JPH0314848B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for making lactone-modified hydrophilic polyurethane resins that are water-insoluble but swell in water and other solvents. More specifically, the present invention provides a polyether urethane resin having active and effective lactone groups in the polymer backbone, and the lactone groups are ring-opened in an alkaline solution to form carboxylate groups or This invention relates to a manufacturing method for forming a carboxyl group. 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,
A 2-di(hydroxymethyl)alkanoic acid is reacted with an organic isocyanate to produce a polyurethane containing unreacted carboxylic acid groups. The method of the present invention comprises (A) condensation of (a) diethylene glycol, (b) long chain polyoxyalkylene diol, (c) one or more diols with one or more dibasic acids; (d) a bifunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids; a reaction product with two or more alkylene diols, one or more diols having an equivalent weight in the range of about 100 to about 3000, selected from the group consisting of; (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) _o CH ₂ OH; n is 0 to
and _R2 is a divalent group of -(CHOH) _n- ; m is an integer of 2 to 10]; and an ether derived from the lactone; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates, to form a polyurethane polymer, which can be produced by further opening the lactone ring by hydrolysis. . 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. It is preferred that the lactone used has at least three, preferably four or more, hydroxyl groups in the molecule, or 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, cycloaliphatic, aliphatic-alicyclic. A hydrocarbon compound having 4 to 26 carbon atoms, aromatic, or aliphatic-aromatic.
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 diisocyanates; 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 proportion of long chain polyglycols and low molecular weight glycols, ie diethylene glycol, used depends on the hydrophobic-hydrophilic balance present in each and desired in the final product. Increasing the molecular weight and/or amount of long chain polyoxylalkylene 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 of this art. is another recognized catalyst for urethane reactions, well known in This reaction can be carried out in the presence or absence of a diluent or solvent. The polyurethane ether resins of the present invention can be advantageously used as burn dressings because of their unique physical properties. The resin can be applied to the burn as a powder, film, or drops from solution in a volatile non-toxic solvent and will form a permeable barrier 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. Single-act polyurethane polyether resins 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 implementation of the present invention will be explained using the following reference examples. The present invention is not limited to these reference examples. Parts are by weight unless otherwise indicated. Reference 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. The 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. To this mixture was added 80.8 parts (0.316 mol) of methylenebiscyclohexyl.
4,4'-Isocyanate (II Dupont)
Add HYLENE W (product labeled as HYLENE W from De Nemo Earth & Company, Wilmington, Delaware) with stirring.
0.5 parts by weight of an organotin catalyst solution; dibutyltin dilaurate (product labeled T ₁₂ manufactured by Metal and Thermite Company of Rahway, New Jersey) is added to the reaction mixture with stirring at a temperature below 45°C. This prevents 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. Reference 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 from the following components by the method described in Reference Example 1. Produce: Polyethylene glycol (molecular weight 1450) 3469 parts (2.37 moles) Diethylene 254 parts (2.39 moles) Delta gluconolactone (as a 20% solution in dimethyl sulfoxide) 116 parts (0.65 moles) HYLENE W 808 parts (3.16 mol) Sibutyltin dilaurate 5 parts 1 of this polymer cast into a cylinder with a volume of 10 ml
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%. Reference Example 3 A lactone group-containing polymer containing a small amount of dissolved base or soluble in a small amount of alcohol with the addition of a small amount of water or other carrier is prepared from the following components by the method described in Reference Example 1. Prepare: Polyethylene 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 moles) Tin Octanoate (T ₉ ) ^* 5 parts *T ₉ is a trademark of Metal and Thermite Company, of Rahway, New Jersey. Reference Example 4 This reference 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 Reference 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 copies * Trademark of Metal and Thermite Company (of Rahway), New Jersey. Reference Example 5 50g of the polyurethane polyether resin described in Reference 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, 10 ml of a 20% aqueous solution of ammonium dichromate (2.0 g of (NH ₄ ) ₂ Cr ₂ O ₄ ) is added. 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. S- 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 polymers that form the photographic image are directly dyed with ink, so the developed film can be used in lithographic processes. Reference Example 6 An anti-fouling marine paint is formulated by ball milling the following ingredients for 3 hours: 150 parts of the polyurethane resin of Reference Example 2 500 parts of 5% ammonium hydroxide in ethanol Dichromic acid Potassium 2 parts Titanium dioxide 50 parts Acetic acid Water Silver 3 parts The product thus obtained is applied to wood and other surfaces and is cross-linked by sunlight to form a film that forms an adherent insoluble protective coating. form.
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. Reference Example 7 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 Reference Example 1 above.
It is produced using a copolymer of a block with a molecular weight of 4750 obtained by addition to a poly(oxyethylene) chain of 950. 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 Reference Example 8 A polyurethane polyether resin was prepared by changing the molecular weight of poly(oxyethylene) groups instead of polyethylene glycol by the method described in Reference Example 1 above.
It is produced using a copolymer of a block with a molecular weight of 7,500 obtained by addition to a poly(oxyethylene) chain of 2,250. 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 Reference Example 9 A copolymer of a block with a molecular weight of 6500 obtained by adding a poly(oxyethylene) group to a poly(oxypropylene) chain with a molecular weight of 3250 is used instead of polyethylene glycol by the method described in . and manufacture. Block copolymer 325 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 Reference Example 10 A polyurethane polyether resin was converted into a poly(oxyethylene) group with a molecular weight of 4000 instead of polyethylene glycol by the method described in Reference Example 1 above. It is produced using a block copolymer with a molecular weight of 13333 obtained by addition to a propylene chain. 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 11 A series of three polyurethane polyether resins are prepared by the method of Reference 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. Reference Example 12 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. Reference example 13 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 2.6 parts of the cured resin 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 reference 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. Reference Example 14 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 can be added 52.9 parts (0.296 moles) of delta gluconolactone, 249.3 parts (0.86 moles) of diethylene glycol adipate and 520 parts (1.85 moles) of methylenebiscyclohexyl-4,4'-isocyanate.
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 rise in temperature due to the heat of reaction. After stirring for 20 minutes, the temperature is 85°C. 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 Reference 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%. Reference Example 15 A polyurethane polymer derived from a linear polyester diol is produced by reacting the following components: 7.95 parts of polyethylene glycol (0.005 mol) 5.2 parts of delta gluconolactone (0.29 mol) 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 of adipate ester and is harder and more rigid than the polymer of Reference Example 14. It is insoluble in basic solutions and methanol. The water absorption of this polymer is less than 15% by weight. Reference Example 16 Repeat the reference example above, but reduce the amount of diethylene glycol adipate present in the reaction mixture.
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 reference 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. Example 1 A mixture of 90 parts by volume of ethanol and water (70:
30), add 10 parts of the polymer of Reference Example 1 and 1 part of sulfadiazine. The PH of the solution was adjusted to 7.0 by adding 1N sodium hydroxide, and the polymer was
Dissolve 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 17 A polymer having the composition described in Reference 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. Example 2 15 parts of the polymer described in the previous reference 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 PH 15.0 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. Example 3 A 20% solution of the polymer described in the previous Reference Example 7 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. Example 4 A hair setting composition is prepared by dissolving the polyurethane polyether resin of Reference Example 8 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. Example 5 20 parts of the unsaturated polyether resin of Reference 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. Example 6 100 g of the resin produced in Reference Example 1 are cut into small pieces and placed in a container containing 1 Kg of 90% ethyl alcohol and allowed to swell for 30 minutes. KOH2.5 in 50g of water
A solution containing g is prepared and sprinkled on the swollen polymer. Stir the mixture to completely dissolve the polymer. If the temperature is lower than 25℃, it will take 2-3 minutes to melt.
It takes time. The resulting solution has the desired pH. PH
At =4, the resin becomes the carboxylic acid form. Example 7 107 g of the resin (a) of Reference Example 11 was cut into small pieces, and 95%
1 of a mixture of 90 parts of aqueous ethanol and 10 parts of 70% aqueous isopropanol. After swelling the resin, 20 g of 10% by weight NaOH solution are added to the mixture. The batch is then stirred until the resin is dissolved. Next, set the pH of this solution to 4±0.2
Make it. This solution is then gradually added to 10 ml of pure water. The resin is precipitated, separated and dried in a stream of hot air. This method removes the salts formed by neutralization and eliminates the unpleasant odor of the dimethyl sulfoxide used in the preparation of the resin. The dried resin is redissolved in ethanol and cast into a film. This carboxyl group significantly improves adhesion. Example 8 123 g of resin (c) from Reference Example 11 are placed in 1.4 g of 90% aqueous methanol and treated with sufficient 10% aqueous NaOH to bring the pH to 12. The batch is stirred and warmed to 50-60°C. Continue stirring until the resin is dissolved. This solution can be adjusted to any desired pH. At low pH, resins made with the stated amount of delta gluconolactone become partially water soluble. Reference Example 18 The polymer of Reference Example 16 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. Reference Example 19 A series of three types of polyurethane polyether resins are produced 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. This mixture was cooled to 45°C and
Mix dibutyltin dilaurate rapidly 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. The polymer can be removed from the pan and stored indefinitely at room temperature or used immediately as a molding resin.
This resin swells in methanol and can be dissolved in alkaline solutions. Reference Example 20 Pour resin (a) from Reference Example 9 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 (1055 Kg/cm ² ). The mold is cooled and the optically clear polymer is removed. Reference Example 21 1 part of 1-rethandrolone (Nilevar) is blended with 30 parts of resin (b) of Reference Example 20 at 40°C in a band mill. The composition is placed in a cylindrical cavity and molded at 15000 psi (1055 Kg/cm ² ) and 125°C to have a pharmacologically effective dose of 1-rethandrolone uniformly distributed throughout its body. Form a cylinder of polyurethane polyester resin. Reference Example 22 An artificial esophagus is made 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 Reference Example 3 prepared as described in Example 2 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 polyurethane polymer by repeated immersion in % isopropanol solution and the coating of polyurethane polymer on the inner surface of the fabric tube is 2 mm thick. Reference Example 23 The polyurethane polymer of Reference 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 24 Resin (b) of Reference Example 19 was heated at 110℃ and 15000psi (1055
Kg/cm ² ) was extruded from an orifice to make surgical sutures. The extruded monofilament is stretched 4 times, rolled onto a rack, heat treated at 100° C. for 30 minutes, and cooled 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 produced by extruding the polymer of Reference Example 23(b) through a spinneret containing the desired number of orifices and braiding the multifilament after heat treatment, as described above in this Reference Example. . Reference Example 25 The polymer solution described above in Example 1 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 26 1 part neo-B-vitamin A and 30 parts reference example 19
A surgical implant is made by blending with the polyurethane polyether resin of (a) in a band mill at 40°C. The composition was placed in a cylindrical mold cavity and molded at 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. Form. In a similar manner, pharmacologically effective doses of hormones, drug protagonists, anti-nodule agents, etc.
Surgical implants containing tubercular drugs or steroids can be formed. Reference Example 27 1 part of lactic acid is blended with 30 parts of the polyurethane polyether resin (c) of Reference Example 19 at 45°C using 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 28 The resin (c) of Reference Example 19 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 29 A woven tube of textile fibers with a diameter of 3 mm is repeatedly dipped into a solution of the polyurethane polyether resin described in Example 1, 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 30 An 8 mm tube of woven collagen strands was coated with a solution of the polyurethane polyether resin described in Example 1 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 31 In a ball mill, 75 parts by weight of the polyurethane polyether resin of Reference Example 10, 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 a household suffering from infectious diarrhea. Reference Example 32 Two polymerized parts of Red Dye No. 2 were added to 98 parts of the polymer solution of Example 3, and this mixture was
Time ball milling. The resulting composition can be used as a cosmetic agent. Reference Example 33 A black braided silk suture is passed through the polymer solution of Example 3, 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 34 The polymer solution described in Example 2 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 35 Put the resin (a) of reference example 19 into a press and press at 15000psi.
(1055 Kg/cm ² ) and 115° C. to form a battery separator plate. Reference Example 36 To the hair setting composition of Example 4, 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 37 A household deodorant composition is prepared by mixing 10 parts of phenol, 50 parts of the polymer solution described in Example 3 above, 5 parts of perfume and 35 parts of water. Reference Example 38 A surgical drape is made by coating one surface of a woven cotton fabric with the polyurethane polyether solution described in Example 3 above. Reference Example 39 Resin (b) of Reference Example 19 is pressed in a hydraulic press at 15000 psi (1055 Kg/cm ² ) and 110° C. to form a polyurethane polyether film with utility 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. Reference Example 40 A diethylene glycol solution of polyethylene glycol is prepared by stirring and heating 109.2 parts (0.075 mol) of polyethylene glycol with a molecular weight of 1450 in 17.4 parts (0.164 mol) of diethylene glycol. The solution is cooled to 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. 80.0 parts (0.316 mol) of methylenebiscyclohexyl-4,4'-isocyanate (I.D.
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 part 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 to eliminate any disadvantages caused by the heat of reaction. Avoid excessive temperature rise. After stirring for 20 minutes, the temperature is 80
rises to ℃. 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 alkylene diols; (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) _o CH ₂ OH; n is 0 to
and R ₂ is a divalent group of -(CHOH) _n -; m is an integer from 2 to 10]; and/or derived from the lactone. ether; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates; A method for producing a hydrophilic polyurethane polymer, which comprises forming a polyurethane polymer having a lactone group or a carboxyl group and a hydroxyl group in the polymer main chain, and further opening the lactone ring by hydrolysis. 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. The method according to claim 1, wherein 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. 4 the diols are polyethylene glycol and diethylene glycol, the lactone is delta gluconolactone, and the urethane precursor is methylene di(cyclohexyl isocyanate);
The 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 dilaurate. Claim 4
Manufacturing method described in section.