WO2015061097A1 - Revêtements antiadhésifs et lubrifiants - Google Patents

Revêtements antiadhésifs et lubrifiants Download PDF

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WO2015061097A1
WO2015061097A1 PCT/US2014/060665 US2014060665W WO2015061097A1 WO 2015061097 A1 WO2015061097 A1 WO 2015061097A1 US 2014060665 W US2014060665 W US 2014060665W WO 2015061097 A1 WO2015061097 A1 WO 2015061097A1
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formula
monomer
group
alkyl
copolymer
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PCT/US2014/060665
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Del Bene NICOLAS
Koroskenyi BALINT
Guinta ALLISON
Bergmann HERMANN
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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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
    • C09D5/4411—Homopolymers or copolymers of acrylates or methacrylates

Definitions

  • the present application relates to lubricious, anti-adhesive coatings, methods of their preparation and uses of said coatings.
  • the coatings are co-polymers formed from at least 2 differing ethylenically unsaturated monomer units (A), (B) and optionally (C).
  • the first monomer unit (A) is formed from an ethylenically unsatured cationic monomer defined herein or an ethylenically unsaturated derivative of lysine.
  • the second monomer unit (B) is formed from an unsaturated cyclic amide, for example vinyl pyrrolidone, and the third ethylenically unsaturated monomer (C) is a polyalkyleneoxide (meth)acrylate.
  • the formed coating gives highly lubricious, anti-adhesive and antimicrobial coatings capable of forming a hydrogel upon exposure to water which are very suitable for example in medical applications.
  • Hydrogels have shown promise for use in a variety of implantable devices and materials due, in part, to the biocompatibility of the hydrogels. Additionally, hydrogel materials may exhibit rubbery and pliable behaviors, and/or have highly lubricious surfaces. An overview of considerations for biological and medical applications of hydrogels can be found in Peppas, et al., Ann. Rev. Biomed. Eng. 2, 9 (2000), which is incorporated by reference in its entirety.
  • hydrogels are considered excellent lubricants for coating onto implantable medical devices.
  • hydrogels do not adhere well to certain metal, polymer and/or ceramic materials commonly used to manufacture implantable devices, and therefore, hydrogel properties need to be improved in order to strengthen the attachment to the surface of the material especially under biological environs.
  • the applicants have overcome many of the drawbacks of prior hydrogels.
  • the applicants have accomplished the above objectives by forming a coating from a copolymer comprising at least several monomer units which functionality simultaneously provides lubricious, anti-adhesive and antimicrobial properties to the substrate surface while at the same time the coating resists delamination in aqueous or biological environs.
  • the application is directed to a coating comprising a copolymer formed from monomer (A), (B) and optionally (C ) wherein monomer (A) is selected from the group consisting of ethylenically unsaturated cationic monomers defined by formulae (I)
  • R 3 is methyl or ethyl
  • X is oxygen or NH, for example oxygen
  • L is a linking group selected from the group consisting of branched or unbranched Ci-C 50 alkylene and branched or unbranched C 2 -C 50 alkylene interrupted by one or more oxygens;
  • R 2 is C 4 -C 2 4, for example C 6 -C 2 o or C 8 -C 18 ;
  • R 4 is C 4 -C 24 , for example C 4 -C 16 or C 4 -C 12 and A " is an organic or inorganic anion for both formula (I) and (II); and a polylysine containing ⁇ . ⁇ -ethylenically unsaturation functionality; monomer (B) is an unsaturated cyclic amide of formula (III)
  • R being H, or Ci-C 4 -alkyl and , R 5 , R 6 together with the N-atom, they are connected to form a 4 to 8 membered heterocycle, comprising a carbonyl group in a-position to the N-atom; and optional monomer (C) is a polyalkyleneoxide (meth)acrylate of formula (IV)
  • R is hydrogen or C1-C4, n is a number 2 to 50 and R 7 is hydrogen or a C C 4 alkyl.
  • a noted embodiment of the above coating comprises the copolymer formed from (A), (B) and (C ), wherein monomer (A) is selected from the group consisting of formula (I) and formula (II), monomer (B) is defined by formula (III) and monomer (C ) is defined by formula (IV).
  • Another very important embodiment of the above coating comprises the copolymer formed from (A), (B) and optionally (C ), wherein (A) is the polylysine containing ⁇ . ⁇ -ethylenically unsaturation functionality, monomer (B) is defined by formula (III) and (C) is defined by formula (IV).
  • Also envisioned is a method of coating the copolymer formed from any one of the three copolymer embodiments above onto a substrate comprising the steps of: i) applying the formed copolymer onto a substrate and ii) UV curing the coated substrate of step i).
  • a particular embodiment of the method above is a method of coating a substrate comprising the steps of i) applying a formed copolymer of any one of the first three embodiment above, for example the copolymer in solution or dispersion, wherein the copolymer is formed from monomer (A) which is the ethylenically unsaturated polylysine, monomer (B) of formula (III), optionally monomer (C) of formula (IV) and a photoinitiator and i) UV curing the coated substrate of step i).
  • R is hydrogen, C 1 -C4 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tertiary butyl,
  • R being H, or d-C 4 -alkyl and , R 5 , R 6 together with the N-atom, they are connected to form a 4 to 8 membered heterocycle, comprising a carbonyl group in a-position to the N-atom; for example N-vinyl pyrrollidone to be novel.
  • R is hydrogen or C 1 -C4,
  • R 3 is methyl or ethyl
  • X is oxygen or NH, for example oxygen
  • L is a linking group selected from the group consisting of branched or unbranched C 2 -C 50 alkylene interrupted by one or more oxygens;
  • R 2 is CrC 24, for example C 4 -C 20 , C 6 -C 20 or C 8 -C 18 is believed to be novel.
  • Substrate for purposes of this application refers to any substrate, for example ceramics, glass, metals and plastics. Plastic or polymeric substrates are of high interest. A plastic substrate would include a polymer as part of the substrate but normally also incorporates other additives or materials such as light stabilizers, fillers, colorants etc.
  • the substrate may be virtually any article of manufacture but medical devices or textiles are of special importance.
  • Anti-adhesive means that the copolymer coating of the application when attached to a substrate surface either by simply coating or by means of covalent bonding are characterized in that platelets and bacteria do not adhere well to the coated substrate surface. The anti- adhesion test is described in the example section of the application.
  • Antimicrobial means a characteristic which serves to at least stop proliferation of
  • microorganisms and more preferably is understood to kill microorganisms coming into contact with the copolymer coating or hydrogel of the copolymer coating of the application.
  • the antimicrobial tests are carried out as explained in the examples under ASTM 2149.
  • Lubricity is a term well known in the art and refers to the feel of a surface or material.
  • the lubricity is measured by determining the frictional force averaged over the distance that a weight is pulled across the coated substrate. The lower the frictional force, the better the lubricity.
  • cationic within this disclosure is understood to cover any cationic entity irrespective of the type of cation to be considered.
  • cationic likewise comprises a positively charged entity obtained by alkylation as well as by protonation.
  • the term "monomer” for purposes of this disclosure means an ethylenically unsaturated compound before polymerization.
  • monomer unit for purposes of this disclosure means the unit formed from the ethylenically unsaturated compound after polymerization.
  • Comprising for purposes of the invention is open ended, that is other components may be included. Comprising is synonymous with containing or including.
  • Polymerizable photocrosslinker photoinitiators refers to photoinitiators which contain ethylenically unsaturated moieties and a photoinitiator moiety.
  • non-polymerizable photocrosslinker photoinitiator when used, what is meant for purposes of this application is the photoinitiator contains a photoinitiator moiety but no ethylenic unsatu ration.
  • hydrogel for purposes of this application means a network of polymer chains that are hydrophilic and will have a tendency to gel when in the presence of water.
  • the presently disclosed copolymer coating when wetted will form a gel like coating in which water is entrapped within the network of polymer chains.
  • Monomer (A) is selected from the group consisting of
  • R 3 is methyl or ethyl
  • X is oxygen or NH, for example oxygen
  • L is a linking group selected from the group consisting of branched or unbranched Ci-C 50 alkylene and C 2 -C 50 branched or unbranched alkylene interrupted by one or more oxygens;
  • R 2 is C 4 -C 2 4, for example C 6 -C 2 o or C 8 -C 18 ;
  • the anion A may be virtually any inorganic or organic anion.
  • the organic or inorganic anion may be a halide, such as chloride, bromide, iodide and fluoride.
  • halide such as chloride, bromide, iodide and fluoride.
  • sulfate, hydrogen sulfate, phosphate, boron tetrafluoride, carbonate and bicarbonate are envisioned.
  • organic anions oxalate or d-C 8 alkyl sulfate, such as methyl sulfate or ethyl sulfate are considered.
  • Further anions may be lactate, formate, acetate, propionate or a complex anion, such as the zinc chloride double salt.
  • anion A " is an inorganic anion and selected from the group consisting of halide, sulfate, phosphate, carbonate and bicarbonate, especially halide such as chloride, bromide and iodide.
  • R 2 and R 4 contain at least a C 4 chain in formulae (I) and (II). However, it is more typical that the R 2 and R 4 moieties are C 6 , C 8 , C 10 or C 12 and above such as C 14 , C 16 , C 18 or C 20 .
  • the C 4 -C 24 chains for R 2 and R 4 would include the entities butyl (n-butyl, isobutyl and tertiary butyl), pentyl, n-hexyl or n-capryl, n-heptyl or n-oenanthyl, n-octyl or n-caprylyl, n-nonyl or n- pelargonyl, n-decyl or n-capryl, n-undecyl, n-dodecyl or n-lauryl, n-tridecyl, n-tetradecyl or n- myristyl, n-pentadecyl, n-hexadecyl or n-palmityl, n-heptadecyl or n-margaryl, n-octadecyl or n- stearyl, n
  • X is for example oxygen and may be most typical.
  • L or the linking group L is most typically branched or unbranched C 1 -C 12 alkylene or C 2 -C 2 o alkylene interrupted one or more time by oxygen.
  • Ci-C, 2 alkylene when applied to L is for example Ci_C 4 alkylene, Ci-C 6 alkylene, Ci-C 8 alkylene, C 1 -C 10 alkylene or Ci-Ci 2 alkylene.
  • Unbranched examples are -CH 2 -, -CH 2 CH 2 - -CH 2 CH 2 CH 2 - , -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 -,
  • Branched example might be -CH 2 CH(R 7 )- or -CH 2 CH 2 CH(R 7 )-.
  • Branched or unbranched C 2 -C 20 alkylene interrupted one or more times by oxygen are for example repeating units of -[CH 2 ] y -[0-CH(R 7 )CH 2 )] x -.
  • R 7 is hydrogen, methyl or ethyl and x and y are independently 1 -10.
  • C 2 -C 8 alkylene interrupted by oxygen is for example -CH 2 -0-CH 2 -, -CH 2 CH 2 -0-CH 2 CH 2 -, -CH 2 CH 2 -0-CH 2 CH 2 -0-CH 2 CH 2 - or -CH 2 -0-CH 2 CH 2 -0-CH 2 CH 2 -.
  • the most typical C 2 -C 8 alkylene interrupted by oxygen is for example -CH 2 CH 2 -0-CH 2 CH 2 - or -CH 2 CH 2 -OCH 2 CH 2 -0- CH 2 CH 2 - and X is oxygen.
  • the linker contains a C 2 -C 50 alkylene interrupted by oxygen it is thought that the insertion of the oxygen in the alkylene chain may work to help plasticize the formed copolymer coating and may increase the antibacterial activity.
  • (A) monomers of formula (I) are for example esters of (meth)acrylic acid with C 2 to C 8 -aminoalcohols said C 2 to C 8 -aminoalcohols being C 4 - to C 2 4-alkylated on the terminal amine nitrogen to form a quaternary amine.
  • An (A) monomer of formula ( ⁇ ) containing an oxygen inserted into the alkylene chain is for example:
  • R , A " , X and R 2 as defined in formula (I) and z may be from 1 to 10, for example 1-4.
  • Monomer (A) esters of formula (I) are selected from monomers of the group consisting of esters or amides of (meth)acrylic acid with linear C 2 - to C 6 -aminoalcohols said C 2 - to C 6 -aminoalcohols being C 4 - to C 24 -alkylated on the terminal amine nitrogen.
  • Esters are for example N,N-dimethylaminomethyl(meth)acrylate, N,N- dimethylaminoethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate,N,N- diethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, N,N- diethylaminopropyl(meth)acrylate, N,N-dimethylaminobutyl(meth)acrylate and N,N-diethylamino- butyl(meth)acrylate, each of which is respectively quaternized with a n-alkyl chain comprising from 4 to 24 carbon atoms or mixtures thereof.
  • Monomers (A) of formula (I) are for example esters selected from the group consisting of N,N- m ethyl , C 6 -C 20 -al kyl am i nom ethyl (m eth )acryl ate , N , N-m ethyl , C 6 -C 20 -alkyl
  • aminoethyl(meth)acrylate N,N-ethyl,C 6 -C 20 -alkyl aminomethyl(meth)acrylate, N,N-ethyl,C 6 -C 20 - alkyl amnoethyl(meth)acrylate, N,N-methyl,C 6 -C 20 -alkyl aminopropyl(meth)acrylate, N,N- ethyl,C 6 -C 20 -alkyl aminopropyl(meth)acrylate, N,N-methyl,C 6 -C 20 -alkyl aminobutyl(meth)acrylate, N,N-ethyl,C 6 -C 20 -alkyl aminobutyl(meth)acrylate or mixtures thereof.
  • Amides of formula (I) are selected from the group consisting of amides of (meth)acrylic acid with C 2 - to C 6 -diamines said C 2 - to C 6 -diamines being C 6 - to C 2 o-alkylated on the terminal amine nitrogen. Due to cost reasons it is more typical to select monomers A from the group consisting of amides of (meth)acrylic acid with linear C 2 - to C 6 -diamines said C 2 - to C 6 -diamines being C 6 - to C 20 -alkylated on the terminal amine nitrogen.
  • Suitable amide monomers (A) are selected from the group consisting of amides of methacrylic acid with C 2 - to C 6 -diamines, for example linear C 2 - to C 6 -diamines, said C 2 - to C 6 -diamines or linear C 2 - to C 6 -diamines being C 6 - to C 20 -dialkylated on the amine nitrogen.
  • amides of monomer (A) of formula (I) are selected from the group consisting of N,N-dimethylaminomethyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N- diethylaminomethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N- dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N,N- dimethylaminobutyl(meth)acrylamide and N,N-diethylaminobutyl(meth)acrylamide each of which respectively being quaternized at the terminal nitrogen by means of an-alkyl chain comprising from 4 to 24 carbon atoms or mixtures thereof.
  • amides of monomer (A) of formula (I) are selected from the group consisting of N,N- methyl,C 6 -C 20 -alkyl aminomethyl(meth)acrylamide, N,N-methyl,C 6 -C 20 -alkyl
  • amides of monomer (A) of formula (I) are selected from the group consisting of N,N dimethylaminoethyl(meth)acrylamide or N,N-dimethylaminopropyl(meth)acrylamide, each of which respectively being quaternized by means of a terminal N-alkyl chain comprising from 6 to 20 carbon atoms or mixtures thereof.
  • Said copolymer may be free of any compound comprising a radically polymerizable ⁇ . ⁇ - ethylenically unsaturated double bond and at least one cationogenic moiety, said cationogenic moiety bearing only terminal N-alkyl chains comprising less than 4 carbon atoms.
  • the coating or coated substrate may comprise a copolymer formed from monomers (A) of Formula (I) in amounts ranging
  • the w% of monomer (A) of formula (I) is based on the total weight of the formed copolymer.
  • R 4 is C 4 -C 24 alkyl, for example C 4 -C 2 o alkyl or C 6 -Ci 8 alkyl, and A " is as defined above.
  • the C4-C24 alkyl is linear or branched but more typically linear.
  • C4-C24 alkyl examples include n-butyl, n-pentyl, n-hexyl or n-capryl, n-heptyl or n-oenanthyl, n- octyl or n-caprylyl, n-nonyl or n-pelargonyl, n-decyl or n-capryl, n-undecyl, n-dodecyl or n-lauryl, n-tridecyl, n-tetradecyl or n-myristyl, n-pentadecyl, n-hexadeyl or n-palmityl, n-heptadecyl or n- margaryl, n-octadecyl or n-stearyl, n-nonadecyl, n-eichosanyl or n-arachid
  • the coating or the coated substrate may comprise a copolymer formed from monomers (A) of Formula (II) in amounts ranging from about 1 to about 25 w%, for example from about 2 to about 20 w%. Alternatively, in an amount ranging from about 2 to about 20 w%, for example about 2 to about 15 w%, from about 3 to about 13.5 w% or about 4 to about 12.5 w% or most typically ranging from about 5 to about 12.5 w%.
  • the Monomer (A) may be selected from a polylysine containing a, ⁇ -ethylenically unsaturated functionality.
  • a typical graphic representation is defined in formula (V)
  • R is hydrogen, C C 4 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tertiary butyl,
  • the weight average molecular weight of the polylysine containing a, ⁇ -ethylenically unsaturation will range from about 300 to about 10,000, more typically about 500 to about 5,000.
  • the coating or coated substrate may comprise a copolymer formed from monomers (A) defined by the polylysine containing ⁇ , ⁇ -ethylenically unsaturation in amounts ranging from about 1 to about 25 w%, for example from about 2 to about 20 w%. Alternatively, in an amount ranging from about 2 to about 20 w%, for example about 2 to about 15 w%, from about 3 to about 13.5 w% or about 4 to about 12.5 w% or most typically ranging from about 5 to about 12.5 w%.
  • the w% of monomer (A) polylysine is based on the total weight of the formed copolymer.
  • the polylysine containing ⁇ , ⁇ -ethylenically unsaturation is formed via synthetic methods. For example, (meth)acylic acid and N-hydroxysuccinimide are reacted to form an intermediate which is then reacted with epsilon-polylysine (available from Wilshire Technologies, weight average molecular weight of about 3,000).
  • the monomer (A) component of the copolymer may be a mixture of the possible
  • the total weight % of the monomer (A) components(that is formula (I), (II) and/or the polylysine derivative) will range in amounts from 1 to about 25 w%, for example from about 2 to about 20 w%. Alternatively, in an amount ranging from about 2 to about 20 w%, for example about 2 to about 15 w%, from about 3 to about 13.5 w% or about 4 to about 12.5 w% or most typically ranging from about 5 to about 12.5 w%.
  • the w% of monomer (A) components is based on the total weight of the formed copolymer.
  • Monomer (B) is an unsaturated cyclic amide of formula (III)
  • R being H, or d-C 4 -alkyl and R 5 , R 6 together with the N-atom, they are connected to, form a 4 to 8 membered heterocycle, comprising a carbonyl group in a-position to the N-atom.
  • said vinyl amide may be selected from the group consisting of N-vinyl-2- pyrrolidone, N-vinyl caprolactam, N-(4-morpholinyl)(meth)acrylamid, N-(4- morpholinyl)acrylamid, N-vinyl piperidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2- pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2- caprolactam, N-vinyl-7-ethyl-2-caprolactam.
  • the most important vinyl amide monomer is N-vinyl-pyrrolidone and derivatives such as N-vinyl- 2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone .
  • the copolymer coating or copolymer coated on the substrate comprising monomers (B) of formula (III), preferably N-vinyl pyrrolidone, makes up about 25 w % or higher, about 25 to about 90 w %, about 30 to about 80 w %, or about 35 to about 75 w % of the formed copolymer, and the w % is based on the total weight of the formed copolymer.
  • monomers (B) of formula (III) preferably N-vinyl pyrrolidone
  • the monomer B makes up about 25 w % or higher of the formed copolymer.
  • the monomer B makes up about 25 to about 90 w %, about 30 to about 80 w %, about 35 to about 75 w % of the formed copolymer when the copolymer is formed from any one of monomer A (formula I or II or polylysine derivative), monomer B and monomer C.
  • the monomer B will make up more of the total formed copolymer when no monomer C is part of the formed copolymer (formed only from monomers (A) and (B)).
  • the monomer B (when there is no monomer C) makes up about 25 w % to about 98 w %, about 40 to about 90 w %, about 60 to about 88 w %.
  • Optional monomer (C) is a polyalkyleneoxide (meth)acrylate of formula (IV)
  • n is a number 2 to 50 for example 3 or 4 to 15.
  • R 7 is hydrogen or a C C 4 alkyl.
  • the weight average molecular weight of the above monomer will vary from about 50 to about 20,000, about 100 to about 10,000 or about 150 to about 800.
  • (Meth)acrylic esters containing CH 2 -CH 2 -O- units of the monomer (C ) of formula (IV) are such ⁇ , ⁇ -ethylenically unsaturated molecules, which comprise an ester moiety a part of which is a CH 2 -CH 2 -0- entity. Said ester moiety is connected to a ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid selected from the group consisting of acrylic acid and methacrylic acid.
  • CH 2 -CH 2 -O- units generally stem from polyetherols or from monoalkylated polyetherols.
  • Suitable polyetherols are linear or branched substances having terminal hydroxyl groups and comprising ether bonds. In general, they have a molecular weight in the range from about 50 to 20,000.
  • the monomer (C ) or the poly(ethylene glycol) (meth)acrylate mono C C 4 alkyl ether or formula (V) appears to increase the resistance to delamination of the hydrogel on a substrate.
  • the coating or coating on a substrate may comprise a copolymer formed from monomer ( C) of formula (IV) and makes up about 10 to about 50 w % of the copolymer, for example about 15 to about 35 w% or about 15 to about 32 w % of the formed copolymer, and the w% is based on the total weight of the formed copolymer.
  • the above coating may be formed from several or at least one of the monomer (A) components (I, II and polylysine derivative), there are coatings or coatings on the substrate of particular interest.
  • These coatings or coatings on a substrate are:
  • the polylysine containing ⁇ , ⁇ -ethylenically unsaturation functionality such as the formula (V) above; wherein A is OH, OR 1 or NHR 1 or C 2 -C 6 alkyl substituted by NH 2, NHR 2 , (for example
  • w is a number from 2 to 50
  • R is hydrogen, C1-C4 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tertiary butyl,
  • a coating or coating on a substrate is of
  • the above embodiments (1 , 2 and 3) may also be crosslinked or non crosslinked. More typically however the copolymer is normally crosslinked during UV curing with the addition
  • embodiments 1 , 2 and 3 recited directly above may further include other optional monomers D and E.
  • the optional D monomers would include hydrophilic monomers different than those defined above under A, B and C.
  • hydrophilic monomers (D) would include hydroxy(meth)acrylates which are esters of(meth)acrylic acid with d-C 4 -alkanediols, anionic monomers such as ⁇ , ⁇ - ethylenically unsaturated mono- or dicarboxylic acids and amides and esters of (meth)acrylic acid with linear C 2 - to C 6 -aminoalcohols.
  • Anionic monomers of monomer (D) are considered for example, ⁇ , ⁇ -ethylenically
  • unsaturated mono or dicarboxylic acids may be selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, ochloroacrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof.
  • Possible esters of (meth)acrylic acid with linear C 2 -C 6 -aminoalcohols of monomer (D) are for example N,N-dimethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N- diethylaminomethyl(meth)acrylate,N,N-diethylaminoethyl(meth)acrylate, N,N- dimethylaminopropyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, N,N- dimethylaminobutyl(meth)acrylate and N,N-diethylaminobutyl(meth)acrylate or mixtures thereof.
  • Possible amides of (meth)acrylic acid with linear C 2 -C 6 diamines are for example selected from the group consisting of amides of (meth)acrylic acid with C 2 - to C 6 -diamines said C 2 - to C 6 - diamines.
  • the possible amides of (meth)acrylic acid with linear C 2 -C 6 diamines may be selected from the group consisting of N,N-dimethylaminomethyl(meth)acrylamide, N,N- dimethylaminoethyl(meth)acrylamide, N,N-diethylaminomethyl(meth)acrylamide, N,N- diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N- diethylaminopropyl(meth)acrylamide, N,N-dimethylaminobutyl(meth)acrylamide and N,N- diethylaminobutyl(meth)acrylamide and mixtures thereof.
  • hydrogel copolymer as previously mentioned comprising monomer A (formula I, II or polylysine derivative such as formula V), monomer B, optionally C and D may also include a polymerizable photocrosslinker photoinitiator as monomer E.
  • Including a polymerizable photocrosslinker photoinitiator into the copolymer, in particular into the copolymer as previously outlined, will confer to the copolymer of the application not only the previously indicated properties, but will also help the copolymer to be covalently bound to a surface/substrate exhibiting C-H bonds. It is to be understood that the polymerizable
  • photocrosslinker in this embodiment comprises a polymerizable entity and in addition a residue suited for photo-activation.
  • the polymerizable photocrosslinker as monomer E is selected from the group consisting of monomers comprising a radically polymerizable, olefinically unsaturated double bond.
  • Olefinically unsaturated means any kind of olefinic and not aromatic double bound located in monomer E.
  • the polymerizable photocrosslinker as monomer E is selected from the group consisting of monomers comprising a radically polymerizable olefinically unsaturated double bond and an entity adapted to proceed for an intermolecular abstraction of a hydrogen atom from for example a substrate. Also for this monomer E, the term “olefinically” has the same meaning as given supra.
  • At least one polymerizable photocrosslinker as monomer E is selected from the group consisting of compounds as outlined by the following formula (VI)
  • R 9 being hydrogen, halide, hydroxy and/or C-i-C 20 -alkyl, viz. an alkyl moiety containing from 1 to 20 carbon atoms, CrC 2 o-alkyloxy as for instance methoxy or ethoxy,
  • R 0 being hydrogen, halide, hydroxy and/or CrC 2 o-alkyl, viz. an alkyl moiety containing from 1 to 20 carbon atoms, C 1 -C 20 -alkyloxy as for instance methoxy or ethoxy, b being an integer ranging from 0 to 4,
  • X being oxygen or a group of formula NR , with R being hydrogen or a moiety with 1 to 6 carbon atoms,
  • R 2 being hydrogen, methyl or ethyl, for example hydrogen or methyl
  • CON being a bond or a connecting group
  • said connecting group CON being selected from the group consisting of entities containing from 1 to 2000 carbon atoms, preferably from 1 to 1000 carbon atoms and more preferably containing from 1 to 500 carbon atoms and entities of formula (VII)
  • R 3 being a bond, an oxygen or sulfur atom or a group of the formula NR 4 , with R 4 being an alkyl group comprising from 1 to 6 carbon atoms; R 3 further being an 0-CO-O- group, an NH-CO-O- group, an HN-CO-NH-group or a connecting alkyl group comprising from 1 to 20 carbon atoms,
  • R 5 , R 6 and R 7 being respectively hydrogen, methyl or ethyl, m and p being an integer ranging from 0 to 2 respectively, n being an integer ranging from 0 to 200, preferably from 1 to 100 and more preferably ranging from 1 to 50.
  • the at least one polymerizable photocrosslinker as monomer E is selected from the group consisting of compounds as outlined by the following formula (VIII)
  • R 8 being selected from the group consisting of C 1 -C 20 alkyl, viz. an alkyl moiety containing from 1 to 20 carbon atoms, aryl, heteroaryl, in particular methyl and ethyl, and of Ci-C 2 o-alkyloxy particularly methoxy and ethoxy;
  • R 0 being hydrogen, halide, hydroxy and/or C-i-C 20 -alkyl, viz. an alkyl moiety containing from 1 to 20 carbon atoms, Ci-C 2 o-alkyloxy as for instance methoxy or ethoxy, b being an integer ranging from 0 to 4,
  • X being oxygen or a group of formula NR , with R being hydrogen or a moiety with 1 to 6 carbon atoms,
  • R 2 being hydrogen, methyl or ethyl, preferably hydrogen or methyl
  • CON being a bond or a connecting group, said connecting group CON being selected from the group consisting of entities containing from 1 to 2000 carbon atoms, preferably from 1 to 1000 carbon atoms and more preferably containing from 1 to 500 carbon atoms and entities of formula (VII) as above.
  • Ci-C 20 -alkoxy is understood to consist of at least one of the moieties methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, n-pentoxy, 2-methyl-butoxy, 1 , 1-deimthyl-pen- toxy, 2,2-dimethyl-pentoxy, 1 ,2-dimethyl-pentoxy, n-hexoxy, 1-methyl-pentoxy, 2-methyl pentoxy, 3-methyl-pentoxy, 1 ,1-dimethyl-butoxy, 1 ,2-demethyl-butoxy, 1 ,3-dimethyl-butoxy, 2,3- dimethyl-butoxy, 1-ethyl-butoxy, 2-ethylbutoxy, 3-ethyl-butoxy, n-heptoxy, 1-methyl-hexoxy, 2- methyl-hexoxy, 3-methyl-hexoxy, 4-methyl-hexoxy, 5-methyl-hexoxy.
  • Ci-C 2 o-alkyl viz. an alkyl moiety containing from 1 to 20 carbon atoms comprises, in a non- exhaustive recitation and preferably consists of at least one of the following moieties, C-i-C 20 - alkyl, Ci-C 2 o-alkylthio, C 2 -C 2 o-alkenyl, cycloalkyl, aryl, hetroaryl or heterocyclyl, with the cycloalkyl, aryl, heteroaryl or heterocyclyl moieties including unsubstituted entities or entities being substituted up to three times and in case of fluorine up to the maximum number of identical or different substituents.
  • Ci-C 2 o-alkyl, C 2 -C 20 -alkenyl moieties are also understood to comprise such entities with non-adjacent saturated carbon atoms to be replaced by
  • C 2 -C 20 -alkenyl moieties also comprise entities having a three - to six-membered ring, which is either substituted or unsubstituted with up to three substituents selected from the group consisting of hydroxyl (-OH), carboxyl (-COOH), formyl, cyano (-CN), sulfonate (S0 3 H), halogen, aryl, aryloxy, arylthio, C 3 - C 8 -cycloalkoxy, C 3 -C 8 -cycloalkylthio, heterocyclyl, heterocyclyloxy or Ci-C 2 -alkoxycarbonyl, the latter comprising methoxycarbonyl or ethoxycarbonyl.
  • Ci-C 2 o-alkyl consists of at least one unbranched or branched hydrocarbon moiety having from 1 to 20 carbon atoms. It comprises in particular hydrocarbon moieties selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, 2-methylpropyl and tert-butyl radical, pentyl, 2-m ethyl butyl, 1 ,1-dimethylpropyl, hexyl, capryl, heptyl, oenanthyl, octyl, caprylyl, 1 ,1 ,3,3-tetramethylbuty, nonyl, pelargonyl, 1-decyl, 2-decyl, undecyl, dodecyl, lauryl, tridecyl, tetradecyl, myristyl, pentadecyl, hex
  • CrC ⁇ -alkylthio consists of at least one of the moieties mentioned in the last paragraph. However, each of which being respectively connected to a sulfur atom.
  • C 2 -C 20 -alkenyl may consist of at least one of the moieties mentioned in the penultimate para., however, each of which comprising one olefinically unsaturated double bond.
  • C 2 -C 20 -alkenyl may also be understood to comprise at least one member selected from the group consisting of vinyl, allyl, 2-methyl-2-propenyl, 2- butenyl , 2-pentenyl, 2-decenyl, 2-eicosenyl.
  • cycloalkyl is understood to preferably consist of C 3 -C 8 -cycloalkoxy and C 3 -C 8 - cycloalkylthio moieties.
  • C 3 -C 8 -cycloalkoxy moieties preferably consist of at least one entity selected from the group consisting of cyclop ropyl cyclobutyl, cyclopentyL cyclohexyl, cycloheptyl or cyclooctyl, each of which respectively being linked via an oxygen.
  • C 3 -C 8 -cycloalkylthio moieties comprise preferably consist of at least one entity selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, each of which respectively being linked via a sulfur atom.
  • aryl within this specification means an isocyclic aromatic moiety having from 6 to 14, preferably from 6 to 12 carbon atoms, such as phenyl, benzyl, naphthyl, biphenylyl, with phenyl to be preferentially used.
  • Aryloxy is meant to consist of an aryl as previously mentioned, said aryl being connected to an oxygen atom and preferably comprises the entities phenoxy, benzyloxy, 1- or 2-naphthyloxy
  • Arylthio within this specification has the aforementioned meaning , however, entities not being connected to an oxygen, but to a sulfur molecule, thus preferably comprising the entities phenylthio, benzylthio, 1- or 2-naphthylthio.
  • heteroaryl within this specification means an aromatic moiety having from 6 to 14, preferably from 6 to 12 carbon atoms, and at least one heteroatom within the cycle like for instance pyridyl.
  • heterocyclyl consists of a heteroaliphatic or heteroaromatic ring system.
  • the "heteroaromatic ring system" within this specification is an aryl moiety in which at least one CH group is replaced by N and/or at least two adjacent CH groups are replaced by S, NH or 0.
  • the "heteroaromatic ring system” is understood to comprise at least one of the entities thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1 ,3,4- oxadiazole, 1 ,3,4-thiadiazole, 1 ,3,4-triazole, 1 ,2,4-oxadiazole, 1 ,2,4-thiadiazole, 1 ,2,4-triazole, 1 ,2,3-triazole, 1 ,2,3,4-tetrazole, benzothiophene, benzofuran, indole, isoindole, benzoxazole, benzothiazole, benzimidazole
  • At least one polymerizable photocrosslinker as monomer E is selected from the group consisting of compounds as outlined by the following formula (X)
  • L is a linking group comprising at least one olefinically unsaturated double bound;
  • a - is a bond;
  • alkylene group which may be interrupted by one or more heteroatoms or
  • heteroatom groups selected from O, S, SO, S0 2 and NR 22 , where in case that the alkylene group is interrupted by two or more O, these are not adjacent, and/or may carry one or more substituents selected from OR 24 , NR 22 R 23 , C(0)R 25 , C(0)OR 24 , C(0)NR 22 R 23 , OC(0)R 25 , NR 22 C(0)R 25 , SR 24 , C(S)R 25 , C(S)SR 24 and C(S)NR 22 R 23 ;
  • cycloalkylene group which may carry one or more substituents selected from C 1-C4- alkyl, OR 24 , NR 22 R 23 , C(0)R 25 , C(0)OR 24 , C(0)NR 22 R 23 , OC(0)R 25 , NR 22 C(0)R 25 , SR 24 , C(S)R 25 , C(S)SR 24 and C(S)NR 22 R 23 ;
  • heterocyclylene group containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from O, N, S, SO, S0 2 , C(O) or C(S) as ring members, where the heterocyclylene group may carry one or more substituents selected from d-d-alkyl, OR , NR R C(0)R 25 , C(0)OR 24 , C(0)NR 22 R 23 , OC(0)R 25 and NR 22 C(0)R 25 ;
  • each R 2 is independently selected from halogen, cyano, azido, nitro, -SCN, -SF 5 , d-d- alkyl, d-d-haloalkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 - haloalkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 -haloalkynyl, OR 24 , -S(0) x R 24 , S(0) 3 " (M a+ ) 1/a , NR 22 R 23 , C(0)R 25 , C(0)OR
  • R 22 and R 23 are selected from hydrogen, d-d-alkyl, d-d-haloalkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 - halocycloalkyl, d-d-alkoxy, d-C 4 -haloalkoxy, C(0)R 25 , C(0)OR 24 , phenyl and benzyl; each R 24 is independently selected from hydrogen, d-C 4 -alkyl, d-d-haloalkyl, C 3 -C 8 - cycloalkyl, C 3 -C 8 -halocycloalkyl, phenyl and benzyl; each R 25 is independently selected from hydrogen, d-C 4 -alkyl, phenyl and benzyl; each R 26 is independently selected from halogen, cyano, d-C 4 -alkyl, d-C 4 -halo
  • (M a+ ) 1 a is a metal equivalent or an optionally substituted ammonium cation; z is 0, 1 , 2, 3, 4 or 5; y is from 1 to 8; and x is 0, 1 , 2 or 3;
  • Such linking group L is considered to be any entity, which is adapted to react with monomers A, B and optionally C as given supra.
  • linking group L is selected from the group consisting of vinyl esters, vinyl amides, vinyl halides, vinylalcohol, vinylacetate, olefinically unsaturated carboxylic acids, preferably ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, like acrylic and methacrylic acid, (meth)acryl amides, (meth)acrylic esters, (meth)acrylonitrile, olefinically unsaturated
  • anhydrides like maleic anhydride and fumaric anhydride.
  • the photocrosslinkable photoinitiators of formula (VI, VIII and/or X), monomers E may make up about 0.1 to about 5 w % of the formed copolymer, for example about 0.5 to about 2.5 w %, based on the formed copolymer.
  • coatings or coating on a substrate of particular interest are those comprising copolymers:
  • w % is based on the total weight of the formed copolymer. 2. formed from about 1 to about 25 w%, for example from about 2 to about 20 w%.
  • the polylysine containing a, ⁇ -ethylenically unsaturation functionality such as the formula
  • V about 25 w % or higher, about 25 to about 90 w %, about 30 to about 80 w %, or about 35 to about 75 w % of monomer (B), an unsaturated cyclic amide of formula (III), preferably N-vinyl pyrrolidone; optionally, about 10 to about 50 w % of the hydrogel copolymer, for example about 15 to about 35 w% or about 15 to about 32 w % of monomer (C) of formula (IV);
  • w % is based on the total weight of the formed copolymer.
  • a coating or coating on a substrate comprising a copolymer formed from (A),(B), optionally (C) and a monomer (E), defined as a polymerizable photocrosslinkable photoinitiator monomer.
  • the copolymer wherein the monomer (E) is selected from the group consisting of a monomer of formula (VI), formula (VIII) and formula (X) is a more particular embodiment envisioned by the present application.
  • the polymerizable photocrosslinking photoinitiator monomer (E) of particular importance is formula (VI).
  • this application is directed to a method of coating a copolymer formed from monomers (A), (B) and optionally (C ) onto a substrate wherein monomer (A) is an ethylenically unsaturated cationic monomer defined by formulae (I), (II) as above or a polylysine containing a, ⁇ -ethylenically unsaturation functionality or as defined in formula (V); monomer (B) of formula (III) as defined above
  • a particular embodiment of the method above of importance is the method of coating a substrate comprising the steps of i) applying a copolymer for example in a solution or dispersion, wherein the copolymer is formed from monomer (A) which is an ethylenically unsaturated polylysine, monomer (B) of formula (III) and optionally monomer (C) of formula (IV) in combination with a photoinitiator and iii) UV curing the coated substrate of step i).
  • a special embodiment of the above method is application of the copolymer formed from monomer (A), (B) and optionally (C), and monomer (E), the polymerizable photocrosslinkable photoinitator onto a substrate and then curing via UV radiation.
  • copolymer is formed from about 1 to about 25 w%, for example from about 2 to about 20 w%. Alternatively, in an amount ranging from about 2 to about 20 w%, for example about 2 to about 15 w%, from about 3 to about 13.5 w% or about 4 to about 12.5 w% or most typically ranging from about 5 to about 12.5 w% of monomer (A) of formula (I); about 25 w % or higher, about 25 to about 90 w %, about 30 to about 80 w %, or about 35 to about 75 w % of monomer (B), an unsaturated cyclic amide of formula (III), preferably N-vinyl pyrrolidone; about 10 to about 50 w % of the copolymer, for example about 15 to
  • a formed copolymer for example a dispersion or solution, which hydrogel is formed from about 1 to about 25 w%, for example from about 2 to about 20 w%.
  • a formed copolymer for example a dispersion or solution, which hydrogel is formed from about 1 to about 25 w%, for example from about 2 to about 20 w%.
  • a formed copolymer for example a dispersion or solution, which hydrogel is formed from about 1 to about 25 w%, for example from about 2 to about 20 w%.
  • a formed copolymer for example a dispersion or solution, which hydrogel is formed from about 1 to about 25 w%, for example from about 2 to about 20 w%.
  • a formed copolymer for example a dispersion or solution, which hydrogel is formed from about 1 to about 25 w%, for example from about 2 to about 20 w%.
  • step ii) UV curing the coated substrate in step i). 3.
  • a method of coating the copolymer onto a substrate comprising the steps of
  • a formed copolymer for example a dispersion or solution, which copolymer is formed from about 1 to about 25 w%, for example from about 2 to about 20 w%.
  • a formed copolymer for example a dispersion or solution, which copolymer is formed from about 1 to about 25 w%, for example from about 2 to about 20 w%.
  • a formed copolymer for example a dispersion or solution, which copolymer is formed from about 1 to about 25 w%, for example from about 2 to about 20 w%.
  • Photoinitiators Further, non-photocrosslinkable photoinitiators may be used during the UV curing step.
  • photoinitiators are: benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, for example 1-hydroxy-cyclohexyl-phenyl ketone, 1- [4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1 -propan-1 -one or 2-hyd roxy-2-m ethyl- 1 - phenyl-propanone, dialkoxyacetophenones, .alpha. -hydroxy- or . alpha.
  • -amino-acetophenones for example (4-morpholino-benzoyl)-1-benzyl-1-dimethylamino-propane or (4- methylthiobenzoyl)-1-methyl-1-morpholino-ethane, 4-aroyl-1 ,3-dioxolanes, benzoin alkyl ethers and benzil ketals, for example 2,2-dimethoxy-1 ,2-diphenylethan-1-one, monoacylphosphine oxides, for example 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bisacylphosphine oxides, for example bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl-phosphine oxide, bis(2,4,6- trimethylbenzoyl)-(2-methylprop-1-yl)-phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenyl- phosphine oxide and tris
  • mixtures of two or more photoinitiators for example mixtures of bis(2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentyl-phosphine oxide or bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide with 1-hydroxy-cyclohexyl-phenyl ketone or hydroxy-2-m ethyl- 1 -phenyl-propanone or 2- methoxy-1 -phenyl-ethane-1 ,2-dione.
  • photoinitiators and photocrosslinkable photoinitiators identified in copending EP applications for patent family may be used in the copolymer of this application.
  • One of the suitable substrates is for example a polymer or plastic.
  • These polymers or plastics may be selected from the group consisting of polyvinyls, polyethers, polyesters, polyamides, polyurethanes, polymers of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids and derivatives thereof, polylactic acid, polyimines, polyolefins, polyethersulfones (PESU), polysulfones (PSU), polyphenylsulfones (PPSU; PPSF), polyetherketones (PEK),
  • PEK polyetherketones
  • PEEK polyetheretherketones
  • polyimides polyimides
  • polyetherimides polyacetals
  • fluoropolymers chloropolymers
  • poly(acrylonitrile) polycarbonates
  • PC polycarbonates
  • silicones natural polymers, mixtures thereof and others.
  • Silicones are of special interest.
  • Polyvinyls are principally all polymers obtained from polymerizing monomers with ethylenically unsaturated C-C double bonds. However, due to their economic importance and huge variety, polyolefins, poly(meth)acrylic acids, poly(meth)acrylates, poly(meth)acrylamides,
  • polyvinyls may be selected form the group consisting of vinylaromatic polymers, vinylheteroaromatic polymers, polyvinyl alcohol (PVA; PVOH), polyvinyl ethers, polyvinyl esters, polyvinyllactams, polyethers, polyesters, polyamides, polyurethanes, polyisocyanates, polyvinylacetals.
  • PVA polyvinyl alcohol
  • polyvinyl ethers polyvinyl esters
  • polyvinyllactams polyethers
  • polyesters polyamides
  • polyurethanes polyisocyanates
  • polyvinylacetals polyvinylacetals.
  • the latter are the reaction product of polyvinyl alcohol with an aldehyde, for example with formaldehyde (resulting in polyvinylformals (PVFM)) or with butyraldehyde (resulting in polyvinylbutyrals (PVB)).
  • Polyvinyls are likewise selected from the group consisting of polyolefins, poly(meth)acrylic acids, poly(meth)acrylates, poly(meth)acrylamides, polyimines, polyethersulfones, polysulfones, polyphenylsulfones, polyimides, polyacetals, fluoropolymers, chloropolymers and
  • poly(acrylonitrile), polycarbonates, silicones, natural polymers and other polymers are examples of poly(acrylonitrile), polycarbonates, silicones, natural polymers and other polymers.
  • Vinyl-aromatic monomers used to prepare the vinyl aromatic polymers include styrene, a- methylstyrene, all isomers of vinyltoluene, ethylstyrene, butylstyrene, dimethylstyrene and mixtures thereof.
  • the vinyl aromatic monomers mentioned above can be
  • copolymerized with other copolymerizable monomers examples include (meth)acrylic acid, C C 4 alkyl esters of (meth)acrylic acid, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, butyl acrylate, amides and nitriles of (meth)acrylic acid such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, butadiene, ethylene, divinylbenzene, maleic anhydride, phenylmaleinimide and the like.
  • Preferred copolymerizable monomers are acrylonitrile, butadiene, (meth)acrylic acid,
  • (meth)acrylates maleic anhydride and phenylmaleinimide, in particular acrylonitrile, butadiene, (meth)acrylic acid and (meth)acrylates.
  • vinylaromatic polymers include polystyrene, poly(p-methylstyrene) and poly(a-methylstyrene).
  • vinylaromatic polymers also include copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, or graft copolymers of styrene or ⁇ -methylstyrene such styrene-arcrylonitrile copolymers, a-methylstyrene-acrylonitrile copolymers, styrene-maleicanhydride copolymers, styrene-phenylmaleinimide copolymers, methylmethacrylate-copolymere, styene- methylmethacrylate-acrylonitrile-copolymers, styrene-acrylonitrile-maleic anhydride-copolymers, styrene-acrylonitrile-phenylmaleinimide-copolymers, a-methylstyrene-acrylonitrile-methyl methacrylate-copolymers, a-methylstyren
  • Vinylheteroaromatic polymers are for example polyvinylimidazole (e.g. poly(l -vinylimidazole)) and polyvinylpyridine (e.g. poly(2- or 4-vinylpyridine)) and copolymers thereof with other ethylenically unsaturated comonomers, such as olefins, the above- and below mentioned vinyl monomers, (meth)acrylic acid, derivatives thereof, maleic acid, derivatives thereof etc..
  • polyvinylimidazole e.g. poly(l -vinylimidazole)
  • polyvinylpyridine e.g. poly(2- or 4-vinylpyridine)
  • copolymers thereof with other ethylenically unsaturated comonomers such as olefins, the above- and below mentioned vinyl monomers, (meth)acrylic acid, derivatives thereof, maleic acid, derivatives thereof etc.
  • Polyvinylethers are for example homopolymers of methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n- pentyl vinyl ether, n-hexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, 1 , 1 ,3,3-tetramethyl butyl vinyl ether, ethylhexyl vinyl ether, n-nonyl vinyl ether, n-decyl vinyl ether, n-undecyl vinyl ether, tridecyl vinyl ether, myristyl vinyl ether, pentadecyl vinyl ether, palmityl vinyl ether, heptadecyl vinyl ether, octadecyl vinyl ether, nonade
  • Polyvinyl esters are for example polyvinyl acetate (PVAc) as well as its partially or completely hydrolysed form, namely polyvinyl acetate-polyvinyl aclcohol or polyvinylalcohol, if used in an non-aqueous environment prior to crosslinking, and copolymers of esters of vinyl alcohol with Ci-C 30 monocarboxylic acids, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl propionate, Versatic acid vinyl esters and the like or mixtures thereof with ethylene or higher olefins and/or (meth)acrylates.
  • Polyvinyllactams polyvinyl acetate (PVAc) as well as its partially or completely hydrolysed form, namely polyvinyl acetate-polyvinyl aclcohol or polyvinylalcohol, if used in an non-aqueous environment prior to crosslinking,
  • Polyvinyllactams are for example poly(N-vinylpyrrolidone) (PVP), poly(N-vinylpiperidone), poly(N-vinylcaprolactam) poly(N-vinyl-5-methyl-2-pyrrolidone), poly(N-vinyl-5-ethyl-2- pyrrolidone), poly(N-vinyl-6-methyl-2-piperidone), poly(N-vinyl-6-ethyl-2-piperidone), poly(N- vinyl-7-methyl-2-caprolactam), poly(N-vinyl-7-ethyl-2-caprolactam) etc.
  • PVP poly(N-vinylpyrrolidone)
  • PVP poly(N-vinylpiperidone)
  • poly(N-vinylcaprolactam) poly(N-vinyl-5-methyl-2-pyrrolidone)
  • poly(N-vinyl-5-ethyl-2- pyrrolidone) poly(N-
  • Polyethers are for example polyethylene glycol (PEG), polypropylene glycol (PPG), mixed EO/PO-polyethers, polytetramethylene glycol (PTMEG; polytetrahydrofuran), mixed polyethers of EO or PO with polyols, such as glycerol, 1 ,1 ,1-trimethylolpropane (TMP), aminopolyethylene glycols, pentaerythritol or sorbitol.
  • PEG, PPG and mixed EO/PO polyethers are typically obtained from the corresponding epoxide (ethylene oxide or propylene oxide or mixtures thereof), while polytetramethylene glycol is typically obtained by acid-catalyzed ring-opening reaction of THF.
  • polyesters and copolyesters are described, for example, in EP-A-0678376, EP-A-0 595 413, and US 6,096,854.
  • Polyesters are condensation products of one or more polyols and one or more polycarboxylic acids or the corresponding lactones.
  • the polyol is a diol and the polycarboxylic acid a dicarboxylic acid.
  • the diol component may be selected from ethylene glycol, 1 ,4-cyclohexanedimethanol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,4-butanediol,
  • diols whose alkylene chain is interrupted one or more times by nonadjacent oxygen atoms. These include diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and the like. In general the diol comprises 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms.
  • Cycloaliphatic diols can be used in the form of their cis or trans isomers or as an isomer mixture.
  • the acid component may be an aliphatic, alicyclic or aromatic dicarboxylic acid.
  • the acid component of linear polyesters is generally selected from terephthalic acid, isophthalic acid, 1 ,4-cyclohexanedicarboxylic acid,
  • polyesters are polyalkylene terephthalates, and polyalkylene naphthalates, which are obtainable by condensing terephthalic acid or naphthalenedicarboxylic acid, respectively, with an aliphatic diol.
  • Preferred polyalkylene terephthalates are polyethylene terephthalates (PET), which are obtained by condensing terephthalic acid with diethylene glycol. PET is also obtainable by transesterifying dimethyl terephthalate with ethylene glycol, with elimination of methanol, to form bis(2-hydroxyethyl) terephthalate, and subjecting the product to polycondensation, releasing ethylene glycol.
  • PET polyethylene terephthalates
  • PAN polyalkylene naphthalates
  • PEN polyethylene 2,6-naphthalates
  • PCT poly-1 ,4-cyclohexanedimethylene terephthalates
  • copolymers are also preferred.
  • copolymers are selected from polycondensates and copolycondensates of terephthalic acid, such as poly- or copolyethylene terephthalate (PET or CoPET or PETG), poly(ethylene 2,6-naphthalate)s (PEN) or PEN/PET copolymers and PEN/PET blends.
  • P PET or CoPET or PETG poly(ethylene 2,6-naphthalate)s
  • PEN poly(ethylene 2,6-naphthalate)s
  • PEN/PET copolymers and PEN/PET blends.
  • Said copolymers and blends depending on their preparation process, may also comprise fractions of
  • Polyamides (abbreviated code PA) have as key structural elements amide groups in the main polymer chain.
  • Polyamide polymers are herein to be understood as being homopolymers, copolymers, blends and grafts of synthetic long-chain polyamides having recurring amide groups in the polymer main chain as an essential constituent.
  • Polyamides can be prepared, for example, by polycondensation from diamines and dicarboxylic acids or their derivatives, such as aminocarbonitriles, aminocarboxamides, aminocarboxylate esters or aminocarboxylate salts.
  • suitable diamines include alkyldiamines such as C 2 -C 2 o-alkyldiamines, e.g., hexamethylenediamine, or aromatic diamines, such as C 6 -C 2 o-aromatic diamines, e.g., m-, o- or p-phenylenediamine or m-xylenediamine.
  • Suitable dicarboxylic acids comprise aliphatic dicarboxylic acids or their derivatives, chlorides for example, such as C 2 -C 2 o-aliphatic dicarboxylic acids, e.g., sebacic acid, decanedicarboxylic acid or adipic acid, or aromatic dicarboxylic acids, examples being C 6 -C 2 o-aromatic dicarboxylic acids or their derivatives, chlorides for example, such as 2,6-naphthalenedicarboxylic acid, isophthalic acid or terephthalic acid.
  • polyamides of this kind are poly-2,4,4- trimethylhexamethyleneterephthalamide or poly-m-phenyleneisophthalamide, PA 66 (nylon-6,6; polyhexamethyleneadipamide), PA 46 (nylon-4,6; polytetramethyleneadipamide), PA 69 (nylon- 6,9; polycondensation product of 1 ,6-hexamethylenediamine and azelaic acid), PA 610 (nylon- 6,10; polyhexamethylenesebacamide; polycondensation product of 1 ,6-hexamethylene diamine and 1 ,10-decanedioic acid), PA 612 (nylon-6, 12; polycondensation product of 1 ,6- hexamethylenediamine and 1 ,12-dodecanedioic acid), PA 1010 (nylon 10,10; polycondensation product of 1 ,10-decamethylenediamine and 1 ,10-decanedicarboxylic acid
  • PA 1212 polycondensation product of 1 ,12-dodecamethylenediamine
  • dodecanedicarboxylic acid the first number in each case indicating the number of carbon atoms in the diamine and the second number the number of carbon atoms in the dicarboxylic acid.
  • PA 6T polycondensation product of hexamethylenediamine and terephthalic acid
  • PA 9T polycondensation product of nonamethylenediamine and terephthalic acid
  • Polyamides are likewise obtainable by polycondensation from amino acids, examples being C 2 - C 20 -amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid or by ring-opening polymerization from lactams, ⁇ -caprolactam being the most prominent example.
  • Examples of polyamides of this kind are PA 4 (synthesized from 4-aminobutyric acid), PA 6 (nylon-6;
  • polycaprolactam synthesized from ⁇ -caprolactam or 6-aminohexanoic acid
  • PA 7 polyenantholactam or polyheptanoamide
  • PA 10 polydecanoamide
  • PA 1 1 nylon-1 1 ; polyundecanolactam
  • PA 12 nylon-12; polydodecanolactam
  • the number after the abbreviation PA indicates the number of carbon atoms in the monomer.
  • Polyamide copolymers may comprise the polyamide building blocks in various ratios.
  • Examples of polyamide copolymers are nylon 6/66 and nylon 66/6 (PA 6/66, PA 66/6, copolyamides made from PA 6 and PA 66 building blocks, i.e. made from caprolactam, hexamethylenediamine and adipic acid).
  • PA 66/6 (90/10) may contain 90% of PA 66 and 10% of PA 6.
  • PA 66/610 nylon-66/610, made from hexamethylenediamine, adipic acid and sebacic acid
  • PA 6/66/136 polycondensation product of caprolactam, hexamethyleneaminadipate and 4,4-diaminodicyclohexylmethanadipate
  • Polyamides further include partially aromatic polyamides.
  • the partially aromatic polyamides are usually derived from aromatic dicarboxylic acids such as terephthalic acid or isophthalic acid and a linear or branched aliphatic diamine. Examples are PA 9T (formed from terephthalic acid and nonanediamine), PA 6T/6I (formed from hexamethylenediamine, terephthalic acid and isophthalic acid), PA 6T/6, PA 6T/6I/66 and PA 6T/66.
  • Polyamides further include aromatic polyamides such as poly-meta-phenyleneisophathalamides (Nomex®) or poly-para-phenylene-terephthalamide (Kevlar®).
  • aromatic polyamides such as poly-meta-phenyleneisophathalamides (Nomex®) or poly-para-phenylene-terephthalamide (Kevlar®).
  • Polyamides further include copolymers made of polyamides and of a further segment, for example taking the form of a diol, polyester, ether, etc., in particular in the form of
  • polyesteramides polyetheresteramides or polyetheramides.
  • the polyamide segment can be any commercial available polyamide, preferably PA 6 or PA 66 and the polyether is usually polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
  • Polyamides can if appropriate be prepared with an elastomer as modifier.
  • suitable copolyamides are block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as with polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
  • polyethers such as with polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
  • EPDM- or ABS-modified polyamides or copolyamides and polyamides condensed during processing (RIM polyamide systems).
  • Polyurethanes are generally synthesized from at least one polyisocyanate and at least one compound having at least two groups per molecule that are reactive toward isocyanate groups.
  • Thermoplastic polyurethane is usually produced by reacting (a) organic and/or modified polyisocyanates with (b) at least one relatively high-molar-mass compound having hydrogen atoms reactive toward isocyanate, (c) if appropriate, low-molar-mass chain extenders in the presence of (d) a catalyst and, if desired, (e) one or more further additives.
  • the polyisocyanates (a) used can be selected from aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates and mixtures thereof. Preferred polyisocyanates are diisocyanates.
  • Preferred aromatic and araliphatic polyisocyanates are selected from the following individual polyisocyanates: toluylene 2,4-diisocyanate, toluylene 2,6-diisocyanate, mixtures composed of toluylene 2,4- and 2,6-diisocyanate, diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'- diisocyanate, diphenylmethane 2,2'-diisocyanate, mixtures composed of diphenylmethane 2,4'- and 4,4'-diisocyanate, urethane-modified liquid diphenylmethane 4,4'- and/or 2,4-diisocyanates, 4,4'-diisocyanato-1 ,2-diphenylethane, naphthylene 1 ,5-diisocyanate and mixtures thereof.
  • Suitable aliphatic and cycloaliphatic diisocyanates used are conventional aliphatic and/or cycloaliphatic diisocyanates. Preferably, they are selected from trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2-methylpentamethylene 1 ,5- diisocyanate, 2-ethylbutylene 1 ,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1 ,4- and/or
  • MXDI dicyclohexylmethane 2,2'-diisocyanate, tetramethylxylylene diisocyanate (MXDI) and mixtures thereof.
  • MXDI is generally termed an aliphatic diisocyanate because the isocyanate groups are bound to the (aliphatic) CH 2 groups.
  • the polyisocyanate (a) used is selected from hexamethylene 1 ,6-diisocyanate (hexamethylene diisocyanate, HDI), diphenylmethane 4,4'-, 2,4'-, or 2,2'-diisocyanate (MDI) and mixtures thereof.
  • Relatively high-molar-mass compounds (b) used having hydrogen atoms reactive toward isocyanates are the well known compounds reactive toward isocyanates, for example polyesterols, polyetherols, and/or polycarbonatediols, which are usually subsumed under the term "polyols", with molar masses from 500 to 8000, preferably from 600 to 6000, in particular from 800 to less than 3000, and preferably with average functionality toward isocyanates of from 1.8 to 2.3, preferably from 1.9 to 2.2, in particular 2.
  • polyesters can be polyesters based on diacids and on diols.
  • Diols preferably comprise diols having from 2 to 10 carbon atoms, e.g. ethanediol, butanediol, or hexanediol, in particular 1 ,4- butanediol, or a mixture thereof.
  • Diacids can comprise any of the known diacids, for example linear or branched-chain diacids having from four to 12 carbon atoms, or a mixture thereof.
  • Adipic acid is preferably used as diacid.
  • Chain extenders (c) used comprise well known aliphatic, araliphatic, aromatic, and/or cycloaliphatic compounds with molar mass of from 50 to 499, preferably difunctional compounds, such as diamines and/or alkanediols having from 2 to 10 carbon atoms in the alkylene radical, in particular 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, and/or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and/or decaalkylene glycols having from 3 to 8 carbon atoms, and preferably corresponding oligo- and/or polypropylene glycols, and it is also possible here to use a mixture of the chain extenders.
  • difunctional compounds such as diamines and/or alkanediols having from 2 to 10 carbon
  • the ratio by weight of the relatively high-molar- mass compound (b) having hydrogen atoms reactive toward isocyanates to chain extender (c) can be from 0.5:1 to 20: 1 , preferably from 1.5: 1 to 13: 1 , and a higher proportion of chain extender here gives a hard product.
  • Suitable catalysts (d) which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxy groups of the structural components (b) and (c) are the tertiary amines which are conventional and known from the prior art, e.g. triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2- (dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane, and the like, and also in particular organometallic compounds, such as titanic esters, iron compounds, e.g. ferric acetylacetonate, tin compounds, e.g.
  • stannous diacetate, stannous dioctoate, stannous dilaurate, or the dialkyltin salts of aliphatic carboxylic acids e.g. dibutyltin diacetate, dibutyltin dilaurate, or the like.
  • the amounts usually used of the catalysts are from 0.0001 to 0.1 part by weight per 100 parts by weight of polyhydroxy compound (b).
  • Polymers of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids and derivatives thereof ⁇ , ⁇ -Ethylenically unsaturated monocarboxylic acids are for example acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid and -chloroacrylic acid.
  • Homopolymers of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids are thus, for example, polyacrylic acid (PAA), polymethacrylic acid (PMAA) and polyethacrylic acid.
  • Copolymers of these acids typically contain one or more of the above- or below-mentioned ethylenically unsaturated comonomers, such as olefins, vinylesters, vinyllactams, ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acid esters, ⁇ , ⁇ - ethylenically unsaturated mono- and dicarboxylic amides, maleic anhydride and the like.
  • ethylenically unsaturated comonomers such as olefins, vinylesters, vinyllactams, ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acid esters, ⁇ , ⁇ - ethylenically unsaturated mono- and dicarboxylic amides, maleic anhydride and the like.
  • ⁇ , ⁇ -Ethylenically unsaturated dicarboxylic acids are for example maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and glutaconic acid. Homopolymers of these dicarboxylic acids are not very common; they are generally used in copolymers.
  • Copolymers of these acids typically contain one or more of the above- or below-mentioned ethylenically unsaturated comonomers, such as olefins, vinylesters, vinyllactams, ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acid esters, ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic amides, maleic anhydride and the like.
  • ethylenically unsaturated comonomers such as olefins, vinylesters, vinyllactams, ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acid esters, ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic amides, maleic anhydride and the like.
  • the acids of the ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids may be also used in form of their salts, in particular as the sodium, potassium and ammonium salts, and the salts with amines.
  • Suitable derivatives of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids are typically their esters, amides and anhydride (especially maleic anhydride).
  • Polyetherketones are polymers having alternating ether and keto groups in their backbone. Most common are polyaryletherketones (PAEK) having between the functional groups 1 ,4-bound aryl groups.
  • PEEK polyetheretherketone
  • polyetheretherketones encompass polyaryleneetheretherketones in general, i.e. polymers containing arylene groups which are linked by ether groups and keto groups, with twice as much ether groups as keto groups.
  • Suitable arylene groups are for example phenylene, naphthylene, anthracenediyl and phenanthrenediyl; these may carry one or more substituents, e.g. halogen atoms, OH groups, alkyl groups, e.g. Ci-C 4 -alkyl groups, alkoxy groups, e.g. CVC ⁇ alkoxy groups, sulfonic acid or sulfonate groups and the like.
  • polyolefin comprises all polymers composed of olefins without further functionality, such as polyethylene, polypropylene, polybut- 1-ene or polyisobutylene, poly-4-methylpent-1-ene, polyisoprene, polybutadiene, polymers of cycloolefins, such as of cyclopentene or norbornene, and also copolymers of monoolefins or diolefins, such as ethylene-propylene copolymers or ethylene-butadiene-copolymers.
  • Suitable polyethylene (PE) homopolymers are for example:
  • PE-ULD ultralow density
  • PE-VLD very low density
  • copolymers and terpolymers of ethylene with up to 10% octene, 4-methylpent-1-ene, and occasionally propylene density between 0.91 and 0.88 g/cm 3 ; barely crystalline, transparent
  • PE-LD low density
  • LD low density
  • ICI high-pressure process
  • PE-LLD linear low density
  • PE-MD middle density
  • the density between 0.93 and 0.94 g/cm 3 can be prepared by mixing PE-LD and PE-HD or directly as a copolymeric PE-LLD.
  • PE-HD high density
  • HD medium-pressure
  • Ziegler low- pressure
  • PE-HD-HMW high molecular weight
  • HMW high molecular weight
  • PE-HD-UHMW ultra high molecular weight
  • Suitable ethylene copolymers are all commercial ethylene copolymers, examples being
  • Luflexen® grades (LyondellBasell), Nordel® and Engage® (The Dow Chemical Company).
  • suitable comonomers include a-olefins having 3 to 10 carbon atoms, especially propylene, but-1-ene, hex-1-ene, 4-methylpent-1-ene, hept-1-ene and oct-1-ene, and also alkyl acrylates and methacrylates having 1 to 20 carbon atoms in the alkyl radical, especially butyl acrylate.
  • Further suitable comonomers are dienes such as butadiene, isoprene, and octadiene, for example.
  • Further suitable comonomers are cycloolefins, such as cyclopentene, norbornene, and dicyclopentadiene.
  • the ethylene copolymers are typically random copolymers or block or impact copolymers.
  • Suitable block or impact copolymers of ethylene and comonomers are, for example, polymers for which in the first stage a homopolymer of the comonomer or a random copolymer of the comonomer is prepared, containing up to 15% by weight of ethylene, and then in the second stage a comonomer-ethylene copolymer with ethylene contents of 15% to 80% by weight is polymerized on.
  • comonomer-ethylene copolymer is polymerized on for the copolymer produced in the second stage to have a fraction of 3% to 60% by weight in the end product.
  • Polypropylene should be understood below to refer both to homopolymers and to copolymers of propylene.
  • Copolymers of propylene comprise minor amounts of monomers copolymerizable with propylene, examples being C 2 -C 8 -alk-1-enes such as ethylene, but-1-ene, isobutene, pent- 1-ene or hex-1-ene, among others, and dienes, such as butadiene. It is also possible to use two or more different comonomers.
  • Suitable polypropylenes include homopolymers of propylene or copolymers of propylene with up to 50% by weight of copolymerized other alk-1-enes having up to 8 C atoms.
  • the copolymers of propylene are in this case random copolymers or block or impact copolymers. Where the copolymers of propylene are of random construction they generally comprise up to 15% by weight, preferably up to 6% by weight, of other alk-1-enes having up to 8 C atoms, especially ethylene, but-1-ene or a mixture of ethylene and but-1-ene.
  • polystyrene resins are homopolymers of higher alkenes or dienes, such as but-1-ene, isobutylene, 4-methyl-1-pentene, butadiene or isoprene, and copolymers thereof, such as isobutylene/isoprene copolymers.
  • the polyolefin may also be selected from copolymers of mono-olefins or diolefins with vinyl monomers and mixtures thereof. These include, for example, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers, and copolymers thereof with carbon monoxide, or ethylene/acrylic acid copolymers and their salts (ionomers).
  • Polyimines are especially polyethyleneimines.
  • Polyethyleneimine (PEI) or polyaziridine is a polymer with repeating unit composed of the amine group and a CH 2 CH 2 spacer.
  • Linear polyethyleneimines contain all secondary amines, in contrast to branched PEIs which contain primary, secondary and tertiary amino groups.
  • polyethersulfone (PESU or PES) is poly(oxy-1 ,4-phenylsulfonyl-1 ,4-phenyl).
  • polyethersulfones encompasses
  • polyarylenethersulfones in general, i.e. polymers containing arylene groups which are at least partly linked by ether groups and sulfonyl groups.
  • Suitable arylene groups are for example phenylene, naphthylene, anthracenediyl and phenanthrenediyl; these may carry one or more substituents, e.g. halogen atoms, OH groups, alkyl groups, e.g. C C ⁇ alkyl groups, alkoxy groups, e.g. CVC ⁇ alkoxy groups, sulfonic acid or sulfonate groups and the like.
  • polysulfone is obtained by polycondensation of bisphenol A and 4,4'- dichlorodiphenylsulfone.
  • polysulfones encompass polyarylensulfones in general, i.e. polymers containing arylene groups which are at least partly linked by ether groups, sulfonyl groups and propan-2,2-diyl (-C(CH 3 ) 2 -) groups.
  • Suitable arylene groups are for example phenylene, naphthylene, anthracenediyl and phenanthrenediyl; these may carry one or more substituents, e.g.
  • arylene groups may be linked by single bonds (in which case the
  • polyphenylsulfone (PPSU or PPSF) is obtained by polycondensation of biphenyl-4-4'-diol and 4,4'-dichlorodiphenylsulfone.
  • polyphenylsulfones encompass in general polymers containing arylene and biarylene groups which are at least partly linked by ether groups and sulfonyl.
  • Suitable arylene groups are for example phenylene, naphthylene, anthracenediyl and phenanthrenediyl; these may carry one or more substituents, e.g. halogen atoms, OH groups, alkyl groups, e.g.
  • Ci-C 4 -alkyl groups alkoxy groups, e.g. CrC 4 -alkoxy groups, sulfonic acid or sulfonate groups and the like.
  • Suitable biarylene groups are for example biphenylene and binaphthylene; these may carry one or more substituents, e.g. halogen atoms, OH groups, alkyl groups, e.g. d-d-alkyl groups, alkoxy groups, e.g. d-d-alkoxy groups, sulfonic acid or sulfonate groups and the like.
  • Polyimides are characterized by imide groups in the backbone. They are usually obtained by reaction between a dianhydride, e.g. pyromellitic dianhydride or naphthalene tetracarboxylic dianhydride, and a diamine or, less common, a diisocyanate to form polyamic acid, abbreviated as PAA, and then react into polyimide under high temperature, imidization and dehydration. Examples are polybismaleinimide (PBMI), polyimidesulfone (PISO) and polymethacrylimide (PMI).
  • PBMI polybismaleinimide
  • PISO polyimidesulfone
  • PMI polymethacrylimide
  • PEI polyetherimides
  • Polyacetals comprise both homopolymers as well as copolymers of polyacetals with cyclic ethers, and polyacetals modified with thermoplastic polyurethanes, acrylates or methyl acrylate/butadiene/styrene copolymers.
  • Polyacetals are produced by the polymerization of aldehydes or of cyclic acetals.
  • One industrially significant polyacetal is polyoxymethylene (POM), which is obtainable through cationic or anionic polymerization of formaldehyde or trioxane, respectively. Modified POM is obtained, for example, by copolymerization with cyclic ethers such as ethylene oxide or 1 ,3-dioxolane.
  • POM-based polymer blends Combination of POM with thermoplastic polyurethane elastomers produces POM-based polymer blends. Unreinforced POM is notable for very high stiffness, strength, and toughness. POM is used preferably for constructing household appliances and for constructing apparatus, vehicles, and machinery, and in sanitary and installation engineering.
  • Fluoropolymers are for example fluorinated ethylene propylene polymers (FEP), polyvinyl fluoride) and poly(vinylidene fluoride).
  • Chloropolymers are for example poly(vinylidene chloride) and polyvinyl chloride).
  • Polycarbonates are for example poly(vinylidene chloride) and polyvinyl chloride).
  • Polycarbonates are prepared, for example, through condensation of phosgene or carbonic esters such as diphenyl carbonate or dimethyl carbonate with dihydroxy compounds.
  • Suitable dihydroxy compounds are aliphatic or aromatic dihydroxy compounds.
  • aromatic dihydroxy compounds mention may be made for example of bisphenols such as 2,2-bis(4- hydroxyphenyl)propane (bisphenol A), tetraalkylbisphenol A, 4,4-(meta-phenylenediiso- propyl)diphenol (bisphenol M), 4,4-(para-phenylenediisopropyl)diphenol, 1 , 1-bis(4- hydroxyphenyl)-3,3,5-trimethylcyclohexane (BP-TMC), 2,2-bis(4-hydroxyphenyl)-2- phenylethane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), and also, if appropriate, mixtures thereof.
  • bisphenols such as 2,2-bis
  • the polycarbonates may be branched by using small amounts of branching agents.
  • Suitable branching agents include phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl)hept-2-ene, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane; 1 ,3,5-tri(4- hydroxyphenyl)benzene; 1 , 1 , 1-tri(4-hydroxyphenyl)heptane; 1 ,3,5-tri(4-hydroxyphenyl)benzene; 1 ,1 , 1-tri(4-hydroxyphenyl)ethane; tri(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4- hydroxyphenyl)cyclohexyl]propane; 2,4-bis(4-hydroxyphenylisopropyl)phenol; 2,6-bis(2-hydroxy- 5'-methylbenzyl)-4-methylphenol; 2-(4
  • Examples of compounds suitable for chain termination include phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol, or mixtures thereof.
  • the fraction of chain terminators is generally 1 to 20 mol%, per mole of dihydroxy compound.
  • Silicones are of special interest. Silicones are more precisely called polymerized siloxanes or polysiloxanes. They are mixed inorganic-organic polymers with the chemical formula [R 2 SiO] n , where R is an organic group such as methyl, ethyl, or phenyl. These materials consist of an inorganic silicon-oxygen backbone ( •• -Si-O-Si-O-Si- ⁇ - ⁇ ) with organic side groups attached to the silicon atoms, which are four-coordinate. In some cases, organic side groups are used to link two or more of these -Si-O- backbones together. By varying the -Si-O- chain lengths, side groups, and crosslinking, silicones can be synthesized with a wide variety of properties and compositions. They can vary in consistency from liquid to gel to rubber to hard plastic.
  • Natural polymers are for example oligo- and polysaccharides, polypeptides (especially proteins), lipids and nucleic acids and crosslinked polyisoprenes also referred to as rubber.
  • Polysaccharides are long carbohydrate molecules of monosaccharide units, such as glucose, fructose, or glyceraldehyde, joined together by glycosidic bonds. They range in structure from linear to highly branched. Oligosaccharides are shorter-chained than polysaccharides, the distinction between the two terms not being strict.
  • Some examples for this large class are disaccharides, amylose, glycogen, starch, hemicellulose, cellulose, chitin, amylopectin, pectin, callose, laminarin, chrysolaminarin, xylan, arabinoxylan, mannan, fucoidan, galactomannan, xanthan gum, dextran, dextran sulfate, chitosan, welan gum, gellan gum, diutan gum, pullulan, heparin, hyaluronic acid, alginic acid, to name just a few.
  • oligo- and polysaccharides also encompasses synthetic derivatives of the natural polymers, such as hydroxym ethyl cellulose, hydroxyethyl cellulose, hydroxyl propyl cellulose, carboxymethyl cellulose, nitrocellulose, cellulose acetate, or cellulose butyrate.
  • polymers suitable for the present composition (and use) not belonging to the above polymer classes are for example polymers with alternating heterocyclic and aliphatic groups. Examples are poly(ethyloxazoline), poly(propyloxazoline), poly(butyloxazoline),
  • Optional additives may be added to the hydrogel copolymer coating.
  • These additives may be selected from blowing agents, surfactants, nucleating agents, lubricants and mold-release agents, dyes, pigments, antioxidants, e.g. with respect to hydrolysis, light, heat, or discoloration, metal deactivators, inorganic and/or organic fillers, reinforcing agents, and plasticizers.
  • hydrogel of this application may be combined with diphenyl ethers such as Triclosan® or Diclosan® registered trademarks of BASF Corporation.
  • antimicrobial active substances which may be combined with the inventive hydrogel coating include phenol derivatives, benzyl alcohols, chlorhexidine, C 12 -C 14 alkylbetaines, C 8 - Ci 8 fatty acid amido alkyl-betaines, amphoteric surfactants, trihalocarbanilides and quaternary ammonium salts.
  • Silver containing antimicrobials are also envisioned such as those under the tradenames Irgaguard® and Hygentic® also available from BASF Corporation.
  • Antibiotics which can typically be included in the hydrogel coating of this applications are for example anthracyclines (e.g., doxorubicin or mitoxantrone), tetracyclines (e.g. minocycline), nitrofuran derivatives (e.g. nitrofuranzone), aminoglycosides (e.g. gentamycin) fluoropyrimidines (e.g., 5-fluorouracil), folic acid antagonists (e.g., methotrexate) and podophylotoxins (e.g., etoposide) can be utilized to enhance the antibacterial activity of the urinary catheter coating.
  • anthracyclines e.g., doxorubicin or mitoxantrone
  • tetracyclines e.g. minocycline
  • nitrofuran derivatives e.g. nitrofuranzone
  • aminoglycosides e.g. gentamycin
  • anthracyclines e.g., doxorubicin or mitoxantrone
  • fluoropyrimidines e.g., 5- fluorouracil
  • folic acid antagonists e.g., methotrexate
  • podophylotoxins e.g., etoposide
  • Polymers of special interest as substrates are those which are used in medical devices.
  • substrates important for medical devices are polysiloxane, silicon rubber, polyolefins, polyvinylchloride, polymethylmethacrylate, polyesters, polytetrafluoroethylene, polyamides, natural rubbers, polyacetal, polysulfones, polyurethanes, thermoplastics
  • TPU polyurethanes
  • polyethers polyethers
  • polycarbonates polycarbonates
  • thermoplastic polyurethanes TPU
  • thermoplastic polyolefins PTO
  • thermoplastic elastomers TPE
  • silicone rubbers or polysiloxanes TPU
  • Such medical articles are selected from the group comprising catheters, urinary catheters, vascular catheters of the peripheral type, central vascular catheters, single lumen central venous catheters, multiple lumen central venous catheters, peripherally inserted central venous catheters, emergency infusion catheters, percutaneous sheath introducer systems,
  • thermodilution catheters including the hubs and ports of such vascular catheters, wound drainage tubes, arterial grafts, soft tissue patches, shunts, stents, tracheal catheters, guide wires, protetic devices, heart valves, LVAD's, leads to electronic devices such as pacemakers, defibrillators, artificial hearts, and implanted biosensors, wound dressings, sutures, gloves.
  • Silicone urinary catheters and central venous catheters are of special interest as the substrate for application of the copolymer coatings discussed above.
  • the copolymer preparation may be applied to the substrate by means of at least one of the techniques selected from the group consisting of dip-coating, dispersing, spray-coating, application in solution, knife-coating, roller-coating, spin coating.
  • the plastic or polymer substrate may be pretreated before application of the copolymer.
  • poly(dimethyl siloxane) may be treated by plasma to cause OH groups to form on the surface of the substrate followed by silanization with 3-methacryloyloxypropyl trimethoxysilane or vinyltrimethoxysilane.
  • the surface is activated with covalently bound methacrylate or vinyl functionality which covalently binds with the hydrogel copolymer when treated via photoinitiator and UV light.
  • the method of coating the copolymer onto the substrate may further comprise a substrate treatment step before step i), wherein the treatment comprises silanization, low temperature plasma, irradiation, a corona discharge, high-energy radiation and/or a flame treatment on the inorganic or organic substrate.
  • PEGMA is poly(ethylene glycol) methacrylate methyl ether
  • NVP N-vinyl pyrrolidone
  • Methacrylic acid (3.15 g) and N-hydroxysuccinimide (4.65 g) are dissolved in 50 mL N- dimethylformamide (DMF). The solution is cooled to 0 °C, and a solution of 7.55 g
  • Dosage 1 23.18 g N-vinyl pyrrolidone, 13.50 g poly(ethylene glycol) methacrylate methyl ether (MW-480), 0.23 g photoinitiator.
  • the polymerizable photoinitiator in all examples is
  • Dosage 2 8.10 g dodecyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium iodide dissolved in 30 g acetone
  • the dosages are sparged with nitrogen for 15 min, then fed into the reactor.
  • the reactor is charged with 90 mL Dl water with the pH adjusted to 7-8 with 0.1 wt% sodium hydroxide.
  • the reactor charge is sparged with nitrogen for 15 min, 0.15 mL of a 5 wt% solution of V50 azo initiator in Dl water is added, then heated under stirring to a reaction temperature of 70 °C.
  • the temperature reaches 60 °C, the feeding of both dosages begins and is continued for 3 h.
  • the feeding rate is adjusted so the dosages are added completely in 3 h. After each hour, another 0.22 mL V50 solution is added.
  • reaction mixture is heated to 85 °C after the monomer feeding is complete, and another 0.30 mL of the V50 solution is added after 1 h. After another 30 min, the reaction mixture is allowed to cool to room temperature. The product is diluted with 550 mL Dl water and dialyzed for 3 days. The polymer solution is then freeze-dried.
  • copolymer 2 is similar to the synthesis of copolymer 1 with the following dosages:
  • Dosage 1 34.65 g N-vinyl pyrrolidone, 4.50 g poly(ethylene glycol) methacrylate methyl ether (MW-480), 0.23 g polymerizable photoinitiator
  • Copolymer 3 is identical to the synthesis of copolymer 1 except that the quat of Example 2 (dodecyl-dimethyl-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl]ammonium iodide) is used.
  • Copolymer 4 is similar to the synthesis of Copolymer 3, but the following dosages are used:
  • Dosage 1 25.65 g N-vinyl pyrrolidone, 13.50 g poly(ethylene glycol) methacrylate methyl ether (MW-480), 0.23 g polymerizable photoinitiator
  • Dosage 2 5.63 g dodecyl-dimethyl-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl]ammonium iodide dissolved in 30g acetone.
  • Copolymer 5 is identical to the synthesis of Copolymer 4 except that the Quaternary of example 1 (Q1 ) is used.
  • Dosage 3 0.4 g tert-butyl hydroperoxide in 9.6 g Dl water.
  • Dosage 4 0.4 g sodium metabisulfite in 9.6 g Dl water.
  • the dosages are sparged with nitrogen for 15 minutes prior to feeding.
  • a 250 ml. reactor is charged with 100 ml. Dl water and purged for 15 min, then the dosages are fed at the rates at times below:
  • Dosage 1 17.10 g N-vinyl pyrrolidone, 9.00 g poly(ethylene glycol) methacrylate methyl ether (MW-480), 0.15 g photoinitiator
  • Dosage 2 3.75 g 1-tetradecyl-3-vinylimidazolinium bromide dissolved in 20 g isopropanol The dosages are sparged with nitrogen for 15 min, then fed into the reactor.
  • the reactor is charged with 190 ml. Dl water with the pH adjusted to 7-8 with 0.1 wt% sodium hydroxide.
  • the reactor charge is sparged with nitrogen for 15 min, 0.10 mL of a 5 wt% solution of V50 azo initiator in Dl water is added, then heated under stirring to a reaction temperature of 70 °C. When the temperature reaches 60 °C, the feeding of both dosages begins and is continued for 3 h. The feeding rate is adjusted so the dosages are added completely in 3 h.
  • trimethoxysilane for 30 min. They are then immersed in ethanol for 30 min, after which they are air dried. This sequence is repeated 3 more times.
  • a solution of the Copolymers 1-5 is prepared in isopropanol at 5% solids.
  • the substrate pretreated according to Example 12 is dip coated with this solution by immersing the substrate into the polymer solution and withdrawing it at a constant speed.
  • the coated substrate is dried in an oven at 50 °C for 2 h.
  • Copolymer 6 is first swollen in a small amount of Dl water (5 g Copolymer 6 in 15 g of water), and then dissolved in isopropanol to give a solid content of 5 %.
  • coated substrates of Examples 14 and 15 are passed under a UV lamp with an H-bulb installed at a speed of about 7 s/pass 5 times.
  • TPU substrate is washed with isopropanol overnight. The substrate is then dried for 3h at 50° C. The samples are dip coated into a 5% solution of Copolymer 4 in isopropanol and dried for 1 h at 50° C and then UV cured according to Example 15.
  • Lubricity of the coated substrate is measured by connecting a sled weighing 480 g to a mini instron (Diastron measuring unit) via two pulleys.
  • Two coated tubular substrates (coated PDMS) are placed side by side in a tray parallel to each other, and the sled covered with a silicone rubber pad is pulled by the instrument on the substrates over a distance of about 8 inches.
  • the frictional force is recorded by a computer and is plotted against the distance.
  • Wet lubricity is measured in a similar fashion, but with a weight of 783 g, and the coatings are first swollen in Dl water and are kept under water during the measurement.
  • Lubricity is measured on the coated PDMS according to the application and 24 Fr All-Silicone Medline® urinary Foley catheters, as well as on 24 Fr Bardex Lubrisil® Foley catheters for comparison.
  • Lubrisil® catheters are marketed as catheters with a lubricious hydrogel coating. The frictional force measured is averaged over the distance that the weight is pulled and is tabulated in Table 1.
  • ASTM 2149 is used to assess the antimicrobial activity of coated substrates. Pieces of 30 cm 2 surface area are subjected to the test in duplicates or triplicates.
  • Copolymer 4 O.OOE+00 O.OOE+00 O.OOE+00 O.OOE+00 O.OOE+00 O.OOE+00 O.OOE+00 O.OOE+00
  • Washing medium 0.85 % Sterile Saline
  • E.coli ATCC# 8539 is inoculated in tryptic soy broth and incubated at 35-37°C overnight.
  • a fluorescent dye reporter is added to measure the amount of cell washed off the test substrates.
  • Syto 9 a general fluorescent nucleic acid stain, is added to the prepared culture in the ratio of 1.5 ⁇ _ to 10.55ml_ culture.
  • Samples are cut to a standard size, placed in microtiter plates, and tested in triplicate. Each well is inoculated using 1 ml_ of the prepared culture. Samples are incubated for 1 hour at 37°C. After incubation, wells are washed 4 times with 1 ml_ of 0.85 % sterile saline. The cell wash is retained for relative fluorescent measurement (RFU). Each replicate is pooled and read for relative fluorescence in triplicate on a microtiter plate reader. Each measurement is averaged, standard deviation is calculated, and percent difference relative to untreated silicone control is recorded in RFU.
  • RFU relative fluorescent measurement

Abstract

La présente demande de brevet concerne des revêtements antiadhésifs et lubrifiants, leurs procédés de préparation et leurs utilisations. Lesdits revêtements sont formés de copolymères à base d'au moins deux motifs monomères éthyléniquement insaturés différents (A) et (B) et, éventuellement, du motif (C) décrit dans les présentes. Le revêtement obtenu est hautement lubrifiant, antiadhésif et antimicrobien et se révèle tout à fait adapté aux utilisations médicales par exemple.
PCT/US2014/060665 2013-10-21 2014-10-15 Revêtements antiadhésifs et lubrifiants WO2015061097A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016182444A1 (fr) 2015-05-12 2016-11-17 Rijksuniversiteit Groningen Résines composites antimicrobiennes pouvant être imprimées en 3d et procédés de fabrication associés
US20180126047A1 (en) * 2015-05-19 2018-05-10 Sabic Global Technologies B.V. Polymeric implantable medical devices and surgical instruments
WO2019034222A1 (fr) * 2017-08-17 2019-02-21 Coloplast A/S Revêtements polymères

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Publication number Priority date Publication date Assignee Title
US3910862A (en) * 1970-01-30 1975-10-07 Gaf Corp Copolymers of vinyl pyrrolidone containing quarternary ammonium groups
US4035478A (en) * 1976-03-08 1977-07-12 American Cyanamid Company Clear, water-white hair conditioning composition
US20100112364A1 (en) * 2007-04-25 2010-05-06 Ciba Corporation Substrates with biopassive coating
US20100209361A1 (en) * 2007-07-17 2010-08-19 Basf Se Highly cationic copolymers based on quaternized nitrogen-containing monomers
KR20130079432A (ko) * 2010-05-27 2013-07-10 난양 테크놀러지컬 유니버시티 안과용 및 의료용 중합성 조성물, 및 그것을 중합해서 수득되는 항균성 조성물

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3910862A (en) * 1970-01-30 1975-10-07 Gaf Corp Copolymers of vinyl pyrrolidone containing quarternary ammonium groups
US4035478A (en) * 1976-03-08 1977-07-12 American Cyanamid Company Clear, water-white hair conditioning composition
US20100112364A1 (en) * 2007-04-25 2010-05-06 Ciba Corporation Substrates with biopassive coating
US20100209361A1 (en) * 2007-07-17 2010-08-19 Basf Se Highly cationic copolymers based on quaternized nitrogen-containing monomers
KR20130079432A (ko) * 2010-05-27 2013-07-10 난양 테크놀러지컬 유니버시티 안과용 및 의료용 중합성 조성물, 및 그것을 중합해서 수득되는 항균성 조성물

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016182444A1 (fr) 2015-05-12 2016-11-17 Rijksuniversiteit Groningen Résines composites antimicrobiennes pouvant être imprimées en 3d et procédés de fabrication associés
US20180126047A1 (en) * 2015-05-19 2018-05-10 Sabic Global Technologies B.V. Polymeric implantable medical devices and surgical instruments
WO2019034222A1 (fr) * 2017-08-17 2019-02-21 Coloplast A/S Revêtements polymères
CN111032102A (zh) * 2017-08-17 2020-04-17 科洛普拉斯特公司 聚合物涂层
EP3668555B1 (fr) 2017-08-17 2021-10-06 Coloplast A/S Revêtements polymères
CN111032102B (zh) * 2017-08-17 2022-03-22 科洛普拉斯特公司 聚合物涂层

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