Chain transfer agent for addition mass polymerization of polycycloolefinic monomers

Patent metadata

Field	Value
Publication number	US-2016289353-A1
Application number	US-201615086185-A
Country	US
Kind code	A1
Filing date	Mar 31, 2016
Priority date	Mar 31, 2015
Publication date	Oct 6, 2016
Grant date	—

Abstract

The present invention relates to use of certain chain transfer agents to control molecular weight of addition mass polymerization of certain polycycloolefinic monomers. More specifically, the present invention relates to use of a series of substituted bicycloalkenes as chain transfer agents in the addition mass polymerization of a series of functionalized norbornene-type monomers. This invention also relates to compositions containing bicycloalkenes as chain transfer agents in forming “in mold” polycycloolefinic polymers by addition mass polymerization.

First claim

What is claimed is:

1 . A reaction composition comprising:
a compound of formula (I):

wherein
a is an integer from 0 to 4;
b is an integer from 0 to 2a+4;
each R is hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, substituted or unsubstituted (C 3 -C 7 )cycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aralkyl, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkoxy, substituted or unsubstituted (C 3 -C 7 )cycloalkoxy, (C 6 -C 10 )aryloxy and (C 6 -C 10 )aralkyloxy;

one or more polycyclic olefin monomers; and
an organo-transition metal compound.

2 . The composition of claim 1 , wherein said one or more polycyclic olefin monomer is of formula (II):

wherein:
c is an integer 0, 1 or 2;
R 1 , R 2 , R 3 and R 4 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 3 -C 6 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 2 -C 6 )alkoxy(C 1 -C 2 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, where each of the aforementioned substituents are optionally substituted with a group selected from halogen or hydroxy.

3 . The composition of claim 1 , wherein said compound of formula (I) is selected from the group consisting of:
bicyclo[3.2.0]hept-6-ene; 2-methylbicyclo[3.2.0]hept-6-ene; 2,4-dimethylbicyclo[3.2.0]hept-6-ene; 2,4,6-trimethylbicyclo[3.2.0]hept-6-ene; bicyclo[4.2.0]oct-7-ene; 2-methylbicyclo[4.2.0]oct-7-ene; 3-methylbicyclo[4.2.0]oct-7-ene; 2,3-dimethylbicyclo[4.2.0]oct-7-ene; 2,3,5-trimethylbicyclo[4.2.0]oct-7-ene; 2,3,4,5-tetramethylbicyclo[4.2.0]oct-7-ene; bicyclo[5.2.0]non-8-ene; 2-methylbicyclo[5.2.0]non-8-ene; 2,5-dimethylbicyclo[5.2.0]non-8-ene; bicyclo[6.2.0]dec-9-ene; and 2-methylbicyclo[6.2.0]dec-9-ene.

4 . The composition of claim 1 , wherein said organo-transition metal compound is selected from the group consisting of:

wherein Py is pyridine.

5 . The composition of claim 1 , wherein said organo-transition metal compound is selected from the group consisting of:

6 . The composition of claim 1 , wherein said organo-transition metal compound is selected from the group consisting of:
trans-[Pd(NCMe)(OAc)(P(i-propyl) 3 ) 2 ]B(C 6 F 5 ) 4 , trans-[Pd(NCC(CH 3 ) 3 )(OAc)(P(i-propyl) 3 ) 2 ]B(C 6 F 5 ) 4 , trans-[Pd(OC(C 6 H 5 ) 2 )(OAc)(P(i-propyl) 3 ) 2 ]B(C 6 F 5 ) 4 , trans-[Pd(HOCH(CH 3 ) 2 )(OAc)(P(i-propyl) 3 ) 2 ]B(C 6 F 5 ) 4 , trans-[Pd(NCMe)(OAc)(P(cyclohexyl) 3 ) 2 ]B(C 6 F 5 ) 4 , Pd(OAc) 2 (P(cyclohexyl) 3 ) 2 , Pd(OAc) 2 (P(i-propyl) 3 ) 2 , Pd(OAc) 2 (P(i-propyl) 2 (phenyl)) 2 , trans-[Pd(NCMe)(OAc)(P(cyclohexyl) 2 (t-butyl)) 2 ]B(C 6 F 5 ) 4 , where OAc is OCOCH 3 .

7 . The composition of claim 1 , wherein said organo-transition metal compound is selected from the group consisting of:
nickel(2,4,6-trifluoromethylphenyl) 2 ; nickel(η 6 -toluene)(pentafluorophenyl) 2 ; nickel (tetrahydrofuran) 2 (pentafluorophenyl) 2 ; [(allyl)Ni(1,4-cyclooctadiene)]PF 6 , [(crotyl)Ni(1,4-cyclooctadiene)]PF 6 ; and [(allyl)Ni(1,4-cyclooctadiene)]SbF 6 .

8 . The composition of claim 1 further comprising a compound of the formula (V):
M ⊕ Z ⊖   (V);

wherein
M ⊕ is a cation selected from lithium, sodium, potassium, cesium, barium, ammonium and linear or branched tetra(C 1 -C 4 )alkyl ammonium;
Z ⊖ is a weakly coordinating anion selected from B(C 6 F 5 ) 4 ⊖ , B[C 6 H 3 (CF 3 ) 2 ] 4 ⊖ , B(C 6 H 5 ) 4 ⊖ , [Al(OC(CF 3 ) 2 C 6 F 5 ) 4 ] ⊖ , BF 4 ⊖ , PF 6 ⊖ , AsF 6 ⊖ , SbF 6 ⊖ , (CF 3 SO 2 )N ⊖ and CF 3 SO 3 ⊖ .

9 . The composition of claim 8 , wherein said compound of the formula (V) is selected from the group consisting of:
lithium tetrafluoroborate; lithium triflate; lithium tetrakis(pentafluorophenyl)borate; lithium tetraphenylborate; lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; lithium tetrakis(2-fluorophenyl)borate; lithium tetrakis(3-fluorophenyl)borate; lithium tetrakis(4-fluorophenyl)borate; lithium tetrakis(3,5-difluorophenyl)borate; lithium hexafluorophosphate; lithium hexaphenylphosphate; lithium hexakis(pentafluorophenyl)phosphate; lithium hexafluoroarsenate; lithium hexaphenylarsenate; lithium hexakis(pentafluorophenyl)arsenate; lithium hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; lithium hexafluoroantimonate; lithium hexaphenylantimonate; lithium hexakis(pentafluorophenyl)antimonate; lithium hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; lithium tetrakis(pentafluorophenyl)aluminate; lithium tris(nonafluorobiphenyl)fluoroaluminate; lithium (octyloxy)tris(pentafluorophenyl)aluminate; lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; and lithium methyltris(pentafluorophenyl)aluminate

10 . The composition of claim 1 , wherein said one or more monomer of formula (II) is selected from the group consisting of:
bicyclo[2.2.1]hept-2-ene (NB); norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB); 5-hexylbicyclo-[2.2.1]hept-2-ene (HexNB); 5-octylbicyclo[2.2.1]hept-2-ene (OctNB); 5-decylbicyclo[2.2.1]hept-2-ene (DecNB); 5-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB); 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).

11 . The composition of claim 1 , wherein said one or more monomers of formula (II) are at least two distinct types of monomers of formula (II).

12 . The composition of claim 1 , wherein at least one of said one or more monomers of formula (II) is 5-decylbicyclo[2.2.1]hept-2-ene (DecNB) or 5-hexylbicyclo-[2.2.1]hept-2-ene (HexNB).

13 . The composition of claim 1 , wherein at least one of said one or more monomers of formula (II) is 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB).

14 . The composition of claim 1 , wherein said compound of formula (I) is present in an amount of at least one mole percent of the total loading of the monomers of formula (II).

15 . The composition of claim 1 , wherein said compound of formula (I) is present in an amount of from one to ten mole percent of the total loading of the monomers of formula (II).

16 . A method of mass polymerizing polycyclic olefin monomers comprising:
combining a compound of formula (I):

wherein
a is an integer from 0 to 4;
b is an integer from 0 to 2a+4;
each R is hydrogen, halogen, methyl, ethyl, (C 3 -C 6 )alkyl, substituted or unsubstituted (C 3 -C 7 )cycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aralkyl, methoxy, ethoxy, (C 3 -C 6 )alkoxy, sub

Assignees

• Promerus Llc

Inventors

• Ng Hendra
• Seto Keitaro
• Zhang Wei

Classifications

• C08F132/08 Primary

  having condensed rings · CPC title

• C08F2/38

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

• C08F2/02 Primary

  Polymerisation in bulk · CPC title

• C08F4/12

  of boron, aluminium, gallium, indium, thallium or rare earths · CPC title

• C08F4/60031

  PO · CPC title