Initiator, preparation method and application thereof, and preparation method of polyvinyl ether

Abstract

The invention provides an initiator, a preparation method and application thereof and a preparation method of polyvinyl ether, and relates to the technical field of new organic materials, and the preparation method of the initiator comprises the step of mixing an alcohol compound, refined iodine and water to obtain the initiator. A novel initiator is researched and developed for polymerization of polyvinyl ether, and compared with an existing initiator, the initiator is easy to prepare, low in cost and high in safety, and used raw materials are simple and easy to obtain.

Description

Technical Field

[0001] The present invention relates to the technical field of new organic materials, and in particular to an initiator, a preparation method and application thereof, and a preparation method of polyvinyl ethyl ether. Background Art

[0002] As a polymer widely used in chemical industry, materials and other fields, polyvinyl ethyl ether plays a key role in warm lubricating oil, making it an indispensable component of many products.

[0003] Currently, the synthesis and preparation processes for polyvinyl ethyl ether all suffer from varying degrees of stringent temperature control conditions, complex solvent systems, and complex and expensive initiators. Furthermore, the initiators in the reaction systems are sensitive to moisture, which inadvertently creates numerous inconveniences for industrialization. For example, patent CN101291901B discloses that Idemitsu Kosan of Japan prepolymerizes vinyl ether and boron trifluoride divinyl ether in an alkane solvent, then continuously adds vinyl ethyl ether dropwise, using an ice bath to control the temperature to synthesize polyvinyl ethyl ether. Alkaline washing, water washing, solvent removal, and catalytic hydrogenation are then performed to obtain a hydrogenated polyvinyl ether polymer (molecular weight 300-3000), which is used as a lubricant for compressed refrigerators. Patent CN105017450B discloses the synthesis of polyvinyl ether by dissolving polyvinyl alcohol, adding a strongly acidic cation exchange resin and a phase inversion catalyst, and then adding toluene or xylene and the corresponding alcohol. The reaction is then heated under reflux to allow the polyvinyl alcohol and the corresponding alcohol to react to form the ether. Patent CN113248644A discloses prepolymerizing vinyl methyl ether and vinyl ethyl ether in the presence of boron trifluoride etherate catalyst, followed by continuous monomer addition in an alkane or alcohol solvent to produce a colorless, transparent, viscous liquid polymethyl ethyl vinyl ether. Patent CN114539455B discloses the synthesis of polyvinyl polyalkyl ethers by cationic polymerization at extremely low temperatures (-50 to -78°C) using a continuous flow method with chloroalkane / toluene / hexaalkane as solvents. Patent CN117362346A discloses the polymerization of polyvinyl ethers with high stereoregularity by mixing vinyl ether monomers, a chain transfer agent, an ion-pair chiral photocatalyst, and an aromatic hydrocarbon solvent, an alkane solvent, or a chlorinated hydrocarbon organic solvent under a protective atmosphere and visible light.

[0004] In addition, in the polymerization process of polyvinyl ether, the initiator kind commonly used is a coordination initiator, for example, the patent of authorized publication number is CN109477014B discloses in toluene and methanol solvent, with boron trifluoride divinyl ether as initiator, vinyl ether is dripped by continuous feed mode, through long reaction, synthetic polyvinyl ether primary product, primary product catalytic hydrogenation in alkane solvent, obtains final polyvinyl ether finished product refrigerator base oil. The patent of authorized publication number is CN111440258B discloses alkane or chloroalkane organic solvent, polyvinyl ether containing acetal end-blocking and protonic acid or Lewis acid cationic initiator are mixed, control lower temperature and slowly add alkene, react after several hours through washing, distillation, promptly obtain the polyvinyl ether compound of olefin polymer end-blocking. Patent publication number CN116239714A describes a process in which vinyl ethyl ether, an initiator, and carboxylic manganese are dissolved in an organic solvent and pumped into a microreactor. The resulting product undergoes light-induced cationic polymerization and is then applied to lubricating oils. Existing initiators are known to have stringent reaction conditions, high costs, and complex product post-processing. Therefore, the technology requires further development. Summary of the Invention

[0005] In view of the various deficiencies in the prior art and in order to solve the above problems, an initiator, a preparation method, an application thereof, and a preparation method of polyvinyl ethyl ether are proposed, and the following technical solutions are provided: A method for preparing an initiator comprises: mixing an alcohol compound, refined iodine and water to obtain the initiator.

[0006] Furthermore, the ratio of the alcohol compound, refined iodine and water is (30-55): (30-50): (4-40) in parts by mass.

[0007] Furthermore, the ratio of the alcohol compound, refined iodine and water is 50:45:5 in parts by mass.

[0008] Furthermore, the alcohol compound is a low-carbon alcohol.

[0009] Furthermore, the low-carbon alcohol is at least one of methanol, ethanol or isopropanol.

[0010] In addition, the present invention also provides an initiator, which is prepared by the above preparation method.

[0011] The present invention also provides application of the initiator, which is applied to the preparation of polyvinyl ethyl ether.

[0012] The present invention also provides a method for preparing polyvinyl ethyl ether, which uses polyvinyl ethyl ether as a raw material and the above-mentioned initiator as an initiator to carry out a polymerization reaction to obtain polyvinyl ethyl ether.

[0013] Furthermore, the polymerization reaction is followed by an acetylation treatment.

[0014] Furthermore, the ethynylation treatment step is: heating to 80-120° C., introducing acetylene into the polymerization reaction system, controlling the acetylene pressure to 0.1-0.3 MPa, and reacting for 2-3 hours.

[0015] Furthermore, the ethynylation treatment is performed after the polymerization reaction for 2-3 hours.

[0016] Beneficial effects: 1. The present invention develops a new type of initiator for the polymerization of polyvinyl ethyl ether. This initiator is simple to prepare, low in cost and highly safe, and the raw materials used are simple and easily available.

[0017] 2. The temperature control process for preparing polyvinyl ethyl ether using the initiator of the present invention is simple and easy to scale up production.

[0018] 3. The polyvinyl ethyl ether polymer prepared by the method for preparing polyvinyl ethyl ether of the present invention is more stable and has a longer application cycle. The viscosity of the prepared polyvinyl ethyl ether is between 60 and 300 cPs, and the moisture content is less than 50 ppm. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a flow chart for the preparation of polyvinyl ethyl ether of the present invention. DETAILED DESCRIPTION

[0020] In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention is clearly and completely described below in conjunction with the embodiments of the present invention. Based on the embodiments in this application, other similar embodiments obtained by ordinary technicians in this field without making any creative work should fall within the scope of protection of this application.

[0021] According to an embodiment of the present invention, a method for preparing an initiator is provided, comprising: mixing an alcohol compound, refined iodine, and water to obtain the initiator. A new initiator has been developed for the polymerization of polyvinyl ethyl ether. Compared with existing initiators, this initiator is simple to prepare, low in cost, and highly safe, using readily available raw materials.

[0022] The raw material ratio of this initiator is as follows: the alcohol compound, refined iodine, and water are in a ratio of (30-55): (30-50): (4-40), calculated by weight. Through multiple experiments, the present invention has determined that the above raw material ratio produces polyvinyl ethyl ether with a viscosity between 60 and 300 cPs and a water content of less than 50 ppm.

[0023] Specifically, the alcohol compound is a low-carbon alcohol, such as at least one of methanol, ethanol or isopropanol.

[0024] A method for preparing polyvinyl ethyl ether comprises the following steps: using vinyl ethyl ether as a raw material and the above-mentioned initiator as an initiator to carry out a polymerization reaction to obtain polyvinyl ethyl ether; performing an ethynylation treatment after the polymerization reaction to eliminate residual and by-product active groups; and performing a hydrogenation treatment to completely alkylate the polyvinyl ethyl ether.

[0025] Example 1 Preparation of initiator: Add 50g (63.4ml) of ethanol, 45g of refined iodine, and 5ml of pure water to a single-necked bottle in sequence, put in a magnetic bar, seal it, and stir it on an electromagnetic stirrer until it dissolves.

[0026] Add 1050ml of ethanol and 250ml of vinyl ether to a 2L pressure reactor, start stirring, add 1.5ml of pre-made initiator, the reaction begins, the reaction temperature rises, and is controlled not to exceed 50°C. When the reaction temperature stabilizes, the reaction is basically completed, and the reaction is kept at a constant temperature for 2 hours. Acetylene is introduced through a bottom tube, and after excluding the air in the reaction system, the acetylene is increased to 0.3MPa, the heating circulator is controlled to 120°C, and the reaction is carried out for 2.5 hours. After the reaction is completed, the temperature is cooled to room temperature, and a hydrogenation catalyst is added through the solid addition port and sealed. After nitrogen replacement is completed, hydrogen is introduced again, and the temperature is raised to 160°C, the pressure is 1.5MPa, and the reaction is carried out for 3.5 hours.

[0027] After the reaction is completed, the solid catalyst is filtered out through a filter, and an equal volume of 1% NaOH aqueous solution is added to mix and wash, and the mixture is transferred to a separatory funnel and allowed to stand. After complete separation, the lower layer is discarded and the upper layer is transferred to a rotary evaporator to remove impurities, residual solvents and water by rotary evaporation to obtain a polymer liquid. The preparation process is as follows: Figure 1 shown.

[0028] Example 2 Preparation of initiator: Add 50g (63.4ml) of ethanol, 30g of refined iodine, and 20ml of pure water to a single-necked bottle in sequence, put in a magnetic bar, seal it, and stir it on an electromagnetic stirrer until it dissolves.

[0029] Add 1050ml of ethanol and 250ml of vinyl ethyl ether to a 2L reaction pressure reactor, start stirring, add 1.5ml of pre-made initiator, the reaction begins, the reaction temperature rises, and is controlled not to exceed 60°C. When the reaction temperature stabilizes, the reaction is basically completed, and the reaction is kept at a constant temperature for 2 hours. Acetylene is introduced through a bottom tube, and after excluding the air in the reaction system, the acetylene is increased to 0.2MPa, the heating circulator is controlled to 100°C, and the reaction is continued for 2 hours. After the reaction is completed, the temperature is cooled to room temperature, and a hydrogenation catalyst is added through the solid addition port and sealed. After nitrogen replacement is completed, hydrogen is introduced again, and the temperature is raised to 140°C, the pressure is 1.2MPa, and the reaction is continued for 3.5 hours.

[0030] After the reaction is completed, the solid catalyst is filtered out through a filter, and an equal volume of 1% NaOH aqueous solution is added for mixing and washing. The mixture is transferred to a separatory funnel and allowed to stand. After complete separation, the lower layer is discarded and the upper layer is transferred to a rotary evaporator. Impurities, residual solvent and water are removed by rotary evaporation to obtain a polymer liquid.

[0031] Example 3 Preparation of initiator: Add 30g (38.0ml) of ethanol, 30g of refined iodine, and 40ml of pure water to a single-necked bottle in sequence, put in a magnetic bar, seal it, and stir it on an electromagnetic stirrer until it dissolves.

[0032] Add 1050ml of ethanol and 250ml of vinyl ether to a 2L pressure reactor, start stirring, add 1.5ml of pre-made initiator, the reaction begins, the reaction temperature rises, and is controlled not to exceed 55°C. When the reaction temperature stabilizes, the reaction is basically completed, and the reaction is kept at a constant temperature for 2 hours. Acetylene is introduced through a bottom tube, and after excluding the air in the reaction system, the acetylene is increased to 0.1MPa, the heating circulator is controlled to 80°C, and the reaction is carried out for 3 hours. After the reaction is completed, the temperature is cooled to room temperature, and a hydrogenation catalyst is added through the solid addition port and sealed. After nitrogen replacement is completed, hydrogen is introduced again, and the temperature is raised to 120°C, the pressure is 1.0MPa, and the reaction is carried out for 3.5 hours.

[0033] After the reaction is completed, the solid catalyst is filtered out through a filter, and an equal volume of 1% NaOH aqueous solution is added for mixing and washing. The mixture is transferred to a separatory funnel and allowed to stand. After complete separation, the lower layer is discarded and the upper layer is transferred to a rotary evaporator. Impurities, residual solvent and water are removed by rotary evaporation to obtain a polymer liquid.

[0034] Example 4 Preparation of initiator: Add 30g (38.0ml) of ethanol, 45g of refined iodine, and 25ml of pure water to a single-necked bottle in sequence, put in a magnetic bar, seal it, and stir it on an electromagnetic stirrer until it dissolves.

[0035] Add 1050ml of ethanol and 250ml of vinyl ether to a 2L pressure reactor, start stirring, add 1.5ml of pre-made initiator, the reaction begins, the reaction temperature rises, and is controlled not to exceed 58°C. When the reaction temperature stabilizes, the reaction is basically completed, and the reaction is kept at a constant temperature for 2 hours. Acetylene is introduced through a bottom tube, and after excluding the air in the reaction system, the acetylene is increased to 0.1MPa, the heating circulator is controlled to 120°C, and the reaction is continued for 2 hours. After the reaction is completed, the temperature is cooled to room temperature, and a hydrogenation catalyst is added through the solid addition port and sealed. After nitrogen replacement is completed, hydrogen is introduced again, and the temperature is raised to 160°C, the pressure is 1.0MPa, and the reaction is continued for 3.5 hours.

[0036] After the reaction is completed, the solid catalyst is filtered out through a filter, and an equal volume of 1% NaOH aqueous solution is added for mixing and washing. The mixture is transferred to a separatory funnel and allowed to stand. After complete separation, the lower layer is discarded and the upper layer is transferred to a rotary evaporator. Impurities, residual solvent and water are removed by rotary evaporation to obtain a polymer liquid.

[0037] Example 5 Preparation of initiator: Add 50g (63.4ml) of ethanol, 45g of refined iodine, and 5ml of pure water to a single-necked bottle in sequence, put in a magnetic bar, seal it, and stir it on an electromagnetic stirrer until it dissolves.

[0038] Add 1050ml of ethanol and 250ml of vinyl ether to a 2L pressure reactor, start stirring, add 1.5ml of pre-made initiator, the reaction begins, the reaction temperature rises, and is controlled not to exceed 45°C. When the reaction temperature stabilizes, the reaction is basically completed, and the reaction is kept at a constant temperature for 2 hours. Acetylene is introduced through the bottom tube, and after excluding the air in the reaction system, the acetylene is increased to 0.3MPa, the heating circulator is controlled to 80°C, and the reaction is carried out for 2.5 hours. After the reaction is completed, the temperature is cooled to room temperature, and a hydrogenation catalyst is added through the solid addition port and sealed. After nitrogen replacement is completed, hydrogen is introduced again, and the temperature is raised to 120°C, the pressure is 1.5MPa, and the reaction is carried out for 3.5 hours.

[0039] After the reaction is completed, the solid catalyst is filtered out through a filter, and an equal volume of 1% NaOH aqueous solution is added for mixing and washing. The mixture is transferred to a separatory funnel and allowed to stand. After complete separation, the lower layer is discarded and the upper layer is transferred to a rotary evaporator. Impurities, residual solvent and water are removed by rotary evaporation to obtain a polymer liquid.

[0040] Example 6 Preparation of initiator: Add 50g (63.4ml) of ethanol, 45g of refined iodine, and 5ml of pure water to a single-necked bottle in sequence, put in a magnetic bar, seal it, and stir it on an electromagnetic stirrer until it dissolves.

[0041] Add 1050ml of ethanol and 250ml of vinyl ether to a 2L pressure reactor, start stirring, add 1.5ml of pre-made initiator, the reaction begins, the reaction temperature rises, and is controlled not to exceed 47°C. When the reaction temperature stabilizes, the reaction is basically completed, and the reaction is kept at a constant temperature for 2 hours. Acetylene is introduced through a bottom tube, and after excluding the air in the reaction system, the acetylene is increased to 0.3MPa, the heating circulator is controlled to 120°C, and the reaction is continued for 2 hours. After the reaction is completed, the temperature is cooled to room temperature, and a hydrogenation catalyst is added through the solid addition port and sealed. After nitrogen replacement is completed, hydrogen is introduced again, and the temperature is raised to 120°C, the pressure is 1.0MPa, and the reaction is continued for 3.5 hours.

[0042] After the reaction is completed, the solid catalyst is filtered out through a filter, and an equal volume of 1% NaOH aqueous solution is added for mixing and washing. The mixture is transferred to a separatory funnel and allowed to stand. After complete separation, the lower layer is discarded and the upper layer is transferred to a rotary evaporator. Impurities, residual solvent and water are removed by rotary evaporation to obtain a polymer liquid.

[0043] Example 7 Preparation of initiator: Add 50g (63.66ml) of isopropyl alcohol, 45g of refined iodine, and 5ml of pure water into a single-necked bottle in sequence, put in a magnetic stirrer, seal, and stir on an electromagnetic stirrer until dissolved.

[0044] Add 1050ml of ethanol and 250ml of vinyl ether to a 2L pressure reactor, start stirring, add 1.5ml of pre-made initiator, the reaction begins, the reaction temperature rises, and is controlled not to exceed 60°C. When the reaction temperature stabilizes, the reaction is basically completed, and the reaction is kept at a constant temperature for 2 hours. Acetylene is introduced through a bottom tube, and after excluding the air in the reaction system, the acetylene is increased to 0.3MPa, the heating circulator is controlled to 120°C, and the reaction is carried out for 3 hours. After the reaction is completed, the temperature is cooled to room temperature, and a hydrogenation catalyst is added through the solid addition port and sealed. After nitrogen replacement is completed, hydrogen is introduced again, and the temperature is raised to 120°C, the pressure is 1.2MPa, and the reaction is carried out for 3.5 hours.

[0045] After the reaction is completed, the solid catalyst is filtered out through a filter, and an equal volume of 1% NaOH aqueous solution is added for mixing and washing. The mixture is transferred to a separatory funnel and allowed to stand. After complete separation, the lower layer is discarded and the upper layer is transferred to a rotary evaporator. Impurities, residual solvent and water are removed by rotary evaporation to obtain a polymer liquid.

[0046] Comparative Example 1 Preparation of initiator: Add 50g (63.4ml) of ethanol and 5ml of pure water to a single-necked bottle in sequence, put in a magnetic stirrer, seal, and stir on an electromagnetic stirrer until dissolved.

[0047] 1050 ml of ethanol and 250 ml of vinyl ether were added to a 2 L pressure reactor, stirring was started, and 1.5 ml of the pre-made initiator was added. No reaction occurred without the addition of refined iodine.

[0048] Comparative Example 2 Preparation of initiator: Add 50g (63.4ml) of ethanol, 20g of refined iodine, and 50ml of pure water into a single-necked bottle in sequence, put in a magnetic bar, seal it, and stir it on an electromagnetic stirrer until it dissolves.

[0049] 1050 ml of ethanol and 250 ml of vinyl ether were added to a 2 L pressure reactor, stirring was started, and 1.5 ml of pre-made initiator was added. The refined iodine was absorbed by the vinyl double bond, the reaction ended quickly, and no target product was obtained.

[0050] Comparative Example 3 Preparation of initiator: Add 50g (63.4ml) of ethanol, 45g of refined iodine, and 5ml of pure water to a single-necked bottle in sequence, put in a magnetic bar, seal it, and stir it on an electromagnetic stirrer until it dissolves.

[0051] In a 2L pressure reactor, add 1050ml of ethanol and 250ml of vinyl ethyl ether, start stirring, and add 1.5ml of pre-made initiator. The reaction begins and the reaction temperature rises, but is controlled not to exceed 50°C. When the reaction temperature stabilizes, the reaction is basically complete, and the reaction is continued at this temperature for 2 hours. After the reaction is completed, cool to room temperature, add hydrogenation catalyst through the solid addition port, seal, and complete nitrogen replacement. Then, introduce hydrogen again, raise the temperature to 160°C, and the pressure to 1.5MPa, and react for 3.5 hours.

[0052] After the reaction is complete, the solid catalyst is filtered through a filter and washed with an equal volume of 1% NaOH aqueous solution. The mixture is then transferred to a separatory funnel and allowed to stand. After complete separation, the lower layer is discarded and the upper layer is transferred to a rotary evaporator. Impurities, residual solvent, and water are removed by rotary evaporation to obtain a polymer liquid. Without acetylation, residual and byproduct active groups cannot be eliminated, which can cause the product to deteriorate during use.

[0053] Comparative Example 4 Preparation of initiator: Add 50g (63.4ml) of ethanol, 45g of refined iodine, and 5ml of pure water to a single-necked bottle in sequence, put in a magnetic bar, seal it, and stir it on an electromagnetic stirrer until it dissolves.

[0054] In a 2L reaction pressure reactor, 1050ml of ethanol and 250ml of vinyl ethyl ether were added, stirring was started, and 1.5ml of pre-made initiator was added. The reaction began, and the reaction temperature rose, but was controlled not to exceed 50°C. When the reaction temperature stabilized, the reaction was basically completed. Immediately after the reaction was basically completed, acetylene was introduced through the bottom tube. After the air in the reaction system was removed, the acetylene pressure was increased to 0.3MPa, the heating circulator was controlled to 120°C, and the reaction was carried out for 2.5 hours. After the reaction was completed, the temperature was cooled to room temperature, and a hydrogenation catalyst was added through the solid addition port and sealed. After nitrogen replacement was completed, hydrogen was introduced again, and the temperature was raised to 160°C and the pressure was 1.5MPa. The reaction was carried out for 3.5 hours. The reaction did not polymerize, and the degree of polymerization of the obtained product was reduced.

[0055] The materials obtained in Examples 1-7 and Comparative Examples 1-4 were tested. The test results are shown in Table 1. Appearance transparency was tested visually. Viscosity was tested using a Brookfield RV-Next, 35°C, rotor 2, 200 rpm, stock solution. Moisture content was determined using the Karl Fischer method.

[0056] Table 1. Comparison of test results and parameters of the examples As can be seen from the above examples, the polyvinyl ethyl ether prepared by the present invention is a colorless, transparent, viscous liquid with a viscosity of 60-300 cPs and a moisture content of less than 50 ppm. The process for preparing polyvinyl ethyl ether using the present invention is simple, and the initiator, solvent, and other additives are safe and low-cost, making it highly amenable to industrial and large-scale production. The resulting polyvinyl ethyl ether has stable performance and can be used in low-temperature lubricants and thermal oils.

[0057] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for preparing an initiator, characterized in that: include: An initiator is obtained by mixing an alcohol compound, refined iodine and water.

2. The method for preparing the initiator according to claim 1, wherein Calculated by mass, the ratio of the alcohol compound, refined iodine and water is (30-55): (30-50): (4-40).

3. The method for preparing the initiator according to claim 2, wherein Calculated by mass, the ratio of the alcohol compound, refined iodine and water is 50:45:

5.

4. The method for preparing the initiator according to claim 1, wherein The alcohol compound is a low-carbon alcohol.

5. The method for preparing the initiator according to claim 4, wherein The low-carbon alcohol is at least one of methanol, ethanol or isopropanol.

6. An initiator, characterized in that The initiator is prepared by the preparation method of the initiator according to any one of claims 1 to 5.

7. Use of the initiator according to claim 6, characterized in that: The initiator is used for the preparation of polyvinyl ethyl ether.

8. A method for preparing polyvinyl ethyl ether, characterized in that: Vinyl ethyl ether is used as a raw material and the initiator described in claim 6 is used as an initiator to carry out a polymerization reaction to obtain polyvinyl ethyl ether.

9. The method for preparing polyvinyl ethyl ether according to claim 8, wherein After the polymerization reaction, an acetylation treatment is performed.

10. The method for preparing polyvinyl ethyl ether according to claim 9, wherein The steps of the ethynylation treatment are: heating to 80-120° C., introducing acetylene into the polymerization reaction system, controlling the acetylene pressure to 0.1-0.3 MPa, and reacting for 2-3 hours.

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