Double-bond-containing high polymer material as well as preparation method and application thereof

Abstract

The invention discloses a double-bond-containing high polymer material as well as a preparation method and application thereof, and belongs to the technical field of polymer preparation. Mixing an initiator with a monomer, reacting, and precipitating by using an inert solvent to obtain a double-bond-containing high polymer material; the monomers are molecules simultaneously containing aldehyde groups and carbon-carbon double bonds or two molecules respectively containing two aldehyde groups and at least two carbon-carbon double bonds; the initiator is prepared from one or more of trifluoromethanesulfonate, ferric trichloride, aluminum trichloride, triethyl oxygen tetrafluoroboric acid and trifluoroacetic acid diamine. Most of the selected monomers are bio-based extractable chemical substances, the other monomers are cheap products in petrochemical engineering, and the chemical substances extracted from biomass are not used for preparing high polymer materials. According to the invention, expensive catalysts are not needed, and the obtained double-bond-containing high polymer material has good physical and chemical properties and can be widely applied to the fields of preparation of thermoplastic plastics, rubber, elastomers, adhesives, coatings or resins and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer preparation, and in particular relates to a double-bond-containing polymer material and a preparation method and application thereof. Background Art

[0002] Aldehyde and olefin compounds, derived from petrochemicals and biofermentation, are widely used in the chemical industry. Through polymerization, they can yield numerous polymer materials with practical value. Among these, polymer materials containing carbon-carbon double bonds are currently the most effectively degradable. However, their preparation methods are often limited to a few schemes, such as dehydrogenation / post-dehydrogenation modification reactions of saturated polymers or the introduction of carbon-carbon double bonds through copolymerization. Developing new polymerization methods to prepare polymer materials containing carbon-carbon double bonds has significant scientific and industrial value. Carbon-carbon double bonds can participate in olefin metathesis reactions and metathesis polymerizations based on them (acyclic diene metathesis polymerization and ring-opening metathesis polymerization). The catalysts used are metal carbene complexes. Commercially available catalysts include Grubbs first-generation catalyst, Grubbs second-generation catalyst, Grubbs third-generation catalyst, Hoveyda-Grubbs first-generation catalyst, and Hoveyda-Grubbs second-generation catalyst, which are relatively expensive. Therefore, developing a new synthesis process for polymer materials containing carbon-carbon double bonds that does not require expensive catalysts would be of great significance for the widespread application of these materials. Summary of the Invention

[0003] In order to solve the above problems in the prior art, the present invention provides a polymer material containing double bonds, a preparation method and an application thereof.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] The present invention provides a method for preparing a double bond-containing polymer material, comprising the following steps: mixing an initiator and a monomer, reacting the mixture, and then precipitating the mixture with an inert solvent to obtain the double bond-containing polymer material;

[0006] The monomer is a molecule containing both an aldehyde group and a carbon-carbon double bond or two molecules containing two aldehyde groups and at least two carbon-carbon double bonds respectively;

[0007] The initiator includes one or more of trifluoromethanesulfonate, ferric chloride, aluminum chloride, triethyloxonium tetrafluoroboric acid and trifluoroacetic acid hydrazine.

[0008] As a preferred technical solution of the present invention, the molecules containing both aldehyde groups and carbon-carbon double bonds include one or more of vanillin, citrus aldehyde, carvone and 4-vinylbenzaldehyde; the molecules containing two aldehyde groups include one or more of o-phthalaldehyde, isophthalaldehyde and terephthalaldehyde; and the molecules containing at least two carbon-carbon double bonds include one or more of squalene, 1,6-hexadiene, 1,8-octadiene and 1,9-decadiene.

[0009] As a preferred technical solution of the present invention, the trifluoromethanesulfonate includes one or more of lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, barium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, nickel trifluoromethanesulfonate, cobalt trifluoromethanesulfonate, ferrous trifluoromethanesulfonate, iron trifluoromethanesulfonate, tin trifluoromethanesulfonate, lead trifluoromethanesulfonate, copper trifluoromethanesulfonate, mercuric trifluoromethanesulfonate, gallium trifluoromethanesulfonate, boron trifluoromethanesulfonate, scandium trifluoromethanesulfonate, ammonium trifluoromethanesulfonate, manganese trifluoromethanesulfonate, silver trifluoromethanesulfonate and pyridine trifluoromethanesulfonate.

[0010] As a preferred technical solution of the present invention, the reaction is carried out in bulk or in solution.

[0011] As a preferred technical solution of the present invention, when the reaction is carried out in a solution, a solvent is added before the reaction, and the solvent includes one or more of dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrachloroethane, toluene and cyclopentyl methyl ether.

[0012] No ligand is required when the initiator is mixed with the olefin ether monomer, and the mixed reaction of the initiator with the various monomers of the present invention does not require strict anhydrous and oxygen-free experimental operation.

[0013] The above monomers are all bio-based and commonly used in the chemical industry and are commercially available (purchased from reagent manufacturers). These initiators generate cations to initiate the carbonyl-olefin metathesis reaction, which follows a stepwise polymerization mechanism to produce polymer products.

[0014] As a preferred technical solution of the present invention, the reaction temperature is -78 to 150° C., and the reaction time is 0.5 to 96 hours.

[0015] As a preferred technical solution of the present invention, the molar ratio of the initiator to the monomer is (1-10):1000; when the monomers are two molecules each containing two aldehyde groups and at least two carbon-carbon double bonds, the molar ratio of the two monomers is 1:1.

[0016] The present invention also provides a double bond-containing polymer material prepared according to the above-mentioned preparation method.

[0017] The present invention also provides a use of the above-mentioned double bond-containing polymer material in the preparation of thermoplastic plastics, rubber, elastomer, adhesive, coating or resin.

[0018] It is used as a chemical additive when preparing resin.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) Most of the monomers used in the present invention are bio-based extractable chemicals, while others are cheap products from petrochemicals. None of the chemicals extracted from biomass have been used to prepare polymer materials.

[0021] (2) The catalysts used in the present invention are all commercially available, cheap and readily available, and are used in small amounts (no more than 1 mol%). They have good tolerance to water and oxygen and are very suitable for industrial-scale production.

[0022] (3) The present invention does not require the use of expensive catalysts, and the obtained double-bond-containing polymer material has good physical and chemical properties and can be widely used in the fields of thermoplastics, rubbers, elastomers, adhesives, coatings or resins. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] Figure 1 Schematic diagram of some catalysts, monomers and polymerization used in the carbonyl-olefin metathesis reaction for polymerization to produce double bond-containing polymer materials in the present invention. DETAILED DESCRIPTION

[0025] Various exemplary embodiments of the present invention are now described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention.

[0026] In addition, for numerical ranges in the present invention, it is understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in the stated range is also included in the present invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

[0027] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0028] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be exemplary only.

[0029] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0030] The raw materials used in the following examples are all commercially available raw materials, without any special restrictions, and normal temperature refers to 20-30° C. The following description will not be repeated.

[0031] Example 1

[0032] To a dry flask, add 2g (14.9mmol) of o-phthalaldehyde monomer, inject 15mL of dichloromethane solvent, and stir until fully dissolved. Then, add an equal molar ratio of squalene (6.12g). Add 0.1 equivalent (0.24g) of ferric chloride and allow to react at room temperature and pressure for 72 hours. After the reaction, add an appropriate amount of tetrahydrofuran to fully dissolve the product. Filter with filter paper to remove iron salt impurities. Use a rubber-tipped dropper to add the filtrate dropwise to 300mL of methanol and stir until fully precipitated. Yield 5g.

[0033] Product structure information: H NMR spectrum, 1H NMR (400MHz, Chloroform-d), δ=7.46–7.36(m,1H),7.36–7.30(m,1H),7.05(t,J= 10.6Hz,1H),6.71–6.65(m,1H),6.05(dt,J=14.8,5.9Hz,1H),5.76–5.60(m,1H),5 .16(tdd,J=5.8,2.5,1.3Hz,1H),5.12–4.99(m,2H),2.49(tdd,J=8.4,5.9,1.2Hz ,4H),2.20–2.02(m,6H),1.98(ddq,J=9.4,8.3,1.0Hz,6H),1.63(q,J=1.1Hz,6H). Gel permeation chromatography (GPC), GPC data (tetrahydrofuran eluent; polystyrene standard): M n =10.2kDa, As an elastomer material, the tensile strength is 6MPa and the elongation at break is 270%.

[0034] Example 2

[0035] To a dry flask, add 2g (14.9mmol) of isophthalaldehyde monomer and 15mL of dichloroethane solvent. Stir until fully dissolved, then add 6.12g of squalene in an equal molar ratio. Add 0.1 equivalent (0.75g) of iron trifluoromethanesulfonate and allow to react at atmospheric pressure and 60°C for 36 hours. After the reaction, add an appropriate amount of tetrahydrofuran to fully dissolve the product. Filter with filter paper to remove iron salt impurities. Use a rubber-tipped pipette to add the filtrate dropwise to 300mL of methanol and stir until fully precipitated. Yield: 6g.

[0036] Product structure information: H NMR spectrum, 1 H NMR (400MHz, Chloroform-d), δ = 7.41–7.30 (m, 1H), 6.73 (t, J = 10.9Hz, 1H), 6. 49–6.43(m,1H),6.18(dt,J=15.0,5.9Hz,1H),5.78–5.61(m,1H),5.16(tdd,J =5.8,2.5,1.3Hz,1H),5.08(tq,J=7.0,1.2Hz,1H),2.44(tdd,J=8.3,5.9,1.0 Hz, 4H), 2.20–2.02 (m, 6H), 1.98 (tq, J=8.3, 1.0Hz, 4H), 1.63 (q, J=1.0Hz, 6H). Gel permeation chromatography (GPC), GPC data (tetrahydrofuran eluent; polystyrene standard): M n =12.5kDa, As an elastomer material, the tensile strength is 7MPa and the elongation at break is 430%.

[0037] Example 3

[0038] To a dry flask, add 2g (14.9mmol) of terephthalaldehyde monomer, inject 15mL of dichloroethane solvent, stir until fully dissolved, then add an equal molar ratio of squalene (6.12g). Add 0.1 equivalent (0.28g) of triethylamine tetrafluoroboric acid, and react at atmospheric pressure and 45°C for 24 hours. After the reaction, add an appropriate amount of tetrahydrofuran to fully dissolve the product. Filter with filter paper to remove iron salt impurities. Use a rubber-tipped dropper to add the filtrate dropwise to 300mL of methanol and stir until fully precipitated. Yield 5.4g.

[0039] Product structure information: H NMR spectrum, 1 H NMR (400MHz, Chloroform-d), δ = 7.47–7.38 (m, 1H), 6.74 (t, J = 16.3Hz, 1H), 6.51 (dd, J=15.3,1.1Hz,1H),6.17(dt,J=15.0,5.9Hz,1H),5.71(tt,J=16.5,7.1Hz,1H),5.16 (tdd, J = 5.8, 2.5, 1.3 Hz, 1H), 5.08 (tq, J = 7.0, 1.2 Hz, 1H), 2.44 (tdd, J = 8.3, 5.9, 1.0 Hz, 4H), 2.20–2.02 (m, 6H), 1.98 (ddq, J = 9.4, 8.3, 1.0 Hz, 4H), 1.63 (q, J = 1.1 Hz, 6H). Gel permeation chromatography (GPC), GPC data (tetrahydrofuran eluent; polystyrene standard): M n =8.9kDa, As an elastomer material, the tensile strength is 7MPa and the elongation at break is 370%.

[0040] Example 4

[0041] To a dry flask, add 2g of citronellal (13mmol) and 15mL of dichloroethane. Add 0.01 equivalents (0.025g) of triethylamine tetrafluoroboric acid and allow to react at atmospheric pressure and 45°C for 96 hours. After the reaction, add an appropriate amount of tetrahydrofuran to fully dissolve the product. Filter with filter paper to remove iron salt impurities. Use a rubber-tipped dropper to add the filtrate dropwise to 300mL of methanol and stir until fully precipitated. Yield: 1.0g.

[0042] Product structure information: H NMR spectrum, 1H NMR (400 MHz, Chloroform-d), δ = 5.75–5.55 (m, 2H), 2.13–1.93 (m, 4H), 1.93–1.83 (m, 2H), 1.57–1.35 (m, 1H), 0.88–0.81 (m, 3H). Gel permeation chromatography (GPC), GPC data (tetrahydrofuran eluent; polystyrene standard): M n =5.1kDa, As an elastomer material, the tensile strength is 4MPa and the elongation at break is 130%.

[0043] Example 5

[0044] To a dry flask, add 2g of citrulline (10.4mmol) monomer, inject 15mL of dichlorobenzene solvent, and add 0.1 equivalent (0.325g) of trifluoroacetic acid hydrazine. React at atmospheric pressure and 40°C for 12 hours. After the reaction, add an appropriate amount of tetrahydrofuran to fully dissolve the product. Filter with filter paper to remove iron salt impurities. Use a rubber-tipped dropper to add the filtrate dropwise to 300mL of methanol and stir until fully precipitated. Yield 0.3g.

[0045] Product structure information: H NMR spectrum, 1 H NMR (400 MHz, Chloroform-d), δ = 5.82–5.63 (m, 2H), 5.48 (tdq, J = 3.8, 1.9, 1.0 Hz, 1H), 2.40 (ddddd, J = 15.3, 8.6, 6.6, 4.8, 1.9 Hz, 1H), 2.29–2.08 (m, 6H), 2.02 (dd qt, J = 6.4, 4.5, 2.1, 1.2 Hz, 2H), 1.70 (td, J = 12.3, 5.9 Hz, 1H), 1.64–1.55 (m, 1H). Gel permeation chromatography (GPC), GPC data (tetrahydrofuran eluent; polystyrene standard): M n =4.3kDa, As an elastomer material, the tensile strength is 5MPa and the elongation at break is 770%.

[0046] Example 6

[0047] To a dry flask, add 2g of carvone (13.3mmol) and 15mL of dichlorobenzene solvent. Add 0.1 equivalent (0.325g) of trifluoroacetic acid hydrazine. React at atmospheric pressure and 60°C for 6h. After the reaction, add an appropriate amount of tetrahydrofuran to fully dissolve the product. Filter with filter paper to remove iron salt impurities. Use a rubber-tipped dropper to add the filtrate dropwise to 300mL of methanol and stir until fully precipitated. Yield 0.7g.

[0048] Product structure information: H NMR spectrum, 1 H NMR (400 MHz, Chloroform-d), δ = 5.65 (tq, J = 5.5, 1.8 Hz, 1H), 2.58–2.39 (m, 3H), 2.20 (dddq, J = 12.5, 7.7, 5.5, 1.0 Hz, 1H), 2.10–2.01 (m, 1H), 1.88 (dt, J = 2.0, 1.0 Hz, 3H), 1.75 (q, J = 1.4 Hz, 3H). Gel permeation chromatography (GPC), GPC data (tetrahydrofuran eluent; polystyrene standard): M n =2.1kDa, As an elastomer material, the tensile strength is 12MPa and the elongation at break is 150%.

[0049] Example 7

[0050] To a dry flask, add 2g (7.6mmol) of 4-vinylbenzaldehyde monomer, 15mL of dichlorobenzene solvent, and 0.1 equivalent (0.15g) of trifluoroacetic acid hydrazine. React at atmospheric pressure and 60°C for 6h. After the reaction, add an appropriate amount of tetrahydrofuran to fully dissolve the product. Filter with filter paper to remove iron salt impurities. Use a rubber-tipped dropper to add the filtrate dropwise to 300mL of methanol and stir until fully precipitated. Yield 0.4g.

[0051] Product structure information: H NMR spectrum, 1 H NMR (400 MHz, Chloroform-d), δ = 7.46 (s, 4H), 6.74 (t, J = 10.9 Hz, 2H). Gel permeation chromatography (GPC), GPC data (tetrahydrofuran eluent; polystyrene standard): M n =2.5kDa, As an elastomer material, the tensile strength is 13MPa and the elongation at break is 360%.

[0052] Other examples are listed in table form:

[0053] Table 1 Preparation of double bond-containing polymer materials using o-phthalaldehyde + squalene monomer (14.9 mmol + 14.9 mmol) as an example

[0054]

[0055] Table 2 Preparation of double bond-containing polymer materials using isophthalaldehyde + squalene monomer (14.9 mmol + 14.9 mmol) as an example

[0056]

[0057]

[0058] Table 3 Preparation of double bond-containing polymer materials using terephthalaldehyde + squalene monomer (14.9 mmol + 14.9 mmol) as an example

[0059]

[0060] Table 4 Preparation of double bond-containing polymer materials using o-phthalaldehyde + 1,5-hexadiene monomer (14.9 mmol + 14.9 mmol) as an example

[0061]

[0062]

[0063] Table 5 Preparation of polymer materials containing double bonds using isophthalaldehyde + 1,5-hexadiene monomer (14.9 mmol + 14.9 mmol) as an example

[0064]

[0065] Table 6 Preparation of double bond-containing polymer materials using terephthalaldehyde + 1,5-hexadiene monomer (14.9 mmol + 14.9 mmol) as an example

[0066]

[0067]

[0068] Table 7 Preparation of double bond-containing polymer materials using o-phthalaldehyde + 1,7-octadiene monomer (14.9 mmol + 14.9 mmol) as an example

[0069]

[0070] Table 8 Preparation of double bond-containing polymer materials using isophthalaldehyde + 1,7-octadiene monomer (14.9 mmol + 14.9 mmol) as an example

[0071]

[0072] Table 9 Preparation of double bond-containing polymer materials using terephthalaldehyde + 1,7-octadiene monomer (14.9 mmol + 14.9 mmol) as an example

[0073]

[0074] Table 10 Preparation of double bond-containing polymer materials using o-phthalaldehyde + 1,9-decadiene monomer (14.9 mmol + 14.9 mmol) as an example

[0075]

[0076] Table 11 Preparation of double bond-containing polymer materials using isophthalaldehyde + 1,9-decadiene monomer (14.9 mmol + 14.9 mmol) as an example

[0077]

[0078] Table 12 Preparation of double bond-containing polymer materials using terephthalaldehyde + 1,9-decadiene monomer (14.9 mmol + 14.9 mmol) as an example

[0079]

[0080] Table 13 Preparation of double bond-containing polymer materials using citronellal (13 mmol) as an example

[0081]

[0082]

[0083] Table 14 Preparation of double bond-containing polymer materials using citrus aldehyde (10.4 mmol) as an example

[0084]

[0085] Table 15 Preparation of double bond-containing polymer materials using carvone (13.3 mmol) as an example

[0086]

[0087]

[0088] Table 16 Preparation of polymer materials containing double bonds using 4-vinylbenzaldehyde (7.6 mmol) as an example

[0089]

[0090] Figure 1 Figure 2 is a schematic diagram of some of the catalysts, monomers, and polymerization methods used in the carbonyl-olefin metathesis reaction to polymerize a double-bond-containing polymer material. Some monomers contain two aldehyde groups or double bonds and need to be copolymerized with another monomer containing a double bond or aldehyde group; some monomers contain both aldehyde groups and double bonds and can be homopolymerized.

[0091] The above description is only a preferred specific embodiment of the present invention, and the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes based on the technical solutions and inventive concepts of the present invention within the technical scope disclosed in the present invention, and these changes should be covered by the scope of protection of the present invention.

Claims

1. A method for preparing a double bond-containing polymer material, characterized in that: The following steps are involved: mixing an initiator and a monomer, reacting them, and then precipitating them with an inert solvent to obtain the double bond-containing polymer material; The monomer is a molecule containing both an aldehyde group and a carbon-carbon double bond or two molecules containing two aldehyde groups and at least two carbon-carbon double bonds respectively; The initiator includes one or more of trifluoromethanesulfonate, ferric chloride, aluminum chloride, triethyloxonium tetrafluoroboric acid and trifluoroacetic acid hydrazine.

2. The preparation method according to claim 1, characterized in that The molecules containing both aldehyde groups and carbon-carbon double bonds include one or more of vanillin, citric aldehyde, carvone and 4-vinylbenzaldehyde; the molecules containing two aldehyde groups include one or more of o-phthalaldehyde, isophthalaldehyde and terephthalaldehyde; the molecules containing at least two carbon-carbon double bonds include one or more of squalene, 1,6-hexadiene, 1,8-octadiene and 1,9-decadiene.

3. The preparation method according to claim 1, characterized in that The trifluoromethanesulfonate includes one or more of lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, barium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, nickel trifluoromethanesulfonate, cobalt trifluoromethanesulfonate, ferrous trifluoromethanesulfonate, iron trifluoromethanesulfonate, tin trifluoromethanesulfonate, lead trifluoromethanesulfonate, copper trifluoromethanesulfonate, mercury trifluoromethanesulfonate, gallium trifluoromethanesulfonate, boron trifluoromethanesulfonate, scandium trifluoromethanesulfonate, ammonium trifluoromethanesulfonate, manganese trifluoromethanesulfonate, silver trifluoromethanesulfonate and pyridine trifluoromethanesulfonate.

4. The preparation method according to claim 1, characterized in that The reaction is carried out in bulk or in solution.

5. The preparation method according to claim 4, characterized in that When the reaction is carried out in a solution, a solvent is added before the reaction. The solvent includes one or more of dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrachloroethane, toluene and cyclopentyl methyl ether.

6. The preparation method according to claim 1, characterized in that The reaction temperature is -78 to 150° C., and the reaction time is 0.5 to 96 hours.

7. The preparation method according to claim 1, characterized in that The molar ratio of the initiator to the monomer is (1-10):1000; when the monomers are two molecules each containing two aldehyde groups and at least two carbon-carbon double bonds, the molar ratio of the two monomers is 1:

1.

8. A double bond-containing polymer material prepared according to the preparation method according to any one of claims 1 to 6.

9. Use of the double bond-containing polymer material according to claim 7 in the preparation of thermoplastic plastics, rubber, elastomer, adhesive, coating or resin.

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