Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene

Definitions

• the invention relates to a process for the polymerization of at least one olefin in the presence of at least one catalyst comprising at least one chain E - M - X in which E represents an oxygen or sulfur atom, M represents a nickel or palladium or platinum, X represents a phosphorus, arsenic or antimony atom, in a medium comprising a continuous liquid phase which comprises more than 30% by weight of water.
• the liquid phase comprising more than 30% by weight of water is subsequently called "aqueous phase".
• the polymerization of olefins by Ziegler catalysis usually involves highly hydrolysable, even pyrophoric, compounds (catalysts and cocatalysts), and it is desirable to be able to use catalysts that are less delicate to handle, convey and store. Furthermore, there is a need for processes for polymerization in water, water being one of the easiest compounds to access and a preferred solvent for many applications (coatings, adhesives for example).
• Nickel catalysts have been described to operate in essentially organic media, as in the following documents: US 4,71 1, 969, US 5,030,606, BG 6031 9.
• the method according to the invention involves a catalyst comprising at least one nickel or palladium or platinum atom and involves a high proportion of water.
• the process according to the invention addresses the above-mentioned problems and leads to a polyolefin with high productivity in a medium rich in water.
• the method according to the invention does not require the use of a cocatalyst capable of activating the metal of the catalyst.
• the invention also opens up an original route to access polyolefin latexes.
• the chain E - M - X is preferably part of a ring with five atoms, two of which are carbon atoms linked to one another by a double bond.
• the metal M is bonded before its introduction into the polymerization medium to a ligand L.
• This ligand L mainly has the function of stabilizing the structure of the catalyst before its use and facilitating its storage and handling.
• a capture compound is brought into contact with the catalyst so as to separate the ligand L from the metal M and allow the polymerization to take place.
• the catalyst can comprise only one atom of metal M.
• Such a catalyst can for example comprise the structure represented by formula (1)
• radicals R 1 , R ⁇ , R 3 , R 4 and R 5 which may be identical or different, may be chosen from hydrogen, alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, halogen, hydroxyl radical , the alkoxide radicals, - C (O) OR 'in which R represents a hydrocarbon radical which may comprise from 1 to 1 5 carbon atoms, - SO 3 Y in which Y is chosen from Li, Na, K, NH 4 ⁇ , NR " 4 ⁇ in which R" represents a hydrocarbon radical which can comprise from 1 to 1 5 carbon atoms, E, M and X having the meanings given above, the unassigned valence connected to M, represented by a dash in the formula ci above, which can be filled with a ligand L to facilitate the use of the catalyst as has already been explained.
• the chain (s) of type E - M - X of the catalyst can be such that M is
• the catalyst comprises at least two E - M - X sequences.
• the E - M - X sequences are separated from each other by intermediate atoms linked to one another by covalent or coordination bonds, the minimum number of atoms between two M atoms preferably ranging from 6 to 42.
• Minimum number of atoms between two M atoms means the minimum number of atoms that one meets in the molecule of the catalyst when one passes from one of the atoms M to the other of the atoms M in following atom by atom links. For example, if the catalyst comprises the structure:
• Ph represents a phenyl radical
• the minimum number of atoms between the Ni atoms is 8 (which corresponds to the sequence: - O - C - C - C - C - C - C - O -) because it doesn ' is not possible to meet less than 8 atoms when going from the first Ni to the second Ni.
• the catalyst may have only two M atoms in its structure.
• the catalyst can for example be one of those represented by the following formula (2):
• radicals R 6 , R 7 , R 8 , R 9 , R 1 0 , R 1 1 , R 1 2 and R 1 3 which may be identical or different, can be chosen from the same list of radicals as R 1 to R 5 above, E - M - X and E "- M" - X "being two sequences of type E - M - X and may be identical or different, R being a bivalent radical.
• the radical R may be chosen from bivalent hydrocarbon radicals comprising, for example, 2 to 38 carbon atoms such as the alkylene, alkenylene, arylene, cycioalkylene, bicycloalkylene, alkylarylene radicals.
• the radical R can also be a radical 1, 1 '- ferrocenylene which can be substituted, for example by one or two monovalent radicals such as - C (O) OR 'or - SO3Y, R and Y having the meanings already given.
• the catalyst can be one of those comprising the structures below:
• Ph represents a phenyl radical
• - (5.6 - NBEN) - represents a radical 5.6 - bicyclo [2,2, 1] heptene-2, that is to say which can be represented by:
• the ligand L When using the catalyst in polymerization, it is advisable to separate the ligand L from the atom (s) M, so that the latter can play their role in the activation of the polymerization reaction.
• the ligand can be removed before the polymerization and even not be introduced into the polymerization medium. It can however be left in the polymerization medium and even be introduced into the polymerization medium in form complexed with the catalyst, as soon as said medium contains a "scavenger" compound capable of complexing or combining in any case suitable with the ligand, so as to release the metal atoms M from their complexing and thus to facilitate the polymerization.
• the capture compound must form a sufficiently strong bond with the ligand for the latter to release the catalyst. It is generally possible to involve the ligand from the synthesis of the catalyst, so that the formation of the catalyst takes place in complexed form with the ligand.
• said catalysts can be produced by reaction of a bis (ceto- ⁇ -ylide) on a nickel compound (O) in the presence of triphenylphosphine (PPh 3 ) playing the role of ligand, according to the following reaction scheme:
• COD representing a cis radical, cis-1, 5cyclooctadiene and Ph representing a phenyl radical.
• the catalyst is therefore obtained by this synthesis in complexed form, each molecule of catalyst being complexed by two molecules of triphenylphosphine.
• ligand a compound chosen from phosphines of formula PR 14 R 1 5 R 1 6 in which R 14 , R 1 5 , R 1 6 , which may be identical or different may represent alkyl, aryl, alkylaryl, arylalkyl, or among phosphine oxides, ethers, esters, nitriles, ketones, amines, pyridine, substituted pyridines, alcohols.
• the “captor” compound can for example be chosen from amine oxides, organic hydroperoxides, hydrogen peroxide and the metal complexes of columns 8, 9 and 1 0 of the periodic table elements according to the new notation as defined in the Handbook of Chemistry and Physics, 75th edition, 1994-1 995, such as for example bis (1, 5-cyclooctadiene) nickel (0), (tetrakis (ethylene) - / / - dichlorodirhodium, bis (ethylene) acetylacetonerhodium (I), bis (acetonitrile) paliadium (II), tetracarbonyinickel or triethylenenickel.
• the capture compound must be introduced into the polymerization medium in an amount sufficient to release the catalyst from the ligand.
• the capture compound can be introduced into the polymerization medium at a rate of 0.1 to 100 moles per mole of metal M supplied by the catalyst.
• the polymerization medium only comprises the aqueous phase as the liquid phase
• the catalyst and the optional “capture” compound are soluble in said aqueous phase.
• Such a third organic body is therefore soluble in the aqueous phase and can generally be an alcohol such as methanol or a ketone such as acetone. Such a third body can be introduced into the aqueous phase, for example at a rate of 5 to 15% by weight. If the catalyst cannot be completely dissolved in the aqueous phase, it is possible to add to the medium a liquid organic phase sufficiently dissolving the catalyst so that the latter is completely dissolved in the polymerization medium, optionally partially in the phase aqueous and partially in the liquid organic phase.
• the catalyst is completely dissolved in a liquid organic phase before the polymerization.
• the liquid organic phase can comprise an organic solvent and / or an olefin to be polymerized.
• the polymerization medium comprises the liquid aqueous phase, a solid phase constituted by the solid polymer resulting from the polymerization, and also comprises, depending on the physical state of the olefin to be polymerized, at least one other phase. gas and / or another liquid phase.
• an olefin to be polymerized is liquid under the temperature and pressure conditions of the polymerization, this olefin may be part of a liquid organic phase distinct from the liquid aqueous phase.
• Such a liquid organic phase can also comprise an organic solvent for said olefin.
• the constituents of the possible liquid organic phase are sufficiently insoluble in water so that, taking into account its quantity involved, the aqueous phase always contains more than 30% of water.
• the organic solvent can be chosen from saturated aliphatic, saturated alicyclic, aromatic hydrocarbons, such as, for example, isobutane, butane, pentane, hexane, heptane, isododecane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, toluene, orthoxylene, paraxylene.
• saturated aliphatic, saturated alicyclic, aromatic hydrocarbons such as, for example, isobutane, butane, pentane, hexane, heptane, isododecane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, toluene, orthoxylene, paraxylene.
• the organic solvent can also be chosen from alcohols and can be a monoalcohol or a diol> comprising for example 5 to 20 carbon atoms.
• the organic solvent can be an ether comprising for example 3 to 15 carbon atoms, such as for example tetrahydrofuran or dioxane.
• the organic solvent can be an ester comprising for example from 2 to 15 carbon atoms, such as for example ethyl or butyl or vinyl acetate, or methyl acrylate.
• the polymerization medium comprises two distinct liquid phases
• these can for example be present so that the phase different from the aqueous phase represents 1 to 50% of the volume of the aqueous phase.
• the aqueous phase can comprise at least 40%, or even at least 50%, or even at least 60%, even at least 70%, or even at least 80% by weight of water.
• the aqueous phase may comprise in dissolved form an organic compound which may be an alcohol or a ketone or a diol such as a glycol, for example ethylene glycol, or such as propane diol or butane diol.
• This organic compound may have the function of increasing the solubility of the olefin to be polymerized in the aqueous phase.
• the catalyst is generally dissolved in at least one liquid phase before polymerization, at a rate of 0.1 micromole to 2 moles per liter, and preferably from 1 micromole to 0.1 mole per liter.
• the optional capture compound is dissolved at least partially, and more preferably completely, in one or more liquid phases of the polymerization medium.
• the capturing compound will, depending on its nature and therefore its affinity for one or the other of the liquid phases, be dissolved predominantly in the aqueous phase or predominantly in the liquid organic phase.
• the polymerization medium is preferably stirred.
• the stirring is preferably sufficient to distribute the different phases uniformly in the reactor.
• At least one dispersing agent can be added to the polymerization medium.
• a dispersing agent can in particular be used when the polymerization medium comprises a liquid organic phase, in which case it helps the dispersion of said liquid organic phase in the form of droplets surrounded by the continuous aqueous phase.
• the polymerization takes place mainly in the droplets, the latter generally having an average diameter of between 100 .- / m and 3 millimeters.
• Such a process is similar to the so-called "radical suspension polymerization" process except that it is not radical.
• the dispersing agent can be one of those known to have this function, such as, for example, a polyvinyl alcohol, methylcellulose, gelatin, kaolin, barium sulfate, hydroxyapatite, magnesium silicate, tricalcium phosphate. , or a combination of several of these dispersing agents.
• the dispersing agent can be introduced into the polymerization medium up to 10% by weight relative to the weight of water used and preferably from 0.01% to 5% by weight relative to the weight of water used.
• At least one emulsifying agent can be added to the polymerization medium.
• the use of such an emulsifying agent is particularly recommended when it is desired that the polymerization leads to a latex, that is to say to a set of polymer particles having a number average diameter less than 1 micrometer , said particles being dispersed in the aqueous phase.
• an emulsifying agent it is generally not necessary for the polymerization medium to contain a dispersing agent.
• the emulsifying agent any of the known surface-active agents may be used, whether anionic, nonionic or even cationic.
• the emulsifying agent can be chosen from anionics such as the sodium or potassium salts of fatty acids, in particular sodium laurate, sodium stearate, sodium palmitate, sodium oleate, mixed sodium or potassium sulphates and fatty alcohol, in particular sodium lauryl sulphate, the sodium or potassium salts of sulphosuccinic esters, the sodium or potassium salts of alkylarylsulphonic acids, in particular sodium dodecylbenzene sulphonate, and sodium or potassium salts of monosulfonates of fatty monoglycerides, or also among nonionic surfactants such as the reaction products between ethylene oxide and alkylphenols. It is of course possible to use mixtures of such surfactants.
• the emulsifying agent can be introduced into the polymerization medium up to 10% by weight relative to the weight of water, and preferably from 0.01% to 5% by weight relative to the weight of water, for example from 0.01% to 3% by weight relative to the weight of water.
• the polymerization takes place in droplets of liquid organic phase, which generally have an average diameter between 1 ⁇ m and 1000 ⁇ m, and in micelles which generally have an average diameter between 1 nanometer and 100 nanometers.
• a process is similar to the so-called "radical emulsion polymerization" process except that it is not radical.
• the concentration of emulsifying agent is increased, the relative importance of the polymerization taking place in the micelles is increased and the formation of a latex at the end of polymerization is favored.
• the process is similar to the process known as "radical polymerization in microemulsion" except that the polymerization is not radical.
• the polymerization medium comprises a liquid organic phase and an emulsifying agent
• a co-surfactant generally has a solubility in water of less than 1.10 -3 moles per liter at 20 ° C.
• a co-surfactant can for example be hexadecane or ethyl alcohol. It can be present up to 10% by weight relative to the weight of water and preferably the ratio of the mass of emulsifying agent to that of co-surfactant ranges from 0.5 to 2.
• this co-surfactant also makes it possible, thanks to sufficient shearing of the medium, to obtain droplets of liquid organic phase of less than 1 ⁇ m and promotes the formation of a latex at the end of polymerization.
• Sufficient shear can for example be obtained by ultrasound or by a homogenizer (such as an apparatus of the ultraturax or diax 600 type from the company Heidolph), ultrasound being preferred.
• the method according to the invention leads to polymer particles whose diameter can range from 10 nanometers to 5 millimeters.
• a latex is obtained.
• the latex optionally contains particles which tend to settle and it may be desired to carry out a separation, for example by filtration so as to remove these particles which are not part latex.
• the polymerization conditions namely the quantity of the ingredients in the polymerization medium and the degree of conversion of monomer to polymer, can be adapted so that the latex has a solid content ranging from 0.1 to 50% by weight.
• the olefin intended to be polymerized is introduced with sufficient stirring of the polymerization medium, for example stirring ranging from 10 to 10,000 revolutions per minute.
• the olefin can be introduced in liquid or gaseous form, depending on its physical state.
• the polymerization can take place between 0 and 300 ° C and preferably between 25 and 200 ° C, at an absolute total pressure ranging from 1 to 200 bars and preferably from 1 to 100 bars. If the polymer to be formed is at least partially crystalline, the polymerization is generally carried out at a temperature below the melting point of the polymer to be formed.
• a high density homopolyethylene is obtained.
• the polymerization of ethylene with at least one olefin other than ethylene leads to the production of an ethylene polymer of lower density than the previously mentioned high density homopolyethylene.
• ethylene comonomer (s) it is therefore possible to obtain a high density ethylene polymer (high density polyethylene), or a medium density ethylene polymer (medium polyethylene). density), or even, with a high comonomer content, a low density ethylene polymer (low density polyethylene).
• high density means that the density is greater than 0.940, by medium density the fact that the density ranges from 0.925 to 0.940 and by low density does the density is less than 0.925.
• the polymerization can therefore lead to a latex of a polymer of at least one olefin, that is to say to a polymer comprising polymerized units of at least one olefin, optionally with other monomer units. polymerized.
• a latex of a polymer of ethylene can be obtained.
• the process according to the invention can therefore lead to a latex of a high density ethylene polymer or to a latex of a medium density ethylene polymer, or even a low density ethylene polymer.
• polymer must be taken in its general sense, so that it covers homopolymers copolymers, interpolymers and mixtures of polymers.
• polymerization should also be taken in an equivalent general sense.
• the set of olefins includes that of ⁇ -olefins.
• olefins mention may be made of ethylene, propylene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1, 4-hexadiene, 1, 9 -decadiene, 1-octene, 1-decene.
• the process according to the invention can be carried out batchwise, semi-continuously or continuously.
• Mw weight average molecular weight
• Mn number average molecular weight
• This catalyst exo, endo- [1, 1 '-bis ⁇ 1 - (diphenylphosphino) -1 - phenylmethylene ⁇ bicyclo [2,2, 1] heptene-2-endimethylenolato-2,3-
• O, P; O ', P'-bis (triphenylphosphino) diphenyldinickel (II), has the following developed structure:
• (5,6-NBEN) represents a 5,6-bicyclo [2,2, 1] heptene-2 radical
• Ph represents a phenyl radical
• PREPARATION OF A CATALYST B The procedure is as for the preparation of catalyst A, except that 5 millimoles of exo, endo-2,3-bis [2-metoxycarbonyl-2- (triphenylphosphoranylidene) acetyl] bicyclo are used , 2, 1) heptene-5, instead of the 5 millimoles of exo, endo-2,3-bis [2-phenyl-2- (triphenylphosphorany lidene) acetyl] bicyclo [2,2, 1] heptene-5.
• This catalyst exo, endo- [1, 1 '- bis ⁇ 1 - (diphenylphosphino) -1 -methoxycarbonylmethylene ⁇ bicyclo [2,2, 1] hep tene-2-endimethylenolato-2,3-O, P; O' , P'-bis (triphenyl-phosphino) diphenyldi nickel (II), has the following structure:
• (5,6-NBEN) represents a 5.6 bicyclo [2,2, 1] heptene-2 radical
• Ph represents a phenyl radical
• HOMOPOLYMERIZATION OF ETHYLENE In 45 ml of toluene, 250 mg of catalyst A and 650 mg of bis (cis, cis-1, 5-cyclooctadiene) nickel (O) are dissolved with stirring and at room temperature. This solution is placed in a 2,500 ml metal reactor heated to 62 ° C. containing 2,000 ml of a solution of 3 g / l of sodium dodecyl sulphate (SDS) in water. This mixture is stirred at 1000 revolutions per minute. After 2 minutes, ethylene is introduced in vapor form so as to obtain a total pressure of 28 bars in the reactor.
• SDS sodium dodecyl sulphate
• Example 2 The procedure is the same as in Example 1 except that the 250 mg of catalyst A is replaced by 45 mg of catalyst B, that 200 mg of bis (cis, cis-1, 5-cyclooctadiene) is used. ) nickel instead of 650 mg which is dissolved in 40 ml of toluene instead of 45 ml.
• the polymerization is carried out at 65 ° C.
• the initial ethylene pressure in the reactor is 36 bars. After three hours of polymerization, it dropped to 17 bars.
• the filtrate is a latex with a solid content of 1.2% by weight, ie 22 g of polyethylene in the form of latex.
• the contents of the second Schlenck tube are reintroduced into the first tube.
• the whole is then placed, still under a nitrogen atmosphere, in a 6 I metal reactor fitted with mechanical stirring and maintained at 45 ° C.
• the filtrate is a latex with a solid content of 3%.
• EXAMPLE 4 2 liters of deionized water are introduced into a 2.5 I Schlenck tube, in which nitrogen is bubbled for 12 hours. 200 ml of this water are taken, which is introduced into a 300 ml Schlenck tube with 6 g of sodium lauryl sulphate (SLS) and nitrogen is bubbled for 2 h. Then 3 ml of hexadecane are added. The contents of the second Schlenck tube are reintroduced into the first tube.
• SLS sodium lauryl sulphate
• the reactor is placed under 2 bars of ethylene and its temperature is brought to 65 ° C. with stirring at 400 revolutions per minute. When the temperature has reached 65 ° C., the ethylene pressure is brought to 20 bars and kept constant for 90 minutes.
• Example 4 The procedure is as in Example 4 except that 76 mg of catalyst C is used instead of 300 mg of catalyst A, 181 mg of bis (cis, cis-1,5-cyclooctadiene) nickel instead of 600 mg and except that the reactor is maintained at 50 ° C instead of 45 ° C during the introduction of the miniemulsion.
• a latex is obtained under the filter. This latex has a solid content of 0.9% and contains 9.7 g of polyethylene having an Mw of 1680 and an Mn of 848.

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