WO2011054349A2

WO2011054349A2 - Functionalization of polymer surfaces by means of functionalized solid particles

Info

Publication number: WO2011054349A2
Application number: PCT/DE2010/001329
Authority: WO
Inventors: Ringo Grombe
Original assignee: Ringo Grombe
Priority date: 2009-11-06
Filing date: 2010-11-05
Publication date: 2011-05-12
Also published as: WO2011054349A4; DE102009053314A1; WO2011054349A3; DE112010004310A5

Abstract

The invention relates to the functionalization of polymer surfaces, which is caused by a mechanical incorporation of functionalized and/or polymer-protected solid particles. A stable, homogeneous and dense functionalization of the substrate can be achieved by means of a mechanical effect on a polymer substrate wetted with functionalized solid particles. A simplification of the functionalization procedure is achieved by applying the described method.

Description

Functionalization of polymer surfaces by means of functionalized solid particles

The invention relates to the functionalization of

Polymer surfaces, wherein this is brought about by a mechanical incorporation of functionalized and at least partially polymer-protected solid particles. The procedure described provides an improvement and simplification in terms of economic and compared to conventional functionalization

ecological aspects.

To polymer materials for applications e.g. in the

To functionalize medical or industrial sectors (automobiles, etc.) various methods are used. Wet-chemical etching with acids and alkalis is also used as well as plasma treatment (reviewed by Chu et al, Mater Sei Eng R 36 2ΘΘ2 143-206),

Coronachemic methods, laser techniques or the method of ion bombardment discussed by Cui et al. (Surf. Coatings Technol. 112 1999 278-285).

A good overview, e.g. for the treatment of

Poly (dimethylsiloxane) surfaces are given by Abbasi et al

(Silicon Elastomers Conference 2006 Frankfurt / M, Polym Int 5 2001 1279-1287) and Makamba et al (Electrophoresis 2003, 24, 3607-3619). The latter concludes that there are many challenges still to be overcome as the

Research in this field counts among a relatively new field. In addition, due to the silicone chain dynamics, the covalent modification of PDMS is not very much so far

successful.

Hu et al reports the successful covalent attachment of acrylic derivatives to PDMS by UV graft polymerization (Anal Chem 74 2ΘΘ2 4117-4123).

The combination of UV and ozone to activate PDMS has been reported by Ouyang et al (J Membrane 177 2ΘΘΘ177-187). Sui et al (Anal Chem 78 2006 5543-5552) explained the acid-catalyzed activation by peroxide

subsequent silanization step.

Lee et al. (Anal Chem 75 2003 6544-6554) describes the purification of silicone by solvent extraction and subsequent reaction of the surface by Diels-Alder.

Qu et al (Polymer Bulletin 46 2001 223-229) describe the grafting of acrylic acid onto HDPE tubing

Electron beam application.

Ohko et al (Biomat 58 2001 97) discuss the

Self-sterilization of Ti02 wetted PDMS catheters with coimmobilization of silicone material.

The disadvantages of wet-chemical etching are

obviously. Either the user has for the

Disposal of corrosive liquids or corrosion reduces the life of the used

Work materials. In addition, as in the case of the UV / ozone method, an increased health and safety risk, as the

media used can be both corrosive and carcinogenic.

The necessary equipment to bring about the

Functionalization as in the case of plasma,

Electron beam or laser technology is complex and expensive.

These above techniques are also unsuitable for Materials, in particular silicone elastomers, with

more complex geometries (e.g., intra-lumen treatment).

The invention is therefore based on the object

Method for homogeneous activation of

Specify polymer materials of different geometry, with a high degree of functionalization to be achieved. At the same time, the use of simple technology is just as desirable as the use of easy-to-use and disposable activation agents. The object is achieved by a method according to the main claim. Advantageous embodiments are given in the appended claims

According to the invention for the production of

functionalized surfaces on polymer substrates by a process involving the use of dispersed functionalized solid particles. The

Dispersion may contain a stabilizing polymer mixture. After application of the dispersion to the surface of the polymer substrate to be functionalized, the solid particles adhere to the polymer surface. Due to the flexibility of the polymer material can be

Incorporate solid particles into the surface of the polymer substrate by the action of mechanical force or ultrasound. In order to further stabilize the functional layer, on the one hand non-embedded

Solid particles by washing the surface with

suitable solvent removed and after a

possible drying step, crosslinking reactions are carried out. For this purpose can

Polymerization reactions (eg., Radical or

Condensation reaction) as well as polymer-analogous reactions (eg, nucleophilic or electrophilic reactions), with additions of radical initiators and / or

Networking can be helpful. Furthermore, technologies (such as etching techniques from lithographic processes) are also known to be more or less targeted

Structural properties for influencing the

Surface roughness bring about. Such

Structuring method can influence the

Surface wetting bring with it. In one embodiment of the invention, in order to achieve a better penetration of the solid particles into the polymer surface prior to the application of the dispersion, a swelling of the polymer substrate is carried out, since in this way an expansion of the polymer network is achieved. Swelling can also be achieved by the production of hydrophilic groups on the surface by hydrolysis in acidic or basic medium.

In a further embodiment of the invention, simpler design of the method already in

Applying the dispersion, a swelling of the

Polymer surface initiated. Such a strategy

avoids higher time and energy consumption and resources are spared.

In a further embodiment of the invention increases by the embedding of the solid particles in the

Polymer substrate the surface roughness. The

The surface finish of a substrate is of great importance for the application of a coating. As a result, as opposed to smooth surfaces, roughness leads to improved wetting. By embedding the solid particles in the polymer substrate, the

Surface roughness increased and a later Coating step favors.

A joint incorporation of (nano) particulate Ti0 ₂ and functionalized and / or polymer-protected Si0 ₂ solids, brings about incorporation of a radical source, whereby a further possibility of

cohesion-stabilizing system crosslinking or correspondingly functionalized target molecules can be immobilized (for example by subsequent polymerization of unsaturated mono- / oligomers).

In another embodiment of the invention, solid particles (e.g., sodium carbonate, silicate, apatites, talc, carbon black, clay minerals, lime, diatomaceous earth,

Aluminum hydroxide, pigments (eg Fe ₂ O ₃ , TiO ₂ , ZnO),

superpara- / para / magnetic compounds (eg Fe ₃ 0 ₄ ) etc.), the functionalizations (such as hydroxyl,

Carboxyl, carbonyl, amino, cyano, epoxy, peroxy, unsaturated groups but also protecting groups, ring-opening functionalities, polymerization initiators, charge carriers and metal chelates) used. The use of solid particles which already have functionalizations corresponds to a further simplification of the procedure. The use of commercially available dispersions of pre-functionalized solid particles is particularly attractive in terms of procurement and continuity. However, the solid particles can also be prepared by methods described elsewhere (Stober et al., Coli Interface, p.26, 1968, 63-68, Gao et al., JACS 2,717,759-7899). In a further embodiment of the invention, solid particles are used which have a dimension in the

Micron / submicron or nanometer range. The Dimension of the solid particles should be in

ikron- / submicron or nanometer range, as larger particle sizes make embedding in the polymer network difficult and insufficient

Functionality density would lead.

In a further embodiment of the invention, a loading of the functionalized surface of the

Polymer substrates with target molecules with the goal of changing the physical properties of the

Support material, such as waterproofness, mechanical strength, chemical resistance,

Light fastness, abrasion resistance, gas and

Moisture permeability, design, appearance, feel, surface design and volume. The method is therefore also suitable for solving technical problems through biologically inspired problems (bionics). The

functionalized surface of the polymer substrate can now be reacted with target molecules. By attaching covalent bonds (by, for example, nucleophilic reactions such as Michael addition, electrophilic reactions,

Condensation reactions or radical type reactions) or the exploitation of physical interactions (such as polarization, charge interactions or

Stereo interaction between D, L isomers) is a stable adhesion of the target molecule layer to the substrate brought about. Within the meaning of the invention, target molecules are understood as meaning all molecules which are bound to the

functionalized surface of the polymer substrate can be bound. In a further embodiment of the invention, the loading of the surface with the target molecules takes place by means of a cohesion-stabilizing method. By means of a Such as polymerization method (this can be chosen from a variety of radical or condensation reactions) or Interpenetrating Network (IPN) or layer-by-layer method using

Charge counterparts or the stereochemical interaction between D, L isomers, the cohesion of the target molecule layer is ensured.

In a further embodiment of the invention, the polymer substrate modified according to the invention is used for bonding functional coatings (e.g., non-reflective, antifouling, lubricating film, etc.);

synthetic / natural target molecules,

hydrogel; Drugs; peptides;

antimicrobial agents; lipids; polysaccharides;

biologically active molecules such as antibodies, nucleotides, enzymes, signal peptides, fluorescent / phosphorescent dyes, minerals, nanoparticles; electrically conductive metal surfaces, photoelectrically active

Surfaces etc. used. The idea involves the mechanical incorporation of

functionalized and / or polymer-coated and / or metallized (such as, for example, according to Zhang et al Catalysis Today 93-95 20Θ4 645-650) solid particles having dimensions in the (sub-) micron range, in a polymer network (natural or synthetic origin). The substrate to be processed may be of any geometry (e.g., surface, tube, sphere, etc.), but should have some flexibility.

The solid particles are embedded in the network - which may be preceded by a swelling of the substrate or the solid particles are dispersed in a swellable solvency - and so the stable fixation of the

Festkörper particles guaranteed. Is another one Stabilization of the system desired, so between the individual components (functionalized particles, particle-stabilized polymer, substrate material)

stabilizing crosslinks, e.g. B. covalent, ionic, complex chemical or other nature, are generated. For this purpose, additives such as radical initiator and / or

Crosslinkers and / or complexing agents and / or surfactants be helpful. Furthermore, stabilization can be brought about by the formation of interpenetrating networks (IPN).

The resulting solid particles / polymer network construct in the result is similar to the product of a polymer material loaded with fillers, which has a high stability. The embedding of the solid particles leads to an increase in the surface roughness, which favors a subsequent wetting with formulations. This can ensure a homogeneous coating without the need to use surfactants with bio-incompatible properties (e.g., hemolytic activity).

To enhance the adhesion of a possible coating, the solid particles carry functionalities that guarantee coupling between solid particles and coating agent. These functionalities may be nucleophiles, electrophiles, unsaturated functions, etallchelates as well as charges.

In order to enhance the adhesion of a possible coating, the polymer stabilizing the solid particles can be used. This can either carry functionalities or functionalities can before the Coating step are generated. These functionalities may be nucleophiles, electrophiles, unsaturated functions, metal chelates, charges as well as complex species such as D, L isomers. In order to enhance the adhesion of a possible coating, the polymer stabilizing the solid particles may be in addition to the formation of interpenetrating

Networks (IPN).

Since the embedded solid particles are micron / submicron or nanometer size particles, high levels of particle size may be required

Functionalization density at the substrate surface

be assumed. This ensures accessibility of the functionalities. The invention is based on

Embodiments will be explained in more detail. The accompanying figure 1 shows a schematic representation of a polymer tube functionalization means

Roller system. Here, a polymer tube filled with a dispersion is passed through a roller system. By the rollers, a mechanical force is exerted on the hose and the components of the dispersion in the

Forced polymer material. This approach is suitable for continuous processing, which further

Production steps (washing, drying, cross-linking,

Coating, etc.) can follow. In a first

Embodiment carried out the functionalization of the inside of a polymer tube. As shown in Fig. 1, a hose (I) filled with a dispersion (II) can be passed through a roller system (III), with mechanical forces acting on the polymer hose as

Material act. In a further embodiment, the

Functionalization of the inside of a polymer tube functionalized solid particles, such as amino-silica (Si0 ₂ -NH ₂ ), dispersed in a suitable solvent. The dispersion is made into a polymer tube

Added silicone elastomer, wherein the solid particles adhere to the surface. By the example shown in Fig.l subsequent massage step, the solid particles are incorporated into the material.

Subsequent washes with a suitable

Solvents remove unbound solid particles and also cause shrinkage of the network. The latter allows a stable embedding of the solid particles in the polymer network. Subsequently, adhesives such as flexible epoxy-functionalized oligomers / polymers may be coupled to the amino-silica functionalized surfaces. The coupling step can be performed by various polymerization methods, such as radical reaction: photo, thermal initiation; Condensation, be realized. Ideally, such surface modifications provide the possibility of incorporation of drug systems or coupling of specific ligands / complexing agents. In this way, biocompatible surfaces can be created.

In another embodiment, the amino-silica functionalized surfaces become different

Peptide sequences (e.g., RGD peptide sequences). The application of solid phase peptide synthesis can be referred to here as

Serve as a basis.

In a further embodiment, the

According to the invention functionalized polymer surfaces for coupling of target molecules by grafting

from '/' grafting on ¹ reactions used. these can by various polymerization methods, such as radical reaction: photo, thermal initiation;

Condensation, be realized.

In a further embodiment, the

According to the invention functionalized polymer surfaces derivatized by successor reactions. Such approaches are exemplified in the publications US2010087343A1,

US2009123772A1 or US6369168B1 described. As a result, on the polymer materials e.g. functional layers such as lubricating films are produced.

In a further embodiment, the

functionalized polymer surfaces according to the invention for functionalization with biologically active molecules such as e.g. Antibodies and nucleotides used. Furthermore, antiseptic monomers, such as e.g.

Isobutylcyanoacrylate, be reacted on the surface. Further polymer-analogous reactions can be used to show additional surface properties.

In a further embodiment, the

According to the invention functionalized polymer surfaces are used for functionalization with organic (nano) particles. If e.g. As used in the pharmaceutical industry Isobutylcyanoacrylatpartikel used, can by their large specific

Surface, antiseptic coatings at one

considerably reduced material consumption are produced. At the resulting surface further target molecules can be reacted.

In a further embodiment, the

According to the invention functionalized polymer surfaces for functionalization with glucan-like oligomers / polymers such as cellulose, starch, heparin, chitosan, hyaluronic acid, etc used.

In a further embodiment, the

functionalized polymer surfaces according to the invention for functionalization with fluorescence / phosphorescence molecules for fluorescence / phosphoresis detection systems

(biocompatible fluorescence Si0 ₂ particles) used.

In a further embodiment, the

According to the invention functionalized polymer surfaces for the immobilization of magnetic (nano) particles for medical imaging systems for investigation

used malignant tissue.

In a further embodiment, the

According to the invention functionalized polymer surfaces used for the immobilization of superparamagnetic iron oxide (nano) particles for metastasis elimination.

In a further embodiment, the

According to the invention, functionalized polymer surfaces are used for the immobilization of lipid membrane viscoses (liposomes) or polymeromas as biocompatible / biodegradable active substance carriers or biological membranes.

In a further embodiment, the

According to the invention, functionalized polymer surfaces are used for the immobilization of surfactant oligomers together with lecithin for the solubilization of cholesterol.

In a further embodiment, the

According to the invention functionalized polymer surfaces for applying a drug-release coatings with a more or less controlled rate of release

used. In a further embodiment, the

According to the invention, functionalized polymer surfaces are used for the method of surface polymerization according to ATRP ARGET (Langmuir 2ΘΘ7 pp4528), thus producing a wide variety of polymer compounds under ambient conditions. As an example, here is the production of quaternary

Ammonium compounds (usually the main active ingredient in Antialgenmitteln) called.

In a further embodiment, the

According to the invention functionalized polymer surfaces used for decoration with antimicrobial agents.

In a further embodiment, the

According to the invention functionalized polymer surfaces used for use for the disinfection of water. In a further embodiment, the

according to the invention functionalized polymer surfaces for the representation of defined metal / polymer

Structural systems used. The latter can be immobilized by a laser chemical treatment

Metal chelates are brought about.

In a further embodiment, the

According to the invention functionalized polymer surfaces used for adhesion promotion between a variety of substrates. In a further embodiment, the

According to the invention functionalized polymer surfaces used for coating with photovoltaic / optoelectronic systems.

In a further embodiment, the

According to the invention functionalized polymer surfaces for Embedding clay minerals, activated carbon, clathrates

(host-host chemical inclusion compounds), cyclodextrin and other supramolecules, e.g. used for water treatment, such as for detoxification or endotoxin excretion. In a further embodiment, the

According to the invention functionalized polymer surfaces used for embedding fuel-cell components.

In a further embodiment, the

functionalized polymer surfaces according to the invention by embedding functional (nano) particles (magnetic, light emitting etc) or solid-state hosts (e.g.

polyurethane / silica composite) used to store laser dyes.

The incorporation of redox-capable systems (e.g., Fe particles) can enable redox surface polymerization. The stabilization of such iron oxide particles has hitherto been achieved by coating with polymers such as dextran (Ferridex®), carboxydextran (Resovist®), albumin and starch, by citrate or a liposomal coating. These represent a possibility for the formation of interpenetrating networks (IPN) with a potential coating system.

In a further embodiment, the

according to the invention functionalized polymer surfaces for coating analytical equipment such.

Chromatography columns used. As a result, novel filling systems can be created.

In a further embodiment, the

According to the invention functionalized polymer surfaces for adhesion promotion between components of the same or different fabric / surface properties

used.

In a further embodiment, the

According to the invention functionalized polymer surfaces used to improve the static and mechanical stability of materials. Such an improvement is

for example, similar to those by Moniereisen in

Concrete constructions, fiberglass reinforced plastics or in the testing of plastic materials (e.g.

Metallreifen in natural rubber) achieved effects.

In a further embodiment, the

According to the invention functionalized polymer surfaces for the production of carbide / nitride or similar curing layers (from, for example, the physical

Vapor phase deposition). This can be the

stabilizing polymer by decomposition e.g. when

Serve carbon / nitrogen or other element source. Furthermore, the polymer phase can be used as an intermediate layer for stress absorption. In a further embodiment, the polymer surfaces functionalized according to the invention are used in combination with stimuli responsive adhesion promoters (with stimuli such as temperature, pH, electromagnetic radiation, etc.) for so-called adhesion on demand systems. Such may e.g. as adhesive joints on a car body replace the welds etc. and thus facilitate the recycle process. For example, hot-melt adhesives such as polyamides, Micropearl F30 (Follmann) and various products from Terepac are to be mentioned as stimuli-responsive adhesion promoters.

In a further embodiment, the According to the invention functionalized polymer surfaces for contacting with semiconductor surfaces, such as silicon surfaces used. For example, thin silicon surfaces can be immobilized on flexible substrates.

In a further embodiment, the

According to the invention functionalized polymer surfaces used for the production of circuits. defined

Structures with a small footprint can be realized by the use of (laser) -optical methods, electron bombardment,

Ion bombardment, or other etching methods can be realized.

In a further embodiment, the functionalized polymer surfaces according to the invention are used in dental or orthopedic applications. When using e.g. Titanium components can thus be achieved an improved compatibility with the body tissue.

In a further embodiment, the polymer surfaces functionalized according to the invention are used for the production of protective coatings on e.g. heat-resistant polymer materials used. By sintering immobilized powder filled pastes, e.g. Aluminide protective coatings which reduce hot air corrosion resistance in e.g. Increase automotive catalytic converters.

In a further embodiment, the functionalized polymer surfaces of the invention are treated with water glass, e.g. in DE4040153A1, coated. As a result, water- and fire-stable surfaces can be produced, which are break-stabilized by the stress-absorbing effect of the particle-protecting polymers.

In a further embodiment, the According functionalized polymer surfaces according to the invention for hydrophobicity and Hydrophobietransfers enabled. The incorporation of particles (eg from ATH), which are mixed with low molecular weight siloxanes, can lead to the permanent hydrophobization of insulator layers and thus increase creepage and arc resistance. Such a procedure is particularly interesting if, instead of silicone elastomer, an alternative rubber with less hydrophobicity must be used.

In a further embodiment, the

According to the invention functionalized polymer surfaces characterized by a magnetic anisotropy. This can be achieved by the incorporation of magnetic nanoparticles, such as ferrite compounds. By incorporating magnetic nanoparticles into elastomer surfaces, magnetoelastic properties can be generated which depend on the direction of an external magnetic field. Such composites can be used to make sensors.

In a further embodiment, the

According to the invention functionalized polymer surfaces characterized by a high or low refractive index. This can be achieved by incorporation of nanoparticles of appropriate composition and size. Such composites are interesting for applications in optical filters, reflectors, optical adhesives,

Antireflective films or solar cells with higher

Efficiency. In a further embodiment, the

According to the invention functionalized polymer surfaces by the increased surface roughness and possible targeted hydrophobization equipped with a kind of lotus effect. Such a property can be exploited to represent self-cleaning surfaces.

LIST OF REFERENCES

I polymer tube

II dispersion level

III pulley

Claims

2Θ claims

1. Process for the preparation of functionalized

Surfaces on polymer substrates include the following

Steps:

Dispersing functionalized / polymer-protected / metallized solid particles in a solvent,

Applying the dispersion to the

functionalized surface of the polymer substrate

Incorporating the dispersed mass into the surface of the polymer substrate by acting

mechanical and / or hydraulic and / or pneumatic force or ultrasound on the surface

Removal of unbound

Dispersion components by washing the surface with a suitable solvent

2. The method according to claim 1, characterized in that prior to the application of the dispersion, a swelling of the

Polymer substrate is provided, wherein the swelling takes place with a swellable solvency.

3. The method according to claim 1, characterized in that during application of the dispersion, a swelling is provided, wherein the swelling takes place with a swellable solvency and wherein the solid particles in a

swellable Solvenz are dispersed.

4 Method according to one of the preceding claims, characterized in that the embedding of the

Solid particles in the polymer substrate, the

Surface roughness increased.

5. The method according to any one of the preceding claims, characterized in that dispersions are used which have functionalized solid particles and / or one or more oligomer / polymer components and / or further additives / surfactants to system stabilizing

To enable crosslinking reactions.

6. The method according to any one of the preceding claims, characterized in that the functionalized surfaces for their additional stabilization between

Solid particles and / or their functionalizations and / or the stabilizing polymer and the

Polymer material have crosslinking.

7. Method according to one of the preceding claims, characterized in that solid particles are used which have a dimension in micron / submicron or

Have nanometer range.

8. The method according to any one of the preceding claims, characterized in that a loading of the functionalized surface of the polymer substrate is carried out with target molecules.

9. The method according to claim 6, characterized in that the loading of the surface with the target molecules by means of an adhesion-stabilizing method.

10. Functionalized polymer substrate prepared by a process according to claims 1 to 8.

Use of a polymer substrate according to claim 8 for the bonding of functional coatings (e.g., non-reflective, antifouling, lubricating film, etc.);

synthetic / natural target molecules,

hydrogel; Drugs; peptides;

antimicrobial agents; lipids; polysaccharides;

Glucosaminoglycans, biologically active molecules such as antibodies, nucleotides, enzymes, proteins,

Signal peptides, fluorescent / phosphorescent dyes, minerals, nanoparticles; electrically conductive

Metal surfaces, photoelectrically active surfaces.