CN110628001A - Sustainable high polymer material and preparation method thereof - Google Patents

Sustainable high polymer material and preparation method thereof Download PDF

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CN110628001A
CN110628001A CN201910917255.7A CN201910917255A CN110628001A CN 110628001 A CN110628001 A CN 110628001A CN 201910917255 A CN201910917255 A CN 201910917255A CN 110628001 A CN110628001 A CN 110628001A
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pinene
compound
monomer
sustainable
vinyl ether
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朱新远
张俊
张宇轩
薛锋
童刚生
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F116/12—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F116/14—Monomers containing only one unsaturated aliphatic radical
    • C08F116/16—Monomers containing no hetero atoms other than the ether oxygen
    • C08F116/18—Acyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
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Abstract

The invention provides a sustainable high polymer material and a preparation method thereof, relating to the technical field of high polymer synthetic chemistry. The method makes pinene raw material widely existing in nature react with vinyl ether or epoxy compound under the catalysis of nonmetal Lewis acid to efficiently prepare polyolefin or polyether high molecular material with high molecular weight. In addition, random or block copolymers with different molecular weights, side group compositions and sequence distribution can be conveniently prepared by changing the external conditions of the polymerization reaction (such as monomer types, reaction temperature, catalyst dosage and the like). The cation hybrid polymerization method adopted by the invention has mild reaction conditions, is simple and safe; the reaction monomer raw material has the advantages of wide source, simplicity and low cost; the prepared polymer has high molecular weight and no metal residue, and accords with the concept of green sustainable chemical development.

Description

Sustainable high polymer material and preparation method thereof
Technical Field
The invention relates to the technical field of polymer synthetic chemistry, in particular to a sustainable high polymer material and a preparation method thereof, and especially relates to a method for preparing the sustainable high polymer material based on natural organic monomer raw materials under the action of a boron-containing nonmetal catalyst.
Background
With the development of green sustainable chemistry, natural biomass raw materials play an increasingly important role in the preparation of high molecular materials. Pinene is used as a biomass organic molecule with low price and wide source, contains double bond groups similar to isobutene in the structure, and is a potential natural raw material for preparing high polymer materials.
At present, the synthesis method for preparing the high polymer material based on the monomer pinene mainly comprises two methods: (1) pinene is converted into lactone, lactam or epoxy compound monomer through multi-step chemical reaction, and then polyester, polyamide or polyether polymer is prepared through ring-opening polymerization, although the prepared polymer material has good application potential, the synthetic process of the method is long and complex; (2) the polyprene homopolymer and the copolymer thereof are prepared by cationic polymerization by virtue of the catalytic action of a metal catalyst (such as aluminum, titanium or copper metal organic). Although the method is simple and convenient, the molecular weight of the polymer is not high and the molecular weight distribution is wide, and the obvious problem of metal residue exists, so that the application of the polymer material in the fields of biomedicine, optics, microelectronic devices and the like is not facilitated. Therefore, the simple and efficient polymerization strategy is found, which is a main problem in the preparation of pinene high molecular materials at present.
The hybrid copolymerization is a reaction for polymerizing two or more monomers with different types to form a new copolymer, and provides a shortcut for synthesizing a novel macromolecule and chemically modifying the macromolecule. At present, the development of hybrid polymerization is still not mature enough, and has many defects, such as the types of monomers suitable for polymerization are relatively limited, the research on the polymerization mechanism is not deep enough, the initiator and the catalytic system are to be optimized, and thus the hybrid copolymerization is very limited in the practical application research. By combining the situations, the monomer type of hybrid copolymerization is developed, particularly natural organic molecules (such as pinene) which do not depend on fossil raw materials are developed, the advantages of hybrid copolymerization are fully exerted, an effective scheme which can solve the difficult problem of synthesizing pinene polymers and promote the development of hybrid polymerization is possible to be provided, and the method has important significance for preparing green sustainable high molecular materials.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a sustainable high polymer material, which overcomes the dilemma that hybrid copolymerization raw materials depend on fossil raw materials. The invention adopts the conventional boron-containing nonmetal Lewis acid catalyst to catalyze the polymerization reaction of organic raw material pinene or pinene and general monomer vinyl ether or epoxy compound which widely exist in nature. The method regulates and controls the reaction rate of active species of different monomers in the hybrid polymerization process by changing the conditions of the charge ratio of the monomers, the polymerization reaction temperature and the like, thereby realizing the regulation and control of the molecular weight, the structural sequence and the property of the polymer and preparing the polyolefin or polyether high molecular material with high molecular weight without metal residue.
The first purpose of the invention is realized by the following technical scheme: a method for preparing sustainable high molecular material, including through polymerization reaction between pinene monomer or through pinene monomer and vinyl ether monomer compound, one kind of epoxy compound carries on polymerization reaction to prepare polyolefin or polyether high molecular material of high molecular weight; the polymerization reaction is shown as formula I, formula II or formula III:
formula I:
formula II:
formula III:
wherein x and y respectively represent the polymerization degree of the polymer, x is more than or equal to 1, and y is more than or equal to 1.
Further, the feeding ratio of the pinene monomer to the vinyl ether monomer compound or the epoxy compound is 1:99-99:1, and the feeding ratio of the pinene monomer to the vinyl ether monomer compound or the epoxy compound is 25:75-75: 25.
Further, the vinyl ether monomer Compound (CH)2CH-OR1) Comprises one or more of linear alkyl vinyl ether (1), isopropyl vinyl ether (2) and 2-chloroethyl vinyl ether (3).
Further wherein the linear alkyl vinyl ether has an alkyl carbon number of 1 to 10. The specific structural formula is as follows:
further, the epoxy compound (R)2CH(O)CHR3) Comprises one or more of methyl propylene oxide (1), cyclopentane epoxide (2), cyclohexane epoxide (3), cyclooctane epoxide (4), linear alkyl ethylene oxide, branched alkyl ethylene oxide (5), linear alkyl glycidyl ether, branched alkyl glycidyl ether (6), phenyl glycidyl ether (7), benzyl glycidyl ether (8), allyl glycidyl ether (9) and glycidyl methacrylate (10).
Still further, the linear alkyl ethylene oxide, branched alkyl ethylene oxide, linear alkyl glycidyl ether, branched alkyl glycidyl ether have an alkyl carbon number of 1 to 10. The specific structural formula is as follows:
further, the preparation method of the sustainable high polymer material specifically comprises the following steps: dissolving a pinene monomer or a pinene monomer and a vinyl ether compound or a pinene monomer and an epoxy compound in an organic solvent, quickly adding a catalyst M, and carrying out closed polymerization reaction in an inert gas atmosphere.
Further, the catalyst M comprises a boron-containing Lewis acid catalyst, the boron-containing Lewis acid catalyst comprises one or more of trifluorobenzene borane, pentafluorophenylboron and boron trifluoride, and the dosage of the catalyst M is 0.5 per mill to 1 percent of the feeding molar quantity of the polymerization monomers.
Further, the organic solvent includes dichloromethane, tetrahydrofuran, toluene, xylene, acetone.
Further, the polymerization reaction temperature is-90 ℃ to 30 ℃, and the reaction time is 10min to 48 h.
Further, the polymerization reaction comprises reacting at-90 ℃ for 10 to 30min and then reacting at-20 ℃ for 1 to 2h to prepare the block copolymer.
Further, the method for preparing the sustainable polymer material further comprises a pretreatment step of a pinene monomer or a vinyl ether monomer compound or an epoxy compound, wherein the pretreatment step specifically comprises the following steps: adding pinene monomer or vinyl ether monomer compound or epoxy compound into a round-bottom flask, adding calcium hydride, continuously stirring for 12h at room temperature, and distilling to obtain liquid.
The second purpose of the invention is to provide a sustainable high molecular material, and the second purpose of the invention is realized by the following technical scheme: a sustainable polymer material, comprising a compound 1, a compound 2, and a compound 3 as shown below;
compound 1:
compound 2:
compound 3:
x is greater than or equal to 1, and y is greater than or equal to 1.
Compared with the prior art, the invention has the following advantages and outstanding effects:
1. the pinene raw material adopted by the hybrid polymerization is an organic molecule from nature, the price is low, the source is wide, the comonomer vinyl ether or epoxy compound is also a universal monomer raw material, and compared with the traditional polymerization which completely depends on stone raw materials such as petroleum, the hybrid polymerization disclosed by the invention converts the natural raw material into a practical high polymer material, and accords with the concept of green sustainable chemical development. The invention provides a cationic hybrid polymerization method based on natural organic raw materials, which is characterized in that pinene monomers or pinene and vinyl ether/epoxy compounds are subjected to hybrid polymerization, and the molecular weight and the sequence structure composition of a copolymer are changed by regulating and controlling the monomer types, the reaction temperature, the catalyst dosage and the like, so that sustainable high polymer materials with different physicochemical properties are prepared.
2. Compared with other catalysis technologies, the catalysis method has the advantages of safe and mild reaction conditions (room temperature or low temperature), low catalyst consumption (equivalent weight of five ten-thousandths of monomers can be reduced) and no metal residue, simple post-treatment, and capability of preparing high molecular weight polymer materials, wherein the molecular weight of the high molecular weight polymer materials is about 3000-48000, and the dispersion coefficient of the high molecular weight polymer materials is 1.2-2.2.
3. The hybrid polymerization method applied by the invention is suitable for various monomers, has convenient sources, is an important embodiment of cationic hybrid polymerization in practical application, solves the problems of the prior hybrid polymerization limited monomer application types and extremely limited application, and is beneficial to the application development of the novel polymerization method.
4. The hybrid polymerization process can prepare random and block polymer materials with different molecular weights and different sequence compositions by regulating and controlling factors such as monomer types and external environments (such as reaction temperature, catalyst dosage and solvent polarity).
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a nuclear magnetic hydrogen spectrum and gel permeation chromatography plot of β -pinene and poly (β -pinene);
FIG. 2 is a nuclear magnetic hydrogen spectrum of polyvinyl ether, poly (. beta. -pinene) and copolymer poly (pinene-co-vinyl ether);
FIG. 3 is a nuclear magnetic hydrogen spectrum of Poly (PCHO), poly (. beta. -pinene) (PPE), and copolymer poly (pinene-co-cyclohexene oxide) (P (PE-co-CHO));
FIG. 4 is a comparison of infrared spectra of Polycyclohexylepoxide (PCHO), poly (. beta. -pinene) (PPE), and copolymer poly (pinene-co-epoxycyclohexane) (P (PE-co-CHO));
FIG. 5 is a gel permeation chromatography graph of random copolymer poly (pinene-co-epoxycyclohexane) (P (PE-co-CHO)) with different compositional proportions;
FIG. 6 is a DSC plot (A) and thermogravimetric plot (B) of Polycyclohexylepoxide (PCHO), poly (. beta. -pinene) (PPE) and copolymer poly (pinene-co-epoxycyclohexane) (P (PE-co-CHO)) of different compositional proportions;
FIG. 7 is a graph of the wide-angle X-ray diffraction patterns of polycyclohexane oxide (PCHO), poly (. beta. -pinene) (PPE), and copolymer poly (pinene-co-cyclohexene oxide) (P (PE-co-CHO)) in different compositional proportions;
FIG. 8 is a nuclear magnetic hydrogen spectrum comparison of a low temperature homopolymer Poly (PCHO) with a block copolymer poly (β -pinene) -b-poly (cyclohexene oxide) (PPE-b-PCHO);
FIG. 9 is a gel permeation chromatogram of a low temperature homopolymer poly (cyclohexene oxide) (PCHO) and a block copolymer poly (beta-pinene) -b-poly (cyclohexene oxide) (PPE-b-PCHO).
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Evaluation standard and evaluation method
Example 1: preparation of poly (beta-pinene)
A preparation method of a sustainable high polymer material specifically comprises the following steps: pretreatment of monomer beta-pinene: the method comprises the following specific steps: circle at 50mLThe flask was charged with 25mL (+) -beta-pinene and calcium hydride (CaH)2) Stirring at room temperature for 12h, and distilling under reduced pressure<1mmHg, 45 ℃) to obtain colorless and transparent liquid which is the monomer beta-pinene.
Polymerization: adding 400 μ L of dry dichloromethane solution into a polymerization bottle weighing beta-pinene (68mg, 0.5mmol), placing in a low temperature bath at-20 deg.C, mixing well, adding boron-containing Lewis acid catalyst B (C) after temperature is stable6F5)3The reaction was continued for 10min with (1%, 2.6mg, 5. mu. mol) catalyst solution.
Terminating the polymerization: the polymerization was terminated by adding 50. mu.L of a methanol solution containing 1% ammonia water, and the product was precipitated in methanol to obtain a white solid polymer. The molecular weight of the polymer was about 3500, the molecular weight distribution was about 1.57, and the structure of poly (. beta. -pinene) is shown by the following formula:
nuclear magnetism of poly (beta-pinene) (PPE)1H NMR(500MHz,CDCl3)δ＝5.28-5.40(1H,-C＝CH-),2.34(1H,-C＝CH-CH2-),2.15(2H,-C(CH3)2-CH2-),1.61-1.87(2H,-CH2CH2-；1H,-C＝CHCH2-),1.43(2H,-CH2CH2-),1.07(1H,-CH2CH(-CH2-)-),0.84-0.93(6H,-CH3).
FIG. 1 is a nuclear magnetic hydrogen spectrum and gel permeation chromatography graph of beta-pinene and poly (beta-pinene).
Example 2: preparation of poly (beta-pinene-co-vinyl ethyl ether)
A preparation method of a sustainable high polymer material specifically comprises the following steps: pretreatment of vinyl ethyl ether: similar to the monomer feed pretreatment of example 1, 30mL of vinyl ethyl ether was added to a 50mL round bottom flask, and a certain amount of CaH was added2Stirring was continued at room temperature for 12h under N2Atmospheric distillation (about 40 ℃) gave a colorless, transparent liquid.
Polymerization: by adjusting the ratio of the monomer beta-pinene to the vinyl etherTo prepare copolymers of different compositions, in the weight ratio β -pinene: vinyl ethyl ether 50:50 for example, poly (β -pinene-co-vinyl ethyl ether) (P (PE-co-VE)) was prepared as follows: weighing beta-pinene (68mg, 0.5mmol) and vinyl ethyl ether (36mg, 0.5mmol) in a glove box, placing in a dry polymerization bottle, adding 400 μ L of dry dichloromethane solution, mixing, placing in a low temperature bath at-20 deg.C, adding boron-containing Lewis acid catalyst B (C) after temperature is stable6F5)3The reaction was continued for 2h with (0.5%, 2.6mg, 5. mu. mol) catalyst solution.
Terminating the polymerization: the polymerization was terminated by adding 50. mu.L of a methanol solution containing 1% ammonia water, and the product was precipitated in methanol to obtain a white solid polymer. By adjusting the ratio of the monomers to the catalyst, copolymers with different structural compositions can be prepared. The structure of the copolymer poly (beta-pinene-co-vinyl ether) is shown as the following formula:
nuclear magnetism of poly (beta-pinene-co-vinyl ether) (P (PE-co-EV))1H NMR(500MHz,CDCl3)δ＝5.31-5.48(1H,-C＝CH-),3.54(H,-CH2CH(-O-)CH2-),3.45(2H,-OCH2CH3),2.29(1H,-C＝CHCH2-),2.15(2H,-C(CH3)2CH2-),1.61-1.87(2H,-CH2CH2-；1H,-C＝CHCH2-),1.43(2H,-CH2CH2-),1.18(3H,-OCH2CH3),1.07(1H,-CH2CH(-CH2-)-),0.84-0.93(6H,-CH3).
FIG. 2 is nuclear magnetic hydrogen spectra of polyvinyl ether, poly (. beta. -pinene) and copolymer poly (pinene-co-vinyl ether).
Example 3: preparation of poly (beta-pinene-co-epoxycyclohexane)
A preparation method of a sustainable high polymer material specifically comprises the following steps: pre-treating epoxy cyclohexane: the pretreatment mode of the monomer raw material epoxy cyclohexane is similar to the beta-pinene treatment mode in the example 1, an oil pump is adopted for reduced pressure distillation, the temperature of fraction collection is about 60 ℃, and colorless and transparent solution is obtained by collection.
Polymerization: the copolymerization of β -pinene with cyclohexene oxide (50:50) is as follows: weighing beta-pinene (68mg, 0.5mmol) and cyclohexene oxide (49mg, 0.5mmol) in a glove box, placing in a dry polymerization bottle, adding 400 μ L of dry dichloromethane solution, mixing, placing in a low temperature bath at-20 deg.C, adding B (C) after temperature is stable6F5)3The reaction was continued for 2h with (0.5%, 2.6mg, 5. mu. mol) catalyst solution.
Terminating the polymerization: the polymerization was terminated by adding 50. mu.L of a methanol solution containing 1% ammonia water, and the product was precipitated in methanol to obtain a white solid polymer. In the same way, by adjusting the feed ratio of the different monomers (75:25 or 25:75), copolymers of different compositions can be prepared. The conversion of both monomers is close to above 98% over a sufficiently long reaction time. The structure of the copolymer poly (beta-pinene-co-epoxycyclohexane) is shown as the following formula:
nuclear magnetic resonance of poly (beta-pinene-co-epoxycyclohexane) (P (PE-co-CHO))1H NMR(500MHz,CDCl3)δ＝5.31-5.48(1H,-C＝CH-),3.38-3.54(2H,-OCH(-CH2-)-),2.29(1H,-C＝CHCH2-),2.15(2H,-C(CH3)2CH2-),1.61-1.87(2H,-CCH2CH2-；1H,-C＝CHCH2-),1.62(2H,-OCH(-CH-)CH2-),1.39(2H,-OCH(-CH-)CH2CH2-),1.43(2H,-CH2CH2-),1.28(2H,-OCH(-CH-)CH2CH2-),1.07(1H,-CH2CH(-CH2-)-),0.84-0.93(6H,-CH3).
FIG. 3 is a nuclear magnetic hydrogen spectrum of Poly (PCHO), poly (. beta. -pinene) (PPE), and copolymer poly (pinene-co-cyclohexene oxide) (P (PE-co-CHO));
FIG. 4 is a comparison of infrared spectra of Polycyclohexylepoxide (PCHO), poly (. beta. -pinene) (PPE), and copolymer poly (pinene-co-epoxycyclohexane) (P (PE-co-CHO));
FIG. 5 is a gel permeation chromatography graph of random copolymer poly (pinene-co-epoxycyclohexane) (P (PE-co-CHO)) with different compositional proportions;
FIG. 6 is a DSC plot (A) and thermogravimetric plot (B) of Polycyclohexylepoxide (PCHO), poly (. beta. -pinene) (PPE) and copolymer poly (pinene-co-epoxycyclohexane) (P (PE-co-CHO)) of different compositional proportions;
FIG. 7 is a graph showing the wide-angle X-ray diffraction patterns of polycyclohexane oxide (PCHO), poly (. beta. -pinene) (PPE) and copolymer poly (pinene-co-cyclohexene oxide) (P (PE-co-CHO)) in different compositional proportions.
Example 4: preparation of poly (beta-pinene) -b-polyepoxycyclohexane block copolymer
A preparation method of a sustainable high polymer material specifically comprises the following steps: the control of the copolymer sequence composition can be realized by changing the temperature, for example, taking the preparation of poly (beta-pinene) -b-polyepoxy cyclohexane block copolymer with the monomer charge ratio of 50:50 as an example, the specific experimental operation is as follows: weighing beta-pinene (68mg, 0.5mmol) and cyclohexene oxide (49mg, 0.5mmol) in a glove box, placing in a dry polymerization bottle, adding 400 μ L of dry dichloromethane solution, mixing, placing in-90 deg.C acetone/liquid nitrogen mixed bath, rapidly adding B (C) after temperature is stable6F5)3After reacting for 10min, the catalyst solution is rapidly heated to a low temperature bath of minus 20 ℃ and continuously reacted for 1h, 50 mul of methanol solution with 1 percent of ammonia water content is added after the reaction is finished to terminate the polymerization reaction, and the white solid polymer product is obtained by settling in methanol. By regulating the charge ratio of different monomers, block copolymers with different compositions can be prepared. The structure of the block copolymer poly (beta-pinene) -b-polyepoxy cyclohexane is shown as the following formula:
nuclear magnetism of poly (beta-pinene) -b-polyepoxycyclohexane (PPE-b-PCHO)1H NMR(500MHz,CDCl3)δ＝5.31-5.48(1H,-C＝CH-),3.38-3.54(2H,-OCH(-CH2-)-),2.29(1H,-C＝CHCH2-),2.15(2H,-C(CH3)2CH2-),1.61-1.87(2H,-CCH2CH2-；1H,-C＝CHCH2-),1.62(2H,-OCH(-CH-)CH2-),1.39(2H,-OCH(-CH-)CH2CH2-),1.43(2H,-CH2CH2-),1.28(2H,-OCH(-CH-)CH2CH2-),1.07(1H,-CH2CH(-CH2-)-),0.84-0.93(6H,-CH3).
FIG. 8 is a nuclear magnetic hydrogen spectrum comparison of a low temperature homopolymer Poly (PCHO) with a block copolymer poly (β -pinene) -b-poly (cyclohexene oxide) (PPE-b-PCHO);
FIG. 9 is a gel permeation chromatogram of a low temperature homopolymer poly (cyclohexene oxide) (PCHO) and a block copolymer poly (beta-pinene) -b-poly (cyclohexene oxide) (PPE-b-PCHO).
Example 5: preparation of poly (beta-pinene-co-epoxy cyclopentane)
A preparation method of a sustainable high polymer material specifically comprises the following steps: the pretreatment of monomer cyclopentane epoxide was similar to the treatment of β -pinene in example 1, except that water pump distillation under reduced pressure was used, the temperature of fraction collection was about 80 ℃, and a colorless and transparent solution was obtained by collection.
The copolymer poly (β -pinene-co-cyclopentane epoxide) was prepared in accordance with the procedure of example 3, except that β -pinene: the charging ratio of the cyclopentane epoxide monomer is 75:25, and the polymerization time is 2 h.
Example 6: preparation of poly (beta-pinene-co-epoxycyclooctane)
A preparation method of a sustainable high polymer material specifically comprises the following steps: the pretreatment of the monomer epoxycyclooctane was similar to the treatment of β -pinene in example 1, except that the mixture was distilled under reduced pressure using a water pump, the temperature of fraction collection was about 80 ℃ and a colorless and transparent solution was obtained.
The copolymer poly (β -pinene-co-epoxycyclooctane) was prepared in accordance with the procedure of example 3, except that β -pinene: the charging ratio of the epoxy cyclooctane monomer is 25:75, and the polymerization reaction time is 2 h.
Example 7: preparation of poly (beta-pinene-co-methyl propylene oxide)
A preparation method of a sustainable high polymer material specifically comprises the following steps: the pretreatment of monomeric methyl propylene oxide was carried out in a similar manner to that of β -pinene treatment in example 1, except that methyl propylene oxide distillation was carried out under atmospheric conditions, and fractions at a temperature of about 60 ℃ were collected, and dried methyl propylene oxide was a colorless transparent solution.
The copolymer poly (. beta. -pinene-co-methyl propylene oxide) was prepared in a manner consistent with the procedure of example 3, except that the polymerization was carried out at 30 ℃ for 48 hours.
Example 8: preparation of poly (beta-pinene-co-2-chloroethyl vinyl ether)
A preparation method of a sustainable high polymer material specifically comprises the following steps: the pretreatment of the monomer 2-chloroethyl vinyl ether was carried out in a similar manner to the treatment of vinyl ether in example 2, except that the 2-chloroethyl vinyl ether was collected under reduced pressure using a water pump at a temperature of 50 ℃ to obtain a colorless transparent solution of the dried 2-chloroethyl vinyl ether.
The copolymer poly (. beta. -pinene-co-2-chloroethyl vinyl ether) was prepared in substantially the same manner as in example 2, and the final polymerization product was a white solid.
Comparative example 1:
a preparation method of a sustainable high polymer material comprises the following steps: beta-pinene is subjected to oxidation of ozone, triethylamine neutralization, hydrogen and Rh (PPh)3)3The preparation method comprises the steps of preparing p-isopropylcyclohexanone under the catalytic reduction of Cl, converting pinene into p-isopropylcaprolactone monomer with polymerization activity through the oxidation of benzoic acid peroxide (mCPBA), and preparing polyester material-poly (4-isopropylcaprolactone) through ring-opening polymerization under the catalysis of stannous isooctanoate. Although the prepared high molecular material has good application potential, the synthesis process of the method is long and complicated;
comparative example 2:
a preparation method of a sustainable high polymer material comprises the following steps: beta pinene (1.76mL, 15mmol) was dissolved in 15mL dry dichloromethaneAdding catalyst aluminium trichloride diphenyl ether (AlCl) into the alkane solution3OPh2) Continuously reacting at 0 ℃ for 0.5min to prepare a homopolymer of the polyprenes; the polymer has a low molecular weight, a broad molecular weight distribution, and significant metal residues.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (10)

1. A method for preparing sustainable high molecular material, wherein include through polymerization reaction between pinene monomer or through pinene monomer and vinyl ether monomer compound, one kind of epoxy compound carries on polymerization reaction to prepare polyolefin or polyether high molecular material of high molecular weight; the polymerization reaction is shown as formula I, formula II or formula III:
formula I:
formula II:
formula III:
x is greater than or equal to 1, and y is greater than or equal to 1.
2. The method for preparing sustainable polymer material according to claim 1, wherein the vinyl ether monomer Compound (CH)2CH-OR1) Comprises one or more of linear alkyl vinyl ether, isopropyl vinyl ether and 2-chloroethyl vinyl ether.
3. The method for preparing a sustainable polymer material according to claim 1, wherein the epoxy compound (R) is2CH(O)CHR3) Comprises one or more of methyl propylene oxide, epoxy cyclohexane, epoxy cyclopentane, epoxy cyclooctane, linear alkyl ethylene oxide, branched alkyl ethylene oxide, linear alkyl glycidyl ether, branched alkyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether and glycidyl methacrylate.
4. The method for preparing a sustainable polymer material according to claim 1, comprising the following steps: dissolving a pinene monomer or a pinene monomer and a vinyl ether compound or a pinene monomer and an epoxy compound in an organic solvent, quickly adding a catalyst M, and carrying out closed polymerization reaction in an inert gas atmosphere.
5. The method for preparing sustainable polymeric material according to claim 4, wherein the catalyst M comprises a boron-containing Lewis acid catalyst, the boron-containing Lewis acid catalyst comprises one or more of trifluorophenylborane, pentafluorophenylboron and boron trifluoride, and the amount of the catalyst M is between 0.5% o and 1% of the molar amount of the monomers fed in the polymerization reaction.
6. The method for preparing sustainable polymer material according to claim 4, wherein the organic solvent comprises dichloromethane, tetrahydrofuran, toluene, xylene, acetone.
7. The method for preparing sustainable polymer material according to claim 4, wherein the polymerization reaction temperature is-90 ℃ to 30 ℃ and the reaction time is 10min to 48 h.
8. The method for preparing sustainable polymer material according to claim 7, wherein the polymerization comprises reacting at-20 ℃ for 1 to 2 hours after reacting at-90 ℃ for 10 to 30 minutes to prepare block copolymer.
9. The method for preparing a sustainable polymer material according to claim 4, further comprising a step of pretreating a pinene monomer, a vinyl ether monomer compound, or an epoxy compound, wherein the step of pretreating specifically comprises: adding pinene monomer or vinyl ether monomer compound or epoxy compound into a round-bottom flask, adding calcium hydride, continuously stirring for 12h at room temperature, and distilling to obtain liquid.
10. A sustainable polymeric material produced by the method according to claims 1 to 9, wherein the sustainable polymeric material comprises compound 1, compound 2 and compound 3;
compound 1:
compound 2:
compound 3:
x is greater than or equal to 1, and y is greater than or equal to 1.
CN201910917255.7A 2019-09-26 2019-09-26 Sustainable high polymer material and preparation method thereof Pending CN110628001A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1185164A (en) * 1995-05-24 1998-06-17 B·F·谷德里奇公司 Homopolymers and copolymers of cationically polymerizable monomers, and prepn. method therefor
JP2010090273A (en) * 2008-10-08 2010-04-22 Nagoya Univ Method for producing beta-pinene polymer
JP2014181298A (en) * 2013-03-19 2014-09-29 Kuraray Co Ltd METHOD FOR MANUFACTURING COPOLYMER OF α,β-UNSATURATED ETHER AND SATURATED CYCLIC ETHER

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1185164A (en) * 1995-05-24 1998-06-17 B·F·谷德里奇公司 Homopolymers and copolymers of cationically polymerizable monomers, and prepn. method therefor
JP2010090273A (en) * 2008-10-08 2010-04-22 Nagoya Univ Method for producing beta-pinene polymer
JP2014181298A (en) * 2013-03-19 2014-09-29 Kuraray Co Ltd METHOD FOR MANUFACTURING COPOLYMER OF α,β-UNSATURATED ETHER AND SATURATED CYCLIC ETHER

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Title
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