EP0660845A1 - Procede de preparation de polymeres olefiniques - Google Patents

Procede de preparation de polymeres olefiniques

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Publication number
EP0660845A1
EP0660845A1 EP93920694A EP93920694A EP0660845A1 EP 0660845 A1 EP0660845 A1 EP 0660845A1 EP 93920694 A EP93920694 A EP 93920694A EP 93920694 A EP93920694 A EP 93920694A EP 0660845 A1 EP0660845 A1 EP 0660845A1
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EP
European Patent Office
Prior art keywords
process according
tert
compound
butyl
die
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP93920694A
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German (de)
English (en)
Inventor
Bruno Rotzinger
Alfred Columberg
Jean-Roch Pauquet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
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Publication of EP0660845A1 publication Critical patent/EP0660845A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups

Definitions

  • the present invention relates to a process for the preparation of olefin polymers in which hydrotalcites, zeolites or metal oxides and optional stabilisers are added during the polymerisation.
  • the invention also relates to the olefin polymers so obtained.
  • the low-pressure polymerisation of olefins with organometallic complex catalysts usually results in a finely powdered polymer which is extruded in an extruder before being shaped by processing.
  • organometallic complex catalysts e.g. Ziegler-Natta catalysts
  • substances such as stabilisers, corrosion inhibitors, colour enhancers, antistatic agents or other processing auxiliaries.
  • this granulation is not always desired or possible, inter alia, with polymers of high molecular weight.
  • modifiers which are important for processing and long-term stability during polymerisation.
  • the addition of many conventional modifiers e.g. stabilisers
  • the machines used in further processing of the polymers are subject to corrosion.
  • the corrosive action of the polymer on metal surfaces is generally attributed to catalyst residues or degradation products of the catalyst system.
  • the invention relates to a process for the preparation of olefin polymers by polymerisation using transition metal catalysts, which comprises carrying out the polymerisation by adding at least one compound of the series of the hydrotalcites, zeolites or metal oxides that do not release water under the reaction conditions.
  • the polymerisation is preferably carried out witii a solid supported transition metal catalyst which has been prepared by reacting an aluminium compound carrying at least one alkyl group with a compound of a metal of the IVth subgroup of the Periodic Table.
  • the olefins polymerisable by this process are ethylene and ⁇ -olefins such as propylene, but-1-ene, 4-methylpent-l-ene or 5-methylhex-l-ene, as well as mixtures of olefins, typically ethylene-propylene or propylene in admixture with minor amounts of higher ⁇ -olef ⁇ ns.
  • ethylene and ⁇ -olefins such as propylene, but-1-ene, 4-methylpent-l-ene or 5-methylhex-l-ene
  • mixtures of olefins typically ethylene-propylene or propylene in admixture with minor amounts of higher ⁇ -olef ⁇ ns.
  • the process for the polymerisation and copolymerisation of propylene is of particular interest
  • the polymerisation catalysts are transition metal catalysts. They typically consist of a magnesium dihalide in active form and a titanium compound. Catalysts with the other metals of the IVth subgroup of the Periodic Table (Zr and Hf) are also suitable.
  • magnesium dihalide in active form is meant one in whose X-ray spectrum the line of strongest reflectivity is broader than the corresponding line in the spectrum of the inactive magnesium halide.
  • magnesium dichloride or magnesium dibromide as magnesium dihalide.
  • the titanium compounds preferably contain at least one titanium-halide bond. It is particularly preferred to use titanium tetrachloride.
  • the titanium compound can be used in conjunction with an electron donor, typically a carboxylic acid ester, as disclosed in EP-A-45 977.
  • the catalyst so prepared is activated by reaction with an aluminium compound which carries at least one alkyl group and is used preferably as a solution in an alkane.
  • aluminium alkyls are A C ⁇ H ⁇ or A QH ⁇ .
  • an electron donor as co-activator, convenienUy an organic silicon compound that contains at least one Si-O-C bond, as disclosed in EP-A-45 977.
  • silicon compounds are phenyl triethoxysilane, phenyl trimethoxysilane, diphenyl dimethoxysilane, methyl triethoxysilane, dimethyl diethoxysilane or ethyl trimethoxysilane.
  • transition metal catalysts typically consist of a chromium compound on a solid support, e.g. alumina or silica or mixtures thereof. Examples of such catalysts, also called Phillips catalysts, will be found in US-A-2 825 721.
  • the polymerisation with these catalysts can be carried out by known methods in liquid phase or in the gas phase.
  • the liquid phase may conveniendy be an aliphatic hydrocarbon or the liquid monomer itself.
  • the compounds of the series of the hydrotalcites, zeolites or metal oxides mat do not release water under the reaction conditions arc added to the polymerisation medium at the start, during, or towards the end of the polymerisation.
  • M 2+ Mg, Ca, Sr, Ba, Zn, Cd, Pb, Sn and or Ni,
  • M 3 * Al, B or Bi
  • a n is an anion of valency n, n is a number from 1 to 4, x is a number from 0 to 0.5, m is a number from 0 to 2, and
  • A OH% C1-, Br, I ⁇ CKV, HCO 3 -, CH 3 COO-, C 6 H 5 COO-, CO 3 2 -, SO 4 % coo- CH 3 CHOHCOO-, SiO 3 2 -, SiO 4 4" , Fe(CN) 6 3 ', Fe(CN) 6 4 - orHPO 4 2 ⁇
  • hydrotalcites which may conveniently be used in the process described above are compounds of the general formula la
  • M 2+ is at least one metal of the series of Mg and Zn, Mg being preferred, A n " is an
  • anion of the series of CO 3 2' , COO/ , OH ' and S 2' , and n is the valency of the anions, m is a positive number, preferably from 0.5 to 5, and x and z are positive numbers, and x is preferably 2 to 6 and z is smaller than 2.
  • Preferred compounds of the series of the hydrotalcites are those of the general formula I
  • M 2+ is Mg or denotes a solid solution of Mg and Zn
  • a n" is CO 3 2 % x is a number from 0 to 0.5 and m is a number from 0 to 2.
  • hydrotalcites are those of formulae
  • n is the charge of the cation M
  • M is an element of the first or second main group of the Periodic Table, y : x is a number from 0.8 to 1.2, and w is a number from 0.5 to 10.
  • the preferred per se known zeolites which may be used in the above process have an average pore diameter of 3-5 A, including those of the NaA type that have an average effective pore diameter of 4 A, for which reason they are also called 4A zeolites.
  • Suitable zeolites are the compounds:
  • Metal oxides can also be used in the process of this invention. Oxides of divalent metals are preferred. Oxides of metals of the second main group or subgroup of the Periodic Table are especially preferred, and zinc or magnesium oxide is most preferred.
  • novel compounds are dried to remove the unbound or only loosely bound water at 50-800°C, preferably 80-400°C, provided tiiey are not already sufficiendy dry and have been stored with exclusion of moisture. Drying can be ca ⁇ ied out under vacuum or inert gas.
  • the surfaces of the substances can be treated with surface active reagants such as carboxylic acids or linear alcohols of 8 or more carbon atoms, convenien ⁇ y stearic acid.
  • the compounds of the series of the hydrotalcites, zeolites or metal oxides or similar synthetically prepared compounds that do not release water under the reaction conditions are normally added in an amount of 0.005 to 5.0 % by weight, preferably from 0.01 to 1 % by weight, based on the polymer.
  • the process is preferably carried out using additional stabilisers.
  • a particularly preferred embodiment of the invention comprises carrying out the above process by the further addition of a compound that contains at least one 2,2,6,6-tetra- methylpiperidine radical and that has a molecular weight above 500, or by the further addition of a phosphorus(III) compound.
  • a compound that contains at least one 2,2,6,6-tetra- methylpiperidine radical and that has a molecular weight above 500 or by the further addition of a phosphorus(III) compound.
  • the use of such a 2,2,6,6-tetramethylpiperidine compound with a phosphorus(III) compound is particularly preferred.
  • the sterically hindered amines preferably piperidines, are known in particular as light stabilisers, but they act here also as antioxidants, i.e. tiiey impart thermal oxidative stability to the polymer.
  • These compounds contain one or more than one group of formula I
  • They may be oligomeric or polymeric compounds.
  • Particularly important stabilisers are the following classes of tetramethylpiperidines:
  • n is a number from 1 to 4, preferably 1 or 2
  • R 1 is hydrogen, oxyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 7 -C 12 aralkyl, -Cgalkanoyl, C 3 -C 5 alkenoyl, glycidyl or a group -CH 2 CH(OH)-Z, wherein Z is hydrogen, methyl or phenyl, the preferred meaning of R 1 being C 1 -C 4 alkyl, allyl, benzyl, acetyl or acryloyl, and R 2 , if n is 1, is hydrogen, which may be interrupted by one or more than one oxygen atom, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or or phosphorus containing acid, or is
  • Substituents defined as C 1 -C 12 alkyl may typically be methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl dar.
  • R 2 as C j -C j galkyl may be the groups listed above and may additionally be n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • R 1 as C 3 -C 8 alkenyl may typically be 1-propenyl, allyl, mediallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl.
  • R 1 as C 3 -C 8 alkynyl is preferably propargyl.
  • R 1 as C 7 -C 12 aralkyl is preferably phenethyl and, most preferably, benzyl.
  • R 1 as C 1 -C 8 alkanoyl is typically formyl, propionyl, butyryl, octanoyl, but is preferably acetyl and, as C 3 -C 5 alkenoyl, is preferably acryloyl.
  • R 2 defined as a monovalent radical of a carboxylic acid is typically the radical of acetic acid, capronic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or ⁇ -(3,5-di- tert-butyl-4-hydroxyphenyl)propionic acid.
  • R 2 defined as a divalent radical of a dicarboxylic acid is typically the radical of malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, phd alic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl-(3,5-di-tert-butyl-4-hy- droxybenzyl)malonic acid or bicycloheptendicarboxylic acid.
  • R 2 defined as a trivalent radical of a tricarboxylic acid is typically the radical of trimellitic acid or of nitrilotriacetic acid.
  • R 2 defined as a tetravalent radical of a tetracarboxylic acid is typically the tetravalent radical of butane- 1,2,3 ,4-tetracarbooxylic acid or of pyromellitic acid.
  • R 2 defined as a divalent radical of a dicarbamic acid is typically the radical of hexamethylenedicarbamic acid or of 2,4-toluylenedicarbamic acid.
  • R 1 is as defined under a
  • R 3 is hydrogen, C ! -C 12 alkyl, C ⁇ -Cshydroxyalkyl, C 5 -C 7 cycloalkyl, C 7 -Cgaralkyl, C 2 -C 18 alkanoyl, C 3 -C 5 alkenoyl or benzoyl and, R 4 , if n is 1, is hydrogen, C C 18 alkyl, C 3 -C 8 alkenyl, C 5 -C 7 cycloalkyl, C r C 4 alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamido group, glycidyl, a group of formula -CH 2 -CH(OH)-Z or of formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; or, if n is 2, R 4 is Q 2 -C 12 alkylene, C 6 -C 12 arylene,
  • Substituents defined as C 5 -C 7 cycloalkyl are preferably cyclohexyl.
  • R 3 as C 7 -C 8 aralkyl is preferably phenylethyl or, most preferably, benzyl.
  • R 3 as C 2 -C 5 hydroxyalkyl is preferably 2-hydroxyethyl or 2-hydroxypropyl.
  • R 3 as C 2 -C 18 alkanoyl is typically propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but is preferably acetyl and, as C 3 -C 5 alkenoyl, is preferably acryloyl.
  • R 4 as C 2 -C 8 alkenyl is typically allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
  • R 4 as Cj- alkyl which is substimted by a hydroxyl, cyano, alkoxycarbonyl or carbamido group typically includes 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylcarbamoyl)ethyl.
  • Substituents defined as C 2 -C 1 alkylene may typically be ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • Substituents defined as C 6 -C 15 arylene may typically be o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
  • D as C 6 -C 12 cycloalkylene is preferably cyclohexylene.
  • polyalkylpiperidine compounds of this class are the following compounds:
  • n 1 or 2
  • R 1 is as defined under a) and R 5 , if n is 1, is C ⁇ -Cgalkylene or -Cghydroxyalkylene or Q-C ⁇ acyloxyalkylene, and, if n is 2, is the (-CH 2 ) 2 C(CH 2 -) 2 group.
  • R 5 as Qz- alkylene or Qz-Cghydroxyalkylene may be ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.
  • R 5 as C 4 -C 2 acyloxyalkylene may be 2-ethyl-2-acetoxymethylpropylene.
  • R 1 is as defined under a
  • R 6 is hydrogen, C -C 12 alkyl, allyl, benzyl, glycidyl or C 2 -C 6 alkoxyalkyl
  • R 7 if n is 1, is hydrogen, C C 12 alkyl, C 3 -C 5 alkenyl, C 7 -C 9 aralkyl, Cs-G / cycloalkyl, -Qhydroxyalkyl, C 2 -C 6 alkoxyalkyl, C 6 -C 10 a ⁇ yl, glycidyl or a group of formula -(CH 2 )p-COO-Q or of formula -(CH ⁇ p-O-CO-Q, wherein p is 1 or 2 and Q is C 1 -C 4 alkyl or phenyl, or if n is 2, is C 2 -C 12 alkylene, C -C 12 alkenylene, C 6 -C 12 arylene,
  • C 1 -C 12 alkyl may typically be methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • Cj-Cigalkyl may be the groups cited above and may additionally be n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • C ⁇ -Cgalkoxyalkyl may typically be methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
  • R 7 as C 3 -C 5 alkenyl may be 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
  • R 7 , T l and T 2 as C 7 -C 9 aralkyl are preferably phenethyl or, most preferably, benzyl.
  • a cycloalkane ring formed by Tj and T 2 togedier with the linking carbon atom may be a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
  • R 7 as -Qhydroxyalkyl may be 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
  • R 7 , T x and T 2 as C 6 -C 10 aryl are preferably phenyl, ⁇ - or ⁇ -naphthyl, which may be substituted by halogen or C 1 -C 4 alkyl.
  • R 7 as C ⁇ -C ⁇ alkylene may typically be ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • R 7 as C -C 12 alkenylene is preferably 2-butenylene, 2-pentenylene or 3-hexenylene.
  • R 7 as C 6 -C 12 arylene is typically o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
  • Z' as C 2 -C 12 alkanoyl may be propionyl, butyryl, octanoyl, dodecanoyl, but is preferably acetyl.
  • D as -Cjoalkylen, -C ⁇ arylene or Ce-C 12 cycloalkylene is as defined under b).
  • polyalkylpiperidines of this class are the following compounds:
  • n 1 or 2 and R 8 is a group of formula
  • R 12 is C ⁇ -C 12 alkyl, cyclohexyl, benzyl, C 1 -C hydroxyalkyl
  • R 13 is hydrogen, C 1 -C 1 alkyl or phenyl, or R 11 and R 12 , when taken together, are -Csalkylene or C 4 -C 5 ⁇ xaalkylene, typically
  • R 11 and R 12 are also each a group of formula
  • C ⁇ -C 12 alkyl may typically be methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl dar.
  • Substiments defined as - hydroxyalkyl may typically be 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
  • a as C ⁇ -Cgalkylene may be ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
  • R 11 and R 12 together as -Csalkylene or oxaalkylene may be tetramethylene, pentamethylene or 3-oxapentamethylene.
  • polyalkylpiperidines of this class are the compounds of die following formulae:
  • Oligomeric or polymeric compounds whose structural repeating unit contains one or more than one 2,2,6,6-tetraalkylpiperidine radical of formula (I), preferably polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)ac ⁇ ylates, polysiloxanes, poly(mem)acrylamides and tiieir copolymers which contain such radicals.
  • 2,2,6,6-tetraalkylpiperidine radical of formula (I) preferably polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)ac ⁇ ylates, polysiloxanes, poly(mem)acrylamides and tiieir copolymers which contain such radicals.
  • 2,2,6,6-polyalkylpiperidine light stabilisers of this class are the compounds of d e following formulae, wherein m is a number from 2 to about 200.
  • classes e) and f) are especially suitable, in particular those tetraalkylpiperidines which contain s-triazine groups.
  • Other particularly suitable compounds are compounds 74, 76, 84, 87, 92 und 95.
  • the amount of tetramethylpiperidine added will depend on die desired degree of stabilisation. Normally 0.01 to 5 % by weight, preferably 0.05 to 1 % by weight, based on die polymer, will be added. It is preferred that the molar ratio of tetramethylpiperidine and aluminium alkyl should not be substantially greater then 1.
  • the phosphorus(m) compounds added as optional additional stabilisers to the polymerisation may be phosphites, phosphonites or phosphimtes. They may contain one or more than one phosphoric ester group. It is preferred to use a phosphorus(III) compound of formula A, B, C or D
  • R x and R 2 are each independendy of die otiier C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl, phenyl, phenyl which is substimted by one to tiiree -C ⁇ alkyl groups, or are a radical
  • R 3 is Cg-C ⁇ alkyl, Cs-Cgcycloalkyl, phenyl or phenyl which is substimted by one to three groups, and
  • R is unsubstituted phenylene or naphthylene or phenylene or naphthylene which are substimted by C C 12 alkyl, or is a radical-O-Rs-O-, wherein
  • R- is unsubstimted phenylene or naphthylene or phenylene or naphthylene which are substimted by or is a radical -Phen-Rg-Phen-, wherein Phen is phenylene,
  • R 6 is -O-, -S-, -SO 2 -, -CH 2 -, or -C(CH 3 ) 2 -,
  • R 7 and R 8 are each independendy of the other phenyl or phenyl which is substimted by one to tiiree groups, and the two substiments R and R 8 may also be linked by a C j -C ⁇ alkylene group, and R 9 is F, Cl, Br or I, preferably F.
  • die compounds of formula A it is preferred to use those compounds wherein Rj and R 2 are a radical -OR 3 and R 3 is - oalkyl, phenyl or phenyl which is substimted by one to tiiree C C 12 alkyl groups.
  • R 2 is a radical -OR 3
  • R 3 is phenyl or phenyl which is substimted by one to three C 1 -C 1 alkyl groups
  • R is a diphenylene radical
  • Rj is a radical -OR 3
  • R 3 is phenyl or phenyl which is substimted by one to tiiree Ci-C ⁇ alk l groups.
  • a phosphorus (HI) compound which contains at least one P-O-Ar group, and Ar is a mono-, di- or trialkylphenyl radical.
  • HI phosphorus
  • triphenyl phosphite decyl diphenyl phosphite, phenyl didecyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di- tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-te_rt-butylphenyl)-4,4'-biphenylene diphosphonite, bis(2,6-di-tert-butyl
  • the amount of phosphorus (HI) compound will depend on d e amount of piperidine compound added. Normally 0.01 to 1 % by weight, preferably 0.05 to 0.5 % by weight, is added, based on the polymer.
  • antioxidants of die sterically hindered phenol type are standard antioxidants for organic materials and are frequentiy used for stabilising polymers. Illustrative examples of such phenolic antioxidants are: 1.
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl- 4,6-dimed ⁇ ylphenol, 2,6-di-tert-butyl-4-ed ⁇ ylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclo- hexyl)-4,6-dimemylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- ( 1 '-methylundec- 1 '-yl)phenol, 2,4-dimemyl-6-( 1 '-methylhept
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-di- octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol and 2,6-didodecyl- thiomethyl-4-nonylphenol.
  • Hvdro uinones and alkylated hvdro uinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octa- decyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5- di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis-(3,5- di-tert-butyl-4-hydroxyphenyl) adipate.
  • Hvdroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphe- nol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis- (6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol) and 4,4'-bis-(2,6-di- med ⁇ yl-4-hydroxyphenyl) disulfide.
  • 2,2'-thiobis(6-tert-butyl-4-methylphe- nol 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis- (6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-
  • Alkylidene bisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methyl- cyclohexyl)phenol], 2,2'-methylenebis(4- ⁇ ethyl-6-cyclohexylphenol), 2,2'-methylenebis- (6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis- (4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert- butyl-4-isobutylphenol), 2,2'-methy- lenebis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethyl
  • Hydroxybenzylated malonates for example dioctadecyl 2,2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)malonate, dioctadecyl 2(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate and bis[4- (1,1 ,3,3-tetramethylbutyl)phenyl] 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hydroxybenzyl compounds for example l,3,5-tris(3,5-di-tert-butyl-4- hydroxybenzyl)-2,4,6-trimethylbenzene, l,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)- 2,3,5,6-tetramethylbenzene and 2,4,6- tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hy- droxyanilino)- 1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)- 1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-l,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl- 4-hydroxybenzyl) isocyanurate, l,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)
  • Benzylphosphonates for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, died yl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl- 4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphos- phonate and the calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhy- dric alcohols for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-no- nanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiediylene glycol, di- ediylene glycol, triethylene glycol, pentaerytiiritol, tris(hydroxyethyl) isocyanurate, N,N'- bis(hydroxyethyl)oxamide, 3-thiaund
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols for example with methanol, etiianol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diediylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane ⁇ diol, trimethylolpropane and4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo- [2.2.2]octane.
  • esters of ⁇ -(3.5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhy ⁇ dric alcohols for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-no- nanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiediylene glycol, di ⁇ ethylene glycol, triethylene glycol, pentaerythritol, rris(hydroxyethyl) isocyanurate, N,N'- bis-(hydroxyethyl)oxamide, 3-ti ⁇ iaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri ⁇ methylolpropane and 4-hydroxymethyl- l-phospha-2,6,7-trioxabicyclo-[2.2.2
  • esters of 3,5-di-tert-butyl-4-hvdroxyphenylacetic acid with mono- or polyhydric alcohols for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonane- diol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiediylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl- l-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
  • Preferred antioxidants are those listed in 6, 8, 9, 12, 13, 14 and 16, especially 6, 8, 9 and 12. Particularly suitable antioxidants are octadecyl ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)- propionate and 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene.
  • the amount of antioxidant added will depend on die amount of phosphorus(m) compound. Normally 0.005 to 0.5 % by weight, preferably 0.01 to 0.2 % by weight, based on d e polymer, is added.
  • the polymerisation is carried out in a 3 litre stirred and tiiermostatically controlled stainless steel autoclave which is evacuated before the start of the polymerisation for 30 minutes at 110°C (13 Pa) and is afterwards flushed for 30 minutes with propylene gas at 110°C.
  • the autoclave is cooled to 20°C and 300 mg of S-l, 300 mg of H-l and 300 mg of P-l are added to die autoclave as solid or as 5-10 % solution in hexane.
  • the solid catalyst component are activated for 10 minutes with half of a solution of 4 mmol of triethyl aluminium and 1.6 mmol of triethoxyphenylsilane in 25 ml of hexane and suspended in d e autoclave under argon.
  • the autoclave is flushed with the second half of the hexane solution.
  • the autoclave is closed and charged with hydrogen (6 kPa) and 600 g of liquid propylene. Widi stirring, the contents of the autoclave are heated to 70°C and kept at tiiis temperature for 4 hours. Excess propylene is then discharged and the resultant polymer is treated with 10 ml of isopropanol at 70°C to deactivate d e catalyst and tiien dried under vaccum for 1 hour at 70°C.
  • the polymer is compression moulded on a hot press for 30 minutes at 280°C between carefully cleaned iron plates.
  • the iron plates are then stored for 24 hours at 100 % humidity at room temperature (c.22°C). Corrosion is assessed visually.
  • the colour of die polymer is characterised by the Yellowness Index (YI) according to ASTM D 1925-70.
  • the polymer corrodes the iron plates only insignificandy. It has a YI of 2.3.
  • Example 1 The procedure of Example 1 is repeated, but without using 300 mg of S-l, to give a polymer which, with the same catalyst yield, severely corrodes the iron plates and has a YI of 2.5.
  • Example 1 The procedure of Example 1 is repeated, replacing S-l witii 300 mg of S-2/300 mg of S-5, to give a polymer that corrodes the iron plates insignificandy/slighdy and has a YI of 2.3/
  • Polypropylene powder prepared as in Example 3, is processed in a Brabender plastograph for 10 minutes at 230°C. The melt is taken from die kneader and compressed to a c.5 mm board. In the corrosion test, the iron plates exhibit no corrosion after the melt processing.
  • the polymer prepared according to comparative Example 2 is processed as described in
  • Example 5 The iron plates are severely corroded after the melt processing.
  • the stability to oxidative degradation is measured by the time taken until marked embritdement of the polymer occurs in oven ageing at elevated temperature.
  • This test is carried out with boards which are obtained by compression moulding polypropylene powder obtained as described in Example 1 by adding 300 mg of S-l, 300 mg of H-l and 300 mg of P-l and 300 mg of S-5, 300 mg of H-l and 300 mg of P-l at 230°C.
  • the time taken until embritdement is 11 days for both polymers at an oven temperature of 135°C.
  • H-2 R-NH-(CH 2 ) 3 -N - (CH 2 ) 2 N-(CH 2 ) 3 -NH-R

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'addition d'au moins un composé de la série des hydrotalcites, des zéolites ou des oxydes de métal, qui ne libère pas d'eau dans des conditions de réaction à la polymérisation d'oléfines avec des catalyseurs supportés solides, provoque une forte réduction de l'action corrosive des polymères, sans affecter négativement la polymérisation elle-même ni les propriétés des polymères. On peut ajouter d'autres stabilisateurs.
EP93920694A 1992-09-17 1993-09-08 Procede de preparation de polymeres olefiniques Withdrawn EP0660845A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH292492 1992-09-17
CH2924/92 1992-09-17
PCT/EP1993/002419 WO1994006831A1 (fr) 1992-09-17 1993-09-08 Procede de preparation de polymeres olefiniques

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EP0660845A1 true EP0660845A1 (fr) 1995-07-05

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JP (1) JPH08501580A (fr)
KR (1) KR950703581A (fr)
CN (1) CN1042338C (fr)
AU (1) AU679453B2 (fr)
CA (1) CA2143103A1 (fr)
CZ (1) CZ66995A3 (fr)
MX (1) MX9305698A (fr)
MY (1) MY110671A (fr)
SK (1) SK34095A3 (fr)
TW (1) TW321658B (fr)
WO (1) WO1994006831A1 (fr)

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US5507980A (en) * 1993-07-06 1996-04-16 Aristech Chemical Corporation Basic inorganic binders
EP0710677A3 (fr) * 1994-11-03 1998-02-04 Ciba SC Holding AG Procédé de préparation de polymères stabilisés
US6503431B1 (en) * 1998-07-08 2003-01-07 Mitsui Chemicals Inc Process for manufacturing an extruded article and an extruded article
JP6882882B2 (ja) * 2016-11-10 2021-06-02 三井化学株式会社 オレフィン重合体の製造方法および流動性改良方法
WO2018181664A1 (fr) * 2017-03-31 2018-10-04 味の素株式会社 Composition d'étanchéité
CN109694437A (zh) * 2017-10-20 2019-04-30 中国石化扬子石油化工有限公司 一种用丙烯气相聚合装置生产共聚聚丙烯的方法
EP3853300A1 (fr) * 2018-09-19 2021-07-28 Borealis AG Utilisation d'un composé à base de triazine de faible poids moléculaire en tant que thermo/photo-stabilisant dans des polymères

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EP0266074B1 (fr) * 1986-10-02 1991-08-14 BP Chemicals Limited Procédé de polymérisation d'une ou de plusieurs 1-oléfines en phase gazeuse en présence de matériaux inorganiques pulvérulents
EP0351360B1 (fr) * 1988-06-30 1995-02-22 Ciba-Geigy Ag Procédé de préparation des polyoléfines thermiquement stabilisées
SE9100383D0 (sv) * 1991-02-07 1991-02-07 Neste Oy Saett att vid plastmaterial avlaegsna ooenskade aemnen
US5262233A (en) * 1991-02-19 1993-11-16 Mitsubishi Petrochemical Co., Ltd. Agricultural film
CA2121469C (fr) * 1991-11-15 2003-09-16 David P. Ashton Compositions polymerisables

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KR950703581A (ko) 1995-09-20
MY110671A (en) 1999-01-30
AU679453B2 (en) 1997-07-03
CN1084181A (zh) 1994-03-23
AU4815793A (en) 1994-04-12
CN1042338C (zh) 1999-03-03
CZ66995A3 (en) 1995-07-12
JPH08501580A (ja) 1996-02-20
MX9305698A (es) 1994-03-31
SK34095A3 (en) 1995-08-09
CA2143103A1 (fr) 1994-03-31
TW321658B (fr) 1997-12-01
WO1994006831A1 (fr) 1994-03-31

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