CN116693733A - Isotactic cis-1, 4-poly-ocimene and preparation method and application thereof - Google Patents

Isotactic cis-1, 4-poly-ocimene and preparation method and application thereof Download PDF

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Publication number
CN116693733A
CN116693733A CN202310681112.7A CN202310681112A CN116693733A CN 116693733 A CN116693733 A CN 116693733A CN 202310681112 A CN202310681112 A CN 202310681112A CN 116693733 A CN116693733 A CN 116693733A
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ocimene
cis
isotactic
poly
methylphenyl
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汪骐远
李世辉
崔冬梅
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/22—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having three or more carbon-to-carbon double bonds

Abstract

The invention discloses an isotactic cis-1, 4-poly-ocimene and a preparation method and application thereof, belonging to the technical field of olefin polymer preparation. The invention provides a novel isotactic cis-1, 4-poly beta-ocimene, wherein the cis-1, 4-structure content is more than or equal to 95 percent, and the isotactic structure content is more than or equal to 90 percent (mm). Meanwhile, the invention provides a rare earth catalyst system with high selectivity of all-high cis-1, 4 structure for beta ocimene monomer polymerization, wherein the cis-1, 4-selectivity can be up to more than 99%, and the isotactic selectivity can be up to more than 99% (mm).

Description

Isotactic cis-1, 4-poly-ocimene and preparation method and application thereof
Technical Field
The invention relates to an isotactic cis-1, 4-poly-ocimene and a preparation method and application thereof, belonging to the technical field of olefin polymer preparation.
Background
As a terpene derivative, ocimene is present in a plant essential oil such as ocimene oil and lavender oil. The conjugated diene monomer contains conjugated diene structural units in the molecule, and is a biobased monomer with larger potential prospect. However, there have been few reports on the highly selective polymerization of Guan Luole olefins. Li Xiaofang et al, beijing university, utilize a cyclopentadienyl scandium, lutetium, yttrium and dysprosium catalyst system to catalyze the homopolymerization 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). Italy Capacchione et al reported that isotactic 1, 2-poly-ocimene was synthesized at low temperature and trans 1, 4-predominantly poly-ocimene (> 70%) was synthesized at high temperature using [ OSSO ] titanium complexes to catalyze ocimene polymerization (Polymer 2017,131,151-159). Recently, valencia et al studied the polymerization of ocimene using a Ziegler-Natta neodymium catalyst, yielding a poly (RSCAAdvances 2020,10,36539-36545) with a 1,4 structure content of about 79% (cis+trans). To date, there has been no report of isotactic cis-1, 4-poly-beta-ocimene.
Disclosure of Invention
The invention aims to provide an isotactic cis-1, 4-poly-ocimene and a catalytic system, a preparation method and application thereof.
The technical scheme of the invention is as follows:
it is an object of the present invention to provide an isotactic cis-1, 4-poly-ocimene having a molecular weight of from 1000 to 1000000 and a structural formula as follows:
wherein n is an integer.
Further defined, the cis 1, 4-structure content in the polymer is greater than or equal to 95% and the isotactic content is greater than or equal to 90%.
The second object of the present invention is to provide a process for preparing isotactic cis-1, 4-poly-ocimene, which comprises the steps of taking rare earth complex, organoboron compound and cocatalyst as a catalytic system under the protection of inert gas, catalyzing the polymerization of ocimene monomer in the presence of organic solvent or no solvent, settling the product after the reaction is finished, and drying to obtain isotactic cis-1, 4-poly-ocimene.
Further defined, the rare earth complex has the structural formula:
wherein Q is a chelating ligand, X 1 And X 2 Is a monoanionic ligand, ln is scandium, yttrium or lanthanide rare earth element, L is tetrahydrofuran, pyridine or ethylene glycol dimethyl ether, and w is 0,1 or 2.
Further defined, Q is selected from one of formulas III-VI;
wherein R is 1 Methyl or tert-butyl; r is R 2 And R is 4 Phenyl, p-methylphenyl, cyclohexyl, isopropyl or tert-butyl; r is R 3 Is hydrogen or methyl; ar (Ar) 1 And Ar is a group 2 Is phenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, p-tert-butylphenyl, m-methylphenyl, m-ethylphenyl, m-isopropylphenyl, mesitylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diethyl-4-methylphenyl, mesitylphenyl, 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-bis (trifluoromethyl) phenyl, 2-fluorophenyl, 3- (trifluoromethyl) phenyl, p-trifluoromethylphenyl or p-fluorophenyl.
Further defined, R 1 Is tert-butyl.
Further defined, R 2 Is phenyl or p-methylphenyl.
Further defined, R 3 Is methyl.
Further defined, R 4 Is phenyl or p-methylphenyl.
Further defined, ar 1 And Ar is a group 2 Is phenyl, p-methylphenyl, o-ethylphenyl, o-isopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diisopropylphenyl or mesityl.
Further defined, ar 1 And Ar 2 Is 2, 6-dimethylphenyl, mesityl or 2, 6-diethylphenyl.
Still further defined, ln is scandium, yttrium, lanthanum, cerium, neodymium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium.
Further defined, ln is lutetium, yttrium, holmium, erbium, lutetium, gadolinium, neodymium, or lanthanum.
Further defined, ln is yttrium, holmium, erbium, gadolinium, neodymium or lanthanum.
Further defined, X 1 And X 2 Is alkyl, allyl, 2-methylallyl, aryl, benzyl, cycloalkyl, borane, silamino, silane, halogen, hydrogen, tetramethyl aluminum or 2-N' N-dimethylbenzyl.
Further defined, X 1 And X 2 Is trimethylsilyl methylene [ CH ] 2 SiMe 3 ] – Bis (trimethylsilyl) methine [ CH (SiMe) 3 ) 2 ] – Bis (trimethylsilyl) amino [ N (SiMe) 3 ) 2 ] – Bis (dimethylsilyl) amino [ N (SiHMe) 2 ) 2 ] – 2-N' N-dimethylbenzyl, benzyl, p-methylbenzyl, [ BH ] 4 ] – Or [ AlMe ] 4 ] – 。
Further defined, X 1 And X 2 Is 2-N' N-dimethylbenzyl, benzyl, p-methylbenzyl, bis (dimethylsilyl) amino, [ BH ] 4 ] – Or [ AlMe ] 4 ] – 。
Further defined, the rare earth complex is one of the following structural formulas:
further defined, the cocatalyst is an organoboron salt and/or an alkyl aluminum compound.
Further defined, the organoboron salt is a salt containing [ B (C 6 F 5 ) 4 ] - Is an organoboron reagent of (a).
Further defined, the organoboron salt is [ NMeH (C 18 H 37 ) 2 ][B(C 6 F 5 ) 4 ]、[Ph 3 C][B(C 6 F 5 ) 4 ]、[PhNMe 2 H][B(C 6 F 5 ) 4 ]One or more of them are mixed in an arbitrary ratio.
In a further more specific definition of the terms, the alkylaluminum compound is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, ethyldi-p-tolylaluminum, diethylbenzylaluminum, dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, dipentylaluminum hydride, dihexylaluminum hydride, dicyclohexylaluminum, dioctylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, ethylbenzylaluminum hydride, ethylp-tolylaluminum hydride, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dipentylaluminum chloride, dicyclohexylaluminum chloride, diphenylaluminum chloride, ditolylaluminum chloride, dibenzylaluminum chloride, ethylaluminum chloride, n-butylaluminum chloride, methylaluminum chloride, or mixtures of any of these compounds.
Further defined, the structural formula of the ocimene monomer is as follows:
further limited, the organic solvent is one or more of saturated alkane, arene, halogenated arene and cycloparaffin and is mixed in any proportion.
Further limited, the organic solvent is one or more of n-hexane, n-heptane, petroleum ether, cyclohexane, decalin, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene mixed in any proportion.
Further limited, the organic solvent is one or more of n-hexane, n-heptane, petroleum ether, cyclohexane, decalin, toluene and chlorobenzene, and the organic solvent is mixed in any proportion.
Further defined, the molar ratio of the ocimene monomer to the rare earth complex is (100 to 10000): 1.
further defined, the molar ratio of the ocimene monomer to the rare earth complex is (500 to 5000): 1.
further defined, the molar ratio of rare earth complex, organoboron compound and promoter is 1: (0-2): (0-500).
Further defined, the molar ratio of rare earth complex, organoboron compound and promoter is 1:1: (0-200).
Further defined, the polymerization temperature is-30 to 100 ℃ and the time is 0.1 to 48 hours.
Further defined, the polymerization temperature is 25 to 80℃and the time is 0.5 to 8 hours.
Further limiting, adding ethanol hydrochloride solution with volume concentration of 10% to terminate the polymerization reaction after the polymerization reaction is completed, pouring the reaction solution into methanol to settle, and obtaining the isotactic-1, 4-poly-ocimene; and then the obtained polymer is placed into a vacuum drying oven for drying, so as to obtain the isotactic-1, 4-poly-ocimene with constant dry weight.
It is a further object of the present invention to provide the use of isotactic cis-1, 4-poly-ocimene, particularly as a rubber material for the preparation of rubber articles.
The invention has the following beneficial effects:
(1) The invention provides a novel isotactic cis-1, 4-poly beta-ocimene, wherein the cis-1, 4-structure content is more than or equal to 95 percent, and the isotactic structure content is more than or equal to 90 percent (mm).
(2) The invention provides a rare earth catalyst system with high selectivity of all-high cis-1, 4 structure for beta ocimene monomer polymerization, wherein the cis-1, 4-selectivity can be up to more than 99%, and the isotactic selectivity can be up to more than 99% (mm).
(3) The novel biomass elastomer isotactic cis-1, 4-poly beta-ocimene provided by the invention can be used as a rubber material for various rubber products.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of isotactic cis-1, 4-poly-ocimene obtained in example 1;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of the isotactic cis-1, 4-poly-ocimene obtained in example 1.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
Under anhydrous and anaerobic conditions, rare earth compound 1 (10.0 mg, 10. Mu. Mol), [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) and Al i Bu 3 1mL of (0.2 mL. Times.0.5M) toluene solution was added to (2 mL) of a toluene solution containing ocimene monomer (0.68 g,5.0 mmol) at 25 ℃. After stirring at high speed for 90min, a small amount of ethanol solution was added to terminate the polymerization. The reaction solution was then poured into a container containing a small amount of hydrochloric acid and a stabilizer (BHT)Sedimentation was performed in methanol (100 ml). The resulting polymer was dried in a vacuum oven at 40℃for 48 hours to give a net weight of 0.5g of polymer (yield 73%). Hydrogen spectrum by nuclear magnetic resonance 1 H-NMR as in FIG. 1) and nuclear magnetic resonance carbon spectrum [ ] 13 C-NMR, as in FIG. 2), analysis of the resulting ocimene homopolymer showed a cis-1, 4-selectivity of greater than 99% and an isotactic selectivity of greater than 99%. The number average molecular weight (M) was determined by GPC analysis n ) 10.5 ten thousand of molecular weight distribution (M w /M n ) 1.16.
Examples 2 to 7
Examples 2 to 7 differ from example 1 in the details given in table 1 below, and the rest of the procedure and the parameter settings are the same as in example 1.
TABLE 1
Note that: the input amount of the rare earth compound is 10 mu mol, and the organic boron salt is selected from [ Ph ] 3 C][B(C 6 F 5 ) 4 ](A)、[NMeH(C 18 H 37 ) 2 ][B(C 6 F 5 ) 4 ](B) Or [ PhNMe ] 2 H][B(C 6 F 5 ) 4 ](C)。
As is clear from the above table, the polymer prepared is isotactic cis-1, 4-poly beta-ocimene, the cis-1, 4-structure content in the structure is more than or equal to 95%, and the isotactic structure content is more than or equal to 90% (mm).
While the invention has been described in terms of preferred embodiments, it is not intended to be limited thereto, but rather to enable any person skilled in the art to make various changes and modifications without departing from the spirit and scope of the present invention, which is therefore to be limited only by the appended claims.

Claims (10)

1. An isotactic cis-1, 4-poly-ocimene, characterized in that the molecular weight of the polymer is 1000-1000000, the structural formula is as follows:
wherein n is an integer.
2. The isotactic cis-1, 4-poly-ocimene of claim 1 wherein the polymer has a cis-1, 4-structure content of not less than 95% and an isotactic content of not less than 90%.
3. A process for preparing isotactic cis-1, 4-poly-ocimene as claimed in claim 1, wherein the rare earth complex, organoboron compound and cocatalyst are used as catalytic system under the protection of inert gas, the polymerization of ocimene monomers is catalyzed in the presence of organic solvent or no solvent, and after the reaction, the product is settled and dried to obtain isotactic cis-1, 4-poly-ocimene.
4. The process for preparing isotactic cis-1, 4-poly-ocimene as claimed in claim 3, wherein the rare earth complex has the formula:
wherein Q is a chelating ligand, X 1 And X 2 Is a monoanionic ligand, ln is scandium, yttrium or lanthanide rare earth element, L is tetrahydrofuran, pyridine or ethylene glycol dimethyl ether, and w is 0,1 or 2.
5. The process for preparing isotactic cis-1, 4-poly ocimene according to claim 4, wherein Q is selected from one of the formulae III to VI;
wherein R is 1 Methyl or tert-butyl; r is R 2 And R is 4 Is phenyl, p-methylphenyl, cyclohexyl, isopropyl or t-butylA base; r is R 3 Is hydrogen or methyl; ar (Ar) 1 And Ar is a group 2 Is phenyl, p-methylphenyl, p-ethylphenyl, p-isopropylphenyl, p-tert-butylphenyl, m-methylphenyl, m-ethylphenyl, m-isopropylphenyl, mesitylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diethyl-4-methylphenyl, mesitylphenyl, 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-bis (trifluoromethyl) phenyl, 2-fluorophenyl, 3- (trifluoromethyl) phenyl, p-trifluoromethylphenyl or p-fluorophenyl.
6. The process for preparing isotactic cis-1, 4-poly-ocimene according to claim 4, wherein X 1 And X 2 Is alkyl, allyl, 2-methylallyl, aryl, benzyl, cycloalkyl, borane, silamino, silane, halogen, hydrogen, tetramethyl aluminum or 2-N' N-dimethylbenzyl.
7. The process for preparing isotactic cis-1, 4-poly-ocimene according to claim 3, wherein the cocatalyst is an organoboron salt and/or an alkylaluminum compound, the organoboron salt being a compound containing [ B (C) 6 F 5 ) 4 ] - Is an organoboron reagent of (a).
8. The method for preparing isotactic cis-1, 4-poly-ocimene according to claim 3, wherein the molar ratio of ocimene monomer to rare earth complex, organoboron compound and cocatalyst is (100 to 10000): 1: (0-2): (0-500).
9. The process for preparing isotactic cis-1, 4-poly-ocimene according to claim 3, wherein the polymerization temperature is from-30 to 100℃and the time is from 0.1 to 48 hours.
10. Use of the isotactic cis-1, 4-poly-ocimene according to claim 1 as a rubber material for the preparation of rubber articles.
CN202310681112.7A 2023-06-09 2023-06-09 Isotactic cis-1, 4-poly-ocimene and preparation method and application thereof Pending CN116693733A (en)

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