DE19646965A1 - New antimicrobial vinyl copolymer having quaternary ammonium groups - Google Patents

Abstract

New polymers (I) with antimicrobial properties comprise: (a) 99-40 wt. % non-functional vinyl monomer units and (b) 1-60 wt. % quaternary ammonium functional vinyl monomer units of formula V-Ay-HSpm-N<+>(R1)4-(m+t)(R2)t. X<-> (II). V = vinyl, acryloyl, methacryloyl, allyl or styryl; A = alkyl, aryl, arylalkyl or hydroxyalkyl linker unit (optionally interrupted by heteroatoms, e.g. in the form of urethane, carbonate, ester, amide or ether groups); y = 0 or 1; HSp = hydrophilic spacer of formula -(O-CH2-CH2)r- and/or -(O-CH2-CHMe)s; r,s = 0-40 and r + s = 2-40; m = 1-3; R1 = methyl, ethyl or benzyl; R2 = 8-20C alkyl; t = 1-3; X<-> = Cl<->, Br<->, I<-> or alkylsulphate. (Meth)acrylate monomers of formula CH2=CR3-CO-(O-CH2-CHR4)nm-N<+>(Me3)4-(m+t)-(R2)t. X<-> (III) are also new. n = 2 -40; R3, R4 = H or Me.

Description

The invention relates to polymers with antimicrobial properties. The Polymers according to the invention consist of vinylically known per se polymerizable monomers, as well as from monomers in which at least one long chain alkyl radical to a quaternary Ammonium group is bound, which in turn has a hydrophilic Spacer and optionally a linking unit with a Vinyl function is connected.

State of the art

EP 0 641 805 A1 describes polymers with antimicrobial (biophobic) Characteristics. The polymers consist of ethylenically unsaturated Monomers that are partially covalently bonded via side groups have antimicrobial phenolic agents.

The phenolic agents are bound in a polymer-analogous manner on building blocks with functional groups with amino or Hydroxyl groups can react. Examples of implementable residues are Hydroxy, hydroxyalkyl, dialkylaminoalkyl or haloalkyl groups. The phenolic residues of the biocidally functional monomers are therefore over relatively short, hydrophobic spacers connected to the polymer matrix.

JP abstract 62 05,936 (Chemical Abstracts, 107, 41977v) antifungal and antibacterial agents. These have one (Meth) acrylic residue on the on an ethylene glycol, propylene glycol or Hydroxypropylene grouping with 1-4 units a fluorinated aromatic is bound. The monomers are in a polyvinyl chloride paste z. B. used as an antimicrobial paper coating. Use in Polymers is not mentioned.

Nazarova et al. (Chemical Abstracts 122: 230183d: Khim.-Farm. Zh. (1993), 27 (2), 30-3) describes biophobic polymers from N- (2- hydroxypropyl) methacrylamide containing bound choramphenicol.  

A higher activity is found in vivo if that Chloramphenicol also via a glycine-leucine-glycine spacer the polymer is bound and is split off from the polymer. The Authors suspect a particularly good effect intracellular microorganisms. Obviously the easy one Removability of the chloramphenicol from the polymer by enzymatic Hydrolysis of the peptide bond is crucial for the good in vivo effect.

The incorporation of a bactericidal monomer is in dental applications J.Dent. Rs. 73 (8), 1437-1443 (1994). An antimicrobial Effect is observed with no release of the active species, whereby It is unclear whether the effectiveness is on a bactericidal or biophobic (antiadhesion) property. The one used Pyridinium compound is via a hydrophobic spacer (long-chain Alkyl residue) bound to the polymer backbone.  

Task and solution

The object of the invention is to provide copolymers by copolymerization with antimicrobial monomers be obtained and which are for the production of coatings or Shaped bodies are suitable, the surfaces of which are biocidal or biophobic Have properties without causing a toxic release Connections are coming. A subsequent, polymer-analog connection of microbiologically active molecules on surfaces should be avoided will. Furthermore, an active substance class should be an alternative to the phenolic compounds can be opened to u. a. by Active substance change or combination a selection of resistant strains avoid and to close gaps in effectiveness.

Polymers of the following structure have been found to have good antimicrobial properties. The polymers are made up of

• a) 99-40% by weight of nonfunctional vinyl polymerizable Monomers and
• b) 1-60% by weight of functional vinylically polymerizable monomers of the general formula (I)
  [VA _y -HSp] _m -N ^⊕ (R ¹ ) _{4- (m + t)} - (R ² ) _t . X⁻ (I)
  With
  V = vinyl, (meth) acroyl, allyl or styryl,
  A = an optionally present linking unit, the alkyl, aryl, arylalkyl or hydroxyalkyl, which can also be interrupted by heteroatoms, for example by heteroatoms in urethane, carbonate, ester, amide or ether groups, where y = 0 or 1,
  HSp = a hydrophilic spacer of the general formula
• (i) - (O-CH ₂ -CH ₂ ) _n - or
• (ii) - (O-CH ₂ -CH (CH ₃ )) _n - or
• (iii) - (O-CH ₂ -CH ₂ ) _r - (O-CH ₂ -CH (CH ₃ )) _s with n = r + s and
  with n = 2-40, as well
  m = 1, 2 or 3 and
  R ¹ = CH ₃ , ethyl or benzyl
  R ² = an alkyl radical with 8-20 C atoms, where
  t = 1, 2 or 3.
  X⁻ = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻.

For the monomers a) it is preferred that these are selected predominantly from the (meth) acrylic acid esters. Polymers in which the monomers b) (meth) acrylic esters of the general formula (II) are particularly preferred

[CH ₂ = CR ³ -CO- (O-CH ₂ -CHR ⁴ ) _n ] _m -N ^⊕ (CH ₃ ) _{4- (m + t)} - (R ² ) _t . X⁻ (II)

are, where
m = 1, 2 or 3, n = 2-40,
R ² = an alkyl radical with 8-20 C atoms, where t = 1, 2 or 3.
R ³ = H or CH ₃ ,
R ⁴ = H or CH ₃
X⁻ = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻.

Although the mode of action is not understood, the inventors assume that the monomers b), in which a combination of the one hydrophilic spacer bound quaternary ammonium group has at least one long chain alkyl radical that is antimicrobial effective principle of the polymers of the invention. This was in in no way predictable. The use of radical  polymerizable monomers containing vinyl groups, in particular (Meth) acrylic acid esters to build up the antimicrobial polymers opens up various possibilities for controlling the others Polymer properties such as glass temperature, minimum film formation temperature, Molecular weight, etc., so that antimicrobial polymers for many Applications are accessible.

Implementation of the invention

The polymers according to the invention with antimicrobial properties can in a manner known per se by radical polymerization of the Monomers in the presence of polymerization initiators and optionally molecular weight regulators can be obtained.

For this purpose a) non-functional vinyl polymerizable monomers and b) functional vinylically polymerizable monomers according to the general formula (I) used. The term functional monomers characterizes the monomers b) in the sense that their presence the antimicrobial property of the polymer is attributed.

The antimicrobial property is a germ-reducing or to understand the germicidal effect that occurs when the polymer and Germs come into contact with each other in the presence of water.

Monomers a)

Suitable nonfunctional vinyl polymerizable monomers after a) z. B. acrylate or methacrylate compounds, Allylyl bonds, styrenes, maleic acid, maleic anhydride or other vinyl compounds, such as vinyl esters, etc.

The monomers a) are preferably predominantly, for. B. at least 90% based on the total amount of monomers a),  (Meth) acrylate compounds. However, smaller proportions, e.g. B. up to = 10%, other monomers a) may be included. Alkyl are preferred (Meth) acrylates with 1 to 20 carbon atoms in the alkyl radical, hydroxy (meth) acrylates or also (meth) acrylate compounds with acid or amide functions. Examples are methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, Ethyl methacrylate, propyl methacrylate, butyl methacrylate. Cyclohexyl methacrylate, hydroxyethyl (meth) acrylate, acrylic acid, Methacrylic acid, acrylamide, methacrylamide. It can also be lesser Share of cross-linking connections such. B. glycol dimethacrylate or Allyl methacrylate may be included. Preferred monomers are Alkyl (meth) acrylates. Particularly preferred monomers a) are Methyl methacrylate and butyl acrylate.

Monomers b)

Functional vinyl polymerizable monomers according to b) have the general structure of the formula (I)

[VA _y -HSp] _m -N ^⊕ (R ¹ ) _{4- (m + t)} - (R ² ) _t . X⁻ (I)

With
V = vinyl, (meth) acroyl, allyl or styryl, preference is given to (meth) acryloyl
A = an optionally present linking unit, the alkyl, aryl, arylalkyl or hydroxyalkyl, which can also be interrupted by heteroatoms, for example by heteroatoms in urethane, carbonate, ester, amide or ether groups, where y = 0 or 1. However, y = 0 is preferred.

Examples of A are:
2-hydroxypropoxy, (2'-hydroxypropoxyphenyl) (2'-hydroxy-3-oxyphenyl) propane (from bisphenol A diglycidyl ether), 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa- 5,12-diazatetradecyl- (from HMDI), 6-ketohexyloxy-, 6-ketohexylamino- etc.

HSp = a hydrophilic spacer of the general formula

• (i) - (O-CH ₂ -CH ₂ ) _n - or
• (ii) - (O-CH ₂ -CH (CH ₃ )) _n - or
• (iii) - (O-CH ₂ -CH ₂ ) _r - (O-CH ₂ -CH (CH ₃ )) _s with n = r + s and
  with n = 2-40,
  preferred is (i) and (ii) with n = 2-40, particularly preferably with n = 2-10 and
  m = 1, 2 or 3, preferably 1 or 2 and
  R ¹ = CH ₃ , ethyl or benzyl, preferably CH ₃
  (if there are several R = 1 residues, these can be the same or different)
  R ² = an unbranched alkyl radical having 8-20, preferably = 1 2-18, particularly preferably 12 or 14 carbon atoms, where
  t = 1, 2 or 3, preferably 1 or 2,
  X⁻ = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻ (preferred alkysulfates are CH ₃ CH ₂ OSO ₃ ⁻ and CH ₃ OSO ₃ ) ⁻, Cl⁻ is preferred.

Preferred for the monomers b) are (meth) acrylic esters of the general formula (II)

[CH ₂ = CR ³ -CO- (O-CH ₂ -CHR ⁴ ) _n ] _m -N ^⊕ (CH ₃ ) _{4- (m + t)} - (R ² ) _t .X⁻ (II)

With
m = 1, 2 or 3, preferably 1 or 2,
n = 2-40, preferably 2-10,
if m <1, n can be the same or different in the individual residues.
R ² = an alkyl radical with 8-20, preferably 12-18, particularly preferably 12 or 14 carbon atoms, where t = 1, 2 or 3, preferably 1 or 2
R ³ = H or CH ₃ , preferably CH ₃
R ⁴ = H or CH ₃ , preferably H
X = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻ preferably Cl⁻.

Preferred monomers b) can have the general formula (III).

in which
u + v = 6-20, preferably 10
R ² = an alkyl radical with 8-20, preferably 12, carbon atoms
R ³ = H or CH ₃ , preferably CH ₃
X⁻ = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻, preferably Cl⁻.

A preferred monomer b) is e.g. B. the compound laurylamine-x-10EO-dimethacrylate quat (Quat A) according to formula (IV)

where u + v = 10 (statistical distribution around the mean u, v = 5)
Monomers b) of the general formula (V) are preferred

CH ₂ = CR ³ -CO- (O-CH ₂ -CH ₂ ) _w -N ^⊕ (CH ₃ ) ₂ -R ² . X⁻ (V)

in which
w = 2-40
R ² = an alkyl radical with 8-20, preferably 14 C atoms,
R ³ = H or CH ₃ , preferably CH ₃
X⁻ = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻ preferably Cl⁻
are.

Another preferred monomer b) is the compound 2- (2'-methacroylethoxy) ethyl-dimethyltetradecylammonium chloride (Quat B) according to formula (VI)

CH ₂ = C (CH ₃ ) -CO- (O-CH ₂ -CH ₂ ) ₂ -N ^⊕ (CH ₃ ) ₂ - (C ₁₄ H ₂₉ ). Cl⁻ (VI)

The monomers a) have long been known by standard Compounds accessible to synthetic processes. The monomers b) are accessible through synthesis.

General description of the synthesis

The monomers b) are based on ethoxylated amines by conversion or Esterification with (meth) acrylic acid or (meth) acrylic acid esters and subsequent quaternization with an alkyl chloride or dialkyl sulfate produced. Can be used as catalysts for transesterification and esterification according to the prior art acids, such as. B. sulfuric acid, para- Toluenesulfonic acid, basic catalysts such as calcium hydroxide, Calcium oxide, lithium hydroxide, lithium amide or the like, tin catalysts such as Dibutyltin oxide, dioctyltin oxide, metal acid esters such as tetraisobutyltitanate u. a. be used. Process stabilization are becoming common Stabilizers such as hydroquinone, hydroquinone monomethyl ether, 4-methyl 2,6-ditert.butylphenol, phenothiazine or similar as well as combinations of these added. The implementation advantageously takes place under azeotropic Distillation of the water of reaction or low-boiling Alcohol.

An alternative production method is the implementation of the ethoxylated amine and the hydroxyalkyl methacrylate with diisocyanates or  Diglycidyl ethers of diols such as bisphenol A followed by Quaternization.

The quaternization is carried out using alkyl chlorides or dialkyl sulfates Substance or in solvents. There may be a reaction in the Autoclaves (pressure) are an advantage. A move or is also conceivable Esterification of hydroxy-functional quaternary ammonium compounds with (meth) acrylic acid or esters.

General Description of the Synthesis of Laurylamine-x-10EO- Dimethacrylate quats (Quat A) and 2- (2'-methacroylethoxy) ethyl dimethyltetradecylammonium chloride (Quat B)

The monomers b) advantageously used, in particular Quat A (according to Formula IV) and Quat B (according to formula VI) are about Methacrylate ester of the corresponding ethoxylated tertiary amines, the obtained by transesterification with methyl methacrylate and isopropyl titanate are produced. The quaternization is advantageously carried out in an autoclave to reach higher temperatures. The quaternization with Fatty alkyl chlorides are preferred in bulk or with polar Solvents, particularly preferably carried out with alcohols.  

Antimicrobial polymers from the monomers a) and b)

The polymers according to the invention with antimicrobial properties can in a manner known per se by radical polymerization of the Monomers in the presence of polymerization initiators and optionally molecular weight regulators can be obtained.

For this purpose, a) non-functional vinyl polymerizable monomers and b) functional vinylically polymerizable monomers according to the general formula (I) used. The term functional monomers characterizes the monomers b) in the sense that their presence the antimicrobial property of the polymer is attributed.

One of the antimicrobial properties is the growth of Microorganisms, in particular bacteria or yeasts, inhibitory or germ-reducing effect understood. Such Effect can be achieved using a number of methods known to those skilled in the art are determined. Is suitable for. B. the method of put on According to Nurdin, Helary and Sauvet ("Biocidal Polymers Active by Contact. II. Biological Evaluation of Polyurethane Coatings with Pendant Quarternary Ammonium Salts ", J. Appl. Pol. Sci. 50, 663-670, 1993). 100 µl of a cell suspension with approx. 10,000 Bacterial cells, e.g. B. Klebsiella pneumoniae, towards a piece of the testing polymer placed and for a defined time, for. B. 3 Hours, incubated. Then the drop with the cell suspension decreased and the number of colony-forming units compared destined for a control. To check whether the antimicrobial effect on the polymer itself or through diffusing contained in the polymer Substances, e.g. B. residual monomers, is suitable for. b. a Test on the polymer pieces for one inoculated with bacteria Medium plate is brought. If diffusing antimicrobial Substances are contained, this can be due to the formation of an inhibitory a clear zone in which bacterial growth is inhibited to prevent  Polymer piece come. Suitable test methods can e.g. B. also from EP-A 641 805 are taken.

The monomers a) can contain 40-99% by weight, preferably 70-99, particularly preferably 80-99, in particular 85-95% by weight be included. The monomers b) are 1-60% by weight, preferably 1-30 % By weight, particularly preferably 1-20% by weight and in particular 5- 15 wt .-% included.

A polymer according to the invention can, for example, 30-70 wt .-%, preferably 50-60% by weight of methyl methacrylate and 70-30% by weight, preferably 35-45% by weight of butyl acrylate as monomers a) and 1-20 preferably 5-15, in particular 8-12% by weight of laurylamine-x-10EO- Dimethacrylate Quat (Quat A) or 2- (2-methacroylethoxy) ethyl Contain dimethyltetradecylammonium chloride (Quat B) as monomer b).

The structure of the polymers

The monomers a) are generally not critical as long as they are not antimicrobial effect of the monomers b) on the polymer surface neutralize. The selection of the monomers a) is therefore based on primarily according to the intended use and the intended Material properties of the polymer.

If hard, mechanically resistant moldings are produced are, the glass transition temperature of the polymers, or Softening temperature in the case of polymers with crystalline components, in generally well above room temperature, for example between 80 and 150 degrees C. Decorative or functional Coatings such as paints are often based on polymers Glass temperatures in the range of 0 to 100 degrees C. The more flexible the Coating is supposed to be, the lower is the Glass temperature. Adhesive coatings for use as Pressure sensitive adhesives usually have glass temperatures well below 0 degrees C. They are soft and very sticky at room temperature. If desired and the  Antimicrobial effect not detrimental, the polymers can crosslink be. The polymers according to the invention have glass transition temperatures in the Range from -60 ° C to 150 ° C. 0 ° C to 60 ° C are preferred. The glass temperature Tg can e.g. B. the Brandrup reference and E.H. Immergut, "Polymer Handbook" Interscience 1966, pp. III-61 to III-63, or the "plastics handbook", volume IX, editors R. Vieweg and F. Esser, Carl-Hanser-Verlag, Munich 1975, pp. 333 to 339 and T.G. Fox in Bull. Am. Physics Soc. ", Vol. I, (3) p. 123 (1956).

The form of application or processing of the polymer can also be used for the glass temperature to be set play a role. The specialist is known for example that in the case of an application as an aqueous Dispersion the choice of monomers is such that the Minimum film forming temperatures MFT determinable according to DIN 53 787 Dispersion does not exceed the drying temperature. In general the MFT will be between 0 and 60 degrees C.

The monomers a) are therefore selected in a manner known per se and way. The person skilled in the art knows how to use monomers whose Homopolymers have high or low glass temperatures ("hardening" or "softening" monomers), must combine, to set the desired material properties.

In the preferred embodiment, the polymer according to the invention is not water-soluble and at most water swellable.

The monomers a) therefore consist of more than 70% of monomers whose water solubility at room temperature is below 30 g / l, in particular below 20 g / l. A proportion of more than 90%, particularly preferably more than 95%, of such monomers is preferred. Examples are monounsaturated monomers such as styrene, ethylene, propylene, vinyl chloride, vinylidene chloride, butadiene, vinyl and allyl esters and ethers such as vinyl acetate, esters of maleic, fumaric and itaconic acid, esters and substituted amides of methacrylic and acrylic acid and methacrylic acid and acrylonitrile. The esters of methacrylic and acrylic acid, optionally in combination with styrene, substituted amides of (meth) acrylic acid and (meth) acrylonitrile are particularly preferred. Only a few representatives from the wide range may be mentioned as examples: C ₁ -C ₂₀ -alkyl esters of (meth) acrylic acid, in particular methyl, ethyl, propyl, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate and short-chain alkyl glycol (meth) acrylates such as ethoxy or butoxyethyl methacrylate or ethyl triglycol methacrylate.

In addition to the monounsaturated monomers, multiple unsaturated monomers depending on the intended use, application form or Manufacturing process be present in more or less large proportions. The person skilled in the art knows in which cases the proportion of such Monomers that crosslink the polymer during the polymerization Can lead polymers, must restrict. An example is the Solution polymerization referred to, in which proportions below 1% Networking and thus lead to retaliation of the approach. On the other hand, when using one consisting of monomers Coating and curing on the substrate surface, for example by UV radiation, almost arbitrarily large proportions of multiple unsaturated monomers can be used. Examples of such Monomers are ethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, Hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Allyl (meth) acrylate, methylene bis methacrylamide or acrylamide, Divinylbenzene and triallyl cyanurate. Restrictive to the content of polyunsaturated monomers would, however, if through a restricted mobility of the crosslinked polymer chains antimicrobial effect would be impaired.

In addition to the monomers with low water solubility, in limited amount of monomers are present, the Water solubility at room temperature is higher than 30 g / l, in particular  than 20 g / l. The proportion is less than 30% of the monomers a) restrict, preferably it should be below 10%, especially below 5 %. The copolymerization of minor parts of such Monomers to achieve certain properties are known. An example of this is the improvement in liability certain substrates, increasing the stability of disperse Systems that improve pigmentability or dyeability or the increase in chemical resistance through subsequent Crosslinking of the polymer. Examples of such monomers are polymerizable carboxylic acids such as (meth) acrylic acid, maleic acid and Itaconic acid, polymerizable phosphonic or sulfonic acids such as B. 1- (Meth) acrylamido-2-methylpropanesulfonic acid, Hydroxyalkyl (meth) acrylates, glycerol monomethacrylate, Glycidyl methacrylate, (meth) acrylamide, N-methylol methacrylamide and its ethers, maleic acid, alkoxypolyalkylene glycol (meth) acrylates, Dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, unsaturated ethylene urea derivatives such as N- (2- Methacryloyloxyethyl) ethylene urea, N-vinyl pyrrolidone, N-vinyl imidazole and saponified vinyl acetate.

Polymerization

In principle, all relevant used are suitable Polymerization process for the preparation of the polymers (see e.g. H. Rauch-Puntigam, Th. Voelker, acrylic and methacrylic compounds, Springer Verlag 1967 or Encyclopedia of Polymer Science and Engineering, Vol 13, pp. 708 ff., John Wiley & Sons, 1988). Usually one uses the radical polymerization using the usual radical initiators. As a method, u. a. the Solution, emulsion, suspension, precipitation and Bulk polymerization. An essential role for the choice of Manufacturing process plays the application form in which the polymer to be applied or the manner of later Processing / shaping. Because of the amphiphilic character and the  cationic charge of the monomer b) can, however, in individual cases Solubility problems or incompatibilities that the Influence the selection of the polymerization process or the Determination of the polymerization conditions are taken into account should.

Such problems are usually predictable for the person skilled in the art, or he is able to conduct suitable preliminary tests To work out polymerization conditions. For example, it can be advisable in the case of emulsion polymerization to the usual used anionic surfactants to avoid intolerance to avoid with the monomers b) and instead to non-ionic or to avoid cationic surfactants or completely without surfactants work. Also the use of polymerizable surfactants, or more general, stabilizing units such. B. Alkoxyethyl polyethylene glycol (meth) acrylates are possible.

In the case of bulk polymerization, if the monomers a) are very hydrophobic, too poor solubility of the monomers b) come so that, for example, the solution or Emulsion polymerization would be preferable.

It is also possible to add the monomer mixture as such to apply and harden the coating substrate. This The procedure is known. The polymerization can by thermal initiator decay or redox reactions can be initiated. In In most cases, however, curing takes place using radiation all UV radiation, using photoinitiators.

The molecular weight of the polymers is not critical with regard to the antimicrobial effect. It is generally set so that requirements for processability and material properties are met. In most cases the molecular weight is between 20,000 and 500,000. Solution polymers and thermoplastics to be processed tend to be in the lower half of this range, for example 100,000, while emulsion polymers usually have higher molecular weights and are in the upper half of this range. The molecular weight M _w can be determined, for example, by gel permeation chromatography or by scattered light method (see, for example, BHF Mark et al., Enzyclopedia of Polymer Science and Engineering, 2nd. Ed., Vol. 10, pages 1 ff, J. Wiley, 1989) . In practice, viscosity measurements are usually preferred.

However, lower or higher molecular weights are also possible up to infinitely high molecular weights in networked systems. The desired molecular weight can be z. B. by molecular weight regulators such as mercaptans, by the initiator or Monomer concentration or the polymerization temperature set will.

When selecting the monomers a) and b) is their Consider copolymerization behavior. This is characterized Copolymerization behavior through copolymerization parameters of Monomer pairs (see Encyclopedia of Polymer Science and Engineering, Vol 13, pp. 708 ff., John Wiley & Sons, 1988).

In order to polymerize all monomers evenly ensure it is advantageous to avoid combinations whose Copolymerization parameters are far apart. On the other hand methods known to those skilled in the art, the copolymerization in certain Limits even with unfavorable copolymerization parameters enforce, for example, by only a part of the preferred polymerizing partner presented and the rest according to the Consumption is metered in during the polymerization. It is also possible uneven copolymerization of the monomers  is even wanted to by the heterogeneous polymer composition to achieve special effects.

However, preference is given to combinations of the monomers a) and b) which expect uniform copolymerization or it make it unlikely that a significant portion of any of the monomers is not built into the copolymer. The copolymerization behavior of the most important monomers a) is known (cf. J. Brandrup, E.H. Immergut, Polymer Handbook, Third Ed., John Wiley & Sons, 1989). The Copolymerization parameters of the monomers b) were from the Not determined inventors. However, it can be assumed that the type of Double bond essentially the copolymerization behavior determined so that monomers b) with a methacryloyl group have similar copolymerization behavior as the known Methacrylates. Monomers b) with a methacryloyl or acryloyl group are therefore particularly suitable for combination with Methacrylates and acrylates of group a) and with styrene. Monomers with a vinyl double bond such as vinyl chloride show no great tendency to Copolymerization with methacrylates or acrylates. Should such Monomers are copolymerized with the monomers b), so it is over Knowledge of the copolymerization parameters is advantageous if as unsaturated group V, for example a vinyl ester group is selected. In the same way, a person skilled in the art can find further combinations of Put together monomers a) and b) which are advantageous Copolymerization behavior can be expected.

Use and advantageous properties of the polymers

The copolymers are preferably water-insoluble and at most limited swellable in water. They are suitable for the production of coatings and moldings in which microbial growth is undesirable and should be avoided. This includes paintings such as ship colors, Facade paints, floor coatings or wood glazes, self-adhesive  Coatings, coatings for tarpaulins and shower curtains, the finishing of textiles such as fabrics or nonwovens, for example for the hygiene area or for filters. As examples of moldings would be Door handles, railings, sanitary or kitchen surfaces, materials for water-carrying parts such as pipes, seals, valves, membranes call. Textile fibers or yarns can also be made according to the invention built copolymers are produced. Ideally, it inhibits antimicrobial surface the growth of microorganisms in the medium adjacent to the surface, so that also a preservative packaging of perishable watery goods is possible without adding toxic or questionable substances or would have to be released from the surface.  

EXAMPLES example 1 Synthesis of Quat A a) Preparation of the dimethacrylate of ethoxylated laurylamine (Laurylamine × 10EO)

160.5 g of ethoxylated laurylamine (MarlazinL10) are dried on a water separator using cyclohexane. After removal of the entrainer by distillation, 52 mg of hydroquinone monomethyl ether, 52 mg of phenothiazine, 130 mg of N, N'-diphenyl-p-phenylenediamine and 100 g of methyl methacrylate (MMA) are added, and the batch is dewatered again by azeotropic distillation. After adding a further 15 ml of MMA, 1.0 g of tetraisopropyl titanate is added at 80 ° C. The batch is heated to boiling and methanol / MMA is distilled off. The reaction is complete after 9 h. With the addition of dilute sulfuric acid, the catalyst is precipitated and filtered off under pressure after neutralization with aqueous sodium carbonate solution. Excess MMA is removed on the rotary evaporator.
The yield was 177.6 g; the structure was confirmed by NMR.

b) Preparation of the Laurylamine x-10EO Dimethacrylate Quat (Quat A)

85.0 g of dimethacrylate of ethoxylated laurylamine, 45.8 g of acetone, 43 mg of N, N'-diphenyl-p-phenylenediamine and 2 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl are added to the teflon insert in the autoclave . 4.5 g of chloromethane are pressed on. The mixture is stirred at 90 ° C. for 24 hours. The pressure (4-5 bar) decreases within this time. After cooling to room temperature, the autoclave is opened. 118.6 g of a clear, brown-colored, acetone solution (66% by weight) are obtained.
Structure confirmation by NMR.

Example 2 Synthesis of 2- (2'-methacroylethoxy) ethyl dimethyltetradecylammonium chloride (Quat B)

25.0 g of 2- [2- (dimethylamino) ethoxy] ethyl meth acrylate, 33.6 ml 1-chlorotetradecane, 22.8 ml ethanol, 50 mg potassium iodide and 12 mg of hydroquinone monomethyl ether with stirring at 105 ° C for 24 h heated. The pressure rises to approx. 2 bar. After cooling to room the temperature of the autoclave was opened. The Quat B is 75% ethanolic solution. The structure is confirmed by NMR.

Example 3 Preparation of the copolymer with Quat A

13.3 g MMA, 10.65 g butyl acrylate, 4.07 g Quat A solution (66% in acetone, 10% by weight Quat A based on the monomer mixture), 0.132 g 2,2'-azobis ( isobutyronitrile) (AIBN) and 0.1 ml of 2-ethylhexylthioglycolate are mixed and filled into a glass chamber (16 × 16 cm glass plate, 1.5 mm spacer cord) without air bubbles. The chambers are closed with putty and provided with clips. Polymerization takes place in the drying cabinet at 50 ° C. for 23 h. After removing the clamps, the mixture is tempered for 1 h at 75 ° C and 2 h at 90 ° C.
Clear, transparent, slightly brownish-colored polymers (glass temperature: 7 ° C.) were obtained.

Example 4 Preparation of the copolymer with Quat B. Emulsion polymerization

6.89 g of MMA, 5.27 g of butyl acrylate and 2.92 g of Quat B (as a 43% solution) and 0.09 g of 2-ethylhexylthioglycolate are added to 30 g of water. The mixture is emulsified at 70 ° C. at a stirring speed of 500 rpm. The mixture is then initiated at a stirring speed of 250 rpm with 0.084 g of 2,2'-azobis (2-aminopropane) dihydrochloride (dissolved in 0.1 g of water). After a reaction time of one hour, a further 0.042 g of initiator (dissolved in 0.5 g of water) is added to the dispersion and the mixture is stirred at 70 ° C. for a further 30 minutes. The mixture is then cooled to room temperature and the dispersion is filtered through a DN 70 metal sieve.

Residual monomer content: 296 ppm methyl methacrylate (MMA), 96 ppm butyl acrylate
Solids content: 29.7%
Particle size: 130 nm (no coagulum).

A clear, transparent film was obtained by pouring the emulsion onto a silicone-enclosed glass plate and drying overnight at 50 ° C.

Glass temperature: 36 ° C.

Example 5 Production of a comparative polymer without functional Monomer b)

Example 3 is repeated, with the difference that a mixture of 22.0 g MMA, 18.0 g butyl acrylate, 0.16 g AIBN and 0.12 g Ethylhexyl thioglycolate is used.

Example 6 Testing of the polymers from Examples 3 and 5 for bactericidal characteristics

The polymer films from Examples 3 and 5 were in water for 24 hours stored, the water was replaced after 8 hours. The movies were then air dried.

The bactericidal activity of these polymer films against the test organisms Staphylococcus aureus and Bacillus cereus was tested as follows:
Each test organism was inoculated with 5 ml of standard I broth in an Erlenmeyer flask and incubated for 16 hours at 37 ° C. as a stand culture. The mixture was then diluted 1: 10,000. Strips of the polymer films to be examined (5 cm × 1 cm) were overlaid with 8 ml of this dilution in sterile test tubes. Thereupon, after 2, 4 and 20 hours, live germ counts (LKZ / g) were determined immediately. The reagent tubes were incubated with shaking. The result is summarized in the table below.

Example 7 Antimicrobial properties of the polymers from Examples 3 and 4 a) Contact inhibition of Klebsiella pneumoniae DSM 798 by the Polymer 4A from Example 3

The polymer film of polymer 4A from Example 3 was in water for 24 h stored and after 8 hours the water was replaced. The foil was then air dried.

K. pneumoniae DSM 798 (DSM = German collection of microorganisms) was grown overnight in full HPG medium (1% yeast extract, 1% peptone and 1% glucose) at 35 ° C. The cells were centrifuged off and taken up in PBS (0.05 M phosphate buffer, pH 7.2, 0.9% NaCl) so that the cell number was 10 ⁵ / ml. A piece of the aqueous treated polymer film of polymer 4A from Example 3 was placed on 100 μl of the suspension. After a contact time of 3 hours in a steam-saturated atmosphere, the drop was removed and diluted in 2 ml of saline. The contact point was washed 3 times with saline. 100 ml portions were plated on HPG agar. After 18 h at 37 ° C, the colonies grown were counted. A piece of polystyrene was used as the control polymer. In parallel, a control for diffusible substances was carried out on HPG agar which had been inoculated with 10 ⁵ germs of K. pneumoniae. No zones of inhibition were obtained. The result is shown in the table below.

b) Selective inhibitory effect of the polymer from Example 4

The contact inhibition test described above was performed with the Polymers (Quat B as comonomer) from Examples 4 and four Bacterial strains and the yeast Candida tropicalis. The The films obtained were immersed in water for 24 hours (changing the Water) and tested after air drying. The kill is in % specified. Surprisingly, selective inactivation of the yeast strain can be found, while in the Bacterial strains have no effect.  

Example 8 Example of use for a polymer

An approx. 8 × 2 cm polyamide film strip was inserted halfway into the Dispersion from Example 4 dipped and then at 70 ° C for 1 h dried. The strip was watered for 18 hours and then at Air dried room temperature.

The strip half coated with the dispersion was now completely in a cell suspension of Staphylococcus aureus (isolate of hygiene Institute Gelsenkirchen from an infected central venous catheter) submerged. Then the strip was briefly air dried, then laid out on a dilute nutrient agar and overnight incubated at 37 ° C.

Result: On the half of the polyamide coated with the dispersion Stripes coated were 4 Staphylococcus aureus colonies grown, but several 100 on the uncoated half.

Claims (14)

1. Polymers with antimicrobial properties consisting of

• a) 99-40% by weight of nonfunctional vinyl polymerizable monomers and
• b) 1-60% by weight of functional vinylically polymerizable monomers of the general formula (1)
  [VA _y -HSp] _m -N ^⊕ (R ¹ ) _{4- (m + t)} - (R ² ) _t . X⁻ (I)
  With
  V = vinyl, (meth) acroyl, allyl or styryl,
  A = an optionally present linking unit, the alkyl, aryl, arylalkyl or hydroxyalkyl, which can also be interrupted by heteroatoms, for example by heteroatoms in urethane, carbonate, ester, amide or ether groups, where y = 0 or 1,
  HSp = a hydrophilic spacer of the general formula
• (i) - (O-CH ₂ -CH ₂ ) _n - or
• (ii) - (O-CH ₂ -CH (CH ₃ )) _n - or
• (iii) - (O-CH ₂ -CH ₂ ) _r - (O-CH ₂ -CH (CH ₃ )) _s with n = r + s and with n = 2-40,
  such as
  m 1, 2 or 3 and
  R ¹ = CH ₃ , ethyl or benzyl
  R ² = an alkyl radical with 8-20 C atoms, where
  t = 1, 2 or 3.
• X⁻ = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻.

2. Polymers according to claim 1, characterized in that the monomers b) (meth) acrylic acid ester of the general formula (II)
[CH ₂ = CR ³ -CO- (O-CH ₂ -CHR ⁴ ) _n ] _m - N ^⊕ (CH ₃ ) _{4- (m + t)} - (R ² ) _t . X⁻ (II)
in which
m = 1, 2 or 3, n = 2-40,
R ² = an alkyl radical with 8-20 C atoms, where t = 1, 2 or 3. R ³ = H or CH ₃ ,
R ⁴ = H or CH ₃
X⁻ = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻. 3. Polymers according to claim 1 or 2, characterized in that the monomers b) (meth) acrylic acid ester of the general formula (III)
With
u + v = 6-20,
R ² = an alkyl radical with 8-20 C atoms,
R ³ = H or CH ₃ ,
X = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻
are. 4. Polymers according to one or more of claims 1 to 3, characterized in that the monomer b) Quat A according to formula (IV)
where u + v = 10 is included. 5. Polymers according to claim 1 or 2, characterized in that the monomers b) (meth) acrylic acid ester of the general formula (V)
CH ₂ = CR ³ -CO- (O-CH ₂ -CH ₂ ) _w -N ^⊕ (CH ₃ ) ₂ -R ² . X⁻ (V)
in which
w = 2-40,
R ² = an alkyl radical with 8-20 C atoms,
R ³ = H or CH ₃ ,
X⁻ = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻
are included. 6. Polymers according to claim 5, characterized in that the monomer b) Quat B of the formula (VI)
CH ₂ = C (CH ₃ ) -CO- (O-CH ₂ -CH ₂ ) ₂ -N ^⊕ (CH ₃ ) ₂ - (C ₁₄ H ₂₉ ). Cl⁻ (VI)
is included. 7. Use of a polymer according to one of claims 1 to 6 for Plastics or plastic coatings with an antimicrobial Surface.   8. (meth) acrylate monomer according to formula (II)
[CH ₂ = CR ³ -CO- (O-CH ₂ -CHR ⁴ ) _n ] _m -N ^⊕ (CH ₃ ) _{4- (m + t)} - (R ² ) _t . X⁻ (II)
with m = 1, 2 or 3, n = 2-40,
R ² = an alkyl radical with 8-20 C atoms, where t = 1, 2 or 3.
R ³ = H or CH ₃ ,
R ⁴ = H or CH ₃
X⁻ = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻. 9. Monomer according to claim 8, characterized by the formula (III)
in which
u + v = 6-20,
R ² = an alkyl radical with 8-20 C atoms,
R ³ = H or CH ₃ ,
X⁻ = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻. 10. Monomer according to claim 8 or 9, characterized by the formula
where u + v = 10. 11. Monomer according to claim 8, characterized by the formula (V)
CH ₂ = CR ³ -CO- (O-CH ₂ -CH ₂ ) _w -N ^⊕ (CH ₃ ) ₂ -R ² . X⁻ (V)
in which
w = 2-40,
R ² = an alkyl radical with 8-20 C atoms,
R ³ = H or CH ₃ ,
X = Cl⁻, Br⁻, I⁻ or alkyl sulfate⁻
is. 12. Monomer according to claim 11, characterized by the formula
CH ₂ = C (CH ₃ ) -CO- (O-CH ₂ -CH ₂ ) ₂ -N ^⊕ (CH ₃ ) ₂ - (C ₁₄ H ₂₉ ). Cl⁻ (VI). 13. Method of making an antimicrobial polymer radical polymerization 99 to 40 wt .-% of non-functional vinyl polymerizable monomers and 1-60% by weight (meth) acrylate Monomers according to one of claims 8 to 12.