DE3344001A1 - HYDROPHILE POLYURETHANE ACRYLATE COMPOSITION AND THEIR USE - Google Patents

Description

3344

description

The invention relates to hydrophilic polyurethane-acrylate compositions. It is particularly directed to compositions that can be obtained by reacting one or several acrylates obtained in the presence of one or more hydrophilic polyurethanes, to which one can react of a polyalkylene glycol with a diisocyanate

can.

In DE-OS 31 45 003 polyurethane diacrylate compositions are already described, which are practically insoluble in an alcohol such as ethanol or methanol. Just like that like these known compositions, form the hydrophilic polyurethane-acrylate compositions of the invention after immersion in water a hydrogel and are permeable to gases, ions and non-ionic materials different molecular weights. In contrast to the known hydrophilic polyurethane diacrylate compositions however, the present compositions dissolve in alcohol.

The hydrophilic polyurethane-acrylate compositions according to the invention can be prepared by adding an acrylate in the presence of one or more hydrophilic polyurethanes implements. The reaction of the acrylate can be initiated by the presence of a free radical catalyst

will.
30th

The hydrophilic polyurethanes required as a component of the hydrophilic polyurethane-acrylate composition according to the invention can be prepared by reacting (A) one or more diols having a number average molecular weight in the range from about 10 6 to 20,000 from the group of
(a) diethylene glycol,

eat

(b) long-chain polyoxyalkylene diols and / or

(c) dialkanolamines,

with

(B) a urethane precursor from the group of organopoly isocyanates and / or nitrile carbonates in the presence of an organotin catalyst.

If desired, this reaction can also be carried out with the addition of a polyfunctional lactone of the general formula 10

R _n , - CH - R ₂ - C = O

wherein R, is a monovalent radical from the group -H, -CH ₉ NH ₉ , -SO ₉ CH, -CHOHCOOH and / or - (CHOH) CH ₉ OH, where η is a number from 0 to 5, and R _{9 is} a divalent radical of the general formula

- (- CH) H) - where m is a number from 2 to 10 m

or an ether derived from such lactones can be carried out in amounts of 0.1 to 30% by weight based on the total reaction mixture.

Polyurethane resins containing such polyfunctional lactones, are described, for example, in U.S. Patent 4,156,066 and U.S. Patent 4,156,067.

The hydrophilic polyurethane component, which is present together with the acrylate at the time of its conversion, contains diethylene glycol and a long-chain diol. The long chain diols should have a molecular weight of at least about 106, and preferably from 1,450 to 7,500. Suitable diols mainly consist of oxyethylene groups or oxypropylene groups, although other oxyalkylene groups as well may be present in smaller quantities.

That for the production of the first component of the invention

Polyisocyanate used according to the hydrophilic polyurethane-acrylate composition has the general formula R (NCO), where η is greater than 1 and preferably 2 to 4 and the substituent R is an aliphatic, alicyclic, aliphatic-alicyclic, aromatic or aliphatic-aromatic Denotes hydrocarbon radical with 4 to 26 carbon atoms, which is preferably 6 to 20 carbon atoms, and in particular 6 to 13 carbon atoms, contains. Examples of such isocyanates are tetramethylene diisocyanate, Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate. Dimer acid diisocyanate, isophorone diisocyanate, diethylbenzene diisocyanate, decamethylene lflO diisocyanate, Cyclohexylene-1,2-diisocyanate or cyclohexylene-1,4-diisocyanate, the aromatic isocyanates, such as 2,4- and 2,6-To-

¹ ^ lylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate or dianisidine diisocyanate, tolidine diisocyanate, polymeric isocyanates such as neopentyl tetraisocyanate, m-xylylene diisocyanate, tetrahydronaphthalene-1,5-diisocyanate or bis (4-isocyanatophenyl).

The preferred isocyanate is methylene di (cyclohexyl isocyanate). Other somewhat less preferred diisocyanates include trimethyl hexamethylene diisocyanate and isophorone diisocyanate.
25th

Other useful compounds are the isocyanate equivalents which form the urethane bridges, such as the nitrile carbonates, for example the adiponitrile carbonate of the formula

0 0

Il Il

0 0 0

To produce the hydrophilic ones required according to the invention Polyurethane resin component can be the reaction

add mixed low molecular weight glycols, such as diethylene glycol or dipropylene glycol, or even aromatic glycols. The preferred low molecular weight aromatic polyols

are bisphenol A and 4,4'-sulfonyldiphenol. 5

The proportions in which the long-chain polyglycol and the low molecular weight glycol, such as diethylene glycol, are in the hydrophilic polyurethane components required according to the invention are present, depend on the hydrophobic-hydrophilic Balance that is present in the particular compound and desired for the finished composition will. An increase in the molecular weight of the long chain polyoxyethylene glycol and / or the amount of this polyol gives the finished product strong hydrophilic properties. This influence can be avoided by increasing the proportion of low molecular weight glycol, such as diethylene glycol or dipropylene glycol.

Taking this into account (according to which the hydrophilic Properties can be determined by the number of polyethylene oxide groups in the polymer molecule) then readily select such mixtures of reactants that the hydrophilic polyurethanes used at the time the implementation of the acrylate must be present, have the desired properties. By choosing the molecular weight of polyethylene glycol or by using. formation of two polyalkylene glycols with different Molecular weight, the hydrophilic polyurethane component can be tailored to a certain extent so that it has a broad molecular weight Property area is sufficient. In the present context, hydrophilic polyurethanes are of course such polyurethanes understood, which form hydrogels by hydrogen bonding and which after immersion in water at least 20 Absorb wt .-% water. The hydrophilic according to the invention Polyurethane-acrylate compositions, like the hydrophilic polyurethane component, form after immersion in Water also hydrogels that contain at least 20% by weight of water

to take.

The hydrophilic polyurethane component made with an acrylate is reacted to form the compositions according to the invention, according to the above information, a polyfunctional Contain lactone. Examples of such polyfunctional Lactones are those that are derived from polysaccharides and monosaccharides, such as mannolactone, Delta-gluconolactone, sorbolactone or D-glucuronolactone.

The lactones to be used advantageously contain at least three and preferably four in their molecule or more hydroxyl groups and have at least one more hydroxyl group than one to form a linear polyurethane chain needs. These free (unreacted) hydroxyl groups remain in the polymer backbone and are available for crosslinking the polymer. The lactone ring is also reactive and can be opened be, for example, by hydrolysis, creating in the polymer backbone Carboxylate groups or carboxy groups are formed.

To produce the first component required according to the invention, the glycols are mixed with the lactone that may be used and the respective polyisocyanate is then reacted with the mixture obtained. However, other techniques can be used instead. The reaction is carried out using catalysts customary for this purpose, expediently tin salts or organotin esters such as dibutyltin dilaurate, tertiary amines such as triethyldiamine (DABCD), N, N, N ¹ , N'-tetramethyl-1 ^ -butanediamine, or others known for urethane reactions Catalysts. The reaction can be carried out in the absence or presence of a diluent or solvent.

The second component of the composition according to the invention

3344C31

is an acrylate. In the present case, these include monoacrylic acid esters or monomethacrylic acid esters of an alcohol with less to be understood as 13 carbon atoms that are produced can be made by reacting one mole of acrylic acid or methacrylic acid with one mole of alcohol. The preferred Acrylates are hydroxyethyl methacrylate, methyl methacrylate and methyl acrylate, although others are also possible Esters of acrylic acid and methacrylic acid can be used.

For producing the hydrophilic polyurethane-acrylate composition according to the invention dissolve 100 parts by weight of one or more polyurethanes, preferably together with about 10 to about 50 parts by weight of one or more acrylates in a solvent such as methanol or 95% ethanol, and then adds a free radical to the respective solution to initiate the polymerization of the acrylate Catalyst. The solution of the two components can be cast into a film and heated to temperatures be cured in the range from 110 to 135 ° C, or you can optionally also the cast film under the influence cure from ultraviolet light. If you want to initiate the composition consisting of two components To make ultraviolet light insoluble, a free radical catalyst does not need to be present. Of the Addition of an ultraviolet absorber, such as Rhodamine B, or an azo catalyst, such as Äzobisisobutyronitrile, to the However, a mixture of the two components can be expedient.

If you want to produce molded articles or tubes from the hydrophilic polyurethane-acrylate compositions according to the invention, then you can simply remove the solvent under reduced pressure and ^{shape the remaining mixture at temperatures of 110 to 135 0} C for about 20 to 60 minutes to make the hydrophilic To cure the polyurethane-acrylate composition.

© ÄS

3344GG1

The hydrophilic polyurethane-acrylate compositions according to the invention absorb water, and the amount of water that is absorbed can be determined by the type of hydrophilic polyurethane present and by the amount and type of the acrylate present in the composition.

The above-described hydrophilic polyurethane acrylate resin compositions are also suitable as coating compounds, molded compounds, absorbents, agents for controlled Active ingredient releases, ion exchange resins and in dental technology as well as for the production of dialysis membranes, cannulas, contact lenses, packaging components, desalination membranes, Burn covers, contraceptive devices, surgical sutures, surgical Implants, blood oxygenators, intrauterine devices, vascular prostheses, oral drug delivery systems, battery separation plates, Eye bandages, corneal prostheses, anti-fog covers, surgical cloths and bandages, oxygen exchange membranes, artificial fingernails, Finger cots, adhesive plasters, adhesive strips, gas-permeable membranes, protective coatings and frictional resistance degrading coatings.

The invention is further illustrated below with the aid of examples.

example 1

To produce a polyurethane polymer, 822.3 parts of a polyethylene glycol with a number average molecular weight of 8000 (CARBOWAX 8000 from Union Carbide Corporation, New York, New York 10017, V.St.A.), 23.0 parts of diethylene glycol and 5.4 parts of water. The mixture is clear and then cooled at about 80 ⁰ C and at 75 ° C. After this temperature of 75 ° C. has been reached, 149.7 parts of methylenebiscyclohexyl-4,4 "isocyanate (namely DESMODUR W ^" from Mobay Chemical Corporation, Penn

BATH ORIGINAL

Lincoln Parkway West, Pittsburgh, Pennsylvania 15205, V.St.A.). The mixture is stirred for 15 minutes at 75 ° C, cooled to 50 ⁰ C and then with 2.0 parts by volume of dibutyltin dilaurate as catalyst (namely, the organotin catalyst with the label T, ₂ of Metal and Thermite Company of Rahway, New Jersey, V. St.A.) moved. After the catalyst has been added, the reaction mixture is allowed to come from 50 ^° C. to 75 ^° C. by exothermic heating. The molten product is poured into polypropylene sheets and heated in an oven at 100 ⁰ C, which causes under the completion of the reaction for the formation of a foamed hydrophilic polyurethane product c then at a temperature of 75 °. When immersed in water, 100 parts of this product absorbs 470 parts of water, which is a water-

! 5 corresponds to an uptake of 470%.

The polyurethane product is cooled to room temperature, removed from the metal sheets and dissolved in 95% strength ethanol, resulting in a solution with a solids content of 9.82% by weight. 6.0 parts of hydroxyethyl methacrylate and 0.427 parts by volume of t-butyl peroctanoate are then added to 305.5 parts of this polyurethane solution in ethanol, while stirring. The solvent is then evaporated at room temperature under vacuum, whereby a product is obtained which contains 100 parts of hydrophilic polyurethane and 20 parts of hydroxyethyl methacrylate and which is then cured at a temperature of 121 ^° C. for 20 minutes. After curing, this product shows a water absorption of 408 to 428% and an elongation value of 70 to 75%.

.

Example 2

• Contact lenses can be made by spinning from a solution. The mixture of 305.5 parts of polyurethane solution in ethanol, 6.0 parts of hydroxyethyl methacrylate and 0.427 parts by volume of t-butyl peroctanoate according to Example 1 above is so under vacuum to increase its solids content

evaporated for a long time until the solution has a viscosity of 12 to 15 dPa.s (12 to 15 poise) (about 11 to 12% non-volatile content).

A concave shape that corresponds to the desired shape of the convex side of a contact lens is converted to a vertical one Mounted shaft that can be rotated at a maximum speed of 200 revolutions per minute.

Half of the concave part of the mold is filled with the solution with a viscosity of 12 to 15 dPa.s. the Form is slowly set in motion and brought to maximum speed within 5 minutes. Then let it turn for another 5 minutes at maximum speed. Then you leave the spinning form come to rest.

The mold is then placed in a nitrogen atmosphere Given oven. The oven temperature is slowly raised to 125 ° C. and maintained for 20 minutes. After cooling down the mold is placed in water, whereby the polymer absorbs water and is separated from the mold.

If desired, those described in Example 1 above can be used Polyurethane-hydroxyethyl methacrylate composition before the stage of curing also with pharmaceutical Mix active ingredients or use them to encapsulate them. Active ingredients that can be distributed in this way, are for example vitamins, hormones, steroids, active ingredient protagonists and active ingredients against tubercles.

A polymer produced and cured in this way sets the active ingredient under the influence of aqueous solutions, Salt solutions or body fluids are slowly released. The resin composition described in this example can can therefore be brought into any suitable form, for example tablets for oral ingestion, implants, Intrauterine devices, diaphragms, or suppositories

3 3 3 4 4 L υ

torien are processed, from which the active ingredient is controlled can be released. If desired, the diaphragm or contraceptive device can be used during the manufacture with a contraceptive relocate, like lactic acid.

Example 3

305.5 parts of the 9.82% strength ethanol solution described in Example 1 and the 30 parts of a hydrophilic solution are added Contains polyurethane resin, with 6.0 parts of methyl acrylate and 0.427 parts of t-butyl peroctanoate. Then the solvent removed by evaporation at room temperature under vacuum, resulting in a product of 100 parts hydrophilic polyurethane and 20 parts of methyl acrylate.

This product can be cured in various forms by heating it in an oven at 121 ° C under nitrogen for 30 to 60 minutes. The polyurethane-methyl acrylate composition thus obtained absorbs 716 to 758% water and has an elongation value of about 112%.

Alternatively, the polyurethane-methyl acrylate composition can also be compressed to form a flat sheet or a contact lens by heating it under pressure in a press at 100 ^° C. and then increasing ^{the temperature to 130 °} C. for 2 minutes while maintaining the pressure. The web obtained can be used as a membrane for the transfer of QQ water and steam, and it is also suitable as a surgical adhesive plaster, which can be provided on one side with an adhesive which can be used particularly well as a wound dressing, in the medicaments, such as SuIfadiazin, may be incorporated. The polyurethane-methyl-Q5 acrylate composition, which contains only 10% by weight of methyl acrylate, is also suitable as a dialysis membrane and can therefore be used for separation techniques.

Example 4

Using the method described in Example 1, starting from the following mixture, a polyurethane-methyl methacrylate composition is made manufactured:

Hydrophilic polyurethane (9.8%

ethanolic solution from Example 1) 305 _r 5 parts

Methyl methacrylate 6.0 parts

t-butyl peroctanoate 0.432 parts

This solution can be evaporated to dryness at room temperature under vacuum, resulting in a product which can be converted into a hydrophilic cannula with desired physical properties by extrusion under heat and pressure. If desired, the resin can also be mixed with a medicament prior to extrusion. The polyurethane-acrylate composition of this example can also be used in ethanolic solution to coat a preformed cannula, which can then be cured ^{at a temperature of 120 ° C. after the solvent has evaporated.}

Curing the above composition in an oven at 201 ⁰ C under an inert atmosphere for 30 minutes gives a product having a water absorption of 726% and a stretching rate of 111%.

Hardened cast or formed films which are suitable as a wound dressing and slowly release the iodine may be prepared from the resin composition of this example by ^w methyl methacrylate into the polyurethane composition by incorporating its cure iodine.

³⁵ Example5

The solution described in Example 1 of 305.5 parts of hy-

drophilem polyurethane (9.82% solids), 6 parts Hydroxyethyl methacrylate and 0.427 parts of t-butyl peroctanoate in ethanol is in 3 wt .-% mercury (I) acetate and 1% by weight beeswax based on the resin solids, suspended. This solution can then be applied to the exterior of a boat and through the actinic radiation of the Sun harden, creating an insoluble coating that lowers drag and sea growth by slow release of mercury. 10

Example 6

The solution described in Example 1 of 305.5 parts of hydrophilic Polyurethane (9.82% solids), 6 parts Hydroxyethyl methacrylate and 0.427 parts of t-butyl peroctanoate in ethanol are used to remove the ethanol at room temperature kept under vacuum. The resulting white solid is below the curing temperature below Pressure is extruded into a tube, which is then cured. In this way one arrives at a water-permeable and gas-permeable hose. Such a tube is suitable, for example, in dialysis machines the kidney.

Claims (10)

FEG-7 FRANCIS E. GOULD AND CHRISTIAN W. JOHNSTON Hydrophilic polyurethane-acrylate composition and their use Claims Hydrophilic polyurethane-acrylate composition that, when immersed in water, forms a hydrogel and is permeable is for gases, ions and non-ionic materials with different molecular weights, thereby characterized in that this composition is about 100 parts by weight of a hydrophilic polyurethane and about Contains 10 to about 50 parts by weight of an acrylate. 2. Composition according to claim 1, characterized in that the acrylate is hydroxyethyl methacrylate is. 3. Composition according to claim 1, characterized labeled in ze ichnet that the acrylate Methylmeth * is acrylate. 4. Composition according to claim 1, characterized in that the acrylate is methyl acrylate is. 5. Composition according to claim 1, characterized characterized in that the acrylate constitutes about 17% by weight of the composition. 6. Composition according to claim 5, characterized in that the acrylate is hydroxyethyl methacrylate is. 7. The composition according to claim 1, characterized in that the polyurethane consists of a Mixture of polyols and a diisocyanate is derived. 8. The composition according to claim 7, characterized in that one of the polyols is a Is polyol having a molecular weight of about 8,000. 9. Process for the preparation of a hydrophilic polyurethane-acrylate composition according to one of claims 1 to 8, characterized in that about 10 to about 50 parts by weight of an acrylate in the presence of about 100 parts by weight of a hydrophilic polyurethane. 10. Use of a composition according to one of the Claims 1 to 8 for the production of burn dressings, implants, possibly containing active ingredients, contraceptive devices in the form of a diaphragm c mas or a device that can be inserted into the uterus, cannulas, oral drug delivery systems, gas-permeable Membranes, corneal prostheses, tubes for transmission -3- 3344 of liquids on gases, wound dressings, dialysis membranes, Blood oxygenators, contact lenses, transparencies ** Objects or moldings or coatings for Boats. \ B ORIGINAL