WO2007036501A2 - Copolymere greffe et son utilisation - Google Patents

Copolymere greffe et son utilisation Download PDF

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Publication number
WO2007036501A2
WO2007036501A2 PCT/EP2006/066674 EP2006066674W WO2007036501A2 WO 2007036501 A2 WO2007036501 A2 WO 2007036501A2 EP 2006066674 W EP2006066674 W EP 2006066674W WO 2007036501 A2 WO2007036501 A2 WO 2007036501A2
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WO
WIPO (PCT)
Prior art keywords
graft copolymer
graft
backbone polymer
dopa
functional groups
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PCT/EP2006/066674
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German (de)
English (en)
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WO2007036501A3 (fr
Inventor
Thomas Friedrich
Andreas SCHÄDLER
Rainer STÜRMER
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Basf Aktiengesellschaft
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Publication of WO2007036501A2 publication Critical patent/WO2007036501A2/fr
Publication of WO2007036501A3 publication Critical patent/WO2007036501A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • Graft copolymer its use and method for bonding or coating surfaces.
  • the present invention relates to a graft copolymer, its uses and a method of bonding or coating surfaces.
  • the invention further relates to surfaces which have been bonded or coated by means of the graft copolymer according to the invention.
  • the mussel (Mytilus edulis) attaches itself to so-called byssus threads firmly on damp or wet ground - whether rocks in the surf, Teflon, flotsam of plastic or metal hulls. For this purpose, it produces sticky proteins, so-called “adhesive mussel proteins” (MAP) .
  • MAP adheresive mussel proteins
  • the functional group to which the graft side chain is bound is a free primary or secondary amino group.
  • the backbone polymer is a cationic polymer.
  • the backbone polymer described therein is for use in the biomedical field. Although polyacrylic acid and hyaluronic acid are mentioned as backbone polymer, these are converted into polyamines.
  • WO 2005/070866 discloses a polymer dispersion or solutions containing 3,4-dihydroxyphenyl groups in an amount of 0.01 millimoles per gram of polymer. The amount of 3,4-dihydroxyphenyl groups preferably does not exceed 5 millimoles per gram of polymer.
  • the copolymer described there is preferably formed from a free-radical polymerization of monomers having a 3,4-dihydroxyphenyl group.
  • the adhesion agent should be as economical as possible to produce, for example by the elimination of protective groups in the preparation of the graft copolymer. Furthermore, the most cost-effective polymers should be used. The starting materials, especially the monomers, should be as inexpensive as possible. Furthermore, the use of enzymes should be kept as low as possible. In particular, a fermentative production should be avoided.
  • the adhesive should be water soluble. A biodegradable polymer should also be provided for adhesive applications.
  • R is a straight-chain or branched alkyl having a chain length of 1 to 6 carbon atoms, wherein the alkyl may contain a halogen or a heteroatom, wherein in the functional group iv and / or vii R may also be the backbone polymer, and two graft side chains or more, the graft side chain comprising at least one compound selected from a group consisting of 3- (3,4-dihydroxyphenyl) alanine (Dopa), the semichinone, the quinone of Dopa, a hydroxyphenyl methyl ether derivative, a hydroxycinnamic acid and a hydroxybenzoic acid and wherein a portion of the functional groups i to xiii of the backbone polymer is covalently linked to one graft side chain and wherein the amount of dopa, semiquinone, quinone of dopa, hydroxyphenylmethyl ether derivative, hydroxycinnamic acid or
  • the invention relates to a graft copolymer according to the invention, wherein the amount of dopa, semiquinone, quinone of dopa, hydroxyphenylmethyl ether derivatives, hydroxycinnamic acid, in particular ferulic acid or hydroxybenzoic acid together from 10 to 90, particularly preferably from 50 to 80 millimoles per gram of graft copolymer or per gram of backbone polymer, preferably per gram of backbone polymer.
  • a graft copolymer according to the invention is neutral or polyanionic.
  • the graft copolymer is preferably polyanionic.
  • the molecular weight is an essential property of a graft copolymer according to the invention. All molecular weight data refer to the number average molecular weight.
  • the molecular weight of the graft copolymer is from 100,000 to 250,000, more preferably from 200,000 to 250,000.
  • a suitable backbone polymer is known per se or can be carried out by processes known per se.
  • Table 1 shows commercial examples or common synthetic routes for a suitable backbone polymer having the functional groups i to xiv.
  • the covalent binding of the graft side chain, in particular of dopa or of ferulic acid, to the functional groups i to xiv can be carried out differently depending on the graft side chain present in each case by methods known to the person skilled in the art. It preferably does not take place via a bond of the amino group of the backbone polymer and a carboxyl group of Dopa.
  • Functional groups are to be understood in this context as the groups i to xiv.
  • the presence of a functional group in the backbone polymer of the invention enhances the reactivity of the backbone polymer.
  • the functional groups i to xiv are generally able to bind covalently to the graft side chain.
  • the functional groups i to iii on the backbone polymer are free to react with a graft side chain.
  • Functional groups such as functional groups iii, iv, v, vi, vii, viii, x, xi, are generally reactive so that they can react with the graft side chains.
  • Functional groups such as the functional groups i, ii, ix, xii, xiii generally need to be made reactive.
  • the covalent attachment of the graft side chain is generated via a coupling reagent such as EDC or DCC (dicyclohexylcarbodiimide) or other common activating reagents.
  • a coupling reagent such as EDC or DCC (dicyclohexylcarbodiimide) or other common activating reagents.
  • auxiliary bases such as DBU (diazabicycloundecene) or DABCO (diazabicyclooctane) or, in general, tertiary amines or phosphines can be used.
  • a peptide bond to the amino group of the dopa can be prepared in aqueous solution at pH 6 to 7. In some cases, hydrolysis takes place, which may be advantageous for the solubility of a graft copolymer according to the invention having a functional group iv.
  • the graft side chain in particular the dopa, can be thermally or using an auxiliary base such as triethylamine, DBU or DABCO.
  • an ester of the graft side chain in particular of the dopa with the functional group vii or viii of the backbone polymer, can be formed with dehydrating agents, optionally acid-catalyzed with removal of the water of reaction by, for example, azeotropic distillation.
  • an aminoalcohol having the amino group of the graft side chain, in particular the dopa can be formed thermally or, if appropriate, by adding an auxiliary base or also a polymer-compatible Lewis acid.
  • the amino group of the graft side chain in particular of the dopa, can add up.
  • esterification can take place with the carboxyl group of the graft side chain, in particular the dopa.
  • esterification can take place with the carboxyl group of the graft side chain, in particular the ferulic acid.
  • a peptide bond to the carboxy group for example of ferulic acid, can be prepared in aqueous solution at pH 6 to 7.
  • a further subject relates to the use of a polymer having functional groups other than the functional groups i to xiv for the preparation of a graft copolymer according to the invention.
  • a further subject relates to a process for the preparation of a graft copolymer according to the invention, wherein a. in a first step, providing a backbone polymer having the functional groups i to xiv b. in a further step, the functional groups i to xiv are each covalently linked to a graft side chain according to the invention, wherein a reactivation may be necessary depending on the functional group i to xiv present.
  • a further subject relates to a process for the preparation of a graft copolymer according to the invention, wherein a. in a first step, providing a backbone polymer having functional groups other than functional groups i to xiii, for example with NH2 as a functional group b. in a further step, the compound from step a is re-functionalized to a functional group i to xiii, in particular to i and c. in a further step, the functional groups of the compound from step b are each covalently bonded to a graft side chain according to the invention.
  • the functional groups i to xiv may already be present in the backbone polymer. It is also according to the invention to re-functionalize different functional groups of the backbone polymer from the functional groups i to xiv to the functional groups i to xiv.
  • An example of this is the carboxylation of polylysine to carbonyl polylysine.
  • existing amino groups can be converted to carboxyl groups by reaction, for example, with maleic anhydride.
  • the preparation of a graft copolymer according to the invention is generally carried out under an inert gas atmosphere, for example noble gases or nitrogen, in particular therefore with the exclusion of oxygen.
  • an inert gas atmosphere for example noble gases or nitrogen, in particular therefore with the exclusion of oxygen.
  • the proportion of the functional groups i to xiv of the backbone polymer, which are covalently bonded to one graft side chain in each case, can vary within wide ranges.
  • the fraction of the functional groups i to xiv of the backbone polymer which are covalently bonded to one graft side chain each, 40 mol% or more, preferably 60 mol% or more, wherein a proportion of 90 mol% or less is preferably not exceeded, and more preferably from 60 to 80 mol%.
  • the mol% data refers to the functional groups i to xiv of the backbone polymer.
  • a functional group is selected from a group consisting of i, ii, iii, iv, v, vi, vii, preferably selected from a group consisting of i, ii and iii as the functional group of the backbone polymer.
  • ii and iii as the functional group of the backbone polymer.
  • the functional groups i to xiv can be present randomly or alternately in the backbone polymer.
  • the functional groups i to xiv can have the same distance.
  • the functional groups i to xiv may also have a different spacing.
  • the molecular weight of a backbone polymer is from 10,000 to 100,000, preferably from 30,000 to 80,000, and more preferably from 60,000 to 80,000.
  • the pK value of a graft copolymer according to the invention is preferably 7.5 or lower, preferably 6 or lower, and more preferably 5 or lower.
  • the pK value of a graft copolymer according to the invention is from 3 to 5.
  • the backbone polymer in a polymer of the invention is preferably water-soluble or water-dispersible.
  • the backbone polymer is selected from a group consisting of carboxyl serum albumins, carboxyl soy proteins, carboxyl milk proteins, carboxyl polylysine, carboxyl polyvinylamine, carboxyl polyallylamine, carboxyl gelatin, polyaspartate, Corboxyl-polyvinylamine, polyacrylic acid , Polyacrylic acid esters and the copolymers thereof.
  • the backbone polymer is selected from a group consisting of carboxyl serum albumins, carboxyl Soy proteins, carboxyl milk proteins, carboxyl polylysine, carboxyl polyvinylamine, carboxyl polyallylamine, carboxyl gelatin, polyaspartate, carboxyl polyvinylamine, polyacrylic acid and polyacrylic acid esters.
  • Dopa is understood as meaning 3-, 4-hydroxyphenylallanine and its semichinone or its quinone, unless the context indicates otherwise.
  • the present invention relates to a graft copolymer according to the invention comprising precursors of dopa which can be hydroxylated to dopa, for example phenylalanine or tyrosine.
  • the graft-side chain can comprise a peptide, preferably of the amino acid chain length 1 to 10, which contains at least one dopa, as proposed for example in JP 060 87 889 or from WO 2003 051 418.
  • the graft side chain is a polyethylene glycol (PEG) -derivatized dopa, as described, for example, in Lee et al., Biomacromolecules (2002), 3 (5), 1038-1047 CODEN: BOMAF6; ISSN: 1525-7797, proposed.
  • the graft side chain consists of at least one compound of the group consisting of dopa, the semiquinone or the quinone of the dopa.
  • the backbone polymer is a protein which contains the functional groups i to xiv or its copolymer.
  • the backbone polymer is a protein that substantially contains the functional group i.
  • hydroxy cinnamic acids or hydroxybenzoic acids are used as the graft side chain of a graft copolymer of the invention.
  • hydroxycinnamic acids or hydroxybenzoic acids
  • An overview of such acids and their occurrence or their production are, for example, Watzl & Rechkemmer, Nutrition Review 48 (2001) Issue 10, 413-416, Li et al. Applied Biochemistry and Biotechnolgy, Vol. 125, 1-10 (2005).
  • a modified polyvinylamine is preferably used as a backbone polymer in the case of ferulic acid as a graft side chain.
  • a modified polyvinylamine is obtainable, for example, by coupling succinic anhydride to polyvinylamine, preferably Lupamine 4595. Such a coupling can be achieved, for example, by adding Succinic anhydride to polyvinylamine, preferably Lupamin 4595 done.
  • the mass ratio of the solids is preferably 1: 1.
  • low molecular weight components are beipsiel intercept separated by dialysis. It is also advantageous to narrow the resulting modified polyvinylamine.
  • the ferulic acid in an equally preferred embodiment, may be coupled to an unmodified polyvinylamine as a backbone polymer.
  • the coupling of the ferulic acid to a modified polyvinylamine is preferably carried out by mixing and stirring with potassium hydrogen phosphate buffer, preferably pH 8.0, water and EDC. This is preferably followed by a separation of low molecular weight reaction products, in particular dialysis. To avoid oxidation, dialysis can be carried out with Na2S2O5. Preferably, then a concentration takes place, for example on a rotary evaporator, for example at 40 ° C.
  • a graft copolymer prepared in accordance with the invention is advantageously stored under nitrogen for safety.
  • the graft side chain is a hydroxyphenylmethyl ether derivative.
  • a graft copolymer according to the invention is obtained, for example, by a copolymerization of a hydroxycinnamic acid or a hydroxybenzoic acid with a monomer, for example with acrylic acid.
  • the hydroxy group of a hydroxycinnamic acid or a hydroxybenzoic acid, preferably of the ferulic acid is preferably protected in a first step by a protective group.
  • the protecting group can be introduced by reaction with methylene chloride, triethylamine, 4-dimethylaminophenol hydrochloride and acetyl chloride, as shown in the following figure.
  • the copolymerization of ferulic acid ethyl ester with acrylic acid can be carried out by reaction of acrylamide solution, water, DMF, and the deprotected ferulic acid, especially in the form of a ferulic acid ethyl ester in DMF (dimethyl formamide), TEMED, APS.
  • the protective group is removed after the polymerization, for example by hydrolysis.
  • a further subject relates to a composition comprising a graft copolymer according to the invention, for example an aqueous solution or a dispersion comprising a graft copolymer according to the invention.
  • Another object is the use of a graft copolymer according to the invention for bonding or for coating surfaces.
  • a graft copolymer according to the invention in particular in the embodiment with dopa as the graft side chain, is stored free of oxygen before use and only comes into contact with oxygen when used.
  • Another object of the present invention is a method for bonding or for coating surfaces, wherein a. in a first step, a mixture containing an inventive
  • Graft copolymer is applied to a surface, wherein the graft side chain contains a semiquinone and / or a quinone of Dopa, and b. in a further step optionally another surface is brought into contact with the surface of step a.
  • Another object is a method for bonding or for coating surfaces, wherein a. in a first step, a mixture comprising a graft copolymer according to the invention, preferably with the semiquinone, particularly preferably with dopa as the top side chain, is applied to a surface, b. in a further step, adding a mixture containing an oxygen donor, and c. in a further step optionally another surface is brought into contact with the surface of step b.
  • Another object is a method for bonding two surfaces, wherein a. in a first step, a mixture containing an inventive
  • Graft copolymer preferably with the semiquinone, particularly preferably with dopa as P ropf side chain is applied to a surface, b. in a further step, a mixture containing an oxygen donor is applied to another surface, and c. in a further step, the surfaces of steps a and b are brought into contact.
  • Another object is a method for bonding or coating of O bervid, wherein a. in a first step, a mixture containing an inventive
  • Graft copolymer preferably mixed with the semiquinone, more preferably with dopa as the graft side chain with an oxygen donor, b. the mixture from step a is applied to a surface and c. in a further step optionally another surface is brought into contact with the surface of step b.
  • aqueous solution or an aqueous dispersion of a drip copolymer according to the invention is used.
  • the crosslinking of a graft copolymer according to the invention can be started by raising the pH, for example from 5 to 7.5 or by adding oxygen.
  • the oxygen supply can be made possible by oxygen donors.
  • the bonding process is oxygen-dependent. A sufficient amount of oxygen allows and accelerates the bonding process.
  • atmospheric oxygen can be used as an oxygen donor. If two surfaces are brought into contact during bonding, the supply of atmospheric oxygen is prevented. It is therefore advantageous to use an oxygen donor and to accelerate the release of oxygen with the aid of a catalyst. The progress of the bonding can generally be read off from the increasing browning.
  • oxygen donors are generally aqueous solutions of salts, in particular inorganic salts, which are able to split off oxygen, for example under heat or exposure to light meant. These are usually present as an aqueous solution.
  • organic hydroperoxides diacyl peroxides or organic peracids can be used as oxygen donors. These are usually dissolved in inert solvents, such as organic solvents.
  • At least one substance selected from a group consisting of H 2 O 2, sodium perborate, sodium percarbonate, sodium peroxodisulfate, tert-butyl hydroperoxide, cumene hydroperoxide, dibenzoyl peroxide, performic acid and peracetic acid is used as the oxygen donor.
  • the oxygen donor used is a 1 to 95, preferably a 1 to 30 and particularly preferably a 1 to 30% aqueous solution of H 2 O 2.
  • a catalyst which accelerates the release of oxygen from the oxygen donor.
  • transition metal ions and their salts or compounds can be generally used.
  • At least one transition metal ion is selected from a group consisting of Fe (III), Mn (VII), Mn (VI), Co (III), Cu (I), Cu (II), Ru (IV) and V (III) used as a catalyst.
  • a transition metal ion can be used. It is also possible to use a mixture of different transition metal ions. Preferably, only one transition metal ion is used. Preference is given to using a Fe (III) Cl.
  • Transition metal ions are usually suitable for all oxygen donors.
  • the catalytic effect can be accelerated photochemically or thermally.
  • a photochemical crosslinking of the graft copolymers according to the invention can be carried out, for example, in the case of transparent surfaces. However, the surfaces with the graft copolymer according to the invention can also be heated in order to accelerate the crosslinking of the graft copolymers according to the invention.
  • aqueous solutions of compounds or salts of the transition metal ions are used.
  • the transition metal ions are present in from 0.1 to 10 wt .-%, preferably from 0.1 to 2 wt .-% and particularly preferably from 0.1 to 1 wt .-%, based on the aqueous solution.
  • the oxygen donor H 2 O 2 can also be provided enzymatically, for example.
  • peroxidases such as the horseradish peroxidases or catalases, tyrosinases or catecholoxidases. Examples of these are known fungal tyrosinases.
  • H2O2 is used as oxygen donor and a peroxidase as catalyst.
  • the amounts of oxygen donor used can vary within wide limits.
  • 1 to 5 ⁇ l of radish peroxidase (10 mg / ml) and 30 to 70 ml of 1% H2O2, to 0.3 to 0.4 g of graft copolymer, preferably in a neutral buffer For example, 0.01 to 0.05 ml of potassium hydrogen phosphate, given.
  • Another object is a kit for bonding surfaces or for coating surfaces containing a. a container containing a mixture containing a graft copolymer gem. one of claims 1 to 9, b. a container containing a mixture containing an oxygen donor, c. optionally a container containing a mixture containing a catalyst which accelerates the release of oxygen and d. optionally a device for metering the components a, b and c.
  • a composition of the invention may contain the usual auxiliaries and additives according to the particular application.
  • fillers such as salsa, quark sand, finely divided silica, barite, calcium carbonate, chalk, dolomite or talc, which are often used together with suitable wetting agents, such as polyphosphates, such as sodium hexamethaphosphate, naphthalene sulfonic acid, ammonium or Natriumpolyacrylklad, wherein the wetting agents in general from o, 2 to 0.6 wt .-% based on the filler may be added.
  • suitable wetting agents such as polyphosphates, such as sodium hexamethaphosphate, naphthalene sulfonic acid, ammonium or Natriumpolyacrylklad, wherein the wetting agents in general from o, 2 to 0.6 wt .-% based on the filler may be added.
  • Fungicides for preservation are, if desired, generally used in amounts of 0.02 to 1 wt .-%, based on the total dispersion or solution.
  • Suitable fungicides are, for example, phenol or cresol derivatives or organotin compounds.
  • auxiliaries and additives customary in adhesive technology include thickeners, plasticizers or even tackifying resins such as natural resins or modified resins such as rosin esters or synthetic resins such as phthalate resins.
  • Another object is a surface which has been glued to another surface using a graft copolymer according to the invention or has been coated by a process according to the invention.
  • a water-soluble adhesive or coating material could be provided. This way, even wet and dirty surfaces can be easily glued in place. Furthermore, it has surprisingly been possible to achieve a high amount of dopa in the graft copolymer according to the invention.
  • a graft copolymer according to the invention in the embodiment with dopa as side chain can furthermore be produced surprisingly favorably on an industrial scale because neither protecting groups nor a peptide synthesis is mandatory. You can still stick in water.
  • a graft copolymer according to the invention in the embodiment with a backbone polymer consisting of a protein is biodegradable, that is to say degradation by proteases is possible, and the degradation products resulting therefrom are generally metabolizable.
  • graft copolymer according to the invention with atmospheric oxygen as the oxygen donor, no toxic, ie physiologically incompatible, starters or constituents are necessary.
  • a graft copolymer of the invention is easy and inexpensive to produce, since already existing polymers can be used as starting materials, for example polyacrylic acid, polyaspartate, polyisocyanates.
  • a graft copolymer according to the invention is insensitive to temperature with a protein as a backbone polymer, that is, it is thermally stable from 4 ° C. to 40 ° C.
  • An inventive graft copolymer is in one embodiment with a synthetic polymer, for example, polyacrylic acid, insensitive to temperature as a backbone polymer, that is, thermally stable from 4 ° C to 90 ° C.
  • the browning when crosslinking the graft copolymers according to the invention can serve as an indicator for the progress of the reaction, ie for the bond or the coating.
  • sample A5 For the preparation of sample A5 according to the invention and comparative example 6, 65 g of polyvinylamine (Lupamine 4595) (25 g of solid) were diluted to 100 ml with water. To this was added 25 g of finely ground succinic anhydride. The reaction mixture was stirred for 3 days at room temperature. Thereafter, the pH was adjusted to 8.0 (150 ml final volume). This volume was transferred to dialysis tubing and dialysed 3 times against 101 water. The final volume (ca ⁇ OOml) was concentrated at 50 ° C to about 60ml. The procedure is analogous with gelatin, bovine serum albumin and for the preparation of the inventive sample A1 1 and the comparative sample A12 with poly-lysine. Polyaspartate already has enough carboxyl groups for further derivatization.
  • Example 2 50 ml of a 10% BSA solution (5 g) obtained from Example 1 were mixed with 50 ml of a 10% dopamine solution (5 g). The solution was adjusted to pH 8.0 with 10 ml of a 1M phosphate buffer. Then, in portions, 10 g EDC (EDC, C 8 H 17 N 3 • HCl; 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide) was added. The reaction was overnight. As a control, ethanolamine (comparative samples) was added in place of the dopamine solution.
  • EDC EDC, C 8 H 17 N 3 • HCl; 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide
  • dopamine derivatives according to the invention and ethanolamine derivatives (for comparison) of polyvinylamine carboxylated according to Example 1 (Lupamine 4595) (inventive sample A5 with dopa and comparative sample 6 with ethanolamine), carboxyl-gelatin, and carboxyl-polylysine ( inventive sample A1 1 with Dopa and comparative sample A12 with thanolamine) as well as polyaspartate.
  • the reaction of polymaleic anhydride is carried out with dopamine without EDC.
  • Example 3 After mixing the adhesive material was applied in Example 3 surfactant on an upper (40 * 40mm) at room temperature and cured overnight.
  • Figure 1 shows the inventive sample A5 from Examples 3 and 4 after 15 min after application to the surface glass once with the presence of a H2O2 decomposing peroxidase (inventive sample A5 +) and without the presence of a H2O2 decomposing peroxidase (sample A5- invention).
  • the sticky polymer material of the sample A5- according to the invention is grasped with the tweezers and a thread can be pulled out of the material.
  • a thread can be drawn, while in the sample A5 + according to the invention no thread can be pulled any longer.
  • Another indication of the cure is the dark color.
  • Adhesive strength The adhesive strength of Inventive Samples A5 and A11 and Comparative Samples A6 and A12 of Examples 3 and 4 were determined as follows. The polymer samples were glued to wooden plates measuring 100x40mm. The adhesive surface was 40x40mm. The wooden tiles are labeled in Figure 2 as a PVC sheet. Force measurements were taken in the Texture Analyzer according to the sketch on the left. The feed was 0.1 mm / s. As a comparison, a sample was measured with the commercially available adhesive UHU Plus® (immediate strength). The experimental setup is shown in Figure 2.
  • Figure 3 shows the results of the adhesion test.
  • the inventive sample A5 and the comparative samples A6 and UhuPlus did not break even after 5 minutes of force of 550 N.
  • the inventive sample A11 broke after about 1 min force at 550 N and the sample A12 broke at about 220 N.
  • FIG. 4 shows the model of the preparation of a graft copolymer according to the invention with Dopa as graft side chain.
  • X denotes a graft copolymer according to the invention.
  • Y denotes the backbone polymer.
  • Z denotes the functional groups i to xiii.
  • the arrow means "responsive".
  • polyvinylamine (Lupamine 4595) (25g solid) was diluted to 100ml with water. To this was added 25 g of succinic anhydride (powdered) and stirred at room temperature for three days. Then, the pH was adjusted to 8.0 with sodium hydroxide solution and dialyzed (150 ml, dialysis tubing 3.5 kDa, 101 water, 3 times). The final volume (470 ml) was concentrated at 50 ° C on a rotary evaporator to 62 ml.
  • the solution is stirred for 4 days at RT and then dialyzed (3.5 kDa, water 4 days, then 5 days against 10OmM sodium hydrogen carbonate pH 9 - hydrolysis of the ester. A strong yellowing is observed.
  • the solution is then dialyzed again for 2 days against phosphate buffer pH 7 and water (4 days).
  • the resulting polymer is concentrated on a rotary evaporator and is ready for use.
  • Figure 5 below shows the inventive polymer from Example 7 after the crosslinking according to Example 10.
  • the upper figure shows a comparative experiment without the addition of horseradish peroxidase.
  • Figure 6 below shows the inventive polymer of Example 9 after crosslinking according to Example 10.
  • the upper figure shows a comparative experiment without the addition of horseradish peroxidase.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne un copolymère greffé, son utilisation, et un procédé pour réaliser le collage de surfaces ou appliquer un revêtement sur des surfaces.
PCT/EP2006/066674 2005-09-26 2006-09-25 Copolymere greffe et son utilisation WO2007036501A2 (fr)

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CN109705504A (zh) * 2018-11-27 2019-05-03 浙江巨化技术中心有限公司 一种改性聚四氟乙烯粉末的制备方法
CN109906248A (zh) * 2016-09-28 2019-06-18 可隆工业株式会社 醌可固化组合物和包含其的粘合剂组合物
CN110066565A (zh) * 2019-05-24 2019-07-30 齐鲁工业大学 一种耐黄变的高粘附性皮革涂饰剂及其制备方法
CN110170068A (zh) * 2019-05-27 2019-08-27 南通大学附属医院 多功效的医用缝线及其制备方法
CN113563809A (zh) * 2021-08-17 2021-10-29 深圳市高仁电子新材料有限公司 一种具有紫外线阻隔功能的丙烯酸光学胶及其制备方法
CN116082587A (zh) * 2023-01-30 2023-05-09 常州工程职业技术学院 一种利用生物基阿魏酸侧链修饰的聚缩醛共聚物的生产工艺

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CN109906248B (zh) * 2016-09-28 2021-10-15 可隆工业株式会社 醌可固化组合物和包含其的粘合剂组合物
CN109906248A (zh) * 2016-09-28 2019-06-18 可隆工业株式会社 醌可固化组合物和包含其的粘合剂组合物
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CN109705504A (zh) * 2018-11-27 2019-05-03 浙江巨化技术中心有限公司 一种改性聚四氟乙烯粉末的制备方法
CN109705504B (zh) * 2018-11-27 2020-12-29 浙江巨化技术中心有限公司 一种改性聚四氟乙烯粉末的制备方法
CN110066565A (zh) * 2019-05-24 2019-07-30 齐鲁工业大学 一种耐黄变的高粘附性皮革涂饰剂及其制备方法
CN110066565B (zh) * 2019-05-24 2021-08-13 齐鲁工业大学 一种耐黄变的高粘附性皮革涂饰剂及其制备方法
CN110170068A (zh) * 2019-05-27 2019-08-27 南通大学附属医院 多功效的医用缝线及其制备方法
CN110170068B (zh) * 2019-05-27 2023-09-26 南通大学附属医院 多功效的医用缝线及其制备方法
CN113563809A (zh) * 2021-08-17 2021-10-29 深圳市高仁电子新材料有限公司 一种具有紫外线阻隔功能的丙烯酸光学胶及其制备方法
CN113563809B (zh) * 2021-08-17 2022-03-08 深圳市高仁电子新材料有限公司 一种具有紫外线阻隔功能的丙烯酸光学胶及其制备方法
CN116082587A (zh) * 2023-01-30 2023-05-09 常州工程职业技术学院 一种利用生物基阿魏酸侧链修饰的聚缩醛共聚物的生产工艺
CN116082587B (zh) * 2023-01-30 2024-02-09 常州工程职业技术学院 一种利用生物基阿魏酸侧链修饰的聚缩醛共聚物的生产工艺

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