WO1981001289A1 - Catalysed alternating copolymerisation and product - Google Patents

Catalysed alternating copolymerisation and product Download PDF

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Publication number
WO1981001289A1
WO1981001289A1 PCT/GB1980/000188 GB8000188W WO8101289A1 WO 1981001289 A1 WO1981001289 A1 WO 1981001289A1 GB 8000188 W GB8000188 W GB 8000188W WO 8101289 A1 WO8101289 A1 WO 8101289A1
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process according
group
atom
unsubstituted
thio
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PCT/GB1980/000188
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French (fr)
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C Bamford
P Malley
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C Bamford
P Malley
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Publication of WO1981001289A1 publication Critical patent/WO1981001289A1/en

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    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles

Definitions

  • This invention relates to copolymerization processes; more particularly, this invention relates to processes for the preparation of copolymers comprising sequences of alternating monomer residues, and to copolymers so prepared.
  • Mixtures of monomers which are capable of copolymerizing when treated with a conventional polymerization catalyst normally form copolymers in which the residues of the monomers are distributed in a more or less random manner along the polymer chain. It has recently been shown that certain monomer mixtures react in the presence of a Lewis acid to give alternating copolymers i.e.
  • This invention seeks to provide an improved process for the preparation of copolymers comprising sequences of alternating monomer residues such that they may readily be obtained using comparatively small proportions of Lewis acid thus providing an easier and more economical process.
  • a transition metal complex comprising at least one ⁇ -acid ligand;
  • an organic compound which may be a polymer, comprising at least one carbon-halogen bond, an acetylenic bond or an ethylenic bond conjugated with one or more electron attracting (-R) groups; and
  • Donor monomers include those mono- or poly-unsaturated compounds having no (-R) substituent conjugated with the or each unsaturated bond and having at most two, preferably at most one, (-I) substituent bonded to any given unsaturated carbon-carbon bond. Classes of such compounds include unsubstituted or substituted hydrocarbons, (thio)ethers, (thio)esters or (thio)amides. Suitable unsubstituted or substituted hydrocarbons include:
  • R 1 and R 2 which may be the same or different, each represents a hydrogen or halogen atom or an unsubstituted or halosubstituted C 1 to C 20 hydrocarbyl group; (v) an internal olefinically unsaturated compound of the general formula:
  • R 3 and R 4 which may be the same or different, each represents an unsubstituted or halo-substituted C 1 to C 20 hydrocarbyl group;
  • R represents a hydrogen atom or an unsubstituted or halosubstituted C 1 to C 20 hydrocarbyl group;
  • R 6 represents an unsubstituted or halo-substituted C 1 to C 20 hydrocarbylene group;
  • R 8 represents a hydrogen atom or a polymerisable unsaturated group containing C 2 to C 20 hydrocarbyl group
  • donor monomers include ethylene, propylene, butene-1, butene-2, isobutylene, pentene-1, pentene-2, 2-methylbutene-1.
  • Suitable (thio)ethers, (thio)esters or (thio)amides have the general formula:
  • R 9 represents an unsubstituted or substituted C 1 to C 20 hydrocarbyl group
  • R 10 represents a polymerisable unsaturated group containing C 2 to C 20 hydrocarbyl group
  • R 11 represents a C 1 to C 20 hydrocarbylene group
  • R 12 represents a hydrogen atom or a C 1 to C 20 hydrocarbyl group
  • Z represents an oxygen or sulphur atom
  • Y represents an oxygen or sulphur atom or an -NR 12 group
  • m represents zero or 1.
  • donor monomers include vinyl acetate, vinyl propionate, vinyl pelargonate, vinyl-2-ethyl- hexanecarboxylate, vinyl stearate, ethylvinyl oxalate, vinyl chloroacetate, vinyl thiolacetate, vinyl benzoate, vinyl cyclohexanecarboxylate, vinyl-norbornane-2-carboxylate, allyl acetate, allyl laurate, allyl cyclobutanecarboxylate,
  • 2-chloroallyl acetate isopropenyl acetate, ⁇ -methallyl acetate, 1-propenyl acetate, 1 Bobutenyl butyrate, N-vinylacetamide, N-allyl-N-methyl-propionic acide amide, N-vinylbenzoic acid amide, N-vinylthioacetamide, N- vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam and vinyl ether.
  • Mixtures of two or more donor monomers may be used in which case the different donor monomer residues will be distributed in a random manner as the alternating donor monomer residues in the copolymer chain.
  • Acceptor monomers include those unsaturated compounds which form a complex with a Lewis acid.
  • Preferred such compounds include olefinically unsaturated compounds having a (-R) substituent conjugated with an unsaturated bond.
  • Suitable olefinically unsaturated compounds have the general formula:
  • R I and R II which may be the same or different, each represents a hydrogen or halogen atom or an unsubstituted or halo-substituted C 1 to C 20 hydrocarbyl group, with the proviso that at least one of R and R represents a hydrogen atom;
  • Q represents a nitrile group or a group of the formula:
  • Y' represents a group of the formula Z"R' ,
  • NR"R'" or R"", Z' and Z" which may be the same or different, each represents an oxygen or sulphur atom
  • R' , R" , R" ' or R" which may be the same or different, each represents a hydrogen atom or a C 1 to C 20 hydrocarbyl group, with the proviso that R"" may also represent a halogen atom and R" and R'" may, together with the nitrogen atom to which they are bonded, represent an N-linked heterocyclic group, and
  • Me represents a salifying metal of valency n.
  • acceptor monomers examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, n-amyl acrylate, n-octylacrylate, octadecyl acrylate, allyl acrylate, o-toluyl.
  • Mixtures of two or more acceptor monomers may be used in which case the different acceptor monomers will be distributed in a random manner as alternating acceptor monomer residues along the copolymer chain.
  • the transmition metal complex (i) may be any such complex stabilised in a low oxidation state, typically
  • a ⁇ -acid ligand Generally the transition metal will be Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni , Pd or Pt, notably Cr, Mo, W, Mn, Re, Fe, Co, Ni and Pt, especially Mn, Re and Ni.
  • Suitable ⁇ -acid ligands are organometallic such ligands and mono- or polydentate alkyl and aryl phosphines and phosphites, and mono- and polydentate pyridines. Examples of organometallic such ligands include carbonyl, alkyl and aryl isocyanides, and organic compounds, notably hydrocarbons, comprising acetylenic, olefinicand aromatic unsaturation.
  • transition metal complexes (i) one or more such ⁇ -acid ligands may be present.
  • Other ligands may also be present.
  • transition metal complexes examples include
  • Mo(CO) 6 Mo(CO) 5 Py; (CO) 4 Mo(PMe 2 ) 2 Mo(CO) 4 ; (CO) 5 MoPMe 2 PMe 2 Mo (CO) 5 : (CO) 5 MoPEt 2 PEt 2 Mo(CO) 5 ; W(CO) 6 ; Cr(CNAr) 6 ; Mo(CNAr) 6 ; W(CNAr) 6 ; Mn 2 (CO) 10 ; (C 5 H 5 )Mn(CO) 3 ; Re 2 (CO) 10 ; Re 2 (co) 8 (PPh 3 ) 2 ; Re(CO) 3 (PPh 3 ) 2 ; Fe(CO) 5 ; Fe(CO) 4 (PPh 3 ); Fe(CO) 5 (PPh 3 ) 2 (CO) 3 Fe(PMe 2 ) 2 Fe(CO) 3 ; (CO) 3 BrFe(PMe 2 ) 2
  • the organic compound (ii) may be any compound from which a chlorine or bromine atom may be removed during the reaction.
  • bromo compounds are more active than chloro compounds and activity is greatest in those compounds having more than one chlorine or bromine atom on one carbon atom or in which a further electron withdrawing substituent is adjacent to the halogenated carbon atom.
  • Examples of such compounds are compounds containing CCI 3 or CBr 3 groups, such as CCI 4 , CHCI 3 ,
  • N-bromo amides or amides such as N-bromosuccinimide and N-chloro-substituted nylon may also be used.
  • Saturated fluorine compounds containing no chlorine or bromine are inactive; iodine compounds have a propensity to liberate molecular iodine which acts as a retarder.
  • Chlorine and bromine-containing donor or acceptor monomers may also serve as component (ii).
  • Other photoinitiating compounds (ii) in which halogen is not removed are organic compounds comprising an acetylenic bond or an ethylenic bond conjugated with one or more (-R) groups.
  • Examples include acetylene and acetylene mono and dicarboxylic acids and their esters, such as acetylenedicarboxylic acid and dimethylacetylenedicarboxylate; olefinic mono and dicarboxylic acids, their esters and anhydrides, such as diethylfumarate, diethyl maleate and maleic anhydride.
  • the Lewis acid (iii) suitably has the general empirical formula: wherein:
  • M represents an aluminium or boron atom
  • R v represents a hydrocarbyl group
  • X represents a fluorine, chlorine or bromine atom; and n represents zero or any number, including fractional numbers, up to and including three; or comprises a mixture of a Group IIB, IIIB or IVB organometallic compound with a Group IIIB or IVB halide.
  • Examples include methylaluminium dichloride, ethylaluminium dichloride, isobutylaluminium dichloride, hexylaluminium dichloride, dodecylaluminium dichloride, phenylaluminium dichloride, cyclohexylaluminium dichloride, methylaluminium dibromide, allylaluminium dichloride, ethylaluminium sesquichloride, ethylaluminium sesquibromide, methylaluminium sesquichloride, diethylaluminium chloride, ethylphenylaluminium chloride, dicyclohexylaluminium chloride, methylboron dichloride, ethylboron dichloride, butylboron, dichloride, hexylboron dichloride, dodecylboron dichloride, phenylboron dichloride, benzylboron dichloride,
  • sesquichloride ethylaluminium dichloride, trimethylgallium, triethylgallium, triethylindium, tetraethylgermanium, tetramethyltin, tetraethylti ⁇ , tetraisobutyltin, dimethyldiethyltin, tetraphenyltiri, tetrabenzyltin, diethyldiphenyltin, triethyltin chloride, diethyltin dichloride, ethyltin trichloride, tetramethyllead, tetraethyllead, dimethyldiethyllead, and triethyllead chloride, mixed with one or more of boron trichloride, boron trifluoride, boron triboromide, boron triiodide, ethylboron.
  • dichloride diethylboron chloride, aluminium trichloride, aluminium tribromide, aluminium triiodine, partially fluorinated aluminium chloride, ethylaluminium dichloride, methylaluminium dibromide, ethylaluminium sesquichloride, diethylaluminium chloride, gallium trichloride, gallium dichloride, germanium tetrachloride, tin tetrachloride, tin tetrabromide, ethyltin trichloride, methyltin trichloride, phenyltin trichloride, dimethyltin dibromide, diethyltin dichloride, diisobutyltin dichloride, triethyltin chloride, lead tetrachloride, and diethyllead dichloride.
  • the process is suitably effected in absence of oxygen, conveniently in vacuum or under a blanket of an inert gas, for example nitrogen.
  • the copolymer may be isolated by any conventional method, for example by precipitation by a non-solvent such as methanol.
  • a slightly elevated temperature for example between 60o and 100o.
  • Organometallic derivatives of molybdenum are especially suitable for use within this temperature range, while those of nickel may have sufficient activity for use down to ambient temperatures.
  • the rate of polymerization may be increased by irradiating the process mixture with ultra-violet light.
  • Suitable concentrations of either monomer in the process mixture are up to 2 mol per litre.
  • Suitable amounts of catalyst will depend on the activity of the catalyst chosen but amounts down to 0.002 mol % of monomer may be used in favourable cases.
  • Suitable amounts of the compound (ii) will depend on the activity of the compound and also on the nature of the transition metal complex (i). Carbon tetrachloride may be used in amounts down to 0.5 mol % of monomer, but with carbon tetrabromide this may be reduced to 0.05 mol %.
  • Amounts of Lewis acid (iii) down to 5 mol % of monomer may be used.
  • component (ii) may itself comprise a polymer which comprises at least one carbon-halogen bond.
  • Such polymers can be produced by free radical polymerization, which may proceed in accordance with the invention or conventionally, in the presence of a monomeric organic compound comprising at least one carbonhalogen bond.
  • a halogen-containing fragment of the organic compound will be present as a terminal group in a homopolymer or a random or alternating copolymer. Two examples will make this clear:
  • Such polymers can also be produced, with a plurality of pendant halogen-containing groups, by homo- or random or alternating copolymerising olefinically unsaturated monomers containing them; for example vinyl trichloracetate can be homo- polymerised to:
  • a block or graft alternating copolymer prepared by the process of the invention and utilising, as component (ii) a polymer as hereinabove defined.
  • Such polymers may comprise one or a plurality of alternating blocks, for example: AAAAACBr 2 BDBDBD ...
  • AAABABBAABCBr 2 DEDEDE ...AAABABBAABCBr 2 DEDEDE... ABABABCBr 2 DEDEDE... or may comprise grafts with alternating branches, for example
  • These branches may cross-link the backbone chains.
  • copolymers obtained are similar in arrangement of the monomer residues, in tacticities and in general properties, to those obtained by the conventional use of peroxide catalysts in presence of Lewis acids.
  • copolymers are of utility in a number of ways. Control of the regularity of the copolymerization may provide copolymers of desired physical or chemical properties in greater consistency. Furthermore copolymers in which reactive groups are distributed regularly rather than at random may facilitate the manufacture of copolymers containing groups which may confer a variety of useful properties on the copolymer.
  • Example 1 The invention is illustrated but not limited by the following Examples.
  • Example 1 The invention is illustrated but not limited by the following Examples.
  • Example 2 The procedure in Example 1 was repeated with 4.1 ml toluene, 3.12 g styrene, 0.86 g methylacrylate, 0.15 g carbon tetrachloride, 0.2 g Al 2 Et 3 Cl 3 and 0.0011 g Mn 2 (CO) 10 . The same product was obtained with a yield of 0.37 g.
  • Example 3 The procedure in Example 1 was repeated with 100 ml toluene, 4.2 g of styrene, 3.4 g of methylacrylate, 1.54 g of carbon tetrachloride, 1.23 g of Al 2 Et 3 Cl 3 and 0.011 g of Mn 2 (CO) 10 .
  • Example 4 100 ml of toluene, 4.2 g of styrene, 3.4 g of methyl acrylate, 1.54 g of carbon tetrachloride, 1.84 g of Al 2 Et 3 Cl 3 and 0.0038 g of Ni(C0) o were mixed, and degassed as described in Example 1. tube was sealed off and allowed to warm up to 25oC. The reaction mixture was held at 25oC for 0.5 hour without irradiation and then poured into excess methanol to give 3.0 g of alternating copolymer.
  • Example 5 The procedure in Example 4 was repeated with 100 ml toluene,
  • Example 6 The procedure in Example 1 was repeated with 5.3 ml toluene, 1.04 g styrene, 1.59 g acrylonitrile, 0.15 g carbon tetrachloride, 0.2 g Al 2 Et 3 Cl 3 and 0,0011 g Mn 2 (CO) 10 .
  • the yield of alternating copolymer was 0.20 g.
  • Example 7 The procedure in Example 1 was repeated with 4.3 ml toluene, 3-12 g styrene, 0.53 g acrylonitrile, 0.15 g carbon tetrachloride, 0.2 g Al 2 Et 3 Cl 3 and 0.0011 g Mn 2 (CO) 10 .
  • the yield of alternating copolymer was 0.28 g.
  • Example 8 Repetition of the procedure of Example 1 using 100 ml toluene, 3-4 g of methylacrylate, 2.2 g of butadiene, 1.54 g of carbon tetrachloride, 2.5 g of Al 2 Et 3 Cl 3 and 0.078 g of Mn 2 (CO) 10 afforded after irradiation for 1 hour 1.23 g of alternating copolymer. Omission of the manganese led to no copolymer.

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Abstract

A Process for the preparation of a copolymer comprising sequences of alternating monomer residues, which process comprises reacting at least one donor monomer with at least one acceptor monomer in the presence of: 1) a transition metal complex comprising at least one (Alpha)-acid ligand; 2) an organic compound, which may be a polymer, comprising at least one carbon-halogen bond, an acetylenic bond or an ethylenic bond conjugated with one or more electron attracting (-R) groups; and 3) a Lewis acid.

Description

CATALYSED ALTERNATING COPOLYMERISATION AND PRODUCT This invention relates to copolymerization processes; more particularly, this invention relates to processes for the preparation of copolymers comprising sequences of alternating monomer residues, and to copolymers so prepared. Mixtures of monomers which are capable of copolymerizing when treated with a conventional polymerization catalyst normally form copolymers in which the residues of the monomers are distributed in a more or less random manner along the polymer chain. It has recently been shown that certain monomer mixtures react in the presence of a Lewis acid to give alternating copolymers i.e. copolymers in which the monomer residues alternate regularly along the polymer chain; and also that this alternating copolymerization proceeds more rapidly if a peroxide is added. Large proportions of Lewis acid are however required; accordingly the process is expensive to operate and may also involve a troublesome separation of Lewis acid from the copolymer formed.
This invention seeks to provide an improved process for the preparation of copolymers comprising sequences of alternating monomer residues such that they may readily be obtained using comparatively small proportions of Lewis acid thus providing an easier and more economical process.
According to the invention there is provided a process for the preparation of copolymer comprising sequences of alternating monomer residues, which process comprises reacting at least one donor monomer with at least one acceptor monomer in the presence of:
(i) a transition metal complex comprising at least one π-acid ligand; (ii) an organic compound, which may be a polymer, compris ing at least one carbon-halogen bond, an acetylenic bond or an ethylenic bond conjugated with one or more electron attracting (-R) groups; and (iii) a Lewis acid. Donor monomers include those mono- or poly-unsaturated compounds having no (-R) substituent conjugated with the or each unsaturated bond and having at most two, preferably at most one, (-I) substituent bonded to any given unsaturated carbon-carbon bond. Classes of such compounds include unsubstituted or substituted hydrocarbons, (thio)ethers, (thio)esters or (thio)amides. Suitable unsubstituted or substituted hydrocarbons include:
(iv) a terminal olefinically unsaturated compound of the general formula:
Figure imgf000004_0001
wherein: R1 and R2, which may be the same or different, each represents a hydrogen or halogen atom or an unsubstituted or halosubstituted C1 to C20 hydrocarbyl group; (v) an internal olefinically unsaturated compound of the general formula:
Figure imgf000004_0002
wherein: R3 and R4, which may be the same or different, each represents an unsubstituted or halo-substituted C1 to C20 hydrocarbyl group; R represents a hydrogen atom or an unsubstituted or halosubstituted C1 to C20 hydrocarbyl group; and R6 represents an unsubstituted or halo-substituted C1 to C20 hydrocarbylene group;
(vi) a C1 to C20 polyene containing at least one olefinically unsaturated group to which are bonded at least two hydrogen atoms; or
(vii) an acetylenic compound of the general formula: R7C ≡ CR8 wherein: R7 represents a hydrogen atom or a C1 to C20 hydrocarbyl group; and
R8 represents a hydrogen atom or a polymerisable unsaturated group containing C2 to C20 hydrocarbyl group Examples of such donor monomers include ethylene, propylene, butene-1, butene-2, isobutylene, pentene-1, pentene-2, 2-methylbutene-1. 3-methylbutene-l, 2-methylbutene-2, hexene-1, hexene-2, hexene-3 , 2-methylpentene-l, 4-methylpentene-l, 2-methylpentene-2, 3-methylpentene-2, heptene-1, heptene-2, heptene-3, 4-methylhexene-1, 3-methylhexene-3, octene-1, decene-1, decene-2, dodecene-1, octadecene-1, octadecene-2; styrene, α-methylstyrene, β-methylstyrene, m-methylstyrne, p-methylstyrene, β-ethylstyrene, allylbenzene, isopropenylbenzene, 4-phenylbutene-l, 4-phenylbutene-2, 5-phenylρentene-2, α-butylstyrene, dihydronaphthalene, vinylnaphthalene, trans-stilbene; 1-methylenecyclobutane, vinylcyclobutane, cyclopentene, vinylcyclopentane, cyclohexene, vinylcyclohexane, norbornene-2; butadiene, isoprene, 1, 3-pentadiene, 1, 4-pentadiene, 1,3-hexadiene, 1,4-hexadiene; acetylene, methylacetylene, ethylacetylene, hexyne-1, phenylacetylene, cyclohexylacetylene, vinylacetylene, divinylacetylene, hexen-1- yne-4, butenylmethylacetylene, allylethylacetylene, allylcyclohexylacetylene; vinyl chloride, vinyl bromide, allyl chloride, allyl bromide, 2-chloropropene-l, 2- (chloromethyl)propene-l, 2-chlorobutene-l, 2-chlorallyl chloride, 3-chlorobutene-l, 4-chlorobutene-l, methallyl chloride, 4,4,4-trichlorobutene,
3-bromopentene-l, 2, 4-dichloropentene-l, 1, 5-dichloropentene-2, l-chloromethylbutene-2, l-chloro-3-methylbutene-2, 2-bromododecene-l, p-chlorostyrene, o-chlorostyrene, m-chlorostyrene, m-bromostyrene, p-fluorostyrene, p-(chloromethyl) styrene, 2, 4-dichlorostyrene, 2, 6-dichlorostyrene, 2, 4-difluorostyrene, 2, 6-difluorostyrene,
3-(trifluoromethyl) styrene, α-chloro:-p-methylstyrene, α-bromostyrene α-chlorostyrene, p-bromo-α-chlorostyrene,α-(bromomethyl) styrene, α-(chloromethyl)styrene, p-chloro-α-methylstyrene, 2,3-dichloro-α-methylstyrene, α-ethyl-m-(trichloromethyl)styrene, p-chloroallylbenzene, 1-chloro-l-benzylethylene, 1, l-bis(p-chlorophenyl)-ethylene, 4-chloro-l-vinylnaphthalene, 1-chloro-l-cyclohexylethylene.
Suitable (thio)ethers, (thio)esters or (thio)amides have the general formula:
Figure imgf000006_0001
wherein: R9 represents an unsubstituted or substituted C1 to C20 hydrocarbyl group; R10represents a polymerisable unsaturated group containing C2 to C20 hydrocarbyl group; R11 represents a C1 to C20 hydrocarbylene group; R12 represents a hydrogen atom or a C1 to C20 hydrocarbyl group;
Z represents an oxygen or sulphur atom; Y represents an oxygen or sulphur atom or an -NR12 group; and m represents zero or 1. Examples of such donor monomers include vinyl acetate, vinyl propionate, vinyl pelargonate, vinyl-2-ethyl- hexanecarboxylate, vinyl stearate, ethylvinyl oxalate, vinyl chloroacetate, vinyl thiolacetate, vinyl benzoate, vinyl cyclohexanecarboxylate, vinyl-norbornane-2-carboxylate, allyl acetate, allyl laurate, allyl cyclobutanecarboxylate,
2-chloroallyl acetate, isopropenyl acetate, α -methallyl acetate, 1-propenyl acetate, 1 Bobutenyl butyrate, N-vinylacetamide, N-allyl-N-methyl-propionic acide amide, N-vinylbenzoic acid amide, N-vinylthioacetamide, N- vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam and vinyl ether. Mixtures of two or more donor monomers may be used in which case the different donor monomer residues will be distributed in a random manner as the alternating donor monomer residues in the copolymer chain.
Acceptor monomers include those unsaturated compounds which form a complex with a Lewis acid. Preferred such compounds include olefinically unsaturated compounds having a (-R) substituent conjugated with an unsaturated bond.
Suitable olefinically unsaturated compounds have the general formula:
RI CH=CRIIQ wherein:
RI and RII, which may be the same or different, each represents a hydrogen or halogen atom or an unsubstituted or halo-substituted C1 to C20 hydrocarbyl group, with the proviso that at least one of R and R represents a hydrogen atom; and
Q represents a nitrile group or a group of the formula:
Figure imgf000007_0001
wherein:
Y' represents a group of the formula Z"R' ,
Figure imgf000007_0002
NR"R'" or R"", Z' and Z" , which may be the same or different, each represents an oxygen or sulphur atom,
R' , R" , R" ' or R"", which may be the same or different, each represents a hydrogen atom or a C1 to C20 hydrocarbyl group, with the proviso that R"" may also represent a halogen atom and R" and R'" may, together with the nitrogen atom to which they are bonded, represent an N-linked heterocyclic group, and
Me represents a salifying metal of valency n.
Examples of such acceptor monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, n-amyl acrylate, n-octylacrylate, octadecyl acrylate, allyl acrylate, o-toluyl. acrylate, benzyl acrylate, cyclohexyl acrylate, 2-chlorethyl acrylate, β-chloroallyl acrylate, methyl α-chloroacrylate, methyl a-bromo acrylate, methylα-(p- chlorophenyl) acrylate, ethyl α -chloroacrylate, methyl thiolacrylate, ethyl thiolacrylate, methyl thionacrylate, methyl di-thioacrylate, acrylonitrile, acrylamide, thioacrylamide, N-methylacrylamide, N-n-butylacrylamide, N-n-octylacrylamide, N-2-ethylhexyl acrylamide, N-stearyl acrylamide, N-cyclohexyl acrylamide, N-toluyl acrylamide, N-methyl thioacrylamide, N,N-dimethyl acrylamide, N-methyl- N-ethyl acrylamide, N, N-di-n-butylacrylamide, acrylyl morpholine, acrylyl pyrrolidine, N,N-dimethylthioacrylamide, acryloyl chloride, acryloyl bromide, thioacryloyl chloride, acrylic acid, thiolacrylic acid, thionacrylic acid, dithioacrylic acid, sodium acrylate, potassium acrylate, zinc acrylate, aluminium acrylate, ammonium acrylate, acrolein, methylvinylketone, ethylvinylketone, phenylvinylketone, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octadecyl methacrylate, benzyl methacrylate, phenyl methacrylate, toluyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, methyl thiolmethacrylate, ethyl thiolmethacrylate, methyl α-ethylacrylate, ethyl α-butylacrylate, methyl α-cyclohexylacrylate, methyl α-phenylacrylate, methacrylamide, N-ethyl methacrylamide, N-cyclohexyl methacrylamide, N,N-dimethyl methacrylamide, methacrylyl piperidine, α-ethylacrylamide, α-chloroacrylamide, α-chloromethyl acrylamide, methacryloyl chloride, α-chloroacryloyl chloride, α-ethylmethacryloyl chloride, methacrylic acid, thiolmethacrylic acid, sodium methacrylate, zinc methacrylate, aluminium methacrylate, ammonium α-fluoroacrylate, methacrolein, methylisopropenylketone, 1-chloro-butenyl-ethylketone, methacrylonitrile, o-ethylacrylonitrile, α-cyclohexylacrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, methyl crotonate, ethyl crontonate, n-butyl crotonate, phenyl crotonate, crotonamide, crotonoyl chloride, crotonitrile, methyl cinnamate, butyl cinnamate, chloromethyl cinnamate, cinnamic nitrile, methyl β - ethylacrylate and methyl β-chloromethylacrylate.
If there are two conjugated electron withdrawing groups they should both be on the same carbon atom.
Mixtures of two or more acceptor monomers may be used in which case the different acceptor monomers will be distributed in a random manner as alternating acceptor monomer residues along the copolymer chain.
It is preferred to use equivalent proportions of donor and acceptor monomers. Any stoichiometric excess of either monomer will usually remain unchanged although in some cases slight formation of homopolymer may take place.
The transmition metal complex (i) may be any such complex stabilised in a low oxidation state, typically
0 or +I, by a π-acid ligand. Generally the transition metal will be Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni , Pd or Pt, notably Cr, Mo, W, Mn, Re, Fe, Co, Ni and Pt, especially Mn, Re and Ni. Suitable ττ-acid ligands are organometallic such ligands and mono- or polydentate alkyl and aryl phosphines and phosphites, and mono- and polydentate pyridines. Examples of organometallic such ligands include carbonyl, alkyl and aryl isocyanides, and organic compounds, notably hydrocarbons, comprising acetylenic, olefinicand aromatic unsaturation.
In the transition metal complexes (i) one or more such π-acid ligands may be present. Other ligands may also be present.
Examples of such transition metal complexes include
Cr(CO)6; (CO)4Cr (PMe2)2 Cr(CO)4 ; (CO)5 Cr PMe2 PMe2 Cr(CO)5 ;
Mo(CO)6; Mo(CO)5 Py; (CO)4 Mo(PMe 2)2 Mo(CO)4 ; (CO)5 MoPMe2 PMe2 Mo (CO)5: (CO)5MoPEt2 PEt2 Mo(CO)5; W(CO)6; Cr(CNAr)6; Mo(CNAr)6; W(CNAr)6; Mn2(CO)10; (C5H5 )Mn(CO)3 ; Re2(CO)10; Re2(co)8 (PPh3)2; Re(CO)3(PPh3)2; Fe(CO)5; Fe(CO)4 (PPh3 ); Fe(CO)5 (PPh3)2 (CO)3 Fe(PMe2)2 Fe(CO)3; (CO)3 BrFe(PMe2)2
FeBr(CO)3; (CO)4 FePMe2PMe2- Fe(CO)4; (CO)3Fe(PMe2)2Fe(CO)2 (PPh3); (CO)3 Co (PPh2)2- Co (CO)3; Co (Co)6(PhC=CCOOMe);
;
Figure imgf000010_0001
The organic compound (ii) may be any compound from which a chlorine or bromine atom may be removed during the reaction.
In general bromo compounds are more active than chloro compounds and activity is greatest in those compounds having more than one chlorine or bromine atom on one carbon atom or in which a further electron withdrawing substituent is adjacent to the halogenated carbon atom. Examples of such compounds are compounds containing CCI3 or CBr3 groups, such as CCI4, CHCI3,
CHBr3, trichloracetic acid and esters thereof, for example ethyl chloroacetate; compounds containing CBr2 and CBr groups, such as α -(di)-bromoketones and benzyl bromide. Compounds containing NCI or NBr groups, for example N-chloro. or
N-bromo amides or amides, such as N-bromosuccinimide and N-chloro-substituted nylon may also be used.
Saturated fluorine compounds containing no chlorine or bromine are inactive; iodine compounds have a propensity to liberate molecular iodine which acts as a retarder. Chlorine and bromine-containing donor or acceptor monomers may also serve as component (ii).
However, fluorine compounds in which at least one fluorine atom is bonded to an unsaturated carbon atom such as mono- or poly-fluoro olefins, are effective photoinitiators, although fluorine is not removed during reaction; rather the fragment of (i) arising from the photolysis adds to the fluorine compound to give a free radical; for example Mn2(CO)10 with CF2=CF2 may give the reactive species (CO)5 MnCF2CF2. Other photoinitiating compounds (ii) in which halogen is not removed are organic compounds comprising an acetylenic bond or an ethylenic bond conjugated with one or more (-R) groups. Examples include acetylene and acetylene mono and dicarboxylic acids and their esters, such as acetylenedicarboxylic acid and dimethylacetylenedicarboxylate; olefinic mono and dicarboxylic acids, their esters and anhydrides, such as diethylfumarate, diethyl maleate and maleic anhydride.
The Lewis acid (iii) suitably has the general empirical formula:
Figure imgf000011_0001
wherein:
M represents an aluminium or boron atom;
Rv represents a hydrocarbyl group;
X represents a fluorine, chlorine or bromine atom; and n represents zero or any number, including fractional numbers, up to and including three; or comprises a mixture of a Group IIB, IIIB or IVB organometallic compound with a Group IIIB or IVB halide.
Examples include methylaluminium dichloride, ethylaluminium dichloride, isobutylaluminium dichloride, hexylaluminium dichloride, dodecylaluminium dichloride, phenylaluminium dichloride, cyclohexylaluminium dichloride, methylaluminium dibromide, allylaluminium dichloride, ethylaluminium sesquichloride, ethylaluminium sesquibromide, methylaluminium sesquichloride, diethylaluminium chloride, ethylphenylaluminium chloride, dicyclohexylaluminium chloride, methylboron dichloride, ethylboron dichloride, butylboron, dichloride, hexylboron dichloride, dodecylboron dichloride, phenylboron dichloride, benzylboron dichloride, cyclohexylboron dichloride, diethylboron bromide, dipropylboron chloride, dibutylboron chloride, dihexylboron chloride, ethylvinylboron chloride, dicyclopentadenylboron chloride, trimethylaluminium, triethylaluminium, tripropylaluminium, tributylaluminium, trihexylaluminium, tridecylaluminium, triphenylaluminium, tricyclohexylaluminium, tribenzylaluminium, trimethylboron, triethylboron, tributylboron, trihexylboron, diethylphenylboron, diethyl p-toluylboron, tricyclohexylboron, aluminium trichloride, aluminium tribromide, boron trichloride, boron trifluoride, boron tribromide, and one or more of diethylzinc, ethylziήc chloride, diethylcadmium, diethylmercury, diphenylmercury, triethylboron, tributylboron, tricyclohexylboron, ethylboron bromide, triethylaluminium, tributylaluminium, trihexylaluminium, tricyclohexylaluminium, vinyldiethylaluminium, diethylaluminium chloride, ethylaluminium. sesquichloride, ethylaluminium dichloride, trimethylgallium, triethylgallium, triethylindium, tetraethylgermanium, tetramethyltin, tetraethyltiή, tetraisobutyltin, dimethyldiethyltin, tetraphenyltiri, tetrabenzyltin, diethyldiphenyltin, triethyltin chloride, diethyltin dichloride, ethyltin trichloride, tetramethyllead, tetraethyllead, dimethyldiethyllead, and triethyllead chloride, mixed with one or more of boron trichloride, boron trifluoride, boron triboromide, boron triiodide, ethylboron. dichloride, diethylboron chloride, aluminium trichloride, aluminium tribromide, aluminium triiodine, partially fluorinated aluminium chloride, ethylaluminium dichloride, methylaluminium dibromide, ethylaluminium sesquichloride, diethylaluminium chloride, gallium trichloride, gallium dichloride, germanium tetrachloride, tin tetrachloride, tin tetrabromide, ethyltin trichloride, methyltin trichloride, phenyltin trichloride, dimethyltin dibromide, diethyltin dichloride, diisobutyltin dichloride, triethyltin chloride, lead tetrachloride, and diethyllead dichloride.
The process is suitably effected in absence of oxygen, conveniently in vacuum or under a blanket of an inert gas, for example nitrogen.
It is preferred to operate the process in an inert solvent, for example a hydrocarbon such as toluene. The copolymer may be isolated by any conventional method, for example by precipitation by a non-solvent such as methanol. In order to obtain an acceptable rate of copolymerization it is desirable in some cases to use a slightly elevated temperature, for example between 60º and 100º. Organometallic derivatives of molybdenum are especially suitable for use within this temperature range, while those of nickel may have sufficient activity for use down to ambient temperatures.
Alternatively the rate of polymerization may be increased by irradiating the process mixture with ultra-violet light.
Irradiation by light of λ = 436 nm is suitable for a copolymer- ization catalysed by an organometallic derivative of manganese, while light of λ = 365 nm is more suitable for use with a rhenium derivative. With photoinitiation, temperatures below OoC are also suitable.
In favourable cases an initial copolymerization rate of 1.5% per minute may be obtained.
Suitable concentrations of either monomer in the process mixture are up to 2 mol per litre.
Suitable amounts of catalyst will depend on the activity of the catalyst chosen but amounts down to 0.002 mol % of monomer may be used in favourable cases.
Suitable amounts of the compound (ii) will depend on the activity of the compound and also on the nature of the transition metal complex (i). Carbon tetrachloride may be used in amounts down to 0.5 mol % of monomer, but with carbon tetrabromide this may be reduced to 0.05 mol %.
Amounts of Lewis acid (iii) down to 5 mol % of monomer may be used.
As noted earlier component (ii) may itself comprise a polymer which comprises at least one carbon-halogen bond. Such polymers can be produced by free radical polymerization, which may proceed in accordance with the invention or conventionally, in the presence of a monomeric organic compound comprising at least one carbonhalogen bond. A halogen-containing fragment of the organic compound will be present as a terminal group in a homopolymer or a random or alternating copolymer. Two examples will make this clear:
(a) methyl methacrylate free radically homo polymerised by heat in the presence of peroxide and CBr4 will give:
Figure imgf000014_0001
(b) styrene and methylacrylate free radically polymerised in accordance with this invention in the presence of CC14 and :
Figure imgf000014_0002
Figure imgf000014_0003
Such polymers can also be produced, with a plurality of pendant halogen-containing groups, by homo- or random or alternating copolymerising olefinically unsaturated monomers containing them; for example vinyl trichloracetate can be homo- polymerised to:
Figure imgf000014_0004
(wherein Ph represents a phenyl group and n represents a number at least 2). In accordance with a further aspect of this invention, therefore, there is provided a block or graft alternating copolymer prepared by the process of the invention and utilising, as component (ii) a polymer as hereinabove defined. Such polymers may comprise one or a plurality of alternating blocks, for example: AAAAACBr2BDBDBD ...
...AAABABBAABCBr2DEDEDE... ABABABCBr2DEDEDE... or may comprise grafts with alternating branches, for example
Figure imgf000015_0001
These branches may cross-link the backbone chains.
The copolymers obtained are similar in arrangement of the monomer residues, in tacticities and in general properties, to those obtained by the conventional use of peroxide catalysts in presence of Lewis acids.
The copolymers are of utility in a number of ways. Control of the regularity of the copolymerization may provide copolymers of desired physical or chemical properties in greater consistency. Furthermore copolymers in which reactive groups are distributed regularly rather than at random may facilitate the manufacture of copolymers containing groups which may confer a variety of useful properties on the copolymer.
The invention is illustrated but not limited by the following Examples. Example 1
4.6 ml toluene, 1.04 g styrene, 2.58 g methylacrylate, 0.15 g carbon tetrachloride, 0.2 g Al2Et3Cl3 and 0.0011 g Mn2(CO)10 were mixed in a glass tube which was then cooled in liquid nitrogen. The mixture was degassed by repeated freezing, evacuating and melting whereafter it was finally cooled in liquid nitrogen, and the tube evacuated and sealed. The tube was next allowed to warm to to room temperature and then irradiated at 25ºC by light of λ. = 436 nm (from a 250 watt high-pressure mercury arc) for 10 minutes. The product mixture was poured into excess methanol to give 0.26 g of alternating copolymer collected by filtration.
The structure was confirmed by nmr examination and elemental analysis. Example 2 The procedure in Example 1 was repeated with 4.1 ml toluene, 3.12 g styrene, 0.86 g methylacrylate, 0.15 g carbon tetrachloride, 0.2 g Al2Et3Cl3 and 0.0011 g Mn2(CO)10. The same product was obtained with a yield of 0.37 g.
Example 3 The procedure in Example 1 was repeated with 100 ml toluene, 4.2 g of styrene, 3.4 g of methylacrylate, 1.54 g of carbon tetrachloride, 1.23 g of Al2Et3Cl3 and 0.011 g of Mn2(CO)10. The degassed mixture was irradiated at 25ºC by light of λ = 436 nm for
0.5 hours. 3-0 g of alternating copolymer was collected by filtration. The structure was confirmed by elemental analysis and nmr examination.
Comparative experiments in which Mn2(CO)10 and/or CC14 were omitted gave 0.2 g of copolymer.
Example 4 100 ml of toluene, 4.2 g of styrene, 3.4 g of methyl acrylate, 1.54 g of carbon tetrachloride, 1.84 g of Al2Et3Cl3 and 0.0038 g of Ni(C0)o
Figure imgf000016_0001
were mixed, and degassed as described in Example 1. tube was sealed off and allowed to warm up to 25ºC. The reaction mixture was held at 25ºC for 0.5 hour without irradiation and then poured into excess methanol to give 3.0 g of alternating copolymer.
Example 5 The procedure in Example 4 was repeated with 100 ml toluene,
4.2 g of styrene, 3.4 g of methylacrylate, 0.5 g of Al2Et3Cl3 and
0.0038 g of Ni(C0) The degassed mixture was held at
Figure imgf000016_0002
25ºC for 0.5 hour, without irradiation and then poured into excess methanol to give 0.3 g of alternating copolymer. When the nickel derivative was omitted no copolymer was precipitated.
Example 6 The procedure in Example 1 was repeated with 5.3 ml toluene, 1.04 g styrene, 1.59 g acrylonitrile, 0.15 g carbon tetrachloride, 0.2 g Al2Et3Cl3 and 0,0011 g Mn2(CO)10. The yield of alternating copolymer was 0.20 g.
Example 7 The procedure in Example 1 was repeated with 4.3 ml toluene, 3-12 g styrene, 0.53 g acrylonitrile, 0.15 g carbon tetrachloride, 0.2 g Al2Et3Cl3 and 0.0011 g Mn2(CO)10. The yield of alternating copolymer was 0.28 g.
Example 8 Repetition of the procedure of Example 1 using 100 ml toluene, 3-4 g of methylacrylate, 2.2 g of butadiene, 1.54 g of carbon tetrachloride, 2.5 g of Al2Et3Cl3 and 0.078 g of Mn2(CO)10 afforded after irradiation for 1 hour 1.23 g of alternating copolymer. Omission of the manganese led to no copolymer.

Claims

1. A process for the preparation of a copolymer comprising sequences of alternating monomer residues, which process comprises reacting at least one donor monomer with at least one acceptor monomer in the presence of: (i) a transition metal complex comprising at least one π -acid ligand; (ii) an organic compound, which may be a polymer, comprising at least one carbon-halogen bond, an acetylenic or an ethylenic bond conjugated with one or more electron attracting (-R) groups; and
(iii) a Lewis acid.
2. A process according to Claim 1 wherein at least one donor monomer is a mono- or poly-unsaturated compound having no (-R) group conjugated with the or each unsaturated bond and having at most one (-1) group bonded to any given unsaturated carbon atom.
3. A process according to Claim 2 wherein the mono- or polyunsaturated such compound is an unsubstituted or substituted hydrocarbon, a (thio)ether, (thio)ester or a (thio)amide.
4. A process according to Claim 3 wherein the unsubstituted or substituted hydrocarbon is:
(iv) a terminal olefinically unsaturated compound of the general formula:
Figure imgf000018_0001
wherein: R1 and R2, which may be the same or different, each represents a hydrogen or halogen atom or an unsubstituted or halo substituted C to C hydrocarbyl group, with the proviso that both R1 and R2 cannot be halogen atoms;
(v) an internal olefinically unsaturated compound of the general formula:
Figure imgf000018_0002
wherein:
R3 and R4, which may be the same or different, each represents an unsubstituted or halo-substituted C1 to C20 hydrocarbyl group; Re represents a hydrogen atom or unsubstituted or halosubstituted C1 to C20 hydrocarbyl group; and
Rr represents an unsubstituted or halo-substituted C1 to C20 hydrocarbylene group;
(vi) a C4to C30 polyene containing at least one olefinically unsaturated group to which are bonded at least two hydrogen atoms; or
(vii) an acetylenic compound of the general formula:
R7C = CR8 wherein:
R7 represents a hydrogen atom or a C1 to C20 hydrocarbyl group; and
Ro represents a hydrogen atom or a polymerisable unsaturated group containing C2 to C20 hydrocarbyl group.
5. A process according to Claim 4 wherein the unsubstituted or substituted hydrocarbon is specifically disclosed herein.
6. A process according to Claim 3 wherein the (thio) ether, thio (ester) or (thio) amide has the general formula:
Figure imgf000019_0001
wherein:
Rq represents an unsubstituted or substituted C1 to C20 hydrocarbyl group; R10 represents a polymerisable unsaturated group-containing C2 to C20 hydrocarbyl group; R11 represents a C1 to C20 hydrocarbylene group; R12 represents a hydrogen atom or a C1 to C20 hydrocarbyl group; Z represents an oxygen or sulphur atom; Y represents an oxygen or sulphur atom or an -NR12 group; and m represents zero or 1.
7. A process according to Claim 6 wherein the (thio) ether,
(thio) ester or (thio) amide is specifically disclosed herein.
8. A process according to any preceding claim wherein at least one acceptor monomer is an unsaturated compound which forms a complex with a Lewis acid.
9. A process according to Claim 8 wherein the unsaturated compound is an olefinically unsaturated compound having a (-R) substituent conjugated with an unsaturated bond.
10. A process according to Claim 9 wherein the olefinically unsaturated compound has the general formula: RI CH = CRIIQ wherein :
RI and RII , which may be the same or different, each represents a hydrogen or halogen atom or an unsubstituted or halo-substituted C1 to C20 hydrocarbyl group, with the proviso that at least one of RI and RII represents a hydrogen atom; and
Q represents a nitrile group or a group of the formula:
Figure imgf000020_0001
wherein: Y' represents a group of the formula Z"R' ,
Figure imgf000020_0002
NR"R"', or R"", Z' and Z", which may be the same or different, each represents an oxygen or sulphur atom,
R' , R", R" ' or R"", which may be the same or different, each represents a hydrogen atom or a C1 to C20 hydrocarbyl group, with the provisos that R"" may also represent a halogen atom and R" and R"' may, together with the nitrogen atom to which they are bonded, represent an N-linked heterocyclic group, and Me represents a salifying metal of valency n.
11. A process according to Claim 10 wherein the olefinically unsaturated compound is specifically disclosed herein.
12. A process according to any preceding claim wherein the transition metal complex (i) is of Cr, Mo, W, Mn Re, Fe, Ru, Os, Co, Ch, Ir, Ni, Pd or Pt.
13. A process according to any preceding claim wherein the transition metal complex (i) comprises a IT-acid ligand which is carbonyl, an alkyl or aryl isocyanide, a mono- or polydentate alkyl or aryl phosphine or phosphite, a mono- or polydentate pyridine or an acetylenically, olefinically or aromatically unsaturated hydrocarbon.
14. A process according to any preceding claim wherein the organic compound (ii) has a plurality of chlorine or bromine atoms on one carbon atom or has a (-1) or (-R) group adjacent to that carbon atom.
15. A process according to any preceding claim wherein the donor monomer and organic compound (ii) are the same,
16. A process according to any preceding claim wherein the reaction mixture is heated.
17. A process according to any preceding claim wherein the reactant mixture is irradiated with ultra-violet light.
18. A process according to Claim 17 wherein the organic compound (ii) has at least one fluorine atom bonded to an unsaturated carbon atom or an acetylenic bond or an ethylenic bond conjugated with one or more (-R) groups.
19. A process according to any preceding claim which is effected in the absence of oxygen.
20. An alternating copolymer whenever prepared by the process of any of the preceding claims.
21. A block or graft alternating copolymer.
PCT/GB1980/000188 1979-11-02 1980-10-31 Catalysed alternating copolymerisation and product WO1981001289A1 (en)

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US5043408A (en) * 1989-06-26 1991-08-27 Sumitomo Chemical Company, Limited Ethylene-aromatic vinyl compound alternating copolymer and process for the production thereof
US5100756A (en) * 1989-08-21 1992-03-31 Brother Kogyo Kabushiki Kaisha Image forming medium coated with microcapsules having photocurable composition
US5670587A (en) * 1993-07-23 1997-09-23 Idemitsu Kosan Co., Ltd. Catalyst for producing aromatic vinyl compound-based polymer composition and process for producing aromatic vinyl compound-based polymer composition using same

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Publication number Priority date Publication date Assignee Title
US5280077A (en) * 1992-07-14 1994-01-18 Air Products And Chemicals, Inc. Process for the synthesis of oligomeric vinylamines

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GB1460040A (en) * 1972-12-27 1976-12-31 Sumitomo Chemical Co Process for producing liquid polymers

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GB1460040A (en) * 1972-12-27 1976-12-31 Sumitomo Chemical Co Process for producing liquid polymers

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CHEMICAL ABSTRACTS, Volume 83, No. 16, issued October 20, 1975, (Columbus, Ohio, US), KAMEDA: "Polymerization of Styrene in a Tris (Triphenylphosphine) Chlororhodium (1)-Organic Halyd System", see page 6, column 1, Abstract No. 13201d, Nippon Kagaku Kaishi 1975, (1), 184-7 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5043408A (en) * 1989-06-26 1991-08-27 Sumitomo Chemical Company, Limited Ethylene-aromatic vinyl compound alternating copolymer and process for the production thereof
US5100756A (en) * 1989-08-21 1992-03-31 Brother Kogyo Kabushiki Kaisha Image forming medium coated with microcapsules having photocurable composition
US5670587A (en) * 1993-07-23 1997-09-23 Idemitsu Kosan Co., Ltd. Catalyst for producing aromatic vinyl compound-based polymer composition and process for producing aromatic vinyl compound-based polymer composition using same

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