A method for the controllable synthesis of styrene-butadiene polymers with different degrees of cyclization using fixed-bed catalytic reaction
By controlling the degree of cyclization through fixed-bed catalytic reaction and utilizing composite catalysts and precipitation reactions, the problems of unevenness and uncontrollability in the production of cyclic polymers in existing technologies have been solved, achieving efficient and low-cost continuous production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN UNIV OF TECH
- Filing Date
- 2025-02-18
- Publication Date
- 2026-06-30
AI Technical Summary
Existing technologies are difficult to produce cyclic polymers continuously and stably, and there are problems such as large backmixing, uneven reaction, and uncontrollable degree of cyclization.
A fixed-bed catalytic reaction was adopted, in which a composite catalyst was used to carry out the cyclization reaction in a fixed-bed reactor. The degree of cyclization was controlled by combining precipitation reaction and vacuum drying. The reactants were continuously pumped in by a peristaltic pump, and a mixture of Lewis acid and inert component was used as the catalyst.
It achieves low backmixing, uniform reaction, controllable cyclization degree, short reaction time, continuous production capability, higher production capacity advantage, readily available and low cost of raw materials, and low energy consumption throughout the preparation process.
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Figure CN119978320B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer material preparation technology, and more specifically, to a method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction. Background Technology
[0002] Cyclic polymers have been extensively studied. The cyclic structure in the main chain gives these polymers excellent heat resistance, low moisture absorption, chemical stability, low valence constant, and good transparency. These materials can be widely used in electronics, optics, packaging and other fields.
[0003] Cyclic olefin polymers are a type of high-performance, high-barrier "bottleneck" material. Most companies are limited by technology in producing cyclic olefin polymers. Therefore, it is extremely important to find alternative cyclic polymers that can be produced continuously and stably. Summary of the Invention
[0004] The purpose of this invention is to overcome the above-mentioned defects in the prior art and provide a method for controllable synthesis of styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction. By using a fixed-bed catalytic reaction, styrene-butadiene polymers with different degrees of cyclization can be controlled. This method has the characteristics of low backmixing, uniform reaction, short reaction time, and controllable degree of cyclization of reaction products. It can be continuously produced and has a more considerable production capacity advantage.
[0005] To achieve the above objectives, the technical solution of the present invention is as follows:
[0006] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0007] (1) Dissolve styrene-butadiene in toluene and preheat to the reaction temperature to prepare solution A;
[0008] (2) The solution A is continuously pumped to a drying device by a peristaltic pump for drying. The dried reactants are added to a fixed bed reactor for cyclization reaction using a composite catalyst. The cyclized solution is then added to a precipitation device for precipitation reaction to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying, the styrene-butadiene polymer is obtained.
[0009] Optionally, in step (1), the mass ratio of styrene-butadiene to toluene is 1:(50-70).
[0010] Optionally, in step (1), the reaction temperature is [temperature value missing].
[0011] Optionally, in step (2), the composite catalyst is a mixture of Lewis acid and inert component;
[0012] Optionally, the Lewis acid includes one or more of the following: aluminum chloride, ferric chloride, ferrous chloride, zinc chloride, boron trifluoride, antimony pentafluoride, tin tetrachloride, titanium tetrachloride, trimethylaluminum, copper chloride, sulfuric acid, and hydroxide.
[0013] Optionally, the inert component is quartz sand with a particle size of 10-1000 mesh, preferably 20-100 mesh.
[0014] Optionally, the mass ratio of the Lewis acid to the inert component is 1:(1-10).
[0015] Optionally, in step (2), the temperature of the cyclization reaction is 0℃-55℃; and the time of the cyclization reaction is 2-25min.
[0016] Optionally, in step (2), the feed rate of the dried reactants is 0.4-3 ml / min.
[0017] Optionally, in step (2), the precipitant used in the precipitation reaction includes methanol or ethanol; the mass ratio of the precipitant to the cyclized solution is (1-5):1.
[0018] Implementing the embodiments of the present invention will have the following beneficial effects:
[0019] This invention provides a method for the controllable synthesis of styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction. By employing a safe and efficient fixed-bed reaction, styrene-butadiene polymers with different degrees of cyclization can be synthesized in a controllable manner. Compared with a batch reactor, the fixed-bed reactor has the advantages of less backmixing, more uniform cyclization, controllable degree of cyclization, shorter reaction time, and continuous operation. At the same time, the reaction conditions are mild and controllable, the raw materials are readily available and the cost is low, and the entire preparation process consumes less energy. Attached Figure Description
[0020] Figure 1 This is a flowchart of the method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction according to the present invention.
[0021] Figure 2 This is a flowchart of the apparatus for the controllable synthesis of styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction according to the present invention.
[0022] Figure 3 The above are the proton nuclear magnetic resonance spectra of the products prepared in Examples 1, 3, 10 and 11 of this invention. Detailed Implementation
[0023] The present invention will be further described below with reference to specific embodiments, but this does not limit the present invention in any way.
[0024] Example 1
[0025] A method for the controllable synthesis of styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction, such as... Figure 1-2 As shown, it includes the following steps:
[0026] (1) Dissolve 1.25g of styrene-butadiene in 87.2g of toluene, stir with a stirrer until homogeneous, and preheat to 10℃ to prepare solution A;
[0027] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to an 18 mL fixed-bed reactor at a feed rate of 1.5 mL / min. A cyclization reaction was carried out at 10 °C for 224 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, a styrene-butadiene polymer with a degree of cyclization of 70% was obtained.
[0028] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 mesh) in a mass ratio of 1:30.6.
[0029] Example 2
[0030] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0031] (1) Dissolve 1.25g of styrene-butadiene in 87.2g of toluene, stir with a stirrer until homogeneous, and preheat to 30℃ to prepare solution A;
[0032] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to an 18 mL fixed-bed reactor at a feed rate of 1.5 mL / min. A cyclization reaction was carried out at 30 °C for 224 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, a styrene-butadiene polymer with a degree of cyclization of 87.2% was obtained.
[0033] The composite catalyst is a mixture of ferric chloride and quartz sand (40-80 mesh) in a mass ratio of 1:15.3.
[0034] Example 3
[0035] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0036] (1) Dissolve 1.25g of styrene-butadiene in 87.2g of toluene, stir with a stirrer until homogeneous, and preheat to 25℃ to prepare solution A;
[0037] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to an 18 mL fixed-bed reactor at a feed rate of 1.5 mL / min. A cyclization reaction was carried out at 25 °C for 224 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, a styrene-butadiene polymer with a cyclization degree of 85% was obtained.
[0038] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 mesh) in a mass ratio of 1:30.6.
[0039] Example 4
[0040] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0041] (1) Dissolve 1.25g of styrene-butadiene in 87.2g of toluene, stir with a stirrer until homogeneous, and preheat to 30℃ to prepare solution A;
[0042] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to an 18 mL fixed-bed reactor at a feed rate of 0.9 mL / min. A cyclization reaction was carried out at 30 °C for 372 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, a styrene-butadiene polymer with a cyclization degree of 98.1% was obtained.
[0043] The composite catalyst is a mixture of titanium chloride and quartz sand (40-80 mesh) in a mass ratio of 1:15.3.
[0044] Example 5
[0045] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0046] (1) Dissolve 1.25g of styrene-butadiene in 87.2g of toluene, stir with a stirrer until homogeneous, and preheat to 42℃ to prepare solution A;
[0047] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to an 18 mL fixed-bed reactor at a feed rate of 0.9 mL / min. A cyclization reaction was carried out at 42 °C for 372 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, a styrene-butadiene polymer with a cyclization degree of 98.5% was obtained.
[0048] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 mesh) in a volume ratio of 1:15.3.
[0049] Example 6
[0050] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0051] (1) Dissolve 1.5g of styrene-butadiene in 104.64g of toluene, stir with a stirrer until homogeneous, and preheat to 40℃ to prepare solution A;
[0052] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to an 18 mL fixed-bed reactor at a feed rate of 0.9 mL / min. A cyclization reaction was carried out at 40 °C for 372 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, a styrene-butadiene polymer with a cyclization degree of 97% was obtained.
[0053] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 mesh) in a mass ratio of 1:15.3.
[0054] Example 7
[0055] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0056] (1) Dissolve 1.5g of styrene-butadiene in 104.64g of toluene, stir with a stirrer until homogeneous, and preheat to 45℃ to prepare solution A;
[0057] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to an 18 mL fixed-bed reactor at a feed rate of 0.9 mL / min. A cyclization reaction was carried out at 45 °C for 372 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, a styrene-butadiene polymer with a cyclization degree of 98.6% was obtained.
[0058] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 mesh) in a mass ratio of 1:15.3.
[0059] Example 8
[0060] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0061] (1) Dissolve 1.5g of styrene-butadiene in 78.48g of toluene, stir with a stirrer until homogeneous, and preheat to 30℃ to prepare solution A;
[0062] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to a 18 mL fixed-bed reactor at a feed rate of 0.9 mL / min. A cyclization reaction was carried out at 30 °C for 372 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, a styrene-butadiene polymer with a cyclization degree of 98% was obtained.
[0063] The composite catalyst is a mixture of titanium chloride and quartz sand (40-80 mesh) in a mass ratio of 1:30.6.
[0064] Example 9
[0065] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0066] (1) Dissolve 1.5g of styrene-butadiene in 78.48g of toluene, stir with a stirrer until homogeneous, and preheat to 48℃ to prepare solution A;
[0067] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to an 18 mL fixed-bed reactor at a feed rate of 0.8 mL / min. A cyclization reaction was carried out at 48 °C for 420 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, a styrene-butadiene polymer with a degree of cyclization of 72% was obtained.
[0068] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 mesh) in a mass ratio of 1:30.6.
[0069] Example 10
[0070] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0071] (1) Dissolve 1.5g of styrene-butadiene in 104.64g of toluene, stir with a stirrer until homogeneous, and preheat to 51℃ to prepare solution A;
[0072] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to an 18 mL fixed-bed reactor at a feed rate of 0.8 mL / min. A cyclization reaction was carried out at 51 °C for 560 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, a styrene-butadiene polymer with a cyclization degree of 95% was obtained.
[0073] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 mesh) in a mass ratio of 1:30.6.
[0074] Example 11
[0075] A method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction includes the following steps:
[0076] (1) Dissolve 1.5g of styrene-butadiene in 78.48g of toluene, stir with a stirrer until homogeneous, and preheat to 51℃ to prepare solution A;
[0077] (2) Solution A was continuously pumped to a drying device using a peristaltic pump and dried. The dried reactants were then added to a 18 mL fixed-bed reactor at a feed rate of 0.9 mL / min. A cyclization reaction was carried out at 51 °C for 373 s using a composite catalyst. The cyclized solution was then added to a precipitation device and precipitated with ethanol at a mass ratio of 1:3 to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying at 35 °C for 15 h, styrene-butadiene polymer with a cyclization degree of 99.8% was obtained.
[0078] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 mesh) in a mass ratio of 1:30.6.
[0079] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.
Claims
1. A method for controllable synthesis of different cyclization degree of styrene-butadiene polymers by fixed-bed catalytic reaction, characterized in that, Includes the following steps: (1) Dissolve styrene-butadiene in toluene and preheat to the reaction temperature to prepare solution A; (2) The solution A is continuously pumped to the drying device by a peristaltic pump for drying. The dried reactants are added to a fixed bed reactor to carry out a cyclization reaction using a composite catalyst. Then the cyclized solution is added to a precipitation device to carry out a precipitation reaction to obtain cyclized styrene-butadiene precipitate. After filtration and vacuum drying, the styrene-butadiene polymer is obtained. In step (2), the temperature of the cyclization reaction is 25℃-40℃; the time of the cyclization reaction is 224s-372s; In step (2), the composite catalyst is a mixture of Lewis acid and inert component; the Lewis acid includes one or more of aluminum chloride, ferric chloride, and titanium tetrachloride; the inert component is quartz sand with a particle size of 10-1000 mesh; the mass ratio of Lewis acid to inert component is 1:(1-30.6). In step (2), the feed rate of the dried reactants is 0.4-1.5 ml / min.
2. The method for controllable synthesis of different cyclization degree of styrene-butadiene copolymer by fixed bed catalytic reaction according to claim 1, characterized in that, In step (1), the mass ratio of styrene-butadiene to toluene is 1:(50-70).
3. The method for controllable synthesis of different cyclization degree of styrene-butadiene copolymer by fixed-bed catalytic reaction according to claim 1, characterized in that, In step (1), the reaction temperature is 25-40℃.
4. The method for controllably synthesizing styrene-butadiene polymers with different degrees of cyclization using a fixed-bed catalytic reaction according to claim 1, characterized in that, In step (2), the precipitant used in the precipitation reaction includes methanol or ethanol; the mass ratio of the precipitant to the cyclized solution is (1-5):1.