Polymerization of diene monomers

Patent metadata

Field	Value
Publication number	US-9862789-B2
Application number	US-201414901846-A
Country	US
Kind code	B2
Filing date	Jul 3, 2014
Priority date	Jul 3, 2013
Publication date	Jan 9, 2018
Grant date	Jan 9, 2018

Abstract

A free radical or controlled radical polymerization process of atom or group transfer radical polymerization. The process comprises radically polymerizing one or more radically (co)polymerizable monomers in the presence of a polymerization system. The one or more radically (co)polymerizable monomers comprise at least one or more radically (co)polymerizable diene monomers. The polymerization system comprises: an initiator having one or more radically transferable atoms or groups; a transition metal-ligand complex catalyst, wherein the ligand comprises any C-, N-, O-, P- or S-containing ligand which coordinates with the transition metal; an optional reducing agent capable of regenerating the lower oxidation state of the transition metal catalyst; and an optional organic solvent or water capable of solubilizing the transition metal-ligand complex catalyst. (Co)polymers produced by the free radical or controlled radical polymerization process of atom or group transfer radical polymerization.

First claim

What is claimed is:

1. A free radical or controlled radical polymerization process of atom or group transfer radical polymerization, said process comprising polymerizing at least one conjugated diene monomer in the presence of an initiator, a transition metal-ligand complex catalyst, a reducing agent, and an organic solvent or water, under reaction conditions and for a time sufficient to controllably polymerize the at least one conjugated diene monomer to form a (co)polymer.

2. The process of claim 1 wherein said conjugated diene monomer is represented by the formula
R 1 ′R 2 ′C═CR 3 ′CR 4 ′═CR 5 ′CR 6 ′ 3

wherein R 1 ′ to R 6 ′ are independently halogen, cyano, hydrogen, a substituted or unsubstituted hydrocarbon residue, or a substituted or unsubstituted heteroatom-containing hydrocarbon residue.

3. The process of claim 1 wherein said at least one conjugated diene monomer comprises a C-, N-, O-, P- or S-containing conjugated diene monomer.

4. The process of claim 2 wherein R 1 ′ to R 6 ′ are independently selected from hydrogen, halogen, alkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl, ester, and cyano.

5. The process of claim 1 wherein the at least one conjugated diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-penta-diene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, and mixtures and derivatives thereof.

6. The process of claim 1 wherein the at least one conjugated diene monomer is selected from conjugated diene monomers that propagate with an allyl radical.

7. The process of claim 1 further comprising polymerizing one or more radically (co)polymerizable monoene monomers with the at least one conjugated diene monomer.

8. The process of claim 7 wherein said one or more radically (co)polymerizable monoene monomer is represented by the formula
R 1 R 2 C═CR 3 R 4

wherein R 1 to R 4 are independently halogen, cyano, hydrogen, a substituted or unsubstituted hydrocarbon residue, or a substituted or unsubstituted heteroatom-containing hydrocarbon residue.

9. The process of claim 7 wherein said one or more radically (co)polymerizable monoene monomer comprises a C-, N-, O-, P- or S-containing monoene monomer.

10. The process of claim 8 wherein R 1 to R 4 are independently selected from hydrogen, halogen, alkyl, cycloalkyl, carboxyalkyl, oxycarbonyl, aryl, aralkyl, alkaryl, a N-, O-, P- or S-containing residue.

11. The process of claim 7 wherein said monoene monomer comprises an acrylate, methacrylate, methacrylamide, ethylene, propylene, butene, hexene, 4-methylpentene-1,1-octene, norbornene, substituted norbornene, styrene, acrylonitrile, methacrylonitrile, vinyl halide, florinated alkene, or mixtures thereof.

12. The process of claim 1 wherein said initiator comprises a halide, pseudohalide, alkyl halide, aryl sulfonyl compound, aryl halide, allyl halide, haloester compound, dithioester, fluoroalkyl halide, polyhalide, fluorinated halide, or mixtures thereof.

13. The process of claim 1 wherein said initiator is represented by the formula
R 11 OR 12 S(═O) 2 —X,

R 11 R 12 S(═O) 2 —X,

R 11 OC(═O)R 12 —X,

R 11 R 12 R 13 C—X,

R 11 C(═O)—X,

R 11 R 12 R 13 Si—X,

R 11 R 12 N—X,

R 11 N—X 2 ,

(R 11 ) n P(O) m —X 3-n ,

(R 11 O) n P(O) m —X 3-n , or

(R 11 )(R 12 O)P(O) m —X

wherein
X is selected from the group consisting of Cl, Br, I, OR 10 , where R 10 is alkyl of from 1 to 20 carbon atoms, SR 14 , SeR 14 , OC(═O)R 14 , OP(═O)R 14 , OP(═O)(OR 14 ) 2 , OP(═O)OR 14 , O—N(R 14 ) 2 , S—C(═S)N(R 14 ) 2 , S—C(═S)(R 14 ) 2 , O—C(═S)N(R 14 ) 2 , S—C(═O)N(R 14 ) 2 , COOR, CN, NC, SCN, CNS, OCN, CNO and N 3 , where R 14 is aryl or a straight or branched C 1 -C 20 alkyl group, or where an N(R 14 ) 2 group is present, the two R 14 groups may be joined to form a 5-, 6- or 7-membered heterocyclic ring;
R 11 , R 12 and R 13 are each independently selected from the group consisting of H, halogen, C 1 -C 20 alkyl, C 3 -C 8 cycloalkyl, R 8 3 Si, C(═Y)R 5 , C(═Y)NR 6 R 7 , where R 5 and R 7 are independently H or alkyl of from 1 to 20 carbon atoms, or R 6 and R 7 may be joined together to form an alkylene group of from 2 to 5 carbon atoms; COCl, OH, CN, C 2 -C 20 alkenyl or alkynyl, oxiranyl, glycidyl, C 2 -C 6 alkylene or alkenylene substituted with oxiranyl or glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl, C 1 -C 6 alkyl in which from 1 to all of the hydrogen atoms are replaced with halogen and C 1 -C 6 alkyl substituted with from 1 to 3 substituents selected from the group consisting of C 1 -C 4 alkoxy, aryl, heterocyclyl, C(═Y)R 5 , C(═Y)NR 6 R 7 , oxiranyl and glycidyl;
m is 0 or 1; and
n is 0, 1 or 2.

14. The process of claim 1 wherein the initiator is selected from the group consisting of 4-methoxybenzenesulfonyl chloride (MBSC), allylbromide (AB), α,α′-dichloro-p-xylene (DCPX), α,α′-dibromo-p-xylene (DBPX), α,α′-dichloro-p-xylene (DCPX), 1,1′-biphenylyl 1,4-bis(2-bromoacetate) (DB1BP), (1-bromoethyl)benzene (BEB), 1,1′-biphenylyl 1,4-bis(2-bromopropionate) (DB2BP), ethyl α-bromoisobutyrate, 1,1′-biphenylyl 1,4-bis(2-bromoisobutyrate) (DB3BP), bis-4,4′-(2-bromoisobutyryloxy)methylphenyl (DB3BPA), 1,1,1-tris(4-(2-bromoiso-butyryloxy)phenyl)ethane (TB3Ph), tetrabromomethane (CBr 4 ), tetrachloromethane (CCl 4 ), bromotrichloromethane (CBrCl 3 ), p-toluenesulfonyl chloride, cis-1,4-dichloro-2-butene, and mixtures thereof.

15. The process of claim 1 wherein the transition metal comprises Cu 0 , Cu 1+ , Cu 2+ , Au 0 , Au + , Au 2+ , Au 3+ , Ag 0 , Ag + , Ag 2+ , Hg 0 , Hg + , Hg 2+ , Ni 0 , Ni + , Ni 2+ , Ni 3+ , Pd 0 , Pd + , Pd 2+ , Pt 0 , Pt + , Pt +2 , Pt +3 , Pt +4 , Rh 0 , Rh + , Rh 2+ , Rh 3+ , Rh 4+ , Co 0 , Co + , Co 2+ , Co 3+ , Ir 0 , Ir + , Ir 2+ , Ir 3+ , Ir 4+ , Fe 0 , Fe 2+ , Fe 3+ , Ru 0 , R 2+ , Ru 3+ , Ru 4+ , Ru 5+ , R 6+ , Os 0 , Os 2+ , Os 3+ , Os 4+ , Re 0 , Re 2+ , Re 3+ , Re 4+ , Re 6+ , Re 7+ , Mn 0 , Mn 2+ , Mn 3+ , Mn 4+ , Cr 0 , Cr 2+ , Cr 3+ , Mo 0 , Mo + , Mo 2+ , Mo 3+ , W 0 , W 2+ , W 3+ , V 0 , V 2+ , V 3+ , V 4+ , V 5+ , Nb 0 , Nb 2+ , Nb +3 , Nb 4+ , Nb 5+ , Ta 0 , Ta 3+ , Ta 4+ , Ta 5+ , Zn 0 , Zn + or Zn 2+ .

16. The process of claim 1 wherein the transition metal comprises Cu 0 , Cu 1+ , Cu 2+ , Fe 0 , Fe 2+ , or Fe 3 .

17. The process of claim 1 wherein the transition metal comprises Cu 0 , Cu 1+ , or Cu 2+ .

18. The process of claim 1 wherein the transition metal-ligand complex comprises a C-, N-, O-, P- or S-containing ligand.

19. The process of claim 1 wherein the ligand is represented by the formula:
R 16 —Z—R 17 ,

R 16 —Z—(R 18 —Z) m —R 17

wherein:
R 16 and R 17 are independently selected from the group consisting of H, C 1 -C 20 alkyl, aryl, heterocyclyl, and C 1 -C 6 alkyl substituted with C 1 -C 6 alkoxy, C 1 -C 4 dialkylamino, C(═Y)R 5 , C(═Y)R 6 R 7 and/or YC(═Y)RB, where Y, R 5 , R 6 , R 7 and R 8 are independently H or alkyl of from 1 to 20 carbon atoms, or R 6 and R 7 may be joined together to form an alkylene group of from 2 to 5 carbon atoms; or
R 16 and R 17 can be joined to form a saturated, unsaturated or heterocyclic ring;
Z is a covalent bond, O, S, NR 19 or PR 19 , where R 19 is selected from the same group as R 16 and R 17 ,
each R 18 is independently a divalent group selected from the group consisting of C 2 -C 4 alkylene (alkanediyl) and C 2 -C 4 alkenylene where the covalent bonds to each Z a

Assignees

• Univ Connecticut

Inventors

• Asandei Alexandru D

Classifications

• C08F36/02 Primary

  the radical having only two carbon-to-carbon double bonds · CPC title

• C08F236/06

  Butadiene · CPC title

• C08F2/48

  by ultraviolet or visible light · CPC title

• C08F4/40

  Redox systems · CPC title

• C08F236/08 Primary

  Isoprene · CPC title