EP1064317A1 - Copolymerisats de monoxyde de carbone derivatises - Google Patents

Copolymerisats de monoxyde de carbone derivatises

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Publication number
EP1064317A1
EP1064317A1 EP99907594A EP99907594A EP1064317A1 EP 1064317 A1 EP1064317 A1 EP 1064317A1 EP 99907594 A EP99907594 A EP 99907594A EP 99907594 A EP99907594 A EP 99907594A EP 1064317 A1 EP1064317 A1 EP 1064317A1
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EP
European Patent Office
Prior art keywords
carbon monoxide
copolymers
monoxide copolymers
compounds
derivatized
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EP99907594A
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German (de)
English (en)
Inventor
Joachim Queisser
Michael GEPRÄGS
Bernhard Rieger
Roland Wursche
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F281/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having carbon-to-carbon triple bonds as defined in group C08F38/00
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds

Definitions

  • the present invention relates to derivatized carbon monoxide copolymers.
  • the invention further relates to a process for the preparation of these carbon monoxide copolymers and their use for the production of graft copolymers.
  • the invention relates to graft copolymers, a process for the preparation of these copolymers and their use for the production of moldings, fibers, films and coatings and their use as phase mediators in polymer mixtures or as a coating component.
  • the invention relates to the use of functionalized carbon monoxide copolymers for the production of derivatized carbon monoxide copolymers.
  • Carbon monoxide copolymers can now be produced from carbon monoxide and ⁇ -olefins such as ethene or propene in the form of strictly alternating linear copolymers catalyzed by transition metals.
  • Suitable catalyst systems are based on palladium complexes chelated with bidentate phosphine ligands (cf. EP-A-0 121,965 and J. Organomet. Chem., 1991, 417, p. 235).
  • Conventional carbon monoxide / ethene or carbon monoxide / ethene / propene copolymers can generally be understood as polymeric materials with a range of thermoplastic properties. They are characterized by good mechanical properties e.g. in impact resistance and abrasion as well as good chemical resistance.
  • Japanese patent applications JP-A 22 32 338 and JP-A 62 26 925 describe the catalytic reduction of alternating carbon monoxide copolymers to 1,4-polyalcohols.
  • the reaction with nitrogen-containing nucleophiles to carbon monoxide / ethene / propene terpolymers with 2,5-pyrrole units is known from the publication US 1346-H.
  • the Mannich reaction can also be carried out on carbon monoxide copolymers 2 as the halogenation of the methylene unit (cf. US 4,424,317 and US 4,616,072).
  • the object of the present invention was therefore to find carbon monoxide copolymers which can be derivatized without problems, without side reactions and molecular weight degradation occurring.
  • the invention was also based on the object of developing derivatized carbon monoxide copolymers which are also suitable for further subsequent reactions.
  • derivatized carbon monoxide copolymers obtainable by reacting functionalized linear strictly alternating carbon monoxide copolymers from carbon monoxide, have at least one 1-alkene (A), where (A) is an aryl compound substituted with at least one terminal allyl or homoallyne unit and at least one hydroxyl or amino group, or an ⁇ represents olefinically unsaturated aliphatic alcohol, and optionally at least one C 1 -C 4 -alkene (B) with an organic compound (C) which has at least one reactive electrophilic group, found in an aprotic organic solvent.
  • graft copolymers Furthermore, graft copolymers, a process for the preparation of these copolymers and their use for the production of moldings, fibers, films and coatings and their 3
  • Suitable functionalized carbon monoxide copolymers which are available here for derivatization reactions, are based on linear alternating carbon monoxide copolymers made of carbon monoxide, at least one 1-alkene (A), one with at least one terminal allyl and / or homoallyne unit and with at least one hydroxy and / or amino group substituted aryl compound or an ⁇ -olefinically unsaturated aliphatic alcohol, and optionally at least one C 2 - to C 20 -1-alkene (B).
  • A 1-alkene
  • B optionally at least one C 2 - to C 20 -1-alkene
  • Y is a compound of the general formula (II)
  • R 1 is hydrogen, linear and branched C 1 to C 10 alkyl, preferably C 1 to C 6 alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, in particular methyl, C 3 - to Cio-cycloalkyl, preferably C 3 to C 6 cycloalkyl, such as cyclopropyl or cyclohexyl, C 6 to Cio-aryl, preferably C 6 to Cio-aryl, in particular phenyl, and
  • R 2 independently of one another hydrogen, linear and branched C 1 -C 10 -alkyl, preferably C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, in particular methyl, C 3 - to Cio-cycloalkyl, preferably C 3 - to C ö -cycloalkyl, such as cyclopropyl or cyclohexyl, C $ - to Ci 4 -aryl, preferably C 6 - to Cio-aryl, especially phenyl, or halogen, such as fluorine, Chlorine, bromine, iodine mean and
  • Q is independently linear or branched C ⁇ ⁇ bis
  • Cio-alkyl preferably C 1 ⁇ to C ⁇ -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl or t-butyl, in particular methyl, i-propyl or t-butyl, C 3 - to Cio-cycloalkyl, preferably C 3 - to C 6 cycloalkyl, such as cyclopropyl or cyclohexyl, C 6 ⁇ C to 4 ⁇ aryl, preferably C 6 - to C ⁇ 0 aryl, especially phenyl, aralkyl having from 1 to 6, preferably 1 to 3 C atoms in the alkyl part, and 6 to 14, preferably 6 to 10 C atoms in the aryl part, for example benzyl, or C 3 - to C 3 o ⁇ organosilyl, for example trimethyl, triethyl, tri isopropyl
  • o an integer from 0 to 4 mean with
  • p denotes an integer from 0 to 6
  • Particularly suitable are those compounds (A) which have a terminal allyl unit, i.e. Compounds of the formulas (Ia) and (Ib) in which q 1.
  • these olefinic monomers preference is again given to those whose terminal allyl unit is located in the ortho position to a hydroxyl or amino group.
  • Naphthyl compounds with an allyl unit in the 1-position and one of the polar groups mentioned in the 2-position or with an allyl unit in the 2-position and a polar group in the 1- and / or 3-position and in particular allylphenyl compounds with one or two orthostane polar groups to the allyl unit.
  • the polar groups X are the hydroxyl and the primary amino group.
  • Suitable compounds are e.g. 2-allylphenol, 2-allyl-p-hydroquinone, 3-allyl-o-hydroquinone, 2-allylaniline, 2-allyl-4-aminophenol or 3-allyl-4-aminophenol, in particular 2-allylphenol.
  • compounds (A) which have more than two or three polar groups X on the phenyl ring (compounds of the formula (Ia)) and more than three or four polar groups on the naphthyl ring (compounds of the formula (Ib)), as long as there is a terminal allyl or homoallyne unit in the aryl derivative.
  • a plurality of allyl or homoallyne units, preferably allyl units can also be bound to the aryl derivative at the same time (a maximum of 5 for compounds of the formula (Ia) and a maximum of 7 for compounds (Ib)), provided that the aromatic skeleton still has a polar group X.
  • Terminal allyl or homoallyne units also include those radicals whose hydrogen radicals, apart from the terminal ones, are independent of one another, for example by Alkyl groups such as methyl, ethyl or isopropyl, aryl groups such as phenyl, aralkyl groups such as benzyl or halogens such as fluorine or chlorine are substituted. Examples include isopropylidene or isobutylidene units. However, unsubstituted allyl and homoallyne units, in particular allyl units, are preferred.
  • the compounds (A) can have further radicals on the aromatic system.
  • the radicals Q described at the outset can be used as substituents.
  • the residues Q in (A) can be identical or different. If the valences on the aromatic ring systems of the formulas (Ia) and (Ib) are not already saturated by the radicals X, Y or Q, they are saturated by hydrogen atoms (CH bonds).
  • Suitable compounds (A) therefore also include 2-allyl-4-methylphenol, 2-allyl-4-t- 6 butylphenol, 2-allyl-6-methylphenol, 2-allyl-4-phenylphenol, 2-allyl-4, 6-dimethylphenol, 2, 6-dimethyl-4-allylphenol, 2-allyl-4-t -butyl-6-methyl-phenol, 2,6-di-t-butyl-4-allyl-phenol, 2-allyl-6-methylaniline, 2-allyl-4-methylaniline or 2-allyl-4-t-5 butylaniline.
  • Suitable 1-alkenes (A) are ⁇ -olefinically unsaturated aliphatic alcohols. These are, in particular, terminal alcohols with a substituted or unsubstituted one
  • 10 C 2 - to Co ⁇ alkylene chain for example allyl alcohol, 3-butene-l-ol, 4-pentene-l-ol, 5-hexen-l-ol, 6-heptene-l-ol, 10-undecene-l -ol or 15-hexadecen-l-ol.
  • Particularly suitable are ⁇ -olefinically unsaturated alcohols with a C to Cis alkylene chain, in particular with a C to Cio alkylene chain such as allyl alcohol or
  • ⁇ -olefins 25 bonds of this class of compounds, for example ⁇ -olefins or diolefins with at least one terminal double bond in question.
  • Suitable ⁇ -olefins are, for example, C 2 - to C 2 ol-alkenes, such as ethene, propene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene and mixtures thereof.
  • 1-alkenes 1-alkenes
  • Suitable are e.g. Styrene, ⁇ -methylstyrene, p-methylstyrene or 2-methylstyrene, styrene is preferred.
  • heteroatom-containing compounds such as (meth) acrylic acid esters or amides or vinyl esters such as vinyl acetate are also used as 1-alkenes.
  • Ethene, propene, 1-butene and styrene, in particular propene, are preferred.
  • the aforementioned 1-alkenes can of course also be used in a mixture.
  • functionalized carbon monoxide terpolymers 40 preference is given to using those composed of carbon monoxide, propene and component (A) and of carbon monoxide, ethene and component (A), in which a terminal allyl unit and a hydroxyl or amino group are present in ortho position in (A).
  • the binary functionalized carbon monoxide copolymers are generally regular poly-1, ketones. Especially when using arylderi- 7 vaten (A), in which the allyl and hydroxy units are ortho, the carbon monoxide copolymers obtained can also have semiketal units. These, in turn, can occur both in blocks and statistically distributed along the linear polymer chain.
  • the ratio of ketone to ketal fragments in these cases is usually in the range from 10: 1 to 1: 5, preferably in the range 4: 1 to 1: 1.
  • the structure of the functionalized carbon monoxide copolymers can be determined by means of 1 H-NMR and 13 C-NMR spectroscopy.
  • the average molecular weights M w of the binary carbon monoxide copolymers are usually in the range from 1000 to 3500000 g / mol, preferably in the range from 3000 to 250000 g / mol and in particular in the range from 5000 to 200000 g / mol (measured by the method of gel permeation chromatography (GPC ) at 25 ° C with Microstyragel (Waters) as column material and chloroform as solvent against polystyrene standard).
  • GPC gel permeation chromatography
  • the binary carbon monoxide copolymers are generally distinguished by narrow molecular weight distributions M w / M n (weight average / number average), measured using the gel permeation chromatography (GPC) method analogous to the previous description.
  • M w / M n values are preferably in the range from 1.1 to 3.5 and in particular assume values ⁇ 2.5.
  • Carbon monoxide copolymers with M w / M n values in the range from 1.1 to 2.2 are particularly preferred.
  • the glass transition temperature values (T g values) of the binary carbon monoxide copolymers are usually in the range from 0 to 120 ° C., preferably in the range from 20 to 100 ° C. and in particular from 30 to 85 ° C.
  • the average molecular weights M w are generally in the range from 5000 to 500000 g / mol, preferably from 20,000 to 300,000 g / mol and in particular from 50,000 to 250,000 g / mol.
  • the T g values of the terpolymers are usually in the range from 0 to 150 ° C., preferably in the range below 90 ° C.
  • the proportion attributable to compound (A) in the terpolymers is generally in the range from 0.1 to 60 mol%, based on the carbon monoxide units in the copolymer (determined on the basis of 1 H-NMR spectra). Suitable terpolymers generally have a proportion of 2 to 50, in particular 3 to 40 mol% of component (A) incorporated. In the terpolymers as well as in higher copolymers as well as in the binary systems 8 In addition to pure 1,4-polyketone units, statistically distributed or block-like, but preferably statistically distributed semiketal structures can also be present. This phenomenon is preferably observed when the polar group in (A) is a hydroxy group.
  • the binary and ternary carbon monoxide copolymers described are generally readily soluble in tetrahydrofuran (THF), toluene, dichloromethane or chloroform.
  • the molar ratio of carbon monoxide to the sum of the structural units in the binary or higher carbon monoxide copolymers attributable to the olefinically unsaturated monomers is generally 1: 1.
  • the functionalized carbon monoxide copolymers can also be prepared according to the methods described in EP-A 0 463 689 and in Sen et al. , Macromolecules, 1996, 29, pp. 5852 -5858. The manufacturing processes described in the cited documents are hereby expressly included in the present disclosure.
  • Suitable organic compounds (C) which have one or more reactive electrophilic groups are, for example, aliphatic or aromatic carboxylic acid chlorides or anhydrides.
  • anhydrides both symmetrical such as hexane or heptanoic anhydride, and also mixed anhydrides such as benzoic acid anhydride or propionic acetic anhydride or cyclic carboxylic acid anhydrides such as glutaric anhydride, succinic anhydride, maleic anhydride, succinic anhydride or amine hydroxylated amide or phthalic anhydride, To derivatize carbon monoxide copolymer.
  • Possible reactants for the amide or ester formation include acidic chlorides such as aromatic acid chlorides such as benzoyl chloride and saturated or unsaturated, linear or branched aliphatic acid chlorides such as acetyl, hexanoyl or (meth) acroyl chloride.
  • Acid chlorides of di- or polycarboxylic acids such as oxalyl chloride or hexanedicarboxylic acid dichloride can also be used.
  • the carboxylic acid group itself can also be used as an electrophilic group 9 occur, especially if suitable coupling reagents or reaction mediators are also used.
  • the amide or ester formation between the functionalized carbon monoxide copolymer and the organic compound (C) can be carried out in a weakly acidic or in a weakly basic medium.
  • Basic compounds include Triethylamine, tributylamine, pyridine, quinoline or ammonium hydroxide in question.
  • reaction mediators such as 4-dimethylaminopyridines, imidazolides such as carbonyldimidazole, dicyclyclohexylcarbodimides, 2, 2'-dipyridyldisulfide / triphenylphosphine or 2-pyrididylthiochlorine can also be added.
  • Aromatic as well as aliphatic or cycloaliphatic isocyanates are suitable. Examples include phenyl, cyclohexyl, isopropyl and 1-phenylethyl isocyanate.
  • the reaction with isocyanates is suitably carried out in the presence of Lewis acids or Lewis bases, which are preferably present in catalytic amounts. In general, all compounds which come under this class can be used as Lewis acids, for example weak and also strong Lewis acids.
  • organometallic compounds of the 4th and 5th main group of the Periodic Table of the Elements are described as Lewis acids, e.g.
  • Tin dioctoate di-butyltin-bis-dodecyl mercaptide, bis (tri-n-butyltin) oxide, dibutyltin oxide, tri-n-butyl-antimony oxide and bismuth oxide, in particular dibutyltin dilaurate, are suitable, for example.
  • Tertiary amines such as diazabicyclooctane (DABCO) are suitable as Lewis bases.
  • DABCO diazabicyclooctane
  • Suitable organic solvents for the derivatization reactions according to the invention are polar aprotic solvents, for example halogenated hydrocarbons such as dichloromethane, 1, 2-dichloroethane or chloroform, furthermore ethers such as diethyl ether or tetrahydrofuran as well as dimethylformamide, dimethyl sulfoxide, hexamethyl phosphoric acid triamide or mixtures of the aforementioned solvents. 10
  • Acid chlorides or isocyanates obtainable derivatized carbon monoxide copolymers according to the invention can generally be obtained with degrees of derivatization greater than 10%, preferably greater than 15% and in particular greater than 20%, the degree of derivatization also depending on the amount of organic compound (C) used.
  • the degree of derivatization based on the free hydroxyl or amino groups in the starting copolymer, reflects the proportion of coupled electrophilic reagent.
  • the degree of derivatization can be determined by means of X H NMR spectroscopy.
  • the molecular weights M w of the derivatized carbon monoxide copolymers according to the invention are generally above 1000 g / mol, preferably above 10000 g / mol and particularly preferably above 25000 g / mol.
  • the derivatized carbon monoxide copolymers differ from the starting compounds, i.e. the functionalized carbon monoxide copolymers over one and possibly also several glass transition temperatures. These are generally above 20, preferably above 30 and particularly preferably above 40 ° C.
  • carbon monoxide copolymers which are derivatized with organic compounds (C) which have two or more electrophilic groups.
  • C organic compounds
  • These compounds include, for example, acid chlorides or anhydrides of dicarboxylic acids such as adipic, glutaric or fumaric acid.
  • this also includes diisocyanate compounds.
  • diisocyanates e.g.
  • 2,4- or 2,6-tolylene diisocyanate isophorone diisocyanate, 4,4'-diisocyanate diphenylmethane, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate or 1,5-naphthyl diisocyanate in question, 2, 4-tolylene diisocyanate and 1 , 6-hexamethylene diisocyanate are preferred.
  • the carbon monoxide copolymers derivatized with the bifunctional or polyfunctional compounds mentioned thus have at least one free electrophilic group.
  • nucleophilic organic compounds In addition to aliphatic or aromatic mono- or polyhydroxy compounds or amino compounds such as methanol, ethanol, i-propanol, n-butanol, t-butanol, 1,4-butanediol, cyclohexanol, phenol, methylamine, dimethylamine, ethylamine, ethylenediamine, di- i-propylamine or cyclohexylamine are in particular also macromers with at least one nucleophilic end group.
  • macromers should be understood to mean oligomers 11 which have an average molar mass M w greater than 100 g / mol and preferably less than 10,000 g / mol.
  • amino- or hydroxy-functionalized macromers are used.
  • suitable macromers are the polyethers derived from polyethylene glycol or poly-1,4-butanediol, such as polyethylene glycol monobutyl ether or poly (1,4-butanediol) bis (4-aminobenzoate).
  • Polymers with functional end or side groups for example polyamides, polybutylene terephthalate, polyphenylene ethers, polyether sulfones or polycarbonates, each with at least one hydroxyl or amino end group, are also suitable for coupling.
  • polymers mentioned which as a rule already have functional end groups or side groups in conventional form, in particular also modified polymers into which hydroxy- or amino-functional groups have been incorporated in a targeted manner.
  • polyamide such as Ultramid ® or Ultramid T
  • polybutylene terephthalate as Ultradur
  • polyethersulfone as Ultra- son ® E
  • polyphenylene ether as Noryl ® (GE Plastics)
  • polycarbonate such as Lexan ⁇ (GE Plastics).
  • Preferred among the aforementioned compounds are the polyamides and polybutylene terephthalate.
  • Polyphenylene ethers with hydroxy end groups can be found, for example, in JE McGrath et al., Poly. Closely. Be. 1977, 17, p. 647.
  • polar aprotic solvents for example halogenated hydrocarbons such as dichloromethane, 1, 2-dichloroethane or chloroform
  • ethers such as diethyl ether or tetrahydrofuran and dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide or mixtures of the abovementioned solvents.
  • Reaction times for the derivatization and for the grafting reactions are usually in the range from 1 to 2 hours to several days.
  • the reaction temperatures in the processes according to the invention mentioned are generally in the range from -10 to 100, preferably in the range from 0 to 80 and particularly preferably from 10 to 60 ° C.
  • the acidic or basic systems described in the derivatization reaction can be used for the grafting reaction.
  • Basic compounds include triethylamine, tributylamine, pyridine, quinoline or ammonium hydroxide 12 the formation of an ester or amide bond in question.
  • reaction mediators such as 4-dimethylaminopyridines, imidazolides such as carbonyldiidazole, dicyclyclohexylcarbodiimides, 2, 2'-dipyridyldisulfide / triphenylphosphine or 2-pyrididylthiochloroform can also be used in the acylation with carboxylic acid chlorides, anhydrides or carboxylic acids.
  • the Lewis acids and Lewis bases used for the derivatization of the functionalized carbon monoxide copolymers can also be used to mediate the reaction.
  • the derivatized carbon monoxide copolymer advantageously, without isolating or purifying it, sets it directly with the nucleophilic organic one
  • reaction components can generally be mixed with one another in any order, but the reaction solution of the derivatized carbon monoxide copolymer is preferred to give a solution of, for example, a macromer bearing a hydroxyl or amino group.
  • the derivatized carbon monoxide copolymers according to the invention can also be carried out with macromers or polymers bearing hydroxyl or amino groups under the conditions of reaction extrusion, as described in the monograph "Reactive Exrusion, Principles and Practice” by M. Xanthos, Carl Hanser Verlag, Kunststoff, 1992 become.
  • Carbon monoxide copolymers derivatized with isocyanates or carboxylic acid chlorides can be obtained by precipitation in, for example, petroleum ether or methanol. Isolation and purification are achieved using conventional techniques by redissolving and re-controlled precipitation of the derivatized product.
  • the graft copolymers according to the invention can be precipitated in e.g. Win methanol or diethyl ether. If appropriate, the grafted products can be taken up again, for example in dichloromethane, in order then to be obtained in a highly pure form by precipitation, free of impurities.
  • the degree of grafting ie the proportion of coupled nucleophile, for example macromer, based on, for example, the free isocyanate groups in the starting compound, is generally above 10%, preferably above 15%.
  • the molecular weights of the graft copolymers depend both on the molecular weights of the derivatized carbon monoxide copolymers and on the coupling component, for example the macro 13 he, as well as the degree of derivatization. As a rule, the graft copolymers according to the invention have molecular weights greater than 10,000 g / mol.
  • the graft copolymers according to the invention are suitable for the production of moldings, fibers, films or coatings and as phase mediators in polymer mixtures. They can also include coating components, e.g. can be used in multilayer film systems.
  • the processes according to the invention for producing the derivatized carbon monoxide copolymers and also the graft copolymers are distinguished, inter alia, by: characterized in that side reactions do not occur and thus chain cleavage or molecular weight reduction are not observed.
  • the acid chlorides and isocyanates and dibutyltin dilaurate (Bu 2 SnLau 2 ) used in the derivatization reactions were obtained from Fluka, poly (ethylene glycol) monobutyl ether and poly (1,4-butanediol) bis (4-aminobenzoate) from Aldrich based. These products were used without further purification.
  • Dichloromethane was dried over CaH and then distilled. All implementations were carried out under standard Schlenk conditions.
  • the 1 H and 13 C NMR spectra were recorded using a Bruker AMX 500 spectrometer.
  • a Perkin-Elmer DSC-7 (heating rate 20 ° / minute) was used for the DSC measurement.
  • the glass transition temperature was determined from the second run after cooling to -50 ° C.
  • the GPC measurements were carried out relative to a standard of linear polystyrene in chloroform or tetrahydrofuran (THF), using a Waters device equipped with Microstyragel columns and an RI detector.
  • the alternating copolymer of CO and 2-allylphenol (APCO) was produced in accordance with the specification of the German patent application 19727271.1. It had an average molecular weight M w of 22,700 g / mol and a polydispersity of 2.2, measured in chloroform. 14

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Abstract

L'invention concerne un procédé de production de copolymérisats de monoxyde de carbone dérivatisés, selon lequel des copolymères de monoxyde de carbone fonctionnalisés linéaires, à forte alternance, constitués de monoxyde de carbone, d'au moins un 1-alcène (A), (A) représentant un composé arylé substitué par au moins une unité terminale allyle ou homoallyle et au moins un groupe hydroxy ou amino, ou bien un alcool aliphatique alpha -oléfiniquement insaturé, et, éventuellement, d'au moins un 1-alcène C2-C20 (B), sont mis à réagir avec un composé organique (C) qui dispose d'au moins un groupe électrophile, dans un solvant organique aprotique.
EP99907594A 1998-03-16 1999-03-04 Copolymerisats de monoxyde de carbone derivatises Withdrawn EP1064317A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19811123A DE19811123A1 (de) 1998-03-16 1998-03-16 Derivatisierte Kohlenmonoxideopolymerisate
DE19811123 1998-03-16
PCT/EP1999/001408 WO1999047583A1 (fr) 1998-03-16 1999-03-04 Copolymerisats de monoxyde de carbone derivatises

Publications (1)

Publication Number Publication Date
EP1064317A1 true EP1064317A1 (fr) 2001-01-03

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP99907594A Withdrawn EP1064317A1 (fr) 1998-03-16 1999-03-04 Copolymerisats de monoxyde de carbone derivatises

Country Status (6)

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US (1) US6306979B1 (fr)
EP (1) EP1064317A1 (fr)
JP (1) JP2002506899A (fr)
AU (1) AU2727999A (fr)
DE (1) DE19811123A1 (fr)
WO (1) WO1999047583A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19906018A1 (de) * 1999-02-16 2000-08-17 Basf Ag Polymerblends aus funktionalisierten Kohlenmonoxidcopolymeren und Polyamiden
DE19906019A1 (de) * 1999-02-16 2000-08-17 Basf Ag Verfahren zur Herstellung von funktionalisierten alternierenden Kohlenmonoxidcopolymeren

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4424317A (en) 1982-12-06 1984-01-03 Standard Oil Company (Indiana) Mannich condensation product of ethylene/propylene/carbonyl polymers
EP0121965B1 (fr) 1983-04-06 1989-12-27 Shell Internationale Researchmaatschappij B.V. Procédé pour la préparation de polycétones
JPS60243116A (ja) * 1984-05-16 1985-12-03 Kureha Chem Ind Co Ltd 熱可塑性接着性樹脂及びその製造方法
US4616072A (en) 1985-06-03 1986-10-07 The Dow Chemical Company Halogenated ethylene-carbon monoxide interpolymer
US4841020A (en) * 1986-11-27 1989-06-20 Shell Oil Company Catalytic polymerization of carbon monoxide with functional substituted ethylenically unsaturated monomer
US5049626A (en) * 1988-09-08 1991-09-17 Du Pont-Mitsui Polychemicals Co., Ltd. Graft copolymer and process for the preparation thereof and use
US5162493A (en) * 1990-06-22 1992-11-10 Shell Oil Company Polymerization of co/olefin/functionally substituted olefin with tetra alkyl diphosphine
EP0946619B1 (fr) * 1996-12-23 2002-06-26 Shell Internationale Researchmaatschappij B.V. Compositions copolymerisees greffees

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9947583A1 *

Also Published As

Publication number Publication date
US6306979B1 (en) 2001-10-23
JP2002506899A (ja) 2002-03-05
DE19811123A1 (de) 1999-09-23
AU2727999A (en) 1999-10-11
WO1999047583A1 (fr) 1999-09-23

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