Radical polymerization method and polymerization reaction apparatus

• US 10,442,873 B2
• Filed: 08/24/2015
• Issued: 10/15/2019
• Est. Priority Date: 08/29/2014
• Status: Active Grant

• Current Assignee: Japan Agency For Marine-Earth Science And Technology
• Original Assignee: Japan Agency For Marine-Earth Science And Technology
• Inventors: Deguchi, Shigeru, Kinoshita, Keigo
• Primary Examiner(s): Cheung, William K
• Application Number:
  US15/507,283
• Publication Number:
  US 20170291964A1
• Time in Patent Office: 1,513 Days
• Field of Search: 526 88
• CPC Class Codes: B01J 19/1812 Tubular reactors
• CPC Class Codes: B01J 19/26 Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
• CPC Class Codes: B60H 1/00885 Controlling the flow of heating or cooling liquid, e.g. valves or pumps B60H1/00899 takes precedence; constructions of valves B60H1/00485
• CPC Class Codes: C08F 2/001 Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer C08F295/00, C08F297/00 take precedence
• CPC Class Codes: C08F 2/01 characterised by special features of the polymerisation apparatus used
• CPC Class Codes: C08F 2/04 Polymerisation in solution C08F2/32 takes precedence
• CPC Class Codes: C08F 4/04 Azo-compounds
• CPC Class Codes: C08F 4/34 Per-compounds with one peroxy-radical
• CPC Class Codes: C08F 4/46 selected from alkali metals
• CPC Class Codes: F16K 17/02 opening on surplus pressure on one side; closing on insufficient pressure on one side check valves F16K15/00
• CPC Class Codes: G05D 23/1333 measuring the temperature of incoming fluid

Abstract

A radical polymerization method that enables synthesis, at a high conversion rate, of polymers having a relatively uniform molecular weight and is applicable to various monomers, and an apparatus used for the method. A reaction solution containing monomer and initiator is continuously or intermittently circulated in the apparatus and is heated in a heating-initiation unit to a predetermined temperature simultaneously across a radial direction of a cross section of the flow path whereby the initiator located in a particular volume of the reaction solution is cleaved all at once. The apparatus includes a heating medium production unit 10, a heating medium-reaction solution mixing unit 20, a cooling unit 30, and a recovery unit 40 for a reaction mixture, all communicatively connected by the flow path and optionally a heating reaction unit 60, a cooling unit 70, and a recovery unit 80, all communicatively connected by the flow path.

Claims

1. A method of producing a polymer by causing a reaction solution containing a monomer and a radical polymerization initiator to continuously or intermittently flow through a flow path of a radical polymerization reaction apparatus, the method comprising:

(1) a step of flowing the reaction solution into a heating-initiation part of the reaction apparatus and heating the flowed reaction solution to a prescribed temperature to cause the radical polymerization initiator in the reaction solution that has flowed into the heating-initiation part to undergo cleavage and thereby initiate radical polymerization of the monomer;

(2) a step of advancing the radical polymerization of the monomer in the reaction solution; and

(3) a step of cooling the reaction solution and obtaining the polymer,

wherein the heating of the reaction solution, which has flowed into the heating-initiation part, to the prescribed temperature in step (1) is carried out by continuously mixing, under pressurization, the reaction solution with a heating medium to form a reaction solution/heating medium mixture in the heating-initiation part.

2. The method according to claim 1, wherein the reaction solution contains water;

the heating medium is water heated to at least 150°

C.; and

the reaction solution and the heating medium are continuously mixed at a flow rate ratio that provides a temperature of at least 100°

C. immediately after mixing.

3. The method according to claim 1, wherein the reaction solution contains an organic solvent;

the heating medium is an organic solvent heated to at least its boiling point; and

the reaction solution and the heating medium are continuously mixed at a flow rate ratio that provides a temperature that is at least the boiling point of the organic solvent immediately after mixing.

4. The method according to claim 1, wherein the heating is carried out under a condition where cleavage of the radical polymerization initiator present in a unit volume of the reaction solution is completed within 1 second.

5. The method according to claim 1, wherein the prescribed temperature for said heating is in the range of T+50°

C. to T+150°

C. where T°

C. is an initiation temperature of the radical polymerization initiator.

6. The method according to claim 1, wherein the polymer has a ratio of weight-average molecular weight (Mw)/number-average molecular weight (Mn) of not more than 3.0.

7. The method according to claim 1, wherein the polymer has a ratio of weight-average molecular weight (Mw)/number-average molecular weight (Mn) of not more than 2.0.

8. A radical polymerization reaction apparatus configured to carry out the method of claim 1 comprising:

(1) a heating medium production part including a heating medium heating part;

(2) a heating medium-reaction solution mixing part including a reaction solution storage and feed part, mixing reaction part, and a reaction residence part, wherein the heating medium heating part merges with the reaction solution storage and feed part at the mixing reaction to form a merged flow path that connects to the reaction residence part; and

(3) a cooling part connected to the reaction part by a flow path; and

a reaction mixture recovery part connected to the cooling part by a flow path.

9. The apparatus according to claim 8, wherein

(1) the heating medium production part includes a heating medium starting material storage part connected to the heating medium heating part;

(2) the cooling part includes a cooling medium storage and feed part, a coolant-reaction mixture mixing part, and a cooling residence part.

10. The apparatus according to claim 9, wherein, in the heating medium production part,

the heating medium starting material storage part is configured to store a heating medium starting material and feed the heating medium starting material to the heating medium heating part, and

the heating medium heating part comprises a flow path through which the heating medium starting material flows, and a heating apparatus that heats this flow path.

11. The apparatus according to claim 9, wherein, in the heating medium-reaction solution mixing part,

the reaction solution storage and feed part is configured to store a reaction solution and feed the reaction solution to the mixing-reaction part, and

the mixing-reaction part is configured to merge and mix a heating medium flow fed via a flow path from the heating medium heating part, with a reaction solution flow fed via a flow path from the reaction solution storage and feed part, and has a structure in which a flow path forms three branches.

12. The apparatus according to claim 9, wherein, in the cooling part 30,

the cooling medium storage and feed part is configured to store a cooling medium and feed the cooling medium to the cooling medium-reaction mixture mixing part,

the cooling medium-reaction mixture mixing part is configured to merge and mix a reaction mixture flow fed via a flow path from the reaction residence part, with a cooling medium flow fed via a flow path from the cooling medium storage and feed part, and

the cooling residence part is configured to hold a temperature hold or cool.

13. The method according to claim 1, wherein the reaction solution contains water;

the heating medium is water heated to at least 150°

C.; and

the reaction solution and the heating medium are continuously mixed at a flow rate ratio that provides a temperature of at least 100°

C. immediately after mixing.

14. The method according to claim 1, wherein the reaction solution contains an organic solvent;

the heating medium is an organic solvent heated to at least its boiling point; and

the reaction solution and the heating medium are continuously mixed at a flow rate ratio that provides a temperature that is at least the boiling point of the organic solvent immediately after mixing.

15. The method according to claim 1, wherein the prescribed temperature for said heating is in the range of T+50°

C. to T+150°

C. where T°

C. is an initiation temperature of the radical polymerization initiator.

16. The method according to claim 1, wherein the polymer has a ratio of weight-average molecular weight (Mw)/number-average molecular weight (Mn) of not more than 3.0.

17. The apparatus according to claim 10, wherein, in the heating medium-reaction solution mixing part,

the reaction solution storage and feed part is configured to store a reaction solution and feed the reaction solution to the mixing-reaction part, and

the mixing-reaction part is configured to merge and mix a heating medium flow fed via a flow path from the heating medium heating part, with a reaction solution flow fed via a flow path from the reaction solution storage and feed part, and has a structure in which a flow path forms three branches.

18. The apparatus according to claim 10, wherein, in the cooling part,

the cooling medium storage and feed part is configured to store a cooling medium and feed the cooling medium to the cooling medium-reaction mixture mixing part,

the cooling medium-reaction mixture mixing part is configured to merge and mix a reaction mixture flow fed via a flow path from the reaction residence part, with a cooling medium flow fed via a flow path from the cooling medium storage and feed part, and

the cooling residence part is configured to hold a temperature or cool.

19. The apparatus according to claim 11, wherein, in the cooling part,

the cooling medium storage and feed part is configured to store a cooling medium and feed the cooling medium to the cooling medium-reaction mixture mixing part,

the cooling medium-reaction mixture mixing part is configured to merge and mix a reaction mixture flow fed via a flow path from the reaction residence part, with a cooling medium flow fed via a flow path from the cooling medium storage and feed part, and

the cooling residence part is configured to hold a temperature hold or cool.

20. The method according to claim 1, wherein the heating is carried out under a condition where cleavage of the radical polymerization initiator present in a unit volume of the reaction solution is completed within 5 seconds.

21. The apparatus according to claim 8, wherein the heating medium production part and the merged flow path communicate linearly, and the reaction solution storage and feed part merges therein at an angle in a range of at least 10°

to 170°

.

22. The apparatus according to claim 8, wherein the reaction solution storage and feed part and the merged flow path communicate linearly, and the heating medium production part merges therein at an angle in a range of at least 10°

to 170°

.