffers from drawbacks such as complex synthesis and high cost. Capacchione et al. from Italy reported using [OSSO]-type titanium complexes to catalyze ocimene polymerization, synthesizing isotrans-1,2-poly-ocimene at low temperatures (below 25°C) and trans-1,4-structure-dominant poly-ocimene (>70%) at high temperatures (Polymer). (2017, 131, 151-159), but the catalytic system has very low activity; recently, Valencia et al. studied the polymerization of ocimene using a Ziegler-Natta type neodymium catalyst and obtained polyocimene with a 1,4 structure content of about 79% (cis + trans) (RSC Advances 2020, 10, 36539-36545), but this catalytic system has the problem of low catalytic activity and selectivity.

[0004] Therefore, although ocimene contains conjugated diene structural units, its unique structural units give it a unique polymerization behavior that differs from other conjugated diene monomers; many of the currently reported highly selective catalytic systems for conjugated dienes cannot effectively catalyze the highly selective and highly active polymerization of ocimene. Summary of the Invention

[0005] To address the aforementioned problems, the first objective of this invention is to provide a method for preparing trans-1,2-poly((E)-β-ocimene), wherein the catalyst composition used in this method comprises rare earth compounds, organoboron reagents, and alkylaluminum compounds. Using this catalyst composition, the polymerization of (E)-β-ocimene can be catalyzed with high activity and high selectivity to obtain trans-1,2-poly((E)-β-ocimene).

[0006] A second object of the present invention is to provide an application of the above-mentioned trans-1,2-polyocimene.

[0007] The first technical solution adopted in this invention is: a method for preparing trans-1,2-polyocimene, comprising the following steps:

[0008] S1: Under the protection of an inert gas, rare earth compounds, organoboron compounds and alkylaluminum compounds are dissolved in an organic solvent in a certain proportion to prepare a catalyst composition solution;

[0009] S2: (E)-β-ocimene is directly added to the catalyst composition solution; or (E)-β-ocimene is dissolved in an organic solvent to prepare an ocimene solution, and the catalyst composition solution is added to the ocimene solution; after mixing (E)-β-ocimene or the ocimene solution with the catalyst composition solution, the mixture is reacted at a preset temperature for a period of time, and a terminator is added to terminate the polymerization reaction;

[0010] S3: After sedimentation and drying, trans-1,2-polyocimene is obtained.

[0011] Preferably, the molar ratio of the rare earth compound to the organoboron compound is 1:0.5 to 2; the molar ratio of the rare earth compound to the alkylaluminum compound is 1:0 to 1000.

[0012] Preferably, the molar ratio of (E)-β-ocimene to the rare earth compound is 250 to 10000:1.

[0013] Preferably, the rare earth compound has a structure as shown in Formula I:

[0014]

[0015] 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 It can be alkyl, silyl, aryl, silamido, alkylamido, allyl, borohydride, chlorine, or bromine; L w It is tetrahydrofuran, pyridine, or ethylene glycol dimethyl ether; w = 0, 1, or 2; Q is a monoanion ligand.

[0016] Preferably, the monoanion ligand has a structure as shown in Formula II, III, IV or V:

[0017]

[0018] Among them, R in general formulas II and III 1 and R 2Each of the following is 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, mestrimethylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diethyl-4-methylphenyl, mestriethylphenyl, 2,6-diethyl-4-tert-butylphenyl, 2,6-diisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, mestrimethylphenyl, 2,6-di-tert-butylphenyl, 2,6-di-tert-butyl-4-methylphenyl, 2,6-diphenylphenyl, 2,6-di-trifluoromethylphenyl, 2-fluorophenyl, 3-trifluoromethylphenyl, p-trifluoromethylphenyl, p-fluorophenyl or 1-naphthyl;

[0019] R in general formula II 3 It is isopropyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, p-tert-butylphenyl, p-phenylphenyl, pentafluorophenyl, p-methoxyphenyl, p-N,N-dimethylphenyl or o-N,N-dimethylphenyl;

[0020] R in general formula III 4 It is trimethylsilylmethyl, bistrimethylsilylmethyl, 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-dimethylphenyl, o-N,N-dimethylbenzyl, 2-pyridimethylene or o-meththiophenyl;

[0021] R in general formulas IV and V 5 It is 2-methylpyridine, 2,6-dimethylpyridinyl or 8-methylquinoline;

[0022] R in general formulas IV and V 6 It can be hydrogen, methyl, ethyl or tert-butyl.

[0023] Preferably, the organoboron compound is an organoboron reagent containing [B(C6F5)4]ˉ anion or B(C6F5)3.

[0024] Preferably, the organoboron compound is [Ph3C][B(C6F5)4], [NEt3H][B(C6F5)4], B(C6F5)3 or [PhNMe2H][B(C6F5)4].

[0025] Preferably, the alkylaluminum compound is one or more selected from alkylaluminum, hydrogenated alkylaluminum, alkylaluminum chloride, and aluminoxane.

[0026] Preferably, the preset temperature in step S3 is 0 to 120°C, the reaction time is 10 minutes to 48 hours, and the terminating agent is hydrochloric acid-acidified ethanol.

[0027] The second technical solution adopted in this invention is the application of trans-1,2-polyocimene prepared according to the preparation method in the first technical solution in the manufacture of adhesives and rubber products (e.g., tires).

[0028] The beneficial effects of the above technical solution are as follows:

[0029] (1) The catalyst composition used in the preparation method of trans-1,2-poly((E)-β-ocimene) disclosed in this invention is a rare earth compound, an organoboron reagent and an alkylaluminum compound as shown in formula (I). This catalyst composition is a highly efficient catalytic system. Using this catalyst composition, the polymerization of (E)-β-ocimene can be catalyzed with high activity and high selectivity to obtain trans-1,2-poly((E)-β-ocimene). The 1,2-structure content of the obtained polymer is greater than 90%.

[0030] (2) The rare earth compounds disclosed in this invention have the characteristics of simple synthesis, low cost, high activity for (E)-β-ocimene polymerization and high 1,2-selectivity.

[0031] (3) The present invention discloses a method for preparing trans-1,2-polyocimene, which is a stereoselective polymerization technique of bio-derived conjugated diene monomers. The trans-1,2-polyocimene can be used in tire manufacturing, adhesives and other rubber products. Attached Figure Description

[0032] Figure 1 The 1H NMR spectrum of a polymer provided in one embodiment of the present invention;

[0033] Figure 2 The carbon NMR spectrum of a polymer provided in one embodiment of the present invention;

[0034] Figure 3 The image shows a polymer DSC curve provided in one embodiment of the present invention. Detailed Implementation

[0035] The present invention will be further illustrated below with specific embodiments. It should be noted that those skilled in the art can make several modifications and improvements without departing from the principle of the present invention, and these should also be considered to fall within the protection scope of the present invention.

[0036] The contents not described in detail in this specification are common knowledge to those skilled in the art.

[0037] This invention discloses a method for preparing trans-1,2-polyocimene (i.e., trans-1,2-poly((E)-β-ocimene)), comprising the following steps:

[0038] S1: Under inert gas protection, rare earth compounds, organoboron compounds, and alkylaluminum compounds are dissolved in an organic solvent in a certain proportion to prepare a catalyst composition solution; the molar ratio of rare earth compounds to organoboron compounds is 1:0.5-2; the molar ratio of rare earth compounds to alkylaluminum compounds is 1:0-1000.

[0039] S2: (E)-β-ocimene is directly added to the catalyst composition solution; or (E)-β-ocimene is dissolved in an organic solvent to prepare an ocimene solution, and the catalyst composition solution is added to the ocimene solution; after mixing (E)-β-ocimene or the ocimene solution with the catalyst composition solution, the reaction is carried out at 0-120°C for 10 minutes to 48 hours, and then an ethanol terminator acidified with hydrochloric acid is added to terminate the polymerization reaction; the molar ratio of (E)-β-ocimene to rare earth compound is 250-10000:1.

[0040] S3: After adding a large amount of methanol or ethanol for precipitation and drying, trans-1,2-polyocimene is obtained.

[0041] Rare earth compounds have structures as shown in Formula I:

[0042]

[0043] In Formula I, the rare earth metal Ln is selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; preferably: Sc, Y, La, Nd, Gd, Dy, Ho, Er, Tm, Yb, or Lu; most preferably: Sc, Y, Nd, Gd, Dy, Ho, Er, Tm, Yb, or Lu.

[0044] X in Formula I 1 and X 2 It is selected from alkyl, silyl, aryl, silamido, alkylamido, allyl, borohydride, chlorine, or bromine; preferably: methyl, trimethylsilylmethylene, di(trimethylsilyl)methimethylene, o-N,N'-dimethylbenzyl, hexamethylsilamido, tetramethylsilamido, allyl, 2-methylallylbenzyl, p-methylbenzyl, boron tetrahydrogen, chlorine, or bromine; most preferably: methyl, trimethylsilylmethylene, o-N,N'-dimethylbenzyl, tetramethylsilamido, allyl, 2-methylallylbenzyl, p-methylbenzyl, or boron tetrahydrogen.

[0045] L in Formula I w It is tetrahydrofuran, pyridine, or ethylene glycol dimethyl ether; w = 0, 1, or 2.

[0046] In Formula I, Q is a monoanion ligand, which has a structure as shown in Formulas II, III, IV or V;

[0047]

[0048] R in general formulas II and III 1 and R 2 Each of the following is 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, mestrimethylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diethyl-4-methylphenyl, mestriethylphenyl, 2,6-diethyl-4-tert-butylphenyl, 2,6-diisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, mestrimethylphenyl, 2,6-di-tert-butylphenyl, 2,6-di-tert-butyl-4-methylphenyl, 2,6-diphenylphenyl, 2,6-di-trifluoromethylphenyl, 2-fluorophenyl, 3-trifluoromethylphenyl, p-trifluoromethylphenyl, p-fluorophenyl or 1-naphthyl;

[0049] R 1 and R 2 Preferably, it is phenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, p-tert-butylphenyl, m-methylphenyl, m-ethylphenyl, m-isopropylphenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, o-phenylphenyl, mestrimethylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, mestriethylphenyl, 2,6-diisopropylphenyl, 2-fluorophenyl or 1-naphthyl;

[0050] R 1 and R 2 More preferably: phenyl, p-methylphenyl, m-methylphenyl, m-ethylphenyl, m-isopropylphenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, mestrimethylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, mestriethylphenyl, 2,6-diisopropylphenyl or 1-naphthyl;

[0051] R 1 and R 2 The most preferred are: phenyl, p-methylphenyl, m-ethylphenyl, m-isopropylphenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, mestrimethylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, mestriethylphenyl, 2,6-diisopropylphenyl or 1-naphthyl.

[0052] R in general formula II 3It is isopropyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, p-tert-butylphenyl, p-phenylphenyl, pentafluorophenyl, p-methoxyphenyl, p-N,N-dimethylphenyl or o-N,N-dimethylphenyl;

[0053] R 3 Preferred compounds are: isopropyl, cyclohexyl, phenyl, and p-methylphenyl;

[0054] R 3 The preferred options are cyclohexyl and phenyl.

[0055] R in general formula III 4 It is trimethylsilylmethyl, bistrimethylsilylmethyl, 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-dimethylphenyl, o-N,N-dimethylbenzyl, 2-pyridimethylene or o-meththiophenyl;

[0056] R 4 Preferred types are: trimethylsilylmethyl, phenyl, p-methylphenyl, pentafluorophenyl, and p-methoxyphenyl;

[0057] R 4 The preferred options are: phenyl and pentafluorophenyl.

[0058] R in general formulas IV and V 5 It is 2-methylpyridine, 2,6-dimethylpyridinyl or 8-methylquinoline;

[0059] R 5 Preferably, it is 2-methylpyridine or 8-methylquinoline.

[0060] R in general formulas IV and V 6 It can be hydrogen, methyl, ethyl or tert-butyl;

[0061] R 6 Preferably, it is hydrogen or tert-butyl.

[0062] The rare earth compounds used in this invention can be synthesized according to existing technologies, and those skilled in the art can synthesize them based on relevant technical information; according to the preferred combination of this invention, the following rare earth complexes 1-20 (i.e., rare earth compounds 1-20) are preferred for polymerizing (E)-β-ocimene:

[0063]

[0064]

[0065] The organoboron compound (i.e., organoboron salt) is an organoboron reagent containing the [B(C6F5)4]ˉ anion or B(C6F5)3, preferably [Ph3C][B(C6F5)4](B1), [NEt3H][B(C6F5)4](B2), B(C6F5)3(B3) or [PhNMe2H][B(C6F5)4](B4).

[0066] The alkylaluminum compound is selected from one or more of alkylaluminum, hydrogenated alkylaluminum, alkylaluminum chloride, and aluminum oxanes;

[0067] The preferred alkylaluminum compounds are trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyl dibenzylaluminum, ethyl di-p-tolylaluminum, diethylbenzylaluminum, dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, dipentylaluminum hydride, dihexylaluminum hydride, dicyclohexylaluminum hydride, dioctylaluminum hydride, and diphenylaluminum hydride. Aluminum, 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, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, and n-butylaluminoxane;

[0068] More preferably, the alkylaluminum compound is one or more of the following: trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, dimethylaluminum hydride, diethylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, and n-butylaluminoxane;

[0069] The most preferred alkyl aluminum compounds are one or more of the following: trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, methylaluminoxane, and ethylaluminoxane.

[0070] The structural formula of (E)-β-ocimene is shown in Formula VI:

[0071]

[0072] In this invention, the preparation of trans-1,2-polyocimene can be carried out by solution polymerization in the presence of a solvent (i.e., (E)-β-ocimene is dissolved in an organic solvent to prepare an ocimene solution, and the catalyst composition solution is added to the ocimene solution), or by bulk polymerization in the absence of a solvent (i.e., (E)-β-ocimene is directly added to the catalyst composition solution).

[0073] The organic solvent used in this invention is selected from one or a mixture of several saturated alkanes, aromatics, halogenated aromatics and cycloalkanes; preferably, it is a mixture of one or more of n-hexane, n-heptane, petroleum ether, cyclohexane, decahydronaphthalene, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene; most preferably, it is a mixture of one or more of n-hexane, n-heptane, petroleum ether, cyclohexane, decahydronaphthalene, toluene and chlorobenzene.

[0074] Example 1

[0075] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 8.2 mg (10 μmol) of rare earth compound 2 (i.e., complex 2), 9.3 mg (10 μmol) of [Ph3C][B(C6F5)4] (B1), and 0.4 mL (0.5 mol / L) of Al were added. i Bu3 was dissolved in 1 mL of toluene to obtain a catalyst composition solution. At 25 °C, the catalyst composition solution was added to 2 mL of toluene solution containing 0.68 g (5.0 mmol) of ocimene monomer. After stirring at 25 °C for 30 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction. The reaction solution was then poured into 100 mL of methanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was placed in a vacuum drying oven at 40 °C and dried for 48 hours to obtain a polymer with a net weight of 0.5 g, which is trans-1,2-polyocimene (yield 73%).

[0076] Using nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis showed that its trans 1,2-structure content was greater than 99%, and the content of isomorphic structures was 32%.

[0077] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The molecular weight distribution (M) is 89,000. w / M n The glass transition temperature (Tg) of the polymer was 2.83; differential scanning calorimetry (DSC) analysis yielded a glass transition temperature (Tg) of -28℃.

[0078] Example 2

[0079] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 10 μmol of rare earth compound 7 (i.e., complex 7), 10 μmol of [Ph3C][B(C6F5)4](B1) and Al were added. i Bu3 was dissolved in 1 mL of toluene to obtain a catalyst composition solution; Al i The molar ratio of Bu3 to rare earth compounds was 100. At 40°C, the catalyst composition solution was added to 20 mL of toluene solution containing 50 mmol of ocimene monomer. After stirring the reaction at 40°C for 180 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction. The reaction solution was then poured into 100 mL of methanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was placed in a vacuum drying oven at 40°C and dried for 48 hours to obtain a polymer with a net weight of 5.7 g, which is trans-1,2-polyocimene.

[0080] Using nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis showed that its trans 1,2-structure content was greater than 99%, and the content of isomorphic structures was 35%.

[0081] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The value was 951,000, and the molecular weight distribution (M) was... w / M n The value was 2.14; differential scanning calorimetry (DSC) analysis of the polymer yielded a glass transition temperature (Tg) of -28℃.

[0082] Example 3

[0083] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 10 μmol of rare earth compound 13 (i.e., complex 13), 10 μmol of [Ph3C][B(C6F5)4](B1) and Al were added. i Bu3 was dissolved in 1 mL of toluene to obtain a catalyst composition solution; Al i The molar ratio of Bu3 to rare earth compounds was 30. At 20°C, the catalyst composition solution was added to 5 mL of toluene solution containing 10 mmol of ocimene monomer. After stirring the reaction at 20°C for 60 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction. The reaction solution was then poured into 100 mL of methanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was placed in a vacuum drying oven at 40°C and dried for 48 hours to obtain a polymer with a net weight of 1.3 g, which is trans-1,2-polyocimene.

[0084] Using nuclear magnetic resonance hydrogen spectrum ( 1H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis, and the polymer's 1H NMR spectrum are shown below. Figure 1 As shown, the carbon NMR spectrum of the polymer is as follows: Figure 2 As shown, the results indicate that the content of its trans-1,2-structure is greater than 99%, and the content of its isomorphic structure is greater than 99%.

[0085] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The value is 122,000, and the molecular weight distribution (M) is... w / M n The value was 1.38; the polymer was analyzed by differential scanning calorimetry (DSC), and the polymer DSC curve is shown below. Figure 3 As shown, its glass transition temperature (Tg) is -29℃.

[0086] Example 4

[0087] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 10 μmol of rare earth compound 14 (i.e., complex 14), 10 μmol of [Ph3C][B(C6F5)4](B1) and Al were added. i Bu3 was dissolved in 1 mL of toluene to obtain a catalyst composition solution; Al i The molar ratio of Bu3 to rare earth compounds was 10. At 20°C, the catalyst composition solution was added to 2 mL of toluene solution containing 5 mmol of ocimene monomer. After stirring the reaction at 20°C for 30 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction. The reaction solution was then poured into 100 mL of methanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was placed in a vacuum drying oven at 40°C and dried for 48 hours to obtain a polymer with a net weight of 0.65 g, which is trans-1,2-polyocimene.

[0088] Using nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis, and the polymer's 1H NMR spectrum are shown below. Figure 1 As shown, the carbon NMR spectrum of the polymer is as follows: Figure 2 As shown, the results indicate that its trans-1,2-structure content is greater than 99%, and the content of isomorphic structures is mmmm = 22%.

[0089] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The molecular weight distribution (M) is 54,000. w / M n The value was 1.67; the polymer was analyzed by differential scanning calorimetry (DSC), and the polymer DSC curve is shown below. Figure 3 As shown, its glass transition temperature (Tg) is -28℃.

[0090] Example 5

[0091] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 10 μmol of rare earth compound 16 (i.e., complex 16), 10 μmol of [Ph3C][B(C6F5)4](B1) and Al were added. i Bu3 was dissolved in 1 mL of toluene to obtain a catalyst composition solution; Al i The molar ratio of Bu3 to rare earth compounds was 10. At 25°C, the catalyst composition solution was added to 2 mL of toluene solution containing 5 mmol of ocimene monomer. After stirring the reaction at 25°C for 30 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction. The reaction solution was then poured into 100 mL of methanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was placed in a vacuum drying oven at 40°C and dried for 48 hours to obtain a polymer with a net weight of 0.64 g, which is trans-1,2-polyocimene.

[0092] Using nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis, and the polymer's 1H NMR spectrum are shown below. Figure 1 As shown, the carbon NMR spectrum of the polymer is as follows: Figure 2 As shown, the results indicate that its trans 1,2-structure content is 92%, and the content of isomorphic structures is 0%.

[0093] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The value is 37,000, and the molecular weight distribution (M) is... w / M n The value was 1.60; the polymer was analyzed by differential scanning calorimetry (DSC), and the polymer DSC curve is shown below. Figure 3 As shown, its glass transition temperature (Tg) is -29℃.

[0094] Example 6

[0095] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 10 μmol of rare earth compound 19 (i.e., complex 19), 10 μmol of [Ph3C][B(C6F5)4](B1) and Al were added. i Bu3 was dissolved in 1 mL of toluene to obtain a catalyst composition solution; Al iThe molar ratio of Bu3 to rare earth compounds was 10. At 25°C, the catalyst composition solution was added to 2 mL of toluene solution containing 5 mmol of ocimene monomer. After stirring the reaction at 25°C for 20 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction. The reaction solution was then poured into 100 mL of methanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was placed in a vacuum drying oven at 40°C and dried for 48 hours to obtain a polymer with a net weight of 1.45 g, which is trans-1,2-polyocimene.

[0096] Using nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis, and the polymer's 1H NMR spectrum are shown below. Figure 1 As shown, the carbon NMR spectrum of the polymer is as follows: Figure 2 As shown, the results indicate that its trans 1,2-structure content is 94%, and the content of isomorphic structures is 0%.

[0097] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The molecular weight distribution (M) is 49,000. w / M n The value was 1.45; the polymer was analyzed by differential scanning calorimetry (DSC), and the polymer DSC curve is shown below. Figure 3 As shown, its glass transition temperature (Tg) is -27℃.

[0098] Example 7

[0099] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 10 μmol of rare earth compound 13 (i.e., complex 13), 10 μmol of [Ph3C][B(C6F5)4](B1) and Al were added. i Bu3 was dissolved in 1 mL of toluene to obtain a catalyst composition solution; Al i The molar ratio of Bu3 to rare earth compounds was 20. At 80°C, the catalyst composition solution was added to 2 mL of toluene solution containing 5 mmol of ocimene monomer. After stirring the reaction at 80°C for 30 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction. The reaction solution was then poured into 100 mL of methanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was placed in a vacuum drying oven at 40°C and dried for 48 hours to obtain a polymer with a net weight of 0.54 g, which is trans-1,2-polyocimene.

[0100] Using nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis, and the polymer's 1H NMR spectrum are shown below. Figure 1 As shown, the carbon NMR spectrum of the polymer is as follows: Figure 2 As shown, the results indicate that its trans-1,2-structure content is greater than 99%, and the content of isomorphic structures is mmmm = 90%.

[0101] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The value is 52,000, and the molecular weight distribution (M) is... w / M n The value was 1.61; the polymer was analyzed by differential scanning calorimetry (DSC), and the polymer DSC curve is shown below. Figure 3 As shown, its glass transition temperature (Tg) is -30℃.

[0102] Example 8

[0103] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 10 μmol of rare earth compound 13 (i.e., complex 13), 10 μmol of [PhNMe2H][B(C6F5)4](B4) and Al were added. i Bu3 was dissolved in 1 mL of toluene to obtain a catalyst composition solution; Al i The molar ratio of Bu3 to rare earth compounds was 10. At 100°C, the catalyst composition solution was added to 2 mL of toluene solution containing 5 mmol of ocimene monomer. After stirring the reaction at 100°C for 10 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction. The reaction solution was then poured into 100 mL of methanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was placed in a vacuum drying oven at 40°C and dried for 48 hours to obtain a polymer with a net weight of 0.52 g, which is trans-1,2-polyocimene.

[0104] Using nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis, and the polymer's 1H NMR spectrum are shown below. Figure 1 As shown, the carbon NMR spectrum of the polymer is as follows: Figure 2 As shown, the results indicate that its trans 1,2-structure content is 97%, and the content of isomorphic structures is 85%.

[0105] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The value is 37,000, and the molecular weight distribution (M) is... w / M n The value was 1.57; the polymer was analyzed by differential scanning calorimetry (DSC), and the polymer DSC curve is shown below. Figure 3 As shown, its glass transition temperature (Tg) is -29℃.

[0106] Example 9

[0107] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 10 μmol of rare earth compound 13 (i.e., complex 13), 10 μmol of [Ph3C][B(C6F5)4](B1) and Al were added. i Bu3 was dissolved in 1 mL of toluene to obtain a catalyst composition solution; Al i The molar ratio of Bu3 to rare earth compounds was 200. At 50°C, the catalyst composition solution was added to 30 mL of toluene solution containing 100 mmol of ocimene monomer. After stirring the reaction at 50°C for 240 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction. The reaction solution was then poured into 100 mL of methanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was placed in a vacuum drying oven at 40°C and dried for 48 hours to obtain a polymer with a net weight of 12.5 g, which is trans-1,2-polyocimene.

[0108] Using nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis, and the polymer's 1H NMR spectrum are shown below. Figure 1 As shown, the carbon NMR spectrum of the polymer is as follows: Figure 2 As shown, the results indicate that its trans-1,2-structure content is greater than 99%, and the content of isomorphic structures is 97%.

[0109] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The molecular weight distribution (M) is 974,000. w / M n The value was 1.84; the polymer was analyzed by differential scanning calorimetry (DSC), and the polymer DSC curve is shown below. Figure 3 As shown, its glass transition temperature (Tg) is -29℃.

[0110] Example 10

[0111] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 10 μmol of rare earth compound 2 (i.e., complex 2) and 5 μmol of [Ph3C][B(C6F5)4] (B1) were dissolved in 1 mL of toluene to obtain a catalyst composition solution. At 25 °C, 2.5 mmol of (E)-β-ocimene was directly added to the catalyst composition solution. After stirring the reaction at 25 °C for 90 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction. The reaction solution was then poured into 100 mL of ethanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle. The obtained polymer was placed in a vacuum drying oven at 40 °C and dried for 48 hours to obtain a polymer with a net weight of 0.28 g, i.e., trans-1,2-polyocimene.

[0112] Using nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis showed that its trans 1,2-structure content was greater than 99%, and the content of isomorphic structures was 32%.

[0113] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The molecular weight distribution (M) is 32,000. w / M n The value was 2.14; differential scanning calorimetry (DSC) analysis of the polymer yielded a glass transition temperature (Tg) of -28℃.

[0114] Example 11

[0115] Under inert gas protection (i.e., under anhydrous and oxygen-free conditions), 10 μmol of rare earth compound 2 (i.e., complex 2), 20 μmol of [Ph3C][B(C6F5)4](B1) and Al were added. i Bu3 was dissolved in 1 mL of toluene to obtain a catalyst composition solution; Al i The molar ratio of Bu3 to rare earth compounds was 1000; 2.5 mmol of (E)-β-ocimene was directly added to the catalyst composition solution at 25 °C; after stirring the reaction at 25 °C for 30 min, a small amount of hydrochloric acid-acidified ethanol solution was added to terminate the polymerization reaction; then the reaction solution was poured into 100 ml of ethanol containing a small amount of hydrochloric acid and stabilizer (BHT) to settle; the obtained polymer was placed in a vacuum drying oven at 40 °C and dried for 48 hours to obtain a polymer with a net weight of 0.3 g, which is trans-1,2-polyocimene.

[0116] Using nuclear magnetic resonance hydrogen spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The polymer (i.e., ocimene homopolymer) obtained by C NMR analysis showed that its trans 1,2-structure content was greater than 99%, and the content of isomorphic structures was 31%.

[0117] The number-average molecular weight (M) of the polymer was determined by GPC analysis. n The value was 0.94 million, and the molecular weight distribution (M) was... w / M n The glass transition temperature (Tg) of the polymer was 2.57; differential scanning calorimetry (DSC) analysis yielded a glass transition temperature (Tg) of -29℃.

[0118] The present invention has been described in detail above with reference to specific embodiments and exemplary examples. These descriptions are exemplary and not exhaustive, and are not limited to the disclosed embodiments; the above descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and implementation methods of the present invention without departing from the spirit and scope of the present invention, and all such modifications and improvements fall within the scope of the present invention; the scope of protection of the present invention is determined by the appended claims.

Claims

1. A method for preparing trans-1,2-polyocimene, characterized in that, Includes the following steps: S1: Under inert gas protection, a rare earth compound, an organoboron compound, and an alkylaluminum compound are dissolved in an organic solvent in a certain proportion to prepare a catalyst composition solution; 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 It can be alkyl, silyl, aryl, silamido, alkylamido, allyl, borohydride, chlorine, or bromine; L w It is tetrahydrofuran, pyridine, or ethylene glycol dimethyl ether; w = 0, 1, or 2; Q is a monoanion ligand; The monoanion ligand has a structure as shown in Formula III, IV or V: Among them, R in general formula III 1 and R 2 Each of the following is 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, mestrimethylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diethyl-4-methylphenyl, mestriethylphenyl, 2,6-diethyl-4-tert-butylphenyl, 2,6-diisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, mestrimethylphenyl, 2,6-di-tert-butylphenyl, 2,6-di-tert-butyl-4-methylphenyl, 2,6-diphenylphenyl, 2,6-di-trifluoromethylphenyl, 2-fluorophenyl, 3-trifluoromethylphenyl, p-trifluoromethylphenyl, p-fluorophenyl or 1-naphthyl; R in general formula III 4 It is trimethylsilylmethyl, bistrimethylsilylmethyl, 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-dimethylphenyl, o-N,N-dimethylbenzyl, 2-pyridimethylene or o-meththiophenyl; R in general formulas IV and V 5 It is 2-methylpyridine, 2,6-dimethylpyridinyl or 8-methylquinoline; R in general formulas IV and V 6 It can be hydrogen, methyl, ethyl or tert-butyl; S2: (E)-β-ocimene is directly added to the catalyst composition solution; or (E)-β-ocimene is dissolved in an organic solvent to prepare an ocimene solution, and the catalyst composition solution is added to the ocimene solution; after mixing (E)-β-ocimene or the ocimene solution with the catalyst composition solution, the mixture is reacted at a preset temperature for a period of time, and a terminator is added to terminate the polymerization reaction; S3: After sedimentation and drying, trans-1,2-polyocimene is obtained.

2. The method for preparing trans-1,2-polyocimene according to claim 1, characterized in that, The molar ratio of the rare earth compound to the organoboron compound is 1:0.5 to 2; the molar ratio of the rare earth compound to the alkylaluminum compound is 1:0 to 1000.

3. The method for preparing trans-1,2-polyocimene according to claim 1, characterized in that, The molar ratio of (E)-β-ocimene to the rare earth compound is 250 to 10000:

1.

4. The method for preparing trans-1,2-polyocimene according to claim 1, characterized in that, The organoboron compound is an organoboron reagent containing the [B(C6F5)4]ˉ anion or B(C6F5)3.

5. The method for preparing trans-1,2-polyocimene according to claim 4, characterized in that, The organoboron compound is [Ph3C][B(C6F5)4], [NEt3H][B(C6F5)4], B(C6F5)3 or [PhNMe2H][B(C6F5)4].

6. The method for preparing trans-1,2-polyocimene according to claim 1, characterized in that, The alkylaluminum compound is one or more selected from alkylaluminum, hydrogenated alkylaluminum, alkylaluminum chloride, and aluminoxane.

7. The method for preparing trans-1,2-polyocimene according to claim 1, characterized in that, The preset temperature in step S3 is 0 to 120°C, the reaction time is 10 minutes to 48 hours, and the terminating agent is hydrochloric acid-acidified ethanol.

8. The use of trans-1,2-polyocimene prepared by any one of claims 1-7 in the manufacture of adhesives and rubber products.

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