WO2000044812A2 - Amino-functionalised polyoxyalkanes - Google Patents

Abstract

The invention relates to amino-functionalised polyoxyalkanes of general formula (I) wherein n = 1-5, m = 5-100, a = 0.1, b = 0.1, R = branched or linear hydrocarbon chains with 1-30 C-atoms, branched or linear single or multiple olefinically unsaturated hydrocarbon chains which have 1-30 C-atoms, or an aromatic hydrocarbon radical, R': the same or another meaning as in R, X: H, OH, NH2, F, Cl, Br, I, CN, NCO, SCN, CNO, NO2, NO, SH, CO2M, SO3M, SO4M, with M = H or alkali metal, X': the same or another meaning as in X, with the proviso that either X or X' mean NH2. The invention also relates to a method for producing the same. The inventive amino-functionalised polyoxyalkanes can be used for surface coating polymeric substrates.

Description

 WO ÖÖ / 44812. PCT / EP00 / 00544

Amino-functionalized polyoxyalkanes

The invention relates to amino-functionalized polyoxyalkanes, a process for their preparation and their use.

The modification of plastic surfaces, especially of technically used products, is of great economic interest, since it enables completely new uses for standard plastics already established in the market to be found. By changing the surface, new products are obtained in an efficient and economical way, which have the properties of the standard plastics and the interface properties optimized for the special purpose. These changed properties can lead, among other things, to hydrophilized, dirt-repellent, printable, more solvent-resistant and flame-retardant surfaces.

An overview of the various possibilities for changing the properties of synthetic polymers such. B. by photo-induced grafting provides Jr. J.C. Arthur, in Dev. Polymer Photochem. 2 (1981) 39.

Surfaces can also be modified by activating the surface by generating reactive groups. For example, the ozonization of a polymer surface or its irradiation in the presence of oxygen to form oxidized reaction centers, as z. B. in US 4311573, US 4589964 or EP 0378511, such a method.

Another method (described, for example, in EP 0574352) is based on plasma pretreatment of surfaces with the addition of oxygen to generate hydroperoxide groups, which in turn can function as reaction centers for downstream processes. In addition, a plasma pretreatment process is described in US Pat. No. 4,731,156 that permits the immediate amino functionalization of surfaces.

The modification of polymer surfaces by direct functionalization using amino groups, e.g. B. according to US 4731156 is a technically and economically Particularly interesting process since amino groups allow a wide range of reaction options

All of the methods mentioned have the disadvantage that the modification or activation takes place directly on the surface of the material, but since polymers, in particular under swelling conditions, have a high mobility of the individual chain segments, the surface modification is often carried out by dipping the reactive functionalities into the material itself counteracted Furthermore, the incorporation of reactive groups in the polymer material can have an undesirable influence on its mechanical properties

This disadvantage was remedied by using spacer molecules, such as, for example, decylamine hydrochloride (J Telden et al, J Biomater Be Polymer Edn, 4, 165-181, (1993)). The spacer molecules ensure a greater separation of the functionality from the surface of the material to be modified

In the medical or hygiene field, hydrophilic surfaces are often desired because they are physiologically harmless, are easy to clean or have bacteria-repellent properties. In particular, amino groups have been retained as functional groups, since they not only have hydrophilic properties but also allow further reactions

An amino-functionalized coating of polymer substrates should have the following properties when using spacer molecules - hydrophilic chain segments

- simple and gentle application

- covalent connection to the substrate

- High proportion of amino groups in the coating

The object of the present invention was to provide a material for the amino functionalization of polymeric substrates which combines these properties Surprisingly, it has been found that amino-functionalized polyoxyalkanes are outstandingly suitable for the production of coatings on polymeric substrates while maintaining an amino-functionalized substrate surface.

The present invention therefore relates to amino-functionalized polyoxyalkanes of the general formula

where n = 1-5, m = 5-100, a = 0.1, b = 0.1, R = branched or linear hydrocarbon chains with 1-30 carbon atoms, branched or linear mono- or poly-olefinically unsaturated hydrocarbon chains with 1 -30 C atoms, or an aromatic hydrocarbon radical, R ': the same or a different meaning of R, X: H, OH, NH ₂ , F, Cl, Br, I, CN, NCO, SCN, CNO, NO ₂ , NO, SH, CO ₂ M,

SO ₃ M, SO M, with M = H or alkali metal, X ': the same or a different meaning of X, with the proviso that either X or X' denote NH ₂ .

Amino-functionalized polyoxyalkanes according to the invention can be used for the surface treatment of polymeric substrates.

For certain purposes, amino-functionalized polyoxyalkanes which have a simple structure are preferably used. For the general formula

are these connections with

• X = NH ₂ , b = 0, n = 1-5, m = 5-100, a = 1, X '= H and

R = branched or linear hydrocarbon chains with 1-30 C atoms, branched or linear mono- or poly-olefinically unsaturated hydrocarbon chains with 1-30 C atoms, or an aromatic hydrocarbon residue.

Simplified:

• X = NH ₂ , b = 0, n = 2, m = 15-30, a = 1, X '= H and R = saturated hydrocarbon radical with 10 to 30 carbon atoms. Simplified:

• X = NH ₂ , b = 0, n = 2, m = 15-30, a = 1, X '= H and

R = monounsaturated hydrocarbon radical with 10 to 30 carbon atoms

Simplified:

The amino functionalized polyoxyalkanes can be covalently attached to a substrate, i. H. As a rule, the polyoxyalkanes according to the invention have an amino group, a polyoxyalkane backbone and other end groups, such as, for example, a long-chain ether or ester. The pronounced bifunctionality of the polyoxyalkanes according to the invention makes it possible to use a polyoxyalkane derivative which has similar polarities at least at one chain end Like the substrate surface Typically, the coating material is first applied to the substrate surface (physisorbed) and then immobilized using physical processes such as plasma activation.In the present case, good compatibility between the substrate surface and polyoxyalkane ensures a high number of pysisorbed molecules and thus a good coating layer in the immobilization step

The polyoxyalkanes according to the invention can also have hydrophilic and hydrophobic components at the same time.Therefore, uniform hydrophilizations of hydrophobic substrates can be made possible, which can otherwise only be achieved incompletely due to incompatibilities between coating material and substrate. Polyoxyethylene stearyl ether amine is an example of such a compound since the stearyl radical a hydrophobic and the aminopolyoxyethylene chain has a hydrophilic character

With the polyoxyalkanes according to the invention, surfaces of polymeric materials in particular can be gently aminofunctionalized, a change in the material properties of the surface by incorporating the amino groups into the material is prevented by the use of polyoxyalkanes as a spacer molecule Functionality is spatially separated from the surface via the spacer molecule Another object of the present invention is a process for the preparation of amino-functionalized polyoxyalkanes of the general formula

where n = 1-5, m = 5-100 and R = branched or linear hydrocarbon chains with 1-30 C atoms, branched or linear mono- or poly-olefinically unsaturated hydrocarbon chains with 1-30 C atoms, or an aromatic hydrocarbon radical, being a polyoxyalkane of the general formula

with n = 1-5, m = 5-100 and R = branched or linear hydrocarbon chains with 1-30 C atoms, branched or linear mono- or poly-olefinically unsaturated hydrocarbon chains with 1-30 C atoms, or an aromatic hydrocarbon radical, amino functionalized becomes.

For amino functionalization of a polyoxyalkane z. B. a polyoxyethylene compound such as polyoxyethylene (20) stearyl ether (z. B. Brij®78 from DuPont) can be used. For this purpose, the spacer molecule by known methods of organic chemistry, such as. B. the synthesis according to M. Mutter, Soluble Polymers in Organic Synthesis: I. Preparation of Polymer Reagents using Polyethylene Glycol with terminal Amino Groups as polymeric Component, Tetrahedron Lett. 31, 1978, 2839, amino functionalized. An exemplary synthesis route is given in the examples.

The in a suitable solvent, such as. B. chloroform, dissolved amino-functionalized polyoxyalkane can then be applied to a material surface or physisorbed.

The immobilization following the physisorption can be carried out by plasma treatment, microwave radiation, UV radiation, γ-rays or corona treatment. A plasma process is described as an example in the examples.

It is possible to physisorb the polyoxyalkanes first on the substrate surface and then to carry out an immobilization step. Alternatively, the substrate surface with the above. Methods activated and then coated with the amino functionalized polyoxyalkane according to the invention. Exemplary procedures are set out in the examples.

Another object of the present invention is the use of the amino-functionalized polyoxyalkanes for the surface coating of polymeric substrates, for the production of medical technology products or for the production of hygiene products or hygiene articles. Medical technology products include catheters, blood bags, drainage, guide wires and surgical instruments, dialysis and oxygenator membranes, intraocular lenses and contact lenses. Hygiene products include toothbrushes, toilet seats, combs and packaging materials. Other items with which many people come into contact, such as telephone receivers, handrails of stairs, door and window handles as well as holding belts and handles in public transport, also fall under the name of hygiene articles.

The polyoxyalkanes according to the invention are particularly suitable for coating polymeric materials. The mixtures to be coated do not have to consist entirely of a polymer; it is only important that the surface consists of a polymeric material which, for. B. undergoes grafting reactions with the polyoxyalkane under plasma conditions. The polymeric substrates, the surfaces of which can be modified with the polyoxyalkanes according to the invention, include homopolymers and copolymers, for example polyolefins, such as polyethylene (HDPE and LDPE), polypropylene, polyisobutylene, polybutadiene, polyisoprene, natural rubbers and polyethylene-co-propylene, and halogen-containing ones Polymers, such as polyvinyl chloride, polyvinylidene chloride, polychloroprene and polytetrafluoroethylene, polymers and copolymers of vinylaromatic monomers, such as polystyrene, polyvinyltoluene, polystyrene-co-vinyltoluene, polystyrene-co-acrylonitrile, polystyrene-co-butadiene-co-acrylonitrile, polycondensates, for example polyester, such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as polycaprolactam, polylaurine lactam and the polycondensate of hexamethylene diamine and adipic acid, polyether block amides, for example from laurine lactam, furthermore polyurethanes, polyethers, polycarbonates, polysulfones, polyether ketones, polyester amides and polyimides, polyacrylates and polyacrylates, polyacrylates and polyimides, polyacrylates and polyacrylates nd -methacrylate Blends of two or more polymers or copolymers can also be modified on the surface with the amino-functionalized polyoxyalkane according to the invention, as can combinations of different polymers which are connected to one another by adhesive bonding, welding or melting together, including the transition points

The amino-functionalized polyoxyalkanes according to the invention allow further functional groups to be applied to polymeric substrates. For example, it is possible to apply carboxylate-containing substances such as polyacrylic acid as a spacer molecule to standard plastics or other substrates via the amino-functional polyoxyalkanes. This can be done, for example, by reaction using N-hydroxysuccinimide ( NHS) and l-ethyl-3- (3-dimethylaminopropyl) carbodiimide (ECD)

It is also possible to bind carboxylic acid anhydrides such as maleic anhydride as carboxylic acid amide, so that a free carboxylic acid function results on the substrate surface

The following examples for the preparation and use of the amino-functionalized polyoxyalkanes according to the invention are intended to explain the invention in more detail without restricting its scope Example 1: Preparation of polyoxyethylene (20) stearyl ether amine

Synthesis of a Tosylate Functionalized Polyoxyethylene (20) Stearyl Ether:

3.8 g of tosyl chloride are dissolved in 50 ml of dichloromethane. The solution is cooled to 0 ° C., then 2.8 ml of triethylamine are added. A solution of 11.52 g of polyoxyethylene (20) stearyl ether (for example Brij78® from Aldrich) in 50 ml of dried dichloromethane is added dropwise to this mixture in the course of two hours under an argon atmosphere. The reaction solution is subsequently stirred at 0 ° C. for five hours in the absence of light, and then at room temperature for a further five days. The reaction mixture is poured into 250 ml of diethyl ether and the precipitated solids (by-products) are filtered off. The solvent mixture is removed from the filtrate on a rotary evaporator, and the remaining residue is recrystallized from ethanol. The resulting product is a waxy white solid.

Synthesis of a Phthalimide Functionalized Polyoxyethylene (20) Stearyl Ether:

3.88 g of the phthalimide potassium salt are added to a solution of 9.14 g of the product from Example 1 in 98 ml of dried N, N-dimethylformamide. The reaction solution is stirred at 118 ° -120 ° C for 24 hours. The warm reaction solution is filtered and the filtrate is poured into 350 ml of diethyl ether. The solids are then filtered off. The solvent mixture is removed from the filtrate on a rotary evaporator and the remaining residue is stirred for four hours in n-hexane at room temperature. The mixture is then cooled to 4 ° C. and stored at this temperature for eight hours, after which the n-hexane is decanted off. Remaining residues of n-hexane and of N, N-dimethylformamide are removed at 50 ° C. in vacuo, so that a waxy, white solid remains. This is dissolved in a large excess of dichloromethane, the solution is stirred for five hours at room temperature, then filtered and the solvent is removed on a rotary evaporator. Hydrazinolysis of a phthalimide-functionalized polyoxyethylene (20) stearyl ether:

3.1 ml of hydrazine monohydrate are added to a solution of 8.3 g of the product from Example 2 in 200 ml of ethanol. The reaction solution is refluxed at 100 ° C for 4 days, 1 ml of hydrazine monohydrate being added every day. The warm solution is then filtered and the filtrate is precipitated in diethyl ether. The precipitated solid is filtered off and the solvents are removed using a rotary evaporator. Polyoxyethylene (20) - stearyl etheramine is obtained as a waxy residue, which is then washed with n-hexane and then with dichloromethane.

Example 2;

Synthesis of a tosylate-functionalized polyoxyethylene (20) stearyl ether:

3.8 g of tosyl chloride are dissolved in 50 ml of dichloromethane. The solution is cooled to 0 ° C., then 2.8 ml of triethylamine are added. A solution of 11.52 g of polyoxyethylene (20) stearyl ether (trade name Brij78®, from Aldrich) in 50 ml of dried dichloromethane is added dropwise to this mixture in the course of two hours under an argon atmosphere. The reaction solution is subsequently stirred at 0 ° C. for five hours in the absence of light, and then at room temperature for a further five days. The reaction mixture is poured into 250 ml of diethyl ether and the precipitated product is filtered off. The solvent mixture is removed from the filtrate on a rotary evaporator, and the remaining residue is recrystallized from ethanol. The resulting product is a waxy white solid.

Synthesis of an amino-functionalized polyoxyethylene (20) stearyl ether:

0.29 g of bis (trimethylsilylamine) sodium amide (Aldrich) and 1.04 g of the product from Example 2 are dissolved in 10 ml of terahydrofuran (THF) under an argon atmosphere, for one hour at room temperature, then for 12 hours at 40 ° C stirred. After the reaction was completed, 10 ml of 2 normal hydrochloric acid solution was added dropwise to the stirred solution. Following the phase separation, the solvent on the system Rotary evaporator withdrawn. The remaining residue is dissolved in an excess of water and dialyzed through a membrane (CE membrane, MWCO 100, Spectra / Por®) against demineralized water.

Example 3:

Coating a polyethylene film with polyoxyethylene (20) stearyl ether amine:

A polyethylene film is placed in a 1 w / v. -% solution of polyoxyethylene (20) - stearyl etheramine (product from Example 1) in chloroform. After 30 minutes, the film is removed and dried in vacuo at room temperature.

Example 4:

Coating a plasma-activated polyethylene film with polyoxyethylene (20) - stearyl etheramine:

A polyethylene film is treated with a static argon plasma (48 watts) for 5 seconds, then rinsed with a 0.1 mM hydrochloric acid solution and distilled water. The film is then placed in a 1% by volume solution of polyoxyethylene (20) stearyl etheramine (from Example 1) in monomolar hydrochloric acid and ethanol in a weight ratio of 1: 1. After 30 minutes, the film is removed and dried in vacuo at room temperature.

Example 5:

Plasma immobilization of a polyethylene film coated with polyoxyethylene (20) stearyl etheramine:

The plasma treatment takes place in a tubular reactor (length 80 cm, inner diameter 6.5 cm). The reactor is evacuated to a pressure of 10 mbar ^"5, then blanketed with argon. This procedure is repeated three times. Then, the polyoxyethylene (20) -stearyletheramin coated polyethylene films on a glass plate in placed in the middle of the reactor. The reactor is evacuated again and an argon flow of 10 cm ³ min ^{"1 is passed} through the reactor. After 15 minutes the argon flow is stopped and the samples are treated with a static plasma (48 watt) for five seconds An argon flow of 10 cm ³ min ^{"1 is again passed} through the reactor for a period of two minutes, after which the pressure is equalized with the surrounding air pressure with argon. The samples are removed, turned over and the back of the samples is now treated like the front according to the procedure described.

Example 6;

Cleaning the plasma-immobilized, coated polyethylene films:

The polyethylene films coated according to Example 4 are washed three times with 0.1 molar hydrochloric acid solution and three times with demineralized water, then dried in vacuo at room temperature.

Example 7:

Synthesis of polyoxyethylene (20) stearyl ether polyacrylic acid:

50 mg of polyacrylic acid (M _w 2000, Aldrich), 1.5 mg of N-hydroxysuccinimide (NHS) and 10.8 mg of polyoxyethylene (20) stearyl etheramine (product from Example 1) are dissolved in 2.5 ml of demineralized water. 1 ml of a 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) stock solution with a concentration of 0.9 g / 1 is added every half hour. During the reaction, the pH of the reaction solution is continuously checked and, if necessary, kept constant at 5.8-5.9 by adding 0.01 molar hydrochloric acid. Half an hour after the last addition of the EDC solution, the pH of the reaction solution is adjusted to a value of 7.5 by adding 0.2 molar sodium hydroxide solution. After stirring for 20 hours, the reaction solution is dialyzed through a membrane (CE membrane, MWCO 6-8000, Spectra / Por®) against demineralized water. For complete cleaning, the solution is dialyzed once more at pH 11 and then freeze-dried. Example 8:

Synthesis of polyoxyethylene (20) stearyl ether polyacrylic acid:

50 mg of polyacrylic acid (M _w 2000, Aldrich), 1.5 mg of N-hydroxysuccinimide (NHS) and 10.8 mg of polyoxyethylene (20) stearyl etheramine (product from Example 2) are dissolved in 2.5 ml of demineralized water. 1 ml of a 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) stock solution with a concentration of 0.9 g / 1 is added every half hour. During the reaction, the pH of the reaction solution is constantly checked and, if necessary, kept constant at 5.8-5.9 by adding 0.01 molar hydrochloric acid. Half an hour after the last addition of the EDC solution, the pH of the reaction solution is adjusted to a value of 7.5 by adding 0.2 molar sodium hydroxide solution. After stirring for 20 hours, the reaction solution is dialyzed through a membrane (CE membrane, MWCO 6-8000, Spectra / Por®) against demineralized water. For complete cleaning, the solution is dialyzed once more at pH 11 and then freeze-dried.

Example 9;

Coating a polyethylene film with polyoxyethylene (29) - stearyl ether polyacrylic acid:

A polyethylene film is treated in a static argon plasma (49 watts) for 3 seconds, then rinsed with a 0.1 mM hydrochloric acid solution. The film is then placed in a 1% by weight solution of polyoxyethylene (20) stearyl ether polyacrylic acid (from Example 7) in monomolar hydrochloric acid and ethanol in a weight ratio of 1: 1. After 30 minutes, the film is removed and dried in vacuo at room temperature.

Example 10:

Plasma immobilization of a polyethylene film from Example 9 coated with polyoxyethylene (20) stearyl ether polyacrylic acid: The plasma treatment takes place in a tubular reactor (length 80 cm, inner diameter 6.5 cm). The reactor is evacuated to a pressure of 10 mbar ^'5, then blanketed with argon. This procedure is repeated three times. Then the polyethylene films coated with polyoxyethylene (20) stearyl ether polyacrylic acid are placed on a glass plate in the middle of the reactor. The reactor is evacuated again and an argon flow of 10 cm ³ min ^{"1 is passed} through the reactor. After 15 minutes the argon flow is stopped and the samples are treated with a static plasma (48 watt) for five seconds An argon flow of 10 cm ³ min ^{"1 is again passed} through the reactor for a period of two minutes, after which the pressure is equalized with the surrounding air pressure with argon. The samples are removed, turned over and the back of the samples is now treated like the front according to the procedure described

Claims

Claims: 1. Amino-functionalized polyoxyalkanes of the general formula

where n = 1-5, m = 5-100, a = 0.1, b = 0.1, R = branched or linear hydrocarbon chains with 1-30 C atoms, branched or linear mono- or poly-olefinically unsaturated hydrocarbon chains with 1-30 C atoms, or an aromatic Hydrocarbon radical, R ': the same or a different meaning of R, X: H, OH, NH ₂ , F, Cl, Br, I, CN, NCO, SCN, CNO, NO ₂ , NO, SH, CO ₂ M, SO ₃ M, SOM, with M = H or alkali metal, X ': the same or a different meaning of X, with the proviso that either X or X' mean NH ₂ describe. 2. Amino-functionalized polyoxyalkanes according to claim 1, characterized in that X = NH ₂ , b = 0, a = 1, m = 5-100, n = 1-5 X '= H and R = branched or linear hydrocarbon chains with 1- 30 carbon atoms, branched or linear mono- or poly-olefinically unsaturated Hydrocarbon chains with 1-30 carbon atoms, or an aromatic hydrocarbon radical. 3. amino-functionalized polyoxyalkanes according to claim 1, characterized in that X = NH ₂ , b = 0, m = 15-30, n = 2, a = 1, X '= H and R = saturated hydrocarbon radical with 10 to 30 carbon atoms. 4. amino-functionalized polyoxyalkanes according to claim 1, characterized in that X = NH ₂ , b = 0, a = 1, m = 15-30, m = 2, X '= H and R = monounsaturated hydrocarbon radical with 10-30 carbon atoms. 5. Process for the preparation of amino-functionalized polyoxyalkanes of the general formula

where n = 1-5, m = 5-100 and R = branched or linear hydrocarbon chains with 1-30 carbon atoms, branched or linear mono- or poly-olefinically unsaturated Hydrocarbon chains with 1-30 C atoms, or an aromatic Hydrocarbon radical, characterized in that a polyoxyalkane of the general formula

with n = 1-5, m = 5-100 and R = branched or linear hydrocarbon chains with 1- 30 C atoms, branched or linear mono- or poly-olefinically unsaturated hydrocarbon chains with 1-30 C atoms, or an aromatic Hydrocarbon residue, amino functionalized. 6. Use of the amino-functionalized polyoxyalkanes according to one of claims 1 to 4 for the surface coating of polymeric substrates. 7. Use of the amino-functionalized polyoxyalkanes according to one of claims 1 to 4 for the manufacture of medical products. 8. Use of the amino-functionalized polyoxyalkanes according to one of claims 1 to 4 for the production of hygiene products.