Method for controllably synthesizing butylbenzene polymers with different cyclization degrees by utilizing fixed bed catalytic reaction

Abstract

The invention discloses a method for controllably synthesizing butylbenzene polymers with different cyclization degrees by utilizing a fixed bed catalytic reaction, which comprises the following steps: dissolving butylbenzene in toluene, and preheating to a reaction temperature to prepare a solution A; continuously pumping the solution A into a drying device by adopting a peristaltic pump, drying, adding the dried reactant into a fixed bed reactor, carrying out cyclization reaction by utilizing a composite catalyst, adding the cyclized solution into a precipitation device, carrying out precipitation reaction to obtain cyclized butylbenzene precipitate, filtering, and carrying out vacuum drying to obtain the butylbenzene polymer. The styrene-butadiene polymers with different cyclization degrees are controllably prepared by adopting the fixed bed catalytic reaction, and the method has the characteristics of small backmixing, uniform reaction, short reaction time, controllable cyclization degree of the reaction product and the like, can realize continuous production, and has more considerable productivity advantage.

Description

Technical Field

[0001] The invention relates to the technical field of polymer material preparation, and more specifically to a method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction. Background Art

[0002] Cyclic polymers have been widely studied. The cyclic structure in the main chain makes this type of polymer have excellent heat resistance, low hygroscopicity, stable chemical properties, low dielectric constant and good transparency. This type of material can be widely used in electronics, optics, packaging and other fields.

[0003] Cyclic olefin polymer is a high-performance, high-barrier "bottleneck" material. Most companies have technical limitations in the production of cycloolefin polymers. Therefore, it is extremely important to seek alternative cyclic polymers and enable continuous and stable production. Summary of the invention

[0004] The purpose of the present invention is to overcome the above-mentioned defects of the prior art and provide a method for controllably synthesizing styrene butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction. By using a fixed bed catalytic reaction, styrene butadiene polymers with different cyclization degrees can be prepared in a controllable manner. The method has the characteristics of small backmixing, uniform reaction, short reaction time, controllable cyclization degree of reaction products, etc., can be produced continuously, and has a more considerable production capacity advantage.

[0005] To achieve the above object, the technical solution of the present invention is as follows:

[0006] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0007] (1) dissolving butylbenzene in toluene and preheating to the reaction temperature to prepare solution A;

[0008] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to a fixed bed reactor for cyclization reaction using a composite catalyst, and then the cyclized solution is added to a precipitation device for precipitation reaction to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried to obtain the butadiene styrene polymer.

[0009] Optionally, in step (1), the mass ratio of butylbenzene to toluene is 1:(50-70).

[0010] Optionally, in step (1), the reaction temperature is.

[0011] Optionally, in step (2), the composite catalyst is a mixture of a Lewis acid and an inert component;

[0012] Optionally, the Lewis acid includes one or more of aluminum chloride, ferric chloride, ferrous chloride, zinc chloride, boron trifluoride, antimony pentafluoride, tin tetrachloride, titanium tetrachloride, trimethylaluminum, cupric 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°C-55°C; and the time of the cyclization reaction is 2-25 min.

[0016] Optionally, in step (2), the feed rate of the dried reactant 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] The invention provides a method for controllably synthesizing butadiene styrene polymers with different cyclization degrees by using a fixed-bed catalytic reaction. Butadiene styrene with different cyclization degrees can be controllably synthesized by using a safe and efficient fixed-bed reaction. Compared with a kettle reactor, the fixed bed has the characteristics of small backmixing, uniform cyclization, controllable cyclization degree, short reaction time, continuous operation, etc. At the same time, the reaction conditions are mild and controllable, the preparation raw materials are easily available, the cost is low, and the whole preparation process has low energy consumption. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The present invention is a flow chart of a method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction.

[0021] Figure 2 The present invention is a flow chart of a device for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction.

[0022] Figure 3 The hydrogen nuclear magnetic resonance spectra of the products prepared in Examples 1, 3, 10 and 11 of the present invention are shown in FIG. DETAILED DESCRIPTION

[0023] The present invention is further described below in conjunction with specific embodiments, but the present invention is not limited in any way.

[0024] Example 1

[0025] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction, such as Figure 1-2 As shown, the following steps are included:

[0026] (1) Dissolve 1.25 g of butylbenzene in 87.2 g of toluene, stir with a stirrer until uniform, and preheat to 10° C. to prepare solution A;

[0027] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 1.5 ml / min, and a cyclization reaction is carried out at 10° C. for 224 seconds using a composite catalyst. The cyclized solution is then added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35° C. for 15 hours to obtain a butadiene styrene polymer with a cyclization degree of 70%.

[0028] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 meshes) in a mass ratio of 1:30.6.

[0029] Example 2

[0030] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0031] (1) Dissolve 1.25 g of butylbenzene in 87.2 g of toluene, stir with a stirrer until uniform, and preheat to 30° C. to prepare solution A;

[0032] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 1.5 ml / min, and a cyclization reaction is carried out at 30° C. for 224 seconds using a composite catalyst. The cyclized solution is then added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35° C. for 15 hours to obtain a butadiene styrene polymer with a cyclization degree of 87.2%.

[0033] The composite catalyst is a mixture of ferric chloride and quartz sand (40-80 meshes) in a mass ratio of 1:15.3.

[0034] Example 3

[0035] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0036] (1) Dissolve 1.25 g of butylbenzene in 87.2 g of toluene, stir with a stirrer until uniform, and preheat to 25° C. to prepare solution A;

[0037] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 1.5 ml / min, and a cyclization reaction is carried out at 25° C. for 224 seconds using a composite catalyst. The cyclized solution is then added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35° C. for 15 hours to obtain a butadiene styrene polymer with a cyclization degree of 85%.

[0038] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 meshes) in a mass ratio of 1:30.6.

[0039] Example 4

[0040] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0041] (1) Dissolve 1.25 g of butylbenzene in 87.2 g of toluene, stir with a stirrer until uniform, and preheat to 30° C. to prepare solution A;

[0042] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 0.9 ml / min, and a cyclization reaction is carried out at 30° C. for 372 seconds using a composite catalyst. The cyclized solution is then added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35° C. for 15 hours to obtain a butadiene styrene polymer with a cyclization degree of 98.1%.

[0043] The composite catalyst is a mixture of titanium chloride and quartz sand (40-80 meshes) in a mass ratio of 1:15.3.

[0044] Example 5

[0045] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0046] (1) Dissolve 1.25 g of butylbenzene in 87.2 g of toluene, stir with a stirrer until uniform, and preheat to 42° C. to prepare solution A;

[0047] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 0.9 ml / min, and a cyclization reaction is carried out at 42° C. for 372 seconds using a composite catalyst. The cyclized solution is then added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35° C. for 15 hours to obtain a butadiene styrene polymer with a cyclization degree of 98.5%.

[0048] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 meshes) in a volume ratio of 1:15.3.

[0049] Example 6

[0050] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0051] (1) Dissolve 1.5 g of butylbenzene in 104.64 g of toluene, stir with a stirrer until uniform, and preheat to 40° C. to prepare solution A;

[0052] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 0.9 ml / min, and a cyclization reaction is carried out at 40° C. for 372 seconds using a composite catalyst. The cyclized solution is then added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35° C. for 15 hours to obtain a butadiene styrene polymer with a cyclization degree of 97%.

[0053] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 meshes) in a mass ratio of 1:15.3.

[0054] Example 7

[0055] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0056] (1) Dissolve 1.5 g of butylbenzene in 104.64 g of toluene, stir with a stirrer until uniform, and preheat to 45° C. to prepare solution A;

[0057] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 0.9 ml / min, and a cyclization reaction is carried out at 45°C for 372 seconds using a composite catalyst. The cyclized solution is then added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35°C for 15 hours to obtain a butadiene styrene polymer with a cyclization degree of 98.6%.

[0058] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 meshes) in a mass ratio of 1:15.3.

[0059] Example 8

[0060] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0061] (1) Dissolve 1.5 g of butylbenzene in 78.48 g of toluene, stir with a stirrer until uniform, and preheat to 30° C. to prepare solution A;

[0062] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 0.9 ml / min, and a cyclization reaction is carried out at 30° C. for 372 seconds using a composite catalyst. The cyclized solution is then added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35° C. for 15 hours to obtain a butadiene styrene polymer with a cyclization degree of 98%.

[0063] The composite catalyst is a mixture of titanium chloride and quartz sand (40-80 meshes) in a mass ratio of 1:30.6.

[0064] Example 9

[0065] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0066] (1) Dissolve 1.5 g of butylbenzene in 78.48 g of toluene, stir with a stirrer until uniform, and preheat to 48° C. to prepare solution A;

[0067] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 0.8 ml / min, and a cyclization reaction is carried out at 48°C for 420 seconds using a composite catalyst. The cyclized solution is then added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35°C for 15 hours to obtain a butadiene styrene polymer with a cyclization degree of 72%.

[0068] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 meshes) in a mass ratio of 1:30.6.

[0069] Example 10

[0070] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0071] (1) Dissolve 1.5 g of butylbenzene in 104.64 g of toluene, stir with a stirrer until uniform, and preheat to 51° C. to prepare solution A;

[0072] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 0.8 ml / min, and a cyclization reaction is carried out at 51° C. for 560 s using a composite catalyst. Then, the cyclized solution is added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35° C. for 15 h to obtain a butadiene styrene polymer with a cyclization degree of 95%.

[0073] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 meshes) in a mass ratio of 1:30.6.

[0074] Embodiment 11

[0075] A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction comprises the following steps:

[0076] (1) Dissolve 1.5 g of butylbenzene in 78.48 g of toluene, stir with a stirrer until uniform, and preheat to 51° C. to prepare solution A;

[0077] (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to an 18 ml fixed bed reactor at a feed rate of 0.9 ml / min, and a cyclization reaction is carried out at 51° C. for 373 seconds using a composite catalyst. The cyclized solution is then added to a precipitation device and reacted with ethanol at a mass ratio of 1:3 to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried at 35° C. for 15 hours to obtain a butadiene styrene polymer with a cyclization degree of 99.8%.

[0078] The composite catalyst is a mixture of aluminum chloride and quartz sand (40-80 meshes) in a mass ratio of 1:30.6.

[0079] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using a fixed bed catalytic reaction, characterized in that: The following steps are involved: (1) dissolving butylbenzene in toluene and preheating to the reaction temperature to prepare solution A; (2) After the solution A is continuously pumped into a drying device by a peristaltic pump for drying, the dried reactant is added to a fixed bed reactor for cyclization reaction using a composite catalyst, and then the cyclized solution is added to a precipitation device for precipitation reaction to obtain a cyclized butadiene styrene precipitate, which is then filtered and vacuum dried to obtain the butadiene styrene polymer.

2. The method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by fixed-bed catalytic reaction according to claim 1, characterized in that: In step (1), the mass ratio of butylbenzene to toluene is 1:(50-70).

3. The method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by fixed-bed catalytic reaction according to claim 1, characterized in that: In step (1), the reaction temperature is 0-50°C.

4. The method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by fixed-bed catalytic reaction according to claim 1, characterized in that: In step (2), the composite catalyst is a mixture of Lewis acid and inert components; The Lewis acid includes one or more of aluminum chloride, ferric chloride, ferrous chloride, zinc chloride, boron trifluoride, antimony pentafluoride, tin tetrachloride, titanium tetrachloride, trimethylaluminum, cupric chloride, sulfuric acid, and hydroxide; the inert component is quartz sand with a particle size of 10-1000 mesh; The mass ratio of the Lewis acid to the inert component is 1:(1-50).

5. The method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by fixed-bed catalytic reaction according to claim 1, characterized in that: In step (2), the temperature of the cyclization reaction is 0°C-55°C; the time of the cyclization reaction is 2-25 min.

6. The method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by fixed-bed catalytic reaction according to claim 1, characterized in that: In step (2), the feed rate of the dried reactant is 0.4-3 ml / min.

7. The method for controllably synthesizing styrene-butadiene polymers with different cyclization degrees by using 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.

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