Method for preparing aliphatic polycarbonate through continuous solution polymerization method

A polycarbonate and aliphatic technology, applied in the field of polymer compound preparation, can solve problems such as poor radial mass transfer effect and cycle power limitation, and achieve the effects of reducing production energy consumption, stabilizing operating pressure, and improving processing stability

Active Publication Date: 2013-07-24
BEIJING RISUN TECH CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0016] In order to solve the deficiencies and problems in the above-mentioned existing carbon dioxide copolymerization process, improve the production efficiency and product quality of aliphatic polycarbonate, and reduce production energy consumption at the same time, the present invention proposes a combination of a loop reactor and a tubular reactor The above problems are solved by means of the circulating liquid flow as the driving force of the loop reactor, which solves the problem that the carbon dioxide content limits the circulation power. While ensuring the circulating mass transfer effect of the loop reactor, the pressure of the reaction system can be adjusted arbitrarily to the reaction The best conditions required by itself; the static mixer built into the tubular reactor solves the problem of poor radial mass transfer effect when the viscosity increases in the later stage of polymerization

Method used

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  • Method for preparing aliphatic polycarbonate through continuous solution polymerization method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] This embodiment is used for continuously preparing polypropylene carbonate. The solvent is dioxane.

[0053] The catalyst is prepared by the method described in Example 2 of Chinese Invention Patent Application No. 03105023.9, and contains 0.65 mol of ethyl zinc per liter of catalyst.

[0054] From catalyst storage tank 3 and epoxy storage tank 2, inject 253L catalyst and 508L propylene oxide in loop reactor 6 through mixer 5, make loop reactor 6 internal temperature keep on 70 ℃, pass carbon dioxide storage tank 1 to The internal pressure of the loop reactor 6 is supplemented to maintain the internal pressure of the reactor at 3.5 MPa. After 3 hours of reaction, 84 L / h of catalyst and 254 L / h of propylene oxide were continuously injected. The internal circulation path is: new epoxy, catalyst and carbon dioxide enter from the bottom of the reactor 6 and mix with the circulating material, flow upward from the inside of the draft tube, flow to the top of the draft tube ...

Embodiment 2

[0061] This embodiment is used to continuously prepare carbon dioxide-propylene oxide-epoxycyclohexane terpolymer, and the solvent is dioxane.

[0062] The catalyst is prepared by the method described in Example 2 of Chinese Invention Patent Application No. 03105023.9, and contains 0.65 mol of ethyl zinc per liter of catalyst.

[0063] From catalyst storage tank 3 and epoxide storage tank 2, inject 253L catalyst, 508L propylene oxide and epoxy cyclohexane 1 / 1 (v / v) mixed monomer by mixer 5 in loop reactor 6, make The internal temperature of the loop reactor 6 is maintained at 70° C., and the pressure in the loop reactor 6 is replenished through the carbon dioxide storage tank 1 to maintain the pressure in the reactor 6 at 3.5 MPa. After 3 hours of reaction, 84 L / h of catalyst and 170 L / h of mixed monomer of propylene oxide and cyclohexane oxide were continuously injected. The internal circulation path is: new epoxy, catalyst and carbon dioxide enter from the bottom of the rea...

Embodiment 3

[0070] This example is used to continuously prepare carbon dioxide-ethylene oxide-propylene oxide random terpolymer, and the solvent is dioxane.

[0071] The catalyst is prepared by the method described in Example 2 of Chinese Invention Patent Application No. 03105023.9, and contains 0.65 mol of ethyl zinc per liter of catalyst.

[0072] Reaction apparatus and condition are all identical with embodiment 1.

[0073] The initial feeding ratio is as follows:

[0074] Catalyst 253L

[0075] Propylene oxide 380L

[0076] Ethylene oxide 128L

[0077] After 4 hours of reaction, the continuous injection ratio is as follows:

[0078]Catalyst 63L,

[0079] Propylene oxide 95L

[0080] Ethylene oxide 32L

[0081] The total flow of dioxane used for dilution is 220L / h. Others are as in Example 1.

[0082] Add terminator (methanol), capping agent (maleic anhydride) and heat stabilizer (boric acid) etc. through the feeding port at the end of the tubular reactor 12 to realize in-situ...

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Abstract

The invention provides a method for preparing aliphatic polycarbonate through a continuous solution polymerization method. The method comprises the following steps of a, injecting an epoxy monomer, carbon dioxide and catalyst into a circulation flow reactor through a continuous way, utilizing a circulation pump to provide power for the reaction materials, circularly returning partial reaction materials to the circulation flow reactor, driving one part of the reaction materials to leave the circulation flow reactor at a speed being identical to the feeding speed to enter a tubular reactor with a built-in static mixer; b, controlling the retention time of the pulp in the tubular reactor through the ratio of the pipe length and the flowing linear speed of the reaction materials, and gradually charging a solvent step by step through a plurality of feeding ports along the length of the tubular reactor; c, feeding an end sealing agent and a stabilizer through a feeding port on the tail end of the tubular reactor to carry out the in-situ chemical or physical modification; d, ensuring the reaction endpoint pulp which continuously flows out of a discharging end to enter a middle-pressure flash evaporator, carrying out the flash evaporation by utilizing the reaction pressure, removing the solvent, and returning the pulp to the tubular reactor after the pulp is condensed; and e, devolatilizing and drying the pulp to obtain a polymerization product.

Description

【Technical field】 [0001] The invention belongs to the field of polymer compound preparation, in particular to a method for preparing aliphatic polycarbonate by copolymerizing carbon dioxide and epoxide through a continuous solution polymerization method. 【Background technique】 [0002] Due to the excessive emission of carbon dioxide caused by the massive burning of fossil fuels, the "greenhouse effect" is increasing, which has a serious impact on the global climate and environment. On the other hand, carbon dioxide is a cheap and widely sourced chemical raw material. Therefore, the chemical utilization of carbon dioxide has good social and economic significance. Aliphatic polycarbonate, a carbon dioxide-based plastic represented by polypropylene carbonate (PPC) produced by the alternating copolymerization of propylene oxide and carbon dioxide, is a class of fully biodegradable polymer materials with broad application prospects. The aliphatic polycarbonate has very broad ap...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G64/42C08G64/34C08G64/02
Inventor 张英伟徐元超孙长江闵加栋王献红
Owner BEIJING RISUN TECH CO LTD
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