WO2012174734A1 - Polymérisation/copolymérisation en solution des diènes, hydrogénation des caoutchoucs diènes et caoutchoucs diènes hydrogénés - Google Patents

Polymérisation/copolymérisation en solution des diènes, hydrogénation des caoutchoucs diènes et caoutchoucs diènes hydrogénés Download PDF

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WO2012174734A1
WO2012174734A1 PCT/CN2011/076267 CN2011076267W WO2012174734A1 WO 2012174734 A1 WO2012174734 A1 WO 2012174734A1 CN 2011076267 W CN2011076267 W CN 2011076267W WO 2012174734 A1 WO2012174734 A1 WO 2012174734A1
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pph
rhcl
diene
accordance
group
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PCT/CN2011/076267
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English (en)
Inventor
Zhenli Wei
Qingchun LIU
Sharon Guo
Matthias Soddemann
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Lanxess Deutschland Gmbh
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Priority to PCT/CN2011/076267 priority Critical patent/WO2012174734A1/fr
Priority to PCT/EP2012/062167 priority patent/WO2012175725A1/fr
Priority to TW101122736A priority patent/TW201319103A/zh
Publication of WO2012174734A1 publication Critical patent/WO2012174734A1/fr

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    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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Definitions

  • This invention generally relates to solution polymerization/co-polymerization of dienes, specifically relates to a catalyst system for the solution polymerization/co-polymerization of diene and vinyl monomers and/or the hydrogenation of the obtained diene rubbers based polymers either in a one-pot manner or in a two-step manner, a process for the solution polymerization/co-polymerization of diene and vinyl monomers in the presence of metal catalysts system, as well as the hydrogenation of the obtained diene rubbers based polymers either in a one-pot manner or in a two-step manner, diene rubber polymers obtained by the solution polymerization and/or the hydrogenation of the obtained diene rubber based polymers either in a one-pot manner or in a two-step manner.
  • Butadiene rubber is a common synthetic rubber obtained by polymerizing monomer of 1,3-diene. Butadiene rubbers are commonly polymerized butadiene in solution, including anionic polymerization and coordination polymerization. Styrene-butadiene rubber (SBR) may be polymerized in solution (such as anionic polymerization), so-called SSBR. Styrene-butadiene rubber (SBR) may also be polymerized in emulsion, so-called ESBR.
  • SBR Styrene-butadiene rubber
  • Nitrile butadiene rubber is commonly produced by free-radical emulsion polymerization.
  • Nitrile butadiene rubber (NBR), a co-polymer comprising at least one conjugated diene, butadiene, at least one unsaturated nitrile and optionally further comonomers, is a specialty rubber, which has good chemical resistance, and excellent oil resistance. Coupled with the high level of mechanical properties of the rubber (in particular the high resistance to abrasion) it is not surprising that NBR has found widespread use in the automotive (seals, hoses, bearing pads), electrical (cable sheathing), mechanical engineering (wheels, rollers) and footwear industries, amongst others.
  • NBR is made by a radical emulsion polymerization process which produces NBR polymer with a relatively broad molecular weight distribution and with a certain level of emulsifier residues.
  • NBR obtained by this process has a Mooney viscosity in the arrange of from 30 to 90, an Mn in the range of from 80,000 to 150,000, an Mw in the arrange of from 250,000 to 350,000 and a polydispersity index greater than 3.2.
  • a metal compound catalyzed solution polymerization process could produce NBR with higher purity and more controlled molecular structure.
  • HNBR hydrogenated nitrile butadiene rubber
  • CRP controlled radical polymerization
  • the mentioned polymerization processes used different types metal catalysts, it is needed to provide a catalyst system for the solution polymerization/co-polymerization of diene and vinyl monomers and/or the hydrogenation of the obtained diene rubbers based polymers either in a one-pot manner or in a two-step manner having controlled molecular weights, narrower molecular weight distributions and a Mooney viscosity in the arrange of from more than 0 to 30, preferably more than 1 to 30.
  • the present invention provides a metal-containing catalyst system, which comprises (1) a metal-containing catalyst, (2) a co-catalyst, and optionally (3) an additive, for a solution polymerization process of diene and/or for hydrogenation of diene-containing polymers, wherein (1) the metal-containing catalyst is selected from ML n X m , MX m , MX m pH 2 0, M(OC(0)R) m , or any combination thereof, wherein M represents a metal selected
  • L is a group selected from 3 , in which R 1; R 2 , and R 3 may be same or different, and each R 1; R 2 and R 3 is independently selected from H, Ci-C 6 alkyl, C 5 -C 7 aryl or C 3 -C 6 cycloalkyl, substituted C 3 -C 6 cycloalkyl, substituted C 5 -C 7 aryl, with a proviso that Ri, R 2 and R 3 are not all of H, X is a halogen, n is a integer of 1 to 5, p is a integer of 1 to 7, and m is equal to the valence of M;
  • the co-catalyst is selected from a halide, an azo-compound, or a peroxide; and optionally
  • the additive is selected from a group consisting of a primary amine (Ri-NH 2 ), a second amine (Ri-NH 2 ), a second amine (Ri-NH 2 ), a second amine (Ri-NH 2 ), a second amine (Ri-NH 2 ), a second amine (Ri-NH 2 ), a second amine (Ri-NH 2 ), a second amine (Ri-NH 2 ), a second
  • R 1; R 2 , and R 3 are defined as the above.
  • the present invention provides a solution polymerization process of diene, comprising homopolymerization of diene or copolymerization of diene together with at least one of comonomers in the presence of at least one of the metal-containing catalyst system of the present application in at least one of organic solvents.
  • the solution polymerization provide a process for the synthesis of low molecular weight nitrile rubber having narrow molecular weight distribution by the direct solution copolymerization of at least one conjugated dienes monomers with at least one ⁇ , ⁇ - unsaturated nitrile and optionally further one or more copolymerizable monomers in the presence of metal-containing catalyst(s) and co-catalyst with or without suitable additive(s) in organic solvents.
  • the present invention is directed to a nitrile rubber having an Mn in the range of less than 1000 to 300000 g/mol, a Mooney viscosity (ML 1+4@100°C) of less than 1 to 30, and a polydispersity index of less than 5.
  • the present invention provides a diene polymer, obtained by the solution polymerization, comprises in the range of from 40 to 85 weight part of repeating units derived from one or more dienes, in the range of from 0 to 70 weight part of repeating units derived from one or more ⁇ , ⁇ -unsaturated nitriles or styrene or any of derivatives of styrene, and in the range of from 0 to 40 weight part of repeating units derived from optional termonomers other than ⁇ , ⁇ -unsaturated nitrile or styrene and any of derivatives of styrene.
  • the present invention provides a use of the dienes polymer obtained by the solution polymerization process of the invention in the hydrogenation in the present hydrogen and a catalyst of Rh, Ru, and/or Pd-based to obtain hydrogenated diene polymers.
  • the present invention provides a one-pot process for synthesis of the hydrogenated diene polymers by directly introducing hydrogen into the reactor after the completion of solution polymerization and reacting at a desired temperature.
  • the invention provides a hydrogenated diene polymer, obtained by the one- pot process for the synthesis of the hydrogenated diene polymers of the invention.
  • the present invention provides a process for hydrogenation of diene polymers, comprising a) solution homopolymerization of diene or copolymerization of diene together with at least one of comonomers in the presence of one of the metal-containing catalyst system of the present invention in at least one of organic solvents to obtain diene rubber, b) directly introducing hydrogen into the mixture of step a) after the completion of solution polymerization to obtain the hydrogenated diene-containing polymers.
  • the present invention provides a process for hydrogenation of diene polymers, comprising: a) dissolving at least one diene polymer into at least one organic solvent in a autoclave reactor, b) adding at least one of the metal-containing catalyst system of the invention into the solution obtained in step a), c) introducing hydrogen into the autoclave reactor and heating the autoclave reactor up to a predetermined temperature for a predetermined time.
  • the present invention provides a process for hydrogenation of diene polymers, comprising a) adding the solution homopolymerization of diene or copolymerization of diene obtained by the solution polymerization process of the invention, and optionally at least one of organic solvents, b) directly introducing hydrogen into the mixture of step a) and heat up to a predetermined temperature to obtain the hydrogenated diene-containing polymers.
  • the invention provides a hydrogenated diene rubber, obtained by the one- pot process for the synthesis of the hydrogenated diene-containing polymers of the invention.
  • the invention provides a use of the catalyst system of the invention in the manufacture of diene polymer.
  • the invention provides a use of the catalyst system of the invention in the manufacture of hydrogenated diene-containing polymer.
  • the invention provides a use of glass tube reactor and/or autoclave in the solution polymerization process of the invention or in the one-pot process for the synthesis of the hydrogenated diene polymers of the invention.
  • the invention provides a use of glass tube reactor and/or autoclave in process for the synthesis of the hydrogenated diene polymers of the invention.
  • the diene rubber polymers provided by the solution polymerization of the present application have a Mn in the range of less than 1000 to 300000 g/mol, a Mooney viscosity (ML 1+4@100 °C) of less than 1 to 30, and a polydispersity index of less than 5, preferably in the range from 1.1 to 5.0 and in particular in the range from 1.1 to 4.0, more preferably in the range from 1.1 to 2.0.
  • the diene rubber polymers provided by the solution polymerization of the present application may be hydrogenated directly in the present of hydrogen.
  • the hydrogenated diene rubber polymers obtained by the one-pot process for the synthesis of the hydrogenated diene-containing polymers of the present application or by the process for hydrogenation of diene polymers, have a Mn in the range of less than 1000 to 300000 g/mol, a Mooney viscosity (ML 1+4@100 °C) of 10 to 60, and a polydispersity index of less than 5, preferably in the range from 1.1 to 5.0 and in particular in the range from 1.1 to 4.0, more preferably in the range from 1.1 to 3.0, still more preferably in the range from 1.1 to 2.0.
  • Figure 1 is the GPC curves of Examples 1-3, wherein numbers of 1-3 represent Examples 1-3;
  • Figure 2 is the GPC curves of Examples 4-6, wherein numbers of 4-6 represent Examples 4-6;
  • Fig. 3a is Mn and PDI of Examples 6-15;
  • Fig. 3b is conversions of the samples of Example 6 and 8-15;
  • Fig. 3c is FT-IR spectra of the samples of Examples 6-16, wherein numbers of 6-16 represent Examples 6-16;
  • Fig. 3d is 'HNMR spectra of the samples of Examples 6-16, wherein numbers of 6-16 represent Examples 6-16;
  • Fig. 3e is 'HNMR spectrum of the sample of Example 6 alone;
  • Fig. 3f is DSC curves of the samples of Examples 6-15, wherein numbers of 6-15 represent the samples of Examples 6-15;
  • Fig. 4a is FT-IR spectra of the samples of Examples 3, 6, 17 and 18;
  • Fig. 4b is 'HNMR spectra of the samples of Examples 3, 6, 17 and 18;
  • Fig. 5a is 'HNMR spectra of the samples of Examples 22-1 to 22-3;
  • Fig. 5b is 'HNMR spectrum of the sample of Examples 22-7;
  • Fig. 6a - 6c are 'HNMR spectra of the samples of Examples 23-4, 23-7 and 23-10;
  • Fig. 7a - 7c are 'HNMR spectra of the samples of Examples 24-1, 24-3 and 24-4;
  • Fig. 7d is 'HNMR spectrum of the sample of Example 24-5;
  • Fig. 8 is 'HNMR spectrum of the sample of Example 25;
  • Fig. 9a is FT-IR spectrum of the sample of Example 26-2;
  • Fig. 9b is 'HNMR spectrum of the sample of Example 26-2;
  • Fig. 10a is FT-IR spectrum of the sample of controlled trail of Example 6;
  • Fig. 10b is 'HNMR spectrum of the sample of controlled trail of Example 6;
  • Fig. 10c is FT-IR spectrum of the sample of Example 27-1 with termonomer n-butyl acrylate
  • Fig. lOd is 'HNMR spectrum of the sample of Example 27-1 with termonomer n-Butyl acrylate
  • Fig. lOe is FT-IR spectrum of the sample of Example 27-2 with termonomer MMA;
  • Fig. lOf is 'HNMR spectrum of the sample of Example 27-2 with termonomer MMA;
  • Fig. lOg is FT-IR spectrum of the sample of Example 27-3 with termonomer MAA;
  • Fig. lOh-lOi are 'HNMR spectra of the sample of Example 27-3 with termonomer MAA;
  • Fig. 10k- 101 are 'HNMR spectra of the sample of Example 27-4 with termonomer IA;
  • Fig. 10m is FT-IR spectrum of the sample of Example 27-5 with termonomer acrylamide
  • Fig. 1 la is FT-IR spectra of the samples of Examples 28-1 and 28-2 which are carried out for different reaction time;
  • Fig. 1 lb is 'HNMR spectrum of the sample of Example 28-4;
  • Fig.12 is the FT-IR spectra and 'HNMR spectra of S-NBR and hydrogenated S-NBR
  • Fig. 13 is the FT-IR spectra of S-NBR and hydrogenated S-NBR.
  • nitrile rubber is intended to have a broad meaning and is meant to encompass a copolymer having repeating units derived from at least one conjugated diene, at least one ⁇ , ⁇ -unsaturated nitrile and optionally further one or more copolymerizable monomers.
  • the conjugated diene may be any known diene, preferably a C 4 -C 6 conjugated diene.
  • Preferred conjugated diene includes 1,3 -butadiene, isoprene, 2,3-dimethylbutadiene, piperylene or mixtures thereof. More preferred C 4 -C 6 conjugated diene includes 1,3- butadiene, isoprene and mixtures thereof. The most preferred C 4 -C 6 conjugated diene is 1,3- butadiene.
  • the ⁇ , ⁇ -unsaturated nitriles may be any known ⁇ , ⁇ -unsaturated nitriles, preferably a (C 3 -C 5 ) ⁇ , ⁇ -unsaturated nitrile.
  • Preferred (C 3 -C 5 ) ⁇ , ⁇ -unsaturated nitriles include acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof.
  • the most preferred (C 3 -C 5 ) ⁇ , ⁇ - unsaturated nitrile is acrylonitrile.
  • the present application provides the solution polymerization diene rubber polymer having a Mn in the range of less than 1000 to 300000 g/mol, a Mooney viscosity (ML 1+4@100 °C) of less than 1 to 30, and a polydispersity index of less than 5 and the hydrogenated diene rubber polymer having a Mn in the range of less than 1000 to 300000 g/mol, a Mooney viscosity (ML 1+4@100 °C) of 10 to 60, and a polydispersity index of less than 5.
  • an embodiment of the invention provides a metal- containing catalyst system of the invention, which comprises (1) a metal-containing catalyst, (2) a co-catalyst, and optionally (3) an additive, for a solution polymerization process of diene and/or for hydrogenation of diene-containing polymers, wherein
  • the metal-containing catalyst is selected from ML n X m , MX m , MX m pH 2 0, M(OC(0)R) m , or any combination thereof, wherein M represents a metal selected from Rh, Pd, Ru, Ir, Mo,
  • L is a group selected from , in which R 1; R 2 , and R 3 may be same or different, and each R 1; R 2 and R 3 is independently selected from H, Ci-C 6 alkyl, C 5 -C 7 aryl or
  • the co-catalyst is selected from a halide, an azo-compound, or a peroxide; and optionally (3) the additive is selected from a group consisting of primary amine (Ri-NH 2 ), a second amine (Ri-NH-R 2 ) , a tertiary amine (N(Ri)(R 2 )(R 3 )), , ascorbic acid, or an ammonium salt, or any combination thereof, in which R 1; R 2 , and R 3 are defined as the above.
  • the metal-containing catalyst system of the invention wherein (1) in the metal -containing catalyst, M represents a metal selected from Rh, Pd, Ru, Ir or Mo, preferably Rh, Pd, Ru, Ir, X is selected from CI or Br, more preferably CI; in , each R 1;
  • R 2 , and R 3 is independently selected from phenyl, C 3 -C 6 cycloalkyl, substituted C 3 -C 6 cycloalkyl, phenyl, substituted phenyl, preferably carboxy-substituted phenyl, sodium sulfonate-substituted phenyl, more preferably PPh 3 , phosphine tricyclohexyl (PCy 3 ), in which the sodium sulfonate group or carboxy group may be in ortho-, meta- or para-position of henyl ring;
  • the halide is selected from
  • the azo-compound is selected from 2,2 '-azobisisobutylnitrile (AIBN), 2,2'-azobis-(2-methylbutylnitrile (AMBN), 2,2'-azobis-(2-methylbutylnitrile (AMBN), dimethyl 2,2'-azobis-(2-methylpropionate, 1- cyano-l-methylethylazoformamide, l, r-azobis(cyclohexane-l-carbonitrile (ACCN), 2,2'- azobis-(2-methylpropionamide)dihydrochloride (AIBA), or 4,4'-azobis-(4-cyanovale
  • the additive is selected from a group consisting of ascorbic acid, methylamine, ethylamine, ethyldiamine, n-propylamine, iso-propylamine, propyldiamine, n-butylamine, iso-butylamine, butyldiamine, dibutylamine, dimethylamine, diethylamine, diiso-propylamine, t-butylamine, amylamines, cyclohexylamine, triethanolamine, trimethylamine, triethylamine, tri-n- propylamine, tri-n-butylamine, cyclo ne, cyclopentylamine, methyltri-n- octylammonium chloride (MTOAC) , or any combination thereof, in which R 1; R 2 , and R 3 are defined as the above.
  • MTOAC methyltri-n- octylammonium chloride
  • the metal-containing catalyst system of the invention wherein the metal-containing catalyst system is selected from:
  • MCl m (PPh 3 ) n (2) one of dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), CH 2 C1 2 , CHC1 3 , CCI 4 , and optionally (3) PPh 3 ;
  • MCl m (PPh 3 ) n (2) at least one of 2,2'-azobisisobutylnitrile (AIBN), 2,2'-azobis-(2-methylbutylnitrile (AMBN), 2,2'-azobis-(2-methylbutylnitrile (AMBN), dimethyl 2,2 ' -azobis-(2-methylpropionate, 1 -cyano- 1 -methylethylazoformamide, 1, 1 '- azobis(cyclohexane-l-carbonitrile (ACCN), 2,2'-azobis-(2- methylpropionamide)dihydrochloride (AIBA), 4,4'-azobis-(4-cyanovaleric acid) (ACVA), and optionally (3) PPh 3 ; or
  • M(OAc) m a group consisting of (1) M(OAc) m , (2) at least one of, CH 2 C1 2 , CHC1 3 , CC1 4 , and optionally (3) P(Ph) 3 ;
  • M is selected from Rh, Pd, Ru, Ir, Mo, preferably selected from Rh, Ru, Pd, and Ir, more preferably selected from Rh, Ru, and Pd, n is a integer of 3, p is a integer of 1 to 7, and m is equal to the valence of M.
  • the metal-containing catalyst system is selected from:
  • RhCl(PPh 3 ) 3 2,2-dichloroacetophenone (DCAP), and optionally PPh 3
  • DCAP 2,2-dichloroacetophenone
  • PPh 3 a group consisting of RhCl 3 or RhCl 3 -3H 2 0, 2,2-dichloroacetophenone and PPh 3
  • RhCl(PPh 3 ) 3 Cl 3 CCOOCH 2 CH 3 , and optionally PPh 3 ;
  • RhCl(PPh 3 ) 3 a group consisting of RhCl(PPh 3 ) 3 , at least one of CH 2 C1 2 , CHC1 3 , CC1 4 and optionally PPh 3 ; a group consisting of RhCl 3 or RhCl 3 -3H 2 0, at least one of CH 2 C1 2 , CHC1 3 , CC1 4 , and PPh 3 ; a group consisting of Pd(OAc) 2 , at least one of CH 2 C1 2 , CHC1 3 ,CC1 4 , and PPh 3 ; or a group consisting of RhCl(PPh 3 ) 3 , azobisisoheptonitrile (ABVN), and optionally PPh 3 .
  • RhCl(PPh 3 ) 3 a group consisting of RhCl(PPh 3 ) 3 , at least one of CH 2 C1 2 , CHC1 3 ,CC1 4 and optionally PPh 3 .
  • the metal-containing catalyst system is selected from the following compositions consisting of, by weight of,
  • RhCl 3 -3H 2 0 : Cl 3 CCOOCH 2 CH 3 : PPh 3 1 : 1.0-10 : 3.0-63;
  • RhCl 3 -3H 2 0 : CC1 4 : PPh 3 1 : 0.3-11 : 3.0-63;
  • the metal-containing catalyst system is selected from the following compositions consisting of, by weight of,
  • RhCl 3 -3H 2 0: DCAP: PPh 3 1 : 2.0-8 : 4.0-44;
  • RhCl 3 -3H 2 0 : Cl 3 CCOOCH 2 CH 3 : PPh 3 1 : 2.0-8 : 4.0-44;
  • RhCl 3 -3H 2 0 : PhCH 2 Cl : PPh 3 1 : 0.3-6.0 : 4.0-44;
  • RhCl 3 -3H 2 0 : CC1 4 : PPh 3 1 : 0.7-7 : 4.0-44;
  • the additive is selected from the group consisting of ascorbic acid, methyltri-n-octylammonium chloride, n-propylamine, iso-propylamine, propyldiamine, n-butylamine, iso-butylamine, n-butylamine, dibutylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, or combination thereof.
  • the invention provide a solution polymerization process of diene, comprising homopolymerization of diene or copolymerization of diene together with at least one of comonomers in the presence of at least one of the metal-containing catalyst system of the invention in at least one of organic solvents.
  • the diene is selected from any known diene, preferably selected from at least one of conjugated dienes, more preferably a C 4 -C 6 conjugated diene, including 1,3 -butadiene, isoprene, 2,3-dimethylbutadiene, piperylene or mixtures thereof, and most preferred 1,3 -butadiene, isoprene or mixtures thereof.
  • the at least one of comonomers are selected from at least one of ⁇ , ⁇ -unsaturated nitriles or styrene-based compounds, and preferably the at least one ofa, -unsaturated nitriles are selected from any known ⁇ , ⁇ -unsaturated nitriles, more preferably ana, -unsaturated (C 3 -C 5 ) nitrile including acrylonitrile, methacrylonitrile, ethylacrylonitrile or mixtures thereof, most preferred acrylonitrile; the styrene-based compounds are selected from styrene, a-methyl styrene or vinyl toluene.
  • the solution polymerization process of the invention wherein the at least one of comonomers are selected from styrene.
  • the at least one of comonomers further comprises termonomers, including vinyl monomers, vinylidene monomers and ⁇ , ⁇ -unsaturated monomers, which is selected from at least one of (math)acrylic acid, any of (math)acrylic acid esters, any of (math)acrylic acid salts, any of olefin, and any of unsaturated carboxylic acid, preferably any of n-butyl (math)acrylate, i-butyl (math)acrylate, t-butyl (math)acrylate, ethylene, propylene, vinylidene monomers, methyl (math)acrylate, ethyl (math)acrylate, n- propyl (math)acrylate, i-propyl (math)acrylate, 2-ethylhexyl (math)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate, benzy
  • the at least one of organic solvents are selected from any organic solvent which does not react with the catalyst or otherwise interfere with the reaction, preferably selected from benzene, toluene, cyclohexane, dimethyl sulfoxide (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1,4-dioxane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone (MEK), N,N-dimethyl formamide (DMF), ⁇ , ⁇ -dimethyl acetamide (DMAC), or the mixture thereof, more preferably selected from monochlorobenzene (MCB), methyl ethyl ketone (MEK), N,N- dimethyl formamide (DMF), or the mixture thereof, more
  • the diene homopolymer or copolymer having a controlled Mn, from 1,000 to 300,000, with PDI from 1.0 to 5.0, preferably the controlled Mn, from 3,000 to 100,000, with PDI from 1.1 to 4.0, more preferably the controlled Mn, from
  • the ACN content in the diene homopolymer or copolymer from 0 to 65 wt%, or styrene content in the diene copolymer from 0 to 80 preferably the ACN content in the diene copolymer from 10 to 63 wt%, or styrene content in the diene copolymer from 20 to 80 wt%, more preferably the ACN content in the diene copolymer from 30 to 60 wt%, or styrene content in the diene copolymer from 20 to 70 wt%, based on the total weight of the diene homopolymer or copolymer.
  • the polymerization is carried out with the feeding weight part of the diene is from about more than 0 to about less than 100, and the feeding weight part of the at least one of comonomers is from about less than 100 to about more than 0.
  • the polymerization is carried out with the feeding weight part of ⁇ , ⁇ -unsaturated nitrile monomer is about 4 to about less than 96, or the feeding weight percent of the styrene and any of derivatives of styreneis from about less than 96 to about 4, preferably the feeding weight part of ⁇ , ⁇ -unsaturated nitrile monomer is about 4 to about less than 90, or the feeding weight percent of the styrene and any of derivatives of styreneis from about less than 96 to about 10.
  • the polymerization is carried out at temperature of 10 °C - 160 °C for 5- 200 hrs, preferably at temperature of 20 °C - 150 °C for 10-180 hrs, more preferably at temperature of 30 °C - 140 °C for 20-170 hrs, further preferably at temperature of 40 °C - 140 °C for 10-150 hrs, still preferably at temperature of 60 °C - 140 °C for 1-100 hrs, and the diene rubber polymers having.
  • the solution polymerization process further comprises a step of removing the metal-containing catalyst, preferably by using ion-exchange resin as described in EP 2 072 532 Al, EP 2 072 533 Al, and CN101463096 A.
  • the reaction mixture was taken out and treated with ion-exchange resin at 100 °C for 48 hours and then precipitated in cold methanol.
  • the degree of hydrogenation of the diene units incorporated into the polymer is usually in the range from 50 to 100%, preferably in the range from 85 to 100% and particularly preferably in the range from 95 to 100%.
  • the conjugated diene can be of any type. It is preferable to use C4-C6 conjugated dienes.
  • 1,3 -butadiene isoprene, 2,3-dimethylbutadiene, piperylene or a mixture thereof.
  • 1,3-butadiene and isoprene or a mixture thereof are very particularly preferred.
  • the ⁇ , ⁇ -unsaturated nitrile used can comprise any known ( ⁇ , ⁇ -unsaturated nitrile, and preference is given to C3-C5 ⁇ , ⁇ -unsaturated nitrites, such as acrylonitrile, methacrylonitrile, ethacrylonitrile or a mixture of these. Acrylonitrile is particularly preferred.
  • Particularly preferred hydrogenated nitrile rubber is provided by a hydrogenated copolymer based on the monomers acrylonitrile and 1,3-butadiene.
  • conjugated diene and the ⁇ , ⁇ -unsaturated nitrile it is also possible to use one or more other monomers known to the person skilled in the art, examples being ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids, or their esters or amides.
  • Preferred ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids here are acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid.
  • Preferred esters used of the ⁇ , ⁇ -unsaturated carboxylic acids are their alkyl esters and alkoxyalkyl esters.
  • the proportions of conjugated diene and of ⁇ , ⁇ -unsaturated nitrile in the HNBR polymers to be used can vary widely.
  • the proportion of the conjugated diene or of the entirety of the conjugated dienes is usually in the range from 40 to 90% by weight and preferably in the range from 55 to 75%, based on the entire polymer.
  • the proportion of the ⁇ , ⁇ -unsaturated nitrile or of the entirety of the ⁇ , ⁇ -unsaturated nitrites is usually from 10 to 60% by weight, preferably from 25 to 45% by weight, based on the entire polymer.
  • the proportions of the monomers in each case give a total of 100% by weight.
  • the amounts that can be present of the additional monomers are from 0.1 to 40% by weight, preferably from 1 to 30% by weight, based on the entire polymer.
  • corresponding proportions of the conjugated diene(s) and, respectively, of the ⁇ , ⁇ -unsaturated nitrile(s) are replaced via the proportions of the additional monomers, and the proportions of all of the monomers here in each case give a total of 100% by weight.
  • the hydrogenation of the nitrile rubbers described above to give hydrogenated nitrile rubber (A) can take place in the manner known to the person skilled in the art.
  • a suitable method is reaction with hydrogen with use of homogeneous catalysts, e.g. the catalyst known as "Wilkinson" catalyst ((PPh 3 ) 3 RhCl) or others.
  • Processes for the hydrogenation of nitrile rubber are known, (see, for example, U.S. Pat. No. 3,700,637, DE-PS-2 539 132, EP- A-134 023, DE-A-35 41 689, DE-A-35 40 918, EP-A-298 386, DE-A-35 29 252, DE-A-34 33 392, U.S. Pat. No. 4,464,515 and U.S. Pat. No. 4,503, 196).
  • Suitable catalysts and solvents for homogeneous-phase hydrogenation are described below and are also disclosed in DE-A-25 39 132 and EP-A-0 471 250.
  • Selective hydrogenation can be achieved, for example, in the presence of a rhodium- containing catalyst, metal -containing catalyst system, which comprises (1) a metal-containing catalyst, (2) a co-catalyst, and optionally (3) an additive, for a solution polymerization process of diene and/or for hydrogenation of diene-containing polymers, wherein the metal-containing catalyst is selected from ML n X m , MX m , MX m pH 2 0, M(OC(0)R) m , or any combination thereof, wherein M represents a metal selected from Rh, Pd, Ru, Ir, Mo, Co, Cu, Fe, or Ti, L is a group selected from 3 , in which R 1; R 2 , and R 3 may be same or different, and each Ri, R 2 and R 3 is independently selected from H, Ci
  • R 1; R 2 , and R 3 are defined as the above.
  • a suitable amount is in the range from 0.01 to 1% by weight, preferably in the range from 0.03 to 0.5% by weight and particularly preferably in the range from 0.1 to 0.3% by weight, based on the weight of the polymer. It is usually advisable to use the catalyst together with a co-catalyst. Suitable co-catalysts are found by way of example in U.S. Pat. No. 4,631,315. Triphenylphosphine is preferred co- catalyst.
  • the amounts used of the co-catalyst are preferably from 0.3 to 5% by weight, preferably in the range from 0.5 to 4% by weight, based on the weight of the nitrile rubber to be hydrogenated.
  • the ratio by weight of the rhodium-containing catalysts to the co-catalyst is moreover preferably in the range from 1 :3 to 1 :55, preferably in the range from 1 :5 to 1 :45.
  • a suitable method uses from 0.1 to 33 parts by weight of the co-catalyst, preferably from 0.5 to 20 parts by weight and very particularly preferably from 1 to 5 parts by weight, in particular more than 2 but less than 5 parts by weight, of co-catalyst, based on 100 parts by weight of the nitrile rubber to be hydrogenated.
  • the practical method for this hydrogenation is well known to the person skilled in the art from U.S. Pat. No. 6,683, 136.
  • the nitrile rubber to be hydrogenated is treated with hydrogen in a solvent such as toluene or monochlorobenzene at a temperature in the range from 100 to 150 °C and at a pressure in the range from 700 to 2 500 Psi for from 2 to 10 hrs.
  • the metal-containing catalyst of Rh, Ru, and/or Pd-based is selected from a metal of Rh, Ru or Pd, or the metal-containing catalyst of Rh, Ru or Pd and PPh 3 of the invention.
  • the invention provides a one-pot process for synthesis of the hydrogenated diene polymers, comprising by directly introducing hydrogen into the reactor after the completion of solution polymerization of the invention and reacting at a desired temperature.
  • the desired temperature is from 60 to 200 °C and the hydrogenation reaction is carried out for 10 min to 20 hrs at a hydrogen pressure of 100-3000 Psi, preferably the desired temperature is from 80 to 180 °C and the reaction is carried out for 10 min to 10 hrs at a hydrogen pressure of 200-2000 Psi, more preferably the desired temperature is from 100 to 160 °C and the reaction is carried out for 30 min to 5 hrs at a hydrogen pressure of 300-1500 Psi, further preferably the desired temperature is from 120 to 150 °C and the reaction is carried out for 30 min to 3 hrs at a hydrogen pressure of 500-1000 Psi.
  • the dienes are selected from any known diene, preferably selected from at least one of conjugated dienes and at least one of unconjugated dienes, more preferably a C 4 -C 6 conjugated diene, including 1,3 -butadiene, isoprene, 2,3- dimethylbutadiene, piperylene or mixtures thereof, or a C 4 -C 6 unconjugated diene, including 1,2-butadiene, and most preferred 1,3 -butadiene, isoprene and mixtures thereof;
  • the at least one of organic solvents are selected from any organic solvent which does not react with the catalyst or otherwise interfere with the reaction, preferably selected from benzene, toluene, cyclohexane, dimethyl sulfoxide (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1,4-dioxane, monochlorobenzene (MCB), dichlorobenzene (DCB),
  • the process for hydrogenation of diene polymers further comprises the step of removing the metal-containing catalyst, preferably by using ion- exchange resin. After hydrogenation reaction completing, the reaction mixture was taken out and treated with ion-exchange resin at 100 °C for 48 hours and then precipitated in cold methanol.
  • the invention provides a process for hydrogenation of diene polymers, comprising:
  • step a) dissolving at least one diene polymer into at least one organic solvent in a autoclave reactor, b) adding at least one of the metal-containing catalyst system of the invention into the solution obtained in step a),
  • the at least one diene polymer is selected from one or more of BR NBR, SBR, preferably one or more of BR NBR, SBR obtained by solution polymerization, and the ACN content in the diene polymer from 0 to 65 wt%, or styrene content in the diene polymer from 0 to 80, preferably the ACN content in the diene polymer from 10 to 63 wt%, or styrene content in the diene polymer from 20 to 80 wt%, more preferably the ACN content in the diene polymer from 30 to 60 wt%, or styrene content in the diene polymer from 20 to 70 wt%, based on the total weight of the diene polymer.
  • the amount of at least one of the metal-containing catalyst system is from 0.000001 to 50 parts by weight based on 100 parts by weight the least one diene polymer, preferably from 0.00001 to 20 parts by weight, more preferably from 0.0001 to 10 parts by weight.
  • the at least one of organic solvents are selected from any organic solvent which does not react with the catalyst or otherwise interfere with the reaction, preferably selected from benzene, toluene, cyclohexane, dimethyl sulfoxide (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1,4-dioxane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone (MEK), ⁇ , ⁇ -dimethyl formamide (DMF), N,N- dimethyl acetamide (DMAC), or the mixture thereof, more preferably selected from monochlorobenzene (MCB), monobromobenzene (MBB), dichlorobenzene (DCB), methyl ethyl ketone (MEK
  • the predetermined temperature is from 80 to 180 °C and the predetermined time is from 10 min to 10 hrs at a hydrogen pressure of 200-2000 Psi, more preferably the predetermined temperature is from 100 to 160 °C and the predetermined time is from 30 min to 5 hrs at a hydrogen pressure of 300-1500 Psi, further preferably the predetermined temperature is from 120 to 150 °C and the predetermined time is from 30 min to 3 hrs at a hydrogen pressure of
  • the metal-containing catalyst may be removed as described in EP 2 072 532 Al, EP 2 072 533 Al, and CN101463096 A.
  • the invention provides a process for hydrogenation of diene polymers, comprising a) adding the solution homopolymerization of diene or copolymerization of diene obtained by the solution polymerization process of the invention, and optionally at least one of organic solvents, b) directly introducing hydrogen into the mixture of step a) and heat up to a predetermined temperature to obtain the hydrogenated diene-containing polymers, wherein the at least one of organic solvents are selected from any organic solvent which does not react with the catalyst or otherwise interfere with the reaction, preferably selected from benzene, toluene, cyclohexane, dimethyl sulfoxide (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1,4-dioxane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB)
  • the invention provides a hydrogenated diene rubber, obtained by the one-pot process for the synthesis of the hydrogenated diene-containing polymers of the invention.
  • the invention provides a use of the catalyst system of the invention in the manufacture of diene polymer.
  • the invention provides a use of the catalyst system of the invention in the manufacture of hydrogenated diene-containing polymer.
  • the invention provides a use of glass tube reactor and/or autoclave in the solution polymerization process of the invention or in the one-pot process for the synthesis of the hydrogenated diene polymers of the invention.
  • the invention provides a use of glass tube reactor and/or autoclave in process for the synthesis of the hydrogenated diene polymers of the invention.
  • a batchwise method i.e. a batch procedure, operations are carried out in a stirred or non-stirred reactor.
  • the inventive solution polymerization process and/or hydrogenation processes can be carried out in any suitable solvent, which does not react with the catalyst or otherwise interfere with the reaction.
  • the solvents used can comprise any solvents suitable for HNBR, examples being benzene, toluene, cyclohexane, dimethyl sulfoxide (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1,4-dioxane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone (MEK), ⁇ , ⁇ -dimethyl formamide (DMF), or ⁇ , ⁇ -dimethyl acetamide (DMAC), and the mixture thereof.
  • solvents suitable for HNBR examples being benzene, toluene, cycl
  • Monochlorobenzene (MBB), methyl ethyl ketone (MEK), ⁇ , ⁇ -dimethyl formamide (DMF), or ⁇ , ⁇ -dimethyl acetamide (DMAC) is preferred.
  • Monochlorobenzene (MCB) and methyl ethyl ketone (MEK), N,N- dimethyl acetamide (DMAC) are more preferred.
  • the inventive process is usually carried out at a temperature in the range from 10 to 200 °C. It has been found that higher temperatures have a favorable effect on the polymerization reaction and/or hydrogenation reaction.
  • the inventive process is therefore preferably carried out at temperatures in the range from 20 to 160 °C, more preferably at temperatures in the range from 60-150 °C.
  • the inventive solution polymerization process is usually carried out in a nature pressure of the monomers and the organic solvents, in the range from 10 to 100 Psi, preferably from 15 to 75 Psi.
  • inventive hydrogenation process is usually carried out for 10 min to 20 hrs at a hydrogen pressure of 100-3000 Psi, preferably the desired temperature is from 80 to 180 °C and the reaction is carried out for 10 min to 10 hrs at a hydrogen pressure of 200-2000 Psi, more preferably the desired temperature is from 100 to 160 °C and the reaction is carried out for 30 min to 5 hrs at a hydrogen pressure of 300-1500 Psi, further preferably the desired temperature is from 120 to 150 °C and the reaction is carried out for 30 min to 3 hrs at a hydrogen pressure of 500-1000 Psi.
  • a feature of the solution polymerization rubbers and the hydrogenated nitrile rubbers obtained in the inventive process is particularly narrow molecular weight distribution and a correspondingly low value for the polydispersity index.
  • the solution polymerization rubbers and the hydrogenated nitrile rubbers having this property profile were hitherto unknown and unobtainable.
  • the invention therefore provides a solution polymerization rubbers and a hydrogenated nitrile rubbers which have a polydispersity index less than or equal to 2, preferably less than 2, particularly preferably less than 1.9 and very particularly preferably less than 1.7.
  • the polydispersity index is more than 1 and less than 2.0, and preferably more than 1 and less than 1.9.
  • the solution polymerization rubbers and a hydrogenated nitrile rubbers obtained in the inventive process have weight-average molecular weight Mw in the range from 30,000 to 250,000, preferably in the range from 30,000 to 150,000 and in particular preferably in the range from 30,000 to 100,000.
  • the Mooney viscosity of the solution polymerization rubbers and/or the hydrogenated nitrile rubbers obtained in the inventive processes is in the range from more than 0 to 50, preferably in the range from 1 to 40, more preferably in the range from 10 to 40.
  • the Mooney viscosity is determined here to ASTM standard D1646.
  • the inventive solution polymerization rubbers and/or the hydrogenated nitrile rubbers having low molecular weight and narrow molecular weight distribution have very good processability.
  • the metal-containing catalyst may be removed after the polymerization and/or hydrogenation reaction completing by using ion-exchange resin as described in EP 2 072 532 Al, EP 2 072 533 Al, and CN101463096 A.
  • the concentration of monomers in the hydrogenated reaction mixture is not critical, but should be such that the reaction is not hampered if the mixture is too viscous to be stirred efficiently during reaction.
  • the glass tube containing a bar magnet and capped by a solid rubber stopper was purged of air, by a vacuum-nitrogen cycle repeated, before being added with the required amount of solvent, the monomers, and the catalyst system, respectively. All these liquids were introduced under nitrogen.
  • the glass tubes were heated in a thermostated oil bath at a desired temperature, and the magnetic stirring was slowly maintained during the reaction. After the required reaction time, the samples were withdrawn from the tube. After reaction completing, the tube was opened, and the reaction mixture was taken out and then precipitated in cold methanol. The polymer was filtered off and dried for 24 hours at 60 °C under vacuum.
  • the reaction pressure was the vapor pressure of the monomers at the reaction temperature. The highest temperature used in these trials was limited to 80 °C due to safety reasons.
  • the metal-containing catalyst may be removed after the polymerization and/or hydrogenation reaction completing by using ion-exchange resin as described in EP 2 072 532 Al, EP 2 072 533 Al, CN101463096 A.
  • the Parr autoclave reactor was used for the copolymerization trials and/or hydrogenation trials in a bigger scale and at a higher temperature. After the required reaction time, the samples were withdrawn from the reactor. After copolymerization and/or hydrogenation reaction completing, the reactor was opened, and the reaction mixture was taken out and treated with ion-exchange resin at 100 °C for 48 hours and then precipitated in cold methanol.
  • the polymer was filtered off and dried for 24 hours at 60 °C under vacuum.
  • the reaction pressure was the vapor pressure of the monomers or hydrogen at the reaction temperature.
  • the temperature used in these trials may be at 10 °C to 200 °C, and usually at room temperature to 160 °C, i.e. hydrogenation temperature.
  • the metal-containing catalyst may be removed after the polymerization and/or hydrogenation reaction completing by using ion-exchange rubber as described in EP 2 072 532 Al, EP 2 072 533 Al, CN101463096 A.
  • the final polymerization conversion could be calculated by the gravimetric method using the initial total amount of monomers and the final amount of dried S-NBR.
  • the DSC test was conducted by: 1) firstly heated from -80 °C to 60 °C at a heating rate of 10 °C/min; 2) kept at 60 °C for 3 minutes and then cooled to -80 °C at a cooling rate of 20 °C/min; 3) kept at -80 °C for 3 minutes, then heated again to 60 °C at a heating rate of 10 °C/min.
  • the Tg value was measured based on the second heating run.
  • FT-IR spectrum of obtained rubber was recorded on a Perkin Elmer spectrum 100 FT-IR spectrometer.
  • the polymer samples were dissolved in MCB and then the solution was cast onto a KBr disk and dried to form a film for the IR test.
  • the hydrogenation conversion is determined by the FT-IR analysis according to the ASTM (D 5670-95) method.
  • H NMR characterization was carried out on a Bruker AV500 machine using CDC1 3 or DMSO-t/6 as the solvent and TMS as the internal standard.
  • the glass tubes containing a bar magnet and capped by a solid rubber stopper were purged of air, by a vacuum-nitrogen cycle repeated three times, before being added with the required amount of solvent, the monomers, and the catalyst system, respectively.
  • the required amount of the metal-containing catalyst system RhCl(PPh 3 ) 3 (77 mg, 0.083 mmol), 2,2- dichloroacetophenone (DCAP) (93 mg, 69 uL, 0.49 mmol), PPh 3 (154 mg, 0.59 mmol), organic solvent monochlorobenzene (MCB) (14.1 mL), 1,3-butadiene (Bd) (2.4 g, 44.4 mmol), acrylonitrile (ACN) (1.7 g, 32.1 mmol) were added into there glass tubes, respectively.
  • Each tube MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl(PPh 3 ) 3 , 77 mg, 0.083 mmol; PPh 3 , 154 mg, 0.59 mmol; 60°C
  • the polymerization was not sensitive to water.
  • the S-NBR rubber may be obtained after the polymerization reaction is carried out for about 10 min to 150 hrs.
  • Fig. 1 is the GPC curves of the samples of Examples 1-3, wherein numbers of 1-3 represent Examples 1-3 and range from right to left. It is seen that the apparent molecular weights of
  • Examples 1-3 increased gradually with the increased reaction time. This suggests that the molecular weight of the polymer obtained by the solution polymerization process of diene according to the present invention may be controlled by adjusting the required reaction time.
  • Each tube MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl(PPh 3 ) 3 , 77 mg, 0.083 mmol; PPh 3 , 154 mg, 0.59 mmol; 80°C
  • the S-NBR rubber may also be obtained after the polymerization reaction is carried out for about 10 min to 150 hrs at a temperature of about 10 °C to about 160 °C.
  • Fig. 2 is the GPC curves of the samples of Examples 4-6, wherein numbers of 4-6 represent Examples 4-6 and range from right to left. It is seen that the apparent molecular weights of Examples 4-6 increased gradually with the increased reaction time. This also suggests that the molecular weight of the polymer obtained by the solution polymerization process of diene and/or at least one of comonomers according to the present invention may be controlled by adjusting the required reaction time. Meanwhile, the conversion of the reaction will increase if the polymerization reaction is carried out for a same time at a higher temperature.
  • MCB was added to reach the 20 mL of scale; 80°C, full time 45 hours; wherein 1,4-Bd represents the polymerization units of which polymerization occurs at 1 ,4-positions of Bd, and 1,2-Bd represents the polymerization units of which polymerization occurs at 1 ,2 -positions of Bd.
  • Fig. 3a is Mn and PDI of the samples of Examples 6-15
  • Fig. 3b is conversions of the samples of Examples 6 and 8-15
  • Fig. 3c is FT-IR spectra of the samples of Examples 6-16
  • Fig. 3d is 'HNMR spectra of the samples of Examples 6-16
  • Fig. 3e is 'HNMR spectrum of the sample of Example 6 alone
  • Fig. 3f is DBS curves of the samples of Examples 6-15.
  • the assignment of the peaks in 'HNMR spectrum was listed as follows:
  • Bd, 1,4- (or 1,4-Bd) represents the polymerization units of which polymerization occurs at 1,4-positions of Bd
  • vinyl (or 1,2-Bd) represents the polymerization units of which polymerization occurs at 1,2-positions of Bd.
  • Bd, 1,4- (or 1,4-Bd) and vinyl (or 1,2-Bd) have the identical meaning herein after if no other specific definition.
  • the solution polymerization process of BD and ACN according to the present invention may provide a S-NBR rubber with a super high level (more than 55wt%) of ACN.
  • This super high level (more than 55wt%) of ACN in S-NBR rubber breaks through the limit of 55wt% of ACN content of the NBR rubber obtained by emulsion polymerization.
  • Example 5 The same catalyst system and monomers were used as in Example 1, and the polymerization reaction was carried out under the same conditions as in Example 1 except that the reaction was carried out at different temperature for different reaction time, and all samples were immediately withdrawn after the reaction time.
  • the results were summarized in Table 5.
  • the contents of 1,4-Bd, 1,2-Bd and ACN were the contents thereof polymerized into the S- NBR rubber.
  • the S-NBR rubber may also be obtained after the polymerization reaction is carried out for about 10 min to 150 hrs at a temperature of about 10 °C to about 160 °C.
  • Fig. 4a is FT-IR spectra of the samples of Examples 3, 6, 17 and 18, and Fig. 4b is 'HNMR spectra of the samples of Examples 3, 6, 17 and 18.
  • 1,4-Bd represents the polymerization units of which polymerization occurs at 1,4-positions of Bd
  • 1,2-Bd represents the polymerization units of which polymerization occurs at 1,2-positions of Bd
  • the comonomer ACN may be copolymerized into S-NBR rubber at different temperatures, and the conversion will reduce if the reaction is carried out at lower temperature for a same reaction time. If the reaction is carried out at lower temperature for a long reaction time, the conversion will increase as well. Polymerization temperature seemed to have slight effect on the ACN content.
  • the S-NBR rubber may also be obtained after the polymerization reaction is carried out for about 10 min to 150 hrs at a temperature of about 10 °C to about 160 °C.
  • comonomer ACN may be copolymerized into S-NBR rubber at different contents of PPh 3 in the catalyst system.
  • the conversion will reduce and the Mn and Mw will increase if the content of PPh 3 increases in the catalyst system.
  • the contents of PPh 3 in the catalyst system seemed to have no effect on the ACN content in S-NBR rubber. Examples 22-1 to 22-12
  • the catalyst systems included RhCl(PPh3)3 of 77 mg, DCAP of 93 mg, PPI13 of 154 mg, together with further additive of MTOAC, n-butylamine or dibutylamine. The results were summarized in Table 7.
  • 1,2-Bd represents the polymerization units of which polymerization occurs at 1,2-positions of Bd
  • MTOAC Methyltri-n-octylammonium chloride, Aliquat® 336.
  • the polymerization was not sensitive to water, and there no macro-gel occurred in all of the samples as well.
  • the S-NBR rubber may also be obtained after the polymerization reaction is carried out for about 10 min to 150 hrs at a temperature of about 10 °C to about 160 °C.
  • Fig. 5a is 'HNMR spectra of the samples of Examples 22-1, 22-2 and 22-3. It was seen that the conversions of the samples which used the catalyst system with further additive of MTOAC, n-butylamine or dibutylamine were at a higher level than that used the catalyst in Example 6, and the ACN contents in the polymer seemed to be slightly higher than that used the catalyst in Example 6.
  • MCB 14.1 mL
  • Bd 2.4 g
  • ACN 1.7 g
  • DCAP 93 mg.
  • the catalyst systems included RhCl(PPh3)3, DCAP, optionally PPI13, together with optionally further additive of Vitamine C.
  • Fig. 5b is 'HNMR spectrum of the sample of Example 22-7.
  • the composition of the polymer of the sample of Example 22-7 was summarized in Table 9.
  • the polymerization was not sensitive to water, and there no macro-gel occurred in all of the samples as well.
  • the S-NBR rubber may also be obtained after the polymerization reaction is carried out for about 10 min to 150 hrs at a temperature of about 10 °C to about 160 °C.
  • Fig. 6a - 6c are 'HNMR spectra of the samples of Example 23-3, 23-7 and 23-10.
  • the co- catalyst PhCH 2 Cl, CC1 4 , or Cl 3 CCOOCH 2 CH 3 may be used replacing DCAP in the catalyst system in Examples 1-3 or 4-6, and copolymer S-NBR may be obtained by using the co- catalyst PhCH 2 Cl, CC1 4 , or Cl 3 CCOOCH 2 CH 3 replacing DCAP in the catalyst system.
  • Example 23-11 which used the catalyst system with further additive of azobisisoheptonitrile (ABVN) without RhCl(PPh 3 ) 3 , was the approximately same as that used the catalyst system with further additive of azobisisoheptonitrile (ABVN) and the metal catalyst of RhCl(PPh 3 ) 3 in Example 23-12, the content of ACN in Example 23-11 was slightly more than that in Example 23-12, and the PDI in Example 23-11 was much more than that in Example 23-12. It indicates that the metal catalyst of RhCl(PPh 3 ) 3 in the catalyst system may control the molecular weight distribution of the S-NBR rubber, and seems to have slightly effect on the content of ACN in the S-NBR rubber.
  • Example 1 The monomers were used as in Example 1, the polymerization reaction was carried out under the same conditions as in Example 3 or 6, and all samples were immediately withdrawn after the reaction time except that the metal-containing catalyst in the catalyst system and the reaction time were different. The results were summarized in Tables 13 -14.
  • Each tube MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol.
  • metal-containing catalyst RhCl 3 -3H 2 0 were used replacing RhCl(PPh 3 ) 3 in the catalyst system.
  • co-catalyst CC1 4 was used replacing DCAP.
  • Fig. 7a - 7c are 'HNMR spectra of the samples of Examples 24-1, 24-3 and 24-4.
  • RhCl 3 -3H 2 0 may be reacted with PPh 3 to obtain RhCl(PPh 3 ) 3 , and then copolymer S-NBR may be obtained by the solution polymerization in Examples 1-3 or 4-6. It indicates that the solution polymerization according to the present application is not sensitive to water. In addition, there no macro-gel occurred in all of the samples as well.
  • Example 1 The catalyst system and monomers were used as in Example 1, the polymerization reaction was carried out under the same conditions as in Example 3, and all samples were immediately withdrawn after the reaction time except that the organic solvent was different. The results were summarized in Tables 15 -16.
  • This tube MEK, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol.
  • Example 25 the organic solvent methyl ethyl ketone (MEK) was used replacing monochlorobenzene (MCB) in the polymerization reaction system.
  • Fig. 8 is 'HNMR spectrum of the sample of Example 25.
  • Table 16 showed the composition of the S-NBR rubber obtained.
  • the other organic solvent such as dimethyl sulfoxide (DMSO), ⁇ , ⁇ -dimethyl acetamide (DMAc) and ⁇ , ⁇ -dimethyl formamide (DMF) may be used in the solution polymerization of the present application as well.
  • DMSO dimethyl sulfoxide
  • DMAc ⁇ , ⁇ -dimethyl acetamide
  • DMF ⁇ , ⁇ -dimethyl formamide
  • each tube MCB, 14.1 mL; Bd, 2.5 g, 46.2 mmol; Styrene, 1.7 g, 16.3 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl(PPh 3 ) 3 , 77 mg, 0.083 mmol; PPh 3 , 154 mg, 0.59 mmol; 45 hours.
  • Mass content 46.1 % 9.2% 44.7% 100% 64.1 % 13.1 % 22.8% 100%
  • Bd, 1 ,4- represents the polymerization units of which polymerization occurs at 1 ,4-positions of Bd
  • Bd vinyl represents the polymerization units of which polymerization occurs at 1,2-positions of Bd.
  • Examples 26-1 to 26-2 the co-monomers butadiene (BD) and styrene (St) were used replacing butadiene (BD) and acrylonitrile (ACN) in the polymerization reaction system.
  • Fig. 9a is FT-IR spectrum of the sample of Example 26-2
  • Fig. 9b is 'HNMR spectrum of the sample of Example 26-2.
  • Table 18 showed the composition of the S-SBR rubber obtained.
  • Bd, trans-1,4 represents the polymerization units of which polymerization occurs at Impositions of Bd and is trans-polymerization
  • Bd vinyl represents the polymerization units of which polymerization occurs at 1,2-positions of Bd.
  • RhCl(PPh3)3/PPli3/DCAP may catalyze the solution polymerization of Bd and St to afford S-SBR rubber. And, the content of styrene (St) in the S-SBR rubber increased when the polymerization reaction was carried out at a lower temperature.
  • Each tube MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl(PPh 3 ) 3 , 77 mg, 0.083 mmol; PPh 3 , 154 mg, 0.59 mmol; 80°C, 45 hours; in which Controlled trial is the same as Example 6, and there is no termonomer.
  • Table 20 was the composition of the controlled trail of the sample of Example 6.
  • Fig. 10a is FT-IR spectrum of the controlled trail of the sample of Example 6, and
  • Fig. 10b is 'HNMR spectrum of the controlled trail of the sample of Example 6.
  • Table 21 was the composition of the sample of Example 27-1 with termonomer n-butyl acrylate (n-BA).
  • Fig. 10c is FT-IR spectrum of the sample of Example 27-1 with termonomer n-butyl acrylate
  • Fig. lOd is 'HNMR spectrum of the sample of Example 27-1 with termonomer n-Butyl acrylate.
  • Table 22 was the composition of the sample of Example 27-2 with termonomer Methyl methacrylate (MMA).
  • Fig. lOe is FT-IR spectrum of the sample of Example 27-2 with termonomer MMA
  • Fig. lOf is 'HNMR spectrum of the sample of Example 27-2 with termonomer MMA.
  • Table 23 was the composition of the sample of Example 27-3 with termonomer methacrylic acid (MAA).
  • Fig. lOg is FT-IR spectrum of the sample of Example 27-3 with termonomer MAA
  • Fig. lOh-lOi are 'HNMR spectra of the sample of Example 27-3 with termonomer MAA.
  • Fig. 10m is FT-IR spectrum of the sample of Example 27-5 with termonomer acrylamide.
  • Figure 10m the assignment of the peaks in FT-IR spectrum was listed as follows:
  • the polymerization reaction of BD with at least one co-monomer in organic solution may be carried out at a broader range of reaction temperature, from to 10 °C to the temperature used for hydrogenation, such as 160 °C.
  • the reaction may be carried out at room temperature to 150 °C, more preferably at 30 °C to 150 °C, further preferably at 60 °C to 150 °C, most preferably at 80 °C to 150 °C.
  • the polymerization is carried out at higher temperature to improve the productivity of the copolymerization with less catalyst.
  • Example 28-2 was hydrogenated continuously in one-pot in the autoclave reactor.
  • the hydrogenation reaction conditions are listed in the following examples.
  • Fig. 1 la is FT-IR spectra of the samples of Examples 28-1 and 28-2 which are carried out for different reaction time
  • Fig. 1 lb is 'HNMR spectrum of the sample of Example 28-4.
  • the polymerization reaction was carried out in the autoclave reactor, and the reaction conditions and the results are listed in Table 26, and the sample was immediately withdrawn after the reaction time except that the co-monomers included termonomer n-butyl acrylate (n- BA).
  • solution polymerization reaction of BD and ACN with termonomer may be carried out in the autoclave reactor as well.
  • the one-pot solution polymerization and hydrogenation process were carried out in 600 mL Parr autoclave reactor. After the solution polymerization completing, the excess monomers and/or DCAP were exhausted from the valve at polymerization temperature. And then, the valve was closed and the temperature was increased to hydrogenation temperature and hydrogen was injected into the autoclave reactor.
  • the scheme of one-pot solution polymerization and hydrogenation (HD) process from butadiene and acrylonitrile to HNBR is listed out in scheme 1 as follows. The experimental conditions and results are shown in Table 27 and Figure 12.
  • the one-pot solution polymerization and hydrogenation (HD) process from butadiene and acrylonitrile or other comonomer, such as styrene, and optionally termonomer to hydrogenated terpolymers, hydrogenated butadiene-styrene copolymers, or hydrogenated butadiene-styrene terpolymers may be synthesized as indicated in Scheme 1 by the different monomers as well. Table 27
  • polymerization polym.
  • hydrogenation HD
  • Fig.12 is the FT-IR spectra and 'HNMR spectra of S-NBR and hydrogenated S-NBR. The assignments of FT-IR spectra and 'HNMR spectra are listed in Fig. 12.
  • the catalyst system of the present invention is not only used as solution polymerization catalyst for BD and at least one comonomer, but also used as hydrogenation catalyst for the polymer obtained by solution polymerization.
  • Example 31-1 Hydrogenation of S-NBR solid product was conducted in Example 31-1.
  • S-NBR solid obtained from the sample in Example 28-4 was used for a hydrogenation trial in Example 31- 1.
  • S-NBR solid was dissolved into the organic solvent (such as MCB, MEK, DMAC, DEAC, particularly MCB).
  • the solution mixture obtained was hydrogenated in the presence of the metal-containing catalyst and additive (such as RhCl(PPh 3 )3/PPh 3 ) of the metal catalyst system of the present invention under desired hydrogen pressure, the experimental conditions and results are listed in Table 28 and Figure 13.
  • Figure 13 is the FT-IR spectra of S-NBR and hydrogenated S-NBR. The assignments of FT- IR spectra and 'HNMR spectra are listed in Fig. 13.
  • Example 31-2 hydrogenation of commercial NBR was conducted in Example 31-2 in the presence of the metal-containing catalyst and additive (RhCl(PPh 3 )3/PPh 3 ) of the metal catalyst system of the present invention and organic solvent (such as MCB), and optionally co-catalyst (such as DCAP) and monomer (such as ACN and/or Bd).
  • the commercial NBR solid was dissolved into the organic solvent (such as MCB, MEK, DMAC, DEAC, particularly MCB).
  • the solution mixture obtained was hydrogenated in the presence of the metal-containing catalyst and additive (such as RhCl(PPh 3 )3/PPh 3 ) of the metal catalyst system of the present invention under desired hydrogen pressure.
  • the experimental conditions and results are listed in Table 29.
  • the metal-containing catalyst may be removed by using ion-exchange resin as described in EP 2 072 532 Al, EP 2 072 533 Al, CN101463096 A. Particularly, after the copolymerization and/or hydrogenation reaction completing, the reaction mixture was taken out and treated with ion-exchange resin at 100 °C for 48 hours and then precipitated in cold methanol.
  • the S-NBR process may simplify the HNBR production by directly providing NBR feedstock in solution form.
  • S-NBR obtained by Controlled Radical Polymerization in solution
  • the one- pot process for HNBR production have the advantages to:

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Abstract

Cette invention concerne des polymères de caoutchouc butadiène ayant de faibles poids moléculaires et des distributions de poids moléculaires plus étroites que celles connues dans la technique. Cette invention concerne également un système de catalyseur contenant un métal, un procédé de polymérisation en solution pour la production dudit caoutchouc butadiène, un procédé monotope pour la synthèse des polymères de di­ènes hydrogénés, et un procédé d'hydrogénation desdits polymères de diènes.
PCT/CN2011/076267 2011-06-24 2011-06-24 Polymérisation/copolymérisation en solution des diènes, hydrogénation des caoutchoucs diènes et caoutchoucs diènes hydrogénés WO2012174734A1 (fr)

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PCT/EP2012/062167 WO2012175725A1 (fr) 2011-06-24 2012-06-22 Polymérisation/copolymérisation en solution de diènes, hydrogénation de caoutchoucs de diène et caoutchoucs de diène hydrogénés
TW101122736A TW201319103A (zh) 2011-06-24 2012-06-25 二烯之溶液聚合／共聚合、二烯橡膠之氫化及經氫化之二烯橡膠

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EP3898706A1 (fr) 2018-12-17 2021-10-27 ARLANXEO Deutschland GmbH Procédé de préparation de solutions de hnbr avec des solvants alternatifs

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