Process for manufacturing hydrogenated polymers from conjugated diolefins

Claim 2

A PROCESS FOR MANUFACTURING HYDROGENATED POLYMERS OR COPOLYMERS FROM AT LEAST ONE CONJUGATED DIOLEFIN, WHICH COMPRISES A FIRST STEP OF MANUFACTURING AN UNSATURED POLYMERR OR COPOLYMER BY SOLUTION POLYMERIZING THE CONJUGATED DIOLEFIN IF 4-12 CARBON ATOMS IN CONTACT WITH A CATALYSTIC QUANTITY OF A DERIVATIVE OF A TRANSITUATION METAL CARBOXYLATE OF THE FORMULA:

Claim 3

A process as defined by claim 1, wherein the second step is carried out by reacting the solution resulting from the first step with hydrogen and adding as the metallic reducing agent at least one compound having one of the formulae R''mM''X''n ; M'''' Al Hp X''4 p and R''q M'', in which R'' is an aromatic, a saturated aliphatic or a saturated cycloaliphatic hydrocarbon radical or a combination thereof, containing 1-20 carbon atoms, m'' is an integer from 1 to 3 inclusive, M'' is aluminum, zinc, lithium, sodium or magnesium, M'''' is lithium or sodium, X'' is a halogen atom, a monovalent hydrocarbon radical or an OR, NR2 or NHR group, where R is a monovalent hydrocarbon radical, n'' is selected from 0, 1 and 2, p'' is from 0 to 4, inclusive and q'' is an integer from 1 to 3 inclusive which is equal to the valence of the metal M''.

Claim 4

A process as defined by claim 1, wherein X is fluorine or chlorine, M is molybdenum, tungsten, nickel or cobalt, each R is selected from the group consisting of a hydride ion, a chlorine atom, a bromine atom, a methyl radical, a pi -allylic radical or a carbonyl group, L is selected from the group consisting of diethylether, 1,2 dimethoxyethane, ethylene-glycol monomethylether, tetrahydrofuran, and methyl ethyl ketone, and q is 1 or 2.

Claim 5

A process as defined by claim 1 wherein the derivative of transition metal carboxylate is selected from the group consisting of

Claim 6

A process as defined by claim 1, wherein the derivative of transition metal carboxylate has the formula:

Claim 7

A process as defined by claim 1, wherein the derivative of transition metal carboxylate has the formula:

Claim 8

A process as defined by claim 1, wherein the derivative of transition metal carboxylate has the formula: (CF3COO)Ni Cl (O (C2H5)2)

Claim 9

A process as defined by claim 1 wherein the derivative of transition metal carboxylate has the formula: (CF3COO) Ni Br )O(C2H5)2)

Claim 10

A process as defined by claim 1 wherein the derivative of transition metal carboxylate has the formula: (CF3 COO)Ni Cl

Claim 11

A process as defined by claim 1 wherein the derivative of transition metal carboxylate has the formula: ((CF3 COO) Ni ( pi -C3H5))2

Claim 12

A process as defined by claim 1 wherein the metallic reducing agent is selected from the group consisting of trimethylaluminum, monoethoxydiethylaluminum, tri-isobutylaluminum, triphenylaluminum, ethyl lithium, n-butyllithium, isobutylsodium, phenyl lithium, phenyl sodium, diethylzinc, dibutylzinc, diethylmagnesium, dibutylmagnesium, diphenylmagnesium, diethylaluminum chloride, ethyl aluminum sesquichloride, butyllithium-aluminum trihydride, lithium aluminum tetrahydride, sodium-aluminum hydride tributylate, diphenylaluminum chloride, phenylmagnesium bromide, t-butylmagnesium chloride, triethylaluminum, and mixtures thereof.

Claim 13

A process as defined by claim 1, wherein n is 3; X is F; M is molybdenum, or nickel; each R is H, Cl, Br, pi -allyl or carbonyl; m is an integer of 1 to 4 inclusive; L is diethyl ether or tetrahydrofuran; p is 0, 1 or 2; q is 1 or 2: and the metallic reducing agent is triethylaluminum, butyllithium or lithium-aluminum hydrode.

Claim 14

A process as defined by claim 1, wherein the concentration of the derivative of transition metal carboxylate is from 0.5 X 10 3 to 5 X 10 2 mole per liter of reaction solution, the molar ratio of the reducing agent to said derivative of transition metal carboxylate is from 1/1 to 20/1, the hydrogen pressure is at least one atmosphere and the temperature is from 0* to 120*C.

Claim 15

A process as defined by claim 13 wherein the unsaturated polymer to be hydrogenated has a concentration in the raw product of 1-50% by weight and said raw product has a viscosity of 0.05-5,000 poises.

Claim 16

A process as defined by claim 14 wherein the hydrogenation pressure is 10-30 atmospheres.

Claim 17

A process as defined by claim 1 wherein at least 90% of the monomer in the first step is polymerized.

Claim 18

A process as defined by claim 1 wherein the conjugated diolefin is 1,3-butadiene, 1,3-pentadiene isoprene, piperylene, 1,3-dimethylbutadiene and mixtures thereof.

Claim 19

A process as defined by claim 1 wherein the conjugated diolefin is selected from the group consisting of 1,3 butadiene, 1,3 pentadiene and isoprene and mixtures thereof; n is 3; X is F; M is molybednum or nickel; each R is H, Cl, Br, pi -allyl or carbonyl; m is an integer of 1 to 4 inclusive; L is diethylether or tetrahydrofura; p is 0, 1 or 2; q is 1 or 2; the metallic reducing agent is triethylaluminum, butyllithium or lithium-aluminum hydride; the concentration of said derivative of transition metal carboxylate is from 0.5 X 10 3 to 5 X 10 2 mole per liter of reaction solution; the molar ratio of said metallic reducing agent to said derivative of transition metal carboxylate is from 1/1 to 5/1; the hydrogen pressure is at least 1 atmosphere; and the temperature is from 30 to 120* C.

Claim 20

A process for manufacturing hydrogenated polymers or copolymers which comprises hydrogenating a solution containing a crude unsaturated polymer Or copolymer and residual catalyst under a sufficient pressure of hydrogen, at a temperature of 0*-120*C, and in the presence of a metallic reducing agent selected from the group consisting of trimethylaluminum, monoethoxydiethylaluminum, tri-isobutylaluminum, triphenylaluminum, ethyl lithium, n-butyllithium, isobutylsodium, phenyl lithium, phenyl sodium, diethylzinc, dibutylzinc, diethylmagnesium, dibutylmagnesium, diphenylmagnesium, diethylaluminum chloride, ethyl aluminum sesquichloride, butyllithium-aluminum trihydride, lithium aluminum tetrahydride, sodium-aluminum hydride tributylate, diphenylaluminum chloride, phenylmagnesium bromide, t-butylmagnesium chloride, triethylaluminum, and mixtures thereof, said solution containing crude unsaturated polymer or copolymer and residual catalysts having been produced by solution polymerizing at least one conjugated diolefin of 4-12 carbon atoms in contact with a catalyst selected from the group consisting of

Claim 21

A process for manufacturing hydrogenated polymers or copolymers which comprises hydrogenating a solution containing a crude unsaturated polymer Or copolymer and residual catalyst under a sufficient pressure of hydrogen, at a temperature of 0*-120*C, and in the presence of a metallic reducing agent selected from the group consisting of trimethylaluminum, monoethoxydiethylaluminum, tri-isobutylaluminum, triphenylaluminum, ethyl lithium, n-butyllithium, isobutylsodium, phenyl lithium, phenyl sodium, diethylzinc, dibutylzinc, diethylmagnesium, dibutylmagnesium, diphenylmagnesium, diethylaluminum chloride, ethyl aluminum sesquichloride, butyllithium-aluminum trihydride, lithium aluminum tetrahydride, sodium-aluminum hydride tributylate, diphenylaluminum chloride, phenylmagnesium bromide, t-butylmagnesium chloride, triethylaluminum, and mixtures thereof, said solution containing crude unsaturated polymer or copolymer and residual catalysts having been produced by solution polymerizing at least one conjugated diolefin of 4-12 carbon atoms in contact with a catalyst selected from the group consisting of

Claim 22

A process as defined by claim 19 wherein the metallic reducing agent is triethylaluminum or triisobutylaluminum, and the molar ratio of said metallic reducing agent to the catalyst employed in the production of the unsaturated polymer being about 2:1 to 5:1 respectively, the hydrogen pressure being at least 1 atmosphere, and the reaction temperature being about 0*-120* C.

Claim 23

A process as defined by claim 20 wherein the unsaturated polymer to be hydrogenated has a concentration in the raw product of 1-50% by weight and said raw product has a viscosity of 0.05-5,000 poises.

Claim 24

A process as defined by claim 21 wherein the hydrogenation pressure is 10-30 atmospheres.

Claim 25

A process as defined by claim 19 wherein not more than 10% free monomer is present in the solution to be hydrogenated.

Claim 26

A process as defined by claim 19 wherein the conjugated diolefin is 1,3-butadiene, 1,3 pentadiene isoprene, piperylene, 1,3-dimethylbutadiene and mixtures thereof.

Claim 27

A process for manufacturing hydrogenated polymers or copolymers, which comprises hydrogenating a solution containing a crude unsaturated polymer or copolymer and residual catalyst under a hydrogen pressure of at least 1 atmosphere, at a temperature of about 30* to 120*C, and in the presence of a metallic reducing agent selected from the group consisting of triethylaluminum, butylithium and lithium aluminum hydride, said solution containing crude unsaturated polymer or copolymer and residual catalyst having been produced by solution polymerizing at least one conjugated diolefin Selected from the group consisting of 1,3 butadiene, 1,3 pentadiene, isoprene and mixtures thereof, in contact with a catalyst consisting of a derivative of a transition metal carboxylate of the formula ((H3 n Xn)C - CO2 M (R)m (L)p)q in which n is 3; X is F; M is molybdenum or nickel; each R is H, Cl, Br, pi -allyl or carbonyl; m is an integer of 1 to 4 inclusive; L is diethylether or tetrahydrofuran; p is 0, 1 or 2; ; q is 1 or 2; the concentration of said derivative of transition metal carboxylate if from 0.5 X 10 3 to 5 X 10 2 mole per liter of reaction solution, said metallic reducing agent being essentially the only catalytic component added to the solution in the hydrogenation step and being added in a molar ratio to said derivative of transition metal carboxylate of from 1/1 to 5/1 to form in situ a hydrogenation catalyst with said residual catalyt in said solution.

Claim 28

A process for manufacturing hydrogenated polymers or copolymers, which comprises hydrogenating a solution containing a crude unsaturated polymer or copolymer and residual catalyst under a hydrogen pressure of at least 1 atmosphere, at a temperature of about 30* to 120*C, and in the presence of a metallic reducing agent selected from the group consisting of triethylaluminum, butylithium and lithium aluminum hydride, said solution containing crude unsaturated polymer or copolymer and residual catalyst having been produced by solution polymerizing at least one conjugated diolefin Selected from the group consisting of 1,3 butadiene, 1,3 pentadiene, isoprene and mixtures thereof, in contact with a catalyst consisting of a derivative of a transition metal carboxylate of the formula ((H3 n Xn)C - CO2 M (R)m (L)p)q in which n is 3; X is F; M is molybdenum or nickel; each R is H, Cl, Br, pi -allyl or carbonyl; m is an integer of 1 to 4 inclusive; L is diethylether or tetrahydrofuran; p is 0, 1 or 2; ; q is 1 or 2; the concentration of said derivative of transition metal carboxylate if from 0.5 X 10 3 to 5 X 10 2 mole per liter of reaction solution, said metallic reducing agent being essentially the only catalytic component added to the solution in the hydrogenation step and being added in a molar ratio to said derivative of transition metal carboxylate of from 1/1 to 5/1 to form in situ a hydrogenation catalyst with said residual catalyt in said solution.