Polyacrylonitrile (PAN) polymers with low polydispersity index (PDI) and carbon fibers made therefrom

Patent metadata

Field	Value
Publication number	US-10189985-B2
Application number	US-201815923368-A
Country	US
Kind code	B2
Filing date	Mar 16, 2018
Priority date	Dec 23, 2013
Publication date	Jan 29, 2019
Grant date	Jan 29, 2019

Abstract

A method for synthesizing polyacrylonitrile (PAN) polymer with a narrow molecular weight distribution is disclosed. The preferred PAN polymer has a PDI (Mw/Mn) of about 2 or less. Such PAN polymer is synthesized by controlled/living radical polymerization using a special RAFT (Reversible Addition-Fragmentation Chain Transfer) agent. Also disclosed is a method for producing carbon fibers from PAN polymer with low PDI.

First claim

What is claimed is:

1. A method for synthesizing a polyacrylonitrile (PAN) polymer with a narrow molecular weight distribution, the method comprising:
a) combining acrylonitrile (AN) monomer with a solvent, at least one co-monomer, and a thiocarbonylthio compound to form a solution;
b) heating the solution to a temperature within the range of 40° C. 85° C.; and
c) adding an initiator to the heated solution to affect polymerization reaction, thereby forming a polymer solution comprising polyacrylonitrile (PAN) polymer,
wherein polymerization is affected by controlled/living radical polymerization, in which the thiocarbonylthio compound functions as a Reversible Addition/Fragmentation Chain Transfer (RAFT) agent,
wherein the thiocarbonylthio compound is selected from the following structures:

where Z 1 is selected from:
—CH 2 —(CH 2 ) 10 —CH 3 ; —(CH 2 ) n —CH 3 , n=0-20;
—C(CH 3 ) m —COOH, m=1-2; —C(CH 3 ) m —COOCH 3 , m=1-2;
—C(CH 3 ) m —COOC 2 H 5 , m=1-2;

R 1 is selected from:

R′ 1 is selected from: —CN;

x=0-1;
R″ 1 is selected from: H; —CH 3 ; —(CH 2 ) m —COOH, m=1-2;
R′″ 1 is H or —CH 3

where Z 2 is selected from:

R is selected from: F, Cl, CN, OCH 3 ;
R 2 is selected from:

R′ 2 is selected from: —CN;

x=0-1;
—C(CH 3 ) m —COOCH 3 , m=1-2;
—C(CH 3 ) m —COOC 2 H 5 , m=1-2;

R″ 2 is selected from: H; —CH 3 ; —(CH 2 ) m —COOH, m=1-2;
R′″ 2 is H or —CH 3

where Z 3 is selected from: —CH 2 —(CH 2 ) 10 —CH 3 ; —(CH 2 ) y —CH 3 , y=1-20;
R 3 is selected from: —CH 2 —(CH 2 ) 10 —CH 3 ; —(CH 2 ) y —CH 3 , y=1-20,

wherein the PAN polymer has a polydispersity index (PDI) of about 2 or less and a molecular weight within the range of 60 kg/mole to 500 kg/mole.

2. The method of claim 1 , wherein the PAN polymer has a molecular weight within the range of 115 kg/mole to 180 kg/mole.

3. The method according to claim 1 , wherein the PAN polymer has a PDI (Mw/Mn) of 1.2 to 1.9.

4. The method according to claim 1 , wherein the solvent is selected from the group consisting of: dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), and dimethyl acetamide (DMAc), a mixture of zinc chloride (ZnCl 2 ) and water, and a mixture of sodium thiocyanate (NaSCN) and water.

5. The method according to claim 1 , wherein the at least one co-monomer is selected from the group consisting of: vinyl-based acids, vinyl-based esters, and vinyl derivatives.

6. The method of claim 5 , wherein the at least one co-monomer is selected from the group consisting of: methacrylic acid (MAA), acrylic acid (AA), itaconic acid (ITA), methacrylate (MA), methyl methacrylate (MMA), vinyl acetate (VA), ethyl acrylate (EA), butyl acrylate (BA), ethyl methacrylate (EMA), vinyl imidazole (VIM), acrylamide (AAm), diacetone acrylamide (DAAm).

7. The method according to claim 1 , wherein the initiator is an azo compound or an organic peroxide.

8. The method according to claim 7 , wherein the initiator is selected from the group consisting of: azobisisobutyronitrile (AIBN), azobiscyanovaleric acid (ACVA), 2, 2′-azobis-(2,4-Dimethyl) valeronitrile (ABVN), dilauroyl peroxide (LPO), ditertbutul peroxide (TBPO), diisopropyl peroxydicarbonate (IPP).

9. The method according to claim 1 , wherein the thiocarbonylthio compound is selected from:
a) 2-cyano-2-propyl dodecyl trithiocarbonate (CPDTC)

and
b) bis-dodecylsufanylthiocarbonyl disulfide (BDSTD)

Assignees

• Cytec Ind Inc

Inventors

• Tang Longgui
• Thomas Alan D
• Harmon Billy D

Classifications

• B29K2055/00

  Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups {B29K2023/00 - B29K2049/00, e.g. having a vinyl group}, as moulding material · CPC title

• C08K5/3725

  containing nitrogen · CPC title

• B29C48/022

  characterised by the choice of material · CPC title

• C08L33/20 Primary

  Homopolymers or copolymers of acrylonitrile (C08L55/02 takes precedence) · CPC title

• C08F2/38 Primary

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title