JPS6237651B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to lactone-modified hydrophilic polyurethane resins that are water-insoluble but swell in water and other solvents. More particularly, the present invention relates to a method for producing polyether urethane resins having active and effective lactone groups in the polymer backbone. This lactone group easily opens and dissolves in alkaline solution to form a carboxylate, which can be converted to a free carbonyl group. Typically, the polyurethane resin is a low melting solid, generally having a melting point in the range of 90 to 250°C, and can be fabricated by typical polymer methods. Numerous polymer systems containing free carboxylic acid groups are known in the art. However, it is difficult to produce polyurethanes with free carboxylic acid groups because isocyanates, which are necessary components in any polyurethane system, are also highly reactive with carboxylic acid groups. One approach to introducing carboxylic acid groups into polyurethane resin chains is described in US Pat. No. 3,412,054. According to this method, 2,2-di(hydroxymethyl)propionic acid,
2-di(hydroxymethyl)alkanoic acid is reacted with an organic isocyanate to produce a polyurethane containing unreacted carboxylic acid groups. The polyurethane of the present invention is obtained from the condensation of (A) (a) diethylene glycol, (b) long chain polyoxyalkylene diol, (c) one or more diols and one or more dibasic acids. (d) a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids; reaction product with one or more alkylene diols; one or more diols having an equivalent weight ranging from about 100 to about 3,000, selected from the group consisting of; (In the formula, R ₁ is -H, -CHNH ₂ , -SO ₂ CH ₃ ,
A monovalent group selected from the group consisting of -CHOHCOOH and -(CHOH) _o CH ₂ OH; n is 0
is an integer of ~5; and R ₂ is -(CHOH) ^- _n
is a divalent group; m is an integer from 2 to 10)
and/or an ether derived from the lactone; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates. Long chain water soluble diols have a molecular weight of at least about
200, preferably from 1450 to over 6000, and can be ether, ester and ether-ester block containing resins. Suitable diols consist primarily of oxyethylene or oxypropylene groups, but may contain small proportions of other oxyalkylene groups. Also useful are block copolymer polyols obtained by adding ethylene oxide to polyoxypropylene chains. Linear polyester diols derived from the condensation of one or more diols and one or more dibasic acids, and one or more diols and one or more dibasic acids. Reaction products with difunctional linear polyesters derived from condensation with acids are useful. Representative examples of polyfunctional lactones are those derived from polysaccharides and monosaccharides, such as monolactone, delta gluconolactone, solbolactone and D-glucuronactone. The lactone used preferably has at least three, preferably four or more, hydroxyl groups in the molecule, or preferably at least one more hydroxyl group than is required to form a linear polyurethane chain. These free (unreacted) hydroxyl groups remain in the polymer and are effective in crosslinking the polymer. The lactone ring is also reactive,
That is, the ring can be opened by hydrolysis to form a carboxylate group or a carboxyl group in the main chain of the polymer. The number of carboxylic acid groups present in the polymer chain will be determined by the amount of lactone present in the reaction mixture. This amount is 0.1 of the weight of the total reaction mixture.
It can be ~30%. Preferably the weight of lactone will be 0.5-15% of the weight of the total reaction mixture. The polyisocyanate used in the present invention is represented by the formula R(NCO) _o , where n is greater than 1, preferably from 2 to 4, and R is aliphatic, alicyclic, or aliphatic-alicyclic. A group, aromatic, or aliphatic-aromatic hydrocarbon compound with a carbon number of 4 to 26,
It is most preferably between 6 and 20, generally between 6 and 13.
Representative examples of the above isocyanates are: tetramethylene diisocyanate; hexamethylene diisocyanate; trimethylhexamethylene diisocyanate; dimeric acidic diisocyanate; isophorone diisocyanate; diethylbenzene diisocyanate; decamethylene-1,10
-Diisocyanate; cyclohexylene-1,2
-Diisocyanate and cyclohexylene-
1,4-diisocyanate; and aromatic isocyanates such as 2,4- and 2,6-tolylene diisocyanate; 4,4-diphenylmethane diisocyanate; 1,5-naphthalene diisocyanate; dianisidine diisocyanate; toluidine diisocyanate; polymers polyisocyanates such as neopentyl tetraisocyanate; m-xylene diisocyanate; tetrahydronaphthalene-1,5-diisocyanate; and bis(4-isocyanatophenyl)methane. A preferred isocyanate is methylene di(cyclohexyl isocyanate). Other less preferred diisocyanates are trimethylhexamethylene diisocyanate and isophorone diisocyanate. Other compounds that are useful are isocyanate equivalents that produce urethane bonds, i.e. adiponitrile carbonate. In producing the polyurethane resins of the invention, low molecular weight glycols such as diethylene glycol and dipropylene glycol or aromatic glycols can be added to the reaction mixture. Preferred low molecular weight aromatic polyols are bisphenol A and 4,4'-sulfonyldiphenol. The ratio of long chain polyglycols to lower molecular weight glycols, ie, diethylene glycol, used depends on the hydrophobicity-hydrophilic balance present in each and desired in the final product. Increasing the molecular weight and/or amount of long chain polyoxyalkylene glycol imparts strong hydrophilic properties to the final product. This effect can be counterbalanced by increasing the proportion of low molecular weight glycols, ie diethylene glycol or dipropylene glycol. Considering the above (i.e., the number of polyalkylene oxide groups in the polymer chain which determines the hydrophilicity, and when polyethylene oxide groups are more hydrophilic than polypropylene oxide groups), the final product is It is easy to select a mixture of reactants such that it has the following properties: By choosing the molecular weight of the polyalkylene glycol or by using two polyalkylene glycols of different molecular weights, "tailor-made" products can be created that satisfy a wide range of properties. Amphoteric hydrophilic polyurethane polymers can be prepared by adding a dialkanol tertiary amine, such as diethanolmethylamine, to the reaction mixture. In producing the polyurethane resin of the present invention, the glycol is mixed with the lactone and the polyisocyanate is reacted with the mixture, although other techniques can also be used. This reaction is catalyzed with catalysts known for such reactions. Suitable catalysts are tin salts and organotin esters, such as dibutyltin dilaurate, tertiary amines such as diethyldiamine (DABCD), N,N,N',N'-tetramethyl-1,3-butanediamine and those known in the art. Other recognized catalysts for well-known urethane reactions. This reaction can be carried out in the presence or absence of a diluent or solvent. The hydrophilic polyurethane polymer of the present invention has a molecular weight of 6000 or more, a water absorption capacity of 10% or more, a pour point lower than 275°C, and has a lactone group or a carboxyl group and a hydroxyl group in the polymer main chain. It can be summarized as something. The polyurethane polyether resins of the present invention can be advantageously used as burn dressings because of their unique physical properties. The resin can be applied to burns as a powder, film, or from solution in a volatile non-toxic solvent and will form a barrier permeable to liquids. In this way, the physician can select drugs that can be applied prior to forming the resin coating or added to the resin for timed release. A particularly advantageous burn dressing comprises from about 1 to about 80 parts by weight of polyvinylpyrrolidone-iodine and from about 20 to about 90 parts by weight of a polyether polyurethane resin having free hydroxyl and carboxylate groups in the polymer backbone. It is a powder obtained by low-temperature milling. The polyurethane polyether resins mentioned are also useful in the following and applications: coatings, molding compounds, absorbents, controlled release agents, ion exchange resins, skin abrasion treatment, dialysis. Manufacture of membranes, dentures, cannulae, contact lenses, solubilized packaging ingredients, hair sprays, cosmetics, burn dressings, contraceptive devices, sutures,
Surgical transplants, blood oxygenators, intrauterine devices, artificial blood vessels, oral release systems, battery separation plates, eye patches, hair removal compositions, artificial corneas, fragrances, deodorants, anti-fog coatings, surgical draperies, oxygen exchange membranes, Artificial finger nails, finger caps, adhesives, gas-permeable membranes, and protective and drag-resistant membranes. The following examples illustrate the implementation of the invention. The invention is not limited to these examples. Parts are by weight unless otherwise indicated. Example 1 A diethylene glycol solution of polyethylene glycol is prepared by stirring and heating 109.2 parts (0.075 moles) of polyethylene glycol having a molecular weight of 1450 in 17.4 parts (0.164 moles) of diethylene glycol. This solution is cooled to below 60°C and a solution of delta gluconolactone prepared by dissolving 11.6 parts (0.065 moles) of delta gluconolactone in 46.4 parts of dimethyl sulfoxide is added. 80.8 to this mixture
(0.316 moles) of methylene biscyclohexyl-4,4'-isocyanate (product marked as HYL ENE W from EI Dupont de Nimoers & Co., Wilmint, Del.) is added with stirring. 0.5 parts by weight of organotin catalyst solution; dibutyltin dilaurate (metal and thermite)
A product designated as T ₁₂ manufactured by Sampany of Rahway, New Jersey) is added to the reaction mixture with stirring at a temperature below 45° C. to prevent undesirable temperature increases caused by the heat of reaction. After stirring for 20 minutes, the temperature rises to 80°C. The reaction mixture was then transferred to a tray and heated to 90°C.
The reaction was completed by placing it in a furnace for 1 hour. This polymer is soft, pliable and pliable in the wet state. Example 2 A polymer that is water-insoluble but soluble in a mixture of a major portion of alcohol and a minor portion of base (1.0N sodium hydroxide) is prepared by the method described in Example 1 from the following components: Manufacture: Polyethylene glycol (molecular weight 1450)
3469 parts (2.37 mol) Diethylene 254 parts (2.39 mol) Delta-gluconolactone (as a 20% solution in dimethyl sulfoxide) 116 parts (0.65 mol) HYLENE W 808 parts (3.16 mol) Dibutyltin dilaurate 5 parts Cylinder with a volume of 10 ml 1 of this polymer cast into a shape
Pieces are weighed, soaked in room temperature water for 12 hours, dried with paper towels to remove surface moisture, and weighed again. The weight increase was 100%. Example 3 A lactone group-containing polymer containing a small amount of dissolved base or soluble in a major amount of alcohol with the addition of a small amount of water or other carrier is prepared from the following ingredients in the process described in Example 1: Prepare: Diethylene glycol (molecular weight 1450)
2000 parts (1.37 moles) Diethylene glycol 107.5 parts (1.64 moles) Delta-gluconolactone (20% solution in dimethyl sulfoxide) 116 parts (0.65 moles) HYLENE W 808 parts (3.16 parts) Tin octoate (T ₉ ) 5 parts 〓 T ₉ is a trademark of Metal and Thermite Company (of Rahway), New Jersey. Example 4 This example illustrates the preparation of a polymer that is soluble in alkaline solution using a 5% excess of cyanate groups. The manufacturing method is described in Example 1. Polyethylene glycol (molecular weight 1450)
1097 parts (0.75 mol) Diethylene glycol 174 parts (1.64 mol) Delta-gluconolactone (as a 20% solution in dimethyl sulfoxide) 116 parts (0.65 mol) HYLENE W 102.4 parts (0.4 mol) Tin octoate (T ₉ ) 5 Department: Trademark of Metal and Thermite Company of Rahway, New Jersey. Reference Example 1 50g of the polyurethane polyether resin described in Example 1 was mixed with 17.4ml of 29% ammonium hydroxide.
Add to 500 ml of an aqueous solution containing. 90% of this solution
Stir at °C until all polymer is dissolved. To this polymer solution is added 10 ml of a 20% aqueous solution of ammonium dichromate [2.0 g of (NH ₄ ) ₂ C _r2 O ₄ ]. This solution is applied to cellulose acetate film with a doctor knife and dried in low light or darkness at room temperature. A yellow, tough film of the photosensitive complex is deposited, which adheres well to the cellulose acetate support. Using a photographic image as a light source
1 sunlamp and an exposure time of 60 seconds onto the film. The film is developed by washing in room temperature water to dissolve the unexposed, uncrosslinked portions of the photographic image. The developed film can be used in lithographic printing processes because the polymers that form the photographic image are directly stained with ink. Reference Example 2 An antifouling marine paint is formulated by ball milling the following ingredients for 3 hours: Polyurethane resin of Example 2 5% ammonium hydroxide in 150 parts ethanol
500 parts potassium dichromate 2 parts titanium dioxide 50 parts mercury acetate 3 parts The product thus obtained is applied to the main material and other surfaces and cross-linked by sunlight to form an adhesive insoluble protection. Forms a film that becomes a coating.
The product is particularly effective when applied to the hull of a boat. Because of the hydrophilic nature of the urethane resin, the mercury salts are released slowly, preventing the growth of myndipods or algae on the paint surface. Example 5 A polyurethane polyether resin was prepared by adding a poly(oxyethylene) group to the molecular weight instead of polyethylene glycol by the method described in Example 1 above.
Using a block copolymer with a molecular weight of 4750 obtained by addition to a poly(oxyethylene) chain of 950,
Manufacture. Block copolymer (molecular weight 4750) 3577 parts diethylene glycol 174 parts delta gluconolactone (20% solution in dimethyl sulfoxide) 116 parts HYLENE W 808 parts dibutyltin dilaurate 5 parts Example 6 A polyurethane polyether resin was prepared as described in Example 1 above. By the method of
Using a block copolymer with a molecular weight of 7500 obtained by addition to a poly(oxyethylene) chain of 2250,
Manufacture. Block copolymer (molecular weight 7500) 1157.4 parts diethylene glycol 32.75 parts delta gluconolactone (as a 20% solution in dimethyl sulfoxide) 116 parts HYLENE W 808 parts dibutyltin dilaurate 5 parts Example 7 A polyurethane polyether resin was prepared from Example 1 above. A block copolymer with a molecular weight of 6,500 obtained by adding a poly(oxyethylene) group to a poly(oxypropylene) chain with a molecular weight of 3,250 was used instead of polyethylene glycol by the method described in . and manufacture. Block copolymer 32.5 parts Diethylene glycol 21.76 parts Delta gluconolactone (20% solution in dimethyl sulfoxide) 41.41 parts HYLENE W 132 parts Dibutyltin dilaurate 0.5 parts Example 8 A polyurethane polyether resin was subjected to the method described in Example 1 above. Therefore, instead of polyethylene glycol, a block copolymer with a molecular weight of 13,333 obtained by adding a poly(oxyethylene) group to a poly(oxypropylene) chain with a molecular weight of about 4,000 is used. Block copolymer 1004 parts diethylene glycol 17.4 parts delta gluconolactone 11.6 parts dimethyl sulfoxide 46.4 parts HYLENE W 80.8 parts dibutyltin dilaurate 3 parts Dissolved in dimethyl sulfoxide. After stirring for 1 hour, the reaction mixture is transferred to a tray and placed in a 90°C oven overnight. Example 9 A series of three polyurethane polyether resins are prepared by the method of Example 1 with varying amounts of delta gluconolactone.

[Table] *Dissolved in dimethyl sulfoxide.
After the initial reaction, instead of curing the resins in an oven, the three resins (3 g each) were mixed with 100 mg of 1 rethandrolone (Nilevar), cast into 1.3 cm x 2.5 cm cylinders, and Polymerize for 30 hours at °C. After removal from the mold, a cylinder suitable for implantation in vivo for the long-term release of 1-rethandrolone (Nilevar) is obtained for use in animal husbandry. Example 10 Delta gluconolactone (14.28 parts) is ground into a fine powder and mixed well with 29.15 parts of polyethylene glycol (molecular weight 200). this mixture
Heat to 60℃ and add 56.57 parts of HYLENE W to this.
Add 0.5 part stannous octoate with stirring. After the exothermic reaction has stopped, the resin is transferred to a tray and placed in a 90°C oven for 1 hour to complete the reaction. Example 11 and Reference Example 3 Polyethylene glycol with a molecular weight of 1450 (218.4
part) with 34.8 parts of diethylene glycol,
The mixture is then heated to melting point while stirring. Add 161.6 parts of HYLENE W to this melt. A solution of delta gluconolactone is prepared by dissolving 23.2 parts of delta gluconolactone in 77 parts of dimethyl sulfoxide. This delta gluconolactone solution is mixed with glycol.
Add to the mixture with HYLENE W while stirring;
The reaction mixture is cooled to 50°C. 0.8 parts of dibutyltin dilaurate catalyst is added to the reaction mixture and stirring is continued until the exothermic reaction has ceased. The resin is then cured in an oven at 90°C for 1 hour. Dissolve the cured resin (2.6 parts) in alkaline methanol (7.4 parts) and add 2.5 parts of a 2% aqueous ammonium dichromate solution. This dichromate-catalyzed resin solution was injected through a 4-foot (122 cm) length of 5 mm Pyrex glass tubing.
Forming a uniform coating on its internal surface. Air dry the coating in ambient light for 5 minutes. One end of the coated tube is closed with a cork passed through a fine hypodermic needle. The tube is filled with tap water and then held upside down to allow the tap water to drip out. It took 24 seconds for all the water to drip out of the tube. This experiment was repeated 10 times. The time required to drain the tube was always 24±1 seconds. In a control experiment, a 4 foot (122 cm) length of uncoated 5 mm Pyrex tubing was washed thoroughly with detergent solution, rinsed with distilled water, and air dried. The tube is closed with the same cork that was passed through the thin hypodermic needle and filled with tap water. When this uncoated tube was inverted (10 experiments), it took 38±1 seconds to drain the tube. In this example, the dichromate catalyzed resin composition described above is applied to the hull and centerboard of a light sailboat and exposed to sunlight for 6 minutes to bridge the coating. Light breezes allow this yacht to outperform other yachts in its class. Example 12 A diethylene glycol solution of polyethylene glycol is prepared by heating and stirring 249.3 parts (0.172 mol) of polyethylene glycol having a molecular weight of 1450 and 79.5 parts (0.883 mol) of diethylene glycol. To this melt 52.9 parts (0.296 mol) delta gluconolactone, 249.3
part (0.86 mol) of diethylene glycol adipate and 520 parts (1.85 mol) of methylenebiscyclohexyl-4,4'-isocyanate are added.
The mixture is stirred with heating to form a homogeneous melt and then cooled to 45°C. A solution of 2.1 parts of dibutyltin dilaurate is added to this reaction mixture with rapid stirring to avoid an undesirable temperature increase due to the heat of reaction. After stirring for 20 minutes,
The temperature is 85℃. The reaction mixture was then transferred to a tray and placed in a 90°C oven for 1 hour to complete the reaction. The resulting polymer contains 21% by weight of adipate ester, is harder and more rigid than the polymer of Example 1, and is insoluble in water and aqueous alkaline solutions. When immersed in water, the weight increase due to water absorption is less than 20%. Example 13 A polyurethane polymer derived from a linear polyester diol is prepared by reacting the following components: Polyethylene glycol (0.005 mol) 7.95 parts delta gluconolactone (0.29 mol) 5.2 parts diethylene glycol adipate
(0.172 mol) 49.86 parts HYLENE W (0.241 mol) 68.0 parts Heat the mixture of reactants with stirring until homogeneous, and 0.24 parts organotin catalyst solution;
Dibutyltin dilaurate (designated T ₁₂ , manufactured by Metal and Termite Company of Rahway, New Jersey) is added to the reaction with stirring to avoid undesirable temperature increases due to the heat of reaction. After stirring for 20 minutes, the temperature rises to 80°C. The reaction mixture is then transferred to a tray and placed in a 90°C oven for 1 hour to complete the reaction. The resulting polymer contains 38% by weight adipate ester and is harder and more rigid than the polymer of Example 14. It is insoluble in basic solutions and methanol. The water absorption of this polymer is less than 15% by weight. Example 14 The above example is repeated, but the amount of diethylene glycol adipate present in the reaction mixture is
It decreases from 49.86 parts to 1.15 parts (1.4% by weight of the reaction mixture). When 1 g of the polymer of this example is immersed in water, it swells and absorbs 0.48 g of water. 1 g of this polymer can be dissolved in a mixture of 9 ml methanol and 1 ml 2N aqueous sodium hydroxide solution. Reference example 4 A mixture of 90 parts by volume of ethanol and water (70:
30), add 10 parts of the polymer of Example 1 and 1 part of sulfadiazine. The pH of the solution is adjusted to 7.0 by adding 1N sodium hydroxide and the polymer is dissolved by stirring. This polymer solution is applied directly to the burn area as a burn dressing, and when the solvent evaporates, a protective film is formed that is permeable to gases and fluids but inhibits the growth of anaerobic organisms beneath the film. Because it prevents, it does not prevent treatment. Reference Example 5 A polymer having the composition described in Example 2 above is prepared by heating and stirring polyethylene, diethylene glycol, delta gluconolactone and HYLENE W to form a homogeneous mixture. The catalyst is added to the reaction mixture at 40° C., stirring is continued until the exothermic reaction ceases (temperature begins to drop), then 232 parts (5% by weight) of cortisone are added with good stirring,
Ensure even distribution. This polymer is 1.5cm×
Cast into a 3cm cylinder and harden at 70℃. After curing, the cylinders are removed from the mold. These are suitable for implantation for long-term cortisone release. Reference Example 6 15 parts of the polymer described in the previous example 3 are placed in 70 parts by volume of a mixture of isopropanol and water (50:50) and 10 parts by volume of 1N sodium hydroxide solution are added. The mixture is refluxed to open the lactone ring and dissolve the polymer. Add this solution to 1N hydrochloric acid.
Titrate to PH5.0 and adjust the solids content of the polymer to 15% with isopropanol. Add 15,000,000 units of phenoxyethylpenicillin to this polymer solution. The resulting solution can be applied to the abraded surface to seal this surface against irritating physical and biological substances. Reference Example 7 A 20% solution of the polymer described in the previous Example 5 is dissolved in a mixture of ethanol and water (50:50) with the addition of sufficient 1N sodium hydroxide to cause dissolution. Prepared by dissolving the polymer. Adjust the pH of this solution to 6.0 with 1N hydrochloric acid. The solution thus obtained is applied topically to form a hypoallergenic base for cosmetic preparations. The polymer composition effectively covers skin blemishes and allows the skin to breathe. Reference Example 8 A hair setting composition is prepared by dissolving the polyurethane polyether resin of Example 6 above in 95% ethanol. Add enough 1N sodium hydroxide to effect dissolution and adjust the PH of the final composition to 7.0. The resulting solution is applied to the hair in the form of a spray, which gives excellent hold with a soft feel. Reference Example 9 20 parts of the unsaturated polyether resin of Example 1,
Dissolve in 80 parts ethanol-water (70:30) and add enough 1N sodium hydroxide to
Adjust to PH9.5. 5.6 parts of calcium thioglycolate are added to the solution thus obtained while stirring. The resulting composition can be used as a depilatory agent. Reference Example 10 Polymer 16 of Example 14 above was extruded to a length of 1.5
m, form a tube with a diameter of 10 mm. Dry nitrogen gas is passed through this tube and into the dry ice trap. Water vapor absorbed by the nitrogen as it flows through the tube precipitates as ice within the trap. Example 15 A series of three polyurethane polyether resins are prepared with varying amounts of delta gluconolactone.

[Table] Polyethylene glycol and diethylene glycol are melted together at 70°C in the absence of a solvent and mixed. Then delta gluconolactone and
Add HYLENE W and continue stirring until mixture is homogeneous. The mixture is cooled to 45° C. and the dibutyltin dilaurate is rapidly mixed with stirring. Stirring is continued for about 15 minutes, during which time the temperature rises to about 85° C. and the viscosity increases due to the exothermic reaction. The polymer is poured into a cooling pan while still viscous and placed in a 75°C oven for 20 minutes. The bread is then removed from the oven and cooled to room temperature. Remove the polymer from the pan and store it at room temperature indefinitely or
Or it can be used immediately as a molding resin. This resin swells in methanol and can be dissolved in alkaline solutions. Reference Example 11 Pour resin (a) from Reference Example 15 above into a water-cooled mold in an amount sufficient to fill the cavity, and heat at 125℃.
It is shaped into a lens by applying a pressure of 15000 psi (1.055 Kg/cm ² ). The mold is cooled and the optically clear polymer is removed. Reference Example 12 1 part of 1-rethantrolone (Nilevar) is blended with 30 parts of the resin (b) of Reference Example 11 at 40°C in a band mill. The composition is placed in the cavity of a cylindrical mold and molded at 15000 psi (1055 Kg/cm ² ) and 125°C to uniformly distribute a pharmacologically effective dose of 1-rethandrolone throughout the body. A cylinder of polyurethane polyester resin is formed. Example 27 An artificial esophagus is constructed from a tube woven from polyethylene terephthalate monofilament. The tube was slipped onto a cylindrical rod of somewhat smaller diameter and the assembly was immersed in a 15% isopropanol solution of the polyurethane polymer of Example 3 prepared as described in Reference Example 6 and air dried. . Repeated dipping and drying forms a 2 mm thick coating on the outer surface of the cloth tube. A polypropylene monofilament with a diameter of 1.5 mm was wound helically around the coated tube at a pitch of 5 turns/cm, and the assembly was
Heat set by placing in oven at °C for 15 minutes. The support rod is then removed from the tube and the tube is coated with 15% polyurethane polymer as described in the previous section.
The polypropylene monofilament is coated with the polyurethane polymer by repeated immersion in a solution of 50% isopropanol and the coating of polyurethane polymer on the inner surface of the fabric tube is 2 mm thick. Reference Example 14 The polyurethane polymer of Example 3 was dissolved in alkaline ethanol to form a 10% by weight solution,
A pair of polycarbonate safety glasses is dipped into this solution and allowed to dry at room temperature. The coating deposited on the polycarbonate lenses of the safety glasses had improved fogging properties when compared to a similar pair of untreated safety glasses. Reference Example 15 Resin (b) of Example 15 was heated at 110℃ and 15000psi.
(1055 Kg/cm ² ) was extruded from an orifice to make surgical sutures. The extruded monofilament was stretched 4 times, rolled onto a rack, and heated at 100°C.
Heat for 30 minutes and cool to room temperature. The resulting suture is cut to length, packaged, and sterilized with gamma radiation. If iodinated sutures are desired, the sutures are soaked in a 10% by weight solution of iodine in ethanol to absorb the desired amount of iodine into the sutures. A multifilament suture can be made by extruding the polymer of Example 24(b) through a spinneret containing the desired number of orifices and braiding the multifilament after heat treatment, as described above in this example. . Reference Example 16 The polymer solution described above in Reference Example 4 is cast onto a flat glass surface to form a film, which is air dried at room temperature. The dry film can be removed from the glass surface and applied directly to the burn surface as a burn dressing, or the film can be pulverized and applied to the burn in powder form. Reference example 17 1 part Neo-B-vitamin A and 30 parts Example 15
A surgical implant is made by blending with the polyurethane polyether resin of (a) in a band mill at 40°C. This composition was placed in a cylindrical mold cavity and heated to 15000 psi (1055 Kg/cm ² ) and 125°C.
to form a cylinder with an effective dose of neo-B-vitamin A evenly distributed throughout its body. In a similar manner, surgical implants containing pharmacologically effective doses of hormones, drug protagonists, tuberculin antibodies, or steroids can be formed. Reference Example 18 1 part of lactic acid is blended with 30 parts of the polyurethane polyether resin (c) of Example 15 at 45°C in a band mill. The composition is placed in the cavity of an annular mold and molded at 15,000 psi (1055 Kg/cm ² ) and 125° C. to form a polymeric ring useful as an intrauterine device. Reference Example 19 The resin (c) of Example 15 is extruded through an annular orifice at 20,000 psi (1406 Kg/cm ² ) and 125° C. to form a cannula. The cannula is immersed in a 10% by weight solution of iodine in ethanol for 24 hours, after which the iodine is distributed throughout the resin body. The cannula is then removed from the iodine solution and air dried. Reference Example 20 A woven fiber tube with a diameter of 3 mm is repeatedly dipped into the solution of the polyurethane polyether resin described in Reference Example 4, air dried, and the gaps between the strands are filled with the polyurethane polymer. Manufacture an effective cannula for use. A tube of woven polyethylene terephthalate strands of larger diameter is similarly treated,
Fills gaps between woven strands. The resulting product can be used by surgeons as a vascular graft. Reference Example 21 An 8 mm tube of woven collagen strands was coated with a solution of the polyurethane polyether resin described in Reference Example 4 and air-dried at room temperature to fill the gaps between the strands and form the inner and outer walls of the tube. An artificial blood vessel is manufactured by coating. The tube is then immersed in heparin to absorb the heparin into the polyurethane coating;
Dry and sterilize with gamma radiation. Reference Example 22 In a ball mill, 75 parts by weight of the polyurethane polyether resin of Example 8, 5 parts by weight of opium benzoin tincture, 10 parts by weight of bismuth suboxide and 10 parts by weight of plantago seeds were mixed with dry ice. By grinding together, a composition is prepared that is effective in controlling dehydration in humans and animals.
This composition can be administered orally to livestock suffering from infectious diarrhea. Reference Example 23 Add 2 parts by weight of Red Dye No. 2 to 98 parts of the polymer solution of Reference Example 7, and add 2 parts by weight of this mixture to 98 parts of the polymer solution of Reference Example 7.
Time ball milling. The resulting composition can be used as a cosmetic agent. Reference Example 7 A black braided silk suture is passed through the polymer solution of Reference Example 7, rolled onto a rack, and air dried.
The resulting suture has improved hand and tie down properties compared to a black braided silk suture that has not been treated in this manner. Reference Example 25 The polymer solution described in Reference Example 6 is adjusted to pH 7 and cast onto a glass surface to form a film, which is air-dried. This dry film can be applied directly to the eye as an eye bandage. Reference example 26 Put the resin (a) of Example 15 into a press and press at 15000psi.
(1055 Kg/cm ² ) and 115° C. to form a battery separator plate. Reference Example 27 To the hair setting composition of Reference Example 8, 2% by weight of fragrance essence is added. When this composition is applied to the hair, the solvent evaporates rapidly, while the fragrance binds to the polyurethane polymer and is slowly released over a 24 hour period. Reference Example 28 A household deodorant composition is prepared by mixing 10 parts of phenol and 50 parts of the polymer solution described in Reference Example 7 above, 5 parts of perfume and 35 parts of water. Reference Example 29 On one surface of the woven cotton cloth, the above Reference Example 7
A sterile surgical cloth is prepared by coating with a polyurethane polyether solution as described in . Reference Example 30 Resin (b) of Example 15 was pressed in a hydraulic press at 15000 psi (1055 Kg/cm ² ) and 110°C,
Forms a polyurethane polyether film that is practical as a dialysis membrane. Films thus produced can be advantageously used as carbon dioxide-oxygen exchange membranes in blood oxygenators, with minimal degradation of blood cells. Example 16 A diethylene glycol solution of polyethylene glycol is prepared by stirring and heating 109.2 parts (0.075 moles) of polyethylene glycol having a molecular weight of 1450 in 17.4 parts (0.164 moles) of diethylene glycol. The solution was cooled to 60° C. and prepared by dissolving 11.6 parts (0.065 moles) of delta gluconolactone in 46.4 parts of dimethyl sulfoxide. Add the solution of delta gluconolactone. 80.8 parts (0.316 mol) of methylenebiscyclohexyl-4,4'-isocyanate (E.I.
and 0.4 parts of dietatoluamine (a product labeled HYLENE W available from Wilmington, Del.) and 0.4 parts of dietatoluamine are added to the mixture with stirring. 0.5 parts by weight of an organotin catalyst solution; dibutyltin dilaurate (Metal and Thermite Company of Rahway, New Jersey) is added to the reaction mixture with stirring at a temperature below 45°C, and the heat of reaction Avoid undesirable temperature rises caused by After stirring for 20 minutes, the temperature is
The temperature rises to 80℃. The reaction mixture is then transferred to a tray and placed in a 90°C oven for 1 hour to complete the reaction. This polymer is amphoteric and is soft, pliable, and pliable when wet.

Claims (1)

[Claims] 1 (A) (a) diethylene glycol, (b) long-chain polyoxyalkylene diol, (c) condensation of one or more diols with one or more dibasic acids (d) a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids; One or more diols having an equivalent weight in the range of 100 to 3000, selected from the group consisting of reaction products with two or more alkykenediols; (B) Formula (In the formula, R ₁ is -H, -CH ₂ NH ₂ , -SO ₂ CH ₃ ,
A monovalent group selected from the group consisting of -CHOHCOOH and -(CHOH)nCH ₂ OH; n is 0
is an integer of ~5; and R ₂ is -(CHOH) ^- _n
is a divalent group; m is an integer from 2 to 10)
and/or an ether derived from the lactone; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates; , the water absorption capacity is 10% or more, and the pour point is 275℃.
A method for producing a hydrophilic polyurethane polymer having a lactone group or a carboxyl group and a hydroxyl group in the polymer main chain. 2. One of the diols is a difunctional linear polyester derived from the condensation of one or more diols and one or more dibasic acids, according to claim 1. manufacturing method. 3. One of the diols is a reaction product of a bifunctional linear polyester derived from the condensation of diethylene glycol and adipic acid, and a polyoxyalkylene diol.
Manufacturing method described in section. 4 the diols are polyethylene glycol and diethylene glycol, the lactone is delta gluconolactone, and the urethane precursor is methylene di(cyclohexyl isocyanate);
2. The production method according to claim 1, wherein the reaction is carried out in the presence of a catalyst. 5 The diol consists of a mixture of 54.6 parts polyethylene glycol (molecular weight 1450) and 8.7 parts diethylene glycol, 5.8 parts delta gluconolactone and 40.4 parts methylene di(cyclohexyl isocyanate) and the catalyst consists of 0.5 parts dibutyltin laurate. The manufacturing method according to claim 4.