WO2021068443A1 - Procédé de préparation et application d'un polymère à base d'huile de tung, et procédé de préparation de dérivés de polymère à base d'huile de tung - Google Patents

Procédé de préparation et application d'un polymère à base d'huile de tung, et procédé de préparation de dérivés de polymère à base d'huile de tung Download PDF

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WO2021068443A1
WO2021068443A1 PCT/CN2020/076089 CN2020076089W WO2021068443A1 WO 2021068443 A1 WO2021068443 A1 WO 2021068443A1 CN 2020076089 W CN2020076089 W CN 2020076089W WO 2021068443 A1 WO2021068443 A1 WO 2021068443A1
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based polymer
tung oil
reaction
oil
solvent
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Chinese (zh)
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杨卓鸿
袁腾
冯业昌
楚状状
胡洋
谢冰清
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华南农业大学
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers 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 a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2447/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers

Definitions

  • the invention belongs to the technical field of polymer materials, and specifically relates to a preparation method and application of a tung oil-based polymer, and a preparation method of a tung oil-based polymer derivative.
  • Cationic polymerization is an important polymerization reaction, which is similar to free radical polymerization. It consists of elementary reactions such as chain initiation, chain extension, chain transfer, and chain termination. However, because it is prone to chain transfer reactions, it is usually difficult to obtain high Molecular polymers. Industrially, polymers obtained by cationic polymerization of monomers such as isobutylene and piperylene have a wide range of applications, such as rubber, coatings and adhesives.
  • Chinese patent CN103881027B discloses a method for synthesizing piperylene resin by copolymerizing piperylene, monoolefin, and isoprene in a weight ratio of 1:(0.1-1.0):(0.1-0.5) Raw material, under the action of catalyst Lewis acid, with inert aliphatic hydrocarbon as solvent, cationic polymerization reaction at 40-70°C under anaerobic conditions, it has good viscosity, oxidation stability and compatibility. Performance of piperylene petroleum resin.
  • the raw materials for the preparation of the above resins are all derived from petroleum.
  • Chinese patent CN105658685B discloses a ⁇ -phellandrene polymer, which is obtained by cationic polymerization of ⁇ -phellandrene using Lewis acid as a catalyst.
  • the organic solvent constituting the reaction solution can be halogenated hydrocarbons, aromatic hydrocarbons, and Aliphatic hydrocarbons, etc., with a reaction temperature of -90°C to 100°C, and a ⁇ -phellandrene polymer with a high degree of polymerization excellent in heat resistance and light transmittance can be obtained.
  • reaction solvents used in cationic polymerization are generally halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons.
  • the above-mentioned solvents are all derived from non-renewable petroleum resources, and their boiling points are generally low and easy to volatilize.
  • volatile organic compounds VOC
  • chlorinated hydrocarbons can also cause harm to the human body.
  • the first object of the present invention is to provide a method for preparing a tung oil-based polymer to solve at least one of the above technical problems.
  • the second object of the present invention is to provide the application of the tung oil-based polymer prepared by the above preparation method in the preparation of plasticizers, so as to solve at least one of the above technical problems.
  • the third object of the present invention is to provide a method for preparing tung oil-based polymer derivatives to solve at least one of the above technical problems.
  • a method for preparing a tung oil-based polymer which includes the following steps:
  • reaction solvent is selected from at least one of olive oil, palm oil and coconut oil
  • first solvent is selected from at least one of ethyl acetate, dichloromethane and tetrahydrofuran
  • second solvent is selected from acetic acid, acetone and ethanol At least one of them.
  • the prepared tung oil-based polymer is represented by the following formula (1).
  • the cationic polymerization reaction among the three carbon-carbon double bonds of methyl eletronate, when only the carbon-carbon double bond at the C9 position is reacted, the resulting tung oil-based polymer is soluble in the first solvent and can be dissolved again. Adding the second solvent can precipitate the tung oil-based polymer. When there are two or three double bonds participating in the reaction, a product with a cross-linked structure is generated, which is difficult to dissolve in the first solvent.
  • the first solvent and the second solvent are sequentially added after the cationic polymerization reaction is completed, which is also beneficial to improve the purity of the tung oil-based polymer.
  • the addition amount of the first solvent can be determined according to the actual situation, so as to fully dissolve the reaction product in step S1; the second solvent is mainly used to precipitate the polymer, and the addition amount can also be determined according to the actual situation.
  • the polymer can be charged and analyzed.
  • Methyl tellonic acid has a conjugated triene structure. In theory, it can be polymerized by cationic polymerization without other chemical modification. Therefore, the inventors performed cationic polymerization of methyl tellonic acid to prepare a tung oil-based polymer. Researched. Through a comparative study of different reaction conditions, the inventors found that: in addition to using aliphatic hydrocarbons such as ethyl acetate and dimethyl carbonate as the reaction solvent and Lewis acid as the catalyst, the tung oil-based polymer represented by formula (I) can be prepared. Using olive oil, palm oil or coconut oil as the reaction solvent and Lewis acid as the catalyst can also carry out cationic polymerization to prepare the tung oil-based polymer represented by formula (I).
  • the inventor further researched and found that the above-mentioned tung oil-based polymer has no obvious plasticizing effect when used as a plasticizer alone, and when it is combined with dioctyl phthalate as a plasticizer, the plasticizer The effect is significantly better than the plasticizing effect when using dioctyl phthalate alone as the plasticizer. Based on the above findings, the present invention has been completed.
  • methyl elenate is prepared from tung oil
  • the reaction solvents are olive oil, palm oil, and coconut oil as renewable bio-based materials
  • methyl elenate is used as the polymerized monomer and double bond.
  • the low content of vegetable oil is the reaction solvent and the Lewis acid is the catalyst.
  • the cationic polymerization reaction is carried out under anaerobic conditions to prepare the tung oil-based polymer.
  • the raw material source is wide and renewable.
  • the preparation process is green and environmentally friendly.
  • the prepared tung oil-based polymer is safe and non-oxygen Toxic, can be used to prepare plasticizers.
  • the weight ratio of the reaction solvent to methyl eletronate may be (1-5):1.
  • the reaction temperature of the cationic polymerization reaction may be 30-60° C., and the reaction time may be 0.5-10 h. Under this reaction condition, two or three double bonds in methyl eleonic acid can be avoided to participate in the reaction, and the obtained reaction product can be completely dissolved in the first solvent, thereby improving the reaction yield.
  • the Lewis acid may be selected from at least one of aluminum trichloride, boron trifluoride ether and titanium tetrachloride, and its addition amount may be 1-10% of the weight of methyl eletronate.
  • the volume ratio of the first solvent and the second solvent is 1: (5-10).
  • the tung oil-based polymer prepared by the method for preparing the tung oil-based polymer provided by the present invention can be used to prepare plasticizers, in particular, it can be compounded with dioctyl phthalate as a plasticizer and applied to plastics, coatings, and adhesives. And other industries, the plasticizing effect is excellent.
  • a method for preparing a derivative of a tung oil-based polymer which includes the following steps:
  • reaction solvent can be selected from At least one of olive oil, palm oil and coconut oil;
  • step S2 after the reaction of step S1 is completed, add an aqueous alkali solution, and react for 3 to 5 hours at a temperature of 70 to 90°C;
  • step S3 and step S2 After the reaction in step S3 and step S2 is completed, acid is added until the pH of the solution is acidic, washed with water and organic solvent, and then dried, filtered, and rotary steamed to obtain the product.
  • the present invention utilizes a one-pot method to first carry out cationic polymerization reaction, and then directly hydrolyze the reaction product (ie tung oil-based polymer) obtained by carrying out cationic polymerization reaction under acid-base catalysis and heating to prepare tung oil-based polymer derivatives.
  • the reaction process does not require separation of intermediate products, which is economical and environmentally friendly.
  • methyl elenate prepared from the bio-based material tung oil is used as the raw material to prepare the tung oil-based polymer, and the renewable bio-based material olive oil, Palm oil or coconut oil replaces organic solvents as reaction solvents, and raw materials have a wide range of sources and are renewable, and the preparation process is green and environmentally friendly.
  • the derivative of the tung oil-based polymer provided by the present invention is a polycarboxyl polymer with the structural formula shown in the following formula (II), which can be applied to the fields of coatings, adhesives, water reducing agents and the like.
  • the weight ratio of the reaction solvent to methyl eletronate may be (1-5):1.
  • the Lewis acid may be selected from at least one of aluminum trichloride, boron trifluoride ether and titanium tetrachloride, and its addition amount may be 1-10% of the weight of methyl eletronate.
  • the base in step S2, may be selected from at least one of potassium hydroxide, sodium hydroxide and sodium carbonate, and the molar ratio of base to methyl elenate may be (1 to 3):1.
  • the concentration of the aqueous solution can be 0.5-8mol/L.
  • the acid may be selected from at least one of sulfuric acid, acetic acid, and hydrochloric acid; the organic solvent may be selected from at least one of ethyl acetate, ethanol, and ether.
  • the present invention has the following beneficial effects:
  • methyl elenate is used as a raw material for cationic polymerization
  • biomass is used in the preparation of polymers
  • the prepared tung oil-based polymer can be applied to prepare plasticizers.
  • the present invention uses renewable vegetable oils as polymerization solvents, instead of traditional petroleum-based solvents such as halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons.
  • Vegetable oil is a renewable resource. Compared with petroleum-based solvents, it has the advantages of wide sources, low price, non-toxic, harmless, and non-depleted.
  • vegetable oils have high boiling points, are not volatile, and will not cause an increase in VOC.
  • vegetable oil is biodegradable and will not bring additional burden to the environment.
  • the tung oil-based polymer provided by the present invention can be used to prepare plasticizers, partially replacing traditional petroleum-based plasticizers.
  • plasticizers most of the commonly used plasticizers on the market belong to the phthalates. Among them, dioctyl phthalate is widely used because of its high plasticizing efficiency. However, these phthalate plasticizers are easy to migrate. , Damage to human reproductive system and other hazards, and these plasticizers are all derived from non-renewable petroleum resources. Partial replacement of tung oil-based polymers with phthalate petroleum-based plasticizers can reduce the harm caused by plasticizers to human health.
  • the tung oil-based polymer and dioctyl phthalate compound provided by the present invention are used as a plasticizer to prepare polyvinyl chloride (PVC) film
  • the glass transition temperature (T g ) of the prepared PVC film Not more than 50°C
  • the tensile strength is greater than 18MPa
  • the elongation at break is greater than 560%.
  • the tensile strength and elongation at break are both Significant improvement, indicating that the plasticizing effect of tung oil-based polymer and dioctyl phthalate as a plasticizer is significantly improved than that of dioctyl phthalate.
  • Figure 1 is an infrared spectrogram of the tung oil methyl polymer prepared in Example 1 of the present invention
  • Figure 2 is a gel permeation chromatogram of tung oil methyl polymer prepared in Examples 1-7 of the present invention.
  • Figure 3 is an infrared spectrogram of a tung oil methyl polymer derivative prepared in Example 8 of the present invention.
  • Fig. 4 is a stress-strain graph of a PVC film prepared by using a plasticizer composed of a tung oil-based polymer and dioctyl phthalate in a mass ratio of 1:1 in Example 1.
  • the yield of the polymer is 75% (about 20% of the methyl eletronate is non-conjugated fatty acid ester), and the purity is 95%.
  • the tung oil-based polymer was coated on the KBr film, and then placed on the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific Company for testing.
  • the scanning wave number range is 4000 ⁇ 400cm -1 , the resolution is 4cm -1 , and the scanning is 32
  • the FTIR spectrum of the tung oil-based polymer was obtained, as shown in Figure 1.
  • 991cm -1 is the peak of conjugated double bond of methyl eletronate.
  • the peak of anti-anticonjugated double bond appears at 989cm -1 , and the intensity of the peak decreases. Prove that the tung oil-based polymer has been successfully prepared.
  • the tung oil-based polymer was dissolved in tetrahydrofuran to prepare a 2mg/ml solution, and then injected into a Waters gel permeation chromatograph.
  • the mobile phase is tetrahydrofuran
  • the chromatographic columns are Styragel HR 2, HR 4 and HR 6, and the flow rate is 0.5 ml/min.
  • the standard curve is obtained from polystyrene standards.
  • the gel permeation chromatography (GPC) chart of the tung oil-based polymer is shown in Figure 2.
  • the number average molecular weight of the tung oil-based polymer is 38,000 and the polydispersity index is 2.1.
  • the FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.
  • the GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatography is shown in Figure 2.
  • the number average molecular weight of the tung oil-based polymer was measured to be 37,850, and the polydispersity index was 1.9.
  • the FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.
  • the GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatograph is shown in Figure 2.
  • the number average molecular weight of the tung oil-based polymer is 35,000 and the polydispersity index is 1.9.
  • the FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.
  • the GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatograph is shown in Figure 2.
  • the number average molecular weight of the tung oil-based polymer is 39744 and the polydispersity index is 2.0.
  • the FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.
  • the GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatography is shown in Figure 2.
  • the number average molecular weight of the tung oil-based polymer was measured to be 37,800, and the polydispersity index was 2.0.
  • the FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.
  • the GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatograph is shown in Figure 2.
  • the number average molecular weight of the tung oil-based polymer measured is 37823, and the polydispersity index is 2.0.
  • the FTIR spectrum of the tung oil-based polymer was obtained by the Nicolet iS10 Fourier Transform Infrared Spectrometer of Thermo Fisher Scientific, and the characteristic peaks obtained were the same as those in Example 1.
  • the GPC chart of the tung oil-based polymer measured by Waters gel permeation chromatography is shown in Figure 2.
  • the number average molecular weight of the tung oil-based polymer was measured to be 37857, and the polydispersity index was 2.0.
  • step S2 After the reaction of step S1 is completed, an aqueous solution of sodium hydroxide is added, and the reaction is carried out at a temperature of 90°C for 3 hours; wherein the molar ratio of sodium hydroxide to methyl eletronate is 2:1, and the sodium hydroxide solution is The concentration is 0.5mol/L;
  • step S3 After the reaction of step S2 is completed, add hydrochloric acid to the reaction product of step S2 until the pH of the reaction product is acidic, and then wash with water and ethyl acetate respectively, and then dry with anhydrous magnesium sulfate, filter, and rotatory steam to obtain
  • the tung oil-based polymer derivative has a yield of 95% and a purity of 97%.
  • step S2 After the reaction of step S1 is completed, an aqueous solution of potassium hydroxide is added to the reaction product of step S1, and the reaction is carried out at a temperature of 70°C for 4 hours; wherein the molar ratio of potassium hydroxide to methyl eletronate is 1: 1.
  • the concentration of potassium hydroxide aqueous solution is 1mol/L;
  • step S3 After the reaction of step S2 is completed, add acetic acid to the reaction product of step S2 until the pH of the reaction product is acidic, and then wash with water and ethanol respectively, and then dry with anhydrous magnesium sulfate, filter, and rotate to obtain a tung oil base.
  • the polymer derivative has a yield of 96% and a purity of 96%.
  • the tung oil-based polymers prepared in Examples 1-7 were mixed with polyvinyl chloride (PVC), dioctyl phthalate (DOP) and tetrahydrofuran, respectively.
  • PVC polyvinyl chloride
  • DOP dioctyl phthalate
  • the quality of the tung oil-based polymer, PVC, DOP and tetrahydrofuran The ratio is 1:4.7:1:10, then dried at room temperature for 12 hours, heated at 80°C for 5 hours, and finally dried in vacuum at 50°C for 5 hours to make a PVC film.
  • PVC, DOP and tetrahydrofuran are mixed in a mass ratio of 2:4.7:10 to make a PVC film.
  • T g glass transition temperature analysis of the film was tested with a NETZSCH DMA 242E dynamic mechanical analyzer.
  • the test frequency was 1Hz
  • the temperature range was -60-110°C
  • the heating rate was 5°C/min.
  • the tensile strength of the film is analyzed, and the mechanical properties of the PVC film are measured using the UTM4204 universal electronic testing machine.
  • the crosshead speed is 10mm/min.
  • the test results of each sample are shown in Table 1.
  • the stress-strain diagram of the PVC film prepared by using the tung oil-based polymer prepared in Example 1 and the plasticizer composed of DOP at a mass ratio of 1:1 is shown in FIG. 4.
  • Example 1 To T g /°C Tensile strength/MPa Elongation at break/% Example 1 48 21.0 651.2 Example 2 46 20.5 601.2 Example 3 43 19.8 610.1 Example 4 48 22.4 598.5 Example 5 49 23.0 580.7 Example 6 43 18.9 620.2 Example 7 50 24.5 569.3 DOP 12 11.0 309.1
  • the key performance parameters of plasticized PVC are T g and elongation at break. From the results in Table 1, it can be seen that the PVC film prepared by using the tung oil-based polymer provided by the present invention and the plasticizer composed of DOP at a mass ratio of 1:1
  • the T g of the product is not greater than 50°C
  • the tensile strength is greater than 18MPa
  • the elongation at break is greater than 560%. It has good elongation and ductility, and its performance fully meets the needs of practical applications.

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Abstract

L'invention concerne un procédé de préparation d'un polymère à base d'huile de tung, qui utilise du tungate de méthyle en tant que matière première, de l'huile d'olive, de l'huile de palme ou de l'huile de noix de coco en tant que solvant de réaction, et un acide de Lewis en tant que catalyseur pour effectuer une réaction de polymérisation cationique destinée à préparer le polymère à base d'huile de tung. Le procédé de préparation du polymère à base d'huile de tung fait appel à des matières premières qui peuvent provenir de nombreuses sources et sont renouvelables. Pendant le procédé de préparation, de l'huile végétale renouvelable est utilisée comme solvant de réaction pour remplacer des solvants à base de pétrole classiques tels que des hydrocarbures halogénés, des hydrocarbures aromatiques et des hydrocarbures aliphatiques. La présente invention est respectueuse de l'environnement, et le polymère à base d'huile de tung préparé est sûr et non toxique et peut être utilisé pour préparer des plastifiants.
PCT/CN2020/076089 2019-10-09 2020-02-21 Procédé de préparation et application d'un polymère à base d'huile de tung, et procédé de préparation de dérivés de polymère à base d'huile de tung WO2021068443A1 (fr)

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CN115873218A (zh) * 2022-12-08 2023-03-31 中国林业科学研究院林产化学工业研究所 一种桐油基多元酸固化剂及其合成方法
CN115873218B (zh) * 2022-12-08 2023-08-15 中国林业科学研究院林产化学工业研究所 一种桐油基多元酸固化剂及其合成方法

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